DE4001856A1 - COLOR LASER LABELING OF PLASTICS - Google Patents

Abstract

A process for producing coloured images in plastics objects of any desired shape, which process comprises a) coating the object to be marked with a soluble lacquer film containing at least one colouring component, b) irradiating the coated object, after drying said film, with a continuously excited laser such that the film and the surface of the object directly adjacent soften at the irradiated areas and the colouring component penetrates the surface of the plastics object, and c) dissolving the residual non-irradiated film with a solvent such that a visual coloured image remains at the irradiated areas of the plastics object. Preferably the plastics for the object is an acrylic polymer, polyester or a polycarbonate; the laser is preferably a CO2 laser or an argon laser.

Description

The present invention relates to a method for colored Laserbe writing of plastic objects of any shape as well as the be written material.

Laser marking of plastic objects with a color contrast Marking at the irradiated sites of the material is known.

For example, in European Patent Application No. 00 36,680 proposed an object of which at least one surface part made of a synthetic synthetic resin material, with a laser beam to mark a certain intensity. The material to be marked contains a dye and a silicon-containing inorganic compound or a silicic dye, wherein the dye is replaced by Laser irradiation decomposes, causing formation at the irradiated sites a white mark with good color contrast to the not irradiated colored part of the material leads.

It is also known to have plastic parts with a colorful contrast Label to mark. Thus, according to the European patent message no. 01 90 997 high molecular weight organic materials in the form of Parts, slides or films labeled, with a discoloration by Laser irradiation causing additive, e.g. an inorganic one and / or organic pigment. It arises at the irradiated point of the material a color change, mostly after black, white or beige.

Also, the Japanese Patent Application Sho 60-1 55 493 is concerned with the Laser marking of plastic parts or films with a colorful contrast marking, wherein the plastic is a yellow iron oxide, optionally in Blend with a yellow, yellowish green or red pigment,  is added. Laser irradiation causes the yellow iron to discolor oxide at the irradiated areas red, so that red, orange or brown Markings arise.

Further, in Japanese Patent Application no. 58-2 10 937 Art suggested substance compositions for the laser marking, wherein the Plastic be mixed with two different colorants, one of which one in the laser irradiation evaporates, discolored or fade and the other remains unchanged, so that a colored contrast mark arises. As examples of changing colorants there are some organic pigments and dyes listed while being stable Compounds of some inorganic pigments are mentioned. Which lasers parameter, e.g. Laser device, power, power, wavelength and pulse duration are not applicable to this document remove.

Finally, in British patent no. 13 53 063 a method for Laser marking of objects made of metal, plastic, paper, wood, Glass, ceramics or concrete proposed, after which one on the mar untied light-absorbing layer applied fine particles is irradiated with a laser. At the radiation are unbound at the irradiated molten areas particles are held in the article, and the rest are not irradiated or unattached particles are then in the usual way and way removed. As particles may according to this document organic or organic pigments, pigment-resin mixtures, colored high molecular weight material or metal powder can be used. On Disadvantage of this method is that in the lettering on the particle applied to the object without being bound to the irradiated Often leave off the surface of the object to be marked be blown so that no significant marking can be generated. In addition, the application of the particles in the form of one is the same moderate, thin layer, especially on non-flat objects, not easy or not easy to put into practice. Furthermore, must the coated objects very carefully before labeling be treated so that the powder layer is not damaged.  

However, the above-listed methods or compositions are capable not always enough to meet today's requirements of practice; mostly the surface of the labeled material is irradiated to the Patches severely damaged, resulting in unwanted grooves, pits or Chemical burns leads and beyond to markings insufficient general qualities, such as insufficient abrasion and scratch resistance, poor resistance to chemicals and pollution, and with unclean edge zones, leads. In addition, these laser marking ver limited to very few shades.

It has now been found a laser marking process, a free programmable marking on any plastic objects in practically arbitrary color shades allowed.

