EP1827859B1 - Zusammensetzung zur herstellung einer lasermarkierbaren schicht und verfahren zur herstellung einer markierung durch laserbelichtung - Google Patents

Zusammensetzung zur herstellung einer lasermarkierbaren schicht und verfahren zur herstellung einer markierung durch laserbelichtung Download PDF

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EP1827859B1
EP1827859B1 EP05853411A EP05853411A EP1827859B1 EP 1827859 B1 EP1827859 B1 EP 1827859B1 EP 05853411 A EP05853411 A EP 05853411A EP 05853411 A EP05853411 A EP 05853411A EP 1827859 B1 EP1827859 B1 EP 1827859B1
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Prior art keywords
laser
coating
composition according
polyurethane
composition
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English (en)
French (fr)
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EP1827859A2 (de
EP1827859A4 (de
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Haixing Wan
Hailing Duan
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Fujifilm Hunt Chemicals USA Inc
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Fujifilm Hunt Chemicals USA Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—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
    • 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
    • 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

Definitions

  • Product and package labeling is becoming increasingly important in various industries, and it is generally beneficial to provide clearly visible, sharp, high contrast marks. In some applications, it can be beneficial to provide color images rather than black and white images.
  • Laser beam marking is a growing area of interest and offers several advantages over conventional marking technologies in terms of cost, marking speed, environmental concerns, safety and/or equipment maintenance.
  • markings can be formed by use of laser ablation.
  • One disadvantage of employing conventional laser ablation means is that it can require strong interaction of the marking substrate with the laser, beam to yield significant color or density changes in comparison with unmarked areas.
  • Packaging materials such as plastic films, containers and glass bottles, can lack sufficient interaction with laser beam energy, the interaction can fail to yield sufficient contrast changes on the material, and/or the interaction can cause undesirable damage to the substrate surface.
  • a coating can be formed on the substrate that is capable of absorbing energy of a laser beam to yield visible marks on the coated substrate.
  • This type of laser-markable coating can contain pigments, dyes, binders, as well as other coating additives.
  • the coating composition can contain a binder which functions substantially as a film forming agent. Besides being utilized for its film-forming function, binders can be used in various applications to obtain special effects in laser-markable coating compositions.
  • interference mark effects can contribute to low mark quality of the marked material.
  • Interference mark effects can be manifested in several different ways. For example, a whiteness, opacity, or haziness can occur in the area near laser exposure, which can be visible with the naked eye.
  • a conventional binder can undergo a physical change when exposed to a laser beam to produce microvoids, bubbles, crosslinks, fine particulates and/or inclusions, which can result in opacity or otherwise degradation of the mark.
  • the interference marks can lead to low mark density, poor color purity, and/or visually unsharp/distorted images in the marked region of the material. Machine and/or human readability can be reduced when the intended marks to be formed by laser exposure are lower in quality than required.
  • US-A-5,792,724 discloses a thermosensitive recording material.
  • GB-A-2,320,582 discloses a reversible thermosensitive recording material.
  • a composition according to claim 1 for forming a laser-markable coating comprising: (a) a first component of a color-forming agent, wherein upon exposure to a laser the first component is capable of reacting with a second component of the color-forming agent to generate a color; and (b) a binder comprising a substituted or unsubstituted polyurethane compound, characterised in that the substituted or unsubstituted polyurethane compound is selected from the group consisting of a polyester-derived polyurethane, a polyether-derived polyurethane, a polycarbonate-derived polyurethane, a castor oil-derived polyurethane and a combination thereof.
  • a laser-markable material according to claim 15 comprising: (a) a coating comprising a substituted or unsubstituted polyurethane compound; and (b) a coating formed from the composition as defmed above.
  • a process according to claim 16 of forming a marking by laser exposure comprising applying a composition comprising the coating composition to a substrate to form a coating and exposing at least a part of the coating to a laser.
  • a process according to claim 18 of forming a marking by laser exposure comprising combining the coating composition with a second composition comprising the second component, applying the resulting composition to a substrate to form a coating, and exposing at least a part of the coating to a laser.
  • the coating composition is useful for forming a coating such as a laser-recordable layer on a substrate.
  • the coating can constitute a part of a multi-layered laser-markable material.
  • a laser mark of relatively high quality can be obtained.
  • the coating composition includes at least one component of a color-forming agent.
  • the color-forming agent can contribute to the generation of a color upon exposure to a laser.
  • the color-forming agent can include at least one component which reacts with at least another component upon exposure to a laser, wherein such reaction results in the generation of a color.
  • the color-forming agent can include an electron donor dye precursor, an electron acceptor developer, or both such components, wherein the reaction between such compounds upon exposure to a laser results in a generation of a color.
  • multiple coating compositions can be formed wherein a first coating composition includes the electron donor dye precursor and the second coating composition includes the electron acceptor developer.
  • first and second compositions can be maintained separately to improve stability of the compositions, and can be combined and/or mixed together prior to use.
  • the electron donor dye precursor can include, for example, a triphenylmethane phthalide series compound, a fluorane series compound, a phenothiazine series compound, an indolyl phthalide series compound, a leucoauramine series compound, a rhodamine lactam series compound, a triphenylmethane series compound, a triazene series compound, a spiropyran series compound, a fluorene series compound, a pyridine series compound, a pyradine series compound and a combination thereof.
  • the electron acceptor developer for reacting with the electron donor dye precursor, can include an acidic substance such as activated bentonite, a metal salt of salicylate, a phenol compound, an organic acid or a metallic salt thereof, an oxybenzoate and a combination thereof.
  • an acidic substance such as activated bentonite, a metal salt of salicylate, a phenol compound, an organic acid or a metallic salt thereof, an oxybenzoate and a combination thereof.
  • the composition can include at least one auxiliary additive such as, for example, a surfactant, an anti-foam agent, a plasticizer, a rheological agent, a biocide, an antistatic agent, a solvent, a photoinitiator for radiation curing or combinations thereof.
  • auxiliary additive can also include an additive for improving laser-marking performance such as a heat transfer agent, a melting agent, an ultraviolet ray absorbing agent, an antioxidant or combinations thereof.
  • the heat transfer agent can include a compound which is capable of absorbing CO 2 laser emission energy at 943 cm -1 , and converting same to heat.
  • the heat transfer agent can include, for example, mica, fumed silica, fumed alumina, and various inorganic and organic compounds having strong absorption in the wavelength range of 900 cm -1 to 1000 cm -1 .
  • the melting agent can function to improve laser responsiveness. Examples can include an aromatic ether, a thioether, an ester aliphatic amide, a ureide or combinations thereof.
  • the ultraviolet ray absorbing agent can include, for example, a benzophenone series ultraviolet ray absorbing agent, a benzotriazole series ultraviolet ray absorbing agent, a salicylic acid series ultraviolet ray absorbing agent, a cyanoacrylate series ultraviolet ray absorbing agent, an oxalic acid anilide series ultraviolet ray absorbing agent or combinations thereof.
  • the antioxidant can include, for example, a hindered amine series antioxidant, a hindered phenol series antioxidant, an aniline series antioxidant, a quinoline series antioxidant or combinations thereof.
  • the coating composition also includes a binder which can function as a medium for the color-forming agent.
  • the binder is capable of being processed into a coating or film.
  • the binder includes a substituted or unsubstituted polyurethane compound.
  • the substituted or unsubstituted polyurethane compound can include a polyurethane formed from the reaction of an isocyanate with, for example, various organic compounds as discussed in "Polyurethane Handbook," 2 nd Ed., edited by Dr. Günter Oertel, Hanser Publishers, Kunststoff, pp. 17-25 (1994).
  • the substituted or unsubstituted polyurethane compound suitable for forming a coating can be a polyester-derived polyurethane, a polyether-derived polyurethane, a polycarbonate-derived polyurethane, a castor oil-derived polyurethane, or combinations thereof.
  • the substituted or unsubstituted polyurethane compound can be present in an amount of at least 50% by weight of the total binder content.
  • the substituted or unsubstituted polyurethane compound can be present in an amount effective to reduce or substantially eliminate the formation of interference marks.
  • the substituted or unsubstituted polyurethane can yield substantially no interference marks after exposure to laser energy, for example, a CO 2 laser beam.
  • the binder is substantially chemically inert with respect to the color-forming agent, and therefore preferably does not interference with the color-forming reaction.
  • the binder can be a water-soluble resin.
  • the polyurethane compound can constitute substantially all of the binder present in the coating composition.
  • additional binder materials can be used in combination with the polyurethane compound.
  • additional binder materials include starch and modified derivatives, cellulose and modified derivatives, gelatin, casein, gum arabic, pectin, sodium alginate, silicate resin, polyvinyl alcohol, polyacrylic resin, epoxy, polystyrene, polyester, polyacrylic amide, styrene-acrylic acid copolymer, styrenebutadiene copolymer, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyvinyl pyrrolidone, acrylic, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer and combinations thereof.
  • An additional binder can be used in combination with
  • the coating composition can contain any suitable amount of binder.
  • the binder can be present in an amount of at least about 50% of the total solids weight of the coating composition.
  • the binder can be present in an amount from about 5% to about 40%, more preferably from about 10% to about 20%, and most preferably about 15% of the total solid weight in the coating composition.
  • the coating composition can be a single-part coating composition which contains substantially all of the various components of the coating composition.
  • multiple coating compositions can be used to provide storage stability prior to use of the compositions, and the binder can be incorporated into any of the multiple coating compositions.
  • the coating composition can be used to form a coating or film using any suitable technique.
  • the coating or film can be aqueous-based, solvent-based such as an organic-solvent-based, radiation-curable such by as UV radiation, and/or an electron beam-curable.
  • the binder containing the polyurethane compound can be employed as the binder material to reduce or substantially eliminate interference mark effects independent of the specific coating formation method of the coating composition.
  • R 1 and R 2 represent a alkyl group, such as a butyl group, a sec.-butyl group, a tert .-butyl group, a propyl group, an ethyl group, a methyl group, etc.
  • R 3 represents a hydrogen, or a alkyl group, such as a butyl group, a sec .-butyl group, a tert .-butyl group, a propyl group, a ethyl group, a methyl group, etc.
  • R 4 represents an imino-benzene group or a hydrogen.
