EP3103649B1 - Wärmeempfindliches aufzeichnungsmedium - Google Patents

Wärmeempfindliches aufzeichnungsmedium Download PDF

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Publication number
EP3103649B1
EP3103649B1 EP15766003.6A EP15766003A EP3103649B1 EP 3103649 B1 EP3103649 B1 EP 3103649B1 EP 15766003 A EP15766003 A EP 15766003A EP 3103649 B1 EP3103649 B1 EP 3103649B1
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EP
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Prior art keywords
thermosensitive recording
undercoat layer
water
recording medium
fluorane
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English (en)
French (fr)
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EP3103649A4 (de
EP3103649A1 (de
EP3103649B2 (de
Inventor
Dai Nagahara
Kotaro Ito
Yoshimi Midorikawa
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • 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
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer

Definitions

  • the present invention relates to a thermosensitive recording medium for recording image by utilizing a color formation reaction between a colorless or pale colored electron donating leuco dye (henceforth referred to as “leuco dye”) and an electron accepting color developing agent (henceforth referred to as “color developing agent”), which has an excellent heat discoloration resistance, especially an excellent heat discoloration resistance in the blank portions.
  • leuco dye colorless or pale colored electron donating leuco dye
  • color developing agent electron accepting color developing agent
  • Thermosensitive recording media are ordinarily prepared by mixing together a colorless or pale-colored leuco dye and a color developing agent, such as a phenolic compound and the like, after grinding them into fine particles, preparing a coating solution by adding a binder, a filler, a sensitivity enhancing agent, a slipping agent and other aids to the mixture and applying the coating solution onto a substrate such as paper, synthetic paper, film, plastic and the like.
  • Thermosensitive recording media are widely used as various recording media.
  • thermosensitive recording media are used extensively in recording media such as facsimile devices, computer terminal printers, automatic ticket dispensers, recorders for meters, receipts at super markets and convenience stores and the like. Furthermore the use of thermosensitive recording media is expanding, such as its use for various ticket, receipts, labels, ATM of Bank, meter reading of gas and electricity, cash vouchers, such as car racing or horseracing betting.
  • the storage stability of the image portion and the blank portion has been required in more severe conditions, for example, in a high temperature condition in a car in midsummer.
  • the color developing agent and the leuco dye and the configuration of the protective layer have been studied (see References 1-3).
  • thermosensitive recording layer which contains inorganic pigments or plastic particles (see References 4,5, etc.).
  • the color developing agent and the leuco dye and the composition of the protective layer have, conventionally, been mainly studied in order to improve the heat discoloration resistance, especially the heat discoloration resistance in the blank portions of the thermosensitive recording medium, as described above (References 1-3), while the present inventors have examined the composition of the undercoat layer in the structure having an undercoat layer between the support and the thermosensitive recording layer, in order to improve the heat discoloration resistance.
  • the objective of the present invention is to provide a thermosensitive recording medium having an excellent heat discoloration resistance, especially an excellent heat discoloration resistance in the blank portions.
  • the inventors have discovered that the heat discoloration resistance of a thermosensitive recording medium, especially the heat discoloration resistance in the blank portions, can be improved by installing an undercoat layer between the support and the thermosensitive recording layer, incorporating a precipitated calcium carbonate as a pigment in the undercoat layer, and limiting its bulk density to a specific bulk density, in which the precipitated calcium carbonate comprises spindle-shaped primary particles aggregated radially to form secondary particles with a characteristic rosette type shape.
  • the undercoat layer containing such a pigment hampers the heat transfer from the support to the thermosensitive recording layer effectively, which is considered to improve the heat discoloration resistance of the thermosensitive recording medium by reducing the heat transfer even when the thermosensitive recording medium is stored at a high temperature condition.
  • the undercoat layer containing such a pigment is considered to have a specific absorbing property for the materials contained in the undercoat layer and the adjacent thermosensitive recording layer.
  • the undercoat layer is considered to absorb the color developing material contained in the thermosensitive recording layer, especially the excess color developing agents that are not involved in the chemical reaction with the leuco dye (i.e. cannot participate in the color developing) after the color developing agent melts by being heated by a thermal head during printing.
  • the printing (recording) run-ability i.e. prevention of head debris
  • this may have an influence on the expression of binders contained in the undercoat layer.
  • thermosensitive recording medium comprising (i) a support, (ii) an undercoat layer installed on the support, comprising a pigment and a binder as main components, and (iii) a thermosensitive recording layer installed on the undercoat layer, comprising a colorless or pale colored electron donating leuco dye and an electron accepting color developing agent as main components, wherein the pigment contained in the undercoat layer is a rosette type precipitated calcium carbonate comprising spindle-shaped primary particles aggregated radially to form secondary particles, and the bulk density of the rosette type precipitated calcium carbonate is 240 g/L or less.
  • thermosensitive recording medium of the present invention comprises (i) a support, (ii) an undercoat layer installed on the support, and (iii) a thermosensitive recording layer installed on the undercoat layer.
  • the undercoat layer comprises a pigment and a binder as main components, wherein the pigment is a rosette type precipitated calcium carbonate comprising spindle-shaped primary particles aggregated radially to form secondary particles.
  • the bulk density of the precipitated calcium carbonate is 240 g/L or less, preferably 150 - 220g/L.
  • the bulk density is measured according to Japanese Industrial Standard JIS-K-5101-12-1 (a test method for pigments - Part 12: Apparent density or apparent specific volume - Section 1: standing method).
  • the rosette type precipitated calcium carbonate for use in the present invention comprises spindle-shaped primary particles aggregated radially to form secondary particles.
  • the "aggregated radially” is referred to those of each primary particle extending to longitudinal direction from the approximate center of the secondary particles.
  • the rosette type precipitated calcium carbonate for use in the present invention is available as Albacar (R) LO (Bulk density: 210g/L), a product of Specialty Minerals Inc., and TP211BM (Bulk density: 220g/L), a product of Okutama Kogyo Co., Ltd., etc.
  • the rosette type precipitated calcium carbonate may be ground before use by using a publicly known grinder such as a ball mill, attritor, sand grinder and the like.
  • the undercoat layer of the present invention may contain other pigments than the rosette type precipitated calcium carbonate of the present invention.
  • a pigment other than the rosette type precipitated calcium carbonate for example, precipitated calcium carbonate formed by secondary particles with irregular shape, precipitated calcium carbonate comprising needle-shaped primary particles aggregated radially to form secondary particles with a chestnuts in burrs type shape, precipitated calcium carbonate comprising spindle-shaped, needle-like, columnar, square-shaped, or spherical primary particles without forming secondary particles, heavy calcium carbonate, (calcined) kaolin, clay, talc, silica, aluminum oxide, zinc oxide, titanium oxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, calcium silicate and the like may be used. These pigments may be used alone or in combination.
  • the amount of the rosette type precipitated calcium carbonate is preferably 50 weight % or more, more preferably 70 weight % or more, most preferably 90 weight % or more of the total pigments contained in the undercoat layer, which contains the rosette type precipitated calcium carbonate.
  • the undercoat layer of the present invention preferably contains organic hollow particles, which further improve the heat discoloration resistance in the blank portions and the heat insulating property of the undercoat layer as well, therefore a thermosensitive recording material with an excellent color developing sensitivity can be obtained.
  • the organic hollow particle used in the present invention is a fine hollow particle, comprising a thermoplastic resin as its shell and air or other gases inside, which is actually in a foamed state.
  • thermoplastic resin examples include polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid ester, polyacrylonitrile, polybutadiene, or copolymers thereof.
  • styrene resins such as polystyrene, acrylic resins such as polyacrylic acid esters and polyacrylonitriles, copolymers thereof, a copolymer resin composed mainly of polyvinylidene chloride and polyacrylonitriles are preferable.
  • Such organic hollow particles are available as SX8782 (JSR Corporation), MH5055 and MH8103K (Nippon Zeon Co., Ltd.), Ropaque (R) HP-91 (Rohm and Haas Japan Co.) and the like.
  • the hollow ratio of the organic hollow particle is preferably from 40 to 90%, more preferably 45 to 90%. If the hollow ratio is less than 40%, the heat discoloration resistance and color developing sensitivity of the blank portion may not be sufficient, since the heat insulation is not sufficient and the thermal energy from a thermal head or the like is easily discharged to outside of the thermosensitive recording medium through the support.
  • the average particle diameter of the organic hollow particles is preferably from 0.5 to 10 ⁇ m, more preferably from 1 to 5 ⁇ m. If the average particle diameter is larger than 10 ⁇ m, a sufficient effect cannot be obtained since the smoothness of the thermosensitive recording layer surface formed on the undercoat layer is reduced and the thermal head or the like cannot closely contact the thermosensitive recording medium. And if the average particle diameter is less than 0.5 ⁇ m, the amount of the gas contained in the hollow particles is not sufficient to yield the effect.
  • the average particle diameter is represented by the median size d 50 , which can be measured by a laser diffraction type particle size distribution measuring apparatus.