The present invention accordingly provides a process for colored laser marking of plastic objects in be lovely form, after which

• a) the object to be labeled with a soluble plastic film containing at least one coloring component is coated,
• b) the article so coated after drying the film of the beam tion of a continuously excited laser is exposed so that the Radiation according to the shape of the applied mark on the Surface of the object to be marked is directed, the film and the immediately adjacent surface of the object to the irradiate soften the areas and the coloring component in the surface penetrates the plastic object, and
• c) the remaining unirradiated film is then dissolved with a solvent is, so that at the irradiated points of the plastic article a visual color contrast mark remains.

The plastic article may be of natural or artificial origin. It can be e.g. be rubber or modified natural substances, for example, chlorinated rubber, or cellulose derivatives, such as cellulo or cellulose ethers, and especially fully synthetic organic Polyplastes, that is to say, plastics produced by polymerization, poly condensation or polyaddition are made. From the class of this Plastics are particularly mentioned as follows: polyolefins, such as poly  ethylene, polypropylene, polybutylene or polyisobutylene, polystyrene, Polyvinyl chloride, polyvinylidene chloride, the fluorine-containing polymers, such as Polytetrafluoroethylene, further polyvinyl acetals, polyacrylonitrile, poly acrylic and polymethacrylic acid esters or polybutadiene, as well as Co polymers thereof, in particular ABS or EVA; Polyester, in particular high molecular weight esters of aromatic polycarboxylic acids with polyfunctional alcohols; Polyamides, polyimides, polycarbonates, polyurethanes, polyethers, such as polyphenylene oxide, also polyacetals, the condensation products of Formaldehyde with phenols, called phenoplasts, and the condensates formation products of formaldehyde with urea, thiourea and melamine, the so-called aminoplasts; the known under the name "epoxy resins" Polyaddition or polycondensation products of epichlorohydrin with e.g. Diols or polyphenols, and further used as coating resins unsaturated polyester such as maleate resins. It should be emphasized that not only the unified compounds, but also mixtures of Polyplasten, and mixed condensates and copolymers, such. such based on butadiene, can be used according to the invention.

For the inventive method are particularly suitable plastics Polyolefins, polyvinyl esters, such as polyvinyl acetals, and also polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polyimides, poly carbonates, polyurethanes, polyethers, in particular polyphenylene oxides, furthermore polyacetals, phenoplasts, aminoplasts or epoxy resins.

Especially suitable plastics are polyacrylic esters, polymetha methyl crylate, polyesters and polycarbonates.

The plastic article can undyed, but also dyed as desired be, for this purpose, known to those skilled, suitable colorant can be used. In principle, all of these can be described below as coloring component listed coloring agent can be used.

As coloring component according to invention come inorganic and organic pigments, as well as polymer-soluble dyes in question, esp especially those that absorb in the visible range.  

Examples of inorganic pigments are white pigments, such as titanium dioxide (anatase, rutile), zinc oxide, antimony trioxide, zinc sulfide, lithopone, basic lead carbonate, basic lead sulphate or basic lead silicate, other colored metal oxides such as iron oxides, nickel antimony titanate, Chromium antimony titanate, manganese blue, manganese violet, cobalt blue, cobalt chrome blue, cobalt nickel gray or ultramarine blue, Berlin blue, lead Chromates, lead sulfochromates, bismuth vanadates, molybdate and molybdenum datrot, and also metal sulfides, such as cadmium sulfide, arsenic disulfide, antimony trisulfide or cadmium sulfoselenides, zirconium silicates such as zirconium vanadium blue and zirconium soda yellow, as well as carbon black or graphite.

Examples of organic pigments are azo, azomethine, methine, Anthraquinone, indanthrone, pyranthrone, flavanthrone, benzanthrone, Phthalocyanine, perinone, perylene, dioxazine, thioindigo, isoindoline, Isoindolinone, quinacridone, pyrrolopyrrole or quinophthalone pigments, further metal complexes, e.g. of azo, azomethine or methine dyes, or metal salts of azo compounds.

