WO2013109268A1 - Composition de revêtement chimique pour former une matière pouvant être marquée par laser et matière pouvant être marquée par laser - Google Patents

Composition de revêtement chimique pour former une matière pouvant être marquée par laser et matière pouvant être marquée par laser Download PDF

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Publication number
WO2013109268A1
WO2013109268A1 PCT/US2012/021752 US2012021752W WO2013109268A1 WO 2013109268 A1 WO2013109268 A1 WO 2013109268A1 US 2012021752 W US2012021752 W US 2012021752W WO 2013109268 A1 WO2013109268 A1 WO 2013109268A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
recording
laser
chemical coating
recording layer
Prior art date
Application number
PCT/US2012/021752
Other languages
English (en)
Inventor
Yuka OGO
Richard Whitehouse
Kazuaki Yoshida
Original Assignee
Fujifilm Hunt Chemicals U.S.A., Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Hunt Chemicals U.S.A., Inc. filed Critical Fujifilm Hunt Chemicals U.S.A., Inc.
Priority to PCT/US2012/021752 priority Critical patent/WO2013109268A1/fr
Publication of WO2013109268A1 publication Critical patent/WO2013109268A1/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
    • B41M5/337—Additives; Binders
    • B41M5/3372—Macromolecular compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/002—Photosensitive materials containing microcapsules
    • 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
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a chemical coating composition, an image recording material using the chemical coating composition, and an image recording method using the chemical coating composition. More particularly, the present invention relates to a chemical coating composition for recording an image on a recording material that forms a color by irradiation with a laser beam.
  • beverage containers On beverage cans, beverage containers, food containers, medicine containers, cosmetics containers, packaging materials, electronic components, electric parts, automotive components and the like (hereinafter referred to as "containers"), a manufacturing lot number, manufacturing date, model, name of manufacturer, and the like are, for example, marked by characters, symbols, marks, patterns, barcodes or the like (hereinafter referred to as "marks").
  • a method of directly printing a colored printing ink on containers by pad printing, screen printing, an ink jet method or the like, and a method of attaching labels having marks printed thereon are used.
  • the direct printing method printing may be difficult depending on the shape of the container to be printed on, and in the method of attaching printed labels, a wide variety of labels must be prepared for respective types of marks.
  • a laser marking layer (hereinafter referred to as "layer"), comprising a color former and a developer, is provided on containers, and a laser beam is irradiated on the layer to cause a chemical reaction to form a color (see, for example, Japanese Patent Application Laid-Open (JP-A) No. 2007-152686).
  • JP-A Japanese Patent Application Laid-Open
  • a mark with sufficient optical density may not be obtained or when a chemical coating composition (hereinafter referred to as "coating composition") including a color former and a developer is stored for several months, a coating composition may not be usable and effective due to increased solution viscosity. As a result, the current laser marking methods are not acceptable for commercial use.
  • coating composition a chemical coating composition including a color former and a developer
  • Embodiments of the present invention have been made in view of the above circumstances and provides a coating, a recording material, and a recording method that overcome the disadvantages of the prior art.
  • a chemical coating composition for a recording material that forms a color image by irradiation with a laser beam, comprising at least one microcapsule encapsulating a basic dye precursor, and at least one plastic dispersion.
  • Another aspect is a recording material using the coating composition, as well as a recording method using the coating composition dried onto a recording material which is then subsequently irradiated with a laser.
  • a coating composition for a recording material to record an image by irradiation with a laser beam comprising at least one microcapsules
  • Embodiments of the present invention are based on the following new findings.
  • One or more plastic dispersions incorporated into a chemical coating composition can significantly increase optical density of a mark formed by laser irradiation.
  • the support of a corrugated fiberboard for outer case can increase lay- down of the coating composition and increase the optical density of the mark formed by the laser irradiation.
  • Addition of at least one plastic dispersion to the coating composition can significantly reduce formation of unfavorable pressure marks by scratching without the use of a protective layer coated onto the recording layer.
  • At least one polyvinyl alcohol compound which contains at least one carboxylic substituent group when incorporated into the chemical coating composition, can stabilize the viscosity of the chemical coating composition during long term storage.
  • the chemical coating composition used to make the recording material that is used in the recording method of the present invention contains at least one color-forming component and at least one plastic dispersion and may further contain other components as needed.
  • the plastic dispersion of the present invention is preferably a plastic wax dispersion, more preferably a polyethylene wax dispersion. Dispersion of a combination of polyethylene wax and polytetrafluoroethylene is the most preferred.
