EP3680110B1 - Matériel d'enregistrement thermosensible - Google Patents

Matériel d'enregistrement thermosensible Download PDF

Info

Publication number
EP3680110B1
EP3680110B1 EP19151664.0A EP19151664A EP3680110B1 EP 3680110 B1 EP3680110 B1 EP 3680110B1 EP 19151664 A EP19151664 A EP 19151664A EP 3680110 B1 EP3680110 B1 EP 3680110B1
Authority
EP
European Patent Office
Prior art keywords
layer
thermosensitive
recording medium
thermosensitive recording
resin
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
EP19151664.0A
Other languages
German (de)
English (en)
Other versions
EP3680110A1 (fr
Inventor
Laurence DAUDIN
Daiki IWATA
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.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
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 Ricoh Co Ltd filed Critical Ricoh Co Ltd
Priority to EP19151664.0A priority Critical patent/EP3680110B1/fr
Publication of EP3680110A1 publication Critical patent/EP3680110A1/fr
Application granted granted Critical
Publication of EP3680110B1 publication Critical patent/EP3680110B1/fr
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
    • B41M5/323—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
    • B41M5/333—Colour developing components therefor, e.g. acidic 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
    • B41M5/3372—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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging

Definitions

  • the present invention relates to a thermosensitive recording medium and a consumer product package which is at least partially transparent and to which a thermosensitive recording medium has been attached.
  • Thermosensitive recording media are known which use a colorant system wherein a dye, such as a leuco dye, in one layer of the medium reacts, upon the application of heat, with another component, a so-called "developer” in order to give rise to a coloured product.
  • a dye such as a leuco dye
  • US 2010/0190644 A1 shows a heat-sensitive recording material, comprising a support; a heat-sensitive recording layer comprising a leuco dye and a developer: and a protective layer comprising a pigment and a binder, where the heat-sensitive recording layer is located between the protective layer and the support, and the binder of the protective layer comprises a water-soluble resin, which comprises polyvinyl alcohol or a modified polyvinyl alcohol, the polyvinyl alcohol or modified polyvinyl alcohol being present in a proportion of about 10 to 45 mass % based on total solids of the acrylic resin.
  • a heat-sensitive recording material wherein one or more heat-sensitive recording layers are formed from one or more heat-sensitive recording layer coating compositions that each contain a leuco dye and a developer, and an intermediate layer is formed from an intermediate layer coating composition that contains a hydrazine-based compound and an oxazoline group-containing compound, and a protective layer is formed from a protective layer coating composition that contains a modified polyvinyl alcohol, is shown in EP 2 329 956 A1 .
  • EP 1 826 018 A1 shows a heat-sensitive recording material comprising a support and a heat-sensitive recording layer, wherein the heat-sensitive recording layer contains a leuco dye and a color developer, the leuco dye is in a form of composite particles comprising the leuco dye and a hydrophobic resin, and the color developer comprises at least 4,4'-cyclohexylidenediphenol and 4,4'-bis(N-p-tolylsulfonylaminocarbonylamino)diphenylmethane.
  • An object of the present invention is to provide a thermosensitive recording medium showing a high transparency level which remains even if the product is dipped in water and which shows at the same time enhanced plasticizer resistance and preprint anchorage. It is also an object to provide acceptable background reflectance. Higher background reflectance value is relevant in reducing greyish appearance. In essence, the thermosensitive recording medium looks more white if applied to a white support.
  • preprint anchorage in typical practical applications, a commercial sample of thermal recording medium, with the ability to display detailed information such as food content information after recording e.g. by thermal printing or laser irradiation, will be subjected on the protective layer surface to (pre-)printing, by another technique such as offset printing, to provide more general commercial information (distributor, general food type etc.).
  • preprint anchorage measured for example by resistance to pre-print removal in a tape tearing test, is a property of value in the present invention.
  • thermosensitive recording medium layer assembly which has high overall transparency, typically measured by haze value i.e. the ratio of transmitted light to the incident light subjected to wide angle scattering.
  • haze value i.e. the ratio of transmitted light to the incident light subjected to wide angle scattering.
  • ASTM D 1003 defines haze as that percentage of light which in passing through deviates from the incident beam greater than 2.5 degrees on the average.
  • thermosensitive recording medium of claim 1 relates to the thermosensitive recording medium of claim 1.
  • the present invention relates to a consumer product package which is at least partially transparent and to which a thermosensitive recording medium of the invention is attached.
  • the consumer product package may be partially or fully transparent, flexible or rigid, and may contain one or more perishable food items, such as delicatessen products or box lunches.
  • the consumer product package may be based on a flexible polymer film such as, for example, a PVC film, with information printed thereupon.
  • the consumer product package may be fully transparent, or alternatively almost fully transparent, for example if the only non-transparent parts of the package are those containing printed information, or alternatively the consumer product package may comprise a transparent portion.
  • thermosensitive recording medium of the invention may be attached to a fully or almost transparent consumer product package, or to the transparent portion of a consumer product package, provides the advantage of allowing further information to be incorporated for the benefit of the consumer without obscuring the inner content of the consumer product package, such as a food content, which is thereby visible both before and after the attachment of the thermosensitive recording medium of the invention.
  • the base layer in the thermosensitive recording medium of the present invention is a transparent support layer suitably selected depending on the intended purpose without any particular restriction.
  • the transparent support used in the present invention is a polymeric material present in the form of a thin film.
  • the total light transmittance of the transparent film is preferably at least 60%, more preferably at least 70% and most preferably at least 90%.
  • Preferred films show a haze value less than 3.
  • the transparent film may also be coloured.
  • the thickness of the transparent film is preferably from 20 ⁇ m to 100 ⁇ m, more preferably 40 ⁇ m to 70 ⁇ m.
