JPH02235686A - Laser tinted marking of plastic material - Google Patents

Abstract

PURPOSE: To mark a plastic object in an arbitrary and appropriate color phase by coating the object with a soluble lacquer film and irradiating the coated object, after drying the film, with a continuously excited laser depending on the profile of the mark. CONSTITUTION: A plastic material suitable for an object is polyacrylate, polymethacrylate, or the like, and a coloring component is an organic, inorganic or polymer soluble dye. The polymer soluble dye includes anthraquinone disperse dye and fluorescent dye and preferably used together with a tiller and/or an inorganic pigment. The coloring agent contains inorganic and organic pigments and it is added by 0.01-15 wt.% to a dry film. The film forming material and the coloring component are then dissolved into an organic solvent or a mixture and all components are combined to produce a homogeneous coloring film material. Subsequently, it is imparted to the object and dried to produce a film which is subjected to marking with a continuously excited laser thus obtaining a color comparison marking of arbitrary combination.

Description

DETAILED DESCRIPTION OF THE INVENTION The invention relates to a method for laser colored marking of plastic objects of arbitrary shape and to objects marked with this method.

Color contrast markings on the irradiation area
It is known to mark plastic objects by irradiation with a laser beam in order to create ast markings. Thus, for example, in European patent application no. ．． The material to be marked contains a dye and a silicon-containing inorganic compound or a silicon-containing dye, which is decomposed by irradiation with a laser beam to form a white mark in the irradiated area, which is the non-irradiation coloration of the material. It has good contrast with other parts. It is also known to mark plastic parts using color contrast markings. For example, European patent application no.
．． No. 190,997 teaches a method for marking high molecular weight organic materials in the form of parts, sheets or films. The method thus involves the use of additives which change color upon irradiation with a laser beam, for example inorganic or organic pigments which change color, usually black, white or beige, at the point of irradiation of the material. JP 60-155,493 also relates to laser beam marking of plastic parts or films.
The method employed involves creating a color contrast marking by mixing yellow iron oxide into the plastic material, which yellow iron oxide may further contain yellow pigment, yellow-green pigment or red pigment. It doesn't have to be there or not. When this plastic material is irradiated with a laser beam, the yellow iron oxide turns red in the irradiated area.
This results in red, orange or brown marks. Furthermore, Japanese Patent Publication No. 58-210,937 discloses a synthetic resin composition for laser marking. The composition contains two different colorants, one that volatilizes, fades or changes color upon irradiation with a laser beam, and the other that remains unchanged. , this forms a colored mark. Many organic pigments and dyes are exemplified as color-changing colorants, while many inorganic pigments are exemplified as stable compounds. This patent announcement covers the type and energy of the laser. Strength.
There is no mention of wavelength or pulse duration. Finally, British Patent No. 1,353,063 discloses a technique for irradiating metal, plastic, paper, wood, etc. with a laser beam onto a non-bonded layer of light-absorbing particles applied to the surface of the object to be marked. ．． A laser marking method for glass-ceramic or concrete objects is proposed.
The irradiation retains a layer of non-bonded particles on the object in the irradiated and melted areas, and the remaining non-irradiated and non-bonded particles are then removed in the usual manner. According to this publication, resins, colored polymeric materials or mixtures of metal powders and inorganic or organic pigments can be used as particles. The disadvantage of this method is that during marking, the layer of non-bonding particles applied to the object is often blown away from the surface of the object in the irradiated area, making it impossible to obtain a clear marking. Furthermore, it is not easy in practice to create a uniform thin layer of particles, especially on non-horizontal surfaces. In addition to this, the coated object must be handled very carefully before marking to avoid damaging the particle layer. However, the methods and synthetic resin compositions described do not meet current requirements in practice in all respects. The surface of the marked material is usually marred in the irradiated area, resulting in undesirable grooves, divots or scratches, and the resulting marks are not sufficiently resistant to abrasion or scratches and are susceptible to chemical and staining. The general quality of the paper is insufficient, such as poor resistance to corrosion and lack of clear contours at edges. Furthermore, these laser marking methods are limited to very few hues. It has now been found that it is possible to create freely programmable markings on plastic objects of any kind, in almost any suitable hue. The present invention relates to a method for laser colored marking of plastic objects of desired shape, the method comprising: (a) marking the object to be marked at least once;
(b) after said film has dried, directing a laser beam onto the surface of the coated object according to the desired marking shape; irradiation with a continuously excited laser such that the film and the surface of the object directly adjacent thereto are softened in the irradiated area and the colored component penetrates into the surface of the plastic object, and (c) the remaining non-irradiated residue The present invention relates to a method for laser colored marking of a plastic object of a desired shape, comprising dissolving a film with a solvent to leave a visually visible color-contrasting marking in the irradiated area of the plastic object.

