WO2008026373A1 - Procédés d'impression sur une résine moulée et résines thermoplastiques moulées - Google Patents

Procédés d'impression sur une résine moulée et résines thermoplastiques moulées Download PDF

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Publication number
WO2008026373A1
WO2008026373A1 PCT/JP2007/063161 JP2007063161W WO2008026373A1 WO 2008026373 A1 WO2008026373 A1 WO 2008026373A1 JP 2007063161 W JP2007063161 W JP 2007063161W WO 2008026373 A1 WO2008026373 A1 WO 2008026373A1
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WIPO (PCT)
Prior art keywords
carbon dioxide
printing
laser
impregnated
nitrogen
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PCT/JP2007/063161
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English (en)
Japanese (ja)
Inventor
Haruo Shikuma
Masayuki Yamamoto
Naoto Kubo
Masahiro Oshima
Original Assignee
Japan Science And Technology Agency
Shiga Industrial Support Center
Shinsei Kagaku Co., Ltd.
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Application filed by Japan Science And Technology Agency, Shiga Industrial Support Center, Shinsei Kagaku Co., Ltd. filed Critical Japan Science And Technology Agency
Priority to JP2008531984A priority Critical patent/JP4327240B2/ja
Publication of WO2008026373A1 publication Critical patent/WO2008026373A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser

Definitions

  • the present invention relates to a method for performing clear printing on a resin molded product by laser irradiation, and a thermoplastic resin molded product obtained by the method.
  • the laser irradiation technique can be expected to be applied as a technique replacing ink printing due to the progress of the laser irradiation apparatus.
  • Laser marking is the ability to alter or remove the base material by irradiating only the necessary part of the base material surface with laser light and heating, or irradiating the coating film coated on the base material surface with the laser. In most cases, the marking is performed by removing the substrate and applying a contrast between the laser-irradiated part (marking part) and the non-irradiated part (background part) of the substrate.
  • laser decoration that irradiates a molded product with a laser to produce full-color color has also been put into practical use.
  • Patent Document 1 marking is performed by irradiating the surface of a molded article formed of a thermoplastic resin composition containing carbon black and an organic pigment dye which is not easily affected by laser light with laser light. A method is disclosed.
  • Patent Document 2 discloses a laser marking method for irradiating a molded product made of a thermoplastic rosin composition containing fine feldspar with laser light.
  • Patent Document 3 discloses a photosensitive layer made of a composition containing styrene (meth) acrylic acid-based thermoplastic resin particles, a substance that generates heat by absorbing light, and the like on a support surface having a hydrophilic surface.
  • An image forming method is disclosed in which a lithographic printing plate precursor is irradiated with laser light and then developed.
  • Patent Document 4 discloses a thermoplastic resin composition for laser marking containing a PC resin, an acrylic resin, a phosphoric ester compound, and a black substance that disappears or discolors by one laser beam.
  • Patent Document 5 carbon dioxide is absorbed after a sheet of amorphous thermoplastic resin is sorbed with carbon dioxide under conditions of a pressure of 1 to 40 MPa and a temperature of 50 ° C or lower.
  • a method for producing a resin molded body for molding a worn sheet-like product is disclosed.
  • Patent Document 6 discloses a foam injection molded article obtained by impregnating a resin with a supercritical inert fluid (carbon dioxide and Z or nitrogen gas) as a foaming agent and injection molding.
  • a supercritical inert fluid carbon dioxide and Z or nitrogen gas
  • Patent Document 7 discloses a method for producing a resin foam in which a supercritical fluid is impregnated with a thermoplastic resin powder in a pressure vessel, and then injected into a molding machine to be molded and foamed. Is disclosed.
  • Patent Document 1 Japanese Patent Laid-Open No. 6-297828
  • Patent Document 2 Japanese Patent Laid-Open No. 10-297095
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2003-167330
  • Patent Document 4 JP 2006-83241
  • Patent Document 5 JP 2006-7657
  • Patent Document 6 Japanese Patent Laid-Open No. 2003-103556
  • Patent Document 7 Japanese Patent Laid-Open No. 2003-261707
  • an object of the present invention is to provide a method for performing clear printing on a resin molded product by laser irradiation, and a thermoplastic resin molded product obtained by the method. .
  • the present inventors solved the above-mentioned problem by irradiating a thermoplastic resin molded body with carbon dioxide and Z or nitrogen and then irradiating with a laser. I found that I could do it.
  • the present invention provides the following (1) to (4).
  • a method for printing on a resin molded article comprising impregnating a thermoplastic resin molded article with carbon dioxide and Z or nitrogen and then irradiating a laser.
  • thermoplastic resin molded article obtained by printing on a surface of a thermoplastic resin molded article impregnated with carbon dioxide and Z or nitrogen by foaming by laser irradiation.
  • thermoplastic resin molding characterized by the above.
  • thermoplastic resin regardless of whether the thermoplastic resin is transparent or opaque, it can be printed clearly and vividly with high contrast by laser irradiation, and the obtained print is hard to disappear! Therefore, it is extremely excellent in practical use.
  • FIG. 1 shows a print obtained by laser irradiation of a diacid-sodium carbon impregnated color acrylic plate (color: blue) obtained in Example 1, and (B ) Shows a print obtained by laser irradiation of the carbon dioxide non-impregnated color acrylic plate (color: blue) of Comparative Example 1.
  • (2) shows the print obtained by laser irradiation of the PC plate impregnated with diacid-carbon obtained in Example 2, and (B) shows the carbon dioxide-free carbon of Comparative Example 2. Prints obtained by laser irradiation of impregnated PC plates are shown.
  • FIG. 6 (A) shows the print obtained by laser irradiation of the nitrogen-impregnated PC plate obtained in Example 12, and (B) shows laser irradiation of the nitrogen-impregnated PC plate of Comparative Example 10. The resulting print is shown.
  • FIG. 7 shows a print obtained by irradiating the nitrogen-impregnated color acrylic plate (color: blue) obtained in Example 13 with a laser beam, and (B) shows the nitrogen not obtained in Comparative Example 11. Prints obtained by laser irradiation of impregnated color acrylic plates (color: blue) are shown.
  • FIG. 9 shows the print obtained by laser irradiation of the PC film impregnated with diacid / carbon obtained in Example 15, and (B) shows the carbon / dioxide / carbon of Comparative Example 13. Prints obtained by laser irradiation of unimpregnated PC film.
  • FIG. 10 shows business card printing obtained by laser irradiation of the PC board impregnated with diacid and carbon dioxide obtained in Example 16, and (B) is obtained in Example 16. Realize some of the printed business card characters The result of magnifying observation with a body microscope is shown, and (C) shows the print obtained by irradiating the carbon plate-unimpregnated PC plate of Comparative Example 14 with laser.
  • FIG. 11 (A) shows a bar code obtained by laser irradiation of the PC plate impregnated with diacid-containing carbon obtained in Example 17, and ( B) shows the diacid-based carbon of Comparative Example 15. ⁇ Prints obtained by laser irradiation of carbon-impregnated PC board.