  • Film materials to be used in the transparent support of the thermosensitive recording medium of the present invention may be selected from the group consisting of: ionomer film (IO), polyethylene film (PE), poly(vinyl chloride) film (PVC), poly(vinylidene chloride) film (PVDC), poly(vinyl alcohol) film (PVA), polypropylene film (PP) including biaxially oriented (bi-oriented) polypropylene (BOPP), polyester film, poly(ethylene terephthalate) film (PET), polyethylene naphthalate) film (PEN), polycarbonate film (PC), polystyrene film (PS), polyacrylonitrile film (PAN), ethylene-vinyl acetate copolymer film (EVA), ethylene-vinyl alcohol copolymer film (EMAA), nylon film (NY), polyamide film (PA), triacetyl cellulose film (TAC), norbornane film (NB), and Arton film.
  • IO ionomer film
  • PE polyethylene
  • Preferred transparent support materials in the present invention are: poly(ethylene terephthalate) film (PET) and biaxially oriented (bi-oriented) polypropylene (BOPP).
  • PET poly(ethylene terephthalate) film
  • BOPP biaxially oriented polypropylene
  • Toyobo Ester (R) film E5107, E5100, E5101, Cosmo Shine (R) A4100, A 4300, A8300 and the like from Toyo Boseki K.K may be cited.
  • As BOPP film Cosmo Films PCT-2 (S/S) LBS, Lichang Plastic PF-P, Jindal Films LL210, and Taghleef Industries LSA, generally produced by co-extrusion, may be cited.
  • the transparent film may also contain various additives such as UV absorption agents, oxidation inhibitors, flame retarding agents, thermal stabilizers, colour developing agents, mould releasing agents, softening materials, and electrostatic inhibitors.
  • the surface of the film is preferably treated in order to achieve a surface tension of 38 dyn/cm at least.
  • This surface treatment is generally carried out by corona or plasma treatment.
  • undercoat is understood by the skilled person to refer to the layer between the support and thermosensitive colouring layer.
  • under layer may also be used synonymously with “undercoat layer” by skilled persons in the field.
  • an undercoat layer may be provided or not i.e. the undercoat layer is merely an option in the present invention, and the thermosensitive recording medium of the present invention may or may not contain such an undercoat layer.
  • thermosensitive recording medium of the present invention if an undercoat layer is used, the technical effect sought after through its used may notably be to improve weakness of adhesion between the substrate and the thermal layer, or to improve printing quality.
  • Such an undercoat layer, if used, should not prevent the thermosensitive recording medium from keeping its transparency, and may appropriately be characterized by a haze value of at most 15.
  • thermosensitive recording medium of the present invention may optionally contain an undercoat layer disposed between the transparent support and the thermosensitive colouring layer.
  • the undercoat layer contains a binder resin, and the undercoat layer may further contain other components such as a filler, and other additives.
  • the binder resin to be used in an undercoat layer either of a water-dispersible resin or a water-soluble resin may be used. Specific examples thereof include conventionally known water-soluble polymers, and aqueous polymer emulsions.
  • the water-soluble polymer that may be used in the binder resin in an undercoat layer may be suitably selected depending on the intended purpose without any restriction.
  • examples thereof include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxy cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, methyl cellulose and ethyl cellulose, polyvinyl pyrrolidone, alkali salts of styrene-maleic anhydride copolymers, alkali salts of isobutylene-maleic anhydride copolymers, alginate soda, gelatin and casein. These may be used alone or in combination.
  • the aqueous polymer emulsion that may be used in the binder resin in an undercoat layer may be suitably selected depending on the intended purpose without any restriction.
  • examples thereof include latexes of, for example, styrene-butadiene copolymers; and emulsions of, for example, vinyl acetate resins, acryl-based resins and polyurethane resins. These may be used alone or in combination.
  • An inorganic filler may be used or may be omitted from an undercoat layer if an undercoat layer is used in the thermosensitive recording medium of the present invention.
  • examples thereof include aluminum hydroxide, calcium carbonate, aluminum oxide, zinc oxide, titanium dioxide, silica, barium sulfate, talc, kaolin, alumina and clay. These may be used alone or in combination.
  • aluminum hydroxide, calcium carbonate, kaolin and clay are preferable in terms of liquid properties in a coating liquid, stability of dispersed particles, and water solubility.
  • thermosensitive recording media As components contained in undercoat layers of thermosensitive recording media, it is known, in order to improve printing quality, to use hollow particles having a hollow ratio of 50% or more or indeed 80% or more, or 90% or more, wherein the hollow ratio (in %) is the (inner diameter of a hollow particle / outer diameter of the hollow particle) x 100.
  • Each of such hollow particles may have a shell made of a thermoplastic resin and contain therein air or other gas, typically with a volume average particle diameter of 1 ⁇ m to 10 ⁇ m, most commonly having a thermoplastic resin as a shell, made from polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic ester, polyacrylonitrile, and polybutadiene, and copolymer resins thereof.
  • a thermoplastic resin made from polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic ester, polyacrylonitrile, and polybutadiene, and copolymer resins thereof.
  • the deposition amount of a first undercoat layer in the thermosensitive recording medium is appropriately 0.4 g/m 2 to 10 g/m 2 , more preferably 0.6 g/m 2 to 4 g/ m 2 .
  • an undercoat layer in a conventional thermosensitive recording medium is to fill up and compensate for the non-uniformity of supports such as paper supports in particular.
  • an undercoat layer is chosen, through its constituents, to be a low-cost layer which ensures a smoother surface before coating with the thermal layer which is expensive - such a way of proceeding optimizes the use of and avoids loss of thermal layer materials.
  • Undercoat layers have been modified to improve pre-print properties and sensitivity by adding hollow fillers which reflect the heat to thermosensitive colouring layer rather than the latter being lost to the paper support layer. In the present invention however, due to the high smoothness of the transparent film support in comparison to paper supports for other thermosensitive recording media, an undercoat layer is not normally necessary.
  • one side of the transparent support layer is in contact with one side of the thermosensitive layer, without any undercoat layer between the transparent support layer and the thermosensitive colouring layer.
  • the base layer in the thermosensitive recording medium is a transparent support layer in the form of a polymeric thin film
  • an undercoat layer may however still be used to effectively utilize generated heat for higher sensitivity, improve adhesiveness between the transparent support and the thermosensitive layer, and prevent permeation of the recording layer materials into the transparent support.
  • thermosensitive colouring layer is situated over the transparent support layer, and the thermosensitive colouring layer contains a leuco dye, a developer and a hydrophobic resin.
  • the thermosensitive colouring layer may be in contact with one face of the transparent support layer or alternatively, as discussed above, an undercoat layer may be present between the transparent support layer and the thermosensitive colouring layer.
