WO1994012352A1 - Composition polymere contenant un polymere et au moins une substance sensible aux radiations - Google Patents

Composition polymere contenant un polymere et au moins une substance sensible aux radiations Download PDF

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Publication number
WO1994012352A1
WO1994012352A1 PCT/NL1993/000250 NL9300250W WO9412352A1 WO 1994012352 A1 WO1994012352 A1 WO 1994012352A1 NL 9300250 W NL9300250 W NL 9300250W WO 9412352 A1 WO9412352 A1 WO 9412352A1
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Prior art keywords
polymer composition
radiation
irradiation
radiation sensitive
polymer
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Ceased
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PCT/NL1993/000250
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English (en)
Inventor
Olav Marcus Aagaard
Hans Klaas Van Dijk
Nicolaas Gerard Marie Hoen
Jozef Albert Put
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Koninklijke DSM NV
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DSM NV
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Priority to AU57191/94A priority Critical patent/AU5719194A/en
Publication of WO1994012352A1 publication Critical patent/WO1994012352A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G03C1/733—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds with macromolecular compounds as photosensitive substances, e.g. photochromic

Definitions

  • the invention relates to a polymer composition
  • a polymer composition comprising a polymer and at least one radiation sensitive substance, which can be modified by means of irradiation in such a way that after the irradiation the part of the surface of the polymer composition that has been subjected to irradiation has a colour that differs from the colour of the non-irradiated surface.
  • Such a polymer composition is known from patent application EP-A-327508.
  • the polymer composition according to that patent application contains a radiation sensitive substance comprising at least one bleachable additive and at least one non-bleachable pigment.
  • the polymer can be a thermoplastic as well as a thermosetting polymer.
  • the bleachable additive is chosen from the group of indanthrone and azo pigments, while the non-bleachable pigment is chosen from the group of organic pigments, inorganic pigments and polymer-soluble colorants.
  • On the surface of the polymer composition a marking is made by irradiating the surface of the polymer composition.
  • a pulsed laser is used as radiation source. The wavelength of the laser light used is between 250 and 780 nm.
  • the surface of the polymer composition shows a marking which has a colour that differs from the colour of the non-irradiated surface of the polymer composition. It is thus possible to make a marking, for instance as a decoration, an inscription or an indication, on the surface of the polymer composition according to EP- A-327508, in a colour which differs, from that of the surface.
  • a disadvantage of the polymer composition described in EP-A-327508 is that only a marking of one chromatic colour differing from the colour of the surface of the polymer composition can be obtained. In a number of applications, for instance in the case of a decoration or an indication, it is desirable, however, to have a marking of several colours differing from the colour of the non-irradiated surface of the polymer composition.
  • the objective of the present invention is the preparation of a polymer composition on which by means of irradiation a marking can be made of several chromatic colours that differ from each other as well as from the colour of the non-irradiated surface of the polymer composition.
  • the polymer composition according to the invention is characterized in that the radiation sensitive substance absorbs radiation in the visible range, the near infra-red region and/or the near ultra-violet region, can be modified in different ways, so that on the surface of the polymer composition several, mutually different chromatic colours can be obtained.
  • the polymer composition according to the invention can be irradiated in a simple way such that on the surface several, mutually different, coloured markings can be obtained. It also appears that the texture of the surface of the polymer composition does not change visibly as a result of the irradiation. In specific cases the gloss of the surface shows no or hardly any change at the place of the irradiation. After the irradiation the markings on the surface appear to be very heat, weather and light resistant under conditions of use. It further appears that the markings are wear and scratch resistant, corrosion resistant, dimensionally stable, free of deformation and well legible. Finally, the physical and mechanical properties of the polymer composition are hardly or not at all affected by the application of a marking.
  • chromatic colours are characterized by one or more absorption bands (absorption maxima and minima) in the visible range. If an absorption band lies between a wavelength of 400 and 430 nm, this means that that part of the incident light is absorbed. The rest of the incident light is scattered, so that the human eye perceives the object as yellow.
  • absorption bands at 430-480 nm, 480-550 nm, 550-600 nm and 600-700 nm give orange, red, violet and blue objects, respectively.
  • the colour of an apparently green object is characterized by two absorption bands, one at 400-450 nm and one at 580-700 nm (see also Heinrich Zollinger, Color Chemistry, 1987, pp. 9-12, VCH Verlagsgesellschaft mbH, einheim, Germany).
  • the colour of an object may also be caused by reflection and/or emission of radiation of a certain wavelength. If radiation with a wavelength of between 600 and 700 nm is emitted, an object looks red. If for instance due to reflection in several layers certain wavelengths are extinguished as a result of interference, this will give the object a certain colour.
  • the radiation sensitive substance in the polymer composition according to the invention can be modified in several ways.
  • the modification of a substance is understood to mean the modification of a substance by means of irradiation in such a way that its colour changes, which is a consequence of the changing of the absorption spectrum or of the interference pattern of the substance at the place of the irradiation. It is possible that the radiation sensitive substance itself absorbs the radiation. It is also well - A -
  • the radiation sensitive substance itself absorbs the radiation.
  • a radiation sensitive substance is understood to mean a substance which can be so modified by the effect of irradiation that the colour of the substance changes. This may mean that a colourless substance is modified to a coloured substance or that a coloured substance is removed or is modified to a colourless substance or that a coloured substance is modified to a differently coloured substance.
  • the radiation sensitive substance in the polymer composition can comprise several radiation sensitive components, but it is also possible that the radiation sensitive substance contains one radiation sensitive component which can be modified under several different irradiation conditions. This enables the surface of the polymer composition to be modified in such a way that a marking is obtained of several chromatic colours that differ from each other as well as from the colour of the non-irradiated surface.
  • the radiation sensitive substance comprises radiation sensitive components that can be chosen for instance from the group of organic and inorganic pigments, organic, inorganic and polymeric colorants, photochromic, thermochromic, piezochromic and prechromic compounds, coloured and uncoloured precursor colorants, coloured fillers, UV stabilizers, antioxidants, flame-retardants, acid formers, photooxidants and photoreductors.
  • a mixture of radiation sensitive components can be used.
