WO2006052843A2 - Milieux fournissant une formation sans contact de marques a haut contraste, et procede d'utilisation correspondant - Google Patents

Milieux fournissant une formation sans contact de marques a haut contraste, et procede d'utilisation correspondant Download PDF

Info

Publication number
WO2006052843A2
WO2006052843A2 PCT/US2005/040202 US2005040202W WO2006052843A2 WO 2006052843 A2 WO2006052843 A2 WO 2006052843A2 US 2005040202 W US2005040202 W US 2005040202W WO 2006052843 A2 WO2006052843 A2 WO 2006052843A2
Authority
WO
WIPO (PCT)
Prior art keywords
media
dye precursor
electron donor
layer
mark formation
Prior art date
Application number
PCT/US2005/040202
Other languages
English (en)
Other versions
WO2006052843A3 (fr
WO2006052843A9 (fr
Inventor
Hailing Duan
Janet M. Carlock
Original Assignee
Fuji Hunt Photographic Chemicals, 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 Fuji Hunt Photographic Chemicals, Inc. filed Critical Fuji Hunt Photographic Chemicals, Inc.
Publication of WO2006052843A2 publication Critical patent/WO2006052843A2/fr
Publication of WO2006052843A9 publication Critical patent/WO2006052843A9/fr
Publication of WO2006052843A3 publication Critical patent/WO2006052843A3/fr

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—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
    • B41M5/323—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

