EP0924095A1 - Verfahren zur Lasermarkierung von Polyolefinharzen - Google Patents

Verfahren zur Lasermarkierung von Polyolefinharzen Download PDF

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Publication number
EP0924095A1
EP0924095A1 EP98124418A EP98124418A EP0924095A1 EP 0924095 A1 EP0924095 A1 EP 0924095A1 EP 98124418 A EP98124418 A EP 98124418A EP 98124418 A EP98124418 A EP 98124418A EP 0924095 A1 EP0924095 A1 EP 0924095A1
Authority
EP
European Patent Office
Prior art keywords
polyolefin resin
carbon black
laser
marking
propylene
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.)
Withdrawn
Application number
EP98124418A
Other languages
English (en)
French (fr)
Inventor
Kenji c/o JAPAN POLYCHEM CORPORATION Matsuoka
Ikuo c/o JAPAN POLYCHEM CORPORATION Tsutsumi
Yoshio c/o RHOMBIC CORPORATION Kobayashi
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.)
Japan Polychem Corp
Rhombic Corp Japan
Rhombic Corp USA
Original Assignee
Japan Polychem Corp
Rhombic Corp Japan
Rhombic Corp USA
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 Japan Polychem Corp, Rhombic Corp Japan, Rhombic Corp USA filed Critical Japan Polychem Corp
Publication of EP0924095A1 publication Critical patent/EP0924095A1/de
Withdrawn legal-status Critical Current