  • thermosensitive colouring layer contains a colorant system wherein a dye, such as a leuco dye, in one layer of the medium reacts, upon the application of heat, with another component, a so-called "developer”, in order to give rise to a coloured product.
  • a dye such as a leuco dye
  • the leuco dye is a compound exhibiting electron donation properties, and may be used singly or in combination of two or more species. However, the leuco dye itself is a colourless or light-coloured dye precursor, and commonly known leuco compounds can be used.
  • the leuco compounds include triphenylmethane phthalide compounds, triarylmethane compounds, fluoran compounds, phenothiazine compounds, thiofluoran compounds, xanthen compounds, indophthalyl compounds, spiropyran compounds, azaphthalide compounds, chlormenopirazole compounds, methyne compounds, rhodamine anilinolactum compounds, rhodamine lactum compounds, quinazoline compounds, diazaxanthen compounds, bislactone compounds.
  • specific examples of such compounds are as follows:
  • the amount of the leuco dye contained in the thermosensitive coloring layer is preferably 3% by mass to 20% by mass.
  • various electron accepting materials are suitably used to react with the aforementioned leuco dye at the time of heating so as to develop colours.
  • examples thereof include phenolic compounds, organic or inorganic acidic compounds and esters or salts thereof. Specific examples thereof include: bisphenol A, tetrabromobisphenol A, gallic acid, salicylic acid, 3-isopropyl salicylate, 3-cyclohexyl salicylate, 3-5-di-tert-butyl salicylate, 3,5-di- ⁇ -methyl benzyl salicylate, 4,4'-isopropylidenediphenol, 1,1'-isopropylidene bis (2-chlorophenol), 4,4'-isopropylidene bis (2,6-dibromophenol), 4,4'-isopropylidene bis (2,6-dichlorophenol), 4,4'-isopropylidene bis (2-methyl phenol), 4,4'-isopropylidene bis (2,6-dimethyl phenol
  • the mixing ratio of the developer to the leuco dye is such that the developer is preferably 0.5 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, relative to 1 part by mass of the leuco dye.
  • thermosensitive recording medium of the present invention a hydrophobic resin is used in the thermosensitive colouring layer along with a leuco dye and a developer. It has been found by the present inventors that a certain amount of hydrophobic resin in the thermosensitive colouring layer is useful to improve transparency both for the product as prepared and after exposure to water of the final product.
  • the hydrophobic resin is preferably a homopolymer or copolymer of one or more monomers selected from the group consisting of: styrene, dienes, alkylenes, vinyl acetate, acrylonitrile, and (meth)acrylic esters.
  • (meth)acrylic esters is understood as including both methacrylic esters, acrylic esters and combinations thereof.
  • Diene monomers that can be used include: butadiene, isoprene, butenylene, and substituted, e.g. halogenated, versions of these dienes.
  • Alkene monomers that can be used include ethylene, propylene, butene, pentene, hexene, heptene, and substituted, e.g. halogenated, versions of these alkenes.
  • the hydrophobic resin to be used in the thermosensitive colouring layer of the present invention may appropriately be one or more selected from the group consisting of: styrene-butadiene resin; styrene-acrylic resin; acrylonitrile-butadiene; acrylate ester resin; ethylene-vinyl acetate resin; methylacrylate-butadiene resin.
  • the hydrophobic resin may also be a urethane resin.
  • styrene-butadiene resin is a particularly preferred hydrophobic resin material for the thermosensitive colouring layer of the thermosensitive recording medium of the present invention.
  • styrene-butadiene resin has been found to provide particularly improved background reflectance.
  • thermosensitive colouring layer In a common situation, hydrophobic resins are distributed commercially as latex materials, dispersed in an aqueous phase.
  • the hydrophobic resin In a preferred method of preparing the thermosensitive colouring layer of the present invention, the hydrophobic resin is provided in water-borne form as a latex and mixed with a leuco dye and a developer in aqueous dispersion and dried in order to form the thermosensitive colouring layer.
  • the hydrophobic resin used in the thermosensitive colouring layer shows a glass transition temperature (Tg) of at least -10°C and at most 0°C.
  • the glass transition temperature is a well-known feature of such hydrophobic resins and is commonly designated in commercial samples.
  • Polymers to be used as the hydrophobic resin in the thermosensitive colouring layer of the present invention may show some degree of solubility in water, whilst showing an appropriate range of glass transition temperature (Tg) for the present invention, i.e. at least -10°C and at most 0°C.
  • the latex particles are stabilized and exist individually.
  • the latex particles come in contact.
  • the particles either keep their shape, or they deform ("melt") and form a polymer film.
  • a fully cured polymer film, where the particles have lost their shape, is usually transparent.
  • a film that still contains the original particles will scatter light at the particle surfaces and will thus be opaque.
  • drying should be performed at temperatures clearly above the Tg.
  • the time of drying is limited by the coating speed and the drying temperature is limited by the fact that the materials used is thermosensitive and will start to react at 50°C, it has been found preferable that the Tg not exceed 25°C to achieve a good transparency with drying temperatures below 60°C.
  • the glass transition temperature (Tg) is as measured by differential scanning calorimetry (DSC) with a previously cooling at a rate of 10 K/mn followed by on heating at a rate of 10 K/mn until transformation from glass to metastable melt is achieved.
  • the exact value of Tg is as determined on the inflection point placed at the middle point between the two tangents. The inflection point corresponds to point B in Figure 5 .
  • the glass transition temperature (Tg) is measured according to standard DIN 51007.
  • the minimum quantity of hydrophobic resin, expressed with respect to 100% weight of all components of the thermosensitive colouring layer taken together, is at least 40%, more preferably at least 45%.
  • the maximum quantity of hydrophobic resin, expressed with respect to 100% total weight of the thermosensitive colouring layer is preferably at most 65%, more preferably at most 61%, and most preferably at most 58%.
  • thermosensitive coloring layer other materials customarily used in thermosensitive recording media, such as a filler, a hot-meltable material, a crosslinking agent, a pigment, a surfactant and a lubricant.
  • the filler is suitably selected depending on the intended purpose without any restriction.
  • examples thereof include inorganic pigments such as calcium carbonate, aluminum oxide, zinc oxide, titanium dioxide, silica, aluminum hydroxide, barium sulfate, talc, kaolin, alumina and clay, and commonly known organic pigments.
  • inorganic pigments such as calcium carbonate, aluminum oxide, zinc oxide, titanium dioxide, silica, aluminum hydroxide, barium sulfate, talc, kaolin, alumina and clay, and commonly known organic pigments.
  • acidic pigments such as silica, alumina and kaolin are preferable, with silica being particularly preferable from the viewpoint of developed color density.
  • the hot-meltable material is suitably selected depending on the intended purpose without any restriction.
  • fatty acids such as stearic acid and behenic acid