Definitions

  • the present invention relates to a media for non-contact rapid marking that can use a focused beam of electromagnetic wave of specific frequencies and intensity to form high contrast and high resolution marks on a mark formation layer through an isolation layer.
  • the markable media can exhibit high storage stability against heat, harmful chemical exposure and mechanical abrasion.
  • the present invention also relates to a method of using the media.
  • Various printing technologies are used for such application, including direct thermal printing on self-adhesive labels, thermal dye-transfer printing, inkjet printing, embossing or stamping, among others.
  • production throughput is often limited due to bottlenecks in the printing speed, particularly when physical contact with each product or label is necessary, such as thermal printing (either direct or dye transfer), drop-on-demand (DOD) type inkjet printing, embossing or stamping.
  • thermal printing either direct or dye transfer
  • DOD drop-on-demand
  • marking technologies rely on physical contact, they are not suitable for marking on products with un-even surfaces.
  • Thermal printing systems also have other disadvantages, such as dirt accumulation on the thermal head and wearing of the contacting surface, which degrades marking quality and readability.
  • CIJ continuous inkjet
  • solvent-based ink systems or mark smearing problem for aqueous-based ink system
  • Another disadvantage of CIJ technology is its low resolution and low contrast in terms of marking quality. This especially becomes a problem for bar- code printing.
  • laser marking Methods are known in the art for non-contacting rapid marking using focused beams of electromagnetic wave of specific wavelengths and intensity, such as laser beams, which is commonly known as "laser marking".
  • laser marking requires strong interaction of the laser beam with the material to be marked, to yield significant color or density changes on unmarked areas.
  • the difficulty is that many packaging materials, such as plastic films or containers, metal cans or glass bottles, either do not have sufficient interaction with laser beam (particularly with low power and/or long wavelength laser beams), or the interaction does not yield significant contrast change on the material to yield high quality marks, or in the case that the interaction is strong, it causes direct damages on the material itself.
  • energy absorbing compounds have been proposed either to be dispersed into the packaging material to be marked on, or to be mixed into a coating composition which in turn is coated on the surface of the material to be marked on.
  • Typical examples of such technology are inorganic based phyllosilicates, metal oxides and silicates compounds, such as talc, kaolin, sericite, mica or metal-oxide coated mica, titanium oxides, tin oxides, iron oxides, or oxides of Sb, As, Bi, Cu, Ga, Ge Si, and the like, as disclosed in US Patent Nos.
  • mark density or contrast are often too weak to become satisfactory commercial products, since it relies on charring or decomposition of the material to be marked on, to either form carbon-rich structures in the material as dark marks, or to generate trapped micro-bubbles (from decomposed material) to form foaming structure in the material as white marks.
  • These mark formation mechanisms often yield poor quality marks because many polymer materials are difficult to carbonize without excessive burning, vaporizing, or complete decomposition, which causes damage to material integrity.
  • Another disadvantage of relying on inorganic laser absorption substances to improve the problem of laser sensitivity is the haziness these additives bring into the material to be marked on, observed as a reduced transparency of the media material. Reduced transparency limits the use of laser markable materials to a narrower range of commercial applications.
  • pigments of organo-metallic complexes, inorganic oxides or salts, or carbon black pigment could be used as additives to be dispersed into the packaging material, or to be mixed into a coating composition which, in turn, is coated on the surface of the material to be marked, hi addition, dual coating layers of contrast colors is also proposed, in which the top coating is to be evaporated (ablated) by the laser marking, and thus expose the bottom coating of contrast color.
  • Typical examples of compounds used in these technologies include organo-metallic complex such as copper phthalocyanines, amine molybdate, or colored metal oxide and hydroxide, or metal phosphate/oxide mixed-phase pigments, sulfide and sulfide/selenium pigments, carbonate pigments, chromate and chromate/molybdate mixed-phase pigments, complex-salt pigments and silicate pigments, as disclosed in U.S. patents and U.S. published patent application nos. 2005/0032957, 6888095, 6855910, 6284184, 6207240, 6139614, 6022905, 5840791, 5667580, 5626966. 5576377, 4861620 and 4401992.
  • organo-metallic complex such as copper phthalocyanines, amine molybdate, or colored metal oxide and hydroxide, or metal phosphate/oxide mixed-phase pigments, sulfide and sulfide/selenium pigments
  • pigment-based laser marking formulation includes the problem of the large particle size of the pigments relative to the desired substrate or coating thickness, and uneven distribution of these solid particles in the media. These problems result in uneven marks and coating coverage, or excessive burning in the marking areas causing damage to media integrity.
  • some of the currently known marking pigments contain heavy metals that have environmental disadvantages.
  • excessive releasing of ablated material or debris into the ambient environment is a significant disadvantage; not only are hazardous materials released into the environment, but also it requires frequent cleaning of the lens on the laser marking head to remove the accumulated fragments or debris released from the ablated marking material.
  • Another disadvantage of the ablation approach is it requires a large laser energy dose, strong enough to completely vaporize the coated layer on the material to be marked. This either leads to slower marking speed which means lower productivity, or more equipment and operation spending for a higher powered laser system.
  • Dye-based laser marking formulations can avoid the above disadvantages, and offer better marking quality with much higher contrast, even at a much lower laser energy dose.
  • Dye based marking technology developed for conventional contacting thermal printing has been proposed for laser marking applications.
  • JP 2001-246860 discloses the use of a thermal recording material which contains a electron donor-type dye precursor and a urea-urethane-type developer
  • U.S. Patent No. 5413629 discloses a method of preparing a laser markable material by using an ink which contains an electron donor-type electron donor-type dye precursor and an electron acceptor-type developer in the printing process.