  • FIG. I 2 shows a barcode obtained by laser irradiation of a carbon dioxide impregnated color acrylic plate (color: blue) obtained in Example I 8 , and ( B) shows The printing obtained by irradiating laser on the carbon dioxide non-impregnated color acrylic plate (color: blue) of Comparative Example 16 is shown.
  • the method for printing on the resin molded body of the present invention includes (1) impregnating a thermoplastic resin molded body with carbon dioxide and Z or nitrogen, and then irradiating with a laser; and (2) It is characterized by irradiating a laser beam onto a molded body formed by molding a thermoplastic resin powder impregnated with carbon and Z or nitrogen.
  • printing refers to writing or marking characters, images, drawings, patterns, etc. on the surface and inside of a thermoplastic resin molding, and is a concept including solid printing.
  • Laser irradiation is a concept that includes so-called laser marking, laser decoration, and photolithography.
  • the “molded body” includes a structure having a planar shape such as a sheet or a film formed only by a structure having a three-dimensional structure.
  • thermoplastic resin constituting the molded article various molded article materials such as films, sheets, and substrates and laminates thereof are generally used, as long as they can be impregnated with carbon dioxide and Z or nitrogen.
  • thermoplastic resin there can be used any deviation between amorphous thermoplastic resin and crystalline thermoplastic resin without limitation.
  • amorphous thermoplastic resin examples include polystyrene-based resin, polycarbonate-based resin, polymethacrylic-based resin, cycloolefin-based resin, and polysalt-vinyl-based resin.
  • Polystyrene resins include general-purpose polystyrene (GPPS), rubber-reinforced polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene.
  • Rene copolymer (ABS), Styrene-isoprene-styrene copolymer (SIS), Styrene-ethylene Z-butylene-styrene block copolymer (SEBS), Styrene methyl methacrylate copolymer, Styrene-methyl methacrylate-butadiene copolymer Examples thereof include styrene and butadiene rubber (SBR).
  • Weight average molecular weight of polystyrene resin (Mw) ⁇ 50, 000-400, 000 force is preferred! / !.
  • Polycarbonate-based resin can be replaced with bis (4-hydroxyphenol), bis (3,5-dialkyl-4-hydroxyphenyl), or bis (3,5-dihalo-4-hydroxyphenyl).
  • a polycarbonate having a hydrocarbon derivative is preferred, and a bisphenol ⁇ -type polycarbonate having 2,2 bis (4-hydroxyphenol) propane (bisphenol ⁇ ) is particularly preferred.
  • the weight average molecular weight (Mw) of the polycarbonate-based resin is from 10,000 to 00: L00,000 force S preferred ⁇ , 10,000 to 70,000 force S preferred ⁇ , depending on circumstances, 10,000 to 50, 000 power is preferred!
  • polymethacrylic resin examples include polymethyl acrylate, polymethyl methacrylate (PMMA), and methyl methacrylate-styrene copolymer.
  • Weight average molecular weight of methacrylic resin (Mw) i 50,000-600,000 force is preferred! / ⁇ .
  • Cyclo (cyclic) olefin-based resin includes cycloolefin polymer manufactured by Nippon Zeon Co., Ltd., trade names “ZEONOR” and “ZEONEX”, ethylene'tetracyclododecene copolymer manufactured by Mitsui Chemicals, Inc., trade name “ “Cappell”, Cyclorefin 'copolymer manufactured by Ticona, trade name “TOPAS” and the like are preferable.
  • polysalt-vinyl resin examples include polysalt-bule (PVC), salt-butene-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, and the like.
  • Weight average molecular weight (Mw) of vinyl chloride-based rosin is between 40,000 and 200,000.
  • thermoplastic resins include polysulfone, polyethersulfone (PES), polyphenylene oxide (PPO), polyarylate (PAR), polyimide (PI), polyetherimide (PEI), polyamideimide, poly Examples thereof include tetrafluoroethylene, polytetrafluoroethylene, polyvinyl acetate, polysalt vinylidene, liquid crystal thermoplastic resin, and biodegradable resin.
  • Biodegradable resin includes aliphatic polyester, polyvinyl alcohol (PVA), Examples include a roulose derivative.
  • Aliphatic polyesters include polylactic acid (PLA) rosin and its derivatives, polyhydroxypropylate (PHB) and its derivatives, polystrength prolacton (PCL), polyethylene adipate (PEA), polytetramethylene adipate, polyglycol. Acids (PGA), condensates of diols and dicarboxylic acids, and the like.
  • PVA polylactic acid
  • PHB polyhydroxypropylate
  • PCL polystrength prolacton
  • PEA polyethylene adipate
  • PGA polytetramethylene adipate
  • condensates of diols and dicarboxylic acids and the like.
  • examples of celluloses include acetyl cellulose, methyl cellulose, and ethyl cellulose. Of these, polylactic acid resin is preferred.
  • Polylactic acid resin is a polycondensate of lactic acid or lactide.
  • Polylactic acid resins include D-isomers, L-isomers, and DL-isomers, including single or mixtures thereof.
  • the weight average molecular weight (Mw) of polylactic acid rosin is between 100,000 and 400,000.
  • thermoplastic resin examples include polyolefin resin, special polystyrene resin, polyamide resin, saturated polyester resin, polyacetal resin, and polyphenylene sulfide resin (PPS).
  • Polyolefin resin includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene ⁇ -olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene metal acrylate copolymer, etc.
  • Weight average molecular weight ( ⁇ w) Power 3 000 to 600,000 positive P-pyrene Moonlight, eye-like nomer, positive butene, Bushidera Polyolefin Examples include fats.
  • Special polyolefin resins include ultra high molecular weight polyethylene, ultra high molecular weight polypropylene, syndiotactic polypropylene (polypropylene homopolymer, propylene-ethylene copolymer, propylene 1-butene copolymer, etc.), poly-4-methyl-pentene 1 And cyclic polyolefin resin.
  • Examples of the special polystyrene-based effect include syndiotactic polystyrene (SPS) and a-methylstyrene copolymer.
  • SPS syndiotactic polystyrene
  • a-methylstyrene copolymer examples include syndiotactic polystyrene (SPS) and a-methylstyrene copolymer.
  • polyamide-based resin examples include nylon 6, nylon 66, aromatic polyamide, aromatic 'aliphatic polyamide copolymer, and the like.
  • saturated polyester resin examples include polyethylene terephthalate and polybutylene terephthalate. And the like.
  • polyacetal resin examples include homopolyoxymethylene and polyoxymethylene copolymers.
  • thermoplastic resins include polyphenylene sulfide resin (PPS), polyphenylene ether (PPE), polyether ether ketone (PEEK), polyketone, polyether ketone, polyether-tolyl, thermoto Mouth-pick liquid crystalline resin (having a molecular structure such as parabenzoic acid, aromatic diol, aromatic dicarboxylic acid or naphthalene ring in the main chain skeleton).
  • rosins particularly preferred as the amorphous olefins are polystyrene-based, polycarbonate-based, polymethacrylic-based, and cycloolefin-based rosins.
  • crystalline resins polypropylene resin, polyamide-based resin, and polyester-fed resin resin are particularly preferable.
  • thermoplastic resin can be used singly or in combination of two or more.
  • an inorganic or organic filler can be blended.