  • fatty acid amides such as stearic acid amide, erucic acid amide, palmitic acid amide, behenic acid amide and palmitic acid amide
  • N-substituted amides such as N-lauryl lauric acid amide, N-stearyl stearic acid amide and N-oleyl stearic acid amide
  • bis fatty acid amides such as methylene bis stearic acid amide, ethylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis capric acid amide and ethylene bis behenic acid amide
  • hydroxyl fatty acid amides such as hydroxyl stearic acid amide, methylene bis hydroxyl stearic acid amide, ethylene bis hydroxyl stearic acid amide and hexamethylene bis
  • the weight amount of hydrophobic resin expressed with respect to the total dry weight of the thermosensitive coloring layer taken as 100%, is limited.
  • the total weight of the thermosensitive coloring layer is the sum of the weight of leuco dye(s), developer(s), hydrophobic resin(s), and any other additive used in the thermosensitive coloring layer, such as filler(s), hot-meltable materia(s), crosslinking agent(s), pigment(s), surfactant(s), and lubricant(s).
  • the components of thermosensitive coloring layer are applied by coating with a liquid solution / suspension, the total weight amount of the thermosensitive coloring layer, and the weight amount of hydrophobic resin, are here expressed as dry weights after removal of solvents and any other volatile materials.
  • thermosensitive coloring layer can be formed by commonly known methods. To avoid reaction between components of the thermosensitive coloring layer, in preferred embodiments, dispersion is carried out separately and then liquids are mixed. Grinding with a binder and other components is performed typically so as to have a particle diameter of 0.2 ⁇ m to 3 ⁇ m, preferably 0.4 ⁇ m to 1 ⁇ m by using a disperser such as a ball mill, an Atriter or a sand mill.
  • the particle size target of each dispersion will be preferably set to get an optimum balance between transparency and background reflectance. Indeed, the lower the particle size is, the higher is the transparency but at the same time, the background reflectance will decrease as thermal layer will become more and more greyish.
  • the resultant dispersion is mixed, if necessary, together with a filler and a hot-meltable material (sensitizer) dispersion liquid in accordance with a predetermined formulation, to thereby prepare a coating liquid of a thermosensitive coloring layer, followed by applying the thus-prepared coating liquid onto a support.
  • a hot-meltable material (sensitizer) dispersion liquid in accordance with a predetermined formulation, to thereby prepare a coating liquid of a thermosensitive coloring layer, followed by applying the thus-prepared coating liquid onto a support.
  • the thickness of the thermosensitive coloring layer varies depending on the composition of the thermosensitive coloring layer and intended use of the thermosensitive recording medium and cannot be specified flatly, but it is preferably 1 ⁇ m to 50 ⁇ m, more preferably 2 ⁇ m to 20 ⁇ m.
  • thermosensitive layer In order to achieve good matching properties to thermal head like no sticking, no scratches as well as various qualities such as water or plasticizer resistance, it is preferable to provide at least one protective layer on the thermosensitive layer.
  • Several different protective layers can be overlaid on each other to focus respectively more on matching or barrier properties.
  • the protective layer(s) in the thermosensitive recording medium of the present invention may be suitably selected depending on the intended purpose without any particular restriction.
  • the protective layer(s) typically contain(s) at least a binder, and each of the protective layer(s) may contain an inorganic filler, a lubricant and a surfactant.
  • the binder of (each of) the protective layer(s) is suitably selected depending on the intended purpose without any restriction, it being possible to use the same binder in each protective layer or a different binder in separate protective layers.
  • binders that may be used in the protective layer(s) include polyvinyl alcohol, modified polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives, polyvinylpyrrolidone, polyethyleneimine, alginate soda, gelatin and casein. Acrylic binders may also be used.
  • Hydrophobic resins that may be used as binders in the protective layer(s) include ones typically provided as aqueous emulsions during preparation of the protective layer(s), such as urethane resins, epoxy resins, vinyl acetate (co)polymers, vinylidene chloride (co)polymers, vinyl chloride (co)polymers, and styrene-butadiene copolymers.
  • the thickness of the protective layer(s) varies preferably 0.2 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m.
  • a protective layer of thickness 2.5 ⁇ m when dry can be used - when added during the manufacturing process the initial wet thickness of this layer is approximately 6 ⁇ m.
  • a preferred maximum cumulative thickness for the sum of all protective layers is 10 ⁇ m for the dried final product.
  • the inorganic filler in the protective layer(s), if used, is suitably selected depending on the intended purpose without any restriction.
  • the inorganic filler include aluminum hydroxide, calcium carbonate, aluminum oxide, zinc oxide, titanium dioxide, silica, barium sulfate, talc, kaolin, alumina and clay. These may be used alone or in combination.
  • aluminum hydroxide, and calcium carbonate are particularly preferable because the protective layer containing such inorganic filler is provided with excellent abrasion resistance with respect to a thermal head when printing is performed for a long period of time.
  • the amount of the inorganic filler in the second protective layer is suitably selected depending on the intended purpose without any restriction.
  • the amount of the inorganic filler depends on types of the filler, but it is preferably 50 parts by mass to 500 parts by mass, relative to 100 parts by mass of the binder resin.
  • the lubricant if used, is suitably selected depending on the intended purpose without any restriction.
  • examples thereof include higher fatty acids such as zinc stearate, calcium stearate, montanate wax, polyethylene wax, carnauba wax, paraffin wax, ester wax and metal salts thereof; higher fatty acid amides, higher fatty acid esters, animal wax, vegetable wax, mineral wax, and petroleum wax.
  • a method for forming the first, second or subsequent protective layer is suitably selected depending on the intended purpose without any restriction. Examples thereof include blade coating, roll coating, wire bar coating, die coating, and curtain coating.
  • An intermediate layer is a layer that may be provided between the thermosensitive colouring layer and the protective layer. Such an intermediate layer is however not required in the present invention, but instead is only optional.
  • An intermediate layer containing a water-soluble resin can prevent the thermosensitive recording layer from being colored due to ultraviolet irradiation performed for forming the protective layer, or a reaction between the protective layer and pigments from the thermosensitive colouring layer.
  • An intermediate layer, similar to a first protective layer may also improve background resistance.
  • An intermediate layer contains a water-soluble resin.