Plastic objects can be natural or synthetic. Such materials include, for example, modified natural materials such as rubber or chlorinated rubber, or cellulose derivatives such as cellulose esters or cellulose ethers, in particular man-made organic resins, i.e. plastics obtained by polymerization, polycondensation and polyaddition. can be included. 1 The following products can be specially mentioned as belonging to this category of plastics. i.e. polyolefins such as polyethylene, polypropylene, polybutylene or polyisobutylene, polystyrene, polyvinyl chloride and polyvinylidene chloride, fluoroplastics such as polytetrafluoroethylene, and polyvinyl acetals, polyacrylonitrile, polyacrylates, polymethacrylates or polybutadienes. , and their copolymers, especially ABS or EVA, polyester. In particular, polymeric esters of aromatic polycarboxylic acids and polyfunctional alcohols, polyethers such as polyamides, polyamides, polycarbonates, polyurethanes, polyphenylene oxides, and polyacetals; Metal shrinkage (phenolic resin)
and metal condensates (aminoblasts) of formaldehyde with urea, thiourea and melamine; polyadducts and polycondensates of shrimp glostohydrin and diols or polyphenols, also known as epoxy resins; and also used as resins for surface coatings. Mention may be made of unsaturated polyesters such as maleic resins. It should be noted that in carrying out the invention it is possible to use not only homogeneous compounds, but also plastic mixtures, cocondensates and copolymers, such as copolymers based on butadiene. Plastic materials which are particularly suitable for the process of the invention include polyolefins, polyvinyl esters such as polyvinyl acetals, and polyacrylates and polymethacrylates, polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, preferably polyphenylene oxides, polyacetals, phenols. resin, aminoplast or Epoquine resin.

The most suitable plastic materials are polyacrylates, polymethacrylates, polyesters and polycarbonates.

The plastic object need not be colored, but may be colored if desired. In the latter case, suitable colorants known to those skilled in the art can be used. In principle, all the coloring components listed below can be used as colorants.

Suitable coloring components for the method of the invention are inorganic and organic pigments and polymer-soluble dyes, especially those which absorb in the visible region. Examples of inorganic pigments include white pigments such as titanium dioxide (anatase, rutile), zinc oxide, antimony dioxide, zinc sulfide, litovone, basic lead carbonate, basic lead sulfate or basic lead silicate, and iron oxide. , nickel antimony titanate, chromium antimony titanate, manganese blue, manganese violet, cobalt blue, cobalt chromium blue, cobalt nickel gray or other colored metal oxides such as ultramarine blue, Berlin blue, lead chromate, sulfochromic acid. Lead, bismuth vanadate, molybdenum orange and molybdenum red, as well as cadmium sulfide, arsenic disulfide, antimony trisulfide or cadmium sulfoselenide (cad-hoi
Examples of organic pigments include azo, azomethine, methine, zirconium silicates, and carbon black or graphite. Anthraquinone, indanthrone, pyranthrone, flavanthrone, benzanthrone. Phthalocyanine, perinone, berylene, dioxazine, thioindigo, isoindoline. isoindolinone, quinacridone, pyrrolopyrrole, or quinophthalone pigments, and e.g. azo,
Examples include metal complex salts of azomethine or methine dyes, and metal salts of azo compounds. Suitable polymer-soluble dyes are anthraquinone disperse dyes, such as hydroxyanthraquinone, aminoanthraquinone, alkylaminoanthraquinone, cyclohexylaminoanthraquinone, arylaminoanthraquinone, hydroxyaminoanthraquinone or phenylmelbutanthraquinone, as well as azo Mention may be made of metal complex salts of dyes, especially 1:2 type chromium or cobalt complexes of monoazo dyes, and fluorescent dyes such as those of the coumarin, naphthalimide, bilazoline, acridine, xanthene, thioxanthene, oxazine, thiazine or penzothiazole series. Polymeric soluble dyes are preferably used in combination with fