WO2010059194A2 - Matériau d'enregistrement sensible à la chaleur - Google Patents

Matériau d'enregistrement sensible à la chaleur Download PDF

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Publication number
WO2010059194A2
WO2010059194A2 PCT/US2009/006120 US2009006120W WO2010059194A2 WO 2010059194 A2 WO2010059194 A2 WO 2010059194A2 US 2009006120 W US2009006120 W US 2009006120W WO 2010059194 A2 WO2010059194 A2 WO 2010059194A2
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WIPO (PCT)
Prior art keywords
dispersion
developer
thermally
fluoran
particle size
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PCT/US2009/006120
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English (en)
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WO2010059194A3 (fr
Inventor
Mark Robert Fisher
Joseph Peter Gusse
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Appleton Papers Inc.
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Publication of WO2010059194A2 publication Critical patent/WO2010059194A2/fr
Publication of WO2010059194A3 publication Critical patent/WO2010059194A3/fr

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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
    • B41M5/30—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
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
    • 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]

Definitions

  • This invention relates to a thermally-responsive record material. It more particularly relates to such record material in the form of sheets coated with color-forming systems comprising chromogenic material (electron-donating dye precursors) and acidic color developer material. This invention particularly concerns a thermally-responsive record material (thermal record material) capable of forming a substantially non-reversible image with improved color-forming efficiency and/or image density.
  • Thermally-responsive record material systems are well known in the art and are described in many patents, for example: U.S. Patent Nos. 3,539,375; 3,674,535; 3,746,675; 4,151,748; 4,181,771; 4,246,318 and 4,470,057 which are incorporated herein by reference.
  • basic chromogenic material and acidic color developer material are contained in a coating on a substrate which, when heated to a suitable temperature, melts or softens to permit said materials to react, thereby producing a colored mark.
  • Thermally-responsive record materials have characteristic thermal responses, desirably producing a color image upon selective thermal exposure.
  • thermal response is defined as the temperature at which a thermally-responsive record material produces a colored image of sufficient intensity (density).
  • the desired temperature of imaging varies with the type of application of the thermally-responsive product and the equipment in which the imaging is to be performed.
  • Desirable features include the ability of a thermally-responsive record material to have improved imaging characteristics such as enhanced image intensity, image density, image retention, image stability, or improved thermal response.
  • Modern thermal printers require ever increasing imaging speeds. Particularly in bar code applications stability of the image and white background or low background discoloration is a sought after feature for thermally imaging record materials particularly direct thermal record materials.
  • sensitizers have been used to reduce the activator temperature and to allow for high speed lower energy printing.
  • sensitizers allow for higher imaging speeds, in practice the lowering of the activation temperature is often accompanied by a more active background meaning the background is more susceptible to discoloration at lower environmental temperatures as well.
  • Such background discoloration can lead to impeding of barcode scanability or give rise to misreads or failure to read the barcode.
  • sensitizers tend to be volatile materials, these materials also can cause fading of the image giving rise to additional impediments to quality barcode scanning.
  • a thermally-responsive record material which is useful for bar coding comprising a support having provided thereon in substantially contiguous relationship a heat sensitive coating comprising at least one chromogenic material, said chromogenic material being selected from compounds of the formula (I)
  • R 1 comprise amino-, nitro-, hydrogen, Cl to C8 alkyl, anilino, dialkylanilino, aniline substituted with halogen, acetamido, or halogen; wherein R 2 comprises hydrogen or Cl to C8 alkyl; wherein R 3 and R 4 each independently comprise alkaryl, cycloalkyl, or Cl to C8 alkyl; and at least one developer of the formula (II)
