EP4259449B1 - Phenol-freie mehrzweck thermodirekt-aufzeichnungsmedien - Google Patents

Phenol-freie mehrzweck thermodirekt-aufzeichnungsmedien Download PDF

Info

Publication number
EP4259449B1
EP4259449B1 EP20838767.0A EP20838767A EP4259449B1 EP 4259449 B1 EP4259449 B1 EP 4259449B1 EP 20838767 A EP20838767 A EP 20838767A EP 4259449 B1 EP4259449 B1 EP 4259449B1
Authority
EP
European Patent Office
Prior art keywords
recording medium
printed
thermally responsive
responsive layer
print quality
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.)
Active
Application number
EP20838767.0A
Other languages
English (en)
French (fr)
Other versions
EP4259449A1 (de
Inventor
Mark R. FISHER
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.)
Appvion LLC
Original Assignee
Appvion LLC
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=74141902&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP4259449(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Appvion LLC filed Critical Appvion LLC
Publication of EP4259449A1 publication Critical patent/EP4259449A1/de
Application granted granted Critical
Publication of EP4259449B1 publication Critical patent/EP4259449B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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

Definitions

  • the present invention relates to sheet-like recording materials adapted to be recorded on or printed on by conventional direct thermal recording techniques.
  • the invention also relates to direct thermal recording media, with particular application to such media that incorporate a leuco dye and an acidic developer to provide a heat-activated printing mechanism.
  • the invention also pertains to related methods, systems, and articles.
  • an image is produced by selectively heating the recording material (sometimes called coated thermochromic paper, thermal paper, thermal recording material or media, or thermally-responsive record material) at selected locations by passing the material under, or otherwise across, a thermal print head.
  • the recording material includes a coating of a thermally responsive layer, and the image is provided by a heat-induced change in color of the thermally responsive layer.
  • Some common uses of direct thermal recording may include, without limitation, cash register receipts, labels for food or other goods, or event tickets.
  • basic colorless or lightly colored chromogenic material such as a leuco dye
  • an acidic color developer material are contained in a coating on a substrate which, when heated to a suitable temperature, melts or softens to permit the materials to react, thereby producing a colored mark or image at the spot where the heat is applied.
  • Thermally-responsive record materials have characteristic thermal responses, desirably producing a colored image of sufficient intensity or contrast upon selective thermal exposure.
  • direct thermal media used as labels in pharmaceutical applications may be exposed to hand sanitizing liquid.
  • Direct thermal media used in other applications may be exposed to environmental agents or conditions peculiar to such applications, such as sweat (water), heat and/or humidity, sunlight, or meat wrapping film, to name a few.
  • a bar code or other image thermally printed on a direct thermal recording material should remain visible and functional when exposed to such agents. But designing such capabilities into a direct thermal product can be difficult and is not always possible or practical.
  • NKK 1304 N-[2-(3-Phenylureido)phenyl]benzenensulfonamide) sold by Nippon Soda Co. Ltd., Tolbutamide (1-butyl-3-(4-methylphenyl) sulfonyl urea), and Dapsone (4,4'-Diamino Diphenyl Sulfone).
  • JP 2016-68418 A discloses a heat-sensitive recording material comprising a combination of 1,3-diphenyl urea, which is a color developing compound, and a non-phenolic color developing compound.
  • the non-phenolic color developing compound may be selected from any one of benzotriazole derivatives, saccharin derivatives, sulfonamide derivatives, malonamide derivatives, thiourea derivatives, benzoic acid derivatives, sulfonamide derivatives, and urea urethane derivatives.
  • JP H08-2112 A discloses a thermal recording material having a thermal color forming layer containing a colorless or light-colored dye precursor and a coupler reacting with the dye precursor at the time of heating to develop a color.
  • the coupler is 1,3-diphenylurea and not used together with a phenol compound.
  • EP 1 116 713 A1 discloses a recording material comprising a substrate and a color-producing layer formed thereon, said color-producing layer comprising a urea-urethane compound.
  • the urea-urethane compound has one or more urea groups and one or more urethane groups in the molecular structure, the number of said urea groups (A) and the number of said urethane groups (B) satisfying the numerical formula 10 & (A + B) & 3, wherein each of A and B is an integer of 1 or more.
  • the unique chemistry can be used to make direct thermal recording materials that are capable of withstanding multiple different types of environmental conditions or agents, and to that extent these recording materials can be described as multi-purpose.
  • the unique chemistry uses a combination of two non-phenolic developers, neither of which by itself (when used with a suitable leuco dye) can produce direct thermal recording materials with such characteristics, but when combined together provide surprising and unexpected results.
  • the two developers are 1,3-diphenyl urea ("DPU"), and urea urethane (“UU").
  • the unique chemistry makes it possible for the thermally responsive layer of the product to have an ultra-low coat weight, i.e. to be ultra-thin. This allows for reduced product mass and a number of related benefits, including a reduction in the post-use waste stream associated with direct thermal recording materials for an improved environmental impact.
  • recording media that include a substrate and a thermally responsive layer carried by the substrate.
  • the recording media is substantially phenol-free, and the thermally responsive layer includes a leuco dye and a plurality of developers including 1,3-Diphenyl urea (DPU) and urea urethane (UU).
  • DPU 1,3-Diphenyl urea
  • UU urea urethane
  • the recording media may further include a basecoat layer between the thermally responsive layer and the substrate, and a topcoat carried by the substrate such that the thermally responsive layer is disposed between the topcoat and the substrate.
  • the thermally responsive layer may have a coat weight of less than 1.48 g/m 2 (1 lb/3300 ft 2 ), or in a range from 0.9 to less than 1.48 g/m 2 .
  • the DPU and the UU may be dispersed throughout the thermally responsive layer. Substantially no developers other than DPU and UU may be present in the thermally responsive layer.
  • the DPU and UU may be present in the thermally responsive layer in a relative weight ratio that falls within a range from 1/3 to 3, or from 1/2 to 2, or which may be substantially 1.
  • the print quality of the recording medium when printed with a thermal printer energy setting of 11.7 mJ/mm 2 at a print speed of 0.1524 m/s (6 inches per second (ips)), i.e., substantially 15 cm/sec, may be characterized by an ANSI value (at a wavelength of 650 nm, or at 670 nm, or at both 650 nm and 670 nm) of at least 1.5.
  • the print quality of the printed recording medium may still be characterized by an ANSI value of at least 1.5 after any one, or some, or all of the printed recording medium is soaked in water for 24 hours and then removed and dried; the printed recording medium is dipped in water, then placed in contact with polyvinyl chloride meat wrapping film under a 7 pound (substantially 3.2 kg) weight for 24 hours, and then removed and dried; the printed recording medium is submerged in boiling water for 20 minutes, then removed and dried; the printed recording medium is heated to 60°C for 24 hours, then removed and cooled; the printed recording medium is exposed to air at 40°C and 90% relative humidity for 24 hours, then removed and cooled; the printed recording medium is subjected to an accelerated sunlight test at 0.67 W/m 2 for 7 hours, then removed; or one drop of a 70% ethyl alcohol-based hand sanitizer is placed on the printed recording medium and allowed to dry.
  • substantially phenol-free recording media that include a flexible substrate and a thermally responsive layer carried by the substrate, the thermally responsive layer including a leuco dye and a plurality of developers including DPU and UU.
  • a print quality of the recording medium when printed with a thermal printer energy setting of 11.7 mJ/mm 2 at a print speed of 0.1524 m/s (6 inches per second (ips)) may be characterized by an ANSI value (at 650 nm, 670 nm, or both 650 and 670 nm) of at least 1.5.
  • the print quality of the printed recording medium may still be characterized by an ANSI value of at least 1.5 after any one, some, or all of the printed recording medium is dipped in water, then placed in contact with polyvinyl chloride meat wrapping film under a 7 pound weight for 24 hours, and then removed and dried; the printed recording medium is heated to 60°C for 24 hours, then removed and cooled; or the printed recording medium is exposed to air at 40°C and 90% relative humidity for 24 hours, then removed and cooled.
  • the new chemistry comprises a combination of two developers which, when used together along with a suitable leuco dye, can produce a multi-purpose direct thermal recording material capable of passing a plurality of environmental exposure tests, but when used individually in an otherwise identical thermal recording material, cannot pass those same environmental exposure tests.
  • one of the two developers when used alone with a suitable leuco dye yields a direct thermal recording material which, upon being imaged by a direct thermal printer and before any environmental exposure tests are done, produces an image that does not meet even the minimum standard for machine-readability for bar codes.
  • the two phenol-free developers of this unique combination are 1,3-diphenyl urea ("DPU"), and urea urethane ("UU").
  • the unique chemistry also makes it possible for the thermally responsive layer of the product to have an ultra-low coat weight, i.e. to be ultra-thin.
  • the low coat weight in turn provides lower material costs, lower manufacturing costs, and lower overall product weight or mass.
  • the reduced product mass also then reduces the post-use waste stream associated with direct thermal recording materials, for an improved environmental impact.
  • Direct thermal recording materials are often manufactured in large roll form on industrial-sized coating machines using a continuous web of paper or other flexible substrate material.
  • a roll 100 of direct thermal recording material 104 is shown schematically in FIG. 1 .
  • the roll 100 can be converted by slitting, cutting, or other standard operations into individual sheets, labels, or smaller rolls.
  • a magnified side or cross-sectional view of the recording material 104 is shown schematically in FIG. 2 to illustrate typical substructure made up of component layers or coatings.
  • the recording material 104 may be made by applying several different coatings to at least one side or major surface 110a of a substrate 110.
  • the major surface 110a as the front surface of the substrate, and the exposed major surface 104a may be the front surface of the recording material 104.
  • the opposite major surface 104b may be the back surface of the recording material.
  • the substrate 110 is coated to carry a basecoat layer 112, a thermally responsive layer 114, and a topcoat layer 116.
  • the coatings are preferably applied in the order shown, with the layer 114 located between the layers 112, 116, and with the layer 112 located between the layer 114 and the substrate 110.
  • the basecoat 112 may be omitted, or the topcoat 116 may be omitted, or both the basecoat and the topcoat may be omitted.
  • the coatings can be formed by any suitable coating technique, including roll coating, knife coating, rod coating, gravure coating, curtain coating, spot coating, and so forth.
  • additional layers and coatings can be added to or included with the recording material on its front and/or back side.
  • one or more coatings can be applied to the opposite side of the substrate, i.e., to the major surface 110b, as discussed further below. But first, the other elements of the direct thermal recording material 104 will now be described in more detail.
  • the substrate 110 can be any material onto which the other layers can be coated or applied, and then carried.
  • the kind or type of substrate material is not critical.
  • the substrate 110 is in sheet or roll form, and may be or include a support member such as a web, ribbon, tape, belt, film, card, or the like.
  • a sheet denotes an article having two large (major) surface dimensions and a comparatively small thickness dimension, and in some cases, the sheet may be wound up to form a roll.
  • the substrate 110 is typically thin and flexible, yet strong enough to withstand forces and tensions experienced in a coating machine, without undue breakage.
  • the substrate 110 can be opaque, transparent, or translucent, and can be colored or uncolored.
  • the substrate material can be fibrous including, for example, paper and filamentous synthetic materials. It can be a film including, for example, cellophane and synthetic polymeric sheets cast, extruded, or otherwise formed. Suitable plastic films include films of polypropylene (including oriented polypropylene (OPP) and biaxially oriented polypropylene (BOPP)), polyethylene (PE), and polyethylene terephthalate (PET).
  • the substrate material can thus be non-cellulosic.
  • An exemplary substrate 110 may be or include a neutral sized base paper.
  • the thickness of the substrate 110 may depend on its composition, but a typical thickness (caliper) range for cellulosic materials is from 1.9 to 12 mils (e.g. 50 to 300 ⁇ m), or other suitable thicknesses.
  • the paper may have a basis weight in a range from 35 to 200 g/m 2 , but other suitable basis weights may also be used.
  • the paper may also be treated with one or more agents, such as a surface sizing agent. Uncoated base papers, including unsized, conventionally sized, and lightly treated base papers, can be used.
  • the substrate 110 may be simple in construction and devoid of glossy coatings, or of other substantial, functional coatings.
  • the substrate 110 may, for example, be substantially uniform in composition throughout its thickness, rather than a multilayered construction or material to which one or more separate, functional coatings have already been applied. In some cases, however, it may be desirable to treat, prepare, or otherwise work the substrate 110 in preparation for coating onto it one or more of the other layers shown in the figure.
  • the basecoat 112 may be applied directly to the surface 110a of the substrate 110 before any other coatings are applied.
  • the basecoat 112 may in some cases be characterized or described as a thermal insulating layer, a separator layer, a heat-reflective layer, an isolation layer, or a prime coat.
  • the basecoat 112 provides a degree of thermal insulation between those two other layers. Such thermal insulation promotes image quality, imaging speed, or both, by ensuring that heat delivered by the thermal print head (not shown) at the front surface 104a is not substantially lost by thermal conduction through the thermally responsive layer 114 to the more massive substrate 110.
  • the basecoat 112 may comprise hollow sphere pigments (HSP), such as product code Ropaque TM TH-2000 or TH-500EF available from The Dow Chemical Company, or other suitable materials.
  • HSP hollow sphere pigments
  • the basecoat 112 can be made by a process in which a dispersion is coated onto the surface 110a of the substrate, and then dried. In some cases, the basecoat 112 may be eliminated and omitted from the product construction.
  • the thermal insulating layer may have a thickness in a range from 2 to 12 ⁇ m, or other suitable thicknesses.
  • the thermally responsive layer 114 may be coated atop the basecoat 112, or atop the substrate 110 if the basecoat is omitted.
  • the layer 114 may alternatively be referred to as a heat-sensitive color-forming layer.
  • This layer 114 comprises a color-forming composition that is thermally sensitive, i.e., it changes color upon sufficient heating.
  • the color-forming composition has two main components: a color-forming dye (electron-donating dye precursor), also known as a leuco dye or chromogenic material, and an acidic developer.
  • the leuco dye and acidic developer are typically ground to individual particle sizes of between 1 to 10 micrometers, dispersed in a binder, and distributed homogeneously and in a contiguous relationship with each other throughout the layer 114.
  • the acidic developer is preferably non-phenolic, and, as already explained above, advantageously includes a combination of two distinct non-phenolic developer materials, in particular, 1,3-diphenyl urea ("DPU"), and urea urethane (“UU").
  • DPU may alternatively be referred by names such as: 1-3-Diphenylurea or 1-3-diphenylurea; N,N'-Diphenylurea; Diphenylurea; Urea, N,N'-diphenyl-; CARBANILIDE; Diphenylcarbamide; or C 13 H 12 N 2 O.
  • UU may alternatively be referred by urethane urea.
  • thermally responsive layer 114 One rationale for using developers that are non-phenolic in the thermally responsive layer 114 is to satisfy the market demand for phenol-free receipts, labels, and the like. As such, it is desirable in many cases, but not necessary in all cases, for not only the thermally responsive layer 114 to be phenol-free or substantially phenol-free, but for the entire direct thermal recording material 104 to be phenol-free or substantially phenol-free.
  • substantially phenol-free to include both items that are absolutely and completely phenol-free, as well as items that may have only trace amounts of phenolic materials below thresholds.
  • DPU nor UU is particularly noteworthy by itself when used with a suitable leuco dye.
  • the resulting direct thermal recording material when imaged by a direct thermal printer, produces an initial image that doesn't even meet the minimum requirement for bar code machine-readability.
  • the UU in such a product is entirely replaced by DPU, i.e. when the DPU is used by itself as the only developer in the layer 114, the image initially produced by the direct thermal printer does meet the minimum requirement for bar code machine-readability, but no longer does so after the printed sample is subjected to any one of a number of environmental exposure tests as explained further below.
  • the resulting direct thermal recording material not only provides a thermally produced image that meets the minimum requirement for bar code machine-readability, but also maintains that image quality after the printed sample is subjected to environmental exposure tests that are not passed by otherwise identical recording materials containing only DPU or only UU as the developer.
  • the DPU, the UU, and the selected leuco dye are each preferably dispersed homogeneously and evenly throughout the thermally responsive layer 114. This does not necessarily mean that these various materials have equal loadings in that layer. In most cases, however, we have found it desirable to have roughly equal loadings of the DPU and UU, i.e., a relative weight ratio of DPU/UU of roughly 1. But other weight ratios of DPU/UU can also be used as demonstrated in the examples below.
  • the DPU/UU weight ratio may for example fall within a range from 1/3 to 3, or from 1/2 to 2, or it may be about 1.
  • the DPU and UU are preferably the only chemical developers used in the layer 114.
  • one or more other chemical developers may also be added besides the DPU and UU. If this is done, such other developer(s) are preferably individually and collectively present in the layer 114 in a weight percentage lower than that of DPU, and lower than that of UU.
  • the thermally responsive layer 114 also of course includes at least one leuco dye tailored to react with the plurality of developers at elevated temperatures to produce a mark or color change.
  • the leuco dye, or dyes may be any known dye(s) capable of such a reaction. Examples include, without limitation:
  • the thermally responsive layer 114 also includes one or more suitable binders to help hold the particles in the layer together.
  • suitable binders may include poly(vinylalcohol), hydroxy ethylcellulose, methylcellulose, isopropyl cellulose, starch, modified starches, gelatin, and the like. Latex materials including polyacrylates, polyvinylacetates, polystyrene, and the like, may also be used.
  • the binder helps maintain the mechanical integrity of the layer 114 in response to brushing or handling forces resulting from use or storage of the recording material 104. Enough of the binder should be present to provide such protection, but not so much so as to interfere with achieving reactive contact between the color-forming reactive materials.