  • An exemplary compound is shown below as Formula 2:
  • the solubility of the electron donor dye precursor can be greater than 10g/100g of ethyl acetate, more preferably greater than about 15g/100g of ethyl acetate, and most preferably greater than about 18g/100g of ethyl acetate.
  • the electron donor dye precursor contains greater than about 80% by weight, more preferably greater than about 90%, and most preferably about 100% by weight, of compound(s) represented by structural the above Formula 1.
  • the color-forming agent can be incorporated in the coating composition using any suitable technique.
  • the color-forming agent can be incorporated by a) dispersing the color-forming agent in solid powder form into the binder medium, b) dissolving the color-forming agent in a solvent and adding the solution of color forming agents to the binder medium, and c) micro-encapsulating the color forming agents and dispersing the encapsulated color forming agents into the binder medium.
  • the color forming agents are microencapsulated and dispersed in the binder medium.
  • At least one of the components of the color-forming agent can be present in the coating composition in the form of a microcapsule.
  • the electron donor dye precursor and/or the electron acceptor developer can be microencapsulated. This can depend on, for example, whether it is advisable to protect either or both of such components from being contacted by any other components of the coating composition.
  • the dye precursor can be micro-encapsulated and separated from the developer.
  • a surface polymerization process can be employed, such that the electron donor dye precursor that becomes a core of the microcapsules is dissolved or dispersed in a hydrophobic organic solvent to prepare an oily phase, which is then mixed with an aqueous phase obtained by dissolving a water-soluble polymer in water.
  • the resulting material is then subjected to emulsification and dispersion by using, for example, an homogenizer, followed by heating, so as to conduct a polymer-forming reaction at the interface of the oily droplets, whereby a microcapsule wall of a polymer substance is formed.
  • Reactants for forming the polymer substance can be added to the interior of the oily droplets and/or the exterior of the oily droplets.
  • Specific examples of the polymer substance include polyurethane, polyurea, polyamide, polyester, polycarbonate, a urea-formaldehyde resin, a melamine resin.
  • polyurethane, polyurea, polyamide, polyester and polycarbonate are preferred, and polyurethane and polyurea are particularly preferred.
  • the microcapsule wall can be easily formed by reacting a polyisocyanate, such as diisocyanate, triisocyanate, tetraisocyanate or a polyisocyanate prepolymer, with a polyamine, such as diamine, triamine or tetramine, a prepolymer having two or more amino groups, piperazine or a derivative thereof, or a polyol, in the aqueous phase by the interface polymerization process.
  • a polyisocyanate such as diisocyanate, triisocyanate, tetraisocyanate or a polyisocyanate prepolymer
  • a composite wall formed with polyurea and polyamide or a composite wall formed with polyurethane and polyamide can be prepared in such a manner that, for example, a polyisocyanate and a secondary substance for forming the capsule wall through reaction therewith (for example, an acid chloride, a polyamine or a polyol) are mixed with an aqueous solution of a water-soluble polymer (aqueous phase) or an oily medium to be encapsulated (oily phase), and subjected to emulsification and dispersion, followed by heating.
  • a polyisocyanate and a secondary substance for forming the capsule wall through reaction therewith for example, an acid chloride, a polyamine or a polyol
  • aqueous phase water-soluble polymer
  • oily medium to be encapsulated oily medium to be encapsulated
  • a compound having an isocyanate group of three or more functional groups is preferred, and a difunctional isocyanate compound may be used in combination therewith.
  • a diisocyanate such as xylene diisocyanate or a hydrogenated product thereof, hexamethylene diisocyanate or a hydrogenated product thereof, tolylene diisocyanate or a hydrogenated product thereof and isophorone diisocyanate, as the main component; a dimer or a trimer thereof (burette or isocyanaurate); a compound having polyfunctionality as an adduct product of a polyol, such as trimethylolpropane, and a difunctional isocyanate, such as xylylene diisocyanate; a compound of an adduct product of a polyol, such as trimethylolpropane, and a difunctional isocyanate, such as xylylene diisocyanate, having a polymer
  • the compounds described in JP-A-62-212190 , JP-A-4-26189 , JP-A-5-317694 and Japanese Patent Application No. 8-268721 can be preferably used.
  • Specific examples of the polyol and/or the polyamine added to the aqueous phase and/or the oily phase as one constitutional component of the microcapsule wall through the reaction with the polyisocyanate include propylene glycol, glycerin, trimethylolpropane, triethanolamine, sorbitol and hexamethylenediamine. In the case where a polyol is added, a polyurethane wall is formed.
  • At least about 90% of the total volume of the dye precursor particles is present in microcapsules having an average particle diameter of from about 0.3 ⁇ m to about 12 ⁇ m, preferably from about 0.2 ⁇ m and about 5 ⁇ m, and most preferably from about 0.2 ⁇ m and about 2 ⁇ m.
  • the microcapsules have an average particle diameter of from about 0.3 to about 12 ⁇ m, preferably from about 0.2 ⁇ m and about 5 ⁇ m, and most preferably from 0.2 ⁇ m and 2 ⁇ m.
  • the thickness of the microcapsule wall can be from about about 0.01 ⁇ m and about 0.3 ⁇ m.
  • Particle size of the microcapsules in the suspension can be measured by diluting the suspension into aqueous solution and using laser scattering method based on Mie-scattering theory to measure the particle size and distribution.