  • the water-soluble resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples of the water-soluble resin include: polyvinyl alcohol resins, starch or derivatives of starch; cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose; water-soluble polymers such as sodium polyacrylate, polyvinyl pyrrolidone, acrylamide-acrylic acid ester copolymers, acrylamide-acrylic acid ester-methacrylic acid terpolymers, styrene-maleic anhydride copolymer alkali salts, isobutylene-maleic anhydride copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, and casein; emulsions of, for example, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic acid ester,
  • water-soluble resins may be used alone or two or more of these water-soluble resins may be used in combination.
  • polyvinyl alcohol resins are preferable, and polyvinyl alcohol resins having a molecular weight of 15,000 or less are more preferable.
  • components of an intermediate layer are not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples of the other components include a cross-linking agent and a surfactant.
  • One of these other components may be used alone or two or more of these other components may be used in combination.
  • the cross-linking agent is not particularly limited so long as the cross-linking agent can reduce water-solubility of the water-soluble resin by reacting with the water-soluble resin.
  • the cross-linking agent include glyoxal derivatives, methylol derivatives, epichlorohydrin, polyamide epichlorohydrin, epoxy compounds, aziridine compounds, hydrazine, hydrazide derivatives, oxazoline derivatives, and carbodiimide derivatives.
  • One of these cross-linking agents may be used alone or two or more of these cross-linking agents may be used in combination.
  • polyamide epichlorohydrin is preferable because polyamide epichlorohydrin is highly safe in handling and takes a short curing time needed for water-resistance treatment.
  • the content of polyamide epichlorohydrin is not particularly limited, may be appropriately selected depending on the intended purpose, and is preferably 10 parts by mass or greater but 80 parts by mass or less and more preferably 20 parts by mass or greater but 60 parts by mass or less relative to 100 parts by mass of the water-soluble resin.
  • the surfactant is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the surfactant include anionic surfactants, nonionic surfactants, amphoteric surfactants, and fluorosurfactants. One of these surfactants may be used alone or two or more of these surfactants may be used in combination.
  • the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, and polyoxyethylene alkyl ether sulfate salt. One of these anionic surfactants may be used alone or two or more of these anionic surfactants may be used in combination.
  • nonionic surfactant examples include acetylene glycol-based surfactants, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, and polyoxyethylene sorbitan fatty acid ester.
  • acetylene glycol-based surfactants polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, and polyoxyethylene sorbitan fatty acid ester.
  • One of these nonionic surfactants may be used alone or two or more of these nonionic surfactants may be used in combination.
  • acetylene glycol-based surfactant examples include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3-diol, and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.
  • One of these acetylene glycol-based surfactants may be used alone or two or more of these acetylene glycol-based surfactants may be used in combination.
  • the method for forming the intermediate layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the intermediate layer can be formed through the step (1) and the step (2) described below.
  • Step (1) The water-soluble resin, and as needed, the cross-linking agent and the surfactant are mixed, to prepare an intermediate layer coating liquid.
  • Step (2) The intermediate layer coating liquid is coated over the thermosensitive recording layer and dried.
  • the coating method is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the coating method include a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, a U-comma coating method, an AKKU coating method, a smoothing coating method, a microgravure coating method, a reverse roll coating method, a 4-roll or 5-roll coating method, a dip coating method, a curtain coating method, a slide coating method, and a die coating method.
  • the amount of the intermediate layer remaining attached after drying is not particularly limited, may be appropriately selected depending on the intended purpose, and is preferably, for example, 0.4 g/m 2 or greater but 3.0 g/m 2 or less, more preferably 0.5 g/m 2 or greater but 1.5 g/m 2 or less, and particularly preferably 0.5 g/m 2 or greater but 1.0 g/m 2 or less.
  • thermosensitive recording medium may contain a back layer containing a pigment, a binder resin, and preferably a crosslinking agent.
  • the back layer if present, is to be disposed on the surface of the transparent support opposite to the surface thereof where the thermosensitive layer is disposed, or where the undercoat layer between the transparent support and the thermosensitive layer is situated, if such an undercoat layer is present.
  • the back layer may further contain other components such as a filler, a lubricant, and an antistatic agent.
  • the binder resin either of a water-dispersible resin or a water-soluble resin can be used. Specific examples thereof include conventionally known water-soluble polymers, and aqueous polymer emulsions.
  • the water-soluble polymer is suitably selected depending on the intended purpose without any restriction.
  • examples thereof include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxy cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, methyl cellulose and ethyl cellulose, polyvinyl pyrrolidone, alkali salts of styrene-maleic anhydride copolymers, alkali salts of isobutylene-maleic anhydride copolymers, alginate soda, gelatin and casein. These may be used alone or in combination.
  • the aqueous polymer emulsion is suitably selected depending on the intended purpose without any restriction.
  • examples thereof include latexes of, for example, styrene-butadiene copolymers; and emulsions of, for example, vinyl acetate resins, acryl-based resins (e.g. acrylic acid-acrylic acid ester copolymer latexes), (meth)acrylamide-based resins, and polyurethane resins. These may be used alone or in combination.
  • the crosslinking agent is suitably selected depending on the intended purpose without any restriction.
  • examples thereof include polyvalent amine compounds such as ethylene diamine; polyvalent aldehyde compounds such as glyoxal, glutalaldehyde and dialdehyde; dihydrazide compounds such as dihydrazide adipate and dihydrazide phthalate; polyamide-epichlorohydrin compounds; water-soluble methylol compounds (urea, melamine and phenol); multifunctional epoxy compounds; multivalent metal salts (e.g., Al, Ti, Zr and Mg); titanium lactate; and boric acid.
  • polyvalent amine compounds such as ethylene diamine
  • polyvalent aldehyde compounds such as glyoxal, glutalaldehyde and dialdehyde
  • dihydrazide compounds such as dihydrazide adipate and dihydrazide phthalate
  • polyamide-epichlorohydrin compounds such as dihydrazide a
  • the amount of the crosslinking agent varies depending on the amounts and types of functional groups of the crosslinking agent, but it is preferably 0.1 parts by mass to 100 parts by mass, more preferably 1 part by mass to 100 parts by mass, relative to 100 parts by mass of the binder resin.
  • an inorganic filler or an organic filler may be used.
  • the inorganic filler include carbonates, silicates, metal oxides and sulfate compounds.