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Classifications

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

Definitions

  • This invention relates to a marking method for a polyolefin resin.
  • Molded articles made of a polyolefin resin such as personal articles, domestic appliances, interior and exterior parts and engine parts of automobiles, are often marked with letters, patterns, symbols, etc.
  • ink marking methods are of low productivity, take time for ink application and baking and involve many steps.
  • ink marks lack durability, and tend to fall off due to insufficient ink adhesion and insufficient resistance to solvents or chemicals.
  • Productivity could be improved by sticking an adhesive label having marks onto a resin molded article, but the durability of the adhesive label is similarly insufficient.
  • the inks or adhesives must be removed from the molded articles to be recycled, which has reduced the applicability for recycling.
  • marking by laser beam processing i.e., laser marking can be carried out easily and rapidly to achieve markedly improved productivity.
  • laser marking a laser beam is applied to a resin molded article having incorporated therein a black pigment which synchronizes with the wavelength of the laser beam to cause the black pigment to burn and evaporate rapidly.
  • the black pigment of the laser beam-irradiated area is released to present a contrast between the irradiated area (marked area) and non-irradiated area (background).
  • the marking since the marking is to release only the pigment, the marks are very excellent in solvent resistance, chemical resistance and durability, and the thus marked articles are highly practical for recycling. For these reasons, various laser marking techniques have been studied recently.
  • JP-A-1-254743 (the term "JP-A” as used herein means an "unexamined published Japanese patent application”) teaches that incorporation of titanium dioxide and carbon black into a resin makes laser marking possible.
  • this method when this method is applied to a polyolefin resin composition, the laser marks formed have a brown or light brown color.
  • the background being black, the marks lack a sufficient contrast to the background and have insufficient visibility.
  • JP-A-4-246456 discloses a technique in which carbon black and/or graphite having high thermal conductivity is incorporated into a polyester resin so as to provide white laser marks.
  • JP-A-7-238210 teaches that an epoxy resin composition containing carbon black, an antioxidant, and a blue colorant in specific ratios provides white laser marks.
  • application of these techniques to a polyolefin resin composition fails to achieve sufficient whitening of laser marks.
  • a polyolefin resin composition for laser marking which comprises a polyolefin resin and a black pigment mainly comprising a metal oxide, which composition is capable of forming a white mark with improved visibility is also known (see JP-A-10-273537).
  • a black pigment comprising a metal oxide which is more expensive than carbon black, has less coloring power than carbon black, it should be added in a larger amount, which leads to an increase of costs.
  • An object of the present invention is to provide a laser marking method for a molded article of a black-colored polyolefin resin composition by which a white mark having improved visibility in clear contrast against the black background can be formed.
  • This object has been achieved by the surprising finding that incorporation of carbon black having specific properties into a polyolefin resin makes the polyolefin resin capable of forming a white mark with improved visibility on its surface upon being irradiated with a laser beam.
  • the present invention provides a method for marking a polyolefin resin comprising irradiating a polyolefin resin composition containing 0.1 to 1.0 part by weight of carbon black having an average secondary particle size of not smaller than 150 nm per 100 parts by weight of the polyolefin resin composition with a YAG laser.
  • the polyolefin resin composition which can be used in the present invention comprises a polyolefin resin and carbon black.
  • the polyolefin resin used in the present invention is not particularly limited, and those generally used in polyolefin molded products can be used.
  • Suitable polyolefin resins include ethylene resins, such as ethylene homopolymers and ethylene copolymers, e.g., ethylene- ⁇ -olefin (e.g., propylene) copolymers; propylene resins, such as propylene homopolymers and propylene- ⁇ -olefin random or block copolymers; and other ⁇ -olefin resins, such as polybutene-1, poly-4-methylbutene-1, poly-3-methylbutene-1, and poly-4-methylpentene-1.
  • ethylene resins such as ethylene homopolymers and ethylene copolymers, e.g., ethylene- ⁇ -olefin (e.g., propylene) copolymers
  • propylene resins such as propylene homopolymers and propylene- ⁇ -o
  • olefin copolymers comprising ethylene or propylene and copolymerizable monomers, such as unsaturated carboxylic acids or derivatives thereof (e.g., acrylic acid, methyl methacrylate, ethyl acrylate, and maleic anhydride), aromatic unsaturated monomers (e.g., styrene and ⁇ -methylstyrene), vinyl esters (e.g., vinyl acetate and vinyl butyrate), vinylsilanes, etc.; and saponification products or metal-ionized products of these copolymers are also useful.
  • unsaturated carboxylic acids or derivatives thereof e.g., acrylic acid, methyl methacrylate, ethyl acrylate, and maleic anhydride
  • aromatic unsaturated monomers e.g., styrene and ⁇ -methylstyrene
  • vinyl esters e.g., vinyl acetate and vinyl butyrate
  • vinylsilanes etc.
  • ethylene resins such as ethylene homopolymers and ethylene-propylene copolymers
  • propylene resins such as propylene homopolymers, propylene-ethylene random copolymers, propylene-ethylene block copolymers, and propylene-ethylene-butene copolymers.
  • the ethylene content of the ethylene-propylene copolymer mainly comprising ethylene is about 60 to 95% by weight, and that of the propylene-ethylene random or block copolymer mainly comprising propylene is about 0.5 to 20% by weight.
  • suitable polyolefin resins are high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, branched low-density polyethylene, ethylene-propylene copolymers, propylene homopolymers, propylene-ethylene random copolymers, propylene-ethylene block copolymers, propylene-ethylene-butene copolymers, polybutene-1, poly-4-methylbutene-1, poly-3-methylbutene-1, and poly-4-methylpentene-1.
  • Particularly suitable polyolefin resins are propylene resins, such as propylene homopolymers and propylene-ethylene block or random copolymers. Propylene-ethylene block copolymers are especially preferred.
  • the polyolefin resin usually used in the present invention should preferably have a melt flow rate (MFR) of about 0.1 to 300 g/10min, more preferably about 1 to 150 g/10 min.
  • MFR melt flow rate
  • Carbon black is classified according to the process of its production into furnace black, channel black, thermal black, etc. and by raw material into acetylene black, ketjen black, oil black, gas black, etc. Any of these carbon black species can be used in the present invention. Acetylene black and ketjen black that have high electrical conductivity are particularly preferred.
