EP0868309B1 - Verfahren zur herstellung eines gegenstands mit farbigen markierung - Google Patents

Verfahren zur herstellung eines gegenstands mit farbigen markierung Download PDF

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Publication number
EP0868309B1
EP0868309B1 EP96941221A EP96941221A EP0868309B1 EP 0868309 B1 EP0868309 B1 EP 0868309B1 EP 96941221 A EP96941221 A EP 96941221A EP 96941221 A EP96941221 A EP 96941221A EP 0868309 B1 EP0868309 B1 EP 0868309B1
Authority
EP
European Patent Office
Prior art keywords
light
colour
process according
mask
laser light
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
EP96941221A
Other languages
English (en)
French (fr)
Other versions
EP0868309A1 (de
Inventor
Wilhelmus Henricus Hubertus 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 EP0868309A1 publication Critical patent/EP0868309A1/de
Application granted granted Critical
Publication of EP0868309B1 publication Critical patent/EP0868309B1/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
    • 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 process for the manufacture of a colour-marked object by irradiating the surface of the object with laser light.
  • a disadvantage of the known process is that the colours obtained are not freely chosen but are achieved by chance. Moreover, the marking can be obtained in only a limited number of colours.
  • the invention aims to provide a process that does not have the aforementioned disadvantages.
  • the object at least at the location where the marking is applied, consists of a plastic composition which contains at least three light-absorbing components which exhibit a maximum in their light absorption spectra at different wavelengths and lose their light-absorbing capacity under the influence of laser light, with the marking being applied in the form of matrix dots by irradiating the object's surface at the location of the matrix dots with laser light of such wavelength and intensity and for such duration that at least one of the light-absorbing components has completely or partially lost its light-absorbing capacity.
  • the marking may contain different colours and markings in different colours can be obtained on the surface of the same plastic composition.
  • the marking can even be obtained on the surface of the same plastic composition in a great many different colours.
  • a matrix dot has the colour of the light, that is absorbed by colour absoring component, before the component has completely or partly lost its light absoring capacity.
  • Light-absorbing components are understood to be components having a chromatic colour, such as dyes and pigments. Light-absorbing components are understood not to include white or black components such as titanium dioxide, chalk, barium sulphide, carbon black or iron sulphide.
  • the light-absorbing components do not lose or only hardly lose their light-absorbing capacity in normal daylight. For this reason, the light-absorbing components possess a colour stability of at least 5, more preferably at least 7 and still more preferably more than 7 on the Wool scale (in accordance with DIN 54003).
  • suitable light-absorbing components are Irgalith® Rubine 4 BP, a magenta-coloured pigment, Irgalith Blue LGLD, a cyan-coloured pigment, or Cromopthal® Yellow 6G and Cromopthal Yellow 3G, two yellow-coloured pigments. Incidentally, most light-absorbing components lose their light-absorbing capacity in whole or part on being irradiated with laser light.
  • the process of the invention allows matrix dots to be applied onto the surface in a simple manner.
  • Irradiation with laser light of a particular wavelength reduces the light-absorbing capacity of a preselected light-absorbing component and the surface on the irradiated sites will reflect the colour which is no longer absorbed by the component in question.
  • the brightness of the reflected colour can be enhanced by increasing the intensity of the laser light or extending the duration of irradiation.
  • a marking of a desired colour is formed by applying a great many matrix dots on the surface.
  • the colour of the surface at the location of the matrix dots is a mixed colour because the colours of the matrix dots strike the eye as though they blend.
  • This method of colour mixing in which the colours to be mixed are located side by side, is called the partitive method.
  • the mixed colour is determined by the ratio of the surface area of the matrix dots and the ratio of the brightness of the colours. In this way, a great many mixed colours can be formed.
  • Mixed colours can be achieved in a variety of fashions.
  • Mixed colours can be achieved by, for example, varying the brightness of the colours of the matrix dots in relation to each other; by, for example, irradiating the matrix dots of a particular colour longer than other matrix dots.
  • the ratio of the total area of the different colours can be varied in relation to each other by, for example, making one matrix dot larger than the other or by forming more matrix dots of one colour than of the other colours.
  • the matrix dots may be round or square but they may also be, for example, triangular or linear for example in order to fill the surface better or to increase the total reflection of the surface.