  • the organic filler include silicone resins, cellulose resins, epoxy resins, nylon resins, phenol resins, polyurethane resins, urea resins, melamine resins, polyester resins, polycarbonate resins, styrene resins, polyethylene resins, and formaldehyde resins.
  • the antistatic agent may, for example, be selected from commonly used ion-conducting antistatic agents and electron-conducting antistatic agents.
  • the ion-conducting antistatic agents include inorganic salts such as sodium chloride; anionic polymers such as sodium polystyrenesulfonate; and resins containing quaternary ammonium salts that are electrolyte cations.
  • the electron-conducting antistatic agents include conductive metal compounds such as conductive tin and antimony oxide; and conductive polymers such as polyaniline.
  • polystyrene sulfonic acid salts in particular, react with aziridine, thereby improving water resistance obtained by means of cross-linkage.
  • salts which have copolymerized with maleic acid are effective in that they have antistatic properties and also improve water resistance.
  • a method for forming the back layer is suitably selected depending on the intended purpose without any restriction.
  • the back layer is preferably formed by applying a coating liquid of the back layer to a support.
  • the coating method is suitably selected depending on the intended purpose without any restriction. Examples thereof include blade coating, roll coating, wire bar coating, die coating, and curtain coating.
  • the thickness of the back layer is suitably selected depending on the intended purpose without any restriction. It is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m.
  • a viscous layer also called an adhesive layer, may be provided in the thermosensitive recording medium of the present invention.
  • Such a viscous layer is however not required in the present invention, but instead is only optional.
  • a viscous layer may be provided on a surface of the transparent support layer opposite to the surface over which the protective layer is formed.
  • the viscous layer may, for example, help to attach the thermosensitive recording medium to a food package in a typical application of the present invention.
  • the viscous layer may also provide antistatic properties.
  • the method for forming the viscous layer is not particularly limited. Examples of the method include common coating methods and laminating methods.
  • the average thickness of the viscous layer is not particularly limited, may be appropriately selected depending on the intended purpose, and is preferably 0.1 micrometers or greater but 20 micrometers or less.
  • the material of the viscous layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples of the material of the viscous layer include urea resins, melamine resins, phenol resins, epoxy resins, vinyl acetate-based resins, vinyl acetate-acrylic-based copolymers, ethylene-vinyl acetate copolymers, acrylic-based resins, polyvinyl ether-based resins, vinyl chloride-vinyl acetate-based copolymers, polystyrene-based resins, polyester-based resins, polyurethane-based resins, polyamide-based resins, chlorinated polyolefin-based resins, polyvinyl butyral-based resins, acrylic acid ester-based copolymers, methacrylic acid ester-based copolymers, natural rubbers, cyano acrylate-based resins, and silicone-based resins.
  • One of these materials may be used alone or two or more of these materials may be used in
  • An image recording method may be used for recording an image on the thermosensitive recording medium of any of the embodiments of the present invention using an image recording unit, which is any one of a thermal head and a laser.
  • the thermal head is suitably selected depending on the intended purpose without any restriction regarding the shape, structure and size thereof.
  • the laser may be selected depending on the intended purpose without any restriction.
  • a CO 2 laser which emits light having a wavelength of 9.3 ⁇ m to 10.6 ⁇ m may be used.
  • a satisfactory laser print image can be obtained without using a photothermal conversion agent such as a phthalocyanine pigment.
  • Other laser types may be used, such as FLDA (Fiber Laser Diode Array).
  • thermosensitive recording layer liquid C 1 Preparation of thermosensitive recording layer liquid C 1 .
  • 2,2'-diallyl-4,4'-sulfonyldiphenol 50 parts by mass
  • a 35% by mass acrylic resin aqueous solution 10 parts by mass
  • ion exchanged water 70 parts by mass
  • D50 50% cumulative volume particle diameter measured by a laser diffraction/scattering particle diameter distribution measuring instrument (instrument name : LA-920, from HORIBA, Ltd.) is less than 0.7 ⁇ m to thereby prepare a developer dispersion liquid [Liquid A1].
  • thermosensitive recording layer liquid [C1] corresponding to an addition of 33% of styrene-butadiene with respect to 100% dry weight of all components.
  • HPD40 commercial grade of styrene-butadiene copolymer latex used for this preparation was HPD40 available from Trinseo Europe GmbH characterized by a glass transition temperature of 0°C.
  • a 20% water-based acrylic resin product name: Bariastar B-2000 available from Mitsui Chemicals, Inc.
  • a 25% slurry of kaolin having a mean volume particle diameter of kaolin having a mean volume particle of 0.7 ⁇ m Product name: UW90, available from Engelhard Corporation
  • a 35% polyethylene wax product name: Michem Emulsion 99235 available from Michelman, Inc.
  • thermosensitive recording medium [Preparation of thermosensitive recording medium]
  • thermosensitive recording medium precursor 1 The [C1] and [D1] liquids were coated and dried in this order over the surface of a bioriented polypropylene film (product name: 35LL410, with a thickness of 35 ⁇ m, available from Jindal Films) such that the amounts of the [C1] and [D1] remaining attached after drying would be 3.6 g/m 2 corresponding to a dye coating weight of 0.6 g/m 2 and 3.0 g/m 2 to obtain a thermosensitive recording medium precursor 1.
  • a bioriented polypropylene film product name: 35LL410, with a thickness of 35 ⁇ m, available from Jindal Films
  • thermosensitive recording medium precursor 1 was put in a high density polyethylene bag, closely sealed, and cured in an environment of 40°C for 15 hours to produce the thermosensitive recording medium 1.
  • thermosensitive recording medium 2 was produced by preparing a thermosensitive recording layer liquid [C2] in the same manner as in Example 1, except that unlike Example 1, 41 parts by mass of 50% styrene butadiene copolymer latex and 44 parts by mass of water were used which corresponds to an addition of 43% of styrene-butadiene with respect to 100 dry weight of all components.
  • thermosensitive recording medium 3 was produced by preparing a thermosensitive recording layer liquid [C3] in the same manner as in Example 1, except that unlike Example 1, 55 parts by mass of 50% styrene butadiene copolymer latex and 30 parts by mass of water were used which corresponds to an addition of 50% of styrene-butadiene with respect to 100 dry weight of all components.
  • thermosensitive recording medium 4 was produced by preparing a thermosensitive recording layer liquid [C4] in the same manner as in Example 1, except that unlike Example 1, 68 parts by mass of 50% styrene butadiene copolymer latex and 16 parts by mass of water were used which corresponds to an addition of 56% of styrene-butadiene with respect to 100 dry weight of all components.