  • Another significant disadvantage of dye-based media relying on direct thermal printing technology is its susceptibility towards undesired chemical exposure, especially exposure to acid and base solutions or organic solvents.
  • the coated substrate often requires strong resistance towards various chemical attacks.
  • solvent based flexographic inks are frequently use, or in some cases a solvent-based primary coat on label films is applied to enhance the leveling and ink adhesion to the film.
  • organic solvents in these formulation often cause undesired color, opacity or density changes on above said imaging layer, due to destabilization of the dye-developer system.
  • U.S. Patent No. 5691757 and Japanese patent JP3391000 disclose laser markable compositions using a high melting point developer, above 200°C, combined with inorganic laser absorption substances such as aluminum oxide and mica, to avoid losing marking sensitivity from using high melting point developer. Such combination leads to a very high mark formation threshold temperature, at least in the range of 200-250°C or even higher.
  • One problem of this approach is the risk of decomposition of the polymer media during the high temperature marking process, and releasing of undesired chemical vapor as
  • U.S. Patent No. 5843547 discloses a method to make a multilayered laser markable label, in which at least one layer of transparent protective film material with a transparent adhesive composition is stacked and adhered to the top of a laser markable media, which is composed of a base layer film material on top of which is coated with a polymeric laser markable layer in which is dispersed 0.1% - 10% of colored pigments and inorganic metal salts, such as copper hydroxide phosphate.
  • the laser marking process is applied through the transparent "cover sheet” to form marks in the underneath laser markable media.
  • the top transparent "cover sheet” along with the transparent adhesive composition can be peeled off from the laser markable media after marking.
  • Similar structures are disclosed in U.S. Patent No. 5340628 and Japanese patent 3391000, except that the laser markable layers are both relying on dye-based thermal printing technology instead of inorganic pigments, and in the case of Japanese patent 3391000, as already described above, a high melting point developer is used in conjunction with inorganic laser absorption additives. While the release of decomposed chemical vapor during laser marking can be prevented by the approaches in these prior arts, the disadvantage of the method disclosed in U.S. Patent No.
  • Figures 1-5 are cross-sections of illustrative media of the invention.
  • a first objective of the present invention is to provide a media that can be marked with a laser provide superior mark quality with high contrast, high resolution, and a high degree of quality consistency, and that does not rely on physical damage to the material integrity on the exposed area, such as ablation, charring, or trapping of gaseous bobbles released from chemical decomposition of coating ingredients.
  • a second objective of the present invention is to provide a media that has a balanced performance between good media storage stability or heat resistance and optimum sensitivity to laser exposure.
  • a third objective of the present invention is to provide a laser markable media that have high degree of transparency to satisfy wider range of application needs.
  • another objective of the present invention is to provide laser markable media configurations that do not release decomposed chemical vapors or debris during laser marking process, and that can isolate the mark formation layer from direct exposure to the environment, and therefore the mark formation layer is protected from direct mechanical abrasions or chemical attacks.
  • a further objective of the present invention is to provide a method of using the media.
  • the mark formation layer comprises at least one kind of electron donor dye precursor encapsulated or isolated by a polymer having a T g of from about 120°C to about 190°C, wherein at least about 80% w/w of said dye precursor has a solubility of higher than lOg/lOOg of ethyl acetate and approximately 90% of the total volume of said dye precursor particles have a diameter of from about 0.2 ⁇ m to about 5 ⁇ m
  • the laser markable material is configured in such a way that the said mark formation layer is located behind a protective substrate or coating, through which the laser irradiation will be applied, and the said protective substrate material is significantly transparent to the wavelength of the laser intend to be used and having an on-set pyrolysis temperature of at least 200°C.
  • the composition of the mark formation layer comprises the following key elements: an electron donor dye precursor preferably micro-encapsulated within a polymer of specific T g range, an electron acceptor compound which can react with the electron donor dye precursor to turn it into a dye with a strong absorption in the wavelength range of visible spectrum, and a polymer dispersion media in which both species are dispersed and coated in such way that they are in close proximity of reaction lengths from each other.
  • Electron donor dye precursor preferably micro-encapsulated within a polymer of specific T g range
  • an electron acceptor compound which can react with the electron donor dye precursor to turn it into a dye with a strong absorption in the wavelength range of visible spectrum
  • a polymer dispersion media in which both species are dispersed and coated in such way that they are in close proximity of reaction lengths from each other.
  • An electron donor dye precursor that can be preferably used in the present invention is not particularly limited as long as it is substantially colorless, and is preferably a colorless compound that has such a nature that it colors by donating an electron or by accepting a proton from an acid.
  • a particularly preferred structural feature in the backbone of the electron donor dye precursor includes a ring structure which is subjected to ring opening reaction or cleavage in the case where it is in contact with an electron accepting compound. Typical examples of such structural feature are a lactone, a lactam, a saltone, or a spiropyran, among others.
  • the electron donor dye precursor examples include 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, and a pyradine series compound.
  • fluorane series compound examples include the compounds described in U.S. Patent Nos. 3624107, 3627787, 3641011, 3462828, 3681390, 3920510 and 3959571.
  • fluorene series compound examples include the compounds described in Japanese Patent Application No. 61-240989.
  • spiropyran series compound examples include the compounds described in U.S. Patent No. 3971808.
  • pyridine series and pyradine series compounds include the compounds described in U.S. Patent Nos. 3775424, 3853869 and 4246318.