  • the median size d 50 is the diameter in which the amount of one group with larger diameter than the diameter and the amount of another group with smaller diameter than the diameter are equivalent by volume.
  • the binders used in the undercoat layer include water-soluble resins and water-insoluble resins.
  • the water-soluble resin polyvinyl alcohols such as completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol and the like; cellulose ethers and derivatives thereof such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, acetyl cellulose and the like; starches such as starch, enzyme modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (for example, such as hydroxyethyl starch), cationic starch and the like; polyacrylamides such as polyacrylamide, cationic polyacrylamides, anionic polyacrylamides, amphoteric polyacrylamide
  • urethane resins such as polyester polyurethane resins, polyether polyurethane resins, polyurethane-based ionomer resin and the like; styrene-butadiene resins such as styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-butadiene-acrylic copolymer and the like; acrylic resins such as those comprising a (meth) acrylic acid and a monomer component that is copolymerizable with (meth) acrylic acid, such as (meth) acrylonitrile; polyolefin-based resins such as those comprising an olefin, such as ethylene, propylene, butylene, and a monomer component that is copolymerizable with an olefin, such as an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid, itac
  • water-soluble resin polyvinyl alcohols, cellulose ethers and their derivatives, and starches are preferable, and polyvinyl alcohols are more preferable.
  • the water-soluble resins can be used by dissolving in a solvent such as water.
  • water-insoluble resin styrene-butadiene resins, acrylic resins, polyolefin-based resins are preferable, and styrene-butadiene resins are more preferable.
  • the water-insoluble resin can be used as an emulsion or a dispersed emulsion as a paste in water or other media.
  • binders may be used in combination of two or more depending on the required quality.
  • the binder used in the undercoat layer of the present invention it is preferable to use a water-soluble resin and a water-insoluble resin at a specific ratio.
  • the weight ratio (in solid content) of water-soluble resin / water-insoluble resin is preferably 35/100 or less, more preferably from 3/100 to 30/100, further preferably from 3/100 to 20/100.
  • the weight ratio of the water-soluble resin / non-water-soluble resin is larger than 35/100, the heat discoloration resistance, printing image quality, prevention of head debris tend to be lowered (see Examples below). Further, if the amount of water-soluble resin is less than 3/100, the prevention of migration (described later) is not sufficient, then the strength of the coating layer may decrease.
  • Water-soluble resins such as polyvinyl alcohols are generally viscous and retain water. Therefore the water-soluble resins penetrate into the voids in the undercoat layer that contains the pigments of the present invention with a specific shape and a specific bulk density, and the water-soluble resins tend to remain there. Accordingly, the water-soluble resins may fill the voids in the undercoat layer, which will deteriorate the heat discoloration resistance, the print quality, and the prevention of head debris.
  • the water-insoluble resins such as styrene-butadiene resins
  • the water-insoluble resins are generally less viscous and retain less water. Therefore the water-insoluble resins may pass through the undercoat layer that contains the pigments of the present invention with a specific shape and a specific bulk density, and penetrate into the support. This problem is called as "migration".
  • various aids such as a dispersion agent, plasticizer, thickeners, surfactants, activator, pH controlling agent, de-foaming agent, water retention agent, preservative, coloring dye, UV light inhibiting agent, antioxidants, water and oil repellants and the like may be added to the undercoat layer in the range that does not adversely affect the desired effects for the problems described above.
  • the amounts of the pigment, the organic hollow particle and the binder used in the undercoat layer are determined according to the required performance and recording properties and are not particularly restricted.
  • the amount (in solid) of the pigment in the undercoat layer is ordinarily from 50 to 95 weight parts, preferably from 70 to 90 weight parts per 100 weight parts of the total solid content of the undercoat layer.
  • the amount (in solid) of the organic hollow particle in the undercoat layer is preferably from 1 to 18 weight parts, more preferably from 3 to 15 weight parts per 100 weight parts of the total solid content of the undercoat layer.
  • the color developing sensitivity will increase as the amount of the organic hollow particles increases, while the printing (recording) run-ability (i.e.
  • the amount (in solid) of the binder is preferably from 7 to 30 weight parts, more preferably from 10 to 25 weight parts per 100 weight parts of the total solid content of the undercoat layer.
  • the method for coating the undercoat layer is not limited in particular, but any well-known conventional techniques may be used to coat on a support of suitable material, such as paper, recycled paper, plastic film, synthetic paper or the like.