  • the radiation sensitive components are wholly or partially bonded chemically or physically to the carrier material.
  • carrier material can be used for instance polymers, dendritic macromolecules and zeolites.
  • the carrier material is porous.
  • the amount of radiation sensitive substance in the polymer composition according to the invention is mostly between 0.001 and 80 wt.%, preferably between 0.005 and 3 wt.% and more preferably between 0,01 and 1 wt.%. This percentage by weight is relative to the total weight of polymers and radiation sensitive substance.
  • Suitable radiation sensitive organic pigments are for instance acetylene black, aniline black, carbon black, animal charcoal, graphite and azo, azomethine, methine, anthrachinone, flavanthrone, phthalocyanine, indanthrone, pyranthrone, perinone, benzanthrone, perylene (for instance Pigment Red C.I. No.
  • metal complexes of azo, azomethine, azopyridon and methine colorants such as the azo condensation pigment Pigment Yellow C.I. No. 93 and the azo pigment Pigment Yellow C.I. No. 116.
  • a survey of such pigments is given by Herbst and Hunger in Industrielle Organische Pigmente, VCH Verlagsgesellschaft, Weinheim (1987); see in particular pp. 583-624.
  • anthrachinone pigments are Pigment Red C.I. No. 177 and Pigment Yellow C.I. No. 147.
  • An example of a flavanthrone pigment is Pigment Yellow C.I. No. 24.
  • Examples of phthalocyanine pigments are Pigment Blue C.I. No. 15:3 and Pigment Green C.I. No. 7.
  • An example of a perylene pigment is Pigment Red C.I. No. 149.
  • Suitable azo pigments for use as radiation sensitive component in the polymer composition according to the invention are for instance mono-, di-, tris- and multi-azo compounds derived from acetoacetarylide, pyrazo ⁇ one, 2,3-oxynaphthoic acid arylide, barbituric acid, thiobarbituric acid, 2,4,6-triamino-l,3-pyrimidine and 3-cyano-4-methylpyridone.
  • Metal salts of azo compounds can also well be used as radiation sensitive component.
  • Examples of highly suitable azo pigments are pigment Brown C.I. No. 23, Pigment Orange C.I. No. 31, Pigment Orange C.I. No. 60, Pigment Orange C.I. No. 64, Pigment Red C.I. No. 160, Pigment Red C.I. No. 220 and Pigment Red C.I. No. 221.
  • Suitable indanthrone pigments are for instance
  • Cromophtal Blue A3R Pigment Blue C.I. No. 60, Ciba-Geigy AG
  • Pigment Blue C.I. No. 64 Pigment Blue C.I. No. 64.
  • Radiation sensitive inorganic pigments are for instance cobalt black, iron oxide (for instance Pigment Red C.I. No. 101), manganese dioxide, barium chromate, titanium dioxide (anatase, rutile), zinc oxide, antimony trioxide, zinc sulphide, lithophone, basic lead carbonate, basic lead sulphate, basic lead silicate, chromium oxide, nickel antimony titanate, chromium hydroxide, cobalt violet, cobalt yellow, iron cyanide blue, chromium antimony titanate, manganese blue, manganese violet, cobalt blue, cobalt chromium blue, cobalt nickel grey, ultramarine blue, ultramarine pink, ultramarine violet, vermilion, zinc chromate, zinc tetroxychromate, Berlin blue, lead chromate, lead sulphochromate, lead cyanamide, molybdenum chromate, nickel titanium yellow, strontium chromate, lead sulphochromate molybdate,
  • Radiation sensitive polymer-soluble colorants are for instance anthrachinone compounds, such as hydroxy, amino, alkylamino, cyclohexylamino, arylamino, hydroxyamino and phenylmercapto anthrachinone, azo colorants, metal complexes of azo colorants, such as 1:2- chromium or cobalt complexes of mono-azo colorants, fluorescent colorants, such as compounds derived from coumarin, naphthalimide, pyrazoline, acridine, xanthene, thioxanthene, oxazine, thiazine and benzothiazole, such as Solvent Yellow C.I. No. 163, Solvent Black C.I. No.
  • the polymer-soluble colorants are mostly transparent and are preferably used in combination with fillers and/or pigments. More preferably, polymer-soluble colorants are used in combination with titanium dioxide.
  • Suitable precursor colorants and photochromic colorants are for instance spiropyran compounds, spirooxazine compounds, fulgides, dianthrylidene compounds, diarylethylene compounds, lactones, fluor anone, carbinol bases, styryl bases, cyanine bases and aromatic condensation products. Fulgides are descril' ⁇ J.* * _ instance in J. Chem. Soc. Perkin I, 1981, 197-201 (N.G.
  • Diarylethylene compounds are described in J. Org. Chem., 1990, 5_5_ 2592-2596. Dianthrylidene compounds have been described by Fischer in Rev. of Chem. Intermediates, 1984, 5 . , 393-422.
  • the spiropyran and spirooxazine compounds, the lactones, fluoranes, spirooxazine compounds, the lactones, fluoranes and bases have been described in Rev. Prog. Coloration, Vol. 19, 1989, 20-23, by Jones.
  • Aromatic condensation products are described for instance in DE-A-4024647. Other aromatic condensation products are for instance oligomers of aniline or derivatives thereof.
  • thermochromic colorants are for instance fluorane compounds as described in Colourage, 1989, 3_6 . , 50-52, by N. Ayyangar.
  • Suitable piezochromic compounds have been described for instance in J. Chem. Physics, 1974, 64_, 4567 ff, by Drickamer et al.
  • Suitable photooxidants are for instance chinone compounds, such as benzochinone and anthrachinone.
  • Suitable photoreductors are for instance amino derivatives, such as hindered amine light stabilizers (HALS compounds) and N' ,N' ,N,N-tetramethyl-p-phenylene diamine.
  • Suitable acid formers are for instance isojodonium and sulphonium compounds as described for instance in Advances in Polymer Science 1984, . 62. by Crivello et al.
  • ester and amide compounds of sulphonic acids as described in Appl. Physics 189, 2___t p. 2126 by Yamaoka et al.
