EP4200139A1 - Matière d'impression thermosensible et couche d'impression thermosensible et composition de revêtement pour la réaliser, utilisations correspondantes et procédé - Google Patents

Matière d'impression thermosensible et couche d'impression thermosensible et composition de revêtement pour la réaliser, utilisations correspondantes et procédé

Info

Publication number
EP4200139A1
EP4200139A1 EP21763350.2A EP21763350A EP4200139A1 EP 4200139 A1 EP4200139 A1 EP 4200139A1 EP 21763350 A EP21763350 A EP 21763350A EP 4200139 A1 EP4200139 A1 EP 4200139A1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording layer
mass
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21763350.2A
Other languages
German (de)
English (en)
Inventor
Claas Boxhammer
Christoph Jörg HAHN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi HiTec Paper Europe GmbH
Original Assignee
Mitsubishi HiTec Paper Europe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Publication of EP4200139A1 publication Critical patent/EP4200139A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3372—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a heat-sensitive recording layer comprising organic color developers free from phenol groups, 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 present invention further relates to the use of the heat-sensitive recording layer for the production of the heat-sensitive recording material, a method for the production of the heat-sensitive recording material and the use of the heat-sensitive recording material in thermal paper applications. Because of its composition, the heat-sensitive recording material of the present invention has particularly good recyclability and high environmental compatibility.
  • Heat-sensitive recording materials (often also referred to as "thermal papers”) have been known for many years and are very popular. This popularity is based, among other things, on the fact that the color-forming components are contained in the recording material itself, meaning that toner-free and color-cartridge-free printers can be used. It is therefore no longer necessary to use, store, change or refill toner or color cartridges. This is how this innovative technology Technology in business life, especially in public transport and in retail, has been widely implemented, where its flexible use in business transactions (at the "point-of-sale”) is valued.
  • Pergafast® 201 corresponds to A/-(4-methylphenylsulfonyl)-A/'-(3-(4-methylphenylsulfonyloxy)phenyl)urea), "D8" (corresponds to 4-hydroxy -4'-isopropoxydiphenylsulfone), A/-[2-(3-phenylureido)phenyl]benzenesulfonamide or A/- ⁇ 2-[(phenylcarbamoyl)amino]phenyljbenzenesulfonamide.
  • document DE 10 2004 004 204 A1 proposes a heat-sensitive recording material whose heat-sensitive recording layer contains conventional dye precursors and the combination of a phenolic color developer and a urea-urethane-based color developer.
  • the document DE 102015 104 306 A1 describes a heat-sensitive recording material that has a carrier substrate and a heat-sensitive color-forming agent containing at least one color former and at least one phenol-free color developer layer, N-phenyl-N'[(phenylamino)sulfonyl]urea, N-(4-methylphenyl)-N'[(4-ethylphenylamino)sulfonyl]urea, N- (4-ethoxycarbonylphenyl)-N'[(4-ethoxycarbonylphenylamino)sulfonyl]urea or structurally similar compounds can be used.
  • the document EP 3 219 507 A1 describes a self-adhesive heat-sensitive recording material which comprises a carrier substrate and a heat-sensitive color-forming layer applied to one side of the carrier substrate.
  • the proportion of sensitizer in the heat-sensitive color-forming layer is more than 5% by weight.
  • the document JP 2014-218062 A describes a heat-sensitive recording material with a heat-sensitive recording layer which contains at least one leuco dye and a color developer on a carrier.
  • a mixture of 4,4'-bis(3-tosylureido)diphenylmethane and N-[2-(3-phenylureido)phenyl]benzenesulfonamide is used as the color developer.
  • WO 2016/136203 A1 describes a crystalline form of N-(2-(3-phenylureido)phenyl)benzenesulfonamide and the use of this crystalline form in a recording material.
  • Document US 2005/0148467 A1 relates to a heat-sensitive recording material which contains at least the components of two color-forming systems to form an irreversible print image, one system being of the chelate type and the other being a conventional leuco-dye system.
  • the documents WO 2018/065328 A1 and WO 2018/065330 A1 each disclose a heat-sensitive recording material comprising a carrier substrate and a heat-sensitive recording layer, the heat-sensitive recording layer comprising a color former and a color developer mixture.
  • the document WO 2019/166608 A1 describes a heat-sensitive recording material and color developer.
  • a printed heat-sensitive recording material is exposed to a variety of different environmental influences, such as humidity, temperature extremes and/or chemicals, given its typical areas of application as tickets, entrance tickets, transport tickets, parking tickets and the like.
  • heat-sensitive recording materials should therefore also have the highest possible resistance to thermal influences.
  • the printed image should be preserved after printing and when exposed to heat, the printed image should fade as little as possible and the unprinted background should not discolor: this would make the print illegible.
  • Thermal resistance is particularly important for parking tickets, which are stored behind the windshield after printing and are therefore exposed to high temperatures and direct sunlight in summer.
  • a further object of the present invention was to provide a heat-sensitive recording material which, in the printed state, has high resistance to environmental influences, such as moisture, heat, fat or fats and/or chemicals.
  • a heat-sensitive recording layer preferably for the production of a heat-sensitive recording material, comprising:
  • K3 one or more crosslinked or uncrosslinked, polymeric organic binders, preferably selected from the group consisting of starch, unmodified polyvinyl alcohols, polyvinyl alcohols modified with carboxyl groups, polyvinyl alcohols modified with silanol groups, polyvinyl alcohols modified with silanol groups, diacetone-modified polyvinyl alcohols, acetoacetyl-modified polyvinyl alcohols, partially and fully saponified polyvinyl alcohols, film-forming acrylic copolymers (preferably alkylene/(meth)acrylic acid copolymers and mixtures thereof;
  • K6 one or more lubricants, the sum of the components K1) to K6) making up >95 percent by weight of the dry weight of the heat-sensitive recording layer.
  • composition of the above-mentioned heat-sensitive recording layer according to the invention makes it possible to use it to produce a heat-sensitive recording material, in particular a thermal paper, which has particularly good recyclability and high environmental compatibility.
  • the heat-sensitive recording layer according to the invention preferably and/or does not contain any developers containing phenol groups, which makes it particularly suitable for the production of heat-sensitive recording material with good recyclability, since such heat-sensitive recording material causes little or no irreversible discoloration, for example in deinking systems .
