EP0680831B1 - Formkörper mit einer Markierung auf einem thermoplastischen Substrat und Verfahren zum Herstellen der Formkörper - Google Patents

Formkörper mit einer Markierung auf einem thermoplastischen Substrat und Verfahren zum Herstellen der Formkörper Download PDF

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Publication number
EP0680831B1
EP0680831B1 EP95201142A EP95201142A EP0680831B1 EP 0680831 B1 EP0680831 B1 EP 0680831B1 EP 95201142 A EP95201142 A EP 95201142A EP 95201142 A EP95201142 A EP 95201142A EP 0680831 B1 EP0680831 B1 EP 0680831B1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
synthetic material
thermoplastic synthetic
agent
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.)
Expired - Lifetime
Application number
EP95201142A
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English (en)
French (fr)
Other versions
EP0680831A1 (de
Inventor
Wilhelmus H.H.A. Van Den Elshout
Olav Marcus Aagaard
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.)
Koninklijke DSM NV
DSM IP Assets BV
Original Assignee
DSM NV
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 DSM NV filed Critical DSM NV
Publication of EP0680831A1 publication Critical patent/EP0680831A1/de
Application granted granted Critical
Publication of EP0680831B1 publication Critical patent/EP0680831B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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

  • the invention relates to a shaped article with a marking on a thermoplastic substrate, which marking is made by foaming the thermoplastic by means of high-energy irradiation.
  • the invention also relates to a process for the manufacture of the shaped article with a marking on a thermoplastic substrate.
  • Such shaped articles are known from EP-A-469982. From this patent specification it is known to make a marking by subjecting a thermoplastic to high-energy irradiation, as a result of which moisture or air present expands and forms bubbles, causing local foaming of the material.
  • 'marking' in the present application is understood a pattern containing information, such as an image, an emblem, a logo, a text consisting of letters and/or digits, a code, such as a bar code etc., or a pattern with an aesthetic or decorative function.
  • Examples of shaped articles bearing a marking are housings of electronic or electrical equipment, keys, buttons, publicity signs, nameplates, company name signs, etc.
  • Other examples are calibrated containers, such as measuring beakers, syringes and coffeemaker reservoirs.
  • markings are applied by subjecting the shaped article to high-energy irradiation in the pattern of the marking, for instance by means of a laser beam, causing the synthetic material to foam.
  • An advantage of such a marking is that it can be applied very accurately on the desired spot.
  • a further advantage is that the shaped articles can be manufactured in series in the known manner without application of a marking, while subsequently any desired marking, different for each individual object, can be applied.
  • An additional advantage of such a marking is that it can be applied simply on mouldings with curved surfaces.
  • a drawback of the known moulding with the marking is that the marking is not abrasion resistant. Fast abrasion of the marking on for instance keys or buttons may result in illegibility, which may be the cause of incorrect setting of equipments and, in consequence, unsafe situations.
  • the aim of the invention is to provide a moulding which does not have this drawback.
  • thermoplastic synthetic material contains an agent which, due to the action of the high-energy irradiation, has caused crosslinking at the spot where the foaming of the thermoplastic synthetic material has occurred.
  • a further advantage of the moulding according to the invention is that the marking possesses good resistance to solvents.
  • Mouldings of a thermoplastic synthetic material comprising an agent are also known from EP-A 0 566 312 and EP-A 572 178.
  • the agents are one or more compounds selected from the group consisting of tetrazole compounds, and also sulfonylhydrazide compounds, nitroso compounds and azo compounds having a decomposition temperature of 210°C or more.