  • chromogenic material and developer are of an average particle size of less than 5 x 10 "7 meters, wherein the composition is substantially free of sensitizer or modifier.
  • the thermally-responsive record material can include in addition a topcoat selected from materials such as polyvinyl alcohol, carboxylated polyvinylalcohol, methylcellulose, ethyl cellulose, polyacrylamide, gelatin, starch, polyvinyl pyrrolidone, and the like.
  • a backcoat is also optional.
  • the chromogenic material is a fluoran, and preferably 3-dibutylamino-6-methyl-7- anilino fluoran.
  • a sensitizer such as a material selected from 1 ,2-diphenoxyethane, acetoacet-o-toluidine, phenyl- 1-hydroxy- 2-naphthoate, and p-benzyl biphenyl is preferably omitted, such that the record material is substantially free of sensitizer or modifier.
  • the thermally-responsive record material color-forming composition can comprise one or more layers coated on the support, such as paper.
  • the chromogenic material or developer can be positioned in a separate layer from the compound of formula II. All such variations are within the scope of the invention contemplated herein and are considered contiguous for purposes hereof.
  • the present invention is a novel thermally-responsive record material comprising a substrate having coated thereon, in substantially contiguous relationship, a thermally-sensitive color-forming composition as a heat sensitive layer comprising a chromogenic material, and an acidic developer material whereby the melting or sublimination of the material produces a change in color reaction.
  • a thermally-responsive record material useful for bar coding comprising a support having provided thereon in substantially contiguous relationship a heat sensitive coating comprising at least one chromogenic material, said chromogenic material being selected from compounds of the formula (I)
  • R 1 comprise amino-, hydrogen, alkyl having less than nine carbons, anilino, anilino substituted with halogen, acetamido, or halogen; wherein R 2 comprises hydrogen or Cl to C8 alkyl; wherein R 3 and R 4 each independently comprise hydrogen, dialkylaminoaryl, alkaryl, cycloalkyl, or Cl to C8 alkyl
  • chromogenic material and developer are of an average particle size of less than 5 x 10 "7 meters (0.5 ⁇ m), wherein the composition is substantially free of sensitizer or modifier.
  • sensitizers are described in U.S. Patent No. 4,531,140 incorporated herein by reference.
  • sensitizers including fatty acid amides such as stearic acid amide, methylenebis stearic acid amide, oleic acid amide, palmitic acid amide, coconut aliphatic acid amide and the like; hindered phenols such as 2,2'- methylenebis (4-methyl-6-tert-butylphenyl), 4,4'-butylidenebis (6-tert-butyl-3- methylphenol), 2,2 '-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-di-tert-butyl-3- methylphenol, 2-hydroxy-4-benzyloxy-benzophenone, l,2-di(3- methylphenoxy)ethane, 1 ,2-diphenoxyethane, 1 -phenoxy-2-(4-methylphenoxy)ethane, naphthyl benzyl ether, benzyl-4-methyl thiophenyl
  • l,2-di(3-methylphenoxy)ethane, 1,2- diphenoxyethane, l-phenoxy-2-(4-methylphenoxy)ethane are generally preferred sensitizers.
  • the usage amount of the sensitizer is adjusted within the range of not more than 4 parts by weight per one part by weight of the color developer.
  • the coating methods there may be used various known means such as air-knife coating, rod-blade coating, dipping, roll application, reverse roll, wire wound rod, bill-blade coating, short-dwell time coating, curtain coating, slot die, slide curtain, Mayer rod, knife over roll, spraying and the like.
  • the amount of the applied coating composition is not also particularly limited, but it is generally controlled within the range of 2 to 12 g/m2, preferably 3 to 10 g/m2 on a dry basis.
  • Compound II bis (4-hydroxy-3-allylphenyl) sulphone is available commercially from vendors such as Nippon Kayaku Co., Ltd. (Trademark: "TGSA”).
  • This material also can be synthesized from starting materials of 4,4'-sulfonyldiphenol or its alkali metal salt with a halogenated allyl compound in the presence of catalyst. The resultant material is heated in excess of 200°C for a rearrangement to form the final product.
  • One route to compound II is by reacting 4,4'-sulfonyldiphenol (25 parts) with allyl -p-toluene sulfonate (44 parts) in the presence of potassium carbonate (15.2 parts) in a solvent such as dimethylformamide (100 parts). Heat at 110° for 8 hours. Distill the solvent, heating and stirring at 200°C for 6 hours. Add 60 parts trichlorobenzene and cool to ambient temperature with stirring. Filter to recover precipitated bis (4-hydroxy-3-allylphenyl) sulphone.
  • the invention comprises a thermally sensitive color-forming composition
  • a thermally sensitive color-forming composition comprising electron donating dye precursor (chromogenic material) and acidic developer material compromising a combination of compounds I and II and binder material.
  • the unexpected feature of this composition is that the inclusion of the combination of compounds of the invention facilitates the color-forming reaction resulting in stable image, a more intense image or faster imaging even in the absence of sensitizer.
  • the image is resistant to fade when subjected to common environmental challenges such as lotion or oil.
  • the record material according to the invention has a non-reversible image in that under normal use conditions such as a record of a transaction, it is substantially non-reversible and stable for many months or even years.
  • the coating of the record material of the invention is basically a dewatered solid at ambient temperature and differs from reversible solvent liquid based compositions such as taught by Kito et al., in U.S. Patent Nos. 4,720,301 and 4,732,810 which erase upon exposure to elevated temperature from 20°C to 50 0 C.
  • the image herein formed is non-reversible at such temperature.
  • the color-forming composition (or system) of the record material of this invention comprises chromogenic material (electron-donating dye precursor) in its substantially colorless state, and acidic developer material comprising the combination of compounds I and II.
  • the color-forming system relies upon melting, softening, or subliming one or more of the components to achieve reactive, color-producing contact.
  • the record material includes a substrate or support material which is generally in sheet form.
  • sheets can be referred to as support members and are understood to also mean webs, ribbons, tapes, belts, films, cards and the like. Sheets denote articles having two large surface dimensions and a comparatively small thickness dimension.
  • the substrate or support material can be opaque, transparent or translucent and could, itself, be colored or not.
  • the material can be fibrous including, for example, paper and filamentous synthetic materials. It can be a film including, for example, cellophane and synthetic polymeric sheets cast, extruded, or otherwise formed. Various kinds or types of substrate material may be used.
  • the components of the color-forming system are in substantially contiguous relationship, substantially homogeneously distributed throughout the coated layer or layers of material deposited on the substrate.
  • substantially contiguous relationship is understood to mean that the color-forming components are positioned in sufficient proximity such that upon melting, softening or subliming one or more of the components a reactive color-forming contact between the components is achieved.
  • these reactive components accordingly can be in the same coated layer or layers which is preferred, or isolated or positioned in separate layers.
  • one component such as the chromogen can be positioned in the first layer, and developer positioned in a subsequent layer or layers.
  • the coating can optionally be applied to all of the substrate or spot printed on a certain portion. All such arrangements are understood herein as being “substantially contiguous” and would be readily apparent to the skilled artisan.
  • the thermal record material can optionally include a variety of precoats such as a base layer of clay, and absorptive pigments such as kaolin clays, insulators such as hollow sphere particles, pigments, particulate clays, starch, or synthetic polymeric materials. Hollow sphere particles are commercially available such as the "Ropaque” materials of Rohm and Haas.
  • the thermally-sensitive color-forming composition can be formed as a top layer on the substrate which top layer is then overcoated with a protective layer top coat or barrier layer formed from one or more water soluble or dispersible polymeric materials such as polyvinyl alcohol, carboxylated polyvinyl alcohol, methyl or ethyl cellulose, polyacrylamide, gelatin, starch or polyvinyl pyrrolidone.
  • a protective layer top coat or barrier layer formed from one or more water soluble or dispersible polymeric materials such as polyvinyl alcohol, carboxylated polyvinyl alcohol, methyl or ethyl cellulose, polyacrylamide, gelatin, starch or polyvinyl pyrrolidone.
  • the components of the heat sensitive coating are reduced to an average partial size approaching nanoparaticles.
  • the chromogenic material and the developer are comminuted to an average particle size of less than 0.5 ⁇ m, more preferable 2 ⁇ m or less.