  • the method for coating may be appropriately selected and used among, for example, off-machine coater and on-machine coater, which is equipped with coaters such as air knife coater, rod blade coater, bent blade coater, bevel blade coater, roll coater, curtain coater and the like.
  • a blade coater such as rod blade coater, bent blade coater, bevel blade coater and the like, since a coating solution can be coated with higher concentration, then undercoat solution is unlikely to penetrate into the support, and then a uniform undercoat layer can be formed.
  • the coating amount of the undercoat layer is not limited in particular, but the typical dried coating amount of the undercoat layer is ordinarily in the range of from 1 to 15g/m 2 .
  • thermosensitive recording layer of the thermosensitive recording medium of the present invention The various materials used in the thermosensitive recording layer of the thermosensitive recording medium of the present invention are shown below. However, a binder, a cross linking agent, a pigment etc. can be used also for other coating layer(s) in the range which does not inhibit the desired effect for the problems described above.
  • thermosensitive recording material of the present invention All of the color developing agents well known in the conventional field of pressure sensitive and thermosensitive recording media may be used as the color developing agent in a thermosensitive recording material of the present invention.
  • the color developing agent is not particularly restricted, activated clay, attapulgite, colloidal silica, inorganic acidic substances such as aluminum silicate and the like, 4,4'-isopropylidene diphenol, 1,1-bis(4-hydroxyphenyl) cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4'-dihydroxy diphenyl sulfone, 2,4'-dihydroxy diphenyl sulfone, 4-hydroxy-4'-isopropxy diphenyl sulfone, 4-hydroxy-4'-n-propoxy diphenyl sulfone,
  • thiourea compounds such as N,N'-di-m-chlorophenyl thiourea and the like, p-chlorobenzoic acid, stearyl gallate, bis [zinc 4-octyloxy carbonylamino] salicylate dihydrate, 4-[2-(p-methoxyphenoxy) ethyloxy] salicylic acid, 4-[3-(p-trisulfonyl) propyloxy] salicylic acid, aromatic carboxylic acids such as 5-[p-(2-p-methoxyphenoxyethoxy) cumyl] salicylic acid and salts of these aromatic carboxylic acids and polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel and the like, and, furthermore, antipirin complexes of zinc thiocyanate and complex zinc salts and the like of terephthal aldehyde acid with other aromatic carboxylic acids, for example, may be cited as the
  • These color developing agents may be used individually and in mixtures of at least two.
  • leuco dyes well known in the conventional field of pressure sensitive and thermosensitive recording media may be used as the electron donating leuco dye in the present invention.
  • the leuco dye is not particularly restricted, triphenylmethane type compounds, fluorane type compounds, fluorene type compounds, divinyl type compounds and the like are preferred as the leuco dye.
  • specific examples of the typical colorless to pale colored basic colorless leuco dye (leuco dye precursors) are shown below.
  • these leuco dye precursors may be used individually and also in mixtures of at least two of them.
  • sensitizers may be used as the sensitizer in the thermosensitive recording medium of the present invention.
  • sensitizers aliphatic acid amides such as stearic acid amide, palmitic acid amide and the like, ethylene bis-amide, montan acid wax, polyethylene wax, 1,2-di-(3-methylphenoxy) ethane, p-benzyl biphenyl, ⁇ -benzyloxy naphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di(p-chlorobenzyl) oxalate, di(p-methylbenzyl) oxalate, dibenzyl terephthalate, benzyl p-benzyloxy benzoate, di-p-tolyl carbonate, phenyl- ⁇ -naphthyl carbonate, 1,4-diethoxynaphthalen
  • kaolin kaolin, calcined kaolin, calcium carbonate, aluminum oxide, titanium oxide, magnesium carbonate, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, silica and the like may be used. These pigments may be used in combinations depending on the required quality.
  • binder used in the present invention completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, pyrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, other modified polyvinyl alcohol; cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, acetyl cellulose and the like; styrene-maleic anhydride copolymer, styrene-butadiene copolymer; casein, gum arabic, oxidized starch, etherified starch, dialdehyde
  • polymeric substances may be used upon dissolving them in a solvent such as water, alcohol, ketones, esters, hydrocarbons and the like or upon emulsifying or dispersing into a paste in water or other media.
  • a solvent such as water, alcohol, ketones, esters, hydrocarbons and the like
  • the polymeric materials may also be used in combinations according to the qualities demanded.