  • the binder may be present at 5 to 30 wt% of the dried coating.
  • the color-forming composition of the layer 114 may also contain one or more materials referred to as modifiers, which aid in color formation.
  • the modifier(s) can function by one or both of (a) lowering the melting point of the dye/developer, and (b) acting as a type of solvent in which the dye and developer dissolve or melt.
  • the modifier(s) may thus facilitate the reaction between the leuco dye and the developer to produce a more intense thermal image, faster imaging, or both. See, for example, U.S. Patents 4,531,140 (Suzuki et al. ), 4,794,102 (Petersen et al. ), 5,098,882 (Teraji et al. ), 6,835,691 (Mathiaparanam et al. ), and 6,921,740 (Hizatate et al. ).
  • the thermally responsive layer of a conventional direct thermal recording material would be applied in a thickness corresponding to a coat weight from 1.5 to 6 pounds/3,300 ft 2 (2.2 to 8.9 g/m 2 ), or more typically from 2-4 pounds/3,300 ft 2 (3.0 to 5.9 g/m 2 ), for a finished dry thickness in a range from 1.2 to 4.8 ⁇ m, or from 1 to 5 ⁇ m.
  • a practical lower limit has been a coat weight of about 1 pound/33,000ft 2 ( ⁇ 1.48 g/m 2 ).
  • the thermally responsive layer 114 of the inventive recording material 104 may also if desired be applied in these same conventional coat weights and thicknesses, but we have found that another benefit of the disclosed combination of developers DPU/UU is that the layer 114 can be made much thinner while still providing acceptable thermal image quality.
  • the layer 114 can be made with a coat weight of less than 1 pound/3,300 ft 2 (1.48 g/m 2 ).
  • the coat weight of the layer 114 may thus be in a range from, for example, 0.9 to 8.9 g/m 2 , or 0.9 to 5.9 g/m 2 , or 0.9 to 2.2 g/m 2 , or 0.9 to 1.48 g/m 2 , or 0.9 up to, but less than, 1.48 g/m 2 .
  • the ability to make the thermally responsive layer 114 ultra-thin has a number of benefits such as lower product weight/mass, lower product cost, and reduced environmental impact in terms of the post-use waste stream.
  • a topcoat layer 116 is shown atop, in contact with, the thermally responsive layer 114.
  • the outer major surface of the topcoat 116 is exposed to air and corresponds to the outer major surface 104a of the direct thermal recording material 104.
  • the topcoat 116 is optional and can be omitted if desired. If it is included, it can protect underlying layers of the recording material 104 from unwanted contaminants or substances. For example, some topcoats can be used as barriers or seals against seepage by oils or other unwanted liquids.
  • the topcoat 116 may be any suitable topcoat of conventional design.
  • the topcoat 116 may for example comprise binders such as modified or unmodified polyvinyl alcohols, acrylic binders, crosslinkers, lubricants, and fillers such as aluminum trihydrate and/or silicas.
  • the topcoat 116 may have a thickness in a range from 0.5 to 2 ⁇ m, or other suitable thicknesses.
  • the disclosed recording materials may also include additional layers and coatings other than those discussed above.
  • Such other layers or coatings include coating(s) that can be applied to the back surface 110b of the substrate 110.
  • One such layer is illustrated in FIG. 2 , labeled 118.
  • This layer 118 may be an adhesive layer comprising a pressure sensitive adhesive (PSA), hot melt adhesive, or other suitable adhesive.
  • PSA pressure sensitive adhesive
  • the recording material can serve as a label and can attach to containers, films, or other bodies while having its front, thermally printed side visible to users.
  • a release liner (not shown) can also be included to cover a PSA layer until ready for use. Release coatings may also be applied to the surface for applications that do not require a liner.
  • Direct thermal recording materials can potentially be used in a variety of settings and, as such, can be exposed to a wide variety of environmental agents, contaminants, and conditions. Images formed by direct thermal printing on such materials are known to be subject to degradation when exposed to at least some of those conditions. A given recording material may experience degradation to more or fewer of these conditions depending on its details of construction, including the chemicals used in the thermally responsive layer. Of course, the more environmental conditions the recording material can withstand without substantial degradation of the image, the more settings and applications it can be used in.
  • Dry heat one environmental condition of interest is exposure of the imaged material to heat, i.e., heat stability.
  • heat stability e.g. approaching a print head temperature of at least about 200 °C
  • the leuco dye will react with the developer throughout the entire thermally responsive layer, causing the entire front surface of the recording material to change color and obliterating any image that was previously formed thereon.
  • a heated environment substantially above ambient room temperature but in the neighborhood of 60 °C, which an imaged recording material may experience if attached as a label to a cup or container of coffee or other hot beverage, or if attached to the package of a food item meant to be heated or cooked in a microwave oven.
  • Plasticizer another environmental condition of interest is contact with a plasticized film, especially polyvinyl chloride (PVC) film used to wrap meat in grocery stores.
  • PVC polyvinyl chloride
  • Direct thermal recording materials can be used as labels applied to such packaged meat.
  • the direct thermal image printed on the front of the label can come into contact with PVC film from other packages.
  • Water another environmental condition of interest is immersion in water. This may happen if a printed receipt or ticket is left in a pocket of clothing and inadvertently sent through the cycle of a washing machine.
  • the most benign version of this environmental condition is where the water is at room temperature, or possibly tepid.
  • Boiling water this environmental condition of interest is like the water immersion condition, but where the water is at the boiling temperature.
  • Sultry another sultry environmental condition of interest is exposure to hot, humid conditions as may be experienced in tropical areas. This may for example involve temperatures around 40 °C and a relative humidity of 90%.
  • Sunlight another environmental condition of interest is exposure to sunlight.
  • Sanitizer another environmental condition of interest is contact with alcohol-based hand sanitizer fluids.
  • dispersion formulations were prepared. These were of two types: dispersion formulations for leuco dyes, and dispersion formulations for acidic developers.
  • the formulations for the leuco dyes followed a first recipe, "A”, and formulations for the developers followed a second recipe, "B", as follows, where all parts or percentages are understood to be parts per weight:
  • Table 1 Dispersion A Formulation Material Parts chromogenic material (leuco dye) 30.0 binder, 20% solution of polyvinyl alcohol in water 25.0 defoaming and dispersing agents 0.4 water 44.6
  • Dispersion B Formulation Material Parts developer material 38.0 binder, 20% solution of polyvinyl alcohol in water 18.0 defoaming and dispersing agents 0.4 water 43.6
  • Dispersion A1 A formulation referred to as Dispersion A1 followed recipe "A” and used ODB-2, i.e., 2-anilino-3-methyl-6-dibutylaminofluoran, as the chromogenic material.
  • ODB-2 i.e., 2-anilino-3-methyl-6-dibutylaminofluoran
  • Dispersion A2 A formulation referred to as Dispersion A2 followed recipe "A” and used BK-305, i.e., 2-anilino-3-methyl-6-dipentylaminofluoran, as the chromogenic material.
  • Dispersion B1 A formulation referred to as Dispersion B1 followed recipe "B” and used DPU, i.e., 1,3-Diphenyl Urea, as the developer material.
  • DPU i.e., 1,3-Diphenyl Urea
  • Dispersion B2 A formulation referred to as Dispersion B2 followed recipe "B” and used UU, i.e., urethane urea (in particular Urea Urethane Compound sold by Chemipro Kasei Kaisha Ltd., CAS No. 321860-75-7 ), as the developer material.
  • UU i.e., urethane urea
  • urethane urea in particular Urea Urethane Compound sold by Chemipro Kasei Kaisha Ltd., CAS No. 321860-75-7
  • Dispersion B3 A formulation referred to as Dispersion B3 followed recipe "B” and used D-8, i.e., 4-Hydroxyphenyl -4-isopropoxyphenylsulfone, as the developer material.
  • Dispersion B4 A formulation referred to as Dispersion B4 followed recipe "B” and used BPS, i.e., 4-Hydroxyphenyl sulfone, as the developer material.
  • BPS i.e., 4-Hydroxyphenyl sulfone
  • Dispersion B5 A formulation referred to as Dispersion B5 followed recipe "B” and used BPS-MBE, i.e., 4-Benzyloxyphenyl-4'-hydroxyphenyl sulfone, as the developer material.
  • BPS-MBE 4-Benzyloxyphenyl-4'-hydroxyphenyl sulfone
  • Dispersion B6 A formulation referred to as Dispersion B6 followed recipe "B” and used Tolbutamide, i.e., 1-butyl-3-(4-methyl phenyl) sulfonyl urea, as the developer material.
  • Tolbutamide i.e., 1-butyl-3-(4-methyl phenyl) sulfonyl urea
  • Dispersion B7 A formulation referred to as Dispersion B7 followed recipe "B” and used Dapsone, i.e., 4,4'-Diamino Diphenyl Sulfone, as the developer material.
  • Dapsone i.e., 4,4'-Diamino Diphenyl Sulfone
  • Dispersion B8 A formulation referred to as Dispersion B8 followed recipe "B" and used Pergafast TM 201, i.e., N-(p-Toluenesulfonyl)-N'-(3-p-toluenesulfonyloxyphenyl) urea, sold by Solenis LLC, as the developer material.
  • Pergafast TM 201 i.e., N-(p-Toluenesulfonyl)-N'-(3-p-toluenesulfonyloxyphenyl) urea, sold by Solenis LLC, as the developer material.
  • Dispersion B9 A formulation referred to as Dispersion B9 followed recipe "B” and used NKK-1304, i.e., N-[2-(3-Phenylureido)phenyl] benzenensulfonamide, sold by Nippon Soda Co. Ltd., as the developer material.
  • NKK-1304 i.e., N-[2-(3-Phenylureido)phenyl] benzenensulfonamide, sold by Nippon Soda Co. Ltd., as the developer material.
  • the first step was to coat a basecoat (see e.g. layer 112 in FIG. 2 ) onto one side or major surface of a substrate (see e.g. substrate 110 in FIG. 2 ).
  • the substrate used was a 63 g/m 2 (gsm) highly refined paper sheet.
  • the basecoat was thermally insulating and comprised a mixture of calcined clay such as Ansilex 93 by BASF Corporation, and Ropaque TM TH-2000 hollow sphere pigment (HSP) by The Dow Chemical Company, along with an SBR binder, and was applied at a coat weight of 4.5 g/m 2 .
  • a thermally-responsive layer (see e.g. layer 114 in FIG. 2 ) was coated atop the basecoat.
  • the coat weight of the thermally-responsive layer was 1.3 g/m 2 unless otherwise indicated.
  • a topcoat (see e.g. topcoat 116 in FIG. 2 ) was coated onto the surface of the thermally-responsive layer.
  • the topcoat was composed of delaminated clay, PVOH, crosslinker, and lubricant such as zinc stearate, and was applied at a coat weight of 1.5 g/m 2 . After the topcoat was dry, no other coatings were applied to the sample, and the sample was ready for thermal printing and testing.
  • the thermal printing was performed on each sample using a Zebra TM thermal printer, model 140-401, at a speed of 0.1524 m/s (6 inches per second (ips)) and using the default energy setting of the print head, which was 11.7 mJ/mm 2 .
  • the printed image was in each case a barcode pattern.
  • the print quality or image quality of the barcode pattern was evaluated using a TruCheck TM barcode verifier (model TC-843) operating at a wavelength of 650 nm, a passing result corresponding to an ANSI value of 1.5 or more, and a failing result corresponding to an ANSI value of less than 1.5.
  • the print quality of the same image was also evaluated at 670 nm using a TruCheck TM barcode verifier model TC-854, where again a passing score corresponded to an ANSI value of 1.5 or more, and a failing score corresponded to an ANSI value of less than 1.5.
  • the printed specimen was exposed to 60 °C (dry) heat for 24 hours, then removed from the heat. After this test the quality of the printed image was tested at both 650 nm and 670 nm.
  • the printed specimen was dipped in room temperature water, then removed and placed in contact with a polyvinyl chloride meat wrapping film under a 7 pound weight for 24 hours, then removed and allowed to dry. After this test the quality of the printed image was tested at 650 nm.
  • the printed specimen was soaked in room temperature water for 24 hours, then removed and allowed to dry. After this test the quality of the printed image was tested at 650 nm.
  • the printed specimen was adhered to a plastic swatch and submerged in boiling water for 20 minutes, then removed and allowed to dry. After this test the quality of the printed image was tested at 650 nm.
  • the printed specimen was exposed to 40 °C heat and 90% relative humidity for 24 hours. After this test the quality of the printed image was tested at both 650 nm and 670 nm.
  • the printed specimen was placed into an accelerated sunlight test chamber (Q-Sun TM Xenon test chamber, sold by Q-Lab Corporation, Westlake, OH) at an irradiance of 0.67 W/m 2 for 7 hours, then removed. After this test the quality of the printed image was tested at both 650 nm and 670 nm.
  • Q-Sun TM Xenon test chamber sold by Q-Lab Corporation, Westlake, OH
  • a "pass” result refers to an ANSI value at 650 nm (and at 670 nm where applicable) of at least 1.5; a "pass*" result refers to an ANSI value at 650 nm of at least 1.5 but an ANSI value at 670 nm below 1.5; and a “fail” result refers to an ANSI value at 650 nm (and at 670 nm where applicable) of less than 1.5.
  • results of Table 5 demonstrate that the relative weight ratio of DPU to UU in the thermally responsive layer need not be 1 but can range at least from 1/3 to 3, as well as narrower ranges such as 1/2 to 2.
  • results of Table 5 further demonstrate that the coat weight of the thermally responsive layer, when DPU and UU are used in combination, can be as low as 0.9 g/m 2 and still produce direct thermal images with acceptable print quality.