  • the heat-sensitive recording layer according to the invention and the heat-sensitive recording material according to the invention also come without classic organic sensitizer compounds (hereinafter referred to as "sensitizers”) such as benzyl 2-naphthyl ether, 1,2-diphenoxyethane, 1,2-bis(3 -methyl-phenoxy)-ethane or 1-phenoxy-2-(4-methylphenoxy)ethane, which are increasingly regarded as unattractive from the point of view of environmental compatibility.
  • sensitizers organic sensitizer compounds
  • the heat-sensitive recording layer according to the invention and the heat-sensitive recording material according to the invention manage without classic organic sensitizer compounds, their presence is not excluded and in specific embodiments of the present invention is not harmful, even if it is preferred that the classic organic sensitizer compounds mentioned are at most in small amounts or preferably not included at all.
  • a heat-sensitive recording layer according to the invention and a heat-sensitive recording material according to the invention each not comprising one or more of the sensitizers from the group consisting of benzyl 2-naphthyl ether, 1,2-diphenoxyethane, 1,2-bis(3-methylphenoxy)ethane and 1-phenoxy-2-(4-methylphenoxy)ethane.
  • the heat-sensitive recording layer according to the invention preferably does not contain any organic hollow body pigments which could get into the environment as unwanted “microplastics”. Dyes that are potentially harmful to the environment or health, such as carbon black, can preferably be completely dispensed with in the heat-sensitive recording layer according to the invention and in the heat-sensitive recording material according to the invention.
  • the above-mentioned heat-sensitive recording layer according to the invention exclusively comprises components (or constituents) which, according to the "Award criteria for printing and press paper mainly made of waste paper", DEUZ 72, January 2020 edition, version 1, for the "Blue Angel” environmental label German Federal Ministry for the Environment, Nature Conservation and Nuclear Safety (hereinafter referred to as “Blue Angel Award Criteria DE-UZ 72") or the "Award Criteria for Graphic Paper and Cardboard Made from 100% Waste Paper (Recycled Paper and Cardboard)", DE-UZ 14a , January 2020 edition, version 2, for the aforementioned “Blue Angel” eco-label (hereinafter referred to as “Award Criteria Blue Angel DE-UZ 14a”).
  • the heat-sensitive recording layer according to the invention specified above comprises, as component K1), one or more organic dye precursors, each of which comprises a fluoran structure.
  • the compound fluoran per se is known as a triarylmethane dye.
  • the chemical structure of the fluoran is of formula I given below also known as the structural core of a number of organic dye precursors, which include substituted derivatives of fluoran (also referred to as "fluorane leuco dyes" and "fluorane leuco dye precursors,” respectively).
  • the abovementioned heat-sensitive recording layer according to the invention preferably comprises as component K1) one or more organic dye precursors which comprise an abovementioned substituted fluoran structure of the formula I as the structural core.
  • the heat-sensitive recording layer according to the invention specified above comprises, as component K4), one or more, preferably synthetic, amide waxes which each have a melting point in the range from 80.degree. C. to 120.degree.
  • amide waxes are preferably synthetically produced waxes, which are preferably produced by reacting technical fatty acids, fatty acid esters and/or triacylglycerols with ammonia, monovalent amines, polyvalent amines and/or amino alcohols.
  • These one or more, preferably synthetic, amide waxes to be used according to the invention as component K4) act as or assume the function of a sensitizer known per se.
  • a sensitizer used in a heat-sensitive recording layer is at least partially melted by the application of heat during printing.
  • the at least partially melted sensitizer dissolves and/or lowers the melting point (or melting range) of the color former and color developer coexisting in a heat-sensitive recording layer, thereby facilitating or inducing a color-developing reaction.
  • the sensitizer does not usually take part in the color development reaction itself.
  • the above-mentioned heat-sensitive recording layer according to the invention (or a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text) therefore preferably contains such sensitizers in a total amount of ⁇ 1 percent by mass, based on the dry mass of the heat-sensitive recording layer, which are selected from the group “Classic” sensitizers consisting of 1,2-bis(3-methylphenoxy)ethane, 1,2-diphenoxyethane, 1-phenoxy-2-(4-methylphenoxy)ethane, benzyl 2-naphthyl ether, 2-(2H- Benzotriazol-2-yl)-p-cresol, 2,2'-bis(4-methoxyphenoxy)diethyl ether, 4,4'-diallyloxydiphenylsulfone, 4-acetylacetophenone, 4-benzylbiphenyl, acetoacetic anilide, benzyl-4-(benzyloxy) benzoate, benz
  • Such preferred heat-sensitive recording layers according to the invention offer the advantage that they (if the other components are selected appropriately) can also be used safely, for example in the food sector, even if, for example, direct or indirect contact of the recording layer with the food cannot be ruled out.
  • the heat-sensitive recording layer according to the invention specified above comprises one or more particulate inorganic pigments as component K5).
  • the particulate inorganic pigments to be used according to the invention preferably not only or not primarily fulfill the function of dyes, but also at least or even predominantly fulfill the function of particulate fillers. If the particulate inorganic pigments to be used according to the invention also have at least the function of dyes, they are preferably white pigments. For more information on the particulate inorganic pigments to be used according to the invention, see also below.
  • the inventive heat-sensitive recording layer specified above preferably comprises organic hollow body pigments (in particular those as specified or defined in document WO 2012/145456 A1) in a total amount of ⁇ 1 percent by mass, based on the dry mass of the heat-sensitive recording layer.
  • organic hollow body pigments in particular those as specified or defined in document WO 2012/145456 A1
  • the above-mentioned heat-sensitive recording layer according to the invention contains no such organic hollow body pigments.
  • the heat-sensitive recording layer according to the invention specified above comprises one or more lubricants as component K6).
  • lubricant is understood to mean - as is customary in the paper industry - additives for plastic materials containing fillers (such as coating colors or coating materials), which preferably serve to make the fillers more easily lubricated and the plastic materials thus lighter to make it malleable or workable.
  • the one or more lubricants of component K6) are preferably selected from the group consisting from metal soaps (preferably salts of fatty acids having a total number of carbon atoms in the range >12 to ⁇ 22 with mono- or di-positively charged metal ions), wax dispersions, paraffin dispersions, sulfated oils and mixtures thereof.
  • metal soaps preferably salts of fatty acids having a total number of carbon atoms in the range >12 to ⁇ 22 with mono- or di-positively charged metal ions
  • wax dispersions preferably salts of fatty acids having a total number of carbon atoms in
  • the sum of the components K1) to K6) makes up >95 percent by weight of the dry weight of the heat-sensitive recording layer.