  • the radiation sensitive components which can be modified under several different irradiation conditions, so that several chromatic colours can be obtained, are chosen for instance from the group of aromatic condensation products, such as for instance described in DE-A-4024647, oligomers of aniline or aniline derivatives, dianthrylidene compounds and lead sulphochromate molybdate.
  • Other suitable radiation sensitive components are for instance the so-called interference pigments. These pigments mostly contain platelet-shaped particles which absorb and/or transmit part of the incident light and reflect the rest so that a colour is perceived. These particles are described extensively in Griffine (Darmstadt) 1992 (2), pp. 3-60 (Merck company).
  • interference pigments are natural pearl essence (a mixture of guanine and hypoxanthine), lead carbonate, bismuth oxychloride and mica particles, which are in whole or in part provided with a metal oxide coating.
  • Other platelet-shaped particles for instance graphite, copper phthalocyanine, titanium dioxide and aluminium, coated with iron oxide, are also suitable for use as radiation sensitive component which can be modified under several different irradiation conditions, so that several chromatic colours can be obtained.
  • the mica particles are platelet-shaped particles which mostly have a thickness of between 300 and 600 rim and a length between 5 and 200 ⁇ m. The length preferably is between 5 and 40 ⁇ m.
  • the metal oxide mostly is Ti0 2 or Fe 2 0 3 . Depending on the thickness of the metal oxide coating, a certain colour is obtained.
  • Mica particles provided with a metal coating onto which a coating of Ti0 2 has been applied are also suitable for use as radiation sensitive component. Such mica particles are described in EP-A-351932.
  • the polymer composition according to the invention contains a coloured, radiation insensitive component.
  • the radiation insensitive component is not modified under the irradiation conditions applied, and can consist of several different components. Examples of such radiation insensitive components are radiation insensitive, polymer soluble colorants and radiation insensitive organic and inorganic pigments.
  • the polymer in the polymer composition according to the invention can be chosen within wide limits; both natural and synthetic polymers are suitable. Depending on the envisaged application of the polymer, one skilled in the art can choose from the normally used groups of thermoplasts, thermosets, elastomers and biopolymers. Optionally, a mixture of polymers from several groups or a mixture of different polymers from a group is used.
  • thermoplastic polymers are for instance polyvinyl chloride or copolymers of vinyl chloride and other vinyl monomers, poly(vinylidene fluoride) or copolymers of vinylidene fluoride and other vinyl monomers, polystyrene or copolymers of vinyl aromatic monomers, such as styrene and ⁇ -methylstyrene, and other monomers, such as for instance maleic anhydride, acrylonitrile and maleimide, poly(meth)acrylates or copolymers of a (meth)acrylate with other monomers, poly(vinyl carbazole), polyolefins, such as for instance polyethylene, ultrahigh molecular weight polyethylene (UHM PE) , polyisobutylene, polybutene, poly(methyl pentene) and polypropylene, poly(vinyl acetate), poly(vinyl alcohol), polyacrylonitrile, poly( (meth)acryl esters), polyamides, polyesters, such as for instance poly(
  • thermosetting polymers are for instance alkyd resins, polyester resins, amino resins, phenol resins, polyurethane resins, epoxy resins, silicone resins, ketone resins, melamine-urethane-formaldehyde resins, urethane-formaldehyde resins, melamine resins and acrylate resins.
  • Suitable elastomers are for instance ethene- propene copolymers, optionally containing a third comonomer, for instance dicylcopentadiene; cyclic rubbers, such as for instance polynorbornene; natural rubber, poly ⁇ butadiene, styrene-butadiene rubbers and norbornene- butadiene rubbers.
  • Suitable biopolymers are for instance polylactic acid, cellulose, cellulose nitrate, cellulose ester, cellulose triacetate, cellulose acetobutyrate, cellulose ether, (m)ethyl cellulose and benzyl cellulose.
  • the radiation sensitive components are mixed with the polymer to form the polymer composition according to the invention in a customary manner known to one skilled in the art.
  • a roller, an extruder, an injection moulding machine or a mixing or grinding device can for instance be used for this purpose. It is also possible to mix the components into a solution, an emulsion or a suspension of the polymer, even during the polymerization of the polymer.
  • the radiation sensitive components should be dispersed as well as possible in the polymer. This has been described for instance by T.B. Reeve and .L. Dills in 'Pigment Dispersion and Rheology in Plastics', Pigment Handbook 1973, John Wiley & Sons, pp. 441-446. It is also well possible, however, to divide the radiation sensitive components inhomogeneously, which may result in great concentration differences in the polymer composition. This is the case for instance if the radiation sensitive components are localized selectively at the surface of the polymer composition, for instance by applying a multi-layer technique.
  • the pigments and colorants described can optionally be used with or without dispersion agents.
  • suitable dispersion agents are fatty acids with at least 12 carbon atoms, for instance stearic acid, the amides, salts or esters of these fatty acids, for instance magnesium stearate, zinc stearate and aluminium stearate, quaternary ammonium compounds, for instance tri- (Cl-C4)-alkyl benzyl ammonium salts, waxes, for instance polyethylene wax, resin acids, for instance abietic acid, rosin soap, hydrated or dimerized rosin, C12-C18 paraffin disulphonic acids and N-alkyl pyrrolidone compounds.
  • fillers and/or antoxidants can be added to the polymer composition.
  • fillers that can be added are chalk, talc, barium sulphate, fibres, kaolin, calcium carbonate, wollastonite, feldspar, aluminium silicate, calcite, dolomite and glass.
  • Adhesion enhancement agents, flow-promoting agents, thickening agents, surface improvement agents, antifoaming agents, corrosion inhibitors, hardening agents, drying agents, conductive materials, such as conductive fibres and conductive flakes, mica, vulcanizing agents, peroxides, accelerators, stabilizers and binding agents can also be added.
  • the polymer composition obtained can be processed by the customary methods to the desired intermediate and/or final products. These products are mostly mouldings, such as films, sheets, tubes, profiles, plates, compression-moulded products or articles which are obtained by injection moulding, blow moulding, rotation moulding or RIM techniques. Further, in specific applications the polymer composition according to the invention is excellently suitable for use as coating on a moulding.
  • the surface is irradiated in such a way that at least one of the radiation sensitive components is wholly or partially modified.