  • Typical equipment used for such measurement are Horiba's LA series, Beckman Coulter's LS series or Malvern Instruments' Mastersizer series.
  • the microencapsulation reaction can also be controlled so that the microcapsule wall has a glass transition temperature, Tg, of from 150°C to 190°C, preferably from about 160°C to about 180°C, and most preferably from about 165°C to about 175°C.
  • Tg glass transition temperature
  • the Tg of the microcapsule wall can be measured by using conventional differential thermal analysis methods, such as DSC (Differential Scanning Calorimeters) or DDSC (Dynamic DSC), which measures specific heat (C p ) change over different temperature ranges.
  • DSC Different Scanning Calorimeters
  • DDSC Dynamic DSC
  • C p specific heat
  • reaction conditions of the microcapsule preparation process can be controlled and adjusted in order to obtain microcapsules having the preferred characteristics.
  • These conditions cam include, for example, emulsification process of the electron donor dye precursor, addition rates and amounts of the polyisocyanate and polyamine to form the microcapsule wall, as well as mixing and reaction temperature, time, and agitation.
  • the reaction rate can be increased, for example, by either maintaining a high reaction temperature or by adding an appropriate polymerization catalyst.
  • the microcapsule wall may further contain, depending on the specific application, a metal-containing dye, a charge adjusting agent, such as nigrosin, and/or other additive substances. These additives may be contained in the capsule wall during wall formation or at other times during the microencapsulation process.
  • a monomer such as a vinyl monomer, can be graft-polymerized depending on necessity.
  • a plasticizer can be used that is suitable for the polymer that is used as the wall material.
  • the plasticizer can have a melting point of about 50 degrees C or more, and more preferably about 120 degrees C or more.
  • plasticizers those in a solid state at ordinary temperature can be preferably employed.
  • a plasticizer a hydroxyl compound, a carbamate compound, an aromatic alkoxy compound, an organic sulfoneamide compound, an aliphatic amide compound, an arylamide compound or combinations thereof can be used.
  • an organic solvent having a boiling point of from about 100 to about 300 degrees C can be used.
  • an organic solvent having a boiling point of from about 100 to about 300 degrees C include an ester compound, dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, dimethylbiphenyl, diisopropyldiphenyl, diisobutylbiphenyl, 1-methyl-1-dimethylphenyl-2-phenylmethane, 1-ethyl-1-dimethylphenyl-1-phenylmethane, 1-propyl-1-dimethylphenyl-1-phenylmethane, triarylmethane (such as tritoluylmethane or toluyldiphenylmethane), a terphenyl compound (such as terphenyl), an alkyl compound, an alkylated diphenyl
  • an ester compound can be preferably used from the standpoint of emulsification stability of the emulsion dispersion.
  • the ester compound include a phosphate, such as triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate or cresylphenyl phosphate; a phthalate, such as dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, octyl phthalate or butylbenzyl phthalate; dioctyl tetrahydrophthalate; a benzoate, such as ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate or benzyl benzoate; an abietate, such as ethyl abietate or benzyl abietate; dioctyl adipate; iso
  • the hydrophobic organic solvent can be used alone or in combinations of two or more. Among these, tricresyl phosphate can be preferably used, either singly or as a mixture with other solvents since it provides high emulsion stability.
  • a low boiling point solvent having high solubility can additionally be used in combination. Examples of the low boiling point solvent include ethyl acetate, isopropyl acetate, butyl acetate and methylene chloride.
  • the content of the electron donor dye precursor is preferably from about 0.1 to about 5.0 g/m 2 , and more preferably from about 1.0 to about 4.0 g/m 2 . While not wishing to be bound by any particular theory, it is believed that when the content of the electron donor dye precursor is in the range of from about 0.1 to 5.0 g/m2, a sufficient coloring density can be obtained, and when the content is 5.0 g/m2or less, a sufficient coloring density can be achieved while the transparency of the laser-sensitive recording layer can also be maintained.
  • water-soluble resins can be added to the aqueous phase of the reaction mixture as a binder in order to stabilize the emulsified dispersion and formed microcapsules.
  • the type and addition amount of the water-soluble resins can be selected so that the viscosity of the coating composition has a viscosity of from about 5 centipoise (cP) to about 30 cP, preferably from about 10 cP to about 25 cP, and most preferably from about 10 cP to about 20 cP. Viscosity can be measured using Brookfield Programmable DV-II+ viscometer with small sample adapter plus a S21 spindle at 100-200 RPM. Regular RV series spindle can also be used depending on sample quantity.
  • the mixing ratio of the oily phase to the aqueous phase is preferably from about 0.02 to about 0.6, and more preferably from about 0.1 to about 0.4.
  • the mixing ratio is in the range of from 0.02 to 0.6, a suitable viscosity can be maintained. This can provide both an improved productivity of use for coating the composition as well as optimized stability of the coating composition.
  • a surfactant can be added to at least one of the oily phase and the aqueous phase.
  • Any suitable surfactant for emulsification can be used.
  • the addition amount of the surfactant can be from about 0.1% to about 5%, more preferably from about 0.5 to about 2%, based on the weight of the oily phase.