  • “Dry mass” in the context of the present invention is preferably understood to mean the water- and moisture-free mass of a sample (here: the heat-sensitive recording layer according to the invention) measured (under laboratory conditions at 23° C. and 50% RH).
  • the dry mass is preferably determined—as is customary in the field—on the sample to be examined (here: the heat-sensitive recording layer according to the invention), which had been dried at 105° C. to constant weight before the determination. Methods for determining the dry matter of a sample are known to those skilled in the art:
  • the dry mass of a sample can be determined for the purposes of the present invention by a sample of defined mass before drying (e.g. 1.5 g of the sample before drying) at 105° C. for five hours dries in the drying oven and then, after cooling to room temperature (in case of doubt to 23 °C) checks for constant weight (sample, e.g. by heating it up again and determining the mass again) in a manner known per se, whereby, of course, reabsorption of water during the cooling process must be avoided (desiccator ).
  • a sample of defined mass before drying e.g. 1.5 g of the sample before drying
  • room temperature in case of doubt to 23 °C
  • the dry mass of a sample in particular a sample of the heat-sensitive recording layer according to the invention
  • a moisture determination device for example a halogen moisture determination device known per se, under the conditions specified above (105° C., heating to constant weight).
  • K7 one or more process aids, preferably selected from the group consisting of defoamers, biocides, dispersants, and wetting agents, preferably in a total amount of ⁇ 5 percent by mass, particularly preferably in a total amount in the range from> 0.1 to ⁇ 3 percent by mass and more preferably in the range of >0.1 to ⁇ 2% by mass based on the dry mass of the heat-sensitive recording layer.
  • process aids preferably selected from the group consisting of defoamers, biocides, dispersants, and wetting agents, preferably in a total amount of ⁇ 5 percent by mass, particularly preferably in a total amount in the range from> 0.1 to ⁇ 3 percent by mass and more preferably in the range of >0.1 to ⁇ 2% by mass based on the dry mass of the heat-sensitive recording layer.
  • the one or more processing aids K7) preferably serve to facilitate or enable the processing of a heat-sensitive recording layer according to the invention (or a coating composition according to the invention for producing a heat-sensitive recording layer according to the invention) in the industrial production process, in particular in the industrial process of paper production.
  • a heat-sensitive recording layer according to the invention as indicated above (or a heat-sensitive recording layer according to the invention indicated as preferred in this text) which additionally comprises one or more optical brighteners may be preferred. If a heat-sensitive recording layer according to the invention additionally comprises one or more optical brighteners, it is preferred if the heat-sensitive recording layer according to the invention contains this one or more optical brighteners in a total amount of ⁇ 1 percent by mass, more preferably in a total amount of ⁇ 0.75 percent by mass, based on the dry mass of the heat-sensitive recording layer. Particularly preferably, the above-mentioned heat-sensitive recording layer according to the invention (or a heat-sensitive recording layer according to the invention which is referred to as preferred in this text) contains no optical brighteners.
  • a heat-sensitive recording layer according to the invention specified above (or a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text), the sum of components K1) to K6) being >97 percent by mass, preferably >98 percent by mass, more preferably >98, 5 percent by mass that makes up the dry mass of the heat-sensitive recording layer, where preferably (in cases in which the heat-sensitive recording layer according to the invention comprises a component K7) the sum of the components K1) to K7) makes up >99 percent by mass, particularly preferably 100 percent by mass, of the dry mass of the heat-sensitive recording layer.
  • thermosensitive recording layer according to the invention as indicated above (or a heat-sensitive recording layer according to the invention indicated as preferred in this text), wherein
  • the one or at least one of the several organic dye precursors K1) is selected from the group consisting of 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-(3'-methylphenylamino)fluoran, 3 -(Diethylamino)-6-methyl-7-(3-methylphenylamino)fluoran (ODB-7), 3-di-n-pentylamino-6-methyl-7-anilinofluoran, 3-di-n-butylamino -7-(2-chloroanilino)fluoran, 3-diethylamino-7-(2-chloroanilino)fluoran, 3-diethylamino-6-methyl-7-xylidinofluoran, 3-diethylamino-7-(2-carbomethoxy-phenylamino) fluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6
  • thermosensitive recording layer according to the invention as specified above (or a heat-sensitive recording layer according to the invention indicated as preferred in this text), wherein
  • each no phenol structural element of the formula II, and/or one or at least one of the several phenol-group-free organic color developers K2) is selected from the group consisting of A/-(4-methylphenylsulfonyl)-/V'-(3-(4-methylphenylsulfonyloxy)phenyl )urea, 5-(N-3-methylphenylsulfonylamido)-(N',N''-bis-(3-methylphenyl)isophthalic acid diamide, A/-[2-(3-phenylureido)phenyl]benzenesulfonamide and their mixtures, and/or
  • the one or more phenol group-free organic color developers K2) are present in a total amount in the range from >12 to ⁇ 35 percent by mass, preferably from >15 to ⁇ 30 percent by mass, based on the dry mass of the heat-sensitive recording layer.
  • color developers which contain phenol groups and which are therefore preferably not used as phenol-group-free organic color developers K2) in an above-mentioned heat-sensitive recording layer according to the invention include in particular the known compounds bisphenol A (4,4'-propane-2,2-diyldiphenol), bisphenol S (4,4'-sulfonyldiphenol), bisphenol AP (1,1-bis(4-hydroxyphenyl) -1-phenylethane CAS RN 1571-75-1), 4-[(4-isopropoxyphenyl)sulfonyl]phenol (aka “D8", CAS RN 95235-30-6), 4,4'-methylenediphenol, 2, 2'-Methylenediphenol, 4-[4'-[(1'-Methylethyloxy)phenyl]sulfonyl]phenol (also known as "D90", CAS RN 191680-83-8), 2,2'-Diallyl-4,4 '-sulfonyldi
  • one or at least one of the several phenol-free organic color developers K2) can be the compound A/-(4-methylphenylsulfonyl)-A/'-(3-(4-methylphenylsulfonyloxy)phenyl)urea of formula III be or include (see above), which is also known under the name "Pergafast 201" (CAS No. 232938-43-1).
  • one or at least one of the several phenol-group-free organic color developers K2) can also contain the compound 5-(N-3-methylphenylsulfonylamido)-(N',N"-bis-(3-methylphenyl )-isophthalic acid diamide of the formula IV be.