  • epichlorohydrin-based resins such as polyamine-epichlorohydrin resin, polyamide-epichlorohydrin resin; polyamine/polyamide type resin such as polyamide-urea resin, polyalkylene polyamine resin, polyalkylene polyamide resin, polyamine polyurea resin, modified polyamine resin, modified polyamide resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea resin; glyoxal, methylol melamine, melamine formaldehyde resins, melamine urea resins, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride, borate sand, boric acid, alum, ammonium chloride and the like may be listed as examples.
  • fatty acid metal salts such as zinc stearate, calcium stearate, and the like; waxes; silicone resins, and the like may be cited.
  • a stabilizing agent that improves oil resistance in recorded images and the like such as 4,4'-butylidene (6-t-butyl-3-methylphenol), 2,2'-di-t-butyl-5,5'-dimethyl-4,4'-sulfonyl diphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and the like may also be added in the range that does not adversely affect the desired effects for the problems described above.
  • UV light absorption agent e.g., a benzophenone type and triazole type UV light absorption agent, dispersion agent, de-foaming agent, antioxidant, fluorescent dye and the like may also be used.
  • the types and amounts of the leuco dye, color developing agent, sensitizer and other various ingredients used in the thermosensitive recording medium of the present invention are determined according to the required performance and printability and are not particularly restricted. However, from 0.5 to 10 parts of the color developing agent, from 0.5 to 20 parts of the pigment, from 0.5 to 10 parts of the sensitizer, from 0.01 to 10 parts of the stabilizing agent and from 0.01 to 10 parts of the other ingredients are ordinarily used per 1 part of the leuco dye.
  • the appropriate amount (in solid) of the binder in the thermosensitive recording layer is from 5 to 25 weight %.
  • the leuco dye, the color developing agent and materials added when needed are finely ground into particles, several microns or smaller in size, using a grinder or a suitable emulsification device such as a ball mill, attritor, sand grinder and the like, and a coating solution is prepared by adding a binder and various additive materials depending on the objective.
  • a coating solution is prepared by adding a binder and various additive materials depending on the objective.
  • Water, alcohol and the like can be used as the solvent for the coating solution and the solid content of the coating solution is about from 20 to 40 weight %.
  • thermosensitive recording medium of the present invention has the undercoat layer installed on the support and the thermosensitive recording layer installed on the undercoat layer
  • the thermosensitive recording medium may further have other layer other than the undercoat layer and the thermosensitive recording layer appropriately.
  • thermosensitive recording medium may further have a protective layer on the thermosensitive recording layer, and a back coat layer on the surface of the support opposite to the thermosensitive recording layer.
  • the method for coating the coating layer other than the undercoat layer is not limited in particular, but any well-known conventional techniques may be used.
  • the method for coating may be appropriately selected and used among, for example, off-machine coater and on-machine coater, which is equipped with coaters such as air knife coater, rod blade coater, bent blade coater, bevel blade coater, roll coater, curtain coater.
  • the coating amount of the coating layer other than the undercoat layer is determined according to the required performance and recording suitability, but is not limited in particular.
  • the dried coating amount of the thermosensitive recording layer is ordinarily in the range of from 2 to 12g/m 2
  • the dried coating amount of the protective layer is preferably in the range of from 0.5 to 5.0 g/m 2 .
  • thermosensitive recording medium field various technologies known in the thermosensitive recording medium field may be used as needed, for example, a flattening treatment such as super calendaring and the like can be conducted after coating individual coating layers.
  • Undercoat layer coating solution was prepared by dispersing and stirring the following formulation: Rosette type precipitated calcium carbonate (Specialty Minerals Inc., Albacar (R) LO, Bulk density: 210g/L, Figure 1 ) 100.0 parts Styrene-butadiene copolymer latex (Zeon Corporation, ST5526, solid content: 48%) 40.0 parts Aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd., PVA117, solid content: 10%) 30.0 parts Water 100.0 parts
  • This undercoat layer coating solution was applied on one side of a support (i.e. groundwood free paper with a basis weight of 60g/m 2 ) by using a bent blade coater with a coating amount (in solid) of 10.0 g/m 2 , and was dried to prepare an undercoated paper.
  • a support i.e. groundwood free paper with a basis weight of 60g/m 2
  • a bent blade coater with a coating amount (in solid) of 10.0 g/m 2
  • a color developing agent dispersion (solution A) and a leuco dye dispersion (solution B) with the following formulation were separately wet ground using sand grinders until the average particle size was about 0.5 ⁇ m.
  • Color developing agent dispersion (Solution A) 4-hydroxy-4'-isopropxy diphenyl sulfone (API Corporation, NYDS) 6.0 parts Aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd., PVA117, solid content: 10%) 18.8 parts Water 11.2 parts Leuco dye dispersion (Solution B) 3-Dibutylamino-6-methyl-7-anilinofluorane (Yamamoto Chemicals Inc., ODB-2) 6.0 parts Aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd., PVA117, solid content: 10%) 4.6 parts Water 2.6 parts
  • thermosensitive recording layer coating solution 1 Color developing agent dispersion (Solution A) 36.0 parts Leuco dye dispersion (Solution B) 13.2 parts Aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd., PVA117, solid content: 10%) 25.0 parts Aluminum hydroxide (Showa Denko K.K, Higilite (R) H-32, 50% dispersion) 12.0 parts
  • thermosensitive recording layer coating solution 1 was applied on the undercoat layer of the above undercoated paper by using a rod blade coater with a coating amount (in solid) of 2.5 g/m 2 and was dried and super calendared so that the smoothness was 500-1,000 seconds to yield a thermosensitive recording medium.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the amount of the styrene-butadiene copolymer latex in the undercoat layer coating solution 1 from 40.0 parts to 45.0 parts and the amount of the aqueous solution of completely saponified polyvinyl alcohol in the undercoat layer coating solution 1 from 30.0 parts to 7.0 parts.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the amount of the styrene-butadiene copolymer latex in the undercoat layer coating solution 1 from 40.0 parts to 44.0 parts and the amount of the aqueous solution of completely saponified polyvinyl alcohol in the undercoat layer coating solution 1 from 30.0 parts to 11.0 parts.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the amount of the styrene-butadiene copolymer latex in the undercoat layer coating solution 1 from 40.0 parts to 39.0 parts and the amount of the aqueous solution of completely saponified polyvinyl alcohol in the undercoat layer coating solution 1 from 30.0 parts to 37.0 parts.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the amount of the styrene-butadiene copolymer latex in the undercoat layer coating solution 1 from 40.0 parts to 36.0 parts and the amount of the aqueous solution of completely saponified polyvinyl alcohol in the undercoat layer coating solution 1 from 30.0 parts to 50.0 parts.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the amount of the styrene-butadiene copolymer latex in the undercoat layer coating solution 1 from 40.0 parts to 35.0 parts and the amount of the aqueous solution of completely saponified polyvinyl alcohol in the undercoat layer coating solution 1 from 30.0 parts to 55.0 parts.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the amount of the styrene-butadiene copolymer latex in the undercoat layer coating solution 1 from 40.0 parts to 23.5 parts and the amount of the aqueous solution of completely saponified polyvinyl alcohol in the undercoat layer coating solution 1 from 30.0 parts to 111.0 parts.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of changing the amount of the styrene-butadiene copolymer latex in the undercoat layer coating solution 1 from 40.0 parts to 15.5 parts and the amount of the aqueous solution of completely saponified polyvinyl alcohol in the undercoat layer coating solution 1 from 30.0 parts to 148.0 parts.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the rosette type precipitated calcium carbonate (Okutama Kogyo Co., Ltd., TP221BM, Bulk density: 230g/L, Figure 2 ) in place of the rosette type precipitated calcium carbonate (Albacar (R) LO).
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the undercoat layer coating solution 2 in place of the undercoat layer coating solution 1.
  • Undercoat layer coating solution 2 Rosette type precipitated calcium carbonate (Albacar (R) LO) 100.0 parts Organic hollow particles (Rohm and Haas, HP1055, Average particle diameter (d 50 ): 1.0 ⁇ m, Hollow ratio: 50%) 20.0 parts Styrene-butadiene copolymer latex (Zeon Corporation, ST5526) 40.0 parts
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the undercoat layer coating solution 3 in place of the undercoat layer coating solution 1.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the rosette type precipitated calcium carbonate (Specialty Minerals Inc., Albacar (R) 5970, Bulk density: 250g/L) in place of the rosette type precipitated calcium carbonate (Albacar (R) LO) in the undercoat layer coating solution 1.
  • the rosette type precipitated calcium carbonate Specialty Minerals Inc., Albacar (R) 5970, Bulk density: 250g/L
  • Albacar (R) LO rosette type precipitated calcium carbonate
  • thermosensitive recording medium was prepared in the same manner described in Example 10 with the exception of using the rosette type precipitated calcium carbonate (Albacar (R) 5970) in place of the rosette type precipitated calcium carbonate (Albacar (R) LO) in the undercoat layer coating solution 2.
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the undercoat layer coating solution 4 in place of the undercoat layer coating solution 1.