  • the marking obtained mostly has a thickness, measured from the surface of the polymer composition, between 0.1 and 1000 ⁇ m, preferably between 1 and 1000 ⁇ m, more preferably between 5 and 500 ⁇ m.
  • a suitable radiation source should emit radiation, for instance thermal or electromagnetic radiation, such as for instance light, of sufficient power to modify at least one of the radiation sensitive components. Lasers are highly suitable for use as radiation source, but lamps, such as for instance IR lamps, UV lamps and VIS lamps, are good alternatives.
  • the polymer composition according to the invention can be irradiated from a stationary radiation source, if necessary with parts of the polymer composition screened off by means of a mask, or with a moving radiation source (writing or making discrete dots). It is also well possible to move the surface to be irradiated under a stationary radiation source. In this way the surface is also engraved by means of a writing technique as it were.
  • the emitted radiation can be bundled by means of a converging system of lenses. If a broad radiation beam is wanted, for instance if a mask is being used, the emitted radiation can be spread by means of a diverging system of lenses. In the case of a stationary radiation source, a radiation source* of a large capacity is mostly used. In the case of - 13 -
  • a moving, or writing, radiation source a radiation source of a small capacity is mostly used.
  • the writing speed of such a radiation source is mostly between 5 and 1000 mm/s, preferably between 15 and 500 mm/s, more preferably between 50 and 300 mm/s.
  • suitable radiation sources are gas lasers, such as for instance C0 2 lasers and N 2 lasers, excimer lasers, argon ion lasers, krypton ion lasers, diode lasers, copper vapour lasers, gold vapour lasers, manganese vapour lasers, lead vapour lasers, titanium sapphire lasers, ruby lasers, Alexandrite lasers, semiconductor lasers, Dye lasers and Neodymium Yttrium Aluminium Garnet (Nd:YAG lasers).
  • Suitable radiation sources may emit a continuous beam of rays, but it is also possible to use a pulsating beam of rays.
  • a survey of highly suitable lasers is given for instance by H.
  • Suitable C0 2 lasers mostly emit light of a wavelength between 9 ⁇ m and 11 ⁇ m, preferably of about 10.6 ⁇ m (infrared).
  • Suitable Nd:YAG lasers emit light of a wavelength of 1064 nm; preferably, frequency doubling is applied, transforming the wavelength of the emitted light to 532 nm.
  • the pulse energy applied is mostly between 0.01 and 100 J/cm 2 , preferably between 1 and 20 J/cm 2 and more ⁇ preferably between 1 and 10 J/cm 2 ? the peak load is about 40 MWatt.
  • the pulse frequency mostly varies between 1 Hz and 10 kHz, preferably between 1 and 6 kHz.
  • the pulse width mostly varies between 10 "15 and 10 "3 second, preferably between 10 ⁇ 12 - 10 ⁇ 6 second, most preferably between 10 -6 - 10 "7 second.
  • the diameter of the parallel light beam mostly varies between 0.01 and 0.5 mm, preferably between 0.02 and 0.15 mm.
  • the current strength applied is mostly between 10 and 25 A, preferably between 10 and 18 A, more preferably between 12 and 15 A.
  • the energy density of the light beam applied is mostly between 0.10 kWatt/cm 2 and 1000 GWatt/cm 2
  • Suitable excimer lasers contain for instance xenon fluoride gas or xenon chloride gas and emit light of a wavelength of for instance 351 nm or 308 nm.
  • Suitable argon lasers emit light having wavelengths of for instance 514.5 nm, 502 nm, 496.5 nm, 488 nm, 476.5 nm and/or 458 nm, at a capacity of for instance 0.1 to 10 Watt.
  • the capacity preferably is 1-5 Watt.
  • Lasers with accurately adjustable parameters, such as for instance the laser capacity and the wavelength, are preferred since they can be optimally adjusted to the specific process.
  • the optimum laser parameters to be applied in marking the polymer composition according to the invention can easily be set by one skilled in the art.
  • the laser parameters should be set in a way that at least one of the radiation sensitive components is wholly or partially modified.
  • the laser parameters can be varied locally during the marking of the surface. Examples of such parameters are the radiation load, the radiation intensity, the pulse mode, the pulse width, the pulse sequence, the writing speed and the wavelength.
  • (part of) the surface of the polymer composition is irradiated sequentially, with one or more laser parameters being varied.
  • At least one of the radiation sensitive components is wholly or partially modified.
  • a colourless component is wholly or partially modified to a coloured component, or that a coloured component is wholly or partially removed or wholly or partially modified to a colourless component (for instance by bleaching it) or that a coloured component is wholly or partially modified to a differently coloured component.
  • part of the surface of the polymer composition is molten, carbonized or foamed during the irradiation. It is also possible to cause a radiation sensitive component to be wholly or partially disintegrated during the irradiation, so that the radiation sensitive component is redispersed. This can result in a change of colour.
  • a moulding is obtained whose surface is provided with at least one marking of a chromatic colour that contrasts with the colour of the non-irradiated surface. If the radiation sensitive component has been modified in several ways, the surface of the moulding can have at least two different chromatic colours differing from the colour of the non- irradiated surface, which can moreover be different from each other.
  • the texture of the surface of the moulding may have slightly changed.
  • the texture of the surface at the place of the irradiation is not essentially different from the texture of the non-irradiated surface.
  • polybutylene terephthalate (Arnite TV4 261, DSM, dried for 4 hours at 140°C and reduced pressure) were dry-coated with 0.03 w/w% Paliogen Red K 3911 HD (perylene type pigment, pigment red 178, BASF), 0.75 w/w% Meteor Plus Teal Blue (Co/Ti oxide, pigment green 50, Engelhard), 0.03 w/w% PV Echtgelb HG (mono-azo pigment, pigment yellow 180, Hoechst), 0.30 w/w% Kronos CL 220 (Ti0 2 , pigment white 6, Kronos) and 0.15 w/w% Mg stearate.
  • Paliogen Red K 3911 HD perylene type pigment, pigment red 178, BASF
  • Meteor Plus Teal Blue Co/Ti oxide, pigment green 50, Engelhard
  • PV Echtgelb HG mono-azo pigment, pigment yellow 180, Hoechst
  • 0.30 w/w% Kronos CL 220 Ti0 2 , pigment white 6, Kronos
  • the resulting mixture was injection- moulded to moss-grey platelets (90 * 80 * 2 mm) using an Arburg Al'rounder (220-90-350) injection moulding machine equipped with a D&L screw (22 mm) and having a cylinder temperature of 260°C.
  • the platelets were engraved using an SHG Nd:YAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) both with low (about 2 J/cm 2 ) and high (about 6 J/cm 2 ) laser beam intensity. With low intensity a pink-red marking was obtained, while with high intensity the marking was of a grey-green colour. In this way platelets with markings in two colours were obtained. In both cases the texture of the surface was not visibly changed.
  • the resulting mixture was injection-moulded to ochre-brown platelets (90 * 80 * 2 mm) at a cylinder temperature of 180°C on a Netstal Neomat 350/130 injection moulding machine, equipped with a standard screw and a Twente mixing ring injection nozzle.
  • one platelet was engraved using an SHG Nd:YAG Q- switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) both with low (about 2
  • Example III 99.50 w/w% acrylonitrile-butadiene-styrene copolymer (Ronfalin FG50, DSM, dried for 2 hours at 80°C) were dry-coated with 0.50 w/w% Horna Orange MLH-84-SQ (lead sulphochromate molybdate, pigment red 104, Ciba- Geigy). The resulting mixture was injection-moulded to orange-pink platelets (65 * 65 * 3 mm) using an Arburg Allrounder (220-90-350) injection moulding machine equipped with a D&L screw (22 mm) and having a cylinder temperature of 240°C.
  • a part of a platelet thus obtained was engraved using an SHG Nd:YAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with low (about 2 J/cm 2 ) intensity.
  • the resulting marking had a pastel-yellow colour.
  • Another part of the injection-moulded platelet was engraved with a high-intensity laser beam (about 6 J/cm 2 ).
  • the resulting marking was of an ochre-brown colour. In this way a platelet with markings in two colours was obtained. In both cases the texture of the surface was not visibly changed.
  • a part of a platelet thus obtained was engraved using an SHG NdrYAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with low (about 2 J/cm 2 ) intensity.
  • the resulting marking had an orange-brown colour.
  • Another part of the injection-moulded platelet was engraved with a high-intensity laser beam (about 6 J/cm 2 ).
  • the resulting marking was of a loam-brown colour.
  • a part of this loam-brown marking was once more engraved with the high-intensity laser beam. This part of the marking had an olive-brown colour. In this way a platelet with markings in three colours was obtained. The texture of the surface was not visibly changed.
  • Example V 76.77 w/w% polypropylene (Stamylan PP 48MN40,
  • a part of the masterbatch granulate was mixed with virgin polypropylene granulate in a ratio of 1:23, after which the resulting mixture was injection-moulded to red-mauve platelets (90 * 80 * 2 mm) using an Arburg Allrounder (220-90-350) injection moulding machine equipped with a D&L screw (22 mm) and having a cylinder temperature of 240°C.
  • 98.21% w/w% acryl ⁇ nitrile-butadiene-styrene (Ronfalin FG-50, DSM) were dry-coated with 0.45 w/w% Kronos CL 220 (Ti0 2 , pigment white 6, Kronos), 0.62 w/w% Bayferrox 130 BM (Fe 2 0 3 , pigment red 101, Bayer), 0.18 w/w% Cromophtal Blue A3R (indanthrone pigment, pigment blue 60, Ciba-Geigy) , 0.09 w/w% Sandorin Green 3 GLSP (halogenated Cu phthalocyanine pigment, pigment green 7, Sandoz) and 0.45 w/w% Mg stearate.
  • Kronos CL 220 Ti0 2 , pigment white 6, Kronos
  • Bayferrox 130 BM Fe 2 0 3 , pigment red 101, Bayer
  • Cromophtal Blue A3R indanthrone pigment, pigment blue 60, Ciba-Gei
  • the resulting mixture was injection-moulded to purple-mauve platelets (90 * 80 * 2 mm) using an Arburg Allrounder (220-90-350) injection moulding machine equipped with a D&L screw (22 mm) and having a cylinder temperature of 240°C.
  • a part of a platelet thus obtained was engraved using an SHG Nd:YAG D-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with a low-intensity laser beam (about 2 J/cm 2 ).
  • the resulting marking had a cobalt- blue colour.
  • the texture of the surface was not visibly changed.
  • a second part of the injection-moulded platelet was engraved with a high-intensity laser beam (about 6 J/cm 2 ). The surface melted and assumed a pale-green colour.
  • a third part of the platelet was irradiated with an SHG Nd:YAG Q-switch laser (1064 nm, Haas Laser 6211 Engraving System, Haas Laser) and turned concrete-grey, while the surface was foamed.
  • 91.50 w/w% acrylonitrile-butadiene-styrene (Ronfalin SFB 34, DSM, dried for 2 hours at 80°C) were dry-coated with 0.20 w/w% Irgalite Blue LGLD (Cu phthalocyanine (B) pigment, pigment blue 15:3, Ciba Geigy), 0.20 w/w% Cromophtal Red G (diazo condensation pigment, pigment red 220, Ciba Geigy) and 8.10 w/w% Kronos CL 220 (Ti0 2 , pigment white 6, Kronos). The resulting mixture was injection-moulded to lilac-grey platelets
  • Another part of the injection-moulded platelet was engraved using an SHG Nd:YAG Q-switch laser (pulse time 10 ns, 532 nm, Quanta Ray DCR 2, Spectra Physics), which resulted in a light-blue marking and did not bring about a visible change in the texture of the surface.
  • Example VII was repeated, using only 0.80 w/w% Kronos CL 220 (Ti0 2 , pigment white 6, Kronos). Mauve-blue platelets were now obtained.
  • a part of an injection- moulded platelet thus obtained was engraved using an SHG Nd:YAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with a high- intensity laser beam (about 6 J/cm 2 ), which caused the surface to melt and resulted in a turquoise marking.
  • Irradiation with low intensity (about 2 J/cm 2 ) at another spot of the platelet resulted in a dark-blue marking, without causing a change in the texture of the surface.
  • Parts of the platelet thus irradiated were subsequently irradiated for 2 to 24 hours by means of an unfiltered high-pressure mercury lamp. With increasing irradiation time, the dark-blue marking progressively became light- blue
  • the pigment composition consisted of 20 parts by weight of Microlith-WA White R-WO (Ti0 2 , pigment white 6, Ciba Geigy), 1 part by weight of Microlith-WA
  • Black C-WA carbon black, pigment black 7, Ciba Geigy
  • Bayferrox 130 BM Fe 2 0 3 , pigment red 101, Bayer
  • Cromophtal Blue A3R indanthrone pigment, pigment blue 60, Ciba-Geigy
  • Irgalite Yellow F4G arylamide pigment, pigment yellow 111, Ciba Geigy
  • a part of a painted plate thus obtained was engraved using an SHG Nd:YAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with low (about 2 J/cm 2 ) intensity.
  • the resulting marking had a dark-green colour.
  • Another part of the painted plate was engraved with a high-intensity laser beam (about 6 J/cm 2 ).
  • the resulting marking was of a light-yellow colour. In both cases the texture of the surface was not visibly changed.
  • a resin mixture was prepared, the pigment composition consisting of 20 parts by weight of Microlith-WA White R-WO (Ti0 2 , pigment white 6, Ciba Geigy), 1 part by weight of Microlith-WA Black C- WA (carbon black, pigment black 7, Ciba Geigy), 2 parts by weight of Bayferrox 130 BM (Fe 2 0 3 , pigment red 101, Bayer), 2 parts by weight of Cromophtal Blue A3R (indanthrone pigment, pigment blue 60, Ciba Geigy) and 1 part by weight of Macrolex Orange 3G (perinone pigment, solvent orange 60, Bayer).
  • Microlith-WA White R-WO Ti0 2 , pigment white 6, Ciba Geigy
  • Microlith-WA Black C- WA carbon black, pigment black 7, Ciba Geigy
  • Bayferrox 130 BM Fe 2 0 3 , pigment red 101, Bayer
  • Cromophtal Blue A3R indanthrone pigment, pigment blue 60, Ciba Geigy
  • part of a mauve-blue plate obtained was engraved using an SHG Nd:YAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with low (about 2 J/cm 2 ) intensity.
  • the resulting marking had a dark-blue colour.
  • Another part of the painted plate was engraved with a high-intensity laser beam (about 6 J/cm 2 ).
  • the resulting marking was of a light-blue colour. In both cases the texture of the surface was not visibly changed. As a function of the laser intensity applied, it appeared to be possible to obtain each shade of blue between said two extremes.
  • Example X was repeated, but now using the following pigment composition: 1 part by weight of Iriodine 9505 red violet (metal oxide coated mica particles, Merck) and 1 part by weight of Iriodine 111 Rutile Fine Satin (Ti0 2 -coated mica particles, Merck).
  • the paint thus obtained was sprayed onto a black ABS plate.
  • a part of the resulting bordeaux-coloured plate was engraved using an SHG Nd:YAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with low (about 2 J/cm 2 ) intensity.
  • the resulting marking had an ultramarine blue colour.
  • Another part of the painted plate was engraved with a high-intensity laser bundle (about 6 J/cm 2 ).
  • the marking obtained was of a pastel turquoise colour. In both cases the texture of the surface was not visibly changed.
  • Irradiation of the surface with an intensity of 10 J/m 2 resulted in a white marking, with some roughening of the surface.
  • w/w% polymethylene oxide (Ultraform N2230, BASF, dried for 2 hours at 80°C) were dry-coated with 0.50 w/w% Meteor Plus Teal Blue (Ti0 2 /CoO, pigment green 50, Engelhard), 0.02 w/w% Paliogen Red K3911 HD (perylene pigment, pigment red 178, BASF), 0.02 w/w% PV Echtgelb HG (benzimidalone pigment, pigment yellow 180, Hoechst), 0.30 w/w% Kronos CL 220 (Ti0 2 , pigment white 6, Kronos) and 0.10 w/w% Mg stearate.
  • Meteor Plus Teal Blue Ti0 2 /CoO, pigment green 50, Engelhard
  • 0.02 w/w% Paliogen Red K3911 HD perylene pigment, pigment red 178, BASF
  • PV Echtgelb HG benzimidalone pigment, pigment yellow 180, Hoechst
  • the resulting mixture was injection moulded to olive-green platelets (90 * 80 * 2 mm) at a cylinder temperature of 180°C on a Netstal Neomat 350/130 injection moulding machine, equipped with a standard screw and a Twente mixing ring injection nozzle.
  • a part of a platelet was engraved using an SHG Nd:YAG Q-switch laser (pulse time 110 ns, 532 nm, Haas Laser 6411 Engraving System, Haas Laser) with the laser beam on high intensity (about 6 J/cm 2 ). This resulted in a cyane-coloured marking, with no visible change in the texture of the surface.
  • Printex 85 carbon black, pigment black 7, Degussa
  • the resulting mixture was injection-moulded to black platelets (90 * 80 * 2 mm) using ' an Arburg Allrounder (220-90-350) injection moulding machine equipped with a D&L screw (22 mm) and having a cylinder temperature of 280°C.
  • a part of the platelet was engraved using an SHG Nd:YAG Q-Switch laser (1064 nm, Haas Laser 6211 Engraving System, Haas Laser), which resulted in a red-mauve marking.
  • test bars Part of these test bars were engraved with an SHG Nd:YAG Q-switch laser (532 nm, Haas Laser Engraving System, Haas Laser), which resulted in a yellow marking without disturbing the surface. This yellow marking was applied both on one side and on two sides of the bars.
  • SHG Nd:YAG Q-switch laser 532 nm, Haas Laser Engraving System, Haas Laser

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Composition polymère comportant un polymère et une substance sensible aux radiations et susceptible d'être modifiée par irradiation de telle sorte que la surface irradiée de ladite composition présente une couleur différente de celle de la surface non irradiée. Cette composition polymère est caractérisée en ce que la substance sensible aux radiations absorbe les radiations comprises dans le champ visible, le domaine infrarouge proche et/ou le domaine ultraviolet proche, et peut être modifiée de différentes façons afin que l'on obtienne à la surface de la composition polymère plusieurs couleurs chromatiques différentes les unes des autres. On a mis en évidence que l'on peut irradier de manière simple ladite composition polymère de manière à obtenir à la surface de celle-ci plusieurs marquages dont les couleurs chromatiques sont différentes les unes des autres. En outre, il s'avère que l'aspect visuel de la surface du polymère n'est pas modifié par l'irradiation. Dans certains cas, le brillant de la surface n'est pas, ou quasiment pas, modifié au niveau de la zone irradiée. Après l'irradiation, les marquages superficiels s'avèrent très résistants à la chaleur, aux intempéries et à la lumière dans les conditions d'utilisation. Par ailleurs, il s'avère que ces marquages sont résistants à l'usure, aux rayures et à la corrosion, que leurs dimensions sont stables, qu'ils ne se déforment pas et qu'ils sont lisibles snas difficultés. Enfin, les propriétés physiques et mécaniques de la composition polymère ne sont pas, ou quasiment pas, altérées par l'application des marquages.
PCT/NL1993/000250 1992-12-02 1993-11-25 Composition polymere contenant un polymere et au moins une substance sensible aux radiations Ceased WO1994012352A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57191/94A AU5719194A (en) 1992-12-02 1993-11-25 Polymer composition comprising a polymer and at least one radiation-sensitive component

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9202096A NL9202096A (nl) 1992-12-02 1992-12-02 Polymeersamenstelling, bevattende een polymeer en tenminste een stralingsgevoelig bestanddeel.
NL9202096 1992-12-02

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WO1994012352A1 true WO1994012352A1 (fr) 1994-06-09

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JPH07278446A (ja) * 1994-03-30 1995-10-24 Bayer Ag レーザーエネルギーにより部分的変色を与えるため、特にカラーマーキングの形成のためのポリマー成形材料
EP0680831A1 (fr) * 1994-05-04 1995-11-08 Dsm N.V. Objet façonné avec un marquage sur un substrat thermoplastique et procédé pour fabriquer cet objet façonné
NL1000331C2 (nl) * 1995-05-10 1996-11-12 Dsm Nv Werkwijze voor de vervaardiging van een gekleurde markering.
WO1997011991A1 (fr) * 1995-09-28 1997-04-03 Alliedsignal Inc. Articles colores ameliores; compositions et procedes pour les fabriquer
NL1001784C2 (nl) * 1995-11-30 1997-06-04 Dsm Nv Werkwijze voor de vervaardiging van een voorwerp met gekleurde markering.
EP0841187A1 (fr) * 1996-11-07 1998-05-13 Bayer Ag Compositions polymères à mouler, marquable au laser
WO1998019868A1 (fr) * 1996-11-07 1998-05-14 Dsm N.V. Procede de fabrication d'un objet a marquage de couleur
US5786123A (en) * 1996-03-19 1998-07-28 Eastman Kodak Company Optical recording elements comprising a polymeric dye
WO1999055773A1 (fr) * 1998-04-29 1999-11-04 General Electric Company Composition pour le marquage au laser
WO2000017709A1 (fr) * 1998-09-18 2000-03-30 Cpfilms Inc. Film plastique photosensible et support d'information
WO2001000419A1 (fr) * 1999-06-25 2001-01-04 Marconi Data Systems Inc. Composition de revetement inorganique thermosensible
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WO2002074548A3 (fr) * 2001-03-16 2003-03-13 Sherwood Technology Ltd Compositions pouvant etre marquees au laser
WO2003039888A1 (fr) 2001-11-02 2003-05-15 Leonhard Kurz Gmbh & Co. Kg Corps multicouche comprenant une premiere et une seconde couche sensible au laser et procede pour produire une image mutlicouche dans ce corps
EP1413456A2 (fr) 2000-11-04 2004-04-28 Leonhard Kurz GmbH & Co. KG Corps en matière plastique sous forme de film, par exemple film de transfert ou film laminé, ou muni d'un tel film et procédé permettant de produire une image polychrome sur ou dans un corps en matière plastique de ce type
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EP1480834A4 (fr) * 2002-03-01 2006-04-05 Markem Corp Marquage de substrats
WO2006039249A1 (fr) * 2004-09-29 2006-04-13 General Electric Company Article marque et procede de production associe
US7198302B1 (en) * 1999-08-30 2007-04-03 Orga Systems Gmbh Card-shaped data carrier and method for producing same
US7255911B2 (en) 2000-11-04 2007-08-14 Leonard Durz Gmbh & Co. Kg Laminate body, in particular a laminate foil and a method of increasing the forgery-proof nature of laminate body
FR2931724A1 (fr) * 2008-06-03 2009-12-04 Ev Consulting Procede de realisation de motifs en relief sur la surface d'un objet
US7897320B2 (en) * 2008-01-25 2011-03-01 The Procter & Gamble Company Thermoplastic material comprising polychromic substances
US8048605B2 (en) 2001-03-16 2011-11-01 Datalase Ltd Laser-markable compositions
DE102012100252A1 (de) 2011-01-26 2012-07-26 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Polymerzusammensetzung und Verfahren zur Herstellung von Produkten mit variabler biologischer Abbaubarkeit
EP3225375A1 (fr) * 2016-03-30 2017-10-04 Wirthwein AG Piece de formage en plastique presentant un marquage uv colore, procede de fabrication d'un marquage pour la piece de formage en plastique et film moule avec pigments photochromes
WO2018138256A1 (fr) 2017-01-30 2018-08-02 Basf Se Composition de polyamide teinte en noir, préparation et utilisation de ladite composition
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EP4096930A1 (fr) * 2020-01-28 2022-12-07 Olikrom Procede de realisation d'un marquage de couleurs differentes irreversibles a partir d'une même composition
WO2024206750A1 (fr) * 2023-03-30 2024-10-03 The Procter & Gamble Company Articles marqués au laser avec des codes lisibles par machine
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EP4416552A4 (fr) * 2021-10-11 2025-10-15 Isp Investments Llc Compositions sensibles au rayonnement comprenant une combinaison de métaux ou de composés métalloïdes
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JPH07278446A (ja) * 1994-03-30 1995-10-24 Bayer Ag レーザーエネルギーにより部分的変色を与えるため、特にカラーマーキングの形成のためのポリマー成形材料
EP0675168B2 (fr) † 1994-03-30 2003-11-19 Bayer Ag Mélange à mouler polymère pour changement partielle de couleurs par l'activité du laser, notamment pour la formation des signes en couleurs
EP0680831A1 (fr) * 1994-05-04 1995-11-08 Dsm N.V. Objet façonné avec un marquage sur un substrat thermoplastique et procédé pour fabriquer cet objet façonné
NL1000331C2 (nl) * 1995-05-10 1996-11-12 Dsm Nv Werkwijze voor de vervaardiging van een gekleurde markering.