  • the compound 5-(N-3-methylphenylsulfonylamido)-(N',N"-bis-(3-methylphenyl)isophthalic acid diamide of the formula IV is known per se, for example from document WO 2019/166608 A1, and can be prepared according to the methods specified there.
  • the compound of the formula IV can be present in several different crystalline forms. These different crystalline forms can have different physical properties which can have influences on a heat-sensitive recording layer containing such crystalline forms as a color developer.
  • crystalline modification "a" as crystalline modification "ß” or as crystalline modification "y”
  • the heat-sensitive recording layer according to the invention can contain any one of these three different crystalline inen forms of the compound of formula IV (as component K2)) and mixtures thereof.
  • a heat-sensitive recording layer according to the invention as described above (preferably a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text), wherein the compound of formula I comprises a crystalline form or wherein the compound of formula IV is present in a crystalline form, wherein preferably the or at least one crystalline form of the compound of formula IV has a melting point in the range from 195°C to 217°C, preferably from 200°C to 215°C, particularly preferably from 205°C to 213°C by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • a heat-sensitive recording layer according to the invention as described above (preferably a heat-sensitive recording layer according to the invention, which is referred to in this text as preferred), wherein the compound of formula IV comprises a crystalline form or wherein the compound of formula IV is present in a crystalline form, wherein the crystalline form of the compound of the formula I is the crystalline modification “a” as described in WO 2019/166608 A1, p. 8, lines 9-13.
  • a heat-sensitive recording layer according to the invention as described above (preferably a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text), wherein the compound of the formula IV comprises a crystalline form or wherein the compound of the formula IV is present in a crystalline form, where the crystalline form of the compound of the formula IV has an X-ray powder diffractogram with diffraction reflections at °20 values (+/ ⁇ 0.2°) of 5.5, 6.1, 6.4, 12.1, 16.1, 16.8, 17.1, 18.3, 19.1, 19.9, 20.2, 21.4, 22.1, 22.7, 23.3, 24.3, 24.7, 25.0, 26.4, 27.7 and 29.3.
  • a heat-sensitive recording layer according to the invention as described above (preferably a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text), in which >95% by mass, preferably all (100% by mass) of the compound of the formula IV , as a crystalline modification "a" (as described above), based on the total mass of the compound of the formula IV present in the heat-sensitive recording layer.
  • the one or at least one of the several phenol-free organic color developers K2) can also be the compound A/-[2-(3-phenylureido)phenyl]benzenesulfonamide of the formula V be.
  • the compound N-[2-(3-phenylureido)phenyl]benzenesulfonamide of the formula V is one, for example from EP 2 923 851 A1, per se well-known connection, for example also under the designation "NKK-1304".
  • the compound of the formula V can exist in several different critical talline forms. These different crystalline forms may have different physical properties, which may have influences on a heat-sensitive recording layer containing such crystalline forms as a color developer.
  • the compound of the formula V which is not differentiated according to polymorphic forms, is assigned CAS RN 215917-77-4 in the literature.
  • the heat-sensitive recording layer according to the invention can contain each of these three different crystalline forms of the compound of the formula V (as component K2)) and mixtures thereof.
  • the first of these crystalline forms of the compound of formula V has a melting point of about 158°C. This crystalline form was described in connection with heat-sensitive recording materials, e.g. in EP 2 923 851 A1.
  • the second crystalline form of the compound of formula V has a melting point of about 175°C.
  • the compound of formula V which is the crystalline form with a melting point of 175°C, has been described, for example, in document WO 2018/065328 A1.
  • the third crystalline form of the compound of formula V has a melting point of about 160°C to 162°C and was described, for example, in document EP 3 263 553 A1.
  • DSC differential thermal analysis
  • DKK differential scanning calorimetry
  • At least the first and the second of the aforementioned crystalline forms of the compounds of formula V can also be distinguished from one another in the IR absorption spectrum.
  • An absorption band in the IR spectrum at 3401 ⁇ 20 cm' 1 is particularly characteristic of the crystalline form of the compound of the formula V used according to the invention. In the crystalline form of the compound of formula V, which has a melting point of 158 °C, this band is not present, but rather a band at 3322 and 3229 cm 1 .
  • a heat-sensitive recording layer is also preferred according to the invention, the crystalline form of the compound of the formula V in the IR spectrum having absorption bands at 689 ⁇ 10 cm' 1 , 731 ⁇ 10 cm' 1 , 1653 ⁇ 10 cm' 1 3364 ⁇ 20 cm' 1 and 3401 ⁇ 20 cnr 1 (“second crystalline form of the compound of formula V”).
  • a heat-sensitive recording material in which the IR absorption spectrum of the crystalline form of the compound of the formula V essentially corresponds to the IR absorption spectrum shown in FIG. 1a), 2a) and/or 3a) of WO 2018/065328 A1 ( "second crystalline form of the compound of formula V").
  • At least the first and the second of the aforementioned crystalline forms of the compound of the formula V can also be distinguished from one another in the X-ray powder diffractogram or diffraction diagram.
  • a heat-sensitive recording material is preferred according to the invention, the crystalline form of the compound of the formula V having an X-ray powder diffractogram with reflections at °20 values of 10.00 ⁇ 0.20, 11.00 ⁇ 0.20, 12.40 ⁇ 0.20, 13.80 ⁇ 0.20 and 15.00 ⁇ 0.20 ("second crystalline form of the compound of formula V").
  • a heat-sensitive recording layer is preferred according to the invention, in which the crystalline form of the compound of the formula V has an X-ray powder diffraction pattern which essentially corresponds to the X-ray powder diffraction pattern shown in FIG. 4b) of WO 2018/065328 A1 (“second crystalline form of the compound of the formula V” ).
  • a compound of the formula V preferably describes the crystalline form which has an absorption band at 3401 ⁇ 20 cm -1 in the IR spectrum or has a melting point of 175° C. or has a transition at a temperature between 170 °C and 178 °C (determined by differential thermal analysis, at a heating rate of 10 K/min) or in the X-ray powder diffractogram diffraction reflections at °20 values of at least 10.00 ⁇ 0.20.1 1.00 ⁇ 0.20, 12.40 ⁇ 0.20, 13.80 ⁇ 0.20 and 15.00 ⁇ 0.20 unless the presence of the other crystal structure is explicitly stated ("second crystalline form of the compound of formula V").