  • a protective layer using the same or different materials can be applied as a back coat to the thermally-sensitive record material.
  • the materials indicated as useful as precoats, such as the hollow sphere particles, pigments, clays and synthetic polymeric particulate materials can also be usefully applied as the back coat.
  • a coating composition which includes a fine dispersion of the components of the color-forming system, polymeric binder material, surface active agents and other additives in an aqueous coating medium.
  • the color-forming composition can additionally contain inert pigments, such as clay, talc, aluminum hydroxide, calcined kaolin clay and calcium carbonate; synthetic pigments, such as urea-formaldehyde resin pigments; natural waxes such as Carnuba wax; synthetic waxes; lubricants such as a zinc stearate; wetting agents; defoamers, and antioxidants.
  • the color-forming system components are substantially insoluble in the dispersion vehicle (preferably water).
  • the polymeric binder material is substantially vehicle soluble although latexes are also eligible in some instances.
  • Preferred water soluble binders include polyvinyl alcohol, hydroxy ethyl-cellulose, methylcellulose, methyl-hydroxypropylcellulose, starch, modified starches, gelatin and the like.
  • Eligible latex materials include polyacrylates, sytrene-butadiene-rubber latexes, polyvinylacetates, polystyrene, and the like.
  • the polymeric binder is used to protect the coated materials from brushing and handling forces occasioned by storage and use of thermal sheets. Binder should be present in an amount to afford such protection and in an amount less than will interfere with achieving reactive contact between color-forming reactive materials.
  • Coating weights can effectively be about 3 to about 9 grams per square meter (gsm) and preferably about 5 to about 6 gsm. The practical amount of color-forming materials is controlled by economic considerations, functional parameters and desired handling characteristics of the coated sheets.
  • Fluorans according to formula I include: 3-diethylamino-6-methyl-7- anilino-fluoran (U.S. Pat. No.
  • the developer is preferably bis(4-hydroxy-3-allylphenyl)sulphone.
  • Acidic developer materials also include, the following compounds: 4,4'- isopropylidinediphenol (Bisphenol A); p-hydroxybenzaldehyde; p- hydroxybenzophenone; p-hydroxypropiophenone; 2,4-dihydroxybenzophenone; 1,1- bis(4-hydroxyphenyl)cyclohexane; salicyanilide; 4-hydroxy-2-methylacetophenone; 2-acetylbenzoic acid; m-hydroxyacetanilide; p-hydroxyacetanilide; 2,4- dihydroxyacetophenone; 4-hydroxy-4'-methylbenzophenone; 4,4'- dihydroxybenzophenone; 2,2-bis(4-hydroxyphenyl)-4-methylpentane; benzyl 4- hydroxyphenyl ketone; 2,2-bis(4-hydroxyphenyl)-5-methylhexane; ethyl-4,4-bis(4- hydroxyphenyl)-pentanoate; isopropyl-4,
  • Examples of other developer compounds include phenolic novolak resins which are the product of reaction between, for example, formaldehyde and a phenol such as an alkylphenol, e.g., p-octylphenol, or other phenols such as p- phenylphenol, and the like; and acid mineral materials including colloidal silica, kaolin, bentonite, aftapulgite, hallosyte, and the like. Some of the polymers and minerals do not melt but undergo color reaction on fusion of the chromogen.
  • phenolic novolak resins which are the product of reaction between, for example, formaldehyde and a phenol such as an alkylphenol, e.g., p-octylphenol, or other phenols such as p- phenylphenol, and the like
  • acid mineral materials including colloidal silica, kaolin, bentonite, aftapulgite, hallosyte, and the
  • a dispersion of a particular system component was prepared by deposition or recrystalization or by milling the component in an aqueous solution of the binder until a particle size of 5 x 10 ⁇ 7 (0.5 ⁇ m) meters or less was achieved.
  • An attritor or other suitable device can be used for milling.
  • the desired average particle size was 5 x 10 ⁇ 7 meters (0.5 ⁇ m) or less and preferably 0.2 ⁇ m or less in each dispersion, ⁇ m is understood as a micron.
  • the submicron, nano-like particulates and suspensions of the materials of the invention can be manufactured through several techniques.
  • One technique can involve crystal precipitation, hi this technique crystals are grown dissolved in solvent. A non-solvent is added to course precipitation or crystallization.
  • Alternative techniques rely on milling or wet milling to achieve submicron particles. With these techniques the crystals are intentionally fractured and comminuted to particles smaller than the crystal size of initial formation, which varies from material to material. [0044] As sizes decrease, various effects not seen with larger particulates are expressed, most notability intense image density in the surprising absence of sensitizer or modifier.