WO1996035585A1 (fr) * 1995-05-10 1996-11-14 Dsm N.V. Procede de fabrication d'une marque coloree
US6982117B2 (en) 1995-09-28 2006-01-03 Honeywell International Inc. Colored articles and compositions and methods for their fabrication
US6514446B1 (en) 1995-09-28 2003-02-04 Alliedsignal Inc. Colored articles and compositions and methods for their fabrication
WO1997011991A1 (fr) * 1995-09-28 1997-04-03 Alliedsignal Inc. Articles colores ameliores; compositions et procedes pour les fabriquer
EP1391479A1 (fr) * 1995-09-28 2004-02-25 Honeywell International Inc. Articles colorés améliorés,compositions et procédés pout les fabriquer
US6440340B1 (en) 1995-09-28 2002-08-27 Alliedsignal Inc. Colored articles and compositions and methods for their fabrication
US6150019A (en) * 1995-09-28 2000-11-21 Alliedsignal Inc. Colored articles and compositions and methods for their fabrication
US6730399B2 (en) 1995-09-28 2004-05-04 Honeywell International, Inc. Colored articles and compositions and methods for their fabrication
US6074742A (en) * 1995-09-28 2000-06-13 Alliedsignal Inc. Colored articles and compositions and methods for their fabrication
US5932309A (en) * 1995-09-28 1999-08-03 Alliedsignal Inc. Colored articles and compositions and methods for their fabrication
US6756120B2 (en) 1995-09-28 2004-06-29 Honeywell International Inc. Colored articles and compositions and methods for their fabrication
AU704581B2 (en) * 1995-11-30 1999-04-29 U-Nica Technology Ag Process for the manufacture of a colour-marked object
CN1076289C (zh) * 1995-11-30 2001-12-19 Dsm有限公司 彩色标记物体的制造方法及激光装置
WO1997021550A1 (fr) * 1995-11-30 1997-06-19 Dsm N.V. Processus de fabrication d'un article marque par des couleurs
NL1001784C2 (nl) * 1995-11-30 1997-06-04 Dsm Nv Werkwijze voor de vervaardiging van een voorwerp met gekleurde markering.
US5824768A (en) * 1996-03-19 1998-10-20 Eastman Kodak Company Polymeric dyes for optical recording layers and elements
US5786123A (en) * 1996-03-19 1998-07-28 Eastman Kodak Company Optical recording elements comprising a polymeric dye
CN1091696C (zh) * 1996-11-07 2002-10-02 Dsm有限公司 带着色标记物的制法、信息载体及塑性组合物
EP0841187A1 (fr) * 1996-11-07 1998-05-13 Bayer Ag Compositions polymères à mouler, marquable au laser
WO1998019868A1 (fr) * 1996-11-07 1998-05-14 Dsm N.V. Procede de fabrication d'un objet a marquage de couleur
BE1010743A3 (nl) * 1996-11-07 1999-01-05 Dsm Nv Werkwijze voor de vervaardiging van een voorwerp met gekleurde markering.
WO1999055773A1 (fr) * 1998-04-29 1999-11-04 General Electric Company Composition pour le marquage au laser
US6214916B1 (en) 1998-04-29 2001-04-10 General Electric Company Composition for laser marking
US6783901B1 (en) 1998-09-18 2004-08-31 Cpfilms, Inc. Photosensitive plastics films and information storage devices
WO2000017709A1 (fr) * 1998-09-18 2000-03-30 Cpfilms Inc. Film plastique photosensible et support d'information
AU767879B2 (en) * 1998-09-18 2003-11-27 Cpfilms, Inc. Photosensitive plastics films and information storage devices
US6528152B1 (en) * 1999-01-25 2003-03-04 “P1”Handels GmbH Stopper of foamed thermoplastic synthetic material
US6478861B1 (en) 1999-06-25 2002-11-12 Videojet Technologies Inc. Laser markable coating
WO2001000419A1 (fr) * 1999-06-25 2001-01-04 Marconi Data Systems Inc. Composition de revetement inorganique thermosensible
US6261348B1 (en) 1999-06-25 2001-07-17 Marconi Data Systems Inc. Laser markable coating
US7198302B1 (en) * 1999-08-30 2007-04-03 Orga Systems Gmbh Card-shaped data carrier and method for producing same
US6207344B1 (en) 1999-09-29 2001-03-27 General Electric Company Composition for laser marking
JP2003510416A (ja) * 1999-09-29 2003-03-18 ゼネラル・エレクトリック・カンパニイ レーザマーキング用組成物
JP4989003B2 (ja) * 1999-09-29 2012-08-01 サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ レーザマーキング用組成物
KR100755292B1 (ko) * 1999-09-29 2007-09-05 제너럴 일렉트릭 캄파니 레이저 마킹용 조성물
WO2001023189A1 (fr) * 1999-09-29 2001-04-05 General Electric Company Composition de marquage au laser
US6376577B2 (en) 1999-12-18 2002-04-23 Merck Patentgesellschaft Laser-markable plastics
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EP1413456A2 (fr) 2000-11-04 2004-04-28 Leonhard Kurz GmbH & Co. KG Corps en matière plastique sous forme de film, par exemple film de transfert ou film laminé, ou muni d'un tel film et procédé permettant de produire une image polychrome sur ou dans un corps en matière plastique de ce type
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AU5719194A (en) 1994-06-22
NL9202096A (nl) 1993-04-01

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