  • a heat-sensitive recording layer according to the invention as described above (preferably a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text), wherein the compound of formula V comprises a crystalline form or wherein the compound of formula V is in a crystalline form ( if the heat-sensitive recording layer comprises, for example, a color developer mixture, the color developer mixture comprising, in addition to a compound of the formula IV, at least one further organic color developer which comprises or is a compound of the formula V), with preferably the or at least one crystalline form of the compound of the formula II im IR spectrum has an absorption band at 3401 ⁇ 20 cm -1 .
  • a heat-sensitive recording layer according to the invention specified above (or a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text) is particularly preferred, wherein the one or at least one of the several phenol-group-free organic color developers K2) is selected from the group consisting of
  • the mass ratio between the compound of the formula V and the compound of the formula III is in the range from 0.5:99.5 to 35:65, preferably in the range from 5:95 to 30:70, particularly preferably in the range from 15:85 to 25:75; or the mass ratio between the compound of the formula V and the compound of the formula III is in the range from 99.5:0.5 to 65:35, preferably in the range from 97:3 to 85:15, particularly preferably in the range from 95: 5 to 90:10; or the mass ratio between the compound of formula V and the compound of formula III is in the range from 0.5:99.5 to 99.5:0.5, preferably in the range from 35:65 to 65:35, more preferably im is in the
  • a color developer mixture containing a compound of formula IV as defined above, where preferably the compound of formula IV is present in the crystalline modification "a" (as defined above), and a compound of formula V (NKK-1304) as defined above, where preferably the compound of formula V is present in a crystalline form which has an absorption band at 3401 ⁇ 20 cm-1 in the IR spectrum, the mass ratio between the compound of formula IV and the compound of formula V preferably being in the range from 5:95 to 99.9:0.1, preferably from 10:90 to 99:1, more preferably from 30:70 to 99:1 and most preferably from 50:50 to 98:2.
  • the compound of the formula III (Pergafast 201) defined above, in the quantitative ratios defined above, and the advantages that can be achieved with this color developer mixture in a heat-sensitive recording layer or in a heat-sensitive recording material are described in the documents WO 2018/065328 A1 and WO 2018/065330 A1 , the contents of which are hereby expressly referred to in connection with the present invention.
  • the one or more polymeric organic binders K3 are present in a total amount in the range from >7 to ⁇ 25 percent by mass, preferably from >8 to ⁇ 20 percent by mass, based on the dry mass of the heat-sensitive recording layer.
  • the one or at least one of the several polymeric organic binders K3) is selected from the group consisting of polyvinyl alcohol and starch, the one or at least one of the several polymeric organic binders K3) preferably being polyvinyl alcohol.
  • the one or more, preferably synthetic, amide waxes K4) comprise or are one or more fatty acid monoamides, each of which has a melting point in the range from 80° C. to 120° C., with the one or at least one of the several amide waxes K4) preferably being a monoamide a saturated fatty acid, the fatty acid residue of which has a total number of carbon atoms in the range from >12 to ⁇ 20, preferably in the range from >14 to ⁇ 18, more preferably in the range from >16 to ⁇ 18; particularly preferably one or at least one of the several amide waxes is selected from the group consisting of lauric acid amide, myristic acid amide, palmitic acid amide, octadecanamide (synonym: stearic acid amide, CAS RN 124-26-5), N-methylolstearic acid amide (synonym: (N-(hydroxymethyl ) octadecanamide, CAS RN 3
  • thermal printouts produced with a heat-sensitive recording layer according to the invention or with a heat-sensitive recording material according to the invention have particularly advantageous properties if the heat-sensitive recording layer used for this purpose contains the one or more amide waxes K4) (preferably the ones mentioned above as preferred designated one or more amide waxes K4) in the total amount indicated above (preferably in the total amounts indicated above as preferred).
  • the particularly advantageous properties of the thermal printouts produced in this way include, in particular, a high level of to plasticizers, high resistance to lanolin, high resistance to water or aqueous ethanol solution, but also high climate resistance and high heat resistance.
  • heat-sensitive recording materials produced with heat-sensitive recording layers according to the invention have a dynamic print density which is generally at least comparable to that of a conventional heat-sensitive recording material and in some cases even better.
  • the dynamic print density of a heat-sensitive recording material indicates how quickly a heat-sensitive recording material can be printed on. The higher the dynamic print density, the faster a thermal printer can print on the heat-sensitive recording material with otherwise unchanged settings.
  • the one or at least one of the several inorganic pigments K5) is selected from the group consisting of calcined kaolin, kaolin, kaolinite, magnesium silicate hydrate, silicon dioxide (including silica), bentonite, calcium carbonate, calcium silicate hydrate, calcium aluminate sulfate, aluminum hydroxide, aluminum oxide, boehmite and mixtures thereof, where preferably one or at least one of the plurality of inorganic pigments K5) is calcium carbonate; and or
  • the one or more inorganic pigments K5) are present in a total amount in the range from >9 to ⁇ 50 percent by mass, preferably from >10 to ⁇ 40 percent by mass, particularly preferably from >10 to ⁇ 35 percent by mass, based on the dry mass of the heat-sensitive recording layer .
  • thermosensitive recording layer according to the invention or a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text, wherein - the one or at least one of the several lubricants K6) is selected from the group consisting of
  • Paraffin waxes preferably with a melting or softening point in the range from 45°C to 80°C and
  • the one or more lubricants K6 are present in a total amount in the range from> 1.5 to ⁇ 10 percent by mass, preferably from> 2 to ⁇ 8 percent by mass, particularly preferably from> 2 to ⁇ 6 percent by mass, based on the dry mass of the heat-sensitive recording layer.
  • the present invention also relates to a coating composition for producing a heat-sensitive recording layer, comprising the components K1) to K6) defined above and preferably component K7) as above for the heat-sensitive recording layer according to the invention (or for a heat-sensitive recording layer according to the invention, which is referred to in this text as preferably designated), wherein preferably the coating composition additionally comprises:
  • one or more carrier liquids preferably selected from the group consisting of (i) water, (ii) monohydric alcohols having a total number of carbon atoms in the range from 1 to 4 and (iii) mixtures of water with one or more monohydric alcohols with a Total number of carbon atoms ranging from 1 to 4.
  • the present invention also relates to a heat-sensitive recording material, preferably thermal paper, comprising or consisting of
  • a substrate preferably a paper substrate, preferably having a front side and a back side opposite the front side and
  • a heat-sensitive recording layer according to the invention as described above (or a heat-sensitive recording layer according to the invention indicated as preferred in this text), which is arranged on at least one of the sides of the substrate.