  • Undercoat layer coating solution 4 Rosette type precipitated calcium carbonate (Albacar (R) 5970) 80.0 parts Calcined clay (BASF Co., Ansilex (R) 93) 20.0 parts Styrene-butadiene copolymer latex (Zeon Corporation, ST5526) 40.0 parts
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the undercoat layer coating solution 5 in place of the undercoat layer coating solution 1.
  • Undercoat layer coating solution 5 Calcined clay (BASF Co., Ansilex (R) 93) 100.0 parts Styrene-butadiene copolymer latex (Zeon Corporation, ST5526) 40.0 parts Aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd., PVA117) 30.0 parts Water 100.0 parts
  • thermosensitive recording medium was prepared in the same manner described in Example 1 with the exception of using the undercoat layer coating solution 6 in place of the undercoat layer coating solution 1.
  • Undercoat layer coating solution 6 Organic hollow particles (Rohm and Haas, HP1055) 20.0 parts Styrene-butadiene copolymer latex (Zeon Corporation, ST5526) 40.0 parts Aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd., PVA117) 30.0 parts Water 100.0 parts
  • thermosensitive recording media obtained were evaluated as described below.
  • thermosensitive recording medium print tester Ohkura Engineering Co., Ltd. TH-PMD equipped with a thermal head by Kyocera Co.
  • the density of the solid pattern was measured by using Macbeth Densitometer (RD-914, with Amber filter) to evaluate the color developing sensitivity.
  • thermosensitive recording medium was treated in an environment of 80 degree C for one hour and stored in an environment of 23 degree C, 50% RH for three hours.
  • the color density of non-printed portion i.e. blank portion
  • Macbeth Densitometer RD-914, with Amber filter
  • the heat discoloration resistance in the blank portion was evaluated on the following criteria. If the evaluation is rated as Good or Fair, no problem happens in the practical use..
  • Background color value (color density of the non-printing portion after the treatment) - (color density of the non-printing portion before the treatment)
  • thermosensitive recording medium was printed a solid pattern by using a thermosensitive recording medium print tester (Ohkura Engineering Co., Ltd. TH-PMD equipped with a thermal head by Kyocera Co.) at applied energy of 0.15 mJ/dot and printing speed of 50mm/sec. Then the print image quality of the solid pattern was visually evaluated on the following criteria. If the evaluation is rated as Excellent, Good or Fair, no problem happens in the practical use..
  • a thermosensitive recording medium print tester Ohkura Engineering Co., Ltd. TH-PMD equipped with a thermal head by Kyocera Co.
  • thermosensitive recording medium was printed a solid pattern by using a print tester (Canon Inc., HT180) at applied energy of 0.20 mJ/dot and at -10 degree C. After printing 1m long, the debris on the thermal head of the printer was visually evaluated on the following criteria. If the evaluation is rated as Excellent, Good or Fair, no problem happens in the practical use..

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (7)

  1. Ein wärmeempfindliches Aufzeichnungsmedium, umfassend
    (i) einen Träger,
    (ii) eine auf dem Träger aufgebrachte Grundierungsschicht, umfassend ein Pigment und ein Bindemittel als Hauptkomponenten, und
    (iii) eine auf der Grundierungsschicht aufgebrachte wärmeempfindliche Aufzeichnungsschicht, die einen farblosen oder blass gefärbten Elektronen spendenden Leukofarbstoff und ein Elektronen-aufnehmende und Farbeentwickelnde Agens als Hauptkomponenten umfasst,
    dadurch gekennzeichnet, dass das in der Grundierungsschicht enthaltene Pigment ein ausgefälltes rosettenartiges Calciumcarbonat ist, das spindelförmige Primärteilchen umfasst, die radial zu sekundären Teilchen aggregiert sind, und dass die Schüttdichte des ausgefällten rosettenartigen Calciumcarbonats 240 g/l oder weniger ist.
  2. Thermosensitives Aufzeichnungsmedium nach Anspruch 1, wobei die Schüttdichte des ausgefällten rosettenartigen Calciumcarbonats von 150 bis 220 g/l beträgt.
  3. Thermosensitives Aufzeichnungsmedium nach Anspruch 1 oder 2, wobei das in der Grundierungsschicht enthaltene Bindemittel ein wasserlösliches Harz und ein wasserunlösliches Harz umfasst und das Gewichtsverhältnis, im Feststoffgehalt, von wasserlöslichem Harz / wasserunlöslichem Harz 35/100 oder weniger ist.