As polymer-soluble dyes are, for example, dispersions dyes, such as those of the anthraquinone series, for example hydroxy, Amino, alkylamino, cyclohexylamino, arylamino, hydroxyamino or Phenylmercapto-anthraquinones, as well as metal complexes of azo dyes, in particular 1: 2 chromium or cobalt complexes of monoazo dyes, furthermore fluorescent dyes, such as those from coumarin, naphthalimide, Pyrazoline, acridine, xanthene, thioxanthene, oxazine, thiazine or Benzthiazolreihe.

The inorganic and organic pigments or polymer-soluble color According to the invention, substances can be used individually or as mixtures, expediently with or without pigment additives. It just has to be on it to be respected with the art used in the invention fabric film are compatible.

Suitable pigment additives are, for example, fatty acids having at least 12 C atoms, such as stearic acid or behenic acid, their amides, salts or esters, such as magnesium stearate, zinc stearate, aluminum stearate or magnesium behenate, furthermore quaternary ammonium compounds, such as tri (C ₁ -C ₄ ) alkylbenzylammonium salts, Waxes such as polyethylene wax, resin acids such as abietic acid, rosin soap, hydrogenated or dimerized rosin, C ₁₂ -C ₁₈ paraffin disulfonic acid or alkylphenols.

Colorants which are preferred according to the invention are inorganic colorful pigments and metal complexes of azo, azomethine or methine color substances, as well as azo, azomethine, methine, anthraquinone, phthalocyanine, Perylene, dioxazine, thioindigo, isoindoline, isoindolinone, Quinacridone or pyrrolopyrrole pigments.

Most preferred in the invention are heat-resistant coloring composites components.

Typical examples of coloring components according to the application are copper phthalocyanines, mono- and disazo pigments of the acetoacetarylide, β- oxynaphthoic acid arylidene and 3-methyl-1-phenylpyrazolone 5-series, and also metal salts of sulfonated α- phenylazo- β- oxy 3-naphthoic acids, nickel, cobalt or copper complex pigments, and heat-resistant polymer-soluble dyes of the anthraquinone series.

The coloring component is appropriate in the invention in question coming film in amounts of 0.01 to 15 wt .-%, in particular from 1 to 8 wt .-%, based on the dry film before.

If the plastic object is colored in color, then in this case a colored marking consisting of the mixed color of the application coloring component and that used in the plastic article Colorant.

The plastic film can also be of natural or artificial origin being made of materials in dissolved form as a film former or Binder can be produced. It can be e.g. to modified Natural products act, e.g. to cellulose derivatives, such as cellulose esters or ethers, such as nitrocellulose, acetylcellulose, cellulose propionate, Cellulose acetobutyrate, ethylcellulose, or mixtures of such substances, also polyvinyl acetate, polyvinyl propionate, polyvinyl alcohol, poly vinyl acetals such as polyvinyl butyral, polyacrylic acid and polymeth  acrylic acid esters, in particular polymethyl methacrylate, polymethyl acrylate, Polyethyl methacrylate, polybutyl acrylate and polyisobutyl acrylate and Mixtures thereof, further polyvinylpyrrolidone, polyamides, polyvinylmix polymers, such as polyvinyl chloride-polyvinyl acetate, spray-soluble resins, such as. Shellacs, further urea-formaldehyde resins, air-drying Oils, e.g. Linseed oils, phenolic resins, resin-modified phenolic resins, melein acid resins, alkyd resins, ketone resins, polyurethanes, epoxy resins, polyesters and starch derivatives such as dextrin.

The plastic film may also be made of materials in monomeric form, such as e.g. monomeric free-radically curing acrylic acid esters.

Preferred film materials according to the invention are nitrocellulose, ethyl cellulose, cellulose propionate, cellulose acetobutyrate, polyvinyl butyral, Polyacrylic and polymethacrylic acid esters, vinyl chloride-vinyl acetate Copolymers, polyvinyl alcohol, polyester, polyurethane or an epoxy resin.

The production of plastic objects takes place according to known Methods, for example, such that you have the required components optionally in the form of masterbatches, e.g. the organic material and the usual additives using extruders, rolling mills, Mixing or grinding apparatus admixed. The material obtained is on this according to known methods such as calendering, pressing, strand pressing, brushing, spinning, pouring, extruding or by spraying cast into the desired final shape. Often it is desirable for the production of non-rigid moldings or for reducing their Brittleness, the organic material before deformation so-called Incorporate plasticizer. As such, e.g. Ester of phosphorus acid, phthalic acid or sebacic acid. The plasticizers can be used before or after the incorporation of the present invention in question coloring components are incorporated into the polymers.

Depending on the intended use, the organic plastic can also be used additional substances are added, such as fillers such as kaolin, Mica, feldspar, wollastonite, aluminum silicate, barium sulfate, calcium sulphate, chalk, calcite and dolomite, furthermore light stabilizer, antioxidant  tien, flame retardants, heat stabilizers, reinforcing fibers, such as e.g. Glass fibers, or processing aids, which in the Verar processing of plastics and are known in the art.

The structure of the plastic film on the plastic object takes place according to methods known per se, e.g. a printing ink after the High-pressure, gravure, planographic or screen printing process constructed becomes. Thus, e.g. the candidate footage and the color optionally together with other film additives in a common organic solvent or solvent mixture be finely dispersed or dissolved. One can proceed in such a way that one the individual components for themselves or also several together disperses or dissolves, and only then brings all the components together. The thus homogenized colored film material is then to be to writing object according to one of the printing methods mentioned above applied and dried, and the resulting film, expediently with a Layer thickness between 5 and 50 microns, then labeled according to the invention.

The application of the film to the plastic article may e.g. also performed by doctoring, spinning, dipping, spraying or brushing become.

It may be advantageous to use only part of the article with the film Cover, expediently only that area, for the Art and size of the label is necessary.

For labeling high-energy sources, such as continuous laser used. The energy radiation of the laser is corresponding to the Shape of the applied characters on the surface of the directed marking material, optionally focused, wherein the Irradiated areas a contrast mark is created. Appropriately leads the labeling device the laser beam perpendicular to the surface of the to be marked object.  

Examples of laser sources are continuously excited or continuous line laser, for example, based on CW Nd: YAG lasers with frequency multiplier, or CW ion laser (Ar, Kr), or possibly powerful semiconductor laser, directly or by frequency doubling emit visible light, further gas lasers, such as CO ₂ laser.

Power densities of 0.1 kilowatt per cm ² to 1 megawatt per cm ² are advantageously used.

Preferably, a continuously excited CO ₂ laser or an argon ion laser is used in the visible spectral range.

The following table lists some commercially available lasers which may come into question according to the invention.

table

According to the method of the invention, for example, a continuous CO ₂ laser is used at about 4 watts of power.

Laser with good adjustability of its laser parameters, such as Power and wavelength, allow optimal adaptation to the Be necessities of the objects to be labeled.

The optimal wavelength to be selected for irradiation is that in which the film and the plastic object to be inscribed or the coloring component in a layer thickness of about 50 microns more than half of the laser radiation absorb. Under softening understands Both the state in which the plastic material softens, as well as the condition in which the material has melted.

For labeling with lasers are generally three different Procedure in question: the mask method, the linear label and the dot-matrix method. In the latter two Beschrif types (dynamic beam guidance), the laser is preferred with a Coupled laser deflection system, so that the object with any, for example, in a computer programmed digits, letters and Special characters can be labeled.

The choice of laser system in terms of performance is basically according to the applied labeling method. High performance is preferably used for mask exposures. Medium to small lei are preferred for captions that have a require dynamic beam guidance. The beam deflection can, for example acoustooptic, holographic, with galvo mirrors or polygon Scanners take place. The dynamic beam guidance allows an extremely flexible labeling or marking as the characters are electronic can be generated.