  • thermal printouts with particularly advantageous properties.
  • thermal printouts include, in particular, high resistance to plasticizers, high resistance to lanolin, high resistance to water or aqueous ethanol solution, but also high climate resistance and high heat resistance.
  • heat-sensitive recording materials produced with heat-sensitive recording layers according to the invention have a dynamic print density which is generally at least comparable to that of a conventional heat-sensitive recording material and in some cases even better.
  • the heat-sensitive recording material has one or more (preferably one) intermediate layers arranged between the substrate and the heat-sensitive recording layer; and or
  • the area-related dry mass of the heat-sensitive recording layer in the range from > 1.8 g/m 2 to ⁇ 2.5 g/m 2 , preferably in the range from > 2.0 g/m 2 to ⁇ 2.4 g/m 2 , more preferably in the range from >2.0 g/m 2 to ⁇ 2.3 g/m 2 and particularly preferably in the range from >2.0 g/m 2 to ⁇ 2.20 g/m 2 ; or the area-related dry mass of the heat-sensitive recording layer in the range from >1.8 g/m 2 to ⁇ 2.3 g/m 2 , preferably in the range from >1.9 g/m 2 to ⁇ 2.2 g/m 2 , particularly preferably in the range from >1.9 g/m 2 to ⁇ 2.15 g/m 2 ; and or
  • the substrate is a paper substrate and the paper substrate contains > 80% by mass of recycled fibers, based on the total mass of the air-dried paper substrate;
  • the substrate is a paper substrate and the paper substrate contains ⁇ 25 percent by mass of fresh fibers, based on the total mass of the air-dried paper substrate.
  • an intermediate layer preferably comprises pigments and/or fillers.
  • the pigments (or fillers) of such an intermediate layer are preferably inorganic pigments (or fillers), particularly preferably selected from the list consisting of calcined kaolin, silicon dioxide, bentonite, calcium carbonate, aluminum oxide and boehmite.
  • inorganic pigments are integrated into the intermediate layer between the recording layer and the substrate, they can absorb the components (e.g. waxes) of the heat-sensitive recording layer that have been liquefied by the heat of the thermal head during the formation of the typeface and thus promote even more reliable and faster functioning of the heat-induced recording.
  • the inorganic pigments (or fillers) of the intermediate layer have an oil absorption of at least 80 cm 3 /100 g and even better of 100 cm 3 /100 g, determined according to Japanese standard JIS K 5101. Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities. Mixtures of several different types of inorganic pigments are also conceivable.
  • a heat-sensitive recording material is preferred according to the invention, the intermediate layer optionally containing, in addition to the inorganic pigments (or fillers), at least one binder, preferably based on a synthetic polymer, with styrene-butadiene latex giving particularly good results.
  • a synthetic binder with the admixture of at least one natural polymer, such as particularly preferably starch, represents a particularly suitable embodiment.
  • a binder-pigment ratio within the intermediate layer of between 3: 7 and 1:9, each based on the percentage by mass in the intermediate layer, represents a particularly suitable embodiment.
  • the dry mass per unit area of an intermediate layer described above is in the range from 5 to 20 g/m 2 , preferably in the range from 7 to 12 g/m 2 .
  • an above-mentioned heat-sensitive recording material according to the invention preferably a heat-sensitive recording material according to the invention, which is referred to as preferred in this text
  • the area-related dry mass of the heat-sensitive recording layer is in the range from >1.8 g/m 2 to ⁇ 2.3 g/m 2 , preferably in the range from >1.9 g/m 2 to ⁇ 2.2 g/ m 2 , particularly preferably in the range from >1.9 g/m 2 to ⁇ 2.15 g/m 2 .
  • Such a variant of the present invention enables a particularly economical production of a heat-sensitive recording material with only a small consumption of material.
  • a further advantage in the case of such a variant is that only relatively small amounts of waste arise when disposing of a heat-sensitive recording material. Since a heat-sensitive recording material according to the invention also largely or preferably exclusively contains components that meet the award criteria of the "Blue Angel" (see above), a heat-sensitive recording material according to the invention has a particularly good life cycle assessment according to this variant.
  • the mass of an "air dry" paper substrate given above is determined under standard ambient conditions (23°C, 50% RH, 1013 hPa). A water content of the paper substrate of 10 percent by mass is assumed for an air-dried paper substrate--as is customary in the technical field.
  • the present invention also relates to the use of an above-described heat-sensitive recording layer according to the invention (or a heat-sensitive recording layer according to the invention, which is referred to as preferred in this text) for the production of a heat-sensitive recording material, preferably for the production of a heat-sensitive recording material according to the invention (or a heat-sensitive according to the invention recording material designated as preferred in this text).
  • the present invention also relates to a method for the production of a heat-sensitive recording material, preferably for the production of a heat-sensitive recording material according to the invention described above (or a heat-sensitive recording material according to the invention, which is referred to as preferred in this text), at least comprising the steps:
  • no organic color developers containing phenol groups are used, preferably no organic color developers containing phenol groups, which are selected from the group consisting of bisphenol A, bisphenol S, bisphenol AP, (4-[(4-isopropoxyphenyl)sulfonyl]phenol, 4, 4'-methylenediphenol, 2,2'-methylenediphenol, 4-[4'-[(1'-methylethyloxy)phenyl]sulfonyl]phenol, 2,2'-diallyl-4,4'-sulfonyldiphenol, 4-4 '-Methylenebis-(oxyethylenethio)diphenol and mixtures thereof, and/or
  • organic sensitizers are used, preferably no organic sensitizers are used which are selected from the group consisting of 1,2-bis(3-methylphenoxy)ethane, 1,2-diphenoxyethane, 1-phenoxy-2-(4-methylphenoxy).
  • no organic hollow body pigments preferably no organic hollow body pigments as described in document WO 2012/145456 A1 are used.
  • V2 producing or providing a substrate, preferably a paper substrate, preferably having a front side and a back side opposite the front side,
  • step V3) Application of the coating composition from step V1) to at least one side of the substrate, or to at least one side of an intermediate layer arranged on the substrate, preferably using a coating device, the coating device preferably being selected from the group consisting of roller doctor coater, knife coater, curtain coater and air brush;
  • step V4) Preferably drying the coating composition applied in step V3) to form a heat-sensitive recording layer, preferably resulting in a heat-sensitive recording material according to the invention.
