EP0868309A1 - Process for the manufacture of a colour-marked object - Google Patents

Process for the manufacture of a colour-marked object

Info

Publication number
EP0868309A1
EP0868309A1 EP96941221A EP96941221A EP0868309A1 EP 0868309 A1 EP0868309 A1 EP 0868309A1 EP 96941221 A EP96941221 A EP 96941221A EP 96941221 A EP96941221 A EP 96941221A EP 0868309 A1 EP0868309 A1 EP 0868309A1
Authority
EP
European Patent Office
Prior art keywords
light
colour
process according
laser
mask
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.)
Granted
Application number
EP96941221A
Other languages
German (de)
French (fr)
Other versions
EP0868309B1 (en
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/en
Application granted granted Critical
Publication of EP0868309B1 publication Critical patent/EP0868309B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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.
  • a marking can be obtained whose colour is determined freely, the marking may contain different colours and markings in different colours can be obtained on the surface of the same plastic composition. Furthermore, 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 chro aticity 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 094/12352 can contain are particularly suitable. Preferably, 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 twin- screw extruder supplied by Werner and Pfleiderer of
  • 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. Markings were subsequently applied onto the surface by means of a laser set-up. Use was made of a tunable wavelength laser set-up (TMW laser set-up).
  • the laser set-up contained a type EEO®-355 seeding laser, which was used as pump laser for a type GCR®-230/50
  • 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
  • Pulse width 5 ns
  • Q-switching frequency 30 Hz
  • dot diameter 3 mm
  • writing speed 10 mm/s line spacing: 0.66 mm
  • focal length +80 mm
  • 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.
  • a lacquer consisting of 65.0 parts by weight of Uracron® 474 CY, a hydroxyfunctional resin supplied by DSM Resins of the Netherlands, 20.8 parts by weight of Tolonate® HDT EV 412, supplied by H ⁇ ls of Germany, 0.6 part by weight of dibutylindilaureate supplied by Aldrich of Belgium, 10.0 parts by weight of Kronos® CL 220, 1.2 parts by weight of Cromoptal® Yellow 3G, a yellow pigment supplied by Ciba Geigy of the

Landscapes

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

Abstract

Process for the manufacture of a colour-marked object by irradiating the surface of the object with laser light, characterized in that 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 wholly or partially lost its light-absorbing capacity.

Description

PROCESS FOR THE MANUFACTURE OF A COLOUR-MARKED OBJECT
The invention relates to a process for the manufacture of a colour-marked object by irradiating the surface of the object with laser light.
Such a process is known from 094/12352. That patent application describes a process whereby the surface of an object is irradiated under arbitrarily chosen conditions such that a colour marking is obtained.
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.
Surprisingly, this is accomplished by that 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.
In this way a marking can be obtained whose colour is determined freely, the marking may contain different colours and markings in different colours can be obtained on the surface of the same plastic composition. Furthermore, 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.
It is essential that 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).
Examples of 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.
It is also possible to apply matrix dots of different colours side by side on the surface. To an observer, 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.
It is essential in this context that the centre-to-centre distance between the dots is small so that the eye cannot distinguish the individual matrix dots. Newspaper photos are coloured in this way also.
As is known from colour printing, very good results are achieved by applying matrix dots of at least three different colours on the surface. This is accomplished by irradiating the surface with laser light of at least three different wavelengths, in which process one of the at least three light-absorbing components wholly or partially loses its light- absorbing capacity at each wavelength. In this manner, the use of at least three colours allows a great many other colours to be formed by mixing the colours in the proper amounts.
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. Alternatively, 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 chro aticity coordinates that determine the colour 's location within the CIE D65 colour diagram (10° observer) as described in the aforementioned standard. Thus, 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.
Preferably, 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 094/12352 can contain are particularly suitable. Preferably, 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.
Preferably, 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.
Preferably, 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.
Preferably, 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. Preferably, the process of the invention is practised with a variable mask. Preferably, use is made of a mask produced by an LCD screen.
More preferably, use is made of a PDLCD (Polymer Dispersed Liquid Crystal Display) mask, which has the added advantage that it does not absorb, but scatters, the non-transmitted laser beam, so that the mask does not become warm.
Advantages of these masks are that 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.
Very good results are achieved if the process of the invention is practised with a laser device which simultaneously irradiates the object's surface with the aid of at least 3 masks positioned adjacent to each other, with the masks being irradiated with laser light of different wavelengths in such a manner that the mask's images are projected onto the object's surface one over the other. The advantage is that the object's surface is irradiated with different masks in a single operation. If in this procedure the masks are variable, an extra advantage is that different markings can be applied in very rapid succession. A set-up of the same kind is known from video projection.
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.
Furthermore, 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.
Preferably, 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.
More preferably, use is made of 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.
Example I
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.
The dry blend was melted in a ZSK®30 twin- screw 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. Markings were subsequently applied onto the surface by means of a laser set-up. Use was made of a tunable wavelength laser set-up (TMW laser set-up). 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). The set-up was supplied by Sperera-Physics of the USA.
The following laser settings were chosen: Pulse width: 5 ns Q-switching frequency: 30 Hz dot diameter: 3 mm writing speed: 10 mm/s line spacing: 0.66 mm focal length: +80 mm
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 Star™ 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. Next, 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. Lastly, the "red mask" was fitted and irradiated with laser light having a wavelength of 650 nm. On completion of this last irradiation an indelible colour photo had been obtained in the plastic, the colour range of which photo was comparable with that of the original.
Example II
A lacquer consisting of 65.0 parts by weight of Uracron® 474 CY, a hydroxyfunctional resin supplied by DSM Resins of the Netherlands, 20.8 parts by weight of Tolonate® HDT EV 412, supplied by Hϋls of Germany, 0.6 part by weight of dibutylindilaureate supplied by Aldrich of Belgium, 10.0 parts by weight of Kronos® CL 220, 1.2 parts by weight of Cromoptal® Yellow 3G, a yellow pigment supplied by Ciba Geigy of the
Netherlands, 1.2 parts by weight of Paliogen® Red L 3910 HD, a red pigment supplied by BASF of the Netherlands and 1.2 parts by weight of Orasol® Blue GN a blue colorant supplied by Ciba Geigy of the Netherlands was prepared in a beaker by vigorous stirring. The lacquer was applied onto an aluminium sheet to a film thickness of 50 micrometres. The lacquer film had a grey hue. Markings were made in the lacquer film as described in example I. The laser settings for this experiment were: pulse width: 5 ns ©-switching frequency: 30 Hz dot diameter : 3 mm writing speed: 25 mm/s line spacing: 0.66 mm focal length: +40 mm

