EP2716466A1 - Wärmeaufzeichnungsmaterial mit fluoreszierendem Stilbendisulfonsäure-Bleichmittel - Google Patents

Wärmeaufzeichnungsmaterial mit fluoreszierendem Stilbendisulfonsäure-Bleichmittel Download PDF

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Publication number
EP2716466A1
EP2716466A1 EP12306219.2A EP12306219A EP2716466A1 EP 2716466 A1 EP2716466 A1 EP 2716466A1 EP 12306219 A EP12306219 A EP 12306219A EP 2716466 A1 EP2716466 A1 EP 2716466A1
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EP
European Patent Office
Prior art keywords
bis
triazin
ylamino
amino
disulfonic acid
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.)
Granted
Application number
EP12306219.2A
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English (en)
French (fr)
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EP2716466B1 (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
Original Assignee
Ricoh Industrie France SAS
Ricoh Co Ltd
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Priority to EP12306219.2A priority Critical patent/EP2716466B1/de
Publication of EP2716466A1 publication Critical patent/EP2716466A1/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
    • 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
    • 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
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • 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

Definitions

  • the present invention relates to a coating composition, which can be used to prepare a layer of 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 material layer assembly is described in EP 2 345 541 .
  • 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.
  • Rod-blade / vari-bar coating and curtain coating technologies are known as typical layer coating methods to manufacture thermal recording materials.
  • the vari-bar technology is a coating method where the applied liquid thickness is adjusted by pressing, to a greater or lesser degree, a rod-blade on the coated surface.
  • Curtain coating technology is a process where a single layer or a multilayer coating (simultaneously) is carried out. Both of these coating technologies used in thermal recording media manufacturing processes, generate strong kinematic stress on coating liquids.
  • thermosensitive layer when a thermal recording media needs higher whiteness properties, it is known that addition of fluorescent whitening agents (FWAs), also known as optical brightener agents (OBAs), into the thermosensitive layer or/and in the protective layer, improves whiteness properties.
  • FWAs fluorescent whitening agents
  • OBAs optical brightener agents
  • An object of the present invention was thus to provide a coating system using a coating composition containing an FWA (OBA), satisfying the potentially contradictory requirements of acceptable viscosity in liquid solution/dispersion, as well as whiteness level and water resistance.
  • OWA FWA
  • coating compositions comprising fluorescent whitening agents (FWAs) that satisfy the requirements of acceptable viscosity in liquid solution/dispersion, as well as whiteness level and water resistance. These coating compositions can be used to provide suitable protective layers (overlayers) of thermal recording materials.
  • FWAs fluorescent whitening agents
  • the present invention thus relates to a coating composition
  • a coating composition comprising:
  • the fluorescent whitening agent has the following structure: wherein:
  • the fluorescent whitening agent does not contain any urea.
  • the resulting liquid composition has a viscosity of 200 mPa ⁇ s or less when the applied shear velocity is 5.0 x 10 4 s -1 .
  • a liquid coating composition that can be obtained by dissolving and/or dispersing in water a solid composition containing a polyvinyl alcohol and a bis[triazinyl-amino]-stilbene disulphonic fluorescent whitening agent as set out hereinabove.
  • a further aspect of the present invention is directed to the use of such a liquid coating composition in order to form a protective layer (overlayer) that is part of a thermal recording material.
  • a further aspect of the present invention is directed to a thermal recording material comprising:
  • the protective layers contain a first protective layer containing the 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 is directed to an image forming method including recording an image on the thermal recording material as set out 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.
  • the undercoat layer(s) is/are suitably selected depending on the intended purpose without any restriction. There may be a single undercoat layer or the undercoat may be formed of two or more layers.
  • a water-soluble resin is used in the undercoat, such as polyvinyl alcohol, or 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, modified polyacrylamide, methyl vinyl ether-maleic anhydride copolymers, carboxyl-modified polyethylene, polyvinyl alcohol-acryl amide block copolymers, melamine-formaldehyde resin, urea-formaldehyde resin, alginate soda, gelatin and casein.
  • polyvinyl alcohol or
  • the amount of the polyvinyl alcohol as water-soluble resin in the undercoat, consisting of the one or more undercoat layers present, is suitably selected depending on the intended purpose without any restriction. It is preferably 20% by mass to 80% by mass. More preferably, the percentage of dry polyvinyl alcohol in the dry mass of the undercoat is at least 30% by mass, more preferably at least 40% by mass, still more preferably at least 50% by mass, most preferably more preferably at least 60% by mass.
  • the amount of the water-soluble resin in the undercoat is less than 20% by mass, 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 more than 80% by mass, 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 . When the deposition amount of the first undercoat layer is less than 0.4 g/m 2 , it is difficult to appropriate air permeance. When the deposition amount is more than 10 g/m 2 , the binding properties of the first undercoat layer may decrease.
  • 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 layer can also be used in the thermosensitive layer.
  • 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.
  • Fluorescent whitening agents Fluorescent whitening agents
  • stilbene disulfonic acid compounds are known, such as:
  • a fluorescent whitening agent having the following structure: wherein:
  • Such molecules can be obtained by the syntheses given in patent applications EP 2 431 519 and WO 2011/033064 .
  • the fluorescent whitening agent does not contain any urea.
  • urea is added as solubilizing agent and it is preferred to use a fluorescent whitening agents which does not require this. This will reduce pollution risks associated with the use of large quantities of such FWAs.
  • an FWA such that when equal amounts, as dry mass, of fluorescent whitening agent and polyvinyl alcohol are dispersed and/or dissolved in water to a dry mass solid content of 7.0 %, the resulting liquid composition has a viscosity of 200 mPa ⁇ s or less when the applied shear velocity is 5.0 x 10 4 s -1 .
  • a capillary Rheometer RH2200 from Malvern Instruments may here be used to measure viscosity.
  • the capillary used in the equipment may be chosen to have a hole diameter of 0.25 mm and a length of 8.0 mm.
  • 50 ml may be passed into the high shear stress machine with a controlled temperature of 20°C, and the dynamic viscosity measured at a shear rate of 5.0 x 10 4 s -1 .
  • a liquid composition containing equal amounts by mass of fluorescent whitening agent and polyvinyl alcohol at a total dry mass solid content of 7.0 % in water show a viscosity of 200 mPa ⁇ s or less when the applied shear velocity is 5.0 x 10 4 s -1 .
  • 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.
  • a polyvinyl alcohol is used as a water-soluble resin, in combination with a bis[triazinyl-amino]-stilbene disulphonic fluorescent whitening agent, wherein the amount of dry mass of fluorescent whitening agent is 1.5 to 150 parts by mass relative to 100 parts by mass of dry polyvinyl alcohol.
  • 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 protective 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 protective layers (overlayers) of the present invention.
  • the water-soluble resins used in the two protective layer may be different.
  • An inorganic filler may be used in protective layers (overlayers), and 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 1.5 to 150 parts by dry mass relative to 100 parts by mass of dry polyvinyl alcohol. If the key focus is to improve whiteness of the layer, an appropriate range is 1.5 to 10 parts of fluorescent whitening agent by dry mass relative to 100 parts by mass of dry polyvinyl alcohol. Above 10 parts by dry mass relative to 100 parts by mass of dry polyvinyl alcohol as water-soluble resin, some yellowing of the layer may be observed. However, this yellowing may be accepted if a maximum value of light resistance is sought after.
  • a minimum amount of 50 parts of fluorescent whitening agent by dry mass relative to 100 parts by mass of dry polyvinyl alcohol may be preferred, or more preferably 100 parts by mass with respect to 100 parts by mass of dry polyvinyl alcohol, so that for a layer with maximum light resistance, a preferable range is between 100 and 150 parts of fluorescent whitening agent by dry mass relative to 100 parts by mass of dry polyvinyl alcohol.
  • 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.
  • 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.
  • the properties of different fluorescent whitening agents were compared.
  • FWAs fluorescent whitening agents
  • OBAs optical brightening agents
  • a mixture was prepared in water with a total solid content of 7.0 %, the mixtures containing simply polyvinyl alcohol (PVA), the FWA (OBA) and water.
  • a total S.C. (solid content) of 7.0% S.C. in the solution is obtained when the coating liquid is prepared, based on a 10% aqueous PVA solution and an 18% S.C. preparation of the FWA (OBA) TP-0306.
  • PVA used was carboxylic PVA KL-318 made by KURARAY CO., LTD.
  • the FWAs were obtained from the Blankophor company.
  • a capillary Rheometer RH2200 from Malvern Instruments was used to measure viscosity.
  • the capillary used in the equipment had a hole diameter of 0.25 mm and a length of 8.0 mm.
  • 50 ml is passed into the high shear stress machine with a controlled temperature of 20°C, and the dynamic viscosity is measured at a shear rate of 5.0 x 10 4 s -1 .
  • multilayer thermal recording material assemblies were provided, and with various protective layer (overlayer) compositions having different types and amounts of optical brightener agents (OBAs), water resistance and whiteness were measured, as well as the coating weight obtained when the same machine coating conditions were used.
  • OOBs optical brightener agents
  • a base paper support wood-free paper having a basis weight of about 60 g/m 2 .
  • Matsumoto Microsphere R-500 are plastic spherical hollow particles obtained from the supplier 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 3.0 g/m 2 on dry basis, and then dried, to thereby form an undercoat layer.
  • 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
  • polyvinyl alcohol used was carboxylic PVA KL-318 made by KURARAY CO., LTD.
  • polyvinyl alcohol used was carboxylic PVA KL-318 made by KURARAY CO., LTD.
  • CW overall coating weight
  • a protective layer On top of the thermal layer, a protective layer (overlayer) was laid down.
  • a coating liquid of a protective layer a [Liquid E] was prepared. This contained PVA resin, as well as various relative amounts of different types of OBA as indicated in the table below:
  • the coating liquid of a protective layer [Liquid E] was uniformly applied and then dried, to thereby form a protective layer.
  • the prepared liquids were used with the high speed machine by keeping for each liquid mixture tested exactly the same machine coating conditions, in order to respect exactly the same sheer coating stress for each evaluated liquid mixture.
  • the top coating surface whiteness was measured according to the CIE norm, using the machine Elrepho-3000 (from Datacolor International). A whiteness value of more than 100 is considered acceptable for a normal user's requirements.
  • samples were dipped for 1 hour in water at 23°C and then put on a glass surface. While the surface is still wet, a finger is used to put sufficient and repeated pressure to make friction on the surface. Each movement back and forth is noted as 1 pass. The number of passes until the surface layer(s) start(s) to peel is recorded. It is possible to carry out 10 passes with no peeling, the evaluation test procedure is stopped. It is entirely acceptable for an ordinary user if there is no peeling after 10 passes.
  • each coated sample's dry coating weight was measured by an X-ray spectrometer, and by using calibration it was possible to determine the real dry coated amount for each sample. For reasonable productivity, it is desired to have a deviation of less than 20%. With a lower variation of this in terms of coating weight, the coating weight can be suitably adjusted using vari-bar pressure. It is considered that there is a correlation between viscosity at high shear (as measured in Example 1 and Comparative Examples 1 to 3 above) and coating weight. Samples with higher viscosity at high shear are expected to provide high, possibly an acceptable, coating weight.
  • Disulphonic acid stilbene such as Blankophor TP-0306
  • a suitable relative amount of the disulphonic acid stilbene such as Blankophor TP-0306, with respect to the water-soluble resin, is also necessary to simultaneously satisfy whiteness and water resistance requirements, as shown by Comparative Examples 7 and 8.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP12306219.2A 2012-10-05 2012-10-05 Wärmeaufzeichnungsmaterial mit fluoreszierendem stilbendisulfonsäure-bleichmittel Active EP2716466B1 (de)

