EP2722190B1 - Optimierte Grundierung für Wärmeaufzeichnungsmaterial - Google Patents

Optimierte Grundierung für Wärmeaufzeichnungsmaterial Download PDF

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Publication number
EP2722190B1
EP2722190B1 EP12306220.0A EP12306220A EP2722190B1 EP 2722190 B1 EP2722190 B1 EP 2722190B1 EP 12306220 A EP12306220 A EP 12306220A EP 2722190 B1 EP2722190 B1 EP 2722190B1
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EP
European Patent Office
Prior art keywords
bis
triazin
ylamino
layer
disulfonic acid
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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.)
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EP12306220.0A
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English (en)
French (fr)
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EP2722190A1 (de
Inventor
Erkan Kocak
Yoshiaki Matsunaga
Florian Huffschmidt
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 Industrie France SAS
Ricoh Co Ltd
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Ricoh Industrie France SAS
Ricoh Co Ltd
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Priority to EP12306220.0A priority Critical patent/EP2722190B1/de
Publication of EP2722190A1 publication Critical patent/EP2722190A1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • 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
    • 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

Definitions

  • the present invention relates to a thermal (thermosensitive) recording material and an image forming method using the same.
  • Thermosensitive recording materials are known which use a colorant system wherein a dye, such as a leuco dye, in one layer of the material 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
  • thermosensitive recording material layer assembly In a typical thermosensitive recording material layer assembly, the following layers are present, constructed in the following order:
  • Thermosensitive recording materials are in common daily use, for example, in the transport industry for train, aeroplane and city underground railway tickets. They are also used in other ticketing applications such as parking, museum, cinema and concert tickets, as well as for displaying information on industrially prepared perishable foods, and also for facsimile machines.
  • thermosensitive recording materials A number of properties are sought after for such thermosensitive recording materials. For example, high image resolution and uniformity is required. At the same time light resistance is important. Simultaneously achieving good performance in more than one area is often difficult.
  • thermosensitive recording material having excellent light and water resistance.
  • It is an object of the present invention is to provide a thermal (thermosensitive) recording material having both high image resolution and uniformity, as well as good light resistance.
  • undercoat whose composition has been optimized.
  • undercoat layers which, collectively or in one and the same layer, contain both a polyvinyl alcohol as water-soluble resin having a certain degree of polymerization, as well as hollow particles, has been surprisingly found to successfully allow the preparation of a thermal (thermosensitive) recording material having the required properties.
  • the present invention thus relates to a thermal recording material comprising:
  • the polyvinyl alcohol used as the water-soluble resin in the undercoat layer has a degree of the polymerisation which is at least 500 and at most 900, preferably at least 600 and at most 800.
  • the thermo-sensitive layer will contain a leuco dye and a developer.
  • the thermal recording material of the invention will show protective layer(s) that contain(s) a water-soluble resin and a fluorescent whitening agent.
  • the protective layers contain a first protective layer containing a water-soluble resin and a fluorescent whitening agent and a second protective layer containing a water-soluble resin but no fluorescent whitening agent, and wherein the first protective layer and the second protective layer are formed in this order over the thermosensitive coloring layer.
  • the present invention relates to an an image forming method including recording an image on the thermal recording material as previously defined hereinabove, using an image recording unit, which is any one of a thermal head and a laser.
  • the laser is a CO 2 laser which emits light having a wavelength of 9.3 ⁇ m to 10.6 ⁇ m.
  • the support is suitably selected depending on the intended purpose without any restriction.
  • any of supports made of woodfree paper, recycled pulp (containing 50% or more of recycled pulp), synthetic paper, polyethylene films, and laminated paper, etc. may be used.
  • undercoat layer There may be a single undercoat layer or the undercoat may be formed of two or more layers.
  • polyvinyl alcohol is used as a water-soluble resin in the undercoat.
  • polyvinyl alcohol is taken to encompass modified polyvinyl alcohols as commonly used by persons skilled in the art.
  • Polyvinyl alcohol is often prepared industrially by polymerisation of vinyl acetate followed by saponification, so that a certain percentage of (-CH 2 -CHO-CO-Me) groups are present, in addition to the main monomer residue of (-CH 2 -CHOH-).
  • the saponification range is normally from 70% to 99%, i.e. the polymer chain contains 70% to 99% of (-CH 2 -CHOH-) units.
  • modified PVAs that can be used in the present invention include sulfonic modified PVAs, diacetonic modified PVAs, and acetoacetyl modified PVAs.
  • the undercoat layer(s) contain(s) substantially only or only PVAs, including modified PVAs, as water-soluble resin.
  • PVAs including modified PVAs
  • other water-soluble polymers can be used in conjunction with the PVAs used in undercoat layers of the present invention.
  • cellulose derivatives such as methoxy
  • the degree of polymerization of the polyvinyl alcohol is between 400 and 1000, i.e. there are between 400 and 1000 monomer units in the polymer chain on average. As explained above, for a perfect PVA homopolymer, all such monomer units would be (-CH 2 -CHOH-). However, typically PVA materials sold commercially and used by persons skilled in the art contain a certain degree of residual ester groups and/or other main chain or side-chain modifications as discussed above.
  • the amount of the polyvinyl alcohol as water-soluble resin in the undercoat, consisting of the one or more undercoat layers present, is preferably at least 30% by mass, more preferably at least 40% by mass, even more preferably at least 50% by mass.
  • amount of the water-soluble resin in the undercoat is too low, it is difficult to reduce air permeance, which is believed to be correlated with reduced light resistance since oxygen participates together with light in reactions that degrade the thermal recording material.
  • it is too high in the case where an image is formed using a thermal head, sufficient coloring sensitivity may not be easily obtained.
  • the undercoat layer(s) is (are) formed by applying a water dispersion of the water-soluble resin, followed by drying. As the components added to the water dispersion and contained in the undercoat layer, hollow particles are used.
  • the hollow particles preferably have a hollow ratio of 80% or more, more preferably 90% or more, wherein the hollow ratio (in %) is the (inner diameter of a hollow particle / outer diameter of the hollow particle) x 100.
  • the hollow ratio is less than 80%, thermal insulating properties and cushioning properties are insufficient.
  • heat energy from the thermal head is emitted to the outside of the thermosensitive recording material via the support, and the adhesion properties between the thermal head and the thermosensitive recording material becomes poor, causing less effect on improving sensitivity and fineness.
  • the practically obtainable hollow particles each have a hollow ratio of 98% or less.
  • Each of the hollow particles has a shell made of a thermoplastic resin and contains therein air or other gas. They are fine hollow particles already in a foamed state, and those having a volume average particle diameter of 2 ⁇ m to 10 ⁇ m are preferably used.
  • the volume average particle diameter (outer particle diameter) is less than 2 ⁇ m, there is a production problem of difficulty in obtaining given hollow ratio.
  • the volume average particle diameter is more than 10 ⁇ m, the smoothness of the dried coated surface decreases, causing decrease in adhesion properties between the thermal head and the thermosensitive recording material, and less effect on improving sensitivity. Accordingly, the hollow particles preferably have a sharp distribution peak with little variation as well as a volume average particle diameter falling within the aforementioned range.
  • the hollow particles are particles each having a thermoplastic resin as a shell
  • the thermoplastic resin include polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic ester, polyacrylonitrile, and polybutadiene, and copolymer resins thereof.
  • the copolymer resins which contain vinylidene chloride and acrylonitrile as main constituents are particularly preferable.
  • the amount of the hollow particles after the undercoat (i.e. the undercoat layer or layers) is dried is preferably 0.2 g or more, more preferably 0.4 g to 5 g, per square meter of the support.
  • the ratio by mass of polyvinyl alcohol as water-soluble resin to the hollow particles, expressed as dry weight, ranges from 50% to 200%.
  • an inorganic filler may also be used.
  • Such an inorganic filler is suitably selected depending on the intended purpose without any restriction.
  • 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.
  • An aqueous emulsion resin may also be used in the undercoat, such as latexes of, for example, styrene-butadiene copolymers, and styrene-butadiene-acryl copolymers; and emulsions of, for example, vinyl acetate resins, vinyl acetate-acrylate copolymers, styrene-acrylate copolymers, acrylate resins, and polyurethane resins. These may be used alone or in combination.
  • the deposition amount of a first undercoat layer in the thermosensitive recording material is suitably selected depending on the intended purpose without any restriction. It is preferably 0.4 g/m 2 to 10 g/m 2 , more preferably 0.6 g/m 2 to 7 g/ m 2 .
  • the deposition amount of the first undercoat layer is less than 0.4 g/m m 2 , it is difficult to appropriate air permeance.
  • the deposition amount is more than 10 g/m m 2 , the binding properties of the first undercoat layer may decrease.
  • the undercoat of the present invention has an air permeance of 150 mL/min or less.
  • the air permeance is more than 150 mL/min, the performance of the undercoat layer required for light resistance, i.e. performance for blocking the oxygen ingression from a surface of the undercoat layer facing the support, is insufficient, and a desired light resistance cannot be attained.
  • the air permeance of the undercoat layer is more preferably 50 mL/min or less, ideally 0 mL/min.
  • the air permeance can be measured using BENDTSEN TESTER (manufactured by Messmer Instruments Ltd.) in accordance with ISO5636 (Bendtsen method).
  • thermosensitive coloring layer contains a colorant system wherein a dye, such as a leuco dye, in one layer of the material 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 colorless or light-colored 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.
  • the amount of the leuco dye contained in the thermosensitive coloring layer is preferably 5% by mass to 20% by mass, more preferably 10% by mass to 15% 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 colors.
  • 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-[alpha]-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-d
  • 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 coloring layer other materials customarily used in thermosensitive recording materials, such as a binder, a filler, a hot-meltable material, a crosslinking agent, a pigment, a surfactant, a fluorescent whitening agent and a lubricant.
  • the binder may be used if necessary in order to improve the adhesiveness and coatability of the layer.
  • the binder is suitably selected depending on the intended purpose without any restriction.
  • Specific examples of the binder resin include starches, hydroxyethyl cellulose, methyl cellulose, carboxy methyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohols, salts of diisobutylene-maleic anhydride copolymers, salts of styrene-maleic anhydride copolymers, salts of ethylene-acrylic acid copolymers, salts of styrene-acryl copolymers and salt emulsions of styrene-butadiene copolymers.
  • 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 amid
  • 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
  • thermosensitive coloring layer when N-aminopolyacryl amide serving as a crosslinking agent is added to the thermosensitive coloring layer and the protective layer, a crosslinking reaction readily occurs, and water resistance can be improved without adding another crosslinking agent that could impede color development.
  • the thermosensitive coloring layer can be formed by commonly known methods. For example, a leuco dye and a developer have been pulverized and dispersed together with a binder and other components so as to have a particle diameter of 1 ⁇ m to 3 ⁇ m by a disperser such as a ball mill, an Atriter and a sand mill. 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 disperser such as a ball mill, an Atriter and a sand mill.
  • 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 thermo
  • the thickness of the thermosensitive coloring layer varies depending on the composition of the thermosensitive coloring layer and intended use of the thermosensitive recording materials and cannot be specified flatly, but it is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 20 ⁇ m.
  • the protective layer(s) contain(s) at least a water-soluble resin and a fluorescent whitening agent, and further contains other components as necessary. By providing the protective layer, it is expected to further improve the light resistance while the background whiteness is maintained.