  • Particulates in the necessary sizes to express these effects can be produced by aerosol methods, or chemical mechanical grinding, (meaning reducing the physical size of). This may entail a ball mill, rod mill, SAG mill, autogenous mill, pebble mill or other means of grinding or comminuting to submicron sizes. In some embodiments the material may be subjected to one or more heating steps during grinding. It is contemplated that grinding or comminuting can be conducted under ambient conditions, under an inert gas, or at elevated temperature or even in the presence of a liquid chemical agent to facilitate small particle formation.
  • the optional liquid medium can include a solvent, surfactant, or lubricant.
  • Formation of nano type or nano-like particles can involve physical and chemical methods.
  • Physical methods include, for example, electrospray, ultrasound, spray drying, superior fluid, solvent/anti-solvent crystallization and cryogenic technology.
  • Electrospraying is disclosed in U.S. Patent No. 3,208,951 ; ultrasound techniques are disclosed in U.S. Patent No. 5,389,379 and supercritical carbon dioxide methods are disclosed in U.S. Patent No. 5,639,441, U.S. Patent No. 6,095,134 and U.S. Patent No. 6,630,121; spray drying using compressed air is disclosed in U.S. Patent No. 6,582,285 and U.S. Patent No. 6,431,478.
  • the thermally-responsive sheets were made by making a coating dispersion.
  • the dispersion was applied to a support with a wire wound rod and dried.
  • the sheets may be calendered to improve smoothness.
  • Nontopcoated sheets with heat-sensitive emulsion can be made and exposed to oil and hand lotion containing ⁇ -hyroxyacid.
  • a mixture of all active components can be made in the following manner:
  • Binder 20% solution of Polyvinyl alcohol in water 25.0
  • Dispersion Al - Chromogenic Material is ODB-2 @ 0.2 ⁇ m
  • Dispersion A2 - Chromogenic Material is ODB-2 @ 0.7 ⁇ m
  • Binder 20% solution of Polyvinyl alcohol in water 18.0
  • Dispersion Bl - Acidic Material is TGSH @ 0.2 ⁇ m
  • Dispersion B2 - Acidic Material is TGSA @ 0.7 ⁇ m
  • Binder 20% solution of Polyvinyl alcohol in water 21.0
  • Dispersion B (Acidic) 40.0
  • Binder 10% solution of polyvinylalcohol in water 25.0
  • Dispersion Al OLB-2 @ 0.2 ⁇ m
  • Dispersion Bl TGSH @ 0.2 ⁇ m
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 TGSH @ 0.7 ⁇ m
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m)
  • Dispersion B2 (BSFD @ 0.2 ⁇ m)
  • Dispersion A2 (ODB-2 @ 0.7 ⁇ m)
  • Dispersion B2 (BSFD @ 0.7 ⁇ m)
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m)
  • Dispersion B2 (D8 @ 0.2 ⁇ m)
  • EXAMPLE 6 Coating Formulation 1 Using
  • Dispersion A2 (ODB-2 @ 0.7 ⁇ m)
  • Dispersion B2 (D8 @ 0.7 ⁇ m)
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 DP-201 @ 0.2 ⁇ m
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 DP-201 @ 0.7 ⁇ m
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 BPA @ 0.2 ⁇ m
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPA @ 0.7 ⁇ m
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m)
  • Dispersion B2 (BPS-MAE @ 0.2 ⁇ m)
  • EXAMPLE 12 Coating Formulation 1 Using
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPS-MAE @ 0.7 ⁇ m
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 BPS-BN @ 0.2 ⁇ m
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPS-BN @ 0.7 ⁇ m
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 UU @ 0.2 ⁇ m
  • Dispersion A2 (ODB-2 @ 0.7 ⁇ m)
  • Dispersion B2 (UU @ 0.7 ⁇ m)
  • Dispersion B (Acidic) 40.0
  • Dispersion C (Sensitizing) 15.0
  • Binder 10% solution of polyvinylalcohol in water 25.0
  • Dispersion Al OLB-2 @ 0.2 ⁇ m
  • Dispersion Bl TGSH @ 0.2 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 TGSH @ 0.7 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 BSFD @ 0.2 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BSFD @ 0.7 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m) Dispersion B2 (D8 @ 0.2 ⁇ m) Dispersion Cl (DPE) COMPARATIVE EXAMPLE 6 Coating Formulation 1 Using
  • Dispersion A2 (ODB-2 @ 0.7 ⁇ m)
  • Dispersion B2 (D8 @ 0.7 ⁇ m)
  • Dispersion Cl (DPE)
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 DP-201 @ 0.2 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 DP-201 @ 0.7 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 BPA @ 0.2 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPA @ 0.7 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m) Dispersion B2 (BPS-MAE @ 0.2 ⁇ m) Dispersion Cl (DPE) COMPARATIVE EXAMPLE 12 Coating Formulation 1 Using