  • a colour can be characterized in accordance with ASTM Standard E 308 by first measuring the tristimulus values of the colour and calculating therefrom the chromaticity coordinates that determine the colour's location within the CIE D65 colour diagram (10° observer) as described in the aforementioned standard.
  • the colour diagram is a graphic representation of all colours in the visible range.
  • the partitive mixing technique allows colours to be formed which in the colour diagram lie in the area between the points representing the at least three different colours of the matrix points in the colour diagram. These points form the vertices of the area.
  • a method of the invention which allows even more different colours to be obtained involves applying matrix dots so that they wholly or partially overlap.
  • This colour mixing technique is referred to as subtractive blending.
  • the colour of the surface is determined by the subtractive mixing of at least three different coloured matrix points.
  • the colour range evolving from subtractive mixtures is greater than in the case of partitive blending in that colours can be formed which in the colour diagram lie outside the area between the points which represent the at least three different colours of the matrix points in the colour diagram.
  • the plastic composition may in principle contain any thermoset or thermoplastic or elastomer. Plastics that the plastic composition mentioned in W094/12352 can contain are particularly suitable.
  • the light-absorbing components are so selected that the area between the points representing the at least three different colours of the matrix points in the colour diagram cover at least 10% of the area of the diagram.
  • this area covers at least 30% of the diagram, more preferably at least 75% of the diagram.
  • the wavelength of the laser light with which the surface is to be irradiated in order for a predetermined light-absorbing component to lose its light-absorbing capacity can readily be determined by experiment.
  • the wavelengths of the laser light with which the surface is irradiated are those at which the maximum occurs in the absorption spectrum of the light-absorbing component which is to lose its light-absorbing capacity. In this manner, very good selectivity and good brightness of the colours are obtained.
  • the process of the invention is practised using one or more masks.
  • Such masks are transmissive in those locations where the surface is to be irradiated and are not transmissive in those locations where the surface is not to be irradiated.
  • Successive irradiation of the surface with different masks and with laser light of different wavelengths permits matrix dots of different colours to be applied on the surface rapidly and readily.
  • An advantage of this is that the size of the matrix dots is determined by the mask, not by the diameter of the laser beam, so that the surface may be irradiated with a large-diameter laser beam. As a result, irradiation will take less time.
  • the process of the invention is practised with a variable mask.
  • PDLCD Polymer Dispersed Liquid Crystal Display
  • the desired mask can be computer-generated on the LCD screen or PDLCD screen, whereupon the surface can be irradiated through the mask. Subsequently, a second mask is retrieved on the screen in the same position. This avoids possible positioning problems.
  • Another advantage is that the various masks can be replaced very rapidly.
  • the process can also be practised using a controlled laser beam of variable intensity. This affords greater flexibility in terms of the shape of the object to be irradiated and the brightness of the colours.
  • a laser device with adjustable wavelength is also most desirable inasmuch as it is then possible to irradiate the surface with laser light of different wavelengths using a single laser device.
  • the laser is capable of emitting light of the different wavelengths that match the maxima of the absorption spectra of the different light-absorbing components. It is then possible to form all possible colours with a single laser device.
  • a laser device in which at least 3 laser beams of different wavelengths are united in a single fibre, it being possible to vary the intensity of each beam independently of the other beams.
  • the advantage of this is that the object's surface can readily be irradiated with the aid of one combined laser beam which is capable of emitting all colours. This results in very high flexibility as to the number of colours that can be selected and the shape of the marking to be applied.
  • a dry blend was prepared from 1897 parts by weight of Ronfalin ® SFA-34, an acrylonitrile-butadiene-styrene copolymer (ABS) supplied by DSM of the Netherlands, 100 parts by weight of Tiofine® R41, a titanium dioxide pigment supplied by Tiofine of the Netherlands, and 1 part by weight of Irgalith® Rubine 4BP, 1 part by weight of Irgalith Blue LGLD and 1 part by weight of Cromopthal® Yellow 6G, respectively magenta, cyan and yellow coloured pigments supplied by Messrs Ciba Geigy of the Netherlands.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the dry blend was melted in a ZSK® 30 twinscrew extruder supplied by Werner and Pfleiderer of Germany, kneaded at 260°C and granulated.