The removal of the film in the places that were not labeled takes place according to methods known per se, for example by Use of a solvent or solvent mixture in which the plastic film is well soluble or dissolves well, however, the Plastic object not. Aqueous-alkaline solutions or aqueous / Alcoholic alkaline solutions may also be used, e.g. With carboxyl-containing polyacrylate films. Examples of suitable Solvents are: methanol, ethanol, n-propanol, isopropanol, butanol, Gasoline, aromatic hydrocarbons, such as toluene, furthermore ketones, such as  Cyclohexanone, acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, glycol esters and ethers, as well as aliphatic hydrocarbons, e.g. n-heptane, n-octane, n-decane and n-dodecane, and mixtures of such substances.

The process of the invention, the most diverse Be be obtained. Examples are: Variable Text programming of numerical characters via text input via a Screen terminal, text programs of standard characters or special characters, like names, initials and dedications, identity stamps, logos or frequently repeating data, consecutive numbering of pieces, Input of measured variables, input of a stored program, lines Lettering or decorations.

The process of the invention, the most diverse art fabric articles, such as arbitrary shapes, plates, films and films, be labeled. Examples include ribbons, panels, pipes and Profiles, buttons and plastic-coated electronic components.

Typical application examples are the labeling of switches, Printed circuit boards, printed circuits, active and passive electro nical components, encapsulated high-voltage transformers, Sockets, housings, mechanical components of fine technology and the watch industry, vehicle components, keyboards, control buttons, electronic components, cables, pipes, films and films, as well Credit cards and identity cards.

The inventive method allows any combination of Color markers with colorful contrast, which are not blurred can and therefore are abrasion and scratch resistant. The invention obtained markings are also corrosion resistant, dimensions stable, deformation-free, light, heat and weather resistant, and good readable and have clean edges. Furthermore, the mechanical and physical properties of the article so labeled practical not impaired, such as the mechanical strength and the chemical resistance. The penetration depth of the marker depends on labeled material. It is usually less than 1 mm,  often less than 0.2 mm. There are thus labels possible, by the eye are recognizable and the strength properties of a workpiece do not interfere with sufficient thickness.

In the following examples, parts are, unless otherwise indicated give, parts by weight.

Examples 1-3 (Labeling of a Polyester)

A) Preparation of a color coating by dissolving the acrylate varnish (consisting of a mixture of 40 g of cyclohexyl methacrylate, 80 g of butyl acrylate, 40 g of methacrylic acid and 40 g of acrylic acid in a mixture of 30 ml of methyl cellosolve and 300 ml of methyl ethyl ketone for 30 hours at 80 ° C polymerized and then precipitated in a mixture of ethanol / water) in ®Dowanol PM (2-methoxy-ethanol, equivalent to a 46% acrylate solution). 30 g of this solution are thoroughly mixed with 1.5 g of a pigment according to the list below for 3 hours at 50 ° C on the magnetic stirrer. The resulting colored air-drying lacquer is applied to a thermoplastic support plate (®Crastin S 600, polyester, Ciba-Geigy AG) of 2 mm thickness using a drawing rod for 12 μm wet film thickness and dried at 50 ° C. for 1 hour.
Used pigments:
®Cromophthal scarlet RN (CI Pigment Red 166; Ciba-Geigy AG);
®Cromophthal green GFN (CI Pigment Green 7, Ciba-Geigy AG);
®Mikrolith Blue 4G-WA (pigment preparation containing CI Pigment Blue 15: 3 and a polyacrylic resin; Ciba-Geigy AG).

B) For labeling, the beam of an argon laser (514 nm. 0.5 W Output power) with a vector labeling device (®GRETAG 6210) focused (lens focal length 200 mm) and under computer control with a speed of 25 mm / s over the coated surface of the Thermoplastic carrier plate out.  

C) After labeling, the plate is developed in an aqueous-alkaline solution (1% Na ₂ CO ₃ and 1% ethanol) (ie the unirradiated film treated) until the colored film has completely peeled off at the unlabelled points.