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPS-MAE @ 0.7 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 BPS-BN @ 0.2 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPS-BN @ 0.7 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 UU @ 0.2 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 UU @ 0.7 ⁇ m
  • Dispersion Cl DPE
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m) Dispersion B2 (BSFD @ 0.2 ⁇ m) Dispersion Cl (BON) COMPARATIVE EXAMPLE 18 Coating Formulation 1 Using
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BSFD @ 0.7 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 D8 @ 0.2 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 D8 @ 0.7 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 DP-201 @ 0.2 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 DP-201 @ 0.7 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m) Dispersion B2 (BPA @ 0.2 ⁇ m) Dispersion Cl (BON) COMPARATIVE EXAMPLE 24 Coating Formulation 1 Using
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPA @ 0.7 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 BPS-MAE @ 0.2 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPS-MAE @ 0.7 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.2 ⁇ m
  • Dispersion B2 BPS-BN @ 0.2 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 BPS-BN @ 0.7 ⁇ m
  • Dispersion Cl BON
  • Dispersion A2 (ODB-2 @ 0.2 ⁇ m) Dispersion B2 (UU @ 0.2 ⁇ m) Dispersion Cl (BON) COMPARATIVE EXAMPLE 30 Coating Formulation 1 Using
  • Dispersion A2 OLB-2 @ 0.7 ⁇ m
  • Dispersion B2 UU @ 0.7 ⁇ m
  • Dispersion Cl BON
  • the examples were coated @ 3.0 gm/m 2 .
  • a topcoat was applied @ 3.5 gm/m 2 .
  • the examples were imaged using a barcode and solid block pattern at std speed( 6 ips) and high speed (12ips) on the default heat setting on the ZEBRA 140-401 printer. Barcode quality was tested using a TRUCHECK verifier @ 650nm. The solid block optical density was measured using a GRETAG densitometer. The results are in the following chart.
  • PCS is also read from the TRUCHECK verifier instrument.
  • the verifier is calibrated to ANSI (American National Standards Institute) Bar Code Print Quality Guideline, X3.182 published 1990.
  • the ANSI guideline defines eight categories of print quality that are measured.
  • the output of the ANSI method is a grade for the bar code A, B, C, D or F based on measurements in each category. Bar codes rated C or better should scan with most properly maintained scanners on the first pass.
  • the ANSI bar code print quality grading method is a measure of the relationship between the printed symbol and the ability of a bar code scanner to interpret the symbol.
  • example 1 illustrates the invention. Note that the
  • Example 1 is the system according to the invention. Comparative example 1 adds sensitizer. Note ANSI performance substantially degrades for all combinations with the exception of Example 1. Comparative example 17 adds a different sensitizer. Similarly, example 2 illustrates different imaging chemistry commonly used. Comparative example 2 adds sensitizer. Comparative example 18 substitutes a different sensitizer for further comparison purposes. Example 1 illustrates the invention. The balance of the examples illustrate alternative chemistries without sensitizer and with sensitizer. [0054] All documents cited in the specification herein are, in relevant part, incorporated herein by reference for all jurisdictions in which such incorporation is permitted.

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

Abstract

La présente invention concerne un matériau d'enregistrement sensible à la chaleur utile pour la codification à barres qui comprend un support recouvert de façon sensiblement contiguë par un revêtement sensible à la chaleur comprenant au moins un matériau chromogène, ledit matériau chromogène étant choisi parmi les fluoranes, et au moins un révélateur de formule (II), le matériau chromogène et le révélateur ayant une granulométrie moyenne inférieure ou égale à 0,7 µm, la composition étant essentiellement exempte de sensibilisateur et de modificateur. Le matériau d'enregistrement de l'invention reproduit de façon remarquable et très rapidement des images stables et intenses avec peu ou pas de décoloration de fond.
PCT/US2009/006120 2008-11-21 2009-11-16 Matériau d'enregistrement sensible à la chaleur WO2010059194A2 (fr)

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US61/199,899 2008-11-21

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DE102018101109A1 (de) 2018-01-18 2019-07-18 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial umfassend eine Mehrzahl von Submikrometerpartikeln mit monomodaler Partikelgrößenverteilung

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WO2010059194A3 (fr) 2010-08-19

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