  • the granulate was injection-moulded to plaques measuring 3.2*120*120mm in an Arburg Allrounder® 320-90-750 injection-moulding machine at a temperature of 240°C.
  • the coloured pigments in the plaques absorb visible light.
  • the plaques were pale grey.
  • the laser set-up contained a type EEO®-355 seeding laser, which was used as pump laser for a type GCR®-230/50 Nd:YAG laser. Furthermore, the laser set-up contained a type MOPO® 710 Optical Parameter Oscillator (OPO), which received the signal from the last-mentioned laser via a Frequency Doubling Optic (FDO).
  • OPO Optical Parameter Oscillator
  • FDO Frequency Doubling Optic
  • a colour photo was applied onto the specimens by means of the aforementioned laser set-up by the method described below.
  • a colour photo was broken down into a "red mask”, a "green mask” and a “blue mask” (option: split channels RGB) by means of "Corel-Photoprint 5.0 for Hewlett Packard" of the Corel Corporation of the USA. These black/white masks were printed onto transparencies using a "Spectra StarTM GTx" colour printer of Messrs General Parametric Corporation of the USA. Position crosses were provided round the images for accurate positioning. Subsequently, the "blue mask” was fitted onto the aforementioned plaques and irradiated with the laser at a wavelength of 450 nm.
  • this mask was removed and replaced with the "green mask", which was accurately positioned over the image obtained with the "blue mask”.
  • This "green mask” was irradiated with laser light having a wavelength of 530 nm.
  • the "red mask” was fitted and irradiated with laser light having a wavelength of 650 nm.
  • an indelible colour photo had been obtained in the plastic, the colour range of which photo was comparable with that of the original.
  • the lacquer film had a grey hue. Markings were made in the lacquer film as described in example I.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Laser Beam Processing (AREA)
  • Bending Of Plates, Rods, And Pipes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Auxiliary Devices For And Details Of Packaging Control (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Verfahren für die Herstellung eines farbmarkierten Objekts durch Bestrahlen der Oberfläche des Objekts mit Laserlicht, dadurch gekennzeichnet, daß das Objekt, zumindest an der Stelle, wo die Markierung aufgetragen wird, aus einer Kunststoffzusammensetzung besteht, die zumindest drei lichtabsorbierende Bestandteile enthält, welche ein Maximum in ihren Lichtabsorptionsspektren bei unterschiedlichen Wellenlängen aufweisen und ihre lichtabsorbierende Fähigkeit unter dem Einfluß von Laserlicht verlieren, wobei die Markierung in Form von Matrixpunkten durch Bestrahlen der Oberfläche des Objekts an der Stelle der Matrixpunkte mit Laserlicht von einer solchen Wellenlänge und Intensität und für solch eine Dauer, daß zumindest eine der lichtabsorbierenden Bestandteile vollständig oder teilweise ihre lichtabsorbierende Fähigkeit verloren hat, aufgetragen wird.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Farbe der Oberfläche durch die subtraktive Mischung von mindestens drei verschiedenfarbigen Matrixpunkten gebildet wird.
  3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Farbe der Oberfläche durch partitives Mischen der Farben der Matrixpunkte gebildet wird.
  4. Verfahren gemäß einem der Ansprüche 1, 2 oder 3, dadurch gekennzeichnet, daß die lichtabsorbierenden Bestandteile so ausgewählt werden, daß der Bereich zwischen den Punkten, die die mindestens drei verschiedenen Farben der Matrixpunkte in dem Farbdiagramm repräsentieren, mindestens 10% des Bereichs des Diagramms abdecken.
  5. Verfahren gemäß einem der Ansprüche 1-4, dadurch gekennzeichnet, daß die Wellenlängen des Laserlichts, mit dem die Oberfläche bestrahlt wird, jene sind, bei welchen die Maxima in den Absorptionsspektren der verschiedenen lichtabsorbierenden Bestandteile auftreten.
  6. Verfahren gemäß einem der Ansprüche 1-5, dadurch gekennzeichnet, daß das Verfahren der Erfindung mit Hilfe von einer oder mehreren Masken praktiziert wird.
  7. Verfahren gemäß einem der Ansprüche 1-6, dadurch gekennzeichnet, daß das Verfahren der Erfindung mit Hilfe von einer variablen Maske praktiziert wird.
  8. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß die Maske durch einen LCD-Schirm hergestellt wird.
  9. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß von einer variablen PDLCD-Maske Gebrauch gemacht wird.
  10. Verfahren gemäß einem der Ansprüche 1-9, dadurch gekennzeichnet, daß die Oberfläche mit einer Laservorrichtung bestrahlt wird, welche gleichzeitig die Objektoberfläche mit Hilfe von mindestens 3 Masken, die aneinandergrenzend positioniert sind, bestrahlt, wobei die Masken mit Laserlicht von unterschiedlichen Wellenlängen in solch einer Weise bestrahlt werden, daß die Maskenabbilder auf die Objektoberfläche eine über der anderen projiziert werden.
EP96941221A 1995-11-30 1996-11-28 Verfahren zur herstellung eines gegenstands mit farbigen markierung Expired - Lifetime EP0868309B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL1001784 1995-11-30
NL1001784A NL1001784C2 (nl) 1995-11-30 1995-11-30 Werkwijze voor de vervaardiging van een voorwerp met gekleurde markering.
PCT/NL1996/000470 WO1997021550A1 (en) 1995-11-30 1996-11-28 Process for the manufacture of a colour-marked object