  • the carbon black used in the present invention it is usually preferred for the carbon black used in the present invention to have an average primary particle size of not smaller than 30 nm, preferably from 40 to 150 nm, still preferably from 60 to 120 nm.
  • the fine carbon black particles having the above particle size it is important for the fine carbon black particles having the above particle size to agglomerate to form secondary particles (aggregate) having a diameter of not smaller than 150 nm, preferably from 150 to 1,000 nm, still preferably from 200 to 500 nm. If carbon black having an average secondary particle size (average aggregate size) of smaller than 150 nm is used, the mark assumes a pale brown color having reduced visibility.
  • the primary and secondary particle sizes of carbon black can be measured as follows.
  • the maximum diameters of selected particles are measured under an electron microscope to obtain a number average.
  • a frequency distribution curve of Stoke's equivalent diameter of secondary particles is prepared according to a centrifugal sedimentation method by means of a disc centrifuge manufactured by Joyes Loebl Co., G.B. and the 50% diameter of the curve is read.
  • the carbon black is used in an amount of 0.1 to 1.0 part by weight, preferably 0.1 to 0.7 part by weight, particularly preferably 0.2 to 0.5 part by weight, per 100 parts by weight of the polyolefin resin composition. If the amount of the carbon black is less than 0.1 part, absorption of laser energy is insufficient for making marks. On the other hand, more than 1 part of carbon black absorbs excessive laser energy to generate excessive heat while being released, which will cause the resin to change its color. It follows that the marked area turns light brown due to scorching and is poorly visible.
  • the polyolefin resin composition used in the present invention can contain inorganic fillers, such as talc and glass fiber.
  • Talc which can be used in the present invention preferably has an average particle size of not greater than 5 ⁇ m, more preferably from 0.5 to 3 ⁇ m, and a specific surface area of preferably not less than 3.5 m 2 /g, more preferably from 3.5 to 6 m 2 /g.
  • the average particle size is obtained as a 50% diameter of a cumulative distribution curve determined according to a liquid phase sedimentation photo-extinction method by use of, e.g., Model CP manufactured by Shimadzu Corp.
  • the specific surface area is measured by an air permeation method by use of, e.g., Model SS-100 (constant pressure type) manufactured by Shimadzu Corp.
  • Talc to be used is prepared by, for example, dry grinding followed by dry classification.
  • talc can be treated with various surface treating agents, such as organic titanate coupling agents, organic silane coupling agents, fatty acids, fatty acid metal salts, and fatty acid esters.
  • surface treating agents such as organic titanate coupling agents, organic silane coupling agents, fatty acids, fatty acid metal salts, and fatty acid esters.
  • Talc is preferably added in an amount of 1 to 60 % by weight based on the polyolefin resin composition.
  • Glass fiber which can be used in the present invention includes glass fiber having been treated with silane coupling agents, such as aminosilanes (e.g., ⁇ -aminopropyltriethoxysilane), epoxysilanes (e.g., ⁇ -glycidoxypropyltrimethoxysilane) and vinylsilanes (e.g., vinyltrichlorosilane).
  • silane coupling agents such as aminosilanes (e.g., ⁇ -aminopropyltriethoxysilane), epoxysilanes (e.g., ⁇ -glycidoxypropyltrimethoxysilane) and vinylsilanes (e.g., vinyltrichlorosilane).
  • Glass fiber having an average fiber diameter of 5 to 25 ⁇ m, particularly 8 to 15 ⁇ m, is preferred. If the fiber diameter is less than 5 ⁇ m, the productivity of strands as well as glass fiber-reinforced resin is considerably reduced and the production costs are increased. Glass fiber thicker than 25 ⁇ m tends to have a too broad distribution of residual fiber length, which deteriorates the appearance of the molded article, and the aspect ratio of glass fibers is diminished so that the degree of improvement in mechanical properties such as flexural modulus is reduced.
  • Glass fiber strands usually consist of 100 to 5,000 filaments, preferably 300 to 3,000 filaments, still preferably 500 to 2,000 filaments.
  • alkali-free glass such as E glass
  • the glass fiber length is usually 2 to 20 mm, preferably 3 to 10 mm, still preferably 4 to 9 mm, particularly preferably 5 to 8 mm.
  • Glass fiber is preferably used in an amount of 1 to 70% by weight, particularly 10 to 40% by weight, based on the polyolefin resin composition.
  • the polyolefin resin composition can further contain other additives as far as the effects of the present invention are not impaired.
  • Useful additives include phenol type, sulfur type or phosphorus type antioxidants; benzophenone type or benzotriazole type weathering agents; nucleating agents, such as organoaluminum compounds, ultraviolet absorbers, organophosphorus compounds, and sorbitol compounds; and dispersants.
  • a YAG laser is a solid state laser using an yttrium-aluminum-garnet (Y 3 Al 5 O 12 ) generally doped with about 1% Nd 3+ and has near infrared output at a wavelength of 1.06 ⁇ m It is capable of pulse oscillation on excitement with light of a xenon flash lamp and continuous oscillation on excitement with continuous light from a tungsten iodine lamp, a krypton arc lamp, etc.
  • Y 3 Al 5 O 12 yttrium-aluminum-garnet
  • a carbon dioxide gas laser is used in place of a YAG laser, the surface of the molded article is only etched with little release of the irradiated pigment so that the resulting mark lacks clear contrast against the background and is not clearly visible.
  • Laser marking on a molded article with a YAG laser can be carried out by imagewise scanning the molded article with a laser beam or irradiating the molded article with a laser beam through a mask.
  • the output of the laser may be continuous or pulsating (normal or Q switch pulses).
  • the mark thus formed on the polyolefin resin being white in color, is distinctly visible in clear contrast against the background. Therefore, the present invention is suitably applied to marking on various polyolefin molded articles, such as personal articles, domestic appliances, interior and exterior parts and engine parts of automobiles, with letters, patterns, and symbols.
  • a molded article of the polyolefin resin composition shown in Table 1 below was marked with a YAG laser or a carbon dioxide gas laser under the following conditions, and the contrast between the mark and the background and the visibility of the mark were evaluated in accordance with the following methods. The results obtained are shown in Table 1.
  • the lightness of the mark and the background was measured with MMP-300A manufactured by Nihon Denshoku Kogyo K.K. to obtain a lightness difference ( ⁇ L) .
  • ⁇ L lightness difference
  • the marking method of the present invention provides a polyolefin resin molded article having highly visible marks such as letters, patterns, and signals in clear contrast against the background.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP98124418A 1997-12-22 1998-12-22 Verfahren zur Lasermarkierung von Polyolefinharzen Withdrawn EP0924095A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP35305097 1997-12-22
JP35305097A JPH11181104A (ja) 1997-12-22 1997-12-22 ポリオレフィン系樹脂のマーキング方法