  • the surfactant contained in the aqueous phase one that does not cause precipitation or aggregation through an action with the binder can be used by appropriately selecting from anionic and nonionic surfactants.
  • the surface-active agent examples include sodium alkylbenzenesulfonate, sodium alkylsulfate, sodium dioctyl sulfosuccinate and a polyalkylene glycol (such as polyoxyethylene nonylphenyl ether).
  • the emulsification can be conducted by subjecting the oily phase containing the foregoing components and the aqueous phase containing the binder and the surfactant to a device generally used for fine particle emulsification, such as high speed agitation or ultrasonic wave dispersion by using a known emulsifying apparatus, such as a homogenizer, Manton Gaulin, an ultrasonic wave disperser, a dissolver or a KADY mill.
  • a known emulsifying apparatus such as a homogenizer, Manton Gaulin, an ultrasonic wave disperser, a dissolver or a KADY mill.
  • the emulsion can be heated to a temperature of from 30 to 70° C for accelerating the capsule wall-forming reaction.
  • water can be added to the emulsion to decrease the probability of collision of the capsules or that sufficient agitation is conducted to prevent aggregation of the capsules.
  • a dispersion containing the polyurethane compound may further be added during the reaction for reducing or substantially preventing aggregation. Formation of a carbon dioxide gas can be observed with progress of the reaction, and termination of the formation can be determined as completion of the capsule wall-forming reaction. In general, the reaction can be conducted for several hours to obtain the objective microcapsules.
  • Examples of the electron acceptor compound which is capable of reacting with the electron donor dye precursor, include an acidic substance, such as activated bentonite, metal salt of salicylate, phenol compound, organic acid or its metallic salt, oxybenzoate or combinations thereof.
  • an acidic substance such as activated bentonite, metal salt of salicylate, phenol compound, organic acid or its metallic salt, oxybenzoate or combinations thereof.
  • bisphenol compound such as 2,2-bis(4'-hydroxyphenyl)propane (generic name: bisphenol A), 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4'-hydroxy-3',5'-dichlorophenyl)propane, 1,1-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-methylpentane, 1,1-bis(4'-hydroxypen
  • the metal salts of salicylate can be preferred employed, for example, zinc salicylate.
  • zinc salicylate for example, it is possible to achieve good coloring characteristics by using such developer.
  • Additional electron acceptor developers that can be used are disclosed in U.S. Patent Nos. 6,797,318 , 5,409,797 and US 5,691,757 , The electron acceptor compounds may be used singly or in a combination of two or more.
  • the electron acceptor compound may be used, for example, as a solid dispersion prepared in a sand mill with water-soluble polymers, organic bases, and other color formation aids or may be used as an emulsion dispersion by dissolution in a high boiling point organic solvent that is only slightly water-soluble or is water-insoluble, mixing with waterborne polyurethane and its modified derivatives as the binder (aqueous phase), followed by emulsification, for example, by a homogenizer.
  • a low boiling point solvent can be used as a dissolving assistant depending on necessity.
  • the electron acceptor compound and the organic base may be separately subjected to emulsion dispersion, and also may be dissolved in a high boiling point solvent after mixing, followed by subjecting to emulsion dispersion.
  • the emulsion dispersion particle diameter can be about 1 ⁇ m or less.
  • the high boiling point organic solvent used can be appropriately selected, for example, from the high boiling point oils described in JP-A-2-141279 .
  • the use of an ester compound is preferred from the standpoint of emulsion stability of the emulsion dispersion, and tricresyl phosphate is particularly preferred.
  • the oils can be used as a mixture thereof and as a mixture with other oils.
  • the binder can be present from an amount of about 5% to about 50%, preferably from about 10 % to about 30%, more preferably about 15% of total solid weight of the coating composition containing the electron acceptor developer.
  • a coating composition containing the electron acceptor developer and a second coating composition containing the electron donor dye precursor can be mixed together to prepare a mixed coating dispersion which is subsequently coated on a substrate for use as a laser-sensitive recording layer for laser marking.
  • the two coating compositions can be mixed in any suitable ratio, for example, such that the ratio of total weight of electron donor dye precursor(s) and the total weight of the developer(s) is from about 1:0.5 to about 1:30, preferably from about 1:1 to about 1:0.
  • a laser-markable material which includes a coating comprising a substituted or unsubstituted polyurethane compound; and a laser-markable layer.
  • the coating can be in contact with the laser-markable layer.
  • the laser-markable material can include additional layers such as a protective layer, an intermediate layer, an undercoating layer (a primer layer), a light reflection preventing layer, and the like.
  • the protective layer can be the uppermost layer of the material, and can be arranged above and/or in contact with the laser-sensitive recording layer.
  • the function of the protective layer is to provide protection for the laser-sensitive recording layer against physical damage such as rubbing, moisture attack, to strengthen the resistance against instant heat impact, etc.
  • the intermediate layer can be applied on the laser-sensitive recording layer.
  • the function of this layer is to reduce or prevent intermixing of the layers and also for blocking a gas (such as oxygen) that may be harmful in order to preserve an image after formation.
  • the undercoating layer, light reflection preventing layer and other functional layers such as an adhesion layer can be applied onto the substrate before coating the laser-sensitive recording layer.