  • flame retardants, antioxidants, ultraviolet absorbers, antistatic agents, plasticizers, lubricants, colorants, and the like can be added as additives.
  • thermoplastic resin molded article is put into a pressure vessel, and diacid carbon and z or nitrogen are supplied into the pressure vessel and kept under heating or caloric pressure for a predetermined time to obtain diacid carbon. And can be impregnated with Z or nitrogen.
  • the powder of thermoplastic resin into a pressure vessel, supply carbon dioxide and Z or nitrogen into the pressure vessel, hold it under heating or pressure for a predetermined time, and then add carbon dioxide to the resin particle And after impregnating with Z or nitrogen, it can shape
  • the resin particles are not particularly limited as long as they refer to powders such as resin powders, granules, pellets, and tablets and can be supplied as a forming raw material.
  • Known molding methods include injection molding, extrusion molding, blow molding, calendar molding, and compression. Molding, transfer molding, laminate molding, cast molding, inflation molding, etc.
  • Thermoplastic ⁇ molded body prior to laser irradiation preferably diacid inhibit carbon from 0.1 to 20.0 mass 0/0, more preferably 0. 2-15.
  • 0 Mass 0 / particularly preferably 0. 5-10. 0 wt%, 0.1 in some cases 5 to 4.0 mass 0/0, preferably from 0.5 to 3.0 mass 0/0, more preferably 0.5 . to 2 5% by weight, and Z or nitrogen preferably 0. 03 ⁇ : L 0 wt%, more preferably 0. 05 ⁇ :.
  • the pressure of impregnation with carbon dioxide and Z or nitrogen is preferably 1 to 40 MPa, more preferably 2 to 20 MPa, still more preferably 2 to 15 MPa, particularly preferably 3 to 12 MPa.
  • the temperature of nitrogen impregnation is preferably not higher than the glass transition temperature (Tg) in the case of amorphous thermoplastic resin, and varies depending on the resin, but more preferably 230 ° C to -30 ° C. C, more preferably 100 ° C. to room temperature.
  • Tg glass transition temperature
  • the impregnation time varies depending on the pressure, temperature, type of resin, etc. Usually 1 minute to 100 hours, preferably 5 minutes to 30 hours, more preferably 15 minutes to 30 hours.
  • the impregnation treatment method a batch method, a method in which a resin molded product or powder is introduced into a treatment zone of carbon dioxide and Z or nitrogen, and continuously treated can be adopted.
  • an organic solvent as an auxiliary agent can be added by about 0.05 to 1% by mass of the plasticizer.
  • organic solvent examples include alcohol solvents, ketone solvents, ether solvents, benzene, toluene, polyol and the like, which are not particularly limited.
  • alcohol solvents examples include methanol, ethanol, n -propanol, isopropanol, n-butanol, tertiary butanol, isobutanol, and diacetone alcohol.
  • ketone solvents include acetone, methyl ethyl ketone, jetyl ketone, and methyl isobutyl ketone.
  • ether solvents include dibutyl ether, tetrahydrofuran, dioxane, and cyclic ethers.
  • alcohol solvents such as ethanol and propanol
  • ketone solvents such as methyl ethyl ketone. Is particularly preferred.
  • Carbon dioxide and Z or nitrogen supplied to the pressure vessel may be in a normal cylinder pressure state at the time of supply, or in a subcritical state or a supercritical state. Further, after being supplied into the pressure vessel, it may be in a subcritical state or a supercritical state.
  • the conditions for impregnating the resin molded body or powder with diacid carbon and Z or nitrogen can be appropriately determined according to the properties and applications of the resin itself.
  • carbon dioxide is supplied into the pressure vessel at room temperature (about 5 MPa) and Z or nitrogen is supplied at room temperature (about 1 LOMPa), and a molded resin or powder is required.
  • it can be impregnated by holding the mixture for 0.25 to 24 hours with appropriate stirring.
  • the impregnation of carbon dioxide and Z or nitrogen differs depending on the resin, and there are some resin materials that require a long time for carbon dioxide and Z or nitrogen impregnation at the cylinder pressure at room temperature. . Therefore, in order to shorten the impregnation time of carbon dioxide and Z or nitrogen, it is preferable to impregnate under the glass transition temperature under the subcritical state or supercritical state.
  • the “subcritical state” of carbon dioxide or nitrogen means that (i) the pressure is not less than the critical pressure of carbon dioxide (7.48 MPa) or not less than the critical pressure of nitrogen (3.4 MPa), Liquid state where the temperature is less than the critical temperature of carbon dioxide (31.1 ° C) or less than the critical temperature of nitrogen (1147 ° C), (ii) the pressure is less than the critical pressure of carbon dioxide or nitrogen A liquid state where the temperature is above the critical temperature, or (iii) the temperature and pressure are both below or close to the critical point of carbon dioxide or nitrogen.
  • the temperature when the temperature is 20 ° C to 31 ° C and the pressure is preferably 5 MPa or more, the temperature is room temperature to 100 ° C and the pressure is 1 to 3.4 MPa. Is preferable.
  • the "supercritical state” refers to a state where the pressure is higher than the critical pressure of carbon dioxide and Z or nitrogen, and the temperature is higher than the critical temperature.
  • the temperature is 40-50 ° C
  • the pressure is 7.38-30 MPa, especially 8-20 MPa. Is preferably room temperature to 100 ° C., pressure 3.4 to 30 MPa, particularly 5 to 20 MPa.
  • a resin molded body impregnated with carbon dioxide and Z or nitrogen can be irradiated with a laser immediately after release of atmospheric pressure. However, after the atmospheric pressure is released, carbon dioxide and Z or nitrogen gas are released from the molded resin, and the amount of impregnation thereof decreases to about 30% by mass (for example, 0.5 to 20 If it is within the time, clear printing can be performed by laser irradiation.
  • the obtained carbon dioxide and Z or nitrogen-impregnated resin can be mixed with unimpregnated resin to adjust the amount of carbon dioxide and Z or nitrogen impregnated with the resin to obtain a molding raw material. .
  • the resin powder granules are quickly supplied to, for example, the most upstream part of the cylinder of the injection molding machine, and injection molding is performed under the molding conditions according to the type of the thermoplastic resin that forms the resin powder granules. It can be set as a molded body of various shapes.
  • the thermoplastic resin can be supplied to the injection molding machine by putting it into a normal raw material supply port of the injection molding machine.
  • the impregnated carbon dioxide and a part of Z or nitrogen are released, but the impregnation amount of carbon dioxide is preferably 0.1 to 20.0% by weight, nitrogen. If the impregnation amount is preferably 0.03 to: L 0% by weight, then laser irradiation can be performed effectively.
  • the form of the thermoplastic resin molded product to which the method of the present invention is applied is not particularly limited, but a thin molded product such as a sheet, film, or substrate having a thickness of 50 / z m to LOmm is particularly suitable.
  • the output is preferably 20 W or less, more preferably 0.2 to: LOW, more preferably 0.2 to 6 W, more preferably 0.3 to 6 W, and particularly preferably 0.3 to 5.
  • Continuous oscillation laser capable of irradiating 5W energy (energy amount: 3 to 55J, energy amount varies depending on marking character and picture content), or ON-OFF output power at 50Hz or 100Hz frequency
  • a pulsed laser capable of irradiating energy of 50 o / o of the rated output is desirable.
  • carbon dioxide laser carbon monoxide laser
  • semiconductor laser yttrium vanadate (YVO) laser
  • YAG yttrium 'aluminum' garnet
  • Excimer laser TEA type carbon dioxide laser (pulse type) and the like.
  • carbon dioxide laser and YVO laser can provide markings with good visibility.
  • Carbon dioxide (CO) lasers generally have wavelengths of 10. and 9.
  • the one with 3 ⁇ m is used, and YVO laser with a wavelength of 1064 ⁇ m is used.
  • a carbon dioxide laser device manufactured by Onizuka Glass Co., Ltd., MODE L PIN-40R laser power: rated 40 W to 10 W, oscillation wavelength: 10., spot diameter: 240 m
  • GSILumonics XY scanning module can be used for laser scanning
  • AutoCAD data can be converted, and the laser can be drawn with the scanning module.
  • this device which is capable of ON-OFF type laser irradiation by pulse oscillation, continuous oscillation by DC discharge was used in the embodiment.
  • a laser beam emitted from a laser generator is incident on a galvano laser scanner and is shaken by two X and Y galvanometers (moves to the respective-axes).
  • the focal length is adjusted by the F ⁇ lens ahead, and desired printing can be performed on the surface and Z of the resin molded body.
  • Scanning data can be created by CAD.
  • the size of characters can be set by the computer font settings. It is possible from enlargement and reduction.
  • the scanned line width can be changed by changing the scanner speed, moving the focal length of the laser, changing the temperature of the sample mounting table by cooling gas blowing, and cooling.
  • a pulsed laser that limits the energy output of one shot can be used in the method of the present invention because printing can be performed with low energy.
  • the thermoplastic resin molded body impregnated with carbon dioxide and Z or nitrogen is affected by the laser output depending on the gas impregnation concentration, the ability to make the laser oscillation method continuous depending on the marking application or the amount of impregnation.
  • the pulse type may be selected according to the desired printing on the surface and Z or inside.
  • you want to print various characters and designs on a thermoplastic resin molding with a large area you can also print a wide range of prints by using masking and moving the irradiated surface using an XY stage. It is also possible to display a large amount of information or complex kanji characters, images, etc. on a single substrate surface in an appropriate size.
  • the resin molded body is impregnated with carbon dioxide and Z or nitrogen in advance, foaming of the surface and Z or the inner layer is facilitated, and the laser output is low even at a low output of 10W or less. Clear and clear printing can be performed.
  • thermoplastic resin molded article the surface and Z or the inside of the thermoplastic resin molded article impregnated with carbon dioxide and Z or nitrogen are subjected to printing foamed by laser irradiation.
  • the line width that can be printed (scanning line width) varies depending on the spot diameter of the laser device and the material properties (molecular weight, molecular weight distribution, viscoelastic behavior) of the thermoplastic resin molding to be used. By carrying out, it can be 400 m or less, preferably 300 ⁇ m or less, more preferably 50 ⁇ m or less under suitable conditions.
  • a concave depression can be formed on the surface of the resin molded product by laser irradiation.
  • the surface of the resin molded product is foamed by laser irradiation, and the laser irradiated portion is raised in a convex shape.
  • the cross-section of this convex ridge has a substantially trapezoidal shape, and the side pieces of the substantially trapezoidal shape have a horizontal plane force of usually 45 to 90 °, preferably 50 to 90 °. For this reason, the contrast with the surface of the resin molded body is improved, resulting in clear and clear printing.
  • the foamed convex ridges there are foam cells having an average cell diameter of 1 to LO m at the side surface and the central portion, and an average cell diameter of 1 to 50 ⁇ m in the vicinity of the printing surface. .
  • the thermoplasticity of the gas-impregnated molded body (diacid-carbon impregnation amount: 0.1 to 20.0 wt% and Z or nitrogen impregnation amount: 0.03 to 0.1 wt%).
  • the surface temperature of the resin is preferably 23 ° C. or less, more preferably 10 to 22 ° C., and more preferably 10 to 21.5 ° C.
  • the surface temperature of the molded body By reducing the surface temperature of the molded body to 23 ° C or less, it is possible to mitigate the release of gas with the strength of the molded body impregnated with the gas. Thus, the residual gas concentration on the surface of the molded body can be maintained at a high level.
  • the residual gas concentration on the surface of the compact is determined by the attenuated total reflection method using an infrared absorption spectrum (IR) method.
  • IR infrared absorption spectrum
  • the gas concentration on the surface of the compact immediately after gas impregnation It is desirable to maintain the residual gas concentration (remaining gas ratio,%) with respect to the amount of preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more.
  • Nitrogen is a homonuclear diatomic molecule and does not show infrared absorption because the dipole moment does not change when vibration occurs. Therefore, when the molded body is impregnated with nitrogen, it is preferable that a Raman scattering peak derived from nitrogen is detected when the surface of the molded body immediately before laser irradiation is observed by Raman spectroscopy.
  • the surface temperature of the molded body is reduced to 23 ° C or less, adverse effects due to heat generation during laser irradiation are alleviated, and the surface shape is stable for 24 to 48 hours after gas impregnation.
  • the foam diameter during the formation of the marking can be made smaller.
  • an inert gas and its cooling gas such as nitrogen gas passed through liquid nitrogen
  • the sample mounting table is cooled using cooling water or the like. Then, it is possible to prevent the sample surface from being heated and melted by the energy at the time of laser irradiation, and the marking effect is improved.
  • thermoplastic resin molded article of the present invention comprises: (1) a surface of a thermoplastic resin molded article impregnated with carbon dioxide and Z or nitrogen is subjected to printing foamed by laser irradiation; 2) A single layer composed of a thermoplastic resin impregnated with carbon dioxide and Z or nitrogen, or the inner layer of a laminate including the inner layer is selectively foamed by laser irradiation. And
  • thermoplastic resin molded article impregnated with carbon dioxide and Z or nitrogen refers to a molded article obtained by impregnating a thermoplastic resin molded article with carbon dioxide and Z or nitrogen, and diacid It means a molded body formed by molding thermoplastic rosin powder impregnated with carbonized carbon and Z or nitrogen.
  • thermoplastic resin molded article by laser irradiation.
  • a method in which the surface of a thermoplastic resin molded article impregnated with carbon dioxide and Z or nitrogen is directly irradiated with laser, and the surface of the resin molded article is finely foamed and (ii) ) A single layer composed of a thermoplastic resin impregnated with carbon dioxide and Z or nitrogen, or the inner layer of a laminate comprising the same as an inner layer is irradiated with laser. Examples thereof include a method of selectively foaming by spraying.
  • a finely processed mask material made of a low thermal conductivity material is superimposed on a thermoplastic resin molded article impregnated with carbon dioxide, Z or nitrogen, and irradiated with laser.