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WO2014124052A1 (en) 2013-02-06 2014-08-14 Fujifilm Hunt Chemicals, Inc. Chemical coating for a laser-markable material
EP3219506A1 (de) 2016-03-17 2017-09-20 Ricoh Company, Ltd. Wärmeempfindliche aufzeichnungsmaterialien mit chelatbildnern
CN110229649A (zh) * 2019-06-16 2019-09-13 石旭艳 一种沥青基高分子自粘防水卷材及其制备方法

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WO2011033066A2 (en) * 2009-09-17 2011-03-24 Kemira Germany Gmbh Disulfo-type fluorescent whitening agents in coating applications
EP2345541A2 (de) 2010-01-15 2011-07-20 Ricoh Company, Ltd. Wärmeempfindliches Aufzeichnungsmaterial und Bildaufzeichnungsverfahren
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WO2011033066A2 (en) * 2009-09-17 2011-03-24 Kemira Germany Gmbh Disulfo-type fluorescent whitening agents in coating applications
WO2011033064A2 (en) 2009-09-17 2011-03-24 Kemira Germany Gmbh Disulfo-type fluorescent whitening agent compositions
EP2345541A2 (de) 2010-01-15 2011-07-20 Ricoh Company, Ltd. Wärmeempfindliches Aufzeichnungsmaterial und Bildaufzeichnungsverfahren
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014124052A1 (en) 2013-02-06 2014-08-14 Fujifilm Hunt Chemicals, Inc. Chemical coating for a laser-markable material
EP2954373A4 (de) * 2013-02-06 2016-11-09 Fujifilm Hunt Chemicals Us Inc Chemische beschichtung für lasermarkierbares material
EP3219506A1 (de) 2016-03-17 2017-09-20 Ricoh Company, Ltd. Wärmeempfindliche aufzeichnungsmaterialien mit chelatbildnern
EP3287292A1 (de) 2016-03-17 2018-02-28 Ricoh Company, Ltd. Wärmeempfindliche aufzeichnungsmaterialien mit chelatbildnern
US10118427B2 (en) 2016-03-17 2018-11-06 Ricoh Company, Ltd. Thermosensitive recording materials containing chelating agents
CN110229649A (zh) * 2019-06-16 2019-09-13 石旭艳 一种沥青基高分子自粘防水卷材及其制备方法
CN110229649B (zh) * 2019-06-16 2021-01-26 广东赛力克防水材料股份有限公司 一种沥青基高分子自粘防水卷材及其制备方法

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