  • these agents ensure foaming of the thermoplastic synthetic material and both documents are silent about the occurrence of crosslinking.
  • the moulding may in principle contain any thermoplastic which can be foamed by means of high-energy irradiation in order to serve as substrate for the marking.
  • ABS acrylontrile-butadiene-styrene copolymer
  • Acrylontrile-butadiene-styrene copolymer is described for instance in EP-A-104695, in which it is described as a polymer composition consisting of:
  • Suitable acrylic compounds are acrylonitrile, methacrylonitrile alkyl acrylate, alkyl acrylate or mixtures thereof.
  • Suitable vinyl aromatic compounds are styrene and substituted styrene compounds like alpha-methylstyrene, p-vinyltoluene or mixtures thereof.
  • the rubber content of the graft copolymer is preferably between 15 and 50 wt% relative to the graft copolymer.
  • Suitable rubbers are butadiene rubbers like polybutadiene, butadiene-styrene, butadiene-acrylonitrile or butadiene-acrylate rubber.
  • High-energy irradiation of a surface is preferably understood to be irradiation of a surface with a laser beam.
  • the agent which brings about the crosslinking does not produce or hardly produces this effect at the processing temperature of the thermoplastic synthetic material, but mainly does so under conditions at which the shaped article is subjected to high-energy irradiation according to the invention, which is accompanied by foaming of the thermoplastic synthetic material.
  • the crosslinking by means of the agent can be brought about by the effect of the very high temperature which occurs during the irradiation or by the effect of UV light which can be present in the high-energy rays used.
  • a preferred embodiment of the invention relates to the shaped article with the marking on a thermoplastic substrate containing an agent which by the effect of high-energy irradiation brings about the crosslinking.
  • An advantage of this embodiment is that only a minor quantity of the agent need be present in the thermoplastic synthetic material, so that the mechanical properties of the thermoplastic synthetic material are preserved better.
  • the agent is preferably present in the thermoplastic synthetic material in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the thermoplastic synthetic material.
  • the agent preferably is a radical generator. Suitable radical generators are for instance compounds which form carbon radicals, such as 2,3-dimethyl-2,3-diphenylbutane.
  • Another preferred embodiment of the invention relates to the shaped article with the marking on a thermoplastic substrate containing an agent which by the effect of high-energy irradiation forms a network within itself.
  • a network extends in the form of a co-continuous phase into the foamed thermoplastic synthetic material.
  • the agent is preferably present in the thermoplastic synthetic material in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the thermoplastic synthetic material.
  • the agent is preferably composed of between 1 and 19 parts by weight of polypropylene glycol per 100 parts by weight of the thermoplastic synthetic material and between 1 and 19 parts by weight of caprolactone polymer per 100 parts by weight of the thermoplastic synthetic material, the sum of the parts by weight of polypropylene glycol and caprolactone polymer being 2-20. In this way it is ensured that the laser marking according to the invention possesses good abrasion resistance, while preserving the mechanical properties of the thermoplastic synthetic material. If the agent is melamine, the particles preferably have a diameter of ⁇ 10 ⁇ .
  • the shaped article according to the invention without the marking applied onto it, can be manufactured in accordance with the known processes and irradiated with high-energy radiation in a pattern corresponding to the shape of the marking.
  • thermoplastic polymer e.g., polystyrene-butadiene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styren
  • the shaped article according to the invention comes in many variants.