  • thermoplastic resin molding Forming a body and irradiating it with a laser to finely foam a thermoplastic resin molded body impregnated with carbon dioxide and Z or nitrogen on the surface of the laminate, (v) impregnated with carbon dioxide and Z or nitrogen On the thermoplastic resin molding, a laminate is formed by laminating a resin molding including carbon dioxide and Z or nitrogen non-impregnated transparent thermoplastic resin film. Thermoplastic resin impregnation impregnated with carbon dioxide and Z or nitrogen (Vi) A laminate in which the central part of a thermoplastic resin laminate composed of a multilayer structure is composed of a thermoplastic resin layer with a high impregnation amount of carbon dioxide and Z or nitrogen.
  • a method of forming a foamed layer by foaming only a thermoplastic resin layer with a high carbon dioxide and Z or nitrogen impregnation content, or foamed characters, images, Examples include a method of forming a printing layer such as a drawing or pattern.
  • the thermoplastic resin molded body before the laser irradiation, the thermoplastic resin molded body is pre-impregnated with carbon dioxide and Z or nitrogen (pretreatment), so that the energy of the irradiated laser beam can be reduced. For this reason, it is possible to reduce the printing cost and to improve the durability of the molded body in which the surface of the thermoplastic resin molded body is hardly destroyed or transpiration occurs during laser irradiation. Also, the resulting foamed print is clear and crisp.
  • CO dissolved amount (mass%) [(weight of cut polymer sample after CO impregnation (g) —cut before impregnation
  • Cut polymer sample weight ( g )] Weight of cut polymer sample before Z impregnation (g) X loo
  • Laser scanning device made by Onizuka Glass Co., Ltd., MODEL PIN-40R (laser power: rated 40W, oscillation wavelength: 10.6 ⁇ m), GSILumonics for laser scanning. It was placed on a sample fixing base (anodized plate: blackboard) in an XY scanning module manufactured by Kobayashi. As a result of measuring the surface temperature of the installed sample with a handy type thermometer (HA-100E) manufactured by Anritsu Keiki Co., Ltd., it was 13.4 ° C. The focal length was 120 mm.
  • the same color acrylic plate treated with carbon dioxide in an autoclave was left at room temperature for 4 hours.
  • the amount of carbon dioxide impregnated on the color acrylic plate after standing was 0.41% by weight.
  • the surface temperature of the color acrylic plate immediately before laser irradiation was 20.3 ° C.
  • Residual ratio of gas [(absorbance of 2338 cm 1 observed immediately before laser irradiation) Z (absorbance of 2338 cm 1 observed immediately after autoclave release)] X 100
  • Example 2 The same commercially available color acrylic plate (cut sample) as in Example 1 was pre-dried and irradiated with laser at an output of 2 w (energy amount: 16 J) by the same laser scanning method as in Example 1. As a result, only the unclear printing shown in Fig. 1 (B) was possible.
  • the width of the frame line measured with a laser microscope was 380 ⁇ m, and the depth from the surface (concave shape) was 77 ⁇ m.
  • an absorption peak with a wave number of 2338 cm 1 derived from carbon dioxide was strong.
  • PC polycarbonate
  • the obtained carbon dioxide-impregnated PC plate (surface temperature: 16.5 ° C.) was irradiated with laser at an output of 1 W (energy amount: 8 J) by the same laser scanning method as in Example 1. As a result, clear and clear printing shown in Fig. 2 (A) was achieved.
  • Example 2 The same commercially available PC plate (cut sample) as in Example 2 was pre-dried and irradiated with a laser at an output of 3 W (energy amount: 2 J) by the same laser scanning method as in Example 1. As a result, only unclear printing as shown in Fig. 2 (B) was possible, smoke was generated from the surface of the PC board during laser irradiation, and the printed part was colored as the grease was decomposed.
  • a commercially available polypropylene (PP) plate (milky white product, thickness 3mm x length 1000mm x width 2000mm) was cut into 3mm x 60mm x 60mm, and 2L autoclave (manufactured by Pressure Industrial Co., Ltd.) was pre-treated. After being installed inside, it was impregnated with carbon dioxide at room temperature and a cylinder pressure of 5.5 MPa for 3 hours. Thereafter, carbon dioxide in the autoclave was depressurized by pouring for 5 minutes. The pretreated PP plate had 1.23% by mass of carbon dioxide.
  • the obtained PP plate impregnated with carbon dioxide was irradiated with a laser at an output of 5 W (energy amount: 40 J) by the same laser scanning method as in Example 1.
  • the surface temperature of the PP plate immediately before laser irradiation was 14.8 ° C.
  • clear and clear printing as shown in Fig. 3 (A) was achieved even with an opaque crystalline PP resin board.
  • the width of the printed frame measured with a laser microscope is 300 m
  • the printed foam (height of the substrate surface) protruding from the surface is 83 ⁇ m
  • the longitudinal section has a trapezoidal shape.
  • Example 3 The same commercially available PP plate as in Example 3 (cut sample) was irradiated with a laser at an output of 6 W (energy amount: 48 J) by the same laser scanning method as in Example 1. As a result, only unclear printing was possible as shown in Fig. 3 (B), and smoke was generated from the PP plate surface during laser irradiation.
  • the surface shape measured with a laser microscope had a frame width of 290 m, and the surface shape was a convex force. The center was depressed, and two peaks were present on both sides (concave shape). .
  • the height of the mountain was 170 m, the height of the two mountains was the same, and the height of the hollow surrounded by both mountains was 31 ⁇ m, and its width was 62 ⁇ m. It was.
  • COC cycloolefin polymer film
  • 2 L autoclave Pressure Industries Co., Ltd.
  • carbon dioxide was impregnated at room temperature (23 ° C) at a cylinder pressure of 5.5 MPa for 30 minutes. Thereafter, the carbon dioxide in the autoclave was depressurized over 5 minutes.
  • the amount of carbon dioxide impregnated in the pretreated COC film was 3.37% by mass.
  • the anodized plate on the sample fixing base (anodized plate: blackboard) was cooled with ice water before use.
  • Example 4 The same commercially available COC film as in Example 4 was irradiated with a laser at an output of 3 W (energy amount: 2 J) by the same laser scanning method as in Example 1. As a result, it was possible to produce only unclear printing similar to that shown in Fig. 1 (B).
  • PET polyethylene terephthalate
  • pre-dried a sample cut to 250 m ⁇ 60 mm ⁇ 60 mm at 80 ° C for 5 hours, and then cut as a pretreatment was placed in a 2 liter autoclave (manufactured by Pressure Resistant Industries Co., Ltd.), and impregnated with carbon dioxide at room temperature (23 ° C) and a cylinder pressure of 5.5 MPa for 30 minutes. Thereafter, the carbon dioxide in the autoclave was depressurized over 5 minutes. The amount of carbon dioxide impregnated in the pretreated PET film was 1.15% by mass. Further, as a result of observing the surface of the obtained PET film impregnated with carbon dioxide with an ATR method, an absorption peak (absorbance: 0.34) having a wavelength of 2 338 cm 1 derived from carbon dioxide was observed.
  • the obtained diacid-carbon-impregnated PET film (surface temperature: 20. 8 ° C) was irradiated with laser at an output of 2 W (energy amount: 16 J) by the same laser scanning method as in Example 1. .
