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WO2014091949A1 - Encre pour marquage par laser - Google Patents

Encre pour marquage par laser Download PDF

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Publication number
WO2014091949A1
WO2014091949A1 PCT/JP2013/082238 JP2013082238W WO2014091949A1 WO 2014091949 A1 WO2014091949 A1 WO 2014091949A1 JP 2013082238 W JP2013082238 W JP 2013082238W WO 2014091949 A1 WO2014091949 A1 WO 2014091949A1
Authority
WO
WIPO (PCT)
Prior art keywords
laser marking
ink
laser
resin
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/082238
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English (en)
Japanese (ja)
Inventor
達郎 的田
鈴木　滋
明 石河
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tomatec Co Ltd
Original Assignee
Tokan Material Technology Co Ltd
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 Tokan Material Technology Co Ltd filed Critical Tokan Material Technology Co Ltd
Priority to JP2014551977A priority Critical patent/JPWO2014091949A1/ja
Publication of WO2014091949A1 publication Critical patent/WO2014091949A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • 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
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B41M5/282—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using thermochromic compounds
    • B41M5/283—Inorganic thermochromic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring

Definitions

  • the present invention relates to an ink for marking by laser irradiation, and more particularly to an ink containing a molybdenum-containing composite oxide that changes its color tone to a black color when irradiated with a CO 2 laser.
  • the marking of characters on electrical / electronic components, etc. is a method of fixing by heating or ultraviolet irradiation after attaching normal ink to the electronic component body in any shape by printing, transferring, printing, etc. It was done.
  • printing may be lost due to friction or the like, marking on fine characters or curved surfaces is difficult, and maintenance for maintaining ink performance is troublesome. Therefore, a printing method that does not use ink is being adopted, and one of them is a printing method that uses a laser marker.
  • the laser marker performs printing by irradiating a laser
  • the printing mechanism includes a method of scattering the surface of the irradiated object and a method of printing using a chemical change of the surface of the irradiated object. .
  • Patent Document 1 a composition containing a copper hydroxide monophosphate, molybdenum oxide or titanium dioxide in a thermoplastic resin, copper phosphate, copper sulfate, basic cupric phosphate and A composition containing at least one selected from the group consisting of copper thiocyanate (Patent Document 2), a composition containing ABS resin containing at least two metal oxides (Patent Document 3), a molybdenum compound and a base Composition containing a porous filler (Patent Document 4), a composition containing an inorganic acid copper hydrate in an epoxy resin (Patent Document 5), and a composition containing a carbon black in a thermoplastic resin (Patent Document 5) 6) Laser marking using a composition containing iron oxide (Patent Document 7), a composition containing sodium molybdate or potassium moly
  • Each of the additives for laser marking described in the above-mentioned patent document acts as an absorber of laser light, and not only carbonizes the resin around the additive in the base material, but the additive is black by laser light. It is described that marking is performed by changing to a product.
  • An object of the present invention is to provide an ink for laser marking containing a marking additive that develops or changes color by laser irradiation, and has a markedly high blackness of marked characters and designs.
  • the ink for laser marking according to the present invention is characterized by containing 0.1% to 90% of an additive for laser marking containing an oxide of yttrium and an oxide of molybdenum.
  • This ink changes its color to a color with high blackness when irradiated with a laser. If the content of the additive for laser marking in the ink is too small, a color tone with high blackness cannot be obtained by laser irradiation, and if it is too large, the durability of the formed ink film layer is deteriorated. Absent.
  • the laser marking additive is preferably a composite oxide composed of an oxide of yttrium and an oxide of molybdenum represented by the following general formula.
  • Y x Mo (1-x) O y (Wherein x and y are 0.001 ⁇ x ⁇ 0.5, 1 ⁇ y ⁇ 3.0, preferably 0.005 ⁇ x ⁇ 0.3, 1.5 ⁇ y ⁇ 3.0, More preferably 0.01 ⁇ x ⁇ 0.2, 2 ⁇ y ⁇ 3.0, most preferably 0.04 ⁇ x ⁇ 0.1, 2 ⁇ y ⁇ 3.0.