  • the shaped article may be made entirely of the thermoplastic synthetic material. It is also possible to apply a coating of the thermoplastic synthetic material onto a shaped article made of metal or a ceramic material.
  • the granulate obtained in this way was injection moulded to black sheets at a temperature of 240°C with an ARBURG Allrounder® (320-90-750) injection shaped article machine.
  • a part of the surface of the sheets was then irradiated with a leaser beam from an SHG Nd:YAG Q-switch laser, type Haas Laser® 6411 Engravity System (from Haas Laser, Germany).
  • the pulse time was 110 nanoseconds, the wavelength was 532 nanometres, at a high radiation energy density (about 20 Joule/cm 2 ).
  • the marking obtained in this way had a white/grey colour.
  • the abrasion resistance of this marking was tested by means of the device used in the Taber abraser test (ASTM D4060: 'Standard Test Method for Abrasion Resistance of Organic Coatings by the Taber Abraser'). The abrasion resistance was qualified as 'good', 'reasonable' or 'poor'.
  • the impact resistance of the marked material was measured in kJ/m 2 according to DIN 51320 (Izod impact test, notched).
  • Comparative experiment A was repeated, but now using 94.3 parts by weight of acrylonitrile-butadiene-styrene copolymer (Ronfalin® SFA-34, from DSM, of the Netherlands), 0.6 part by weight of carbon black (Black Pearls® 880, from CABOT, of the Netherlands) and 0.1 part by weight of titanium dioxide (Tiofine® R41, from TIOFINE, of the Netherlands), 2.5 parts by weight of PPG 2000 (polypropylene glycol 2000, from Hofag Chemical Corporation, of the USA) and 2.5 parts by weight of CAPA® 656 (from Interox Chemicals Ltd., of the UK).
  • Ronfalin® SFA-34 acrylonitrile-butadiene-styrene copolymer
  • carbon black Black Pearls® 880, from CABOT, of the Netherlands
  • titanium dioxide Teofine® R41, from TIOFINE, of the Netherlands
  • PPG 2000 polypropylene glycol 2000, from Hofag Chemical Corporation, of
  • Example I was repeated, but now PPG 2000 and CAPA (TM) 656 were replaced by 5 parts by weight of Perkadox (TM) 30 (from AKZO Chemicals Division, of the Netherlands).
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 5 parts by weight of Spinflam (TM) MF83 (from Himont, of Italy).
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 5 parts by weight of Ceepree (TM) C-200 (from ICI Chemicals & Polymers Ltd., of the UK).
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 5 parts by weight of Ceepree (TM) Microfine (from ICI Chemicals & Polymers Ltd., of the UK).
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 2 parts by weight of pentaerythritol (Qual. R., pulverized, from Degussa, of Germany) and 3 parts by weight of Exolyt (TM) 422 (ammonium polyphosphate, from Hoechst Holland n.v., of the Netherlands).
  • TM pentaerythritol
  • TM Exolyt
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 2 parts by weight of Dures 22091 (novolac, from Occidental Chemical, of Belgium) and 3 parts by weight of Exolyt (TM) 422 (ammonium polyphosphate, from Hoechst Holland n.v., of the Netherlands).
  • TM Perkadox
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 1 part by weight of Madurit (TM) MW909 (cured melamine-formaldehyde resin, from Hoechst Holland n.v., of the Netherlands) and 94.3 parts by weight of ABS were replaced by 98.3 parts by weight of ABS.
  • TM Perkadox
  • TM Madurit
  • MW909 cured melamine-formaldehyde resin
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 3 parts by weight of Melamine Superfine (TM), D90 ⁇ 5 m ⁇ (from DSM, of the Netherlands) and 94.3 parts by weight of ABS were replaced by 96.3 parts by weight of ABS.
  • TM Perkadox
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 2 parts by weight of trishydroxyethyl isocyanurate (from BASF AG, of Germany) and 3 parts by weight of Exolyt (TM) 422 (ammonium polyphosphate, from Hoechst Holland n.v., of the Netherlands).
  • TM Trishydroxyethyl isocyanurate
  • TM Exolyt
  • Example II was repeated, but now Perkadox (TM) 30 was replaced by 3 parts by weight of Melamine Superfine (TM), D90 ⁇ 100 m ⁇ (from DSM, of the Netherlands) and 94.3 parts by weight of ABS were replaced by 96.3 parts by weight of ABS.
  • TM Perkadox
  • TM Melamine Superfine
  • D90 ⁇ 100 m ⁇ from DSM, of the Netherlands
  • ABS 94.3 parts by weight