Publications (2)

Publication Number Publication Date
EP0868309A1 EP0868309A1 (de) 1998-10-07
EP0868309B1 true EP0868309B1 (de) 2000-08-02

Family

ID=19761944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96941221A Expired - Lifetime EP0868309B1 (de) 1995-11-30 1996-11-28 Verfahren zur herstellung eines gegenstands mit farbigen markierung

Country Status (16)

Country Link
EP (1) EP0868309B1 (de)
JP (1) JP2000501042A (de)
KR (1) KR19990071729A (de)
CN (1) CN1076289C (de)
AT (1) ATE195100T1 (de)
AU (1) AU704581B2 (de)
CZ (1) CZ167898A3 (de)
DE (1) DE69609629T2 (de)
ES (1) ES2150148T3 (de)
HK (1) HK1019721A1 (de)
HU (1) HUP9901261A3 (de)
IL (1) IL124686A0 (de)
NL (1) NL1001784C2 (de)
PL (1) PL326974A1 (de)
PT (1) PT868309E (de)
WO (1) WO1997021550A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4323578B2 (ja) * 1998-02-23 2009-09-02 大日本印刷株式会社 レーザーマーキング形成用物品
WO2000043213A1 (fr) 1999-01-20 2000-07-27 Societe De Technologie Michelin Procede de marquage et article susceptible d'etre marque avec un laser
US7158145B1 (en) 1999-11-18 2007-01-02 Orga Systems Gmbh Method for applying colored information on an object
JP2005529004A (ja) * 2002-05-08 2005-09-29 レオナード　クルツ　ゲーエムベーハー　ウント　コンパニー　カーゲー 少なくとも一部分に紙材料を含む基材を備えた多層体およびそのような多層体にレーザ誘起マークを作成する方法
JP3915930B2 (ja) * 2002-10-01 2007-05-16 Ｎｏｋ株式会社 マーキング方法およびマーキングされた成形品
US7823366B2 (en) * 2003-10-07 2010-11-02 Douglas Machine, Inc. Apparatus and method for selective processing of materials with radiant energy

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU597240B2 (en) * 1985-02-05 1990-05-31 Ciba-Geigy Ag Laser marking of pigmented systems
EP0327508A3 (de) * 1988-02-03 1991-02-06 Ciba-Geigy Ag Verfahren zur Laserbeschriftung pigmentierter Systeme
DE59008746D1 (de) * 1989-08-18 1995-04-27 Ciba Geigy Ag Lasermarkierung von Kunststoffgegenständen in an sich beliebiger Form mit besonderen Effekten.
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
DE69609629T2 (de) 2001-04-12
PT868309E (pt) 2001-01-31
HK1019721A1 (en) 2000-02-25
CN1076289C (zh) 2001-12-19
JP2000501042A (ja) 2000-02-02
HUP9901261A2 (hu) 1999-08-30
AU1041997A (en) 1997-07-03
KR19990071729A (ko) 1999-09-27
IL124686A0 (en) 1998-12-06
ES2150148T3 (es) 2000-11-16
CN1208376A (zh) 1999-02-17
PL326974A1 (en) 1998-11-09
ATE195100T1 (de) 2000-08-15
EP0868309A1 (de) 1998-10-07
WO1997021550A1 (en) 1997-06-19
HUP9901261A3 (en) 2002-11-28
NL1001784C2 (nl) 1997-06-04
AU704581B2 (en) 1999-04-29
CZ167898A3 (cs) 1998-11-11
DE69609629D1 (de) 2000-09-07

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