Landscapes

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

Claims (15)

  1. Aufzeichnungsmedium (104), mit:
    einem Substrat (110); und
    einer von dem Substrat (110) getragenen thermisch responsiven Schicht (114), wobei die thermisch responsive Schicht (114) einen Leuko-Farbstoff und mehrere Entwickler beinhaltet;
    wobei das Aufzeichnungsmedium (104) im Wesentlichen phenolfrei ist; und
    wobei die mehreren Entwickler 1,3-Diphenylharnstoff, nachfolgend "DPU", und Harnstoffurethan, CAS No. 321860-75-7, nachfolgend "UU", beinhalten.
  2. Aufzeichnungsmedium (104) nach Anspruch 1, ferner beinhaltend:
    eine Basisbeschichtung (112) zwischen der thermisch responsiven Schicht (114) und dem Substrat (110).
  3. Aufzeichnungsmedium (104) nach Anspruch 1 oder 2, ferner beinhaltend:
    eine von dem Substrat (110) derart getragene Oberschicht (116), dass die thermisch responsive Schicht (114) zwischen der Oberschicht (116) und dem Substrat (110) angeordnet ist.
  4. Aufzeichnungsmedium (104) nach einem der Ansprüche 1 bis 3, wobei die thermisch responsive Schicht (114) ein Beschichtungsgewicht von weniger als 1,48 g/m2 aufweist.
  5. Aufzeichnungsmedium (104) nach einem der Ansprüche 1 bis 4, wobei das Beschichtungsgewicht der thermisch responsiven Schicht (114) wenigstens 0,9 g/m2 beträgt.
  6. Aufzeichnungsmedium (104) nach einem der Ansprüche 1 bis 5, wobei der DPU und das UU in der ganzen thermisch responsiven Schicht (114) verteilt sind.
  7. Aufzeichnungsmedium (104) nach einem der Ansprüche 1 bis 6, wobei im Wesentlichen keine anderen Entwickler als DPU und UU in der thermisch responsiven Schicht (114) vorhanden sind.
  8. Aufzeichnungsmedium (104) nach einem der Ansprüche 1 bis 7, wobei der DPU und das UU in der thermisch responsiven Schicht (114) in einem relativen Gewichtsanteil vorhanden sind, der in einen Beriech von 1/3 bis 3 fällt.
  9. Aufzeichnungsmedium (104) nach Anspruch 8,
    wobei der relative Gewichtsanteil in einen Beriech von 1/2 bis 2 fällt; oder wobei der relative Gewichtsanteil 1 beträgt.
  10. Aufzeichnungsmedium (104) nach einem der Ansprüche 1 bis 9, wobei eine Druckqualität des Aufzeichnungsmedium (104), wenn es mit einer Thermo-Drucker-Energie-Einstellung von 11,7 mJ/mm2 bei einer Druckgeschwindigkeit von 15 Zentimetern pro Sekunde (6 Zoll pro Sekunde) bedruckt wurde, durch einen ANSI-Wert, gemessen mit einem bei einer Wellenlänge von 650 nm arbeitenden Barcode-Leser, von wenigstens 1,5 charakterisiert ist.
  11. Aufzeichnungsmedium (104) nach Anspruch 10,
    wobei die Druckqualität des Aufzeichnungsmedium (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) für 24 Stunden mit Wasser vollgesogen und dann herausgenommen und getrocknet wurde; oder
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) in Wasser getunkt und dann für 24 Stunden unter einem Gewicht von 3,2 kg (7 Pfund) in Kontakt mit einer Polyvinylchlorid-Fleisch-Einpackfolie gebracht, und dann entfernt und getrocknet wurde; oder
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) für 20 Minuten in kochendem Wasser untergetaucht, dann entfernt und getrocknet wurde.
  12. Aufzeichnungsmedium (104) nach Anspruch 10,
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) für 24 Stunden auf 60°C erhitzt, und dann entfernt und abgekühlt wurde; oder
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) für 24 Stunden Luft bei 40°C und 90% relativer Feuchtigkeit ausgesetzt, dann entfernt und abgekühlt wurde; oder
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) für 7 Stunden einem beschleunigten Sonnenlicht-Test bei 0,67 W/m2 unterzogen, und dann entfernt wurde.
  13. Aufzeichnungsmedium (104) nach Anspruch 10, wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem ein Tropfen eines 70%igen Ethylalkohol-basierten Handreinigers auf das bedruckte Aufzeichnungsmedium aufgebracht und dann eintrocknen gelassen wurde.
  14. Aufzeichnungsmedium (104) nach Anspruch 1,
    wobei das Aufzeichnungsmedium (104) im Wesentlichen phenolfrei ist;
    wobei das Substrat (110) flexibel ist;
    wobei der DPU und das UU beide in der ganzen thermisch responsiven Schicht (114) verteilt sind;
    wobei der DPU und das UU in einem relativen Gewichtsanteil in der thermisch responsiven Schicht (114) vorhanden sind, der in einen Bereich von 1/3 bis 3 fällt; und
    wobei eine Druckqualität des Aufzeichnungsmediums (104), wenn es mit einer Thermo-Drucker-Energie-Einstellung von 11,7 mJ/mm2 bei einer Druckgeschwindigkeit von 15 Zentimetern pro Sekunde (6 Zoll pro Sekunde) bedruckt wurde, durch einen ANSI-Wert, gemessen mit einem bei einer Wellenlänge von 650 nm arbeitenden Barcode-Leser, von wenigstens 1,5 charakterisiert ist.
  15. Aufzeichnungsmedium (104) nach Anspruch 14,
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) in Wasser getunkt und dann für 24 Stunden unter einem Gewicht von 3,2 kg (7 Pfund) in Kontakt mit einer Polyvinylchlorid-Fleisch-Einpackfolie gebracht, und dann entfernt und getrocknet wurde;
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) für 24 Stunden auf 60°C erhitzt, und dann entfernt und abgekühlt wurde; und
    wobei die Druckqualität des bedruckten Aufzeichnungsmediums (104) immer noch durch einen ANSI-Wert von wenigstens 1,5 charakterisiert ist, nachdem das bedruckte Aufzeichnungsmedium (104) für 24 Stunden Luft bei 40°C und 90% relativer Feuchtigkeit ausgesetzt, dann entfernt und abgekühlt wurde.
EP20838767.0A 2020-12-10 2020-12-10 Phenol-freie mehrzweck thermodirekt-aufzeichnungsmedien Active EP4259449B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2020/064342 WO2022125104A1 (en) 2020-12-10 2020-12-10 Multi-purpose phenol-free direct thermal recording media

Publications (2)

Publication Number Publication Date
EP4259449A1 EP4259449A1 (de) 2023-10-18
EP4259449B1 true EP4259449B1 (de) 2024-06-19

Family

ID=74141902

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20838767.0A Active EP4259449B1 (de) 2020-12-10 2020-12-10 Phenol-freie mehrzweck thermodirekt-aufzeichnungsmedien

Country Status (5)

Country Link
EP (1) EP4259449B1 (de)
JP (1) JP7842760B2 (de)
KR (1) KR102945498B1 (de)
FI (1) FI4259449T3 (de)
WO (1) WO2022125104A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12427798B2 (en) 2021-11-30 2025-09-30 Nippon Kayaku Kabushiki Kaisha Heat-sensitive recording composition

Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH082112A (ja) 1994-06-27 1996-01-09 Nippon Paper Ind Co Ltd 感熱記録体
WO2000014058A1 (en) 1998-09-04 2000-03-16 Asahi Kasei Kabushiki Kaisha Novel color-developing compound and recording material
US20010044553A1 (en) 1998-09-04 2001-11-22 Kazuo Kabashima Novel compound for color-producing composition, and recording material
JP2002187364A (ja) 2000-12-20 2002-07-02 Nippon Paper Industries Co Ltd 感熱記録紙
JP2002283744A (ja) 2001-03-26 2002-10-03 Nippon Paper Industries Co Ltd 感熱記録体
JP2004223871A (ja) 2003-01-23 2004-08-12 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2004255842A (ja) 2003-02-28 2004-09-16 Mitsubishi Paper Mills Ltd 感熱記録材料
DE102004004204A1 (de) 2004-01-27 2005-08-11 Mitsubishi Hitec Paper Bielefeld Gmbh Wärmeempfindliches Aufzeichnungsmaterial
JP2005330291A (ja) 1998-09-04 2005-12-02 Asahi Kasei Chemicals Corp 新規ウレアウレタン化合物
JP2006104219A (ja) 1998-09-04 2006-04-20 Asahi Kasei Chemicals Corp 新規なウレアウレタン化合物
JP2006143741A (ja) 1998-09-04 2006-06-08 Asahi Kasei Chemicals Corp ウレアウレタン化合物
JP2006143740A (ja) 1998-09-04 2006-06-08 Asahi Kasei Chemicals Corp 新しいウレアウレタン化合物
EP1681174A1 (de) 2003-10-23 2006-07-19 Chemipro Kasei Kaisha, Ltd. Dispersionszusammensetzung und aufzeichnungsmaterial
JP2008194986A (ja) 2007-02-15 2008-08-28 Nippon Paper Industries Co Ltd 感熱記録体
EP2033800A1 (de) 2007-09-04 2009-03-11 Mitsubishi HiTec Paper Flensburg GmbH Wärmeempfindliches Aufzeichnungsmaterial
EP2033799A1 (de) 2007-09-04 2009-03-11 Mitsubishi HiTec Paper Flensburg GmbH Wärmeempfindliches Aufzeichnungsmaterial
JP2013237234A (ja) 2012-05-17 2013-11-28 Osaka Sealing Printing Co Ltd 感熱記録材料および感熱記録紙
WO2015181291A1 (de) 2014-05-28 2015-12-03 Papierfabrik August Köhler Se Wärmeempfindliches aufzeichnungsmaterial
US20160031254A1 (en) 2013-03-27 2016-02-04 Mitsubishi Hitec Paper Europe Gmbh Composition For Developing A Visually Discernible Colour And Corresponding Heat-Sensitive Recording Material
JP2016068418A (ja) 2014-09-30 2016-05-09 日本化薬株式会社 感熱記録材料
WO2016150428A1 (de) 2015-03-23 2016-09-29 Papierfabrik August Koehler Se Wärmeempfindliches aufzeichnungsmaterial
JP2017081107A (ja) 2015-10-30 2017-05-18 日本化薬株式会社 感熱記録材料
WO2018015178A1 (de) 2016-07-18 2018-01-25 Papierfabrik August Koehler Se Wärmeempfindliches aufzeichnungsmaterial
JP2018065338A (ja) 2016-10-21 2018-04-26 日本化薬株式会社 感熱記録材料
EP3395583A1 (de) 2015-12-25 2018-10-31 Nippon Kayaku Kabushiki Kaisha Hitzeempfindliches aufzeichnungsmaterial
WO2018215287A1 (de) 2017-05-24 2018-11-29 Papierfabrik August Koehler Se Nicht-phenolischer farbentwickler und wärmeempfindliches aufzeichnungsmaterial
JP2019084758A (ja) 2017-11-07 2019-06-06 日本化薬株式会社 感熱記録材料
JP2019130879A (ja) 2018-02-01 2019-08-08 日本化薬株式会社 感熱記録材料
WO2020039601A1 (ja) 2018-08-23 2020-02-27 日本化薬株式会社 エネルギー線硬化型樹脂組成物の水中油滴型エマルション及び感熱記録材料
EP3636446A1 (de) 2017-06-08 2020-04-15 Nippon Soda Co., Ltd. Aufzeichnungsmaterial und verbindung

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1135540A (en) 1966-06-01 1968-12-04 Ncr Co Temperature responsive record material
US3746675A (en) 1970-07-15 1973-07-17 Ncr Heat sensitive record material
US3674535A (en) 1970-07-15 1972-07-04 Ncr Co Heat-sensitive record material
US4181771A (en) 1977-11-04 1980-01-01 Ncr Corporation Thermally responsive record material
US4151748A (en) 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
US4246318A (en) 1979-04-09 1981-01-20 Appleton Papers Inc. Thermally-responsive record material
US4470057A (en) 1982-07-26 1984-09-04 Appleton Papers Inc. Thermally-responsive record material
KR910007066B1 (ko) 1983-09-08 1991-09-16 간사끼 세이시 가부시기가이샤 감열(感熱)기록체
US4794102A (en) 1987-09-03 1988-12-27 Appleton Papers Inc. Thermally-responsive record material
US5098882A (en) 1989-08-24 1992-03-24 Daio Paper Corporation Heat-sensitive recording medium
US5955398A (en) 1997-04-25 1999-09-21 Appleton Papers Inc. Thermally-responsive record material
US6921740B1 (en) 1999-08-31 2005-07-26 Mitsubishi Paper Miils Ltd. Electron-receiving compound and thermal recording material
US6835691B2 (en) 2000-01-05 2004-12-28 Appleton Papers Inc. Thermally-responsive record material
JP2016165835A (ja) * 2015-03-10 2016-09-15 王子ホールディングス株式会社 感熱記録体
KR20170073100A (ko) * 2015-12-18 2017-06-28 이영애 감열기록지용 현색제 조성물