  • the present invention also relates to the use of a heat-sensitive recording material according to the invention described above (or a heat-sensitive recording material according to the invention, which is referred to as preferred in this text) as a flight, train, ship or bus ticket, gambling receipt, parking ticket, label, receipt , self-adhesive label, medical chart paper, fax paper and/or barcode label.
  • inventive use of a heat-sensitive recording material according to the invention and in this regard possible combinations of one or more aspects of the invention specified here above with one another, the above apply to the heat-sensitive recording layer according to the invention and / or for the coating composition according to the invention and / or for the inventive heat-sensitive recording material and/or for the use according to the invention of a heat-sensitive recording layer according to the invention and/or for the method according to the invention for the production of a heat-sensitive recording material corresponding to the explanations given in each case, and vice versa.
  • a raw paper with a mass per unit area of 42 g/m 2 was provided as the paper substrate.
  • a coating composition for forming an intermediate layer having a basis weight (dry weight) of 9 g/m 2 was applied on the front side of this paper substrate with a bar coater and dried conventionally. Water was used as the carrier liquid for the coating composition for forming an intermediate layer.
  • a coating composition according to the invention (for the production of a heat-sensitive recording layer) was prepared by mixing the constituents listed below in Table 2 with one another, water being used as the carrier liquid.
  • Table 2 Constituents of a coating composition according to the invention for producing a heat-sensitive recording layer
  • compositions according to the invention were prepared in accordance with the preparation process described here above, with the amount of octadecanamide being varied in each case, while the proportion of the other components was not changed.
  • the coating compositions prepared in this way, their abbreviations and the total amounts of octadecanamide used in each case (in percent by mass, based on the dry mass of the coating composition) in these coating compositions are given in Table 3 below.
  • a coating composition according to the invention for the production of a heat-sensitive recording layer was provided (for production see Example 2 above) and a paper substrate which was coated on its front side with an intermediate layer (for production see Example 1 above).
  • the coating composition according to the invention was then applied to the intermediate layer of the paper substrate by means of a roller doctor blade.
  • a paper substrate coated on its front side with an intermediate layer (prepared as in Example 1) and a conventional coating composition not according to the invention for the production of a heat-sensitive recording layer were provided.
  • the conventional, non-inventive coating composition for the production of a heat-sensitive recording layer was produced by mixing the components given below in Table 5 components together, with water being used as the carrier liquid.
  • the components of the non-inventive coating composition and their amounts (in mass percent based on the dry weight of the coating composition) are given in Table 5 below: TABLE 5 Components of a non-inventive coating composition for producing a heat-sensitive recording layer
  • Example 5 Determination of the heat resistance of heat-sensitive recording materials at 60° C./24 hours
  • the print density was determined with a spectral -Densitometer of the type TECHKON Spectro-Dens Advanced carried out.
  • the mean value (“before heating”) was formed from the measured values for the black-colored areas (“image”) and for the uncolored areas (“background”).
  • the thermal test prints were then hung in a drying cabinet at 60 °C. After 24 hours, the thermal paper printouts were removed again, cooled to room temperature (23 °C) and the print density was again determined at three points each on the black colored areas and the uncolored areas of the thermal test printouts (averaging and densitometer as described above; " after heating).
  • the durability of the print image determined under the test conditions in “%” corresponds to the quotient of the mean value formed of the print density of the colored areas "before heating” and after storage in the drying cabinet ("after heating"), multiplied by 100.
  • the determined under the test conditions The contrast of the print image in “%” corresponds to the quotient of the mean value of the print density of the uncolored areas (“background”) “before heating” and after storage in the drying cabinet (“after heating”), multiplied by 100.
  • Table 6 Durability of the print image of heat-sensitive recording materials before and after heating to 60 °C / 24 hours.
  • a heat-sensitive recording material (WAME-1 to WAME-6) according to the invention has excellent heat resistance of the printed image or background, even compared to a conventional heat-sensitive recording material (WAMV-1). and thus enables permanent, very high-contrast printouts.
  • Example 6 Determination of the climate resistance of heat-sensitive recording materials at 40 °C/24 hours and 90% RH.
  • the print densities on the black colored areas (“image”) and for the uncolored areas (“background”) before and after storage in a climatic cabinet at 40 °C and 90 % RH for 24 hours; instead of storage in a drying cabinet at 60 °C for 24 hours as determined in Example 5).
  • Table 7 Durability of the print image of heat-sensitive recording materials before and after storage in a climatic cabinet at 40 °C and 90 % RH for 24 hours.
  • Example 7 Determination of the resistance of heat-sensitive recording materials to lanolin (exposure time 10 minutes)
  • the print density was determined using a densitometer TECHKON SpectroDens Advanced - spectral densitometer. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • the created thermal proof of the heat-sensitive recording material to be tested was generously coated with lanolin by hand.
  • the lanolin was carefully wiped off and the print density was again measured in three places each on the black colored areas and the uncolored areas of the thermal test prints using a densitometer TECHKON SpectroDens Advanced - spectral densitometer certainly.
  • the mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • the determined resistance of the thermal prints to lanolin in "%" corresponds to the quotient of the mean value of the print density formed before the lanolin treatment and after the lanolin treatment, multiplied by 100.
  • Table 8 Resistance of the printed image of heat-sensitive recording materials to lanolin (exposure time 10 min.)
  • a heat-sensitive recording material according to the invention (WAME-1 to WAME-6) has at least one improvement over a conventional heat-sensitive recording material (WAMV-1). comparable - and in many cases even better - resistance of the printed image to lanolin.
  • Example 8 Determination of the resistance of heat-sensitive recording materials to water and aqueous ethanol solution (23 °C, 50% RH, 24 hours)
  • test liquids are used to assess the resistance of an image produced on the heat-sensitive recording layer of heat-sensitive recording materials to water or to a 25% (v/v) aqueous ethanol solution (“test liquids”).
  • a drop of distilled water or the selected aqueous 25% ethanol solution was applied to the printed areas produced with the printer ATLANTEK Model 400-Thermal Response Test System with the energy level medium level 10.
  • the excess test liquid is dabbed off with a filter paper or cotton cloth and the test sheet is then stored in a room climate (23 °C, 50 % relative humidity) for 24 hours.
  • the optical density of the printed areas and their difference were determined with the densitometer TECHKON SpectroDens Advanced - spectral densitometer (mean value from measurements on three printed areas).