  • the compounds represented by following structural formula (1) are preferable because these can be incorporated into the microcapsules in very high concentration and hence can provide high mark density.
  • Rl and R2 are each independently selected from hydrogen, C]-C 8 alkyl, unsubstituted or C 1 -C 4 alkyl- or halogen-substituted C 4 -C 7 cycloalkyl, unsubstituted phenyl or C 1 -C 4 alkyl-, hydroxyl- or halogen-substituted phenyl, C 3 -C 6 alkenyl, Ci- C 4 alkoxy, phenyl-Ci-C 4 alkyl, Ci-C 4 alkoxy-Ci-C 4 alkyl and 2-tetrahydrofuranyl, or Rl and R2 together with the linking nitrogen atom are an unsubstituted or Ci-C 4 alkyl-substituted pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino ring.
  • phthalide series compound examples include the compounds described in U.S. Patent Nos. Re. 23024, 3491111, 3491112, 3491116, and 3509174.
  • the compounds represented by following structural formula (2) are most preferable because it can be incorporated into the microcapsules at a very high concentration and can provide high mark density.
  • a preferable embodiment of the present invention is that the solubility of the said electron donor dye precursor is higher than about lOg/lOOg in ethyl acetate, more preferably is higher than about 15 g/100 g in ethyl acetate, and most preferably is higher than about 18 g/100 g in ethyl acetate.
  • a preferable embodiment of the present invention is that more than about 80% by weight of the electron donor dye precursors are compounds represented by structural formula (1) or formula (2), and a more preferable embodiment is that more than about 90% by weight are said compounds and a most preferable embodiment is that about 100% by weight are said compounds.
  • the electron donor dye precursor in the composition of the present invention be used after being formed into a microcapsule, preferably via a surface polymerization process.
  • polymer capsule materials include polyurethane, polyurea, polyamide, polyester, polycarbonate, a urea- formaldehyde resin, a melamine resin, polystyrene, a styrene-methacrylate copolymer and a styrene-acrylate copolymer.
  • 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 emulsif ⁇ cation 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
  • the conditions for the microencapsulation reaction are set so that at least about 90% of the total volume of said electron donor dye precursor particles have an average particle diameter of the microcapsules that are formed of between about 0.3 to about 12 ⁇ m, preferably between about 0.2 ⁇ m and about 5 ⁇ m, and most preferably between about 0.2 ⁇ m and about 2 ⁇ m.
  • the microcapsule material and microencapsulation reaction are also carefully selected and controlled so that the microcapsule wall has a glass-transition temperature, T g , of from about 120°C to about 190°C, preferably from about 150°C to about 180 0 C.
  • the microcapsule wall may further contain, depending on necessity, a metal- containing dye, a charge adjusting agent, and other arbitrary additive substances.
  • additives may be contained in the capsule wall if added before or during wall formation or added at other arbitrary times as required.
  • a monomer such as a vinyl monomer
  • graft-polymerized depending on necessity.
  • a plasticizer that is suitable for the polymer of the chosen wall material.
  • the plasticizer preferably has a melting point of about 12O 0 C or higher.
  • the wall material comprises polyurea or polyurethane
  • a hydroxyl compound, a carbamate compound, an aromatic alkoxy compound, an organic sulfonamide compound, an aliphatic amide compound, and an arylamide compound are preferably used as a plasticizer.
  • the core of the microcapsule can be prepared by dissolving the electron donor dye precursor compound in a hydrophobic organic solvent having a boiling point of preferably from about 100 to about 300 0 C so as to form the oily phase.
  • the solvent 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 ether (such as propyldiphenyl ether), hydrogenated terphenyl (such as hexahydroterphenyl) and diphenylter
  • a low boiling point solvent having high solubility may additionally be used in combination.
  • Preferred examples of the low boiling point solvent include ethyl acetate, isopropyl acetate, butyl acetate, and methylene chloride.
  • water-soluble polymers are added to the aqueous phase of the reaction mixture to form a protective colloid in order to stabilize the emulsified dispersion.
  • the type and addition amount of the water- soluble polymers are selected so that the viscosity of the coating composition of the present invention falls into a range of from about 5 centipoises (cps) to about 30 cps, preferably from about 10 cps to about 25 cps, and most preferably from about 10 cps to about 20 cps. Viscosity is measured using Brookfield Programmable DV-II+ viscometer with S21 small size spindle at 100-200 RPM. Regular RV series spindle may also be used depending on sample quantity.
  • the water-soluble polymer used to form the protective colloid can be appropriately selected from known anionic polymers, nonionic polymers and amphoteric polymers.
  • the water-soluble polymer preferably has a solubility of 5% or more in water at the temperature at which the emulsification is to be conducted.
  • polyvinyl alcohol and a modified product thereof polyacrylic amide and a derivative thereof, an ethylene-vinyl acetate copolymer, a styrene-maleic anhydride copolymer, an ethylene-maleic anhydride copolymer, an isobutylene-maleic anhydride copolymer, polyvinyl pyrrolidone, an ethylene-acrylic acid copolymer, a vinyl acetate-acrylic acid copolymer, a cellulose derivative, such as carboxymethyl cellulose and methyl cellulose, casein, gelatin, a starch derivative, gum arabic and sodium alginate.
  • a surface-active agent may be added into at least one of either the oily phase or the aqueous phase.
  • the addition amount of the surface-active agent is preferably from about 0.1% to about 5%, and more preferably from about 0.5 to about 2%, based on the weight of the oily phase.
  • appropriate selection should be given to those anionic or nonionic surface-active agents that do not cause precipitation or aggregation through interactions with the protective colloid.
  • Such surface-active agent include sodium alkylbenzenesulfonate, sodium alkylsulfate, sodium dioctyl sulfosuccinate and a polyalkylene glycol (such as polyoxyethylene nonylphenyl ether).
  • the electron acceptor compound which reacts with the electron donor dye precursor, may be used singly or in a combination of two or more.
  • the electron acceptor compound include an acidic substance, such as a phenol compound, an organic acid or a metallic salt thereof and an oxybenzoate; specific examples thereof include the compounds described in JP-A-61-291183, the contents of what are incorporated by reference. Among these, a bisphenol compound is preferred from the standpoint of obtaining good coloring characteristics.