  • thermosensitive coloring layer There may be a single protective layer or more than one protective layer, such as two protective layers. It is preferred that a first protective layer containing the water-soluble resin and the fluorescent whitening agent, and a second protective layer containing the water-soluble resin but no fluorescent whitening agent be formed in this order over the thermosensitive coloring layer. In this case, even though the amount of the fluorescent whitening agent is increased in the entire protective layer, background whiteness can be maintained while the background is suppressed from being turned into yellow color. Moreover, it can be expected to further improve the light resistance due to the fluorescent whitening agent, as well as improving the water resistance.
  • a first protective layer may contain the fluorescent whitening agent and the water-soluble resin, and further contain a crosslinking agent.
  • the fluorescent whitening agent is suitably selected depending on the intended purpose without any restriction.
  • a stilbene compound is preferable from the standpoint of exhibiting excellent light resistance.
  • the stilbene compound is suitably selected depending on the intended purpose without any restriction.
  • Examples thereof include 4,4'-bis(2-amino-4-anilino-1, 3, 5-triazinyl-6-amino) stilbene-2, 2'-disulfonic acid, disodium 4,4'-bis(2,4-dianilino-1,3,5-triazin-6-yl-amino)stilbene-2,2'-disulfonic acid, 4,4'-bis(2-anilino-4-hydroxyethylamino-1,3,5-triazinyl-6-amino)stilbene disulfonic acid, sodium 4,4'-bis ⁇ 2-anilino-4-di(hydroxyethyl)amino-1,3,5-triazinyl-(6)-amino ⁇ stilbene-2,2'-disulfonic acid, sodium 4,4'-bis[2-(2-methylanilino)-4-bis(hydroxyethyl)amino-1,3,5-triazinyl
  • the dry mass of the fluorescent whitening agent in the first protective layer is preferably 0.5 g/m 2 to 1.5 g/m 2 , and the amount of the fluorescent whitening agent in the first protective layer is preferably 20% by mass or more relative to the total amount of the first protective layer.
  • the dry mass of the fluorescent whitening agent is less than 0.5 g/m 2 , the light resistance cannot be sufficiently obtained.
  • the dry mass is more than 1.5 g/m 2 , the degree of the light resistance is not changed, but the deposition amount of the entire protective layer is required to increase so as to prevent the background of the thermosensitive recording material from turning into yellow color, possibly causing decrease in coloring properties.
  • the amount of the fluorescent whitening agent is less than 20% by mass, it is necessary to increase the deposition amount of the first protective layer in order to obtain a predetermined amount of the fluorescent whitening agent, possibly causing decrease in the coloring properties of the thermosensitive recording material. From these standpoints, the amount is preferably 30% by mass or more.
  • the maximum amount is preferably 80% by mass or less in terms of making the thermosensitive recording material water resistance.
  • the dry mass and amount of the fluorescent whitening agent in the first protective layer are measured as follows.
  • the first protective layer is separated from the thermosensitive recording material, followed by dissolving the first protective layer in a solvent, and then component analysis is performed on the resulting solution by HPLC analysis, IR analysis, or mass spectrometry, etc.
  • the water-soluble resin of the protective layer is suitably selected depending on the intended purpose without any restriction.
  • examples thereof include polyvinyl alcohol, modified polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives, poly(meth)acrylate and alkali salts thereof, poly(meth)acrylamide and alkali salts thereof, (meth)acrylamide copolymers and alkali salts thereof, alkali salts of styrene-maleic anhydride copolymers, polyvinylpyrrolidone, polyethyleneimine, alginate soda, gelatin and casein.
  • an aqueous emulsion resin may be used as the water-soluble resin.
  • aqueous emulsion resin examples thereof include emulsions of, for example, acryl copolymers, acrylic acid copolymers, (meth)acrylate copolymers, urethane resins, epoxy resins, vinyl acetate (co)polymers, vinylidene chloride (co)polymers, vinyl chloride (co)polymers; latexes of, for example, styrene-butadiene copolymers, and styrene-butadiene-acryl copolymers.
  • polyvinyl alcohol, and diacetone-modified polyvinyl alcohol are preferable, in term of barrier properties, head matching properties, and mechanical strength.
  • 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 in the (first) protective layer is suitably selected depending on the intended purpose without any restriction.
  • 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 50 parts by mass, relative to 100 parts by mass of the binder resin.
  • a second protective layer contains the water-soluble resin but no fluorescent whitening agent, and further contains a crosslinking agent, an inorganic filler, and a lubricant, and the like.
  • the water-soluble resin is suitably selected depending on the intended purpose without any restriction.
  • the water-soluble resins used in the first protective layer may be used.
  • the water-soluble resin used in the second protective layer the same as or different from the water-soluble resin used in the first protective layer may be used.
  • a polyvinyl alcohol resin is preferably used similarly in the first protective layer.
  • the crosslinking agent is suitably selected depending on the intended purpose without any restriction.
  • the crosslinking agent used in the first protective layer may be used.
  • the crosslinking agent used in the second protective layer the same as or different from the crosslinking agent used in the first protective layer may be used.
  • the amount of the crosslinking agent in the second protective layer is suitably selected depending on the intended purpose without any restriction.
  • 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 50 parts by mass, relative to 100 parts by mass of the binder resin.
  • the inorganic filler 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 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.
  • the amount of the fluorescent whitening agent is preferably 55% by mass or less relative to the total amount of the fluorescent whitening agent contained in the first protective layer and the water-soluble resin contained in the first protective layer and the second protective layer. When the amount is more than 55% by mass, the water resistance of the thermosensitive recording material becomes poor, and peeling may occur.
  • the minimum amount of the fluorescent whitening agent is preferably 20% by mass or more in terms of the decrease in the coloring properties caused by the increase of the total amount of the protective layers.
  • the amount of the fluorescent whitening agent in the total amount of the fluorescent whitening agent contained in the first protective layer and the water-soluble resin contained in the first protective layer and the second protective layer is measured as follows.
  • the first protective layer and the second protective layer are both separated from the thermosensitive recording material, followed by dissolving each layer in a solvent, and then component analysis is performed on each resulting solution by HPLC analysis, IR analysis, or mass spectrometry, etc.
  • a method for forming the first protective layer and the second 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.
  • thermosensitive recording material may appropriately contain a back layer containing a pigment, a water-soluble resin (binder resin) and a crosslinking agent, disposed on the surface of the support opposite to the surface thereof where the undercoat layer is disposed.
  • a back layer containing a pigment, a water-soluble resin (binder resin) and a crosslinking agent, disposed on the surface of the support opposite to the surface thereof where the undercoat layer is disposed.
  • the back layer may further contain other components such as a filler, a lubricant, an antistatic agent, and the like.
  • the binder resin either of a water-dispersible resin or a water-soluble resin is 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, polyacrylate soda, polyvinyl pyrrolidone, acryl amide-acrylate copolymers, acryl amide-acrylate-methacrylic acid terpolymers, alkali salts of styrene-maleic anhydride copolymers, alkali salts of isobutylene-maleic anhydride copolymers, polyacrylamide, 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, acrylate copolymers, styrene-butadiene copolymers and styrene-butadiene-acryl copolymers; and emulsions of, for example, vinyl acetate resins, vinyl acetate-acrylate copolymers, styrene-acrylate copolymers, acrylate resins and polyurethane resins. These may be used alone or in combination.
  • crosslinking agent the same crosslinking agent as those in the second protective layer may be used.
  • 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, acrylic resins, polyethylene resins, formaldehyde resins and polymethyl methacrylate resins.
  • 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.
  • An image recording method of the present invention includes recording an image on the thermosensitive recording material 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 is suitably 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 is preferably used.
  • a satisfiable laser print image can be obtained without using a photothermal conversion agent such as a phthalocyanine pigment.
  • a base paper support wood-free paper having a basis weight of about 60 g/m 2 .
  • PVA PW n number of 600 an itaconic-modified PVA available from Kurare was used with PVA PW n number of 600.
  • the PW is the chain length I+m+n, comprising the (average) sum of monomer residues in the polymer chain, where I is the number of (-CH 2 -CHOH-) groups, m is the number of (-CH 2 -CHO-CO-Me) groups, and number of (-CH 2 -C(CO 2 Na)(CH 2 CO 2 Na)-) groups.
  • the commercial supplier of R-500 plastic spherical hollow particles was Matsumoto Yushi-Seiyaku Co., Ltd.
  • the coating liquid of the undercoat layer [Liquid A] was uniformly applied to a surface of a base paper support so as to have a deposition amount of 0.75 g/m 2 of hollow particle coating weight on a dry basis, and then dried, to thereby form an undercoat layer.
  • Example 2 and the Comparative Examples 1 and 2 use different grades of PVA with different n numbers.
  • thermosensitive coloring layer With regard to the preparation of a coating liquid of a thermosensitive coloring layer, the following compositions were prepared:
  • 2-anilino-3-methyl-6-(di-n-butylamino)fluoran 20 parts 10% itaconic-modified polyvinyl alcohol aqueous solution: 20 parts Water : 60 parts
  • the coating liquid of a protective layer [Liquid E] was uniformly applied so as to have a deposition amount of 3.0 g/m 2 on a dry basis, and then dried, to thereby form a protective layer.
  • the multilayered product was then kept at 40°C for 3 days. Then, surface treatment by calendaring was performed to produce a surface smoothness of 3000 s.
  • underlayer compositions for Examples 1 and 2 and for Comparative Examples 1 to 3 were as follows: PVA PW n number PVA dry ratio Hollow particle dry ratio Hollow particle dry CW (g/m 2 ) Total dry CW g/m 2 Example 1 600 1.00 1.00 0.75 2.4 Example 2 1000 1.00 1.00 0.75 2.4 Comp. Ex. 1 300 1.00 1.00 0.75 2.4 Comp. Ex. 2 1400 1.00 1.00 0.75 2.4 Comp. Ex. 3 1700 1.00 1.00 0.75 2.4
  • This ranking is in descending order of preference, 5 being the best performance, and a ranking of at least 4, i.e. 4 or 5, is preferred in order to meet a normal user's expectations under normal conditions.
  • a colour pigment 0.01 ratio was added. In effect, the under coat colour is white. Thus, using only the undercoat liquid, it is difficult to analyse layer uniformity. For facilitating detection, a colour pigment was thus added, malachite green solution.
  • a ranking of at least 4, i.e. 4 or 5, is preferred in order to meet a normal user's expectations under normal conditions.
  • testing was carried out using Printer 110 Xi4 of Zebra Technologies Corporation, run at a speed of 200 m/sec with energy temperature 25.
  • Air permeance (3) was measured using a Bendtsen tester (manufactured by Messmer Instruments Ltd.) in accordance with ISO5636.
  • a MarkPoint MK2 printer was used to print images using several different amounts of energy, measured in mJ of energy per mm 2 of printed area.
  • the image density was measured using Densieye (DensiEye 700 from X-rite Inc.). The energy value is calculated that is needed for an image density of 1.0, and thus the sensitivity is determined.
  • a value of 6.5 mJ/ mm 2 corresponds to an ordinary user's requirement.
  • the inventors determined from the above experiments that with a PVA/hollow particle dry ratio of more than 2.0, the sensitivity energy value exceeded the target maximum value of 6.5 mJ/ mm 2 . Consequently, a 2.0 ratio was determined as an appropriate upper limit. With respect to air permeance (permeability), in order to achieve a target value of less than 150 ml/minute, it appears that a PVA/hollow particle dry ratio of only 0.25 is not appropriate and a lower limit of 0.5 appears appropriate. To achieve both satisfactory results for image resolution and air permeability (correlated with light resistance), for a hollow particle dry weight of 1.0, a relative PVA weight of 0.5 to 2.0 was thus determined to be appropriate.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (7)

  1. Thermisches Aufzeichnungsmaterial, umfassend:
    - eine Basisschicht;
    - eine oder mehrere Grundierungsschichten, welche auf der Basisschicht niedergelegt ist/sind, wobei die Grundierungsschicht(en) ein wasserlösliches Harz und hohle Partikel enthält (enthalten);
    - eine wärmeempfindliche Färbeschicht, welche auf der obersten Grundierungsschicht auf der gegenüberliegenden Seite in Bezug auf die Basisschicht niedergelegt ist; und
    - eine oder mehrere Schutzschichten, welche auf der wärmeempfindlichen Färbeschicht auf der gegenüberliegenden Seite in Bezug auf die Grundierungsschicht(en) niedergelegt ist/sind;
    wobei das wasserlösliche Harz ein Polyvinylalkohol mit einem Polymerisationsgrad, welcher zumindest 400 und höchstens 1000 ist, ist und wobei das Massenverhältnis von wasserlöslichem Harz im getrockneten Zustand zu den hohlen Partikeln im getrockneten Zustand mindestens 50% und höchstens 200% ist.
  2. Thermisches Aufzeichnungsmaterial nach Anspruch 1, wobei der Polyvinylalkohol einen Polymerisationsgrad aufweist, welcher zumindest 500 und höchstens 900, bevorzugt zumindest 600 und höchstens 800 ist.
  3. Thermisches Aufzeichnungsmaterial nach Anspruch 1 oder 2, wobei die wärmeempfindliche Schicht einen Leukofarbstoff und einen Entwickler umfasst.
  4. Thermisches Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 3, wobei die Schutzschicht(en) ein wasserlösliches Harz und einen fluoreszierenden Weißmacher umfasst (umfassen).
  5. Thermisches Aufzeichnungsmaterial nach Anspruch 4, wobei die Schutzschichten eine erste Schutzschicht, welche ein wasserlösliches Harz und einen fluoreszierenden Weißmacher umfasst, und eine zweite Schutzschicht, welche ein wasserlösliches Harz aber keinen fluoreszierenden Weißmacher umfasst, umfassen und wobei die erste Schutzschicht und die zweite Schutzschicht in dieser Reihenfolge über der wärmeempfindlichen Färbeschicht gebildet sind.
  6. Bilderzeugungsverfahren, umfassend ein Aufzeichnen eines Bildes auf dem thermischen Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 5 unter Verwendung einer Bildaufzeichnungseinheit, welche eines aus einem Thermokopf und einem Laser ist.
  7. Bilderzeugungsverfahren nach Anspruch 6, wobei der Laser ein CO2-Laser ist, welcher Licht mit einer Wellenlänge von 9,3 µm bis 10,6 µm emittiert.
EP12306220.0A 2012-10-05 2012-10-05 Optimierte Grundierung für Wärmeaufzeichnungsmaterial Active EP2722190B1 (de)

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US9604486B2 (en) 2014-08-19 2017-03-28 Zih Corp. Sealed thermacolor tag and label structure
EP3219506B1 (de) 2016-03-17 2019-11-06 Ricoh Company, Ltd. Wärmeempfindliche aufzeichnungsmaterialien mit chelatbildnern
WO2020067045A1 (ja) * 2018-09-26 2020-04-02 王子ホールディングス株式会社 感熱記録体
WO2021075547A1 (ja) * 2019-10-17 2021-04-22 王子ホールディングス株式会社 感熱記録体及びその製造方法

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JP4184017B2 (ja) * 2002-09-24 2008-11-19 株式会社リコー 感熱記録材料
JP5310719B2 (ja) * 2008-04-02 2013-10-09 王子ホールディングス株式会社 感熱記録体及びその製造方法
US8722576B2 (en) * 2009-09-03 2014-05-13 Nippon Paper Industries Co., Ltd. Thermosensitive recording label
US8546300B2 (en) 2010-01-15 2013-10-01 Ricoh Company, Ltd. Thermosensitive recording material and image recording method

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