Patent Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH082112A (ja) 1994-06-27 1996-01-09 Nippon Paper Ind Co Ltd 感熱記録体
JP2005330291A (ja) 1998-09-04 2005-12-02 Asahi Kasei Chemicals Corp 新規ウレアウレタン化合物
EP1116713A1 (de) 1998-09-04 2001-07-18 Asahi Kasei Kabushiki Kaisha Farbentwicklungs-verbindung und aufzeichnungsmaterial
US20010044553A1 (en) 1998-09-04 2001-11-22 Kazuo Kabashima Novel compound for color-producing composition, and recording material
WO2000014058A1 (en) 1998-09-04 2000-03-16 Asahi Kasei Kabushiki Kaisha Novel color-developing compound and recording material
JP2006104219A (ja) 1998-09-04 2006-04-20 Asahi Kasei Chemicals Corp 新規なウレアウレタン化合物
JP2006143741A (ja) 1998-09-04 2006-06-08 Asahi Kasei Chemicals Corp ウレアウレタン化合物
JP2006143740A (ja) 1998-09-04 2006-06-08 Asahi Kasei Chemicals Corp 新しいウレアウレタン化合物
JP2002187364A (ja) 2000-12-20 2002-07-02 Nippon Paper Industries Co Ltd 感熱記録紙
JP2002283744A (ja) 2001-03-26 2002-10-03 Nippon Paper Industries Co Ltd 感熱記録体
JP2004223871A (ja) 2003-01-23 2004-08-12 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2004255842A (ja) 2003-02-28 2004-09-16 Mitsubishi Paper Mills Ltd 感熱記録材料
EP1681174A1 (de) 2003-10-23 2006-07-19 Chemipro Kasei Kaisha, Ltd. Dispersionszusammensetzung und aufzeichnungsmaterial
DE102004004204A1 (de) 2004-01-27 2005-08-11 Mitsubishi Hitec Paper Bielefeld Gmbh Wärmeempfindliches Aufzeichnungsmaterial
JP2008194986A (ja) 2007-02-15 2008-08-28 Nippon Paper Industries Co Ltd 感熱記録体
EP2033799A1 (de) 2007-09-04 2009-03-11 Mitsubishi HiTec Paper Flensburg GmbH Wärmeempfindliches Aufzeichnungsmaterial
EP2033800A1 (de) 2007-09-04 2009-03-11 Mitsubishi HiTec Paper Flensburg GmbH Wärmeempfindliches Aufzeichnungsmaterial
JP2013237234A (ja) 2012-05-17 2013-11-28 Osaka Sealing Printing Co Ltd 感熱記録材料および感熱記録紙
US20160031254A1 (en) 2013-03-27 2016-02-04 Mitsubishi Hitec Paper Europe Gmbh Composition For Developing A Visually Discernible Colour And Corresponding Heat-Sensitive Recording Material
WO2015181291A1 (de) 2014-05-28 2015-12-03 Papierfabrik August Köhler Se Wärmeempfindliches aufzeichnungsmaterial
JP2016068418A (ja) 2014-09-30 2016-05-09 日本化薬株式会社 感熱記録材料
WO2016150428A1 (de) 2015-03-23 2016-09-29 Papierfabrik August Koehler Se Wärmeempfindliches aufzeichnungsmaterial
JP2017081107A (ja) 2015-10-30 2017-05-18 日本化薬株式会社 感熱記録材料
EP3395583A1 (de) 2015-12-25 2018-10-31 Nippon Kayaku Kabushiki Kaisha Hitzeempfindliches aufzeichnungsmaterial
WO2018015178A1 (de) 2016-07-18 2018-01-25 Papierfabrik August Koehler Se Wärmeempfindliches aufzeichnungsmaterial
JP2018065338A (ja) 2016-10-21 2018-04-26 日本化薬株式会社 感熱記録材料
WO2018215287A1 (de) 2017-05-24 2018-11-29 Papierfabrik August Koehler Se Nicht-phenolischer farbentwickler und wärmeempfindliches aufzeichnungsmaterial
EP3636446A1 (de) 2017-06-08 2020-04-15 Nippon Soda Co., Ltd. Aufzeichnungsmaterial und verbindung
JP2019084758A (ja) 2017-11-07 2019-06-06 日本化薬株式会社 感熱記録材料
JP2019130879A (ja) 2018-02-01 2019-08-08 日本化薬株式会社 感熱記録材料
WO2020039601A1 (ja) 2018-08-23 2020-02-27 日本化薬株式会社 エネルギー線硬化型樹脂組成物の水中油滴型エマルション及び感熱記録材料

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BJÖRNSDOTTER MARIA K; DE BOER JACOB; BALLESTEROS-GÓMEZ ANA: "Bisphenol A and replacements in thermal paper: A review", CHEMOSPHERE, vol. 182, 15 May 2017 (2017-05-15), GB , pages 691 - 706, XP085069105, ISSN: 0045-6535, DOI: 10.1016/j.chemosphere.2017.05.070
ECKARDT MARTIN; KUBICOVA MARIE; TONG DUYEN; SIMAT THOMAS J.: "Determination of color developers replacing bisphenol A in thermal paper receipts using diode array and Corona charged aerosol detection—A German market analysis 2018/2019", JOURNAL OF CHROMATOGRAPHY A, vol. 1609, 7 August 2019 (2019-08-07), AMSTERDAM, NL, pages 1 - 11, XP086039416, ISSN: 0021-9673, DOI: 10.1016/j.chroma.2019.460437
ECKARDT MARTIN; SIMAT THOMAS J.: "Bisphenol A and alternatives in thermal paper receipts - a German market analysis from 2015 to 2017", CHEMOSPHERE, vol. 186, 11 August 2017 (2017-08-11), GB , pages 1016 - 1025, XP085165279, ISSN: 0045-6535, DOI: 10.1016/j.chemosphere.2017.08.037

Also Published As

Publication number Publication date
EP4259449A1 (de) 2023-10-18
FI4259449T3 (fi) 2024-08-01
KR20230107361A (ko) 2023-07-14
KR102945498B1 (ko) 2026-03-30
JP7842760B2 (ja) 2026-04-08
WO2022125104A1 (en) 2022-06-16
JP2024502544A (ja) 2024-01-22

Similar Documents

Publication Publication Date Title
US12151498B2 (en) Multi-purpose phenol-free direct thermal recording media
US20240424820A1 (en) Developer composition for phenol-free direct thermal recording media
EP2130681B1 (de) Thermisches aufzeichnungsmaterial
KR20030094013A (ko) 감열기록재료
EP4259449B1 (de) Phenol-freie mehrzweck thermodirekt-aufzeichnungsmedien
US5811369A (en) Thermal recording medium
US8916497B2 (en) Thermally-responsive record material
US12545045B2 (en) Direct thermal recording media with diarylurea combinations for oil resistance
KR20010043232A (ko) 감열기록체
US7049269B2 (en) Thermal recording material and production method thereof
KR100549037B1 (ko) 신규한 발색제 및 기록 재료
JP2026069557A (ja) 多目的フェノール不含有直接感熱記録媒体
US20100130356A1 (en) Thermally-responsive record material
JP2007038633A (ja) 感熱記録材料および感熱記録方法
JP4200818B2 (ja) 感熱記録媒体用樹脂組成物、及びそれを使用してなる感熱記録媒体とその印刷物
JP2004299354A (ja) 感熱記録材料および感熱記録方法
JP2003175678A (ja) 感熱記録体
JP2003175679A (ja) 感熱記録体
JP2006239895A (ja) 感熱記録材料
JP2006239894A (ja) 感熱記録材料

Legal Events

Date Code Title Description
REG Reference to a national code

Ref country code: DE

Ref legal event code: R138

Ref document number: 202020006063

Country of ref document: DE

Free format text: GERMAN DOCUMENT NUMBER IS 602020032735

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230621

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
INTG Intention to grant announced

Effective date: 20240126

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20240411

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020032735

Country of ref document: DE

REG Reference to a national code

Ref country code: FI

Ref legal event code: FGE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240920

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240919

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240920

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240919

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1695695

Country of ref document: AT

Kind code of ref document: T

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20241021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20241021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20241019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20241019

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602020032735

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

26 Opposition filed

Opponent name: KOEHLER INNOVATION & TECHNOLOGY GMBH

Effective date: 20250311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20241210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240619

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20241231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20241231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20241231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20241210

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20251229

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20251226

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20251226

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20251229

Year of fee payment: 6