  • the resistance of the thermal print image on a heat-sensitive recording material in "%" to water or aqueous ethanol solution corresponds to the quotient of the mean value of the print density formed before and after treatment with the respective test liquid, multiplied by 100.
  • Example 9 Determination of the resistance of heat-sensitive recording materials to plasticizers of an adhesive film (23 °C, 50% RH)
  • the resistance of the thermal print image on a heat-sensitive recording material in "%" to plasticizers contained in a graphic adhesive film corresponds to the quotient of the mean value formed of the print density before application and after application of the graphic adhesive film, multiplied by 100.
  • the measurement results obtained as above are shown in Table 10 below:
  • Table 10 Resistance of the printed image of heat-sensitive recording materials to plasticizers contained in a graphics adhesive film
  • a heat-sensitive recording material according to the invention (WAME-1 to WAME-6) has a print image durability which is at least comparable to that of a conventional heat-sensitive recording material (WAMV-1) and in many cases even improved compared to plasticizers contained in a graphic adhesive film.
  • Example 10 Determination of the dynamic print density (or the dynamic sensitivity) of heat-sensitive recording materials
  • the sensitivity of a heat-sensitive recording material defines the degree of reaction at a certain energy supply. It is usually shown in graphs that show the generated image density or optical density (OD) as a function of the energy or heat supplied.
  • Optical density is a measure of the ratio between incident and reflected light.
  • An optical density, given in “optical density units” (ODU), of approx. 1.1 is generally completely black for the human eye. Therefore, lower optical densities result in different shades of gray.
  • static and dynamic sensitivity or static and dynamic pressure density.
  • the dynamic sensitivity (or dynamic print density) of a heat-sensitive recording material indicates how quickly a heat-sensitive recording material can be printed on. The higher the dynamic sensitivity, the faster a thermal printer can print the heat-sensitive recording material with otherwise unchanged settings.
  • a heat-sensitive recording material according to the invention (WAME-1 to WAME-6) has a dynamic print density which is at least comparable to a conventional heat-sensitive recording material (WAMV-1) and in some cases even improved .

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Abstract

L'invention concerne une couche d'impression thermosensible comprenant un révélateur organique exempt de groupes phénol, une composition de revêtement pour la réalisation de la couche d'impression thermosensible et une matière d'impression thermosensible, notamment du papier thermique, comprenant une couche d'impression thermosensible. L'invention concerne par ailleurs l'utilisation de la couche d'impression thermosensible pour la réalisation d'une matière d'impression thermosensible, un procédé pour la réalisation d'une matière d'impression thermosensible et l'utilisation de la matière d'impression thermosensible dans des applications de papier thermique. La matière d'impression thermosensible présente grâce à sa composition une particulièrement bonne aptitude au recyclage et une bonne éco-compatibilité.
EP21763350.2A 2020-08-19 2021-08-19 Matière d'impression thermosensible et couche d'impression thermosensible et composition de revêtement pour la réaliser, utilisations correspondantes et procédé Pending EP4200139A1 (fr)

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EP20191807.5A EP3957488A1 (fr) 2020-08-19 2020-08-19 Matériau d'enregistrement thermosensible ainsi que couche d'enregistrement thermosensible et sa composition de revêtement de fabrication, utilisations correspondantes et procédé
PCT/EP2021/073080 WO2022038242A1 (fr) 2020-08-19 2021-08-19 Matière d'impression thermosensible et couche d'impression thermosensible et composition de revêtement pour la réaliser, utilisations correspondantes et procédé

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EP21763350.2A Pending EP4200139A1 (fr) 2020-08-19 2021-08-19 Matière d'impression thermosensible et couche d'impression thermosensible et composition de revêtement pour la réaliser, utilisations correspondantes et procédé

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EP1400368B1 (fr) * 2001-06-01 2006-11-29 Fuji Photo Film Co., Ltd. Materiau d'enregistrement thermosensible
FI110677B (fi) 2001-10-12 2003-03-14 Jujo Thermal Oy Lämpöherkkä tallennusmateriaali
DE102004004204A1 (de) 2004-01-27 2005-08-11 Mitsubishi Hitec Paper Bielefeld Gmbh Wärmeempfindliches Aufzeichnungsmaterial
WO2012145456A1 (fr) 2011-04-20 2012-10-26 Rohm And Haas Company Matériau d'enregistrement
CN104797429B (zh) 2012-11-21 2017-04-19 日本曹达株式会社 使用非酚类化合物的记录材料、记录片和将非酚类化合物用于显色剂的方法
JP5967013B2 (ja) 2013-05-10 2016-08-10 王子ホールディングス株式会社 感熱記録体
DE102014107567B3 (de) 2014-05-28 2015-11-05 Papierfabrik August Koehler Se Wärmeempfindliches Aufzeichnungsmaterial
US10265984B2 (en) 2015-02-25 2019-04-23 Nippon Soda Co., Ltd. Crystalline modification of N-(2-(3-phenylureido)phenyl)benzenesulfonamide and recording material using same
DE102015104306B4 (de) 2015-03-23 2018-05-03 Papierfabrik August Koehler Se Wärmeempfindliches Aufzeichnungsmaterial
DE102016219091B4 (de) * 2015-10-02 2021-12-02 Mitsubishi Paper Mills Limited Thermisches Aufzeichnungsmaterial
EP3219507A1 (fr) 2016-03-14 2017-09-20 Papierfabrik August Koehler SE Matériel d'enregistrement autocollant sensible à la chaleur
EP3305538A1 (fr) 2016-10-07 2018-04-11 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la chaleur
EP3523134A1 (fr) 2016-10-07 2019-08-14 Mitsubishi HiTec Paper Europe GmbH Matériau d'enregistrement thermosensible
DE102018102177A1 (de) 2018-01-31 2019-08-01 Mitsubishi Hitec Paper Europe Gmbh Beschichtungszusammensetzung, wärmeempfindliche Aufzeichnungsschicht, wärmeempfindliches Aufzeichnungsmaterial sowie entsprechende Verwendungen und Verfahren
EP3533619A1 (fr) 2018-03-02 2019-09-04 Basf Se Matériel d'enregistrement sensible à la chaleur et révélateur de couleur
JP2021146642A (ja) 2020-03-19 2021-09-27 株式会社リコー 感熱記録媒体、感熱記録媒体の製造方法、及び物品

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