  • a protective coating composition can also be provided according to an exemplary embodiment.
  • the protective coating composition not only can provide the demanded protection as described above, but also be effective to reduce or eliminate the formation of interference marks that affect the mark quality of a laser marked material.
  • the binder quantity for the protective layers can be, for example, about 50% of total solid weight in the coating composition.
  • the percentage of binder quantity can vary in from about 10% to about 80% according to different application, more preferably from about 30% to about 60% by weight.
  • substantially only a polyurethane compound as the binder for the additional layers is preferred for a good mark quality.
  • a combination between polyurethane and other type of resins, such as acrylic, epoxy, cellulose, etc., can be a selected when a special technical property is demanded for a laser markable material.
  • the amount of polyurethane and its modified derivatives is preferably not less than 50% of the total binder quantity in a coating composition to reduce or avoid intensifying the interference mark effect.
  • the additional layer(s) can include auxiliary additives such as regular coating additives, such as surfactants, anti-foam agents, plasticizers, rheological agents, biocides, antistatic agents, solvents, water, photoinitiator for radiation curing, hardening agents, etc.
  • auxiliary additives such as regular coating additives, such as surfactants, anti-foam agents, plasticizers, rheological agents, biocides, antistatic agents, solvents, water, photoinitiator for radiation curing, hardening agents, etc.
  • the additional layer(s) can include a fine particle substance having a refractive index of from about 1.45 to about 1.75 from the standpoint that the transparency of the laser markable material is maintained.
  • Table 1-2 Scan Rates for Each Line in Figure 1 , (bits/ms) Joncryl® 89 (A, from top to bottom of the slide) Macekote® 9525 (B, from left to right of the slide), 500 2000 5000 4000 4000 7000 2000 10000 10000 1000
  • Joncryl® 89 (A) and Macekote® 9525 (B) produced very different responses when scanned at comparable rates.
  • Macekote® 9525 had comparatively little response to the laser beam.
  • the experimental results show that Macekote® 9525 (a polyether-based polyurethane) provided superior results in comparison with the other tested resins in terms of generating less interference marks under CO 2 laser exposure.
  • Example 2 Laser Exposure of Various Inventive and Comparative Binders
  • the experimental procedure included the following: a) coating the tested samples solution on a 2.54cm x 10.16cm (1" x 4") glass slide using a K Control Coater (RK Print Coat Instruments, Ltd.), wherein No. 7 coating bar was used to produce a film thickness of 80 micrometers when wet; b) drying the coated sample solution overnight under ambient condition; c) exposing the coated samples with a Domino S100 laser maker (Domino Amjet, Inc.) under a matrix exposure.
  • the design of the test marking matrix was such that each row consisted of 7 characters, with increasing laser power output from 26.5% to 100% (5.2W ⁇ 19.6W from left to right), and 20% power increment between neighboring characters, and each column consisted of 10 characters, with increasing marking speed from 1300 bits/msec to 9500 bits/msec (from bottom to top), and 20% speed increment between neighboring characters.
  • polyurethane and its derivatives including polyether-based polyurethane, polyester-based polyurethane, polycarbonate-based polyurethane and castor oil-based polyurethane can provide improved performance in comparison with polyvinyl alcohol and styrened acrylate, in reducing interference marking caused by CO 2 laser exposure.
  • the above ethyl acetate solution was added in 53 g of 6%w/w polyvinyl alcohol aqueous solution (Kurary Poval MP-103, Kuraray Co., Ltd.) and emulsified with a homogenizer at 15,000 rpm for 5 minutes. 80g of water and 0.75 g of tetraethylenepentamine were added and mixed with a stirrer at 400 rpm for 4 hours for encapsulation reaction. Part A was completed, and the coating composition is referred to as A ref .
  • the particle size distribution of the encapsulated electron donor-type dye precursor particles and the viscosity of the liquid coating composition were measured with Beckman Coulter's LS-100Q particle size analyzer and Brookfield Programmable DV-II+ viscometer with S21 small size spindle at 100-200 RPM.
  • the Tg of the microcapsule wall was measured by using Perkin Elmer's Diamond DSC, Sapphire DSC, HyperDSCTM, or TA Instruments' Q-series.
  • a blank suspension without microcapsule was prepared under the same conditions as a reference sample. Both the microcapsule-containing suspension and the blank suspension were placed in the sample trays before measurement.
  • Part B was completed at this step, and the coating composition is hereinafter referred to as B ref .
  • Part A samples were mixed with its corresponding Part B sample (A i +B i ).
  • the mixing ratio was as set forth below: Part A 5.04 g Part B 19.13 g Deionized Water 6.40 g To make coating pot solution 30.57 g
  • T i The coating pot solutions formed from from from A i +B i are referred to hereafter as T i .
  • Each of the above mixtures was coated in an amount of 15ml/m 2 on a film of A4 size and 75 ⁇ m thickness PET, which was preliminarily coated with SBR lutex and gelatin, and the following laser marking was conducted after drying. Coating was conducted using a K Control Coater (RK Print Coat Instruments, Ltd.), and a No. 3 coating bar was used to form a film thickness of 24 micrometers when wet.
  • the coated samples were exposed by a Domino S100 laser maker (Domino Amjet, Inc.) under a matrix exposure as described in Example 2.