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)

Claims (10)

  1. Formartikel mit einer Markierung auf einem thermoplastischen Substrat, wobei die Markierung durch Schäumen des Thermoplasten mithilfe von Hochenergiebestrahlung erfolgt, dadurch gekennzeichnet, daß das thermoplastische synthetische Material ein Mittel enthält, das durch die Wirkung der Hochenergiebestrahlung eine Vernetzung an der Stelle herbeigeführt hat, wo das Schäumen des thermoplastischen synthetischen Materials aufgetreten ist, wobei thermoplastische Substrate, die ein oder mehrere Verbindungen der Gruppe aus Tetrazolverbindungen, Sulfonylhydrazidverbindungen, Nitrosoverbindungen und Azoverbindungen, die eine Zersetzungstemperatur von 210°C oder mehr haben, ausgeschlossen sind.
  2. Formartikel gemäß Anspruch 1, dadurch gekennzeichnet, daß ABS (Acrylnitril-Butadien-Styrol-Copolymer) als thermoplastisches synthetisches Material verwendet wird.
  3. Formartikel gemäß Anspruch 1, dadurch gekennzeichnet, daß das Mittel durch Vernetzung des thermoplastischen synthetischen Materials eine Vernetzung herbeigeführt hat.
  4. Formartikel gemäß Anspruch 3, dadurch gekennzeichnet, daß das Mittel im thermoplastischen synthetischen Material in einer Menge von 0,01 bis 10 Gewichtsteilen pro 100 Gewichtsteile des thermoplastischen synthetischen Materials vorhanden ist.
  5. Formartikel gemäß den Ansprüchen 3 und 4, dadurch gekennzeichnet, daß das Mittel ein Radikalbildner ist.
  6. Formartikel gemäß Anspruch 5, dadurch gekennzeichnet, daß das Mittel 2,3-Dimethyl-2,3-diphenylbutan ist.
  7. Formartikel gemäß Anspruch 1, dadurch gekennzeichnet, daß das Mittel die Vernetzung durch die Bildung eines Netzes in sich selbst herbeigeführt hat.
  8. Formartikel gemäß Anspruch 7, dadurch gekennzeichnet, daß das Mittel im thermoplastischen synthetischen Material in einer Menge von 0,1 bis 20 Gewichtsteilen pro 100 Gewichtsteile des thermoplastischen synthetischen Materials vorhanden ist.
  9. Formartikel gemäß Anspruch 7, dadurch gekennzeichnet, daß das Mittel zwischen 1 und 19 Gewichtsteile Polypropylenglykol pro 100 Gewichtsteile des thermoplastischen synthetischen Materials und zwischen 1 und 19 Gewichtsteile Caprolactonpolymer pro 100 Gewichtsteile des thermoplastischen synthetischen Materials enthält, wobei die Summe der Gewichtsteile von Polypropylenglykol und Caprolactonpolymer 2-20 beträgt.
  10. Formartikel gemäß den Ansprüchen 7 und 8, dadurch gekennzeichnet, daß das Mittel Melamin ist und die Melaminteilchen einen Durchmesser von <10 µm haben.
EP95201142A 1994-05-04 1995-05-03 Formkörper mit einer Markierung auf einem thermoplastischen Substrat und Verfahren zum Herstellen der Formkörper Expired - Lifetime EP0680831B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9400464A BE1008341A3 (nl) 1994-05-04 1994-05-04 Vormdeel met een markering op een ondergrond van een thermoplastische kunststof en een werkwijze voor de bereiding van het vormdeel.
BE9400464 1994-05-04

Publications (2)

Publication Number Publication Date
EP0680831A1 EP0680831A1 (de) 1995-11-08
EP0680831B1 true EP0680831B1 (de) 1998-07-08

Family

ID=3888141

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Application Number Title Priority Date Filing Date
EP95201142A Expired - Lifetime EP0680831B1 (de) 1994-05-04 1995-05-03 Formkörper mit einer Markierung auf einem thermoplastischen Substrat und Verfahren zum Herstellen der Formkörper

Country Status (4)

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EP (1) EP0680831B1 (de)
AT (1) ATE168074T1 (de)
BE (1) BE1008341A3 (de)
DE (1) DE69503309T2 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5977514A (en) * 1997-06-13 1999-11-02 M.A. Hannacolor Controlled color laser marking of plastics
US5976411A (en) * 1997-12-16 1999-11-02 M.A. Hannacolor Laser marking of phosphorescent plastic articles
KR20040086466A (ko) * 2002-03-01 2004-10-08 마켐 코포레이션 기판 마킹
EP2110260A1 (de) * 2008-04-15 2009-10-21 Gemalto SA Benutzerdefinierbarer Datenträger, der mit verschiedenen Mitteln zur Fälschungssicherung ausgestattet ist und Herstellungsverfahren eines solchen Datenträgers
JP6897642B2 (ja) * 2018-08-31 2021-07-07 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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60206845A (ja) * 1984-03-30 1985-10-18 Kanegafuchi Chem Ind Co Ltd 発泡性熱可塑性共重合体粒子
JPH03167246A (ja) * 1989-11-29 1991-07-19 Nippon Oil Co Ltd 樹脂組成物
JPH0489285A (ja) * 1990-07-31 1992-03-23 Sony Corp 合成樹脂成形体への印字方法
JP3102818B2 (ja) * 1992-04-16 2000-10-23 日本ジーイープラスチックス株式会社 レーザーマーキング用樹脂組成物
NL9202096A (nl) * 1992-12-02 1993-04-01 Dsm Nv Polymeersamenstelling, bevattende een polymeer en tenminste een stralingsgevoelig bestanddeel.

Also Published As

Publication number Publication date
EP0680831A1 (de) 1995-11-08
DE69503309D1 (de) 1998-08-13
DE69503309T2 (de) 1999-04-15
BE1008341A3 (nl) 1996-04-02
ATE168074T1 (de) 1998-07-15

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