  4. Thermosensitives Aufzeichnungsmedium nach Anspruch 1 oder 2, wobei das in der Grundierungsschicht enthaltene Bindemittel ein wasserlösliches Harz und ein wasserunlösliches Harz umfasst und das Gewichtsverhältnis, im Feststoffgehalt, von wasserlöslichem Harz / wasserunlöslichem Harz von 3/100 bis 30/100 ist.
  5. Thermosensitives Aufzeichnungsmedium nach einem der Ansprüche 3 oder 4, wobei das wasserlösliche Harz Polyvinylalkohol ist.
  6. Thermosensitives Aufzeichnungsmedium nach einem der Ansprüche 3 bis 5, wobei das wasserunlösliche Harz Styrol-Butadien-Harz ist.
  7. Thermosensitives Aufzeichnungsmedium nach einem der Ansprüche 1 bis 6, wobei die Menge des ausgefällten rosettenartigen Calciumcarbonats 70 Gew.-% oder mehr der gesamten in der Grundierungsschicht enthaltenen Pigmente beträgt.
EP15766003.6A 2014-03-17 2015-03-06 Wärmeempfindliches aufzeichnungsmedium Active EP3103649B2 (de)

Applications Claiming Priority (2)

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JP2014052924 2014-03-17
PCT/JP2015/056651 WO2015141497A1 (ja) 2014-03-17 2015-03-06 感熱記録体

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JP6447246B2 (ja) * 2015-03-04 2019-01-09 日本製紙株式会社 感圧複写紙
JP2017056727A (ja) * 2015-09-16 2017-03-23 日本製紙株式会社 感熱記録体
US11376879B2 (en) * 2019-11-22 2022-07-05 Appvion, Llc Water-dispersible direct thermal or inkjet printable media
CN114472115A (zh) * 2020-11-11 2022-05-13 湖南鼎一致远科技发展有限公司 无墨打印金属广告板
US12115803B2 (en) 2020-12-10 2024-10-15 Appvion, Llc Fade-resistant water-dispersible phenol-free direct thermal media
US12151498B2 (en) 2020-12-10 2024-11-26 Appvion, Llc Multi-purpose phenol-free direct thermal recording media
JP2025528105A (ja) 2022-08-10 2025-08-26 アプヴィオン エルエルシー 耐油性のためのジアリール尿素の組合せを用いた直接感熱記録媒体

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JPH05162446A (ja) 1991-12-11 1993-06-29 Oji Paper Co Ltd 感熱記録紙
US5364610A (en) 1993-06-15 1994-11-15 P. H. Glatfelter Company Process for preparation of high opacity precipitated calcium carbonate by reacting sodium carbonate with calcium hydroxide
WO2008006474A1 (de) 2006-07-12 2008-01-17 Papierfabrik August Koehler Ag Wärmeempfindliches aufzeichnungsmaterial
DE102008057270A1 (de) 2008-11-13 2010-05-20 Kanzan Spezialpapiere Gmbh Aufzeichnungsmaterial
EP1910281B1 (de) 2005-07-28 2013-07-03 Basf Se Stabile wässrige dispersionen von farbentwicklern
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EP2213466B1 (de) * 2007-11-19 2012-08-01 Nippon Paper Industries Co., Ltd. Tintenstrahlaufzeichnungspapier
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JPH05162446A (ja) 1991-12-11 1993-06-29 Oji Paper Co Ltd 感熱記録紙
US5364610A (en) 1993-06-15 1994-11-15 P. H. Glatfelter Company Process for preparation of high opacity precipitated calcium carbonate by reacting sodium carbonate with calcium hydroxide
EP1910281B1 (de) 2005-07-28 2013-07-03 Basf Se Stabile wässrige dispersionen von farbentwicklern
WO2008006474A1 (de) 2006-07-12 2008-01-17 Papierfabrik August Koehler Ag Wärmeempfindliches aufzeichnungsmaterial
DE102008057270A1 (de) 2008-11-13 2010-05-20 Kanzan Spezialpapiere Gmbh Aufzeichnungsmaterial
WO2014121788A1 (de) 2013-02-08 2014-08-14 Papierfabrik August Koehler Se Wärmeempfindliches aufzeichnungsmaterial

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Also Published As

Publication number Publication date
CN106103122B (zh) 2019-06-14
WO2015141497A1 (ja) 2015-09-24
JPWO2015141497A1 (ja) 2017-04-06
EP3103649A4 (de) 2017-02-22
JP5823086B1 (ja) 2015-11-25
EP3103649A1 (de) 2016-12-14
EP3103649B2 (de) 2025-01-22
CN106103122A (zh) 2016-11-09

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