Publications (1)

Publication Number Publication Date
EP0924095A1 true EP0924095A1 (de) 1999-06-23

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EP98124418A Withdrawn EP0924095A1 (de) 1997-12-22 1998-12-22 Verfahren zur Lasermarkierung von Polyolefinharzen

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EP (1) EP0924095A1 (de)
JP (1) JPH11181104A (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1162232A4 (de) * 1998-07-27 2003-05-02 Daicel Chem Laserbeschriftete harzzusammensetzung, beschriftungsverfahren und beschrifteter gegossener gegenstand
WO2009053876A3 (en) * 2007-10-23 2009-06-25 Philips Intellectual Property Nir emitters excitable in the visible spectral range and their application in biochemical and medical imaging
US8980413B2 (en) 2009-09-18 2015-03-17 Youl Chon Chemical Co., Ltd. Cell packaging material and method for manufacturing same
EP3466708A1 (de) 2017-10-04 2019-04-10 Borealis AG Polyolefin zusammensetzung für verbesserte laserdruck
EP3584088A1 (de) 2018-06-19 2019-12-25 Borealis AG Polyolefinzusammensetzung zur bereitstellung einer markierung durch fluoreszenz
EP3584089A1 (de) 2018-06-19 2019-12-25 Borealis AG Polyolefinzusammensetzung mit verbessertem kontrast von lasermarkierungen
CN114316442A (zh) * 2021-12-21 2022-04-12 天津金发新材料有限公司 一种易热熔焊接、高透明、易激光打标改性pp材料及其制备方法和应用
CN116478474A (zh) * 2023-04-26 2023-07-25 江苏金发科技新材料有限公司 一种可激光打标半透光数显聚丙烯复合材料及其制备方法和应用
EP4491663A1 (de) * 2023-07-10 2025-01-15 Borealis AG Flammhemmende polypropylenzusammensetzung mit lasermarkierungsfähigkeit
WO2025025449A1 (zh) * 2023-08-03 2025-02-06 华南理工大学 一种激光快速热解聚烯烃制备乙烯基封端聚合物的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6371548B1 (en) * 2000-07-25 2002-04-16 Textron Automotive Company Inc. Automotive trim panel with electrical wiring incorporated therein