  • the quantity of the plastic dispersion in the chemical coating composition is from about 0.1% w/w to about 20% w/w, preferably from about 1% w/w to about 10% w/w.
  • the color-forming component may be a component that has good transparency before laser exposure but quickly forms an image by laser exposure.
  • the color-forming component include a two-component type color- forming components, which contains a substantially colorless color-forming component A and a substantially colorless color-forming component B that reacts with the color-forming component A to form an image.
  • a combination of a basic dye precursor and an electron-accepting compound is used, wherein the basic dye precursor is encapsulated in
  • the basic dye precursor which is used in the invention may be any basic dye precursor that is substantially colorless, but not limited thereto.
  • the precursor may have a nature of donating an electron to form a color, or accepting a proton from an acid to form a color, and is preferably a colorless compound having a partial skeleton of lactone, lactam, sultone, spiropyran, ester, amide or the like, the skeleton being opened or cleaved when the compound contacts with an electron- accepting compound.
  • Examples of the basic dye precursor include
  • triphenylmethanephthalide compounds triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leuco auramine compounds, rohdamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, fluorene compounds, pyridine compounds and pyrazine compounds.
  • triphenylmethanephthalide compounds include compounds described in U.S. Reissued Pat. No. 23,024, and U.S. Pat. Nos. 3,491,111, 3,491,112, 3,491,116, and 3,509,174, the disclosures of which are incorporated by reference herein.
  • fluorane compounds include compounds described in U.S. Pat. Nos. 3,624,107, 3,627,787, 3,641,011, 3,462,828, 3,681,390, 3,920,510, and 3,959,571, the disclosures of which are incorporated by reference herein.
  • spiropyran compounds include compounds described in U.S. Pat. No. 3,971,808, the disclosures of which are incorporated by reference herein.
  • pyridine compounds and the pyrazine compounds include compounds described in U.S. Pat. Nos. 3,775,424, 3,853,869 and 4,246,318, the disclosures of which are incorporated by reference herein.
  • fluorene compounds include compounds described in JP-A No 63-094878, the disclosure of which is incorporated by reference herein.
  • a particularly preferable example is 2- arylamino-3-[H, halogen, alkyl or alkoxy-6-substituted aminofluorane], which forms a black color.
  • More specific examples thereof include bisphenol compounds such as
  • 2,2-bis(4'-hydroxyphenyl)propane [common name: bisphenol A], 2,2-bis(4'- hydroxyphenyl)pentane, 2,2-bis(4'-hydroxy-3',5'-dichlorophenyl)propane, l,l-bis(4'- hydroxyphenyl)cyclohexane, 2,2-bis(4'-hydroxyphenyl)hexane, 1,1 -bis (4'- hydroxyphenyl)propane, 1 , 1 -bis(4'-hydroxyphenyl)butane, 1 , 1 -bis(4'- hydroxyphenyl)pentane, 1 , 1 -bis (4'-hydroxyphenyl)hexane, 1 , 1 -bis(4'- hydroxyphenyl)heptane, 1 , 1 -bis (4'-hydroxyphenyl)octane, 1 , 1 -bis(4'- hydroxyphenyl)-2-methyl-pent
  • salicylic acid derivatives such as 3,5-di-[alpha]- methylbenzylsalicylic acid, 3,5-di-tert-butylsalicylic acid, -3 [alpha] -[alpha] - dimethylbenzylsalicylic acid, and 4-([beta]-p-methoxyphenoxyethoxy)salicylic acid;
  • polyvalent metal salts of the salicylic acid derivatives preferably, zinc and aluminum salts of the salicylic acid derivatives
  • oxybenzoic acid esters such as benzyl p-hydroxybenzoate, 2- ethylhexyl p-hydroxybenzoate, and [beta]-resorcylic acid-(2-phenoxyethyl)ester; and
  • phenols such as p-phenylphenol, 3,5-diphenylphenol, cumylphenol,
  • the bisphenol compounds are particularly preferable since they give a satisfactory color forming property.
  • a single electron-accepting compound may be used or multiple electron-accepting compounds may be simultaneously used. (Microcapsules)
  • the interfacial polymerization method, the internal polymerization method, and the external polymerization method are known as methods for producing microcapsules. Any one thereof may be employed.
  • the coating composition of this invention contains microcapsules encapsulating a basic dye precursor. It is particularly preferable to employ the interfacial polymerization method which comprises the step of mixing an oil phase prepared by dissolving or dispersing the basic dye precursor, which will be the core of the capsules, in a hydrophobic organic solvent with a water phase comprising a dissolved water-soluble polymer, the step of emulsifying the mixture by means of a homogenizer or the like, and the step of heating the emulsion to cause a polymer forming reaction at the interface between the oil droplets and water, thereby forming microcapsule walls made of a polymer material.
  • the interfacial polymerization method which comprises the step of mixing an oil phase prepared by dissolving or dispersing the basic dye precursor, which will be the core of the capsules, in a hydrophobic organic solvent with a water phase comprising a dissolved water-soluble polymer, the step of emulsifying the mixture by means of a homogenizer or the like,
  • the wall materials for making the polymer material are added to the inside and/or the outside of the oil droplets.
  • the polymer material include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea- formaldehyde resin, melamine resin, polystyrene, and styrene-methacrylate copolymer, styrene-acrylate copolymer.
  • polyurethane, polyurea, polyamide, polyester, and polycarbonate are preferable.
  • Polyurethane and polyurea are more preferable.
  • the microcapsule walls can easily be formed by allowing a polyisocyanate such as a diisocyanate, triisocyanate, tetraisocyanate or polyisocyanate prepolymer to react with a polyamine such as a diamine, triamine or tetraamine, a prepolymer having 2 or more amino groups, piperazine or a derivative thereof, or a polyol in the above- mentioned water phase by the interfacial polymerization method.
  • a polyisocyanate such as a diisocyanate, triisocyanate, tetraisocyanate or polyisocyanate prepolymer to react with a polyamine such as a diamine, triamine or tetraamine, a prepolymer having 2 or more amino groups, piperazine or a derivative thereof, or a polyol in the above- mentioned water phase by the interfacial polymerization method.
  • composite walls composed of polyurea and polyamide, or composite walls composed of polyurethane and polyamide can be prepared by incorporating polyisocyanate and a second material which reacts with the polyisocyanate to form capsule walls (for example, acid chloride, polyamine or polyol) into an aqueous solution (water phase) of a water-soluble polymer or an oil medium (oil phase) to be encapsulated, emulsifying the mixture, and heating the resultant emulsion.
  • capsule walls for example, acid chloride, polyamine or polyol
  • the capsule wall material preferably contains at least one isophorone diisocyanate compound.
  • the capsule wall is made hydrophobic, water adsorption at high humidity is decreased, and water desorption at low humidity is decreased, whereby the ambient humidity dependence of the thermal response of the microcapsule is decreased. As a result, the ambient humidity dependence of the sensitivity of the recording material is decreased.
  • the capsule wall material preferably contains at least one isophorone diisocyanate compound.
  • the wall material preferably contains an isophorone diisocyanate compound as a main component (the content in the wall material being 50% by mass or more), and the content of a material derived from isophorone diisocyanate is preferably 50% by mass or more.
  • the isophorone diisocyanate compound may be either monomer or multimer of isophorone diisocyanate, and trimer is particularly preferred.
  • a mixture of dimer and trimer of isophorone diisocyanate is also preferably used as a wall material, and the rate of trimer is preferably 20% by mass or more and more preferably 50% by mass or more in the total weight of the capsule wall material.
  • polyisocyanate compounds In a range not impeding the effect of decreasing the ambient humidity dependence of the sensitivity of the recording material, in addition to the isophorone diisocyanate compound, other polyisocyanate compounds may be used.
  • Other polyisocyanate compounds are preferably compounds having three or more isocyanate groups. However, a compound having three or more isocyanate group may be used in combination with a compound having two isocyanate groups, or a compound having two isocyanate groups may be used alone.
  • xylene diisocyanate and a hydrate thereof hexamethylene diisocyanate, trilene diisocyanate and a hydrate thereof
  • a dimer or trimer (biuret or isocyanurate) of a diisocyanate such as isophorone diisocyanate
  • a multifunctional adduct of a polyol such as trimethylol propane and a difunctional isocyanate such as xylene diisocyanate
  • a formalin condensate of benzene isocyanate such as xylene diisocyanate
  • the isophorone diisocyanate compound is preferably added such that the average particle diameter of the microcapsules is from 0.3 to 12 um and the thickness of the capsule walls is from 0.01 to 0.3 um.
  • the size of the dispersed particle is generally from about 0.2 to 10 um.
  • polyol and/or the polyamine which is added to the water phase and/or the oil phase as one of the components that react with a polyisocyanate to form a microcapsule wall, include propylene glycol, glycerin, trimethylolpropane, triethanloamine, sorbitol, and hexamethylenediamine.
  • a polyol is added thereto, polyurethane walls are formed.
  • a charge adjusting agent such as a metal-containing dye or nigrosin, or any other additive may be added to the microcapsule walls. These additives can be added at the time of forming the walls, or at any other time, to be incorporated in the walls of the capsules. If necessary, a monomer such as a vinyl monomer may be graft-polymerized in order to adjust the charging property of the surfaces of the capsule walls.
  • plasticizer suitable for the polymer used as the wall material.
  • the plasticizer preferably has a melting point from about 50°C to about 120°C. It is particularly preferable to select a plasticizer which has such a melting point and takes a solid form at ordinary temperature.
  • the wall material is polyurea or polyurethane
  • an organic solvent having a boiling point of from 100 to about 300°C as a hydrophobic organic solvent in which the basic dye precursor or the photolytic diazo compound is dissolved for forming cores of microcapsules.
  • esters dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, dimethylbiphenyl, diisopropylbiphenyl, diisobutylbiphenyl, 1 -methyl- 1 -dimethylphenyl-2-phenylmethane, 1 -ethyl- 1 - dimethylphenyl- 1 -phenylmethane, 1 -propyl- 1 -dimethylphenyl- 1 -phenylmethane, triallylmethane (such as tritoluylmethane and toluyldiphenylmethane), terphenyl compounds (such as terphenyl), alkyl compounds, alkylated diphenyl ether compounds (such as propyldiphenyl ether), hydrogenated terphenyl compounds (such as hexahydro terphenyl), and diphenyl
  • esters are particularly preferable from the viewpoints of the emulsification stability of the emulsion.
  • the esters include phosphate esters such as triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate and cresylphenyl phosphate; phthalic esters such as dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, octyl phthalate, and butylbenzyl phthalate; dioctyl tetrahydrophthalate; benzoic esters such as ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, and benzyl benzoate; abietic esters such as ethyl abietate, and benzyl abietate; dioctyl adipate; isode
  • the organic solvent tricresyl phosphate alone or in combination with other solvent(s) since the stability of the emulsion becomes most satisfactory.
  • the above-mentioned oils may be used in any combination thereof, or the oil(s) may be used together with an oil other than the above-mentioned oils.
  • a low boiling point solvent in which the basic dye precursor dissolves well may be used simultaneously as an auxiliary solvent.
  • the low boiling point solvent include ethyl acetate, isopropyl acetate, butyl acetate and methylene chloride.
  • a low boiling point solvent may be used as a solvent for forming microcapsules.
  • the above- mentioned low boiling point solvent as an auxiliary solvent may be suitably used.
  • the content of the basic dye precursor is preferably from 0.1 to 5.0 g/m 2 , more preferably from 1.0 to 4.0 g/m 2.
  • the content of the basic dye precursor is within the above- mentioned range, a sufficient color density can be obtained.
  • the content of the basic dye precursor compound is 5.0 g/m2 or less, a sufficient color density can be obtained and the transparency of the recording layer can be maintained.
  • the water phase may be an aqueous solution comprising a dissolved water-soluble polymer as a protective colloid.
  • the above-mentioned oil phase is added to the water phase, and then the mixture is emulsified with a homogenizer or the like.
  • the water-soluble polymer acts as a dispersing medium for achieving homogeneous dispersion easily and stabilizing the emulsified solution.
  • a surfactant may be added to at least one of the oil phase and the water phase in order to achieve more homogenous and stable dispersion.
  • the surfactant a well-known surfactant for emulsification can be used.
  • the amount of the surfactant to be added is preferably from 0.1 to 5%, more preferably from 0.5 to 2% by mass of the amount of the oil phase.
  • a surfactant which does not cause precipitation or aggregation caused by a reaction with the protective colloid is appropriately selected from anionic and nonionic surfactants.
  • surfactant examples include sodium
  • alkylbenzenesulfonate sodium alkylsulfate, sodium dioctyl sulfosuccinate, polyalkylene glycol (such as polyoxyethylene nonyl phenyl ether), acetylene glycol and the like.
  • the oil phase containing the above-mentioned components and the water phase containing the protective colloid and the surfactant can be emulsified by a known ordinary means for emulsifying fine particles, such as high-speed stirring means or ultrasonic wave dispersing means.