Claims

C L I M S
1. Process for the manufacture of a colour-marked object by irradiating the surface of the object with laser light, characterized in that 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.
2. Process according to claim 1, characterized in that the colour of the surface is formed by the subtractive mixing of at least three different coloured matrix points.
3. Process according to claim 1, characterized in that the colour of the surface is formed by partitive mixing of the colours of the matrix dots.
4. Process according to any one of claims 1, 2 or 3, characterized in that 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.
5. Process according to any one of claims 1-4, characterized in that the wavelengths of the laser light with which the surface is irradiated are those at which the maxima occur in the absorption spectra of the different light-absorbing components.
6. Process according to any one of claims 1-5, characterized in that the process of the invention is practised with the aid of one or more masks.
7. Process according to any one of claims 1-6, characterized in that the process of the invention is practised with the aid of a variable mask.
8. Process according to claim 6, characterized in that the mask is produced by an LCD screen.
9. Process according to claim 6, characterized in that use is made of a variable PDLCD (Polymer Dispersed Liquid Crystal Display) mask.
10. Process according to any one of claims 1-9, characterized in that the surface is irradiated with a laser device which simultaneously irradiates the object's surface with the aid of at least 3 masks positioned adjacent to each other, with the masks being irradiated with laser light of different wavelengths in such a manner that the mask's images are projected onto the object's surface one over the other.
11. Laser device characterized in that 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.
EP96941221A 1995-11-30 1996-11-28 Process for the manufacture of a colour-marked object Expired - Lifetime EP0868309B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL1001784A NL1001784C2 (en) 1995-11-30 1995-11-30 Method of manufacturing an object with colored marking.
NL1001784 1995-11-30
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 true EP0868309A1 (en) 1998-10-07
EP0868309B1 EP0868309B1 (en) 2000-08-02

Family

ID=19761944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96941221A Expired - Lifetime EP0868309B1 (en) 1995-11-30 1996-11-28 Process for the manufacture of a colour-marked object

Country Status (16)

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

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4323578B2 (en) * 1998-02-23 2009-09-02 大日本印刷株式会社 Articles for forming laser marking
ES2199763T3 (en) 1999-01-20 2004-03-01 Societe De Technologie Michelin MARKING PROCEDURE AND SUSCEPTIBLE ARTICLE OF BEING MARKED WITH A LASER.
ATE264199T1 (en) 1999-11-18 2004-04-15 Orga Kartensysteme Gmbh METHOD FOR APPLYING COLORED INFORMATION TO AN OBJECT
DE10297782D2 (en) * 2002-05-08 2005-05-12 Kurz Leonhard Fa Multilayer body with a laser-sensitive layer
WO2004030920A1 (en) * 2002-10-01 2004-04-15 Nok Corporation Marking method and marked molding
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 (en) * 1988-02-03 1991-02-06 Ciba-Geigy Ag Process for laser marking of pigmented systems
DE59008746D1 (en) * 1989-08-18 1995-04-27 Ciba Geigy Ag Laser marking of plastic objects in any shape with special effects.
NL9202096A (en) * 1992-12-02 1993-04-01 Dsm Nv POLYMER COMPOSITION CONTAINING A POLYMER AND AT LEAST A RADIATION-SENSITIVE COMPONENT.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9721550A1 *