It creates a clear, decorative lettering in the original Color of the pigment used (scarlet, green or blue) on the white background of the support plate; the caption is against moderate mechanical stress and mild solvents (alcohol) resistant.

Examples 4-6

According to the method of Examples 1-3 above instead of ®Crastin plates made of transparent polycarbonate be coated. The labeling and development is analogous to Bei play 1-3. The corresponding colored markings are created the transparent material, either on a light background or in transmitted light.

Examples 7-9

Plates are prepared analogously to Examples 1-3, but instead of the argon laser, a continuous wave CO ₂ laser (wavelength 10.6 μm) is used (power 3-4 watts, labeling speed 100 mm per sec.). There are also labels in the color of the pigment used on a white background.

Examples I to XIII

The following plastics are after the Skilled in the art to plates in the format 3 × 8 cm (Length x width) and 2 mm thickness processed:

Examples No .: I Polypropylene ® Simona PP-Devu (Simona GmbH, FRG); II Polycarbonate®Lexan (General Electric Plastics); III ABS clear, ®Terluran 877M (BASF); IV ABS white (with TiO₂), ®Terluran 877M (BASF); V PMMA® Plexiglas (Bayer); VI PMMA white, plexiglass (Bayer); VII PVC gray, ® Troidur EN (Dynamit Nobel); VIII PVC white, ® Troidur ET (Dynamit Nobel); IX PVC transparent, ® Troidur ET (Dynamit Nobel); X PBTP nature, ®Crastin S600 (Ciba-Geigy AG); XI PBTP orange, ®Crastin S600 (Ciba-Geigy AG) with 0.3% ® Cadmopur Orange; XII PBTP yellow, ®Crastin S600 (Ciba-Geigy AG) with 0.3% ® Cadmopur Yellow; XIII Polyamide ® Rilsan Besno P40.

The following colored paints are used for the coating of these sample plates manufactured:

1. 2 g of Polivinylbutyral ®Mowital B 60 T (Hoechst) in 18 ml of ethanol 4% (based on the polymer weight) of one of the intensively mixed following pigments:

• a) ®Mikrolith Blue 4G-WA (C.I. No. 74 160);
• b) ® Irgalith Blue GLSM (C.I. No. 74,160);
• c) ®Mikrolith Roth 2B-WA (C.I. Pigment Red 221);

2. 3 g of polymethyl methacrylate ® Elvacite 2043 (DuPont) in 20 ml of 2-ethoxy ethanol dissolved, containing 4% dye from the following selection mixed and stirred until complete dissolution:

• a) ®Filester Red 2973-A (anthraquinone derivative, Ciba-Geigy AG);
• b) ®Oracet Yellow GHS (C.I. No. 58,840);
• c) ®Orasol Red 3GL (C.I. Solvent Red 130);

3. a) Approx. 1.25 g of polycarbonate ®Luvican M 170 (BASF) in a Lösungsmit dissolved mixture of chloroform / toluene (1: 1), with 8% (based on dry polymer) Colored pigment ®Mikrolith Blue 4G-WA (C.I. 74 160) intensively mixed.

The paints according to Examples 1 and 2a-c can for better Adhesion to the above plastics or support materials with 0.5% Additive / wetting agent no. 29 from Dow Corning.

The above lacquers are then coated with a draw bar for 100 μm wet film thickness on the rectangular, flat plates of the above listed plastic Supported materials I to XIII.  

The thus coated plastic plates are lettered 2-4 mm in height analogously to Example 1 above, and next to rectangles of 4 × 20 mm (length × width) are drawn, both with an argon laser and with a CO ₂ lasers.

The inscription with the argon laser is carried out according to Example 1B above, while the inscription with the CO ₂ laser is carried out according to Examples 7-9 above.

The following table summarizes the experiments as well as the results obtained together, those given in the last column of this table Rating numbers represent a visual assessment and as follows interpret :.