  • a known ordinary means for emulsifying fine particles such as high-speed stirring means or ultrasonic wave dispersing means.
  • Specific examples of the means include a homogenizer, a Manton-Gaulin, an ultrasonic wave disperser, a dis solver, or a Kdmill.
  • a dispersion agent for preventing aggregation may be newly added.
  • target microcapsules can be obtained by several hours reaction.
  • the coupler compound can be solid-dispersed together with, for example, a water-soluble polymer, an organic base, and other color-forming auxiliary/auxiliaries, by means of a sand mill or the like before use.
  • a high boiling point organic solvent which is scarcely soluble or insoluble in water
  • a low boiling point solvent may be used as a dissolving auxiliary if necessary.
  • the coupler and the organic base may be separately emulsified or may be mixed with each other, dissolved into a high boiling point organic solvent and emulsified.
  • the size of the emulsified particle is preferably 1 um or less.
  • the high boiling point organic solvent used in this case can be appropriately selected from the high boiling point oils described in JP-A No. 2- 141279, the disclosure of which is incorporated by reference herein.
  • oils it is preferable to use esters from the viewpoint of the emulsification stability of the resultant emulsion.
  • esters tricresyl phosphate is particularly preferable.
  • the above oils may be used in any combination thereof, or the oil(s) may be used simultaneously with an oil other than the above oils.
  • the water-soluble polymer contained as the protective colloid can be appropriately selected from known anionic polymers, nonionic polymers and amphoteric polymers.
  • the water-soluble polymer has a solubility in water of preferably 5% or more at a temperature at which the emulsification is conducted.
  • Specific examples of the water-soluble polymer include: polyvinyl alcohol and modified products thereof, polyacrylic amide and derivatives thereof, ethylene-vinyl acetate copolymer; styrene-maleic anhydride copolymer; ethylene-maleic anhydride copolymer; isobutylene-maleic anhydride copolymer; polyvinyl pyrrolidone;
  • ethylene- acrylic acid copolymer vinyl acetate- acrylic acid copolymer
  • cellulose derivatives such as carboxymethylcellulose and methylcellulose
  • casein gelatin
  • starch derivatives gum arabic
  • sodium alginate sodium alginate
  • polyvinyl alcohol derivatives are more preferable, and polyvinyl alcohol contained carboxy substitute is particularly preferable for stabilizing viscosity of the coating composition.
  • the mixing ratio of the oil phase to the water phase is preferably from 0.02 to 0.6, more preferably from 0.1 to 0.4.
  • the mixing ratio is within the range of 0.02 to 0.6, the liquid coating composition has an appropriate viscosity, thus the production of the recording material is easier, and the stability of the liquid coating composition with time is superior.
  • the amount of the electron-accepting compound is preferably from 0.5 to 30 parts by mass, more preferably from 1.0 to 10 parts by mass based on 1 part by mass of the basic dye precursor.
  • the coating composition for forming the recording layer can be prepared, for example, by mixing the microcapsule solution and the emulsion prepared as described above.
  • the water-soluble polymer used as a protective colloid during the preparation of the microcapsule solution and the water-soluble polymer used as a protective colloid during the preparation of the emulsion function as binders in the recording layer.
  • a binder other than these protective colloids may preferably be further added during the preparation of the coating composition for forming the recording layer.
  • binder contained in the coating composition examples include polyvinyl alcohol derivatives, hydroxyethylcellulose, hydroxypropylcellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride- salicylic acid copolymer, polyacrylic acid, polyacrylic amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin.
  • polyvinyl alcohol derivatives are more preferable, and polyvinyl alcohol containing carboxy substituents is particularly preferable for stabilizing viscosity of the coating composition.
  • any water-resistance imparting agent may be added in order to provide water resistance, and/or an emulsion of a hydrophobic polymer.
  • these include styrene-butadiene rubber latex and acrylic resin emulsion, may be added.
  • the coating composition for forming the recording layer is applied to a support
  • a known application means used for water-based or organic solvent-based coating composition is used.
  • at least one chemical is selected from the following which can be included in the coating composition for the recording material that is used in the invention: methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, starch, gelatin, polyvinyl alcohol, polyacrylamide, polystyrene or copolymers thereof, polyester or copolymers thereof, polyethylene or copolymers thereof, epoxy resin, acrylate resin or copolymers thereof, methacrylate resin or copolymers thereof, polyurethane resin, polyamide resin, polyvinyl butyral resin, styrene- butadiene latex, and the like.