  • the mark density of a specific letter "M” that best represents the marking results after receiving a fixed quantity of laser energy in the matrix was observed, and the experimental results are shown in Figures 3A to 3E .
  • employing a substituted or unsubstituted polyurethane compound as a binder in the coating composition was effective to improve the mark density of a laser markable material.
  • Example 4 Laser Exposure of a Binder-containing Protective Layer
  • Table 4-1 Chemical Supplier Amount, g 1 Deionized Water 73.24 2 Surfactant A, 72% w/w (TAYCAPOWER® BN2070M) TAVCA 1.34 3 Surfactant B, 50% w/w (Surfynol® 104E) NISSAN Chemical Industries 1.44 4 Polyvinyl Alcohol (PVA124C) Kurary Co.,Ltd.
  • the protective coating composition was completed at this step.
  • the coating composition is referred to hereinafter as PC ref .
  • Example 3 Each of the coated films (T 1 , T 2 , T 3 and T 4 ) in Example 3 was coated with the protective layer coating composition prepared above.
  • T i was coated with PC i and PC ref to observe any differences in laser mark quality.
  • T 1 was coated with PC 1 and PC ref , and so on.
  • Coating was conducted using a K Control Coater (RK Print Coat Instruments, Ltd.), wherein a No. 3 coating bar was used to give the film thickness of 24 micrometer when wet.
  • the coated samples were exposed by a Domino S100 laser maker (Domino Amjet, Inc.) under a matrix exposure described in Example 2.
  • the mark density of a specific letter "M” that best represents the marking result after receiving a fixed quantity of laser energy in the matrix was observed, and the experimental results are shown in Figures 4A to 4H .
  • replacing polyvinyl alcohol with the polyurethane compounds as a binder in a protective layer showed improvements in retaining the mark density of markings formed in the recording layer of a laser-markable material.

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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)
  • Paints Or Removers (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (19)

  1. Zusammensetzung zur Herstellung einer lasermarkierbaren Schicht, umfassend:
    (a) eine erste Komponente eines farbbildenden Mittels, wobei die erste Komponente unter Einwirkung eines Lasers in der Lage ist, mit einer zweiten Komponente des farbbildenden Mittels zu reagieren, um eine Farbe zu bilden; und
    (b) einen eine substituierte oder nichtsubstituierte Polyurethan-Verbindung umfassenden Binder, dadurch gekennzeichnet, dass die substituierte oder nichtsubstituierte Polyurethan-Verbindung ausgewählt ist aus der Gruppe bestehend aus einem aus einem Polyester abgeleiteten Polyurethan, einem aus einem Polyether abgeleitetem Polyurethan, einem aus einem Polycarbonat abgeleiteten Polyurethan, einem aus Rizinusöl abgeleiteten Polyurethan und Mischungen davon.
  2. Zusammensetzung nach Anspruch 1, wobei die Zusammensetzung darüber hinaus die zweite Komponente des farbbildenden Mittels umfasst.
  3. Zusammensetzung nach Anspruch 1, wobei die Polyurethan-Verbindung mit einem Anteil von mindestens 50 Gew.% des Binders vorhanden ist.
  4. Zusammensetzung nach Anspruch 1, wobei die Polyurethan-Verbindung mit einem Anteil von mindestens 80 Gew.% des Binders vorhanden ist.
  5. Zusammensetzung nach Anspruch 1, wobei die Polyurethan-Verbindung eine mit Wasser verdünnbare Polyurethan-Verbindung ist.
  6. Zusammensetzung nach Anspruch 1, wobei die erste Komponente ein elektronenabgebender Farbvorstoff oder ein elektronenaufnehmender Farbentwickler ist.
  7. Zusammensetzung nach Anspruch 6, wobei die erste Komponente ein eine Verbindung mit einer Fluorenfolge umfassender elektronenabgebender Farbvorstoff ist.
  8. Zusammensetzung nach Anspruch 6, wobei der elektronenabgebende Farbvorstoff eine Löslichkeit größer als 10g/100g in Äthylacetat aufweist.
  9. Zusammensetzung nach Anspruch 1, wobei die erste Komponente in einer Vielzahl von verkapselten Mikropartikeln enthalten ist.
  10. Zusammensetzung nach Anspruch 9, wobei die verkapselten Mikropartikel eine Glasumwandlungstemperatur von 150 Grad bis 190 Grad Celsius aufweisen.
  11. Zusammensetzung nach Anspruch 9, wobei die verkapselten Mikropartikel eine mittlere Teilchengröße von 0.2 µm bis 2 µm aufweisen.
  12. Zusammensetzung nach Anspruch 6, wobei die erste Komponente ein ein Metallsalz der Salizylsäure umfassender elektronenaufnehmender Farbentwickler ist.
  13. Zusammensetzung nach Anspruch 12, wobei der elektronenaufnehmende Farbentwickler ein Zinksalizylat ist.
  14. Lasermarkierbarer Stoff umfassend eine aus einer Zusammensetzung nach Anspruch 1 gebildete Schicht.
  15. Lasermarkierbarer Stoff umfassend:
    (a) eine eine substituierte oder nichtsubstituierte Polyurethan-Verbindung umfassende Schicht; und
    (b) eine aus einer Zusammensetzung nach Anspruch 1 gebildete Schicht.
  16. Verfahren zur Herstellung einer Markierung durch Lasereinwirkung umfassend das Auftragen einer Zusammensetzung nach Anspruch 1 auf einen Träger zur Herstellung einer Schicht und das Einwirken eines Lasers auf mindestens einen Teil der Schicht.
  17. Verfahren nach Anspruch 16, wobei mindestens ein Teil der Schicht einem CO2-Laser ausgesetzt wird.
  18. Verfahren zur Herstellung einer Markierung durch Lasereinwirkung, umfassend das Kombinieren der Schichtzusammensetzung nach Anspruch 1 mit einer zweiten die zweite Komponente umfassenden Zusammensetzung, das Auftragen der erhaltenen Zusammensetzung auf einen Träger, um eine Schicht auszubilden, und das Einwirken eines Lasers auf mindestens einen Teil der Schicht.
  19. Verfahren nach Anspruch 18, wobei mindestens ein Teil der Schicht einem CO2-Laser ausgesetzt wird.
EP05853411A 2004-12-08 2005-12-08 Zusammensetzung zur herstellung einer lasermarkierbaren schicht und verfahren zur herstellung einer markierung durch laserbelichtung Expired - Fee Related EP1827859B1 (de)

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US20070098900A1 (en) * 2004-11-05 2007-05-03 Fuji Hunt Photographic Chemicals, Inc. Media providing non-contacting formation of high contrast marks and method of using same, composition for forming a laser-markable coating, a laser-markable material and process of forming a marking
US20080194719A1 (en) * 2006-09-05 2008-08-14 Fujifilm Hunt Chemicals U.S.A., Inc. Composition for forming a laser-markable coating and a laser-markable material containing organic absorption enhancement additives
WO2009009066A1 (en) * 2007-07-09 2009-01-15 Fujifilm Hunt Chemicals U.S.A., Inc. Coating composition for forming laser-markable material having heat and humidity stability
WO2009010405A1 (en) * 2007-07-18 2009-01-22 Basf Se Laser-sensitive coating formulation
RU2011120235A (ru) 2008-10-23 2012-11-27 Дейталейз Лимитед Теплопоглощающие добавки
EP2342295A1 (de) 2008-10-27 2011-07-13 DataLase Ltd Beschichtungszusammensetzung zur kennzeichnung von substraten
PL2797818T3 (pl) * 2011-09-27 2017-12-29 Crown Packaging Technology, Inc Wieczka puszek mające informacje odczytywalne komputerowo

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5866948A (ja) 1981-10-16 1983-04-21 Fuji Photo Film Co Ltd カプセルトナ−
JPS62212190A (ja) 1986-03-13 1987-09-18 Kanzaki Paper Mfg Co Ltd 感熱記録体
JPH0426189A (ja) 1990-05-21 1992-01-29 Mitsubishi Electric Corp プリント配線板の洗浄方法
US5409797A (en) 1991-03-04 1995-04-25 Fuji Photo Film Co., Ltd. Heat-sensitive recording material for laser recording
JP2915206B2 (ja) 1992-05-19 1999-07-05 富士写真フイルム株式会社 感熱記録材料
US5691757A (en) 1993-12-22 1997-11-25 Nippon Kayaku Kabushiki Kaisha Laser marking method and aqueous laser marking composition
US5837051A (en) 1994-12-27 1998-11-17 Bayer Ag Process for the thermal treatment of iron oxides in a circulating fluidized bed
JP3674796B2 (ja) * 1995-04-24 2005-07-20 株式会社リコー 感熱記録材料
JP3760431B2 (ja) * 1996-12-20 2006-03-29 株式会社リコー 可逆性感熱記録媒体
EP0993964A3 (de) * 1998-10-16 2000-11-22 Markem Corporation Mit Laserlicht beschriftbare Überzüge
US6037094A (en) * 1998-10-23 2000-03-14 Cycolor, Inc. Photosensitive material employing microcapsules and superabsorbent polymer
NL1013644C2 (nl) * 1999-11-23 2001-05-28 Dsm Nv Laser-markeerbare polymeersamenstelling.
JP2001242249A (ja) * 2000-03-01 2001-09-07 Japan Atom Power Co Ltd:The 放射線感応組成物含有マイクロカプセル及びその利用方法
JP2002055445A (ja) * 2000-08-10 2002-02-20 Cycolor System Co Ltd 自己発色型感光性感圧記録材料及びその製造方法並びにその画像形成方法
US6797318B2 (en) 2000-08-30 2004-09-28 Fuji Photo Film Co., Ltd. Heat-sensitive recording material and heat-sensitive recording process
DE60232829D1 (de) * 2001-03-16 2009-08-13 Datalase Ltd Verfahren zur Erzeugung eines Bildes durch Laser
US8048605B2 (en) * 2001-03-16 2011-11-01 Datalase Ltd Laser-markable compositions
JP2005279008A (ja) * 2004-03-30 2005-10-13 Brother Ind Ltd 刺繍データ作成装置、刺繍データ作成方法、刺繍データ作成制御プログラム及び刺繍方法

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WO2006063165A2 (en) 2006-06-15

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