  • Compositions of electron acceptor developers are disclosed in U.S. Patent No. 6797318 Example-1 as Developer Emulsion Dispersion, U.S. Patent No. 5409797 Example-1 as Emulsion Dispersion, and U.S. Patent No. 5691757 Example as Color Developer. The contents of the U.S. patents are incorporated by reference.
  • the electron acceptor compound may be used 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 a polymer aqueous solution (aqueous phase) containing a surface-active agent and/or a water-soluble polymer as a protective colloid, followed by emulsification, for example, by a homogenizer.
  • a low boiling point solvent may 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 conducting emulsion dispersion.
  • the emulsion dispersion particle diameter is preferably 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 may be used as a mixture thereof and as a mixture with other 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 preferably has a solubility of about 5% or more in water at a temperature at which the emulsification is to be conducted.
  • polyvinyl alcohol and a modified product thereof include polyacrylic amide and a derivative thereof, an ethylene-vinyl acetate copolymer, a styrene-maleic anhydride copolymer, an ethylene-maleic anhydride copolymer, an isobutylene-maleic anhydride copolymer, polyvinyl pyrrolidone, an ethylene-acrylic acid copolymer, a vinyl acetate-acrylic acid copolymer, a polyurethane, a polyether, a polyether based polyurethane copolymer, a styrene acrylic polymer, a polymer of acrylic or methacrylic acid and their derivative thereof, a polyester or a derivative thereof, a cellulose derivative, such as carboxymethyl cellulose and methyl cellulose, casein, gelatin, a starch derivative, gum arabic and sodium alginate.
  • polyvinyl alcohol, gelatin, and a cellulose derivative are examples thereof.
  • Mixing ratio of the oily phase to the aqueous phase is preferably from 0.02 to 0.6, and more preferably from 0.1 to 0.4 by weight.
  • the mixing ratio is in the range of from 0.02 to 0.6, a suitable viscosity can be maintained, and thus the production adequacy and stability of the coating composition become excellent.
  • the other components in the mark formation layer are not particularly limited and can be appropriately selected depending on necessity, and examples thereof include known laser absorption enhancing additives, melting agents, known
  • UV absorbing agents UV absorbing agents, and known antioxidants.
  • laser absorption enhancing additives should depend on the type of laser used and its emitting wavelength. For example, if a CO 2 laser is used, the emitting wavelength should be in the range of 9.4 ⁇ m to 10.6 ⁇ m, depending on design. In such a case, mica, SiO 2 , Al x O y , CaSiO 3 , kaolin or their mixed salts or oxides may be used as laser absorption enhancing additives. If a YAG laser is used, the emitting wavelength should be about 1.06 ⁇ m. hi such case, oxides or salts of Ti,
  • the addition amount and particle size or morphology should be selected in such way that the addition of these additives does not substantially affect the transparency of the mark formation layer.
  • a melting agent may be contained in the mark formation layer in order to accelerate dye formation reaction.
  • melting agents include an aromatic ether, a thioether, an ester, an aliphatic amide and an ureide. Specific examples thereof are described in JP-A-58-57989, JP-A-58-87094, JP-A-61-58789, JP-A-62- 109681, JP-A-62- 132674, JP-A-63-151478, JP-A-63-235961, JP-A-2-184489 and JP-A-2-215585.
  • UV absorbing agent examples include a benzophenone series, a benzotriazole series, a salicylic acid series, a cyanoacrylate series and an oxalic acid anilide series. Specific examples thereof are described in JP-A-47-10537, JP-A-58-111942, JP-A-58-212844, JP-A-59-19945, JP-A-59-46646, JP-A-59-109055, JP-A-63-53544, JP-B-36-10466, JP-B-42-26187, JP-B-48-30492, JP-B-48-31255, JP-B-48-41572, JP-B-48-54965, JP-B-50- 10726, and U.S.
  • Preferred examples of the antioxidant include a hindered amine series, a hindered phenol series, an aniline series and a quinoline series. Specific examples thereof are described in JP-A-59-155090, JP-A-60- 107383, JP-A-60-107384, JP-A-61-137770, JP-A-61-139481 and JP-A-61-160287.
  • the coating amount of the other components is preferably from about 0.05 to about 1.0 g/m 2 , and more preferably from about 0.1 to about 0.4 g/m 2 .
  • the other components may be added either inside the microcapsules or outside the microcapsules, or in the dispersion of the electron acceptor compounds of the composition of the present invention.
  • the above key components may be mixed uniformly and dispersed within a selected polymer media (binder).
  • the mix ratio of the coating composition of the present invention is such that the ratio of total weight of electron donor dye precursors and that of the electron acceptor compounds is between from about 1:0.5 to about 1:30, preferably from about 1 :1 to about 1:10.
  • the amount of the electron donor dye precursor in the said mark formation layer is preferably in the range of from about 0.1 to 5.0 g/m 2 . hi this range, both a sufficient coloring density can be achieved and the transparency of the laser- sensitive recording layer can also be maintained. More preferably, the amount of the electron donor dye precursor is from about 1.0 to about 4.0 g/m 2 .
  • both the water-soluble polymer used as the protective colloid when preparing for the electron donor dye precursor composition or its microcapsule composition and the water-soluble polymer used as the protective colloid when preparing the electron acceptor dispersion of this invention function as the binder of the mark formation layer. Adding and mixing another binder separately from the above protective colloids is also possible.
  • water soluble polymers are generally used, and examples thereof include polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic salicylic anhydride copolymer, polyacrylic amide, methylol-modified polyacrylamide, casein and gelatin.
  • a water resisting agent may be added thereto, and an emulsion of a hydrophobic polymer, specifically a styrene- butadiene rubber latex, a styrene acrylic polymer, a acrylic or methacrylic series polymer or a copolymer and their derivative thereof, a polyester or a copolymer thereof, may be added thereto.
  • a hydrophobic polymer specifically a styrene- butadiene rubber latex, a styrene acrylic polymer, a acrylic or methacrylic series polymer or a copolymer and their derivative thereof, a polyester or a copolymer thereof
  • the mark formation layer of the present invention may further contain methyl cellulose, carboxymethyl cellulose, carboxyl- modified polyvinyl alcohol, polystyrene or a copolymer thereof, polyether, polyurethane resin or a derivative thereof, polyether based polyurethane copolymer, polyethylene or a copolymer thereof, epoxy resin, polyamide resin, polyvinyl butyral resin or starch compounds.