  • x and y are smaller than the above range, the amount of yttrium dissolved in the molybdenum oxide is small.
  • x and y are larger than the above range, a composite of molybdenum oxide and yttrium oxide is present. As a result, the structure of the obtained composite oxide becomes strong in any case.
  • the ratio of the composite oxide in the ink component is 0.01 to 90% by weight, preferably 1 to 60% by weight.
  • the additive for laser marking is coated on a substrate selected from the group consisting of mica flakes, mica flakes coated with a metal oxide, SiO 2 flakes and glass fillers, or It may be mixed with a substrate.
  • the additive for laser marking can be synthesized using an oxide of an element constituting the additive, or a precursor compound that becomes the oxide by applying heat.
  • a sintering inhibitor, a synthesis auxiliary agent or the like may be added.
  • the synthesis method may be any of a solid phase method, a liquid phase method, and a gas phase method.
  • yttrium source yttrium oxide, yttrium nitrate, yttrium hydroxide and the like are preferably used, and as the molybdenum source, molybdenum trioxide, ammonium molybdate and the like are preferably used.
  • a preferred additive for laser marking is an oxide of an element constituting the additive, or a raw material compound in which a precursor compound that becomes an oxide by applying heat is blended in a predetermined ratio by dry mixing with a pulverizer.
  • the resulting mixture is prepared by firing at a temperature of 300 ° C. or higher, preferably in the range of 600 to 820 ° C.
  • the “predetermined ratio” is, for example, a general formula, Y x Mo (1-x) O y (where x and y are 0.001 ⁇ x ⁇ 0.5, 1 ⁇ y ⁇ 3.0, preferably 0.005 ⁇ x ⁇ 0.3, 1.5 ⁇ y ⁇ 3.0, more preferably 0.01 ⁇ x ⁇ 0.2, 2 ⁇ y ⁇ 3.0, most preferably 0.04 ⁇ x ⁇ 0.1 and 2 ⁇ y ⁇ 3.0.)
  • the ratio of the raw material compounds necessary to obtain the composite oxide represented by:
  • the additive for laser marking is usually used as fine particles having a particle diameter of 0.1 to 10 ⁇ m, preferably 0.5 to 5 ⁇ m.
  • the ink for laser marking according to the present invention may contain inorganic or organic pigments and dyes.
  • the amount of inorganic or organic pigment and dye in the ink is preferably 1 to 30%, more preferably 4 to 15%.
  • inorganic pigments examples include white pigments such as titanium oxide, zinc oxide, antimony oxide, and zinc sulfide; extender pigments such as magnesium oxide and calcium oxide; iron oxide, ultramarine blue, bitumen, carbon black; titanium yellow, cobalt blue, etc. Color pigments such as complex oxide pigments; high luster pigments such as mica pigments coated with bismuth oxychloride, titanium oxide and the like.
  • organic pigments examples include azo, azomethine, methine, anthraquinone, phthalocyanine, perylene, thioindigo, quinacridone, and quinophthalone pigment.
  • the dye examples include anthraquinone series, azo dye metal complexes, and fluorescent dyes such as coumarin, naphthalimide, xanthene, and thiazine.
  • Examples of the resin included in the laser marking ink according to the present invention include urethane resin, acrylic resin, polyacetal resin, polyamide resin, polyimide resin, polyester resin, polyvinyl chloride resin, polyolefin resin, polycarbonate resin, polystyrene resin, polysulfone resin, and the like.
  • Thermosetting resins such as thermoplastic resins, epoxy resins, diallyl phthalate resins, silicone resins, phenol resins, unsaturated polyester resins, melamine resins, urea resins, copolymers thereof, etc. may be used. In view of good adhesion, urethane resin or acrylic resin is preferable.
  • the laser marking ink according to the present invention may contain an organic solvent, a reactive monomer compound and a pigment, and a stabilizer that prevents decomposition and discoloration of the resin.
  • organic solvents include toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, isopropyl acetate, npropyl acetate, nbutyl acetate, isobutyl acetate, methanol, ethanol, npropyl alcohol, isopropyl alcohol, nbutyl alcohol, isobutyl alcohol , Sec-butyl alcohol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether , Ethylene glycol monoethyl ether acetate, etc. It is below.
  • reactive monomer compounds include N-vinylpyrrolidone, dipropylene glycol diacrylate, tripropylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, Glycerol propoxytriacrylate, pentaerythritol triacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, trimethylolpropane trimethacrylate, di (3-methacryloxy-2- Hydroxypropyl ether), bisphenol A di (2 methacrylate) Oxyethyl ether), di-bisphenol A - (3- acryloxy-2-hydroxypropyl ether) and di (2-acryloxyethyl ether of bisphenol A), and the like
  • stabilizer examples include ultraviolet absorbers and antioxidants such as benzophenone, benzotriazole, cyanoacrylate, benzoate, formamidine, hindered amine, aminobenzoic acid, and aminobenzoic acid ester.
  • the ink of the present invention is a base coating solution such as flood coating ink, flexographic / gravure ink, UV curable offset printing ink, and conventional offset printing ink by adding the above organic solvent, reactive monomer compound, stabilizer and the like. It can be used as
  • a sand mill, a bead mill, an attritor or the like can be used for dispersing the complex oxide. All components may be mixed and then dispersed, but the pigment may be dispersed in advance using a known disperser such as a dissolver, homomixer, ball mill, cocoon roll mill, stone mill, or ultrasonic disperser. good.
  • a known disperser such as a dissolver, homomixer, ball mill, cocoon roll mill, stone mill, or ultrasonic disperser. good.
  • surface treatment may be applied to improve the dispersibility of the composite oxide.
  • a dispersant In dispersing the composite oxide in the ink, a dispersant, a surface treatment agent, a sensitizer for improving laser characteristics, and the like may be added.
  • known additives such as a light stabilizer, a flame retardant, glass fiber, an antistatic agent, and an electromagnetic wave shielding additive may be used in combination depending on the application.
  • the present invention provides a laser marking printed matter obtained by coating the above-described laser marking ink on at least one surface of a substrate, an ink film layer made of the laser marking ink provided on the substrate, A laser marking multi-layer body comprising a transparent surface protective layer provided on an ink film layer, and further, a laser marking product obtained by applying a marking to the laser marking printed matter or the laser marking multi-layer body by laser irradiation. Also provide.
  • the substrate may be made of a plastic film, paper, metal foil, glass, ceramic, wood, or the like.
  • the type of the synthetic resin constituting the plastic film is not particularly limited, and may be a thermoplastic resin, a thermosetting resin, or a UV / EB curable resin.
  • thermoplastic resins include polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene, polyacryl methacrylate, polyamide, nylon, polyacetal, polycarbonate, polybutylene terephthalate, polyethylene Examples thereof include terephthalate, polyphenylene sulfide, polysulfone, polyimide, polyamide, a mixture thereof, and a copolymer based on these.
  • thermosetting resins include phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, thermosetting polyimides, and mixtures thereof.
  • the thickness of the plastic film is not particularly limited. For example, it is preferably 12 to 40 ⁇ m for PET and 20 to 50 ⁇ m for OPP.
  • paper art paper, coated paper, high-quality paper, Japanese paper, synthetic paper, etc. can be used.
  • aluminum foil one having a thickness suitable for printing, for example, one having a thickness of 5 to 150 ⁇ m can be used.
  • the shape and size of the substrate may be arbitrary. Examples thereof include members, containers, packages, electronic parts, cards, and coating compositions.
  • the thickness of the transparent surface protective layer constituting the multilayer body for laser marking is not particularly limited, but is preferably 1 ⁇ m or more, particularly preferably 10 ⁇ m or more.
  • the surface protective layer is usually formed by a method of applying and drying a coating liquid to be a surface protective layer on an ink film layer made of laser marking ink.
  • the surface protective layer is formed on the ink film layer.
  • the coating solution is applied, dried, and then formed by curing by ultraviolet irradiation or the like, or the film to be the surface protective layer is bonded directly or via an adhesive layer on the ink film layer.
  • a binder resin of the coating liquid for example, water-soluble cellulose, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, polyacrylic acid, casein, Gelatin, styrene / maleic anhydride copolymer salt, isobutylene / maleic anhydride copolymer salt, polyacrylic acid ester, polyurethane resin, acrylic / styrene resin and the like can be mentioned.
  • water-soluble cellulose for example, water-soluble cellulose, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, polyacrylic acid, casein, Gelatin, styrene / maleic anhydride copolymer salt, isobutylene / maleic anhydride copolymer salt, polyacrylic acid ester, polyurethane resin, acrylic / styrene resin and the like can be mentioned.
  • Solvent type resins include styrene / maleic acid, acrylic / styrene resin, polystyrene, polyester, polycarbonate, epoxy resin, polyurethane resin, polybutyral resin, polyacrylate ester, styrene / butadiene copolymer, styrene / butadiene / acrylic acid copolymer Examples include polymers and polyvinyl acetate.
  • a curing agent can be used in combination for the purpose of improving the film strength, heat resistance, water resistance, solvent resistance and the like of the surface protective layer.
  • a monomer having one or more ethylenically unsaturated bonds, a prepolymer oligomer, or the like is used.
  • monomers that can be used in the present invention include N-vinylpyrrolidone, acrylonitrile, styrene, acrylamide, 2-ethylhexyl acrylate, 2-hydroxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl.
  • Tetrafunctional monomers such as trifunctional monomers, pentaerythritol polypropoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Other 5 dipentaerythritol penta (meth) acrylate as a functional or more monomers, dipentaerythritol hexa (meth) acrylate.
  • monomers, prepolymers and oligomers are used as the radiation curable composition, it is preferable to use the trifunctional or higher functional monomers, prepolymers and oligomers within 20 to 95% by weight.
  • the film density and film strength of the surface protective layer are low, and the smoothness of the printed surface may be lowered in some cases, and the physical properties such as water resistance, oil resistance, and wear resistance will also be reduced.
  • the surface protective layer becomes too hard, and when the printed matter is bent, the surface protective layer is easily peeled off.
  • a photopolymerization initiator and, if necessary, a sensitizer are required.
  • photopolymerization initiators acetophenone, benzophenone, thioxanthone, benzoin, benzoin methyl ether, etc.
  • Amine compounds such as tri-n-butylphosphine, Michler's ketone and the like can be used.
  • curing can be performed without using the above-mentioned photopolymerization initiator, sensitizer and the like.
  • the film When a film is used for the surface protective layer, the film is directly laminated on the surface protective layer, or a laminated film obtained by previously laminating the film and the adhesive layer is bonded to the ink film layer.
  • the present invention further provides a laser marking product obtained by marking a multilayer body for laser marking by irradiating a laser.
  • the laser may be a CO 2 laser, a YAG laser, or a YVO 4 laser, and the wavelength may be 532 to 10600 nm.
  • a CO 2 laser whose wavelength center is 10600 nm is preferable.
  • the laser irradiation conditions are appropriately selected depending on the printing method, printing conditions, the type of substrate, and the like.
  • the laser marking ink according to the present invention usually takes a form dissolved in an organic solvent.
  • organic solvent known solvents used for printing can be used, and examples thereof include ethanol, isopropyl alcohol, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, 1-methoxy-2-propanol, toluene, xylene and the like.
  • an ink for laser marking that has excellent color-changing ability due to laser irradiation and has markedly high blackness of marked characters and designs.
  • Synthesis example 1 91.9 g of molybdenum trioxide and 8.1 g of yttrium oxide were dry mixed with a Henschel mixer. The mixture was packed in a crucible and placed in an electric furnace and baked at 600 ° C. for 6 hours. The obtained fired product was pulverized in an automatic mortar for 3 hours to obtain a white composite oxide for laser marking having an average particle diameter of 1 to 2 ⁇ m.
  • Synthesis example 2 91.9 g of molybdenum trioxide and 17.1 g of yttrium oxide were dry mixed with a Henschel mixer. The mixture was packed in a crucible and placed in an electric furnace and baked at 600 ° C. for 6 hours. The obtained fired product was pulverized in an automatic mortar for 3 hours to obtain a white composite oxide for laser marking having an average particle diameter of 1 to 2 ⁇ m.
  • Synthesis example 3 91.9 g of molybdenum trioxide and 29.0 g of yttrium oxide were dry mixed with a Henschel mixer. The mixture was packed in a crucible and placed in an electric furnace and baked at 600 ° C. for 6 hours. The obtained fired product was pulverized in an automatic mortar for 3 hours to obtain a white composite oxide for laser marking having an average particle diameter of 1 to 2 ⁇ m.
  • Synthesis example 4 67.5 g of molybdenum trioxide, 12.5 g of yttrium oxide, and 20.0 g of mica were dry mixed with a Henschel mixer. The mixture was packed in a crucible and placed in an electric furnace and baked at 600 ° C. for 6 hours. The obtained fired product was pulverized in an automatic mortar for 3 hours to obtain a white composite oxide for laser marking having an average particle diameter of 1 to 2 ⁇ m.
  • Synthesis example 5 91.9 g of molybdenum trioxide and 72.0 g of yttrium oxide were dry-mixed with a Henschel mixer. The mixture was packed in a crucible and placed in an electric furnace and baked at 600 ° C. for 6 hours. The obtained fired product was pulverized in an automatic mortar for 3 hours to obtain a white composite oxide for laser marking having an average particle diameter of 1 to 2 ⁇ m.
  • Example 1 Using the composite oxide obtained in Synthesis Example 1, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • a CO 2 laser having a wavelength center of 10600 nm (3Axis CO 2 laser marker ML-Z9500 / 9510 manufactured by Keyence Corporation) was irradiated to discolor the ink film layer.
  • the laser irradiation conditions were a laser output of 10% and a scanning speed of 1000 mm / second.
  • the discolored portion was measured with a spectrophotometer (Daiichi Seika Kogyo Co., Ltd., Karakom C) and evaluated according to the following criteria.
  • Examples 2-4 Using the composite oxides of Synthesis Examples 2 to 4, an ink film layer having a thickness of 4 ⁇ m was prepared in the same manner as in Example 1, and the laser marking characteristics were evaluated. The evaluation results are shown in Table 1.
  • Example 5 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • Example 6 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • Example 7 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • Example 8 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • Example 9 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • Example 10 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • Example 11 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • Example 12 Using the composite oxide obtained in Synthesis Example 2, the following compounding ingredients were placed in a container, glass beads were added, and the mixture was dispersed for 120 minutes with a paint conditioner to prepare an acrylic ink.
  • Example 13-15 Using the ink prepared in Example 2, an ink film layer was formed on the substrate described in Table 1 in the same manner as in Example 1, and the laser marking characteristics were evaluated. The evaluation results are shown in Table 1.
  • Example 16 A lithographic ink varnish (SOV322 manufactured by Showa Varnish Co., Ltd.) was exhibited as a protective layer on the upper surface of the ink film layer prepared in Example 2 with a bar coater (RD S Laboratory Coating Rod, ROD No. 3). Colored and dried at 100 ° C. In this manner, a multilayer body was prepared, and laser marking characteristics were evaluated in the same manner as in Example 1. The laser irradiation conditions were a laser output of 20% and a scanning speed of 1000 mm / second. The evaluation results are shown in Table 1.
  • Examples 17-19 A lithographic ink varnish (SOV322 manufactured by Showa Varnish Co., Ltd.) was applied to the bar coater (RDS Laboratory Coating Rod, ROD No. 3) as a protective layer on the upper surface of the ink film layer prepared in Examples 13 to 15. And then dried at 100 ° C. Thus, the multilayer body was created on the base material of Table 1, and the laser marking characteristic was evaluated. The laser irradiation conditions were a laser output of 20% and a scanning speed of 1000 mm / second. The evaluation results are shown in Table 1.