Also Published As

Publication number Publication date
EP0868309B1 (en) 2000-08-02
PT868309E (en) 2001-01-31
HK1019721A1 (en) 2000-02-25
ES2150148T3 (en) 2000-11-16
KR19990071729A (en) 1999-09-27
PL326974A1 (en) 1998-11-09
HUP9901261A2 (en) 1999-08-30
DE69609629T2 (en) 2001-04-12
IL124686A0 (en) 1998-12-06
WO1997021550A1 (en) 1997-06-19
CN1208376A (en) 1999-02-17
DE69609629D1 (en) 2000-09-07
CZ167898A3 (en) 1998-11-11
AU1041997A (en) 1997-07-03
JP2000501042A (en) 2000-02-02
AU704581B2 (en) 1999-04-29
HUP9901261A3 (en) 2002-11-28
CN1076289C (en) 2001-12-19
NL1001784C2 (en) 1997-06-04
ATE195100T1 (en) 2000-08-15

Similar Documents

Publication Publication Date Title
EP0187352B1 (en) A method of ink jet colour printing
EP0828613B1 (en) Method for the manufacture of a coloured mark
US4741930A (en) Ink jet color printing method
US7465018B2 (en) Printing system
JP2008019446A (en) Dye set, inkjet cartridge thereof and imaging method
DE19926460A1 (en) Infrared absorbing cyanine colorants for laser colorant transfer
JPH02127482A (en) Ink jet recording
EP0938418B1 (en) Process for the manufacture of an object with a coloured marking
EP0868309B1 (en) Process for the manufacture of a colour-marked object
EP0019270B1 (en) Multicolour print and process for the manufacture of the printing forms for this print
DE3623483A1 (en) HEAT-SENSITIVE RECORDING MATERIAL
DE60111281T2 (en) STABILIZED INFRARED ABSORBING CYANING ELEMENT FOR LASER COLOR TRANSFER
US5196236A (en) Ink jet color printing method
US5014086A (en) Adjustable dot gain simulation for color proofing
DE60315000T2 (en) IMPROVEMENTS ON THE THERMAL TRANSFER PRESSURE
US5028840A (en) Image display panel
DE19944284A1 (en) Transmission imaging display material with biaxially oriented polyolefin film
US4879267A (en) Method for color and black and white reproduction and formulation used therewith
US6987533B2 (en) Camera reference device and method of making camera reference device
CA2357989C (en) Camera reference device and method of making camera reference device
DE3346712C2 (en)
JP5087208B2 (en) Printing method and printed matter
JPH0655854A (en) Coating for laser marking
Stroh Basic color theory and color in computers
DE691539C (en) Method for reproducing multicolor cinematographic images

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19980527

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19990907

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000802

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000802

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000802

REF Corresponds to:

Ref document number: 195100

Country of ref document: AT

Date of ref document: 20000815

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69609629

Country of ref document: DE

Date of ref document: 20000907

ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO ROMA S.P.A.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001102

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2150148

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001128

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20001025

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20011123

Year of fee payment: 6

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030531

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20030531

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: DSM IP ASSETS B.V.

Free format text: DSM N.V.#HET OVERLOON 1#6411 TE HEERLEN (NL) -TRANSFER TO- DSM IP ASSETS B.V.#HET OVERLOON 1#6411 TE HEERLEN (NL)

NLS Nl: assignments of ep-patents

Owner name: DSM IP ASSETS B.V.

Effective date: 20050915

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: KONINKLIJKE DSM N.V.

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: U-NICA TECHNOLOGY AG

Free format text: DSM IP ASSETS B.V.#HET OVERLOON 1#6411 TE HEERLEN (NL) -TRANSFER TO- U-NICA TECHNOLOGY AG#SINSERSTRASSE 65#6330 CHAM (CH)

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: U-NICA TECHNOLOGY AG

Free format text: U-NICA TECHNOLOGY AG#SINSERSTRASSE 65#6330 CHAM (CH) -TRANSFER TO- U-NICA TECHNOLOGY AG#INDUSTRIESTRASSE 4#7208 MALANS (CH)

Ref country code: CH

Ref legal event code: NV

Representative=s name: ISLER & PEDRAZZINI AG

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20090430 AND 20090506

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20151118

Year of fee payment: 20

Ref country code: CH

Payment date: 20151111

Year of fee payment: 20

Ref country code: IT

Payment date: 20151124

Year of fee payment: 20

Ref country code: FI

Payment date: 20151111

Year of fee payment: 20

Ref country code: DE

Payment date: 20151119

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20151118

Year of fee payment: 20

Ref country code: FR

Payment date: 20151119

Year of fee payment: 20

Ref country code: ES

Payment date: 20151111

Year of fee payment: 20

Ref country code: NL

Payment date: 20151118

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69609629

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20161127

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20161127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20161127

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20170306

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20161129