  • thermosensitive recording medium 5 was produced by preparing a thermosensitive recording layer liquid [C5] in the same manner as in Example 1, except that unlike Example 1, 82 parts by mass of 50% styrene butadiene copolymer latex and 3 parts by mass of water were used which corresponds to an addition of 60% of styrene-butadiene with respect to 100 dry weight of all components.
  • thermosensitive recording medium 6 was produced by preparing a thermosensitive recording layer liquid [C6] in the same manner as in Example 3, except that unlike Example 3, the 50% styrene butadiene copolymer latex commercial grade used for this preparation is characterized by a glass transition temperature of -25 °C (Product name : HPD42 available from Trinseo Europe GmbH).
  • thermosensitive recording medium 7 was produced by preparing a thermosensitive recording layer liquid [C7] in the same manner as in Example 3, except that unlike Example 3, the 50% styrene butadiene copolymer latex commercial grade used for this preparation is characterized by a glass transition temperature of -10 °C (Product name : HPD41 available from Trinseo Europe GmbH).
  • thermosensitive recording medium 8 was produced by preparing a thermosensitive recording layer liquid [C8] in the same manner as in Example 3, except that unlike Example 3, the 50% styrene butadiene copolymer latex commercial grade used for this preparation is characterized by a glass transition temperature of 15 °C (Product name : HPD39 available from Trinseo Europe GmbH).
  • thermosensitive recording medium 9 was produced by preparing a thermosensitive recording layer liquid [C9] in the same manner as in Example 1, except that unlike Example 1, the 50% styrene butadiene copolymer latex was replaced by a 41% self-crosslinking acrylic emulsion (Product name: FLX 5020 available from BTC Europe GmbH) (67 parts by mass) and 18 parts by mass of water were used which corresponds to an addition of 50 % of acrylic emulsion with respect to 100 dry weight of all components.
  • a thermosensitive recording layer liquid [C9] in the same manner as in Example 1, except that unlike Example 1, the 50% styrene butadiene copolymer latex was replaced by a 41% self-crosslinking acrylic emulsion (Product name: FLX 5020 available from BTC Europe GmbH) (67 parts by mass) and 18 parts by mass of water were used which corresponds to an addition of 50 % of acrylic emulsion with respect to 100 dry weight of all components.
  • thermosensitive recording medium 10 was produced by preparing a thermosensitive recording layer liquid [C10] in the same manner as in Example 1, except that unlike Example 1, the 50% styrene butadiene copolymer latex was replaced by a 46% styrene acrylic emulsion (Product name : Joncryl Eco 2117 available from BTC Europe GmbH) (60 parts by mass) and 25 parts by mass of water were used which corresponds to an addition of 50 % of styrene acrylic emulsion with respect to 100 dry weight of all components.
  • a thermosensitive recording layer liquid [C10] in the same manner as in Example 1, except that unlike Example 1, the 50% styrene butadiene copolymer latex was replaced by a 46% styrene acrylic emulsion (Product name : Joncryl Eco 2117 available from BTC Europe GmbH) (60 parts by mass) and 25 parts by mass of water were used which corresponds to an addition of 50 % of styrene acrylic emulsion
  • thermosensitive recording medium 11 was produced in the same manner as in Example 3, except that unlike Example 3, an intermediate layer coating liquid composed of styrene butadiene (Product name: HPD40 available from Trinseo Europe GmbH) was coated and dried over the surface of the bioriented polypropylene film such that the amount of the liquid remaining attached after the drying would be 6.0 g/m 2 , to form an undercoat layer.
  • an intermediate layer coating liquid composed of styrene butadiene (Product name: HPD40 available from Trinseo Europe GmbH) was coated and dried over the surface of the bioriented polypropylene film such that the amount of the liquid remaining attached after the drying would be 6.0 g/m 2 , to form an undercoat layer.
  • thermosensitive recording medium 12 was produced by preparing a thermosensitive recording layer liquid [C11] in the same manner as in Example 1, except that unlike Example 1, 7 parts by mass of 50% styrene butadiene copolymer latex and 78 parts by mass of water were used which corresponds to an addition of 11% of styrene-butadiene with respect to 100 dry weight of all components.
  • thermosensitive recording medium 13 was produced by preparing a thermosensitive recording layer liquid [C12] in the same manner as in Example 1, except that unlike Example 1, 14 parts by mass of 50% styrene butadiene copolymer latex and 71 parts by mass of water were used which corresponds to an addition of 20% of styrene-butadiene with respect to 100 dry weight of all components.
  • thermosensitive recording medium 14 was produced by preparing a thermosensitive recording layer liquid [C13] in the same manner as in Example 9, except that unlike Example 9, 17 parts by mass of the self-crosslinking acrylic emulsion and 68 parts by mass of water were used which corresponds to an addition of 20% of acrylic emulsion with respect to 100 dry weight of all components.
  • thermosensitive recording layer liquid [C14] which corresponding to an addition of 50% of itaconic acid modified polyvinyl alcohol with respect to 100% dry weight of all components.
  • thermosensitive recording medium 15 The [C14] and [D1] liquids were coated and dried in the same manner as in Example 1, except that unlike Example 1, the amounts of [C14] remaining attached after drying would be 4.8 g/m 2 , corresponding to the same dye coating weight as in Example 1 to form the thermosensitive recording medium 15.
  • thermosensitive recording medium 16 was produced by preparing a thermosensitive recording layer liquid [C15] in the same manner as in Comparative Example 4, except that unlike Comparative Example 4, a 10% by mass partially hydrolyzed polyvinyl alcohol aqueous solution (Product name : Poval PVA 235 available from Kuraray Europe GmbH) was used in replacement of itaconic acid modified polyvinyl alcohol.
  • thermosensitive recording medium of Examples 1 to 11 and Comparative Examples 1 to 5 “transparency” (haze degree), water resistance transparency” (haze degree), “color” (background reflectance), “preprint anchorage” and “plasticizer resistance” were evaluated.
  • thermosensitive recording medium was evaluated by measuring a haze degree with a haze meter (instrument name: Haze-gard i, available from BYK-Gardner GmbH) and evaluated according to evaluation criteria below. For a value of "A” or "B", the thermosensitive recording medium is at an acceptable level.
  • thermosensitive recording medium The water resistance remaining transparency was evaluated by firstly dipping a piece (5 ⁇ 6 cm) of the thermosensitive recording medium during 15 hours in a 150 ml glass beaker filled with tap water and drying it at 23°C 50% RH until no trace of water remains and then by measuring haze degree as described above. Evaluation was done according to criteria below. For a value of "A” or "B", the thermosensitive recording medium is at an acceptable level.
  • thermosensitive recording medium is at an acceptable level.
  • thermosensitive recording medium was heated to confirm if peeling included thermosensitive coated layer or not. Evaluation was done according to evaluation criteria below. For a value of "A" or "B", the thermosensitive recording medium is at an acceptable level.
  • thermosensitive recording medium is at an acceptable level.