  • Example 20 Using the composite oxide obtained in Synthesis Example 2, the following compounding ingredients were put in a container, glass beads were added, and dispersed for 20 minutes with a paint conditioner to prepare a urethane-based ink.
  • an adhesive obtained by diluting 25 parts by weight of polyurethane dry laminate adhesive (trade name: Takelac A-315 / Takenate A-50, manufactured by Mitsui Chemicals) with 75 parts by weight of ethyl acetate is a bar coder.
  • the laminate film was sandwiched with a simple dry laminator (manufactured by Rikua Co., Ltd.) to produce a laminated multilayer body, and the laser marking characteristics were evaluated.
  • the laser irradiation conditions were a laser output of 30% and a scanning speed of 2000 mm / sec. The evaluation results are shown in Table 1.
  • Example 21-22 Using the ink prepared in Example 20, an ink film layer was formed on the base material described in Table 1 by the same method as in Example 20 to obtain a laminated multilayer body.
  • Example 23 Using the composite oxide obtained in Synthesis Example 2, the following blending components were placed in a container, glass beads were added, and the mixture was dispersed with a paint conditioner for 120 minutes to prepare a urethane-based ink.
  • the laser marking characteristics of the obtained printed film were evaluated.
  • the laser irradiation conditions were a laser output of 20% and a scanning speed of 2000 mm / second.
  • the evaluation results are shown in Table 1.
  • Example 24 A two-component polyurethane adhesive was applied on the printing surface of the gravure printing film prepared in Example 23 to a thickness of 3 ⁇ m, and a laminate film was obtained by superimposing a 60 ⁇ m polyethylene film with a commercially available laminator. Laser marking characteristics were evaluated. The laser irradiation conditions were a laser output of 20% and a scanning speed of 2000 mm / second. The evaluation results are shown in Table 1.
  • Example 25 Using the composite oxide obtained in Synthesis Example 2, a rosin-modified phenolic resin-based printing ink was prepared by passing the following blending components three times with three rolls.
  • Rosin-modified phenolic resin 46.0 parts Pigment dispersant (DiSPERBYK-180) 1.0 part Composite oxide (Synthesis example 2) 50.0 parts Cobalt naphthenate 0.50 parts Manganese naphthenate 0.50 parts Ultraviolet absorber ( TINUVIN 111FDL) 2.0 parts
  • RI tester simple offset printing machine
  • Example 26 On the offset printed matter produced in Example 25, an aqueous varnish was applied to a thickness of 3 ⁇ m with a roll coater, and the laser marking characteristics were evaluated.
  • the laser irradiation conditions were a laser output of 20% and a scanning speed of 2000 mm / second. The evaluation results are shown in Table 1.
  • Comparative Example 1 An ink film layer was prepared in the same manner as in Example 1 using the composite oxide of Synthesis Example 5 instead of the composite oxide of Synthesis Example 1, and the laser marking characteristics were evaluated. The evaluation results are shown in Table 1.
  • Table 1 shows preparation compositions (molar ratios) and parts by weight of composite oxides (Synthesis Examples 1 to 5) used in Examples 1 to 26 and Comparative Example 1, presence / absence of coloring pigment, type of substrate, protective layer The presence or absence of resin and the resin colorability are described.
  • Resin colorability Degree of coloration of the resin when the ink film layer was created (standard was white) ⁇ Very darkly colored white, ⁇ deeply colored white, ⁇ Lightly colored white, ⁇ Almost white
  • Synthesis Examples 1 to 4 used in Examples 1 to 22 described in Table 1 are compounds having the general formula Y x Mo (1-x) O y as a composite oxide composed of an oxide of yttrium and an oxide of molybdenum. (Wherein x and y are values having a relationship of 0.001 ⁇ x ⁇ 0.5 and 1 ⁇ y ⁇ 3.0, respectively). It can be seen that the ink film layers obtained in Examples 1 to 6 have excellent laser marking characteristics with a CO 2 laser. In addition, from the results of Examples 1 to 15, the obtained ink film layer has excellent laser marking characteristics with a CO 2 laser regardless of whether the substrate is art paper, PET film, aluminum foil, or glass. ing.
  • Comparative Examples 2-7 An ink film layer is prepared in the same manner as in Example 1 using copper carbonate, which is a known additive for laser marking, or a molybdenum compound that is not a composite oxide, instead of the composite oxide of Synthesis Example 1, and a laser. The marking characteristics were evaluated. The evaluation results are shown in Table 2.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Laser Beam Processing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

La présente invention concerne une encre pour marquage par laser, contenant un additif de marquage qui développe une couleur ou change de couleur lorsqu'il est irradié par un laser, où l'encre confère un contraste supérieur de façon exceptionnelle à des textes et des éléments graphiques marqués. La présente invention est une encre pour un marquage par laser, contenant 0,1 %-90 % d'un additif de marquage qui comprend un oxyde d'yttrium et un oxyde de molybdène, et de préférence une encre pour un marquage par laser dans lequel l'additif de marquage est un oxyde complexe représenté par YxMo(1-x)Oy (formule dans laquelle x et y représentent respectivement des valeurs ayant les relations 0,001 < x < 0,5, 1 < y < 3).
PCT/JP2013/082238 2012-12-13 2013-11-29 Encre pour marquage par laser Ceased WO2014091949A1 (fr)

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JP2017075222A (ja) * 2015-10-14 2017-04-20 Ｄｉｃグラフィックス株式会社 紫外線硬化型レーザーマーキング用オフセットインキ組成物
WO2018101123A1 (fr) * 2016-12-01 2018-06-07 Ｄｉｃグラフィックス株式会社 Composition d'encre de marquage laser
JP2018193514A (ja) * 2017-05-22 2018-12-06 株式会社サクラクレパス プラズマ処理検知用組成物及びそれを用いたプラズマ処理検知インジケータ
JP2019172761A (ja) * 2018-03-27 2019-10-10 日本カーバイド工業株式会社 赤外線レーザ照射用樹脂組成物及び赤外線レーザ照射用樹脂フィルム
JP2020185614A (ja) * 2020-08-21 2020-11-19 三信化工株式会社 レーザーマーキングされた樹脂製成形体およびその製造方法
US12204119B2 (en) 2019-08-06 2025-01-21 3M Innovative Properties Company Optical films and methods of manufacturing such optical films

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JP2007517953A (ja) * 2004-01-14 2007-07-05 データレイズ・リミテッド レーザ画像形成
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JP2012131885A (ja) * 2010-12-21 2012-07-12 Tokyo Printing Ink Mfg Co Ltd レーザー記録用インキ組成物、記録用積層体および記録体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017075222A (ja) * 2015-10-14 2017-04-20 Ｄｉｃグラフィックス株式会社 紫外線硬化型レーザーマーキング用オフセットインキ組成物
WO2018101123A1 (fr) * 2016-12-01 2018-06-07 Ｄｉｃグラフィックス株式会社 Composition d'encre de marquage laser
JPWO2018101123A1 (ja) * 2016-12-01 2018-11-29 Ｄｉｃグラフィックス株式会社 レーザーマーキング用インキ組成物
JP2018193514A (ja) * 2017-05-22 2018-12-06 株式会社サクラクレパス プラズマ処理検知用組成物及びそれを用いたプラズマ処理検知インジケータ
JP2019172761A (ja) * 2018-03-27 2019-10-10 日本カーバイド工業株式会社 赤外線レーザ照射用樹脂組成物及び赤外線レーザ照射用樹脂フィルム
US12204119B2 (en) 2019-08-06 2025-01-21 3M Innovative Properties Company Optical films and methods of manufacturing such optical films
JP2020185614A (ja) * 2020-08-21 2020-11-19 三信化工株式会社 レーザーマーキングされた樹脂製成形体およびその製造方法
JP6997475B2 (ja) 2020-08-21 2022-01-17 三信化工株式会社 レーザーマーキングされた樹脂製成形体およびその製造方法

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