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330869A1 (de) * 1988-02-18 1989-09-06 Bayer Ag Laser-beschriftbares Material
EP0413664A2 (de) * 1989-08-18 1991-02-20 Ciba-Geigy Ag Lasermarkierung von Kunststoffgegenständen in an sich beliebiger Form mit besonderen Effekten
EP0710570A1 (de) * 1994-11-04 1996-05-08 Quantum Chemical Corporation Polymerzusammensetzung und Verfahren zur Beschriftung der Oberfläche dieser Zusammensetzung durch Laser
EP0827980A2 (de) * 1996-09-10 1998-03-11 Daicel Chemical Industries, Ltd. Harzzusammenstellung zur Erzeugung weisser Markierungen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330869A1 (de) * 1988-02-18 1989-09-06 Bayer Ag Laser-beschriftbares Material
EP0413664A2 (de) * 1989-08-18 1991-02-20 Ciba-Geigy Ag Lasermarkierung von Kunststoffgegenständen in an sich beliebiger Form mit besonderen Effekten
EP0710570A1 (de) * 1994-11-04 1996-05-08 Quantum Chemical Corporation Polymerzusammensetzung und Verfahren zur Beschriftung der Oberfläche dieser Zusammensetzung durch Laser
EP0827980A2 (de) * 1996-09-10 1998-03-11 Daicel Chemical Industries, Ltd. Harzzusammenstellung zur Erzeugung weisser Markierungen

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1162232A4 (de) * 1998-07-27 2003-05-02 Daicel Chem Laserbeschriftete harzzusammensetzung, beschriftungsverfahren und beschrifteter gegossener gegenstand
WO2009053876A3 (en) * 2007-10-23 2009-06-25 Philips Intellectual Property Nir emitters excitable in the visible spectral range and their application in biochemical and medical imaging
US8980413B2 (en) 2009-09-18 2015-03-17 Youl Chon Chemical Co., Ltd. Cell packaging material and method for manufacturing same
EP3466708A1 (de) 2017-10-04 2019-04-10 Borealis AG Polyolefin zusammensetzung für verbesserte laserdruck
WO2019068815A1 (en) 2017-10-04 2019-04-11 Borealis Ag POLYOLEFIN COMPOSITION FOR ENHANCED LASER PRINTING
CN112292267A (zh) * 2018-06-19 2021-01-29 博里利斯股份公司 通过荧光提供标记的聚烯烃组合物
AU2019290964B2 (en) * 2018-06-19 2022-04-28 Borealis Ag Polyolefin composition providing improved contrast of laser marks
WO2019243132A1 (en) 2018-06-19 2019-12-26 Borealis Ag Polyolefin composition providing marking by fluorescence
WO2019243134A1 (en) 2018-06-19 2019-12-26 Borealis Ag Polyolefin composition providing improved contrast of laser marks
CN112236308A (zh) * 2018-06-19 2021-01-15 北欧化工公司 提供改进激光标记对比度的聚烯烃组合物
EP3584088A1 (de) 2018-06-19 2019-12-25 Borealis AG Polyolefinzusammensetzung zur bereitstellung einer markierung durch fluoreszenz
RU2759596C1 (ru) * 2018-06-19 2021-11-15 Бореалис Аг Полиолефиновая композиция, обеспечивающая улучшенный контраст лазерных знаков
RU2764841C1 (ru) * 2018-06-19 2022-01-21 Бореалис Аг Полиолефиновая композиция, обеспечивающая маркировку с помощью флуоресценции
US12049552B2 (en) 2018-06-19 2024-07-30 Borealis Ag Polyolefin composition providing improved contrast of laser marks
EP3584089A1 (de) 2018-06-19 2019-12-25 Borealis AG Polyolefinzusammensetzung mit verbessertem kontrast von lasermarkierungen
US11958957B2 (en) 2018-06-19 2024-04-16 Borealis Ag Polyolefin composition providing marking by fluorescence
CN114316442B (zh) * 2021-12-21 2023-06-20 天津金发新材料有限公司 一种易热熔焊接、高透明、易激光打标改性pp材料及其制备方法和应用
CN114316442A (zh) * 2021-12-21 2022-04-12 天津金发新材料有限公司 一种易热熔焊接、高透明、易激光打标改性pp材料及其制备方法和应用
CN116478474A (zh) * 2023-04-26 2023-07-25 江苏金发科技新材料有限公司 一种可激光打标半透光数显聚丙烯复合材料及其制备方法和应用
EP4491663A1 (de) * 2023-07-10 2025-01-15 Borealis AG Flammhemmende polypropylenzusammensetzung mit lasermarkierungsfähigkeit
WO2025012290A1 (en) * 2023-07-10 2025-01-16 Borealis Ag Use of flame retardant polypropylene composition for laser marking
WO2025025449A1 (zh) * 2023-08-03 2025-02-06 华南理工大学 一种激光快速热解聚烯烃制备乙烯基封端聚合物的方法

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