  • polyvinyl alcohol derivatives are more preferable, and polyvinyl alcohol contained carboxy substituents is particularly preferable for stabilizing the viscosity of the coating composition.
  • Such other components can be appropriately selected, without particular limitation, in accordance with the specific purpose of the coating.
  • examples thereof include additives known in the art, such as a thermally-meltable material, an ultraviolet absorber, and an antioxidant.
  • the amount of each of such other components to be applied is preferably from about 0.05 to 1.0 g/m 2 , more preferably from about 0.1 to 0.4 g/m 2.
  • Such components may be included in the inside and/or on the outside of the microcapsules.
  • the thermally-meltable material can be included in the recording layer in order to improve the thermal responsiveness thereof.
  • thermally-meltable material examples include am aromatic ether, a thioether, an ester, an aliphatic amide and an ureido.
  • these compounds are described in JP-A Nos. 58-57989, 58-87094, 61-58789, 62-109681, 62-132674, 63-151478, 63-235961, 2-184489 and 2-215585, the disclosures of which are incorporated by reference herein.
  • the ultraviolet ray absorber include benzophenone ultraviolet ray absorbers, benzotriazole ultraviolet ray absorbers, salicylic acid ultraviolet ray absorbers, cyanoacrylate ultraviolet ray absorbers, and oxalic acid anilide ultraviolet ray absorbers. Examples thereof are described in JP-A Nos. 47-10537, 58-111942, 58-212844, 59-19945, 59-46646, 59-109055 and 63- 53544, Japanese Patent Application Publication (JP-B) Nos. 36-10466, 42-26187, 48-30492, 48-31255, 48-41572, 48-54965 and 50-10726, and U.S. Pat. Nos.
  • antioxidants examples include hindered amine antioxidants, hindered phenol antioxidants, aniline antioxidants, and quinoline antioxidants. Antioxidants thereof are described in, for example, JP-A Nos. 59-155090, 60- 107383, 60-107384, 61-137770, 61-139481 and 61-160287, the disclosures of which are incorporated by reference herein.
  • the recording layer is applied such that a solid application amount thereof after application and drying will be from 0.5 to 25 g/m and the thickness of the recording layer will be 0.5 to 25 um.
  • a plurality of such recording layers may be provided.
  • the solid application amount of all the recording layers is preferably from 0.5 to 25 g/m.
  • the recording material can have a protective layer as an uppermost layer at the recording layer side of the material.
  • the protective layer is formed by applying a liquid chemical coating composition for the protective layer.
  • a liquid chemical coating composition for the protective layer is described in, for example, JP-A 2007-152686A.
  • the recording material that is used in the invention has preferably no protective layer applied on the recording layer.
  • the present invention is based on the new finding that the removal of a protective layer on the recording layer can significantly increase optical density of the mark formed by the laser irradiation.
  • any kind of support can be used. These are described in, for example JP-A 2007-152686A.
  • the recording material that is used in the invention has preferably the support of a corrugated fiberboard for outer case.
  • Embodiments of the present invention are based on the new finding that the support of a corrugated fiberboard for outer case can increase lay-down of the chemical coating composition and increase the optical density of the mark formed by the laser irradiation.
  • an ultraviolet ray filter layer may be provided at any position on the support.
  • the ultraviolet ray filter layer contains an ultraviolet ray absorber compound such as benzotriazole compounds, benzophenone compounds, and hindered amine compounds.
  • an antireflection layer may be provided.
  • the antireflection layer can be formed by a mixture containing particles that are usable in the back layer as a preferable matting agent.
  • an undercoat layer may be provided on the support before the recording layer and the like are provided on the support.
  • the undercoat layer may comprise at least one compound selected from acrylic ester copolymers, polyvinylidene chloride, SBR, aqueous polyesters and the like.
  • the thickness thereof is preferably from 0.05 to 0.5 um.
  • the undercoat layer may swell by water contained in the coating composition solution for forming the recording layer so that the image recorded in the recording layer may deteriorate. It is therefore preferable to use a hardening agent such as a dialdehyde (such as glutaraldehyde or 2,3-dihydroxy-l,4-dioxane) or boric acid to harden the layer.
  • a hardening agent such as a dialdehyde (such as glutaraldehyde or 2,3-dihydroxy-l,4-dioxane) or boric acid to harden the layer.
  • the amount of the hardening agent to be added may be any hardening agent such as glutaraldehyde or 2,3-dihydroxy-l,4-dioxane.