  • a known coating method suitable for aqueous or organic solvent series coating composition is used.
  • the isolation layer of the laser markable media of the present invention is defined as the medium between the mark formation layer and the laser irradiation source. It can be a supporting sheet on which the mark formation layer is coated, or a coating layer on top of the mark formation layer.
  • the isolation layer and the mark formation layer can be in tight contact through coating or pressure lamination, or in a close proximity through an adhesive layer. In the latter case, the adhesive material should satisfy the same transmittance criteria of the isolation material defined below.
  • This isolation medium are: a) block the releasing of undesired chemical vapor resulting from decomposition of the materials in the mark formation layer during laser marking process, b) protect the mark formation layer from mechanical abrasion as well as chemical attack, including harmful gases in the atmosphere, such as O 2 , O 3 and SO 2 , which tend to accelerate mark fading, background fogging, or yellowing over long period of storage.
  • the isolation material should be substantially transparent to the specified wavelength of the laser selected.
  • the transmittance of the isolation layer is at least about 70% or higher, more preferably about 80% or higher, and most preferably about 90% or higher.
  • Higher transmittance at the specific wavelength of the selected laser ensures minimum attenuation of the delivered laser energy at the mark formation layer, and thus enables a maximum achievable marking speed for at a given laser power.
  • a second benefit of higher transmittance at the specific wavelength of the selected laser is that heat generation within the isolation media, which could induce undesired thermal stress of the material and cause physical distortion, is minimized.
  • the isolation layer material should have an on-set pyrolysis temperature that is well above the mark formation temperature. This will ensure that no decomposition of the isolation material occurs during the marking process, and thus no undesired chemical vapor is released.
  • the T g of the microcapsulation material of the present invention should be controlled within a range such that it is well below the on-set pyrolysis temperature of the isolation material.
  • the electron donor dye precursor and the electron acceptor compound are separated by other dispersing means, either the glass-transition temperature or the melting point of the dispersing or separation media should be chosen to be well below the on-set pyrolysis temperature of the isolation material. In either case, the preferable on-set pyrolysis temperature of the isolation material of the present invention should be at least about 200 0 C, more preferably about 25O 0 C and above.
  • the isolation material of the invention be transparent in the wavelength range of the visible spectrum (about 400-700nm), depending on the application requirements.
  • a transparent isolation material in the wavelength range of visible spectrum is preferred, which will give a visible mark that is protected by the isolation layer from mechanical abrasion as well as chemical attack.
  • Suitable isolation materials include polymer films or coating compositions, examples of which include, but are not limited to, a polyolefin film, such as polypropylene, polyethylene, or biaxially oriented polypropylene (BOPP), a polyester film, such as polyethylene terephthalate or polybutylene terephthalate, a cellulose triacetate film, a polylactide film, a polysulfone film, a polystyrene film, a polyether etherketone film, a polymethylpentene film, a nylon film, and coating compositions based on polyurethane resin or polyurethane copolymer, such as urethane-acrylate copolymer and polyether polyurethane copolymer, polyamide resin, epichlorohydrin-modified polyamide, polyacrylates, poly(meth)acrylates or derivatives thereof, core-shell acrylic latex, polyacrylic amide, styrene acrylic polymer polystyrene or a copo
  • polyolefin films and coating formula based on polyurethane or polyurethane copolymer resins are preferred materials for the isolation layer of the present invention. It is understand that not all of the materials in the above list that are suitable for all the emitting wavelengths of the types of lasers listed in the following section describing laser marking equipment. Support layer
  • the support layer of the laser markable media of the present invention is defined as the substrate layer on which the mark formation layer is coated. In the case that the mark formation layer is coated onto the isolation layer described above, the support layer thus becomes the isolation layer. In other cases, the support layer is behind the mark formation layer, furthest from the direction of the incident laser beam.
  • a transparent support with a wavelength range within the visible spectrum is preferably used in the present invention.
  • the transparent support include, but are not limited to, synthetic polymer materials, examples of which include a polyester film, such as polyethyleneterephthalate or polybutyleneterephthalate, a cellulose triacetate film, a polylactide film, a polysulfone film, a polystyrene film, a polyether etherketone film, a polymethylpentene film, a Nylon film, a polyolefin film, such as polypropylene, polyethylene, or BOPP, and polyacrylates, poly(meth)acrylates, urethane acrylates, polycarbonate, polystyrene, and epoxy which can be used singly or in a combination of two or more by lamination.
  • synthetic polymer materials examples of which include a polyester film, such as polyethyleneterephthalate or polybutyleneterephthalate, a cellulose triacetate film, a polylactide film,
  • the laser-markable material of the present invention may further comprise, on the support, other layers, such as a primer layer, an adhesive layer followed with a releasing liner.
  • the primer layer may be provided on the support before coating the mark formation layer, in order to improve the adhesion of the mark formation layer to the support.
  • an adhesive layer and, if needed, a releasing liner may be coated/laminated on the opposite side of the support from the mark formation layer, to form a laser markable self-adhesive media.
  • an acrylate copolymer polyvinylidene chloride, styrene- butadiene rubber (SBR), or an aqueous polyester
  • the thickness of the layer is preferably from 0.05 to 0.5 ⁇ m.
  • a hardening agent such as a dialdehyde compound, e.g., glutaraldehyde or 2,3-dihydroxy-l,4-dioxane, and boric acid.
  • the addition amount of the hardening agent is appropriately determined depending on the material of the primer layer and selected from the range of from 0.2 to 3.0% by weight corresponding to a desired degree of hardening.
  • the layer preferably also includes 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 media is maintained.
  • the laser-markable media of the present invention can be preferably produced by the process described below, but it is not limited thereto.
  • the production process of a laser-markable media of the present invention includes the steps of: coating the primer layer (if it is used) onto the support, coating a mark formation layer onto the primer layer (if it is used) on the support; and in the case that the support layer is not the isolation layer, coating an isolation layer on top of the mark formation layer, hi the case that the support layer also serves as the isolation layer, the primer layer may optionally be coated on both sides of the support, to facilitate additional printing on the opposite side of the mark formation layer. Depending on necessity, other layers are also formed.
  • the mark formation layer and the isolation layer may be optionally coated simultaneously, and in this case, the coating compositions of the mark formation layer and the isolation layer are subjected to multilayer coating, whereby the mark formation layer and the isolation layer can be simultaneously formed.
  • the technology of multilayer simultaneous coating is particularly suitable, in the case that the mark formation layer is further comprised of separate layers of electron donor dye precursor dispersion and dispersion of electron acceptor compounds.
  • the laser-markable media of the present invention may be coated sequentially with known coating methods, in the following order: the primer layer, the mark formation layer, and the isolation layer. Examples of these coating methods include, but are not limit to, a blade coating method, an air knife coating method, a gravure coating method, a roll coating method, a spray coating method, a dip coating method and a bar coating method.
  • the mark formation layer 1 is sandwiched between the support 2 and the isolation layer 3, which may be coated or laminated onto the mark formation layer.
  • the mark formation layer comprises the electron donor dye precursor 4 encapsulated by capsule wall 5 and the electron acceptor compound 6, both dispersed in a same polymer medium 7 in close proximity of reaction length, but are prevented from direct contact by the capsule wall and the polymer of the media, when the laser markable material is under ambient temperature below the T g of the polymers.
  • the capsule wall expands and opens, which leads to direct contact between the two compounds through migration or diffusion, and the dye precursor is turned into dye. Volatile compounds in the mark formation layer generated during the marking process are kept underneath the isolation layer. The result is that no undesired chemicals are released.
  • the electron donor dye precursor 4 and electron acceptor compound 6 are dispersed and coated into two distinct layers of polymer medium T and 7" (which can be the same or different material) isolated by an optional 3 rd polymer spacing layer 9, having a glass transition temperature T g similar to that of the capsulation wall above, and additional laser absorption enhancing additive 10 may optionally be dispersed into either this spacing layer alone, or also into the electron acceptor layer.
  • polymer medium T and 7 which can be the same or different material
  • additional laser absorption enhancing additive 10 may optionally be dispersed into either this spacing layer alone, or also into the electron acceptor layer.
  • the spacing polymer is melted or softened locally, enabling cross-layer diffusion and a reaction between the electron donor dye precursor and the electron acceptor to form marks 11.
  • the laser markable media has the same configuration as in Figure 1.
  • this support layer 12 now becomes an isolation layer
  • the isolation layer 13 is substantially transparent in the wavelength range of visible spectrum, and thus the marks formed in the mark formation layer 1 become visible from the back side.
  • an adhesive layer (not shown) may be coated on the other side of the support / isolation layer 12, which, of necessity, must also be substantially transparent to the wavelength of the laser beam.
  • both isolation layers 14 and 15 are substantially transparent in the wavelength range of visible spectrum.
  • the isolation layer 14 is also substantially transparent to laser beam 8' with emission wavelength ⁇ (l)
  • the isolation layer 15 is also substantially transparent to laser beam 8" with emission wavelength ⁇ (2), where ⁇ (l) and ⁇ (2) may or may not be the same and the two isolation layers may or may not be significantly transparent to both ⁇ (l) and ⁇ (2), if they are different.
  • the two isolation layer may also be both rigid or flexible or one rigid one flexible, made from different materials.
  • the encapsulated electron donor dye precursor 4 and the electron acceptor compound are located in polymer medium 7 of the mark formation layer 1 which further includes particles of laser absorption additive 16.
  • the marks may be formed by marking beams of the same or different frequencies from both sides.
  • the formed marks in this embodiment are therefore resistant to chemical attacks and mechanical abrasions from both sides, hi addition, since the marking beam energy is absorbed only in the mark formation layer, which is sandwiched between two isolation layers, thus there is no release of decomposed chemicals or vaporized ingredients into the atmosphere during the marking process.
  • the mark formation layer 1 also serves as an adhesive layer on isolation layer/support 16. Both the encapsulated electron donor dye precursor 4 and the electron acceptor compound 6 are dispersed in an adhesive medium 17.
  • the laser markable media of this embodiment may be adhered onto a product packaging surface, and then marked with a laser beam 8, or the reverse.
  • the laser markable media of the present invention may be marked with a CO 2 laser, a YAG laser, a solid laser such as a ruby laser, or a diode laser such as, but not limited to, InGaAsP and GaAs.
  • a 5-20W CW CO 2 laser in the emitting wavelength range of 9.4-10.6 ⁇ m is preferred.
  • a preferred laser marking system is one in which a Galvonometer beam steering technology that allows computer to control the beam with one or more rotating mirrors in X or X/Y-axes is used. Both Vector and Raster scanning schemes may be used depending on the application.
  • the combination of laser beam quality, f- ⁇ lens quality, and focal distance will allow the marking spot- size at the focal plane to be below about 300 micron, more preferably to be below about 100 micron.
  • the above dispersion (A) and dispersion (B) were mixed as follows.
  • the above coating composition was coated onto a 175 ⁇ m thick A4 size transparent PET film at ⁇ 10 ⁇ m coating thickness with a bar coater, followed with about 3 minutes drying at 6O 0 C.
  • the PET film had been preliminarily coated with SBR latex and gelatin mixture as primer.