Landscapes

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

Claims (9)

  1. Milieu d'enregistrement thermosensible (1) comprenant au moins :
    - une couche de support transparente (13) ;
    - une couche de coloration thermosensible (12) sur la couche de support transparente, la couche de coloration thermosensible contenant un colorant leuco, un révélateur et une résine hydrophobe ;
    - une couche protectrice (11) sur la couche de coloration thermosensible ; et
    caractérisé en ce que
    - la quantité de masse sèche de résine hydrophobe, exprimée par rapport à 100 % de masse sèche totale de la couche de coloration thermosensible (12) est d'au moins 45 % et d'au plus 58 % ; et
    - la résine hydrophobe dans la couche de coloration thermosensible (12) présente une température de transition vitreuse d'au moins -10°C et d'au plus 0°C comme mesurée selon la norme DIN 51007.
  2. Milieu d'enregistrement thermosensible (1) selon la revendication 1, dans lequel la résine hydrophobe est un homopolymère ou copolymère d'un ou plusieurs monomères choisis dans le groupe consistant en : styrène, diènes, alkylènes, acétate de vinyle, acrylonitrile, esters (méth)acryliques.
  3. Milieu d'enregistrement thermosensible (1) selon l'une quelconque de la revendication 1 ou 2, dans lequel la résine hydrophobe est une ou plusieurs choisies dans le groupe consistant en : résine de styrène-butadiène ; résine de styrène-acrylique ; acrylonitrile-butadiène ; résine d'ester d'acrylate ; résine d'éthylène-acétate de vinyle ; résine d'acrylate de méthyle-butadiène ; et résine d'uréthane.
  4. Milieu d'enregistrement thermosensible (1) selon l'une quelconque des revendications 1 à 3, dans lequel la résine hydrophobe dans la couche de coloration thermosensible (12) est une résine de styrène-butadiène.
  5. Milieu d'enregistrement thermosensible (1) selon l'une quelconque des revendications 1 à 3, dans lequel au moins une sous-couche de revêtement (14) est présente entre la couche de support transparente (13) et la couche de coloration thermosensible (12), et dans lequel la sous-couche de revêtement présente une valeur de voile d'au plus 15.
  6. Milieu d'enregistrement thermosensible (1) selon la revendication 5, dans lequel la sous-couche de revêtement (14) ne contient pas de particules creuses.
  7. Emballage de produit de consommation qui est au moins partiellement transparent et sur lequel un milieu d'enregistrement thermosensible (1) selon l'une quelconque des revendications 1 à 6 est fixé.
  8. Emballage de produit de consommation selon la revendication 7, dans lequel l'emballage de produit de consommation comprend une portion transparente et le milieu d'enregistrement thermosensible (1) selon l'une quelconque des revendications 1 à 6 est fixé à la portion transparente.
  9. Emballage de produit de consommation selon la revendication 7 ou 8, dans lequel l'emballage est destiné à une ou plusieurs denrées alimentaires périssables.
EP19151664.0A 2019-01-14 2019-01-14 Matériel d'enregistrement thermosensible Active EP3680110B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19151664.0A EP3680110B1 (fr) 2019-01-14 2019-01-14 Matériel d'enregistrement thermosensible

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19151664.0A EP3680110B1 (fr) 2019-01-14 2019-01-14 Matériel d'enregistrement thermosensible

Publications (2)

Publication Number Publication Date
EP3680110A1 EP3680110A1 (fr) 2020-07-15
EP3680110B1 true EP3680110B1 (fr) 2022-11-09

Family

ID=65023804

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19151664.0A Active EP3680110B1 (fr) 2019-01-14 2019-01-14 Matériel d'enregistrement thermosensible

Country Status (1)

Country Link
EP (1) EP3680110B1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273752B1 (fr) 1986-12-25 1992-08-19 Fuji Photo Film Co., Ltd. Méthode de fabrication d'un matériau d'enregistrement sensible à la chaleur
EP1538005B1 (fr) 2002-09-13 2008-03-26 Oji Paper Co., Ltd. Materiau de thermogravure
US7897541B2 (en) * 2004-12-13 2011-03-01 Oji Paper Co., Ltd. Thermosensitive recording medium
CN102171054B (zh) * 2008-10-03 2013-06-05 王子控股株式会社 热敏记录体及其制造方法
US8415270B2 (en) * 2009-01-27 2013-04-09 Kanzaki Specialty Papers Heat sensitive recording material comprising a protective layer

Also Published As

Publication number Publication date
EP3680110A1 (fr) 2020-07-15

Similar Documents

Publication Publication Date Title
EP1972459B1 (fr) Matériel d'enregistrement sensible à la chaleur
EP2163393B1 (fr) Matériel d'enregistrement thermosensible
AU2012336896B2 (en) Thermosensitive recording label
US8247347B2 (en) Thermosensitive recording medium
EP1844947B1 (fr) Support d'impression thermosensible
US8546300B2 (en) Thermosensitive recording material and image recording method
EP1079356B1 (fr) Etiquette adhésive pour l'enregistrement par la chaleur
EP2295257A1 (fr) Matériel d'enregistrement thermosensible et son procédé de production
JP2014226848A (ja) 感熱記録体
JP2014218062A (ja) 感熱記録体
US7098168B2 (en) Heat-sensitive recording material
JP2014151611A (ja) 感熱記録体
US11571921B2 (en) Thermosensitive recording medium
EP2722190B1 (fr) Sous-couche optimisée pour matériau d'enregistrement thermique
EP3680110B1 (fr) Matériel d'enregistrement thermosensible
EP0778157B1 (fr) Milieu d'enregistrement sensible à la chaleur
JP2015134428A (ja) 感熱記録体
WO2023153481A1 (fr) Support d'impression thermosensible
JP2004264830A (ja) インジケータ、ラベル及び温度／時間履歴検知方法
US7132387B2 (en) Heat sensitive recording material
US20210039414A1 (en) Imaging medium

Legal Events

Date Code Title Description
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: 20190114

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

AX Request for extension of the european patent

Extension state: BA ME

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20211223

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

INTG Intention to grant announced

Effective date: 20220629

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

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

Ref country code: AT

Ref legal event code: REF

Ref document number: 1530111

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602019021579

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20221109

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1530111

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221109

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: 20221109

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: 20230309

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: 20230209

Ref country code: LT

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: 20221109

Ref country code: FI

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: 20221109

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: 20221109

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: 20221109

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

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: 20221109

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: 20221109

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: 20221109

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: 20230309

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: 20221109

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: 20230210

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

Effective date: 20230522

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: 20221109

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: 20221109

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: 20221109

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: 20221109

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: 20221109

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: 20221109

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602019021579

Country of ref document: DE

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: 20221109

Ref country code: AL

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: 20221109

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

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: 20230114

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20230131

26N No opposition filed

Effective date: 20230810

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

Ref country code: LI

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

Effective date: 20230131

Ref country code: CH

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

Effective date: 20230131

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

Ref country code: SI

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: 20221109

Ref country code: BE

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

Effective date: 20230131

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: 20230114

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

Ref country code: DE

Payment date: 20240119

Year of fee payment: 6

Ref country code: GB

Payment date: 20240123

Year of fee payment: 6

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: 20221109

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

Ref country code: FR

Payment date: 20240122

Year of fee payment: 6

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: 20221109