  • the recording material used in embodiments of the invention may be manufactured, for example, in the following procedure, but the method is not limited thereto.
  • a liquid coating composition for forming a recording layer (hereinafter referred to as a "recording layer coating liquid”) is applied to form a recording layer using flexo printing machine, gravure printing machine, off set printing machine, roller coating machine, curtain coating machine, and other coating methods. It is preferably applied onto the support as an ink using flexo printing machine, gravure printing machine.
  • the recording method of the invention is a method of recording an image on the above-mentioned recording material by irradiating a laser.
  • the laser preferably has a wavelength of 1 to 11 um.
  • the wavelength of the C02 laser to be irradiated is preferably 9 to 11 um, more preferably 9.2 to 10.6 um.
  • the C02 laser is not particularly limited, as far as a C02 laser light having a wavelength of 9 to 11 um can be irradiated, and may be properly selected depending on the purpose, and a commercial laser can be used. Examples include BLAZAR 6000 manufactured by LaserTechnics, Inc., Unimark manufactured by Ushio Inc., Zymark 7000 manufactured by Coherent, Inc., ML-9110 manufactured by Keyence, Smart Rays 110 manufactured by EDM CORP., and Domino Scanning Laser manufactured by Cornes Dodwell.
  • the C02 laser is preferably irradiated while adjusting such that the energy on the recording material surface is 10 to 200 mJ/mm . More preferably, the energy on the recording material surface is 10 to 150 mJ/mm ⁇ 2>. If the energy by the C02 laser is less than 10 mJ/ mm , sufficient color-forming may not be achieved, or if exceeding 200 mJ/ mm , ablation may occur and the colored recording layer may be lost.
  • a recording layer liquid coating composition was prepared by mixing
  • the recording layer liquid coating composition was applied by Phantom Hand Proofer (manufactured by Harper Scientific) that is flexographic-type proofing systems incorporated ceramic anilox roller (anilox roller cell volume is 10 BCM), steel doctor blades and solvent resistant rubber rolls., and then dried, whereby a recording layer was formed on the support.
  • the liquid coating composition temperature of each layer was adjusted in a range of 23°C to 27°C.
  • the coating speed was 100 feet/min, the support was subsequently air-dried at a temperature of 45°C to 55°C.
  • the recording layer liquid coating composition is applied by a Phantom Hand Proofer (manufactured by Harper Scientific) that is a flexographic-type proofing systems incorporating a ceramic anilox roller (anilox roller cell volume is 10 BCM), steel doctor blades, and solvent resistant rubber rolls, and then dried, whereby a recording layer was formed on the support.
  • a Phantom Hand Proofer manufactured by Harper Scientific
  • the temperature of each layer of the liquid coating composition was adjusted in a range of 23°C to 27°C.
  • the coating speed was 100 feet/min, and the support was subsequently air-dried at a temperature of 45°C to 55°C.
  • the recording layer liquid coating composition was applied by a Phantom Hand Proofer (manufactured by Harper Scientific) that is a flexographic-type proofing systems which incorporates ceramic anilox rollers (anilox roller cell volume is 10 BCM), steel doctor blades, and solvent-resistant rubber rollers, and then dried, whereby a recording layer was formed on the support.
  • the liquid coating composition liquid temperature of each layer was adjusted in a range of 23°C to 27°C.
  • the coating speed was 100 feet/min, and the support was subsequently air dried at a temperature of 45°C to 55°C.
  • the recording layer liquid chemical coating composition was applied by Phantom Hand Proofer (manufactured by Harper Scientific) that is a flexographic-type proofing systems incorporating ceramic anilox roller (anilox roller cell volume is 10 BCM), steel doctor blades, and solvent resistant rubber rolls, and then dried, whereby a recording layer was formed on the support.
  • Phantom Hand Proofer manufactured by Harper Scientific
  • the coating liquid temperature of each layer was adjusted in a range of 23°C to 27°C.
  • the coating speed was 100 feet/min, and the support was subsequently air dried at a temperature of 45°C to 55°C.
  • Viscosity of the recording layer coating liquids in example 1 and 2, and comparative example 1 and 2 were measured before and after storage under the temperature at 50°C for 2 weeks by Zahn Cup No. 2. Results are shown in Table 1. Table 1
  • the laser marking density is high, the scratching density is very low, and viscosity stability is excellent in Examples 1 and 2.
  • a corrugated fiberboard support is preferable.