  • a clear and clear mark j similar to Fig. 1 (A) was obtained.
  • a commercially available PET OHP sheet (thickness: 100 ⁇ m) was cut into 100 m ⁇ 60 mm ⁇ 60 mm to prepare a sample.
  • the cut sample was placed in a 2L autoclave (made by Kogyo Kogyo Co., Ltd.) and then impregnated with carbon dioxide for 1 hour at room pressure (23 ° C) and a cylinder pressure of 5.5 MPa. . Thereafter, the carbon dioxide in the autoclave was depressurized over 5 minutes. The amount of carbon dioxide impregnated in the pretreated OHP film was 1.78% by mass.
  • the same as in Example 1 was applied to the obtained carbon dioxide impregnated OHP film (surface temperature 21.0 ° C). Laser irradiation was performed with an output of 2W (energy amount: 16J) by laser scanning. As a result, even when the sample thickness was as thin as 100 m, clear and clear printing similar to that shown in Fig. 1 (A) was achieved.
  • Example 5 The same commercially available PET film as in Example 5 was irradiated with a laser at an output of 3 W (energy amount: 2 J) by the same laser scanning method as in Example 1. As a result, it was possible to produce only unclear printing similar to that shown in Fig. 1 (B). The same result was obtained for the OHP sheet.
  • PC pellet After drying pellets of commercially available polycarbonate (Mitsubishi Engineering Plastics Co., Ltd., trade name: HL 4000, Mw: 12,000) at 100 ° C for 5 hours, this pellet (hereinafter referred to as “PC pellet”) lOOOg Place in a stainless steel wire mesh cylindrical rod ( ⁇ , length 200mm), set in a 2L autoclave (made by pressure-resistant industry), and then at room temperature (22 ° C), cylinder pressure 5. OMPa 24 Carbon dioxide impregnation treatment was performed for a time. Thereafter, the carbon dioxide in the autoclave was depressurized and taken out over 5 minutes. The mass force shown below The calculated amount of PC pellet impregnated with carbon dioxide (CO 2) was 5.05% by mass.
  • PC pellet commercially available polycarbonate
  • CO dissolution amount (mass%) ⁇ [cylindrical rod after CO impregnation + pellet mass after CO impregnation
  • Injection conditions Injection speed 150mmZ seconds, 120MPa, 1.5 seconds, mold clamping: 20 tons
  • Molding temperature Raw material supply port 250 ° C, Nozzle: 290V
  • the obtained flat plate sample was allowed to stand at room temperature for 4 hours. During this period, more than 50% of the carbon dioxide impregnated in the first pellet is considered to be released during molding and standing at atmospheric pressure.
  • Example 6 The same PC pellet lOOOg as used in Example 6 was placed in a stainless steel wire mesh cylindrical rod (100 m ⁇ , length 200 mm), and inside a 2 liter autoclave (made by pressure-resistant industry) After installation, the sample was impregnated with nitrogen at room temperature (22 ° C) and cylinder pressure (lOMPa) for 24 hours. Thereafter, the nitrogen in the autoclave was depressurized over 5 minutes. As a result of calculating the nitrogen impregnation amount of this PC pellet mixture, it was 0.84% by mass.
  • the amount of nitrogen impregnation in the pellet mixture was 0.42% by weight.
  • a sample (dimensions: 30 x 50 x 1 mm) was prepared in the same manner as in Example 6, and a frame of 21 mm x 28 mm was implemented along with the letters (2 mm square) of “Shiga Prefectural Industrial Support Plaza”.
  • Laser irradiation was performed at an output of 2 W (energy amount: 16 J) by the same laser scanning method as in Example 1.
  • the surface temperature of the PC board immediately before laser irradiation was 21.0 ° C.
  • the nitrogen impregnation amount measured for the produced flat plate sample by releasing the residual gas with a vacuum dryer at 80 ° C. for 5 days was 0.21% by weight.
  • Example 8 A nitrogen non-impregnated PC flat plate sample obtained under the injection conditions described in Example 7 was irradiated with a laser at an output of 2 W (energy amount: 16 J) by the same laser scanning method as in Example 7. As a result, it was possible to produce only unclear printing as shown in Fig. 2 (B).
  • Example 8 A nitrogen non-impregnated PC flat plate sample obtained under the injection conditions described in Example 7 was irradiated with a laser at an output of 2 W (energy amount: 16 J) by the same laser scanning method as in Example 7. As a result, it was possible to produce only unclear printing as shown in Fig. 2 (B).
  • Example 8 A nitrogen non-impregnated PC flat plate sample obtained under the injection conditions described in Example 7 was irradiated with a laser at an output of 2 W (energy amount: 16 J) by the same laser scanning method as in Example 7. As a result, it was possible to produce only unclear printing as shown in Fig. 2 (B).
  • Example 8 A nitrogen non-impregnated PC
  • ABS plate acrylonitrile butadiene styrene copolymer, color: beige, thickness 6 mm x length 500 mm x width 1000 mm
  • the sample cut to 6 mm x 60 mm x 60 mm was pre-dried at 80 ° C for 5 hours.
  • the cut sample is placed in a 2L autoclave (made by pressure-resistant industry), and then impregnated with carbon dioxide at room temperature (23 ° C) at a cylinder pressure of 4. OMPa for 1 hour. It was. Thereafter, the carbon dioxide in the autoclave was depressurized over 5 minutes.
  • the pretreated ABS plate was impregnated with 0.62 mass% of carbon dioxide (CO).
  • the obtained diacid-carbon-impregnated ABS plate (surface temperature 13.4 ° C) is the same laser as in Example 1.
  • the line width (bottom base) of the print frame measured with a laser microscope is 401 ⁇ m
  • the height from the surface (substrate surface) is 73 ⁇ m. It has a trapezoidal shape (upper base 185 m) and a vertical section!
  • the pretreatment time was changed to 4 hours at room temperature and under the same pressure (4. OMPa), and the impregnation treatment was performed in an autoclave.
  • the amount of carbon dioxide impregnated in the obtained ABS plate was 1.86% by weight.
  • laser irradiation was performed in the same manner as described above.
  • the surface temperature of the ABS plate immediately before laser irradiation was 15.7 ° C.
  • the substrate had a high contrast and printing with high visibility was achieved.
  • the line width (bottom base) of the printed frame measured with a laser microscope is 475 ⁇ m
  • the height from the surface (substrate surface) is 84 ⁇ m.
  • the longitudinal section had a trapezoidal shape (top bottom 198) m.
  • Example 8 The same ABS plate as used in Example 8 was placed in the autoclave having a capacity of 2 L, and then impregnated with nitrogen at room temperature (22 ° C.) and under a cylinder pressure lOMPa for 24 hours. Thereafter, the nitrogen in the autoclave was depressurized over 5 minutes. Results of calculation of the nitrogen impregnation amount of the ABS plate was 0.098 mass 0/0.
  • the laser scanning method is the same as in Example 8, and the surface of the ABS plate is irradiated with laser at an output of 1.5 W (amount of energy: 9 J).
  • the surface temperature of the ABS plate immediately before laser irradiation was 17.0 ° C.