The evaluation takes into account the factors color contrast, relief formation and Hue of the marking / lettering. The numbers mean:

Grade 4: very good in all 3 above factors;
Grade 3: very good in at least 2 of these factors;
Grade 2: good in at least 2 of these factors;
Grade 1: good in at least 1 factor.

table

Claims (14)

1. A method for colored laser marking of plastic objects in any form, according to what

• a) the article to be inscribed is coated with a soluble plastic film containing at least one coloring component,
• b) subjecting the article thus coated, after drying the film, to the radiation of a continuously excited laser so as to direct the radiation to the surface of the object to be marked in accordance with the shape of the mark to be applied, the film and the immediately adjacent surface of the article softening the irradiation sites and the coloring component penetrates into the surface of the plastic article, and
• c) the remaining unirradiated film is then dissolved with a solvent dissolves, so that at the irradiated points of the plastic article remains a visual colored contrast mark.

2. The method according to claim 1, wherein the laser used is a CO ₂ laser or an argon ion laser in the visible spectral range. 3. The method according to claim 1, wherein the material of the plastic Subject matter a polyolefin, polyvinyl esters, polyacrylic acid or poly methacrylic acid ester, polyester, polyamide, polyimide, polycarbonate, Polyurethane, polyether, polyacetal, phenoplast, aminoplast or epoxy resin is. 4. The method according to claim 1, wherein the coloring component in the absorbed visible area. 5. The method according to claim 1, wherein the coloring component a inorganic or organic pigment or a polymer-soluble color fabric is.   6. The method according to claim 5, wherein the inorganic pigment is a White pigment, a colorful metal oxide, Berlin blue, a lead chromate, Lead sulfochromate, bismuth vanadate, molybdate orange, molybdate red, metal sulfide and a zirconium silicate, carbon black or graphite. A method according to claim 5, wherein the organic pigment is an azo, Azomethine, methine, anthraquinone, indanthrone, pyranthrone, Flavanthrone, benzanthrone, phthalocyanine, perinone, perylene, Dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, Pyrrolopyrrol- or Chinophthalonpigment, further a metal complex or is a metal salt of azo compounds. 8. The method according to claim 5, wherein the coloring component a inorganic colored pigment or a metal complex of azo, azomethine or methine dyes, or an azo, azomethine, methine, anthra quinone, phthalocyanine, perylene, dioxazine, thioindigo, isoindoline, Isoindolinone, quinacridone or pyrrolopyrrole pigment. 9. The method according to claim 1, wherein the polymer-soluble dye is a Disperse dye of the anthraquinone series, a metal complex of Azo dyes, or a fluorescent dye from coumarin, naphthalene imide, pyrazoline, acridine, xanthene, thioxanthene, oxazine, thiazine or benzothiazole series. 10. The method according to claim 1, wherein the coloring component in from 0.01 to 15% by weight, based on the dried film, is used. 11. The method according to claim 1, wherein the plastic film a Cellulose derivative, polyvinyl acetate, polyvinyl propionate, polyvinyl alcohol, Polyvinyl acetal, polyacrylic or polymethacrylic acid ester, poly vinylpyrrolidone, polyamide, polyvinyl copolymer, gas-soluble Resin, urea-formaldehyde resin, air-drying oil, phenolic resin, resin-modified phenolic resin, meleinic acid resin, alkyd resin, ketone resin, Polyurethane, epoxy resin, polyester or a starch derivative is.   12. A method according to claim 11, wherein the film nitrocellulose, Ethylcellulose, cellulose propionate, cellulose acetobutyrate, polyvinyl butyral, a polyacrylic and polymethacrylic acid ester, vinyl chloride Vinyl acetate copolymer, polyvinyl alcohol, polyester, polyurethane or a Is epoxy resin. 13. The method according to claim 1, wherein the remaining unirradiated film with an aqueous-alkaline or aqueous-alcoholic alkaline Solution is dissolved away. 14. The labeled according to claim 1 material.