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

Abstract

La présente invention porte sur une composition de revêtement chimique qui permet d'enregistrer une image sur une matière d'enregistrement en formant une image colorée par exposition à un faisceau laser. En outre, la composition de revêtement chimique comporte au moins une microcapsule encapsulant un précurseur de colorant basique, et au moins une dispersion plastique. L'invention porte également sur une matière d'enregistrement utilisant la composition de revêtement chimique de la présente invention, ainsi que sur un procédé d'enregistrement utilisant la composition de revêtement chimique séchée sur une matière d'enregistrement, celle-ci étant subséquemment exposée à un laser.
PCT/US2012/021752 2012-01-18 2012-01-18 Composition de revêtement chimique pour former une matière pouvant être marquée par laser et matière pouvant être marquée par laser WO2013109268A1 (fr)

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Cited By (5)

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EP3173249A1 (fr) * 2015-11-30 2017-05-31 Agfa-Gevaert Compositions marquables au laser et procédés pour fabriquer un emballage avec celui-ci
EP3470134A1 (fr) 2017-10-13 2019-04-17 Agfa Nv Composition comprenant un solvant et des capsules résistant à la chaleur
EP3470135A1 (fr) 2017-10-13 2019-04-17 Agfa Nv Composition comprenant un solvant et des capsules résistant à la chaleur
EP3838610A1 (fr) 2019-12-17 2021-06-23 Agfa Nv Articles pouvant être marqués au laser
EP3838609A1 (fr) 2019-12-17 2021-06-23 Agfa Nv Articles pouvant être marqués au laser

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US5051333A (en) * 1989-06-22 1991-09-24 Fuji Photo Film Co., Ltd. Optical image-recording material
EP0587410A2 (fr) * 1992-09-10 1994-03-16 Appleton Papers Inc. Matériau d'enregistrement
US5368973A (en) * 1990-10-31 1994-11-29 Fuji Photo Film Co., Ltd. Light-sensitive element and process for preparation thereof
US6265128B1 (en) * 1996-11-15 2001-07-24 Foto-Wear, Inc. Imaging transfer system and process for transferring image and non-image areas thereof to a receptor element
US7410744B2 (en) * 2005-12-02 2008-08-12 Fujifilm Corporation Recording method

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US5051333A (en) * 1989-06-22 1991-09-24 Fuji Photo Film Co., Ltd. Optical image-recording material
US5368973A (en) * 1990-10-31 1994-11-29 Fuji Photo Film Co., Ltd. Light-sensitive element and process for preparation thereof
EP0587410A2 (fr) * 1992-09-10 1994-03-16 Appleton Papers Inc. Matériau d'enregistrement
US6265128B1 (en) * 1996-11-15 2001-07-24 Foto-Wear, Inc. Imaging transfer system and process for transferring image and non-image areas thereof to a receptor element
US7410744B2 (en) * 2005-12-02 2008-08-12 Fujifilm Corporation Recording method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3173249A1 (fr) * 2015-11-30 2017-05-31 Agfa-Gevaert Compositions marquables au laser et procédés pour fabriquer un emballage avec celui-ci
WO2017093228A3 (fr) * 2015-11-30 2017-07-13 Agfa-Gevaert Compositions marquables au laser et procédés pour fabriquer un emballage à l'aide de celles-ci
CN108290434A (zh) * 2015-11-30 2018-07-17 爱克发-格法特公司 可激光标记的组合物和用其制造包装的方法
EP3470134A1 (fr) 2017-10-13 2019-04-17 Agfa Nv Composition comprenant un solvant et des capsules résistant à la chaleur
EP3470135A1 (fr) 2017-10-13 2019-04-17 Agfa Nv Composition comprenant un solvant et des capsules résistant à la chaleur
WO2019072749A1 (fr) 2017-10-13 2019-04-18 Agfa Nv Composition comprenant un solvant et des capsules résistant à la chaleur
WO2019072758A1 (fr) 2017-10-13 2019-04-18 Agfa Nv Une composition comprenant un solvant et des capsules résistant à la chaleur
EP3838610A1 (fr) 2019-12-17 2021-06-23 Agfa Nv Articles pouvant être marqués au laser
EP3838609A1 (fr) 2019-12-17 2021-06-23 Agfa Nv Articles pouvant être marqués au laser
WO2021121927A1 (fr) 2019-12-17 2021-06-24 Agfa Nv Articles marquables au laser
WO2021121919A1 (fr) 2019-12-17 2021-06-24 Agfa Nv Articles pouvant être marqués au laser

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