Abstract

L'invention concerne un milieu, marquable au laser, capable de fournir une qualité de marque supérieure, à haut contraste, haute résolution et à haut degré de consistance de la qualité, et ne dépendant pas d'endommagements physiques occasionnés à l'intégrité du matériau sur la zone exposée. Le milieu marquable au laser fournit en outre une performance équilibrée entre une bonne stabilité au stockage du milieu, une résistance à chaud et une sensibilité optimale à l'exposition au laser. L'invention concerne en outre un milieu marquable au laser, présentant un haut degré de transparence pour correspondre à un éventail d'exigences d'application bien plus large que celui existant dans l'état de la technique. L'invention concerne en outre un procédé d'utilisation des milieux précités.
PCT/US2005/040202 2004-11-05 2005-11-07 Milieux fournissant une formation sans contact de marques a haut contraste, et procede d'utilisation correspondant WO2006052843A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62512204P 2004-11-05 2004-11-05
US60/625,122 2004-11-05

Publications (3)

Publication Number Publication Date
WO2006052843A2 true WO2006052843A2 (fr) 2006-05-18
WO2006052843A9 WO2006052843A9 (fr) 2006-08-31
WO2006052843A3 WO2006052843A3 (fr) 2007-02-01

Family

ID=36337083

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/040202 WO2006052843A2 (fr) 2004-11-05 2005-11-07 Milieux fournissant une formation sans contact de marques a haut contraste, et procede d'utilisation correspondant

Country Status (1)

Country Link
WO (1) WO2006052843A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP2064069A1 (fr) * 2006-03-31 2009-06-03 Fuji Hunt Photographic Chemicals, Inc. Composition de revetement pour former un materiau marquable au laser et ce meme materiau
US9982157B2 (en) 2008-10-27 2018-05-29 Datalase Ltd. Aqueous laser-sensitive composition for marking substrates
EP3327088A1 (fr) 2016-11-28 2018-05-30 Agfa-Gevaert Nv Procédé de marquage laser polychrome

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8865620B2 (en) 2007-03-15 2014-10-21 Datalase, Ltd. Heat-sensitive coating compositions based on resorcinyl triazine derivatives
ATE538185T1 (de) 2007-08-22 2012-01-15 Datalase Ltd Laserempfindliche beschichtungszusammensetzung
CN101896669A (zh) 2007-11-07 2010-11-24 巴斯夫欧洲公司 新纤维产品

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525571A (en) * 1994-09-14 1996-06-11 Fuji Photo Film Co., Ltd. Heat-sensitive recording material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525571A (en) * 1994-09-14 1996-06-11 Fuji Photo Film Co., Ltd. Heat-sensitive recording material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2064069A1 (fr) * 2006-03-31 2009-06-03 Fuji Hunt Photographic Chemicals, Inc. Composition de revetement pour former un materiau marquable au laser et ce meme materiau
EP2064069A4 (fr) * 2006-03-31 2010-02-17 Fuji Hunt Photo Chem Composition de revetement pour former un materiau marquable au laser et ce meme materiau
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
US9982157B2 (en) 2008-10-27 2018-05-29 Datalase Ltd. Aqueous laser-sensitive composition for marking substrates
EP3327088A1 (fr) 2016-11-28 2018-05-30 Agfa-Gevaert Nv Procédé de marquage laser polychrome
WO2018096096A1 (fr) 2016-11-28 2018-05-31 Agfa-Gevaert N.V. Procédé de marquage au laser multicolore

Also Published As

Publication number Publication date
WO2006052843A3 (fr) 2007-02-01
WO2006052843A9 (fr) 2006-08-31

Similar Documents

Publication Publication Date Title
US20070098900A1 (en) 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
EP0637514B1 (fr) Méthode de marquage à laser et utilisation d'une composition comme composition pour marquage à laser
JP4329744B2 (ja) 記録材および記録方法
EP0659583B1 (fr) Méthode pour marquage par laser et composition aqueuse pour enregistrement par laser
EP0754564B1 (fr) Matériau d'enregistrement sensible à la chaleur et méthode d'enregistrement.
JP4338702B2 (ja) 像形成性コーティングにおける遷移金属化合物の使用
JP2751089B2 (ja) レーザーマーキング方法及び印刷インキ
JP5971295B2 (ja) 熱可逆記録媒体及びそれを用いた画像処理方法
WO2006052843A2 (fr) Milieux fournissant une formation sans contact de marques a haut contraste, et procede d'utilisation correspondant
JP3766468B2 (ja) レーザ印字用媒体
WO2006030654A1 (fr) Materiau d'enregistrement et procede d'enregistrement
CN108290434A (zh) 可激光标记的组合物和用其制造包装的方法
EP2067074B1 (fr) Compositions destinées à la formation d'un revêtement marquable par laser et matériau marquable par laser contenant des additifs organiques favorisant l'absorption
US5888283A (en) High solids direct thermal ink composition and method of making and using same
EP1827859B1 (fr) Composition servant a former un revetement pouvant etre marque au laser, et procede de formation d'un marquage par exposition a un laser
EP1677990B1 (fr) Perfectionnements relatifs a du papier thermique
WO2013109268A1 (fr) Composition de revêtement chimique pour former une matière pouvant être marquée par laser et matière pouvant être marquée par laser
US8415270B2 (en) Heat sensitive recording material comprising a protective layer
JP2007182020A (ja) 感熱記録用ラベル
JPH10250228A (ja) 偽造防止シート及び偽造防止粘着ラベル
JP3465766B2 (ja) レーザー感熱記録用インキ組成物
JP3526491B2 (ja) レーザー感熱記録用インキ組成物
JP2004045549A (ja) 可逆性感熱記録材料への加筆方法と消去方法
JPH0796673A (ja) レーザーマーキング方法
US20210323333A1 (en) Imaging medium

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 05825573

Country of ref document: EP

Kind code of ref document: A2