  • the line width of the printed frame measured with the laser microscope is 292 ⁇ m at the base (lower base), the height of the surface (substrate surface) force is 47 ⁇ m, and the vertical section is trapezoidal (upper With bottom 218 m).
  • Comparative Example 8 The same commercially available ABS plate (cut sample) as in Example 8 was pre-dried and irradiated with laser at an output of 2 W (energy amount: 12 J) by the same laser scanning method as in Example 8. As a result, only the unclear printing shown in Fig. 4 (C) was achieved.
  • the width of the frame line measured with the laser microscope was 332 m and the height from the surface was 4.
  • the surface force slightly increased due to volume expansion due to heat. However, the printed state cannot be observed because of no contrast.
  • the obtained carbon dioxide-impregnated PS plate (surface temperature: 17.5 ° C.) was irradiated with laser at an output of 1.5 W (energy amount: 9 J) by the same laser scanning method as in Example 8. As a result, clear and clear printing shown in Fig. 5 (A) was achieved.
  • the pretreatment time was changed to 16 hours at room temperature and the same pressure (4. OMPa), and the impregnation treatment was performed in the autoclave.
  • the amount of carbon dioxide impregnated in the obtained PS plate was 6.83% by weight.
  • laser irradiation was performed in the same manner as described above.
  • the surface temperature of the PS plate immediately before laser irradiation was 19.0 ° C.
  • the substrate was high in contrast and high in visibility and printed.
  • Example 10 The same PS plate used in Example 10 was placed in an autoclave having a capacity of 2 L, and then impregnated with nitrogen at room temperature (22 ° C.) and under a cylinder pressure of lOMPa for 24 hours. Then, the nitrogen in the autoclave was depressurized over 5 minutes. As a result of calculating the nitrogen impregnation amount of this PS plate, 0. It was 51% by mass.
  • the obtained nitrogen-impregnated PS plate (surface temperature 17.7 ° C.) was irradiated with laser at an output of 1.5 W (energy amount: 9 J) by the same laser scanning method as in Example 8.
  • an output of 1.5 W energy amount: 9 J
  • Example 10 laser irradiation was performed with an output of 2 W (energy amount: 12 J) by a laser scanning method without performing the carbon dioxide impregnation treatment.
  • a character having a concave shape melted by the substrate surface force laser irradiation energy and the character portion was depressed
  • FIG. 5 (C) it was hard to observe as clear text printing.
  • Example 2 The same polycarbonate plate (cut sample) used in Example 2 was placed in an autoclave having a capacity of 2 L, and then impregnated with nitrogen for 24 hours at room temperature (22 ° C.) and under a cylinder pressure lOMPa. Thereafter, the nitrogen in the autoclave was depressurized over 5 minutes. As a result of calculating the nitrogen impregnation amount of this PC plate, it was 0.23% by mass.
  • the obtained nitrogen-impregnated PC plate (surface temperature 17.9 ° C.) was irradiated with a laser at an output of 1.5 W (energy amount: 9 J) by the same laser scanning method as in Example 8. As a result, clear and clear printing shown in Fig. 6 (A) was achieved.
  • Example 12 laser irradiation was performed with an output of 2 W (energy amount: 12 J) by a laser scanning method without performing nitrogen impregnation treatment.
  • 2 W energy amount: 12 J
  • Fig. 6 (B) Only unclear printing as shown in Fig. 6 (B) was possible, and smoke was generated from the PC plate surface during laser irradiation, and the print surface became extremely dirty as the grease was decomposed (white in the figure). The visible part is dirty with smoke).
  • Example 2 The same color acrylic plate (color: blue) used in Example 1 was placed in an autoclave with a capacity of 2 L, and then impregnated with nitrogen for 24 hours at room temperature (22 ° C) and under a cylinder pressure of lOMPa. . Thereafter, the nitrogen in the autoclave was depressurized over 5 minutes.
  • This color acrylic board The amount of nitrogen impregnated was calculated to be 0.051% by mass.
  • the obtained nitrogen-impregnated colored acrylic plate (surface temperature 14.9 ° C.) was irradiated with a laser at an output of 1.5 W (energy amount: 9 J) by the same laser scanning method as in Example 8. As a result, clear and clear printing as shown in FIG.
  • the line width of the printing frame line measured with the laser microscope was 392 m
  • the height from the surface (base material surface) was 25 m
  • the vertical section had a trapezoidal shape.
  • Example 13 laser irradiation was performed with an output of 2 W (energy amount: 12 J) by a laser scanning method without performing nitrogen impregnation treatment. As a result, only unclear printing as shown in Fig. 7 (B) was achieved.
  • the width of the frame line measured with a laser microscope was 397 ⁇ m, and the depth from the surface (concave shape) was 18.6 ⁇ m.
  • the cross-sectional shape of the printing (printing) part is observed with a scanning microscope (manufactured by Keyence Corporation, 3D Real Surface View Microscope, VE-9800), it takes a trapezoidal shape protruding from the substrate surface, and the line width of the printing frame line Is a convex shape with a height of 430 m and a height of 28. l / zm from the surface (base material surface)
  • the longitudinal section had a trapezoidal shape (upper base 367 / zm).
  • a foamed structure with a bubble diameter of 1.5 to 8.2 m was formed inside the protruding trapezoidal shape.
  • Example 14 laser irradiation was performed with an output of 2 W (energy amount: 12 J) by a laser scanning method without performing the carbon dioxide impregnation treatment. As a result, only the unclear printing shown in Fig. 8 (B) was possible.
  • the width of the frame line measured with a laser microscope was 466 m, and the depth from the surface (concave shape) was 19 m.
  • PC polycarbonate
  • the cross-sectional shape of the printing (printing) part is observed with a scanning microscope (manufactured by Keyence Corporation, 3D Real Surface View Microscope, VE-9800), it takes a shape that protrudes from the surface of the substrate (bow shape), and the printing border It had a convex shape with a line width of 333 m and a height from the surface (base material surface) of 41 m.
  • a foamed structure with a bubble diameter of 1.6 to 9 was formed inside the protruding shape.
  • Example 15 laser irradiation was performed with an output of 2 W (energy amount: 12 J) by a laser scanning method without performing the carbon dioxide impregnation treatment. As a result, only unclear printing as shown in Fig. 9 (B) was achieved.
  • the line width of the printed frame measured with the scanning microscope is 469 m
  • the height of the surface (base material surface) force is 35.5 / zm
  • the vertical section is trapezoidal (top bottom 157 m)
  • PC polycarbonate
  • Example 2 transparent product, cut sample: thickness 3 mm x length 70 mm x width 70 mm
  • the carbon dioxide impregnation treatment was performed for 5 hours. Thereafter, the carbon dioxide in the autoclave was depressurized over 5 minutes.
  • the amount of carbon dioxide impregnated in the pretreated PC plate was 1.98% by mass.
  • an absorption peak (absorbance: 0.31) having a wavelength of 2338 cm 1 derived from carbon dioxide was observed.
  • the obtained carbon dioxide impregnated PC board (surface temperature 15.6 ° C) is 3—Axis laser marker device (manufactured by Keyence Corporation, MODEL ML-Z9550 (laser power: 30W, oscillation wavelength: 10.6 m, spot) Diameter: 35 ⁇ m, pulse width: 40 ns, fine wire type)) Installed on the lower sample fixing table.
  • the focal length was 130 mm.
  • Fig. 10 (A) For printing, business card characters (thin characters of 2 mm square or less) are displayed within a character range of 25 mm X 50 mm Power was 7.5W (energy amount: 15J), scanning speed: 1000mmZs, frequency: 25KHz, and laser marking was applied to the surface of the PC board for marking.
  • Fig. 10 (B) shows a part of the 2mm square characters printed (marked) magnified 25x with a stereomicroscope (manufactured by Kohcon Co., Ltd .: SMZ1500). It can be seen that the intersections of the characters are clear despite the foaming.
  • clear business card characters were similarly printed on the thin PC film of Example 15 described above.
  • Example 16 laser irradiation was performed with an output of 9 W (energy amount: 18 J) using a 3-Axis laser marker device without performing the carbon dioxide impregnation treatment. As a result, only unclear printing as shown in Fig. 10 (C) was achieved.
  • PC polycarbonate
  • Example 2 transparent product, cut sample: thickness 3 mm x length 70 mm x width 70 mm
  • Carbon dioxide treatment was performed at OMPa for 30 hours. Thereafter, the carbon dioxide in the autoclave was depressurized over 5 minutes.
  • the pretreated PC plate had a carbon dioxide content of 5.76% by mass. Further, as a result of observing the surface of the obtained diacid-carbon-impregnated PC plate by the ATR method, an absorption peak (absorbance: 0.41) having a wavelength of 2338 cm 1 derived from diacid-carbon was observed.
  • the obtained PC board impregnated with carbon dioxide was stored in a container containing dry ice for 24 hours.
  • the extracted PC plate had a carbon dioxide impregnation amount of 2.02 mass% and a surface temperature of 16.5 ° C.
  • an absorption peak (absorbance: 0.12) having a wavelength of 2338 cm 1 derived from diacid-carbon was observed.
  • the residual gas ratio on the surface of the molded body according to the above formula was 29.3%.
  • This carbon dioxide impregnated PC board is made into a CO laser marker device (Horiuchi Electric Co., Ltd.
  • LLS—S050VAH laser power 12W, spot diameter: 150 ⁇ m, continuous oscillation.
  • the focal length was 100 mm.
  • Example 17 the carbon dioxide impregnation treatment was performed without performing the carbon dioxide impregnation treatment.
  • Example 1 acrylonitrile-styrene copolymer (AS), color: blue, thickness 2 mm x length 60 mm x width 60 mm) was placed in an autoclave with a capacity of 2 L, and then room temperature (23 ° C) Below, cylinder pressure 5. Carbon dioxide treatment was performed at OMPa for 30 hours. Thereafter, the carbon dioxide in the autoclave was depressurized over 5 minutes. The pretreated color acrylic plate had a carbon dioxide content of 19.1% by weight. Further, as a result of observing the surface of the obtained carbon dioxide impregnated color acrylic plate with an ATR method, an absorption peak (absorbance: 0.53) having a wavelength of 2338 cm 1 derived from carbon dioxide was observed.
  • AS acrylonitrile-styrene copolymer
  • the resulting diacid-carbon-impregnated color acrylic plate was stored for 24 hours in a container containing dry ice. After storage, the extracted color acrylic plate had a carbon dioxide impregnation amount of 9.55% by mass. The surface temperature was 14.5 ° C.
  • an absorption peak (absorbance: 0.20) having a wavelength of 2338 cm 1 derived from diacid-carbon was observed.
  • the residual gas ratio on the surface of the molded body according to the above formula was 37.7%.
  • the focal length was 100 mm.
  • a barcode mark was printed in the range of 10mm x 40mm by irradiating laser at an output of 1.2W (energy amount: 11.7J) and scanning speed: lOOmmZs.
  • a clear and clear bar code shown in FIG. 12 (A) could be printed.
  • This marked bar code could be read by a bar code reader.
  • Example 17 Comparative Example 16 In Example 17, the carbon dioxide impregnation treatment was performed without performing the carbon dioxide impregnation treatment.
  • the printing method of the present invention can be suitably used in general printing fields using a laser irradiation technique for a resin molded body.
  • genuine parts' device identification, product origin indication (manufacturing date, expiry date, etc.), applications that require printing or changing patterns for each product (lot number, manufacturing information, different languages Display symbols), on-demand printing, anti-counterfeiting displays, backlight switches, etc. (automobile and audio panels, switches), printing on products used in harsh environments such as hot water and organic solvents Is available.
  • organic pigments' dyes there is no concern about contamination with pigments, so it can be applied to printing on medical devices.
  • the characters on the surface of the transparent resin molded body are inverted, and the back side force can be seen clearly even when printed, so that it can be used for printing on display boards and the like, reflecting the features of the present invention.
  • the application can be expanded.

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Abstract

L'invention concerne des procédés d'impression nette sur un moulage de résine par irradiation au laser ; et des moulages de résine thermoplastique obtenus par les procédés. (1) L'un des procédés d'impression sur un moulage de résine comprend l'imprégnation d'un moulage de résine thermoplastique par du dioxyde de carbone et/ou de l'azote, puis son irradiation par un laser. (2) L'autre procédé d'impression sur un moulage de résine comprend le moulage de particules de résine thermoplastique imprégnées par du dioxyde de carbone et/ou de l'azote et l'irradiation au laser du moulage résistant. (3) L'un des moulages de résine thermoplastique est celui que l'on a imprimé en soumettant la surface d'un moulage de résine thermoplastique imprégnée par du dioxyde de carbone et/ou de l'azote à un moussage par irradiation au laser. (4) L'autre moulage de résine thermoplastique est un moulage que l'on a obtenu en faisant mousser de manière sélective par irradiation au laser soit une couche unique constituée d'une résine thermoplastique imprégnée par du dioxyde de carbone et/ou de l'azote, soit la couche interne d'une structure multicouche comprenant la couche unique en tant que couche interne.
PCT/JP2007/063161 2006-08-31 2007-06-29 Procédés d'impression sur une résine moulée et résines thermoplastiques moulées WO2008026373A1 (fr)

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KR20150032521A (ko) 2012-06-22 2015-03-26 미쯔비시 레이온 가부시끼가이샤 도광체 예비성형물용 수지 조성물, 도광체 예비성형물, 적층 도광체 예비성형물, 면광원 장치용 도광체 및 면광원 장치
JP2017052910A (ja) * 2015-09-11 2017-03-16 東洋製罐グループホールディングス株式会社 加飾発泡プラスチック成形体
JP2020032671A (ja) * 2018-08-31 2020-03-05 カシオ計算機株式会社 熱膨張性シート、熱膨張性シートの製造方法、造形物及び造形物の製造方法

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JP2017052910A (ja) * 2015-09-11 2017-03-16 東洋製罐グループホールディングス株式会社 加飾発泡プラスチック成形体
JP2020032671A (ja) * 2018-08-31 2020-03-05 カシオ計算機株式会社 熱膨張性シート、熱膨張性シートの製造方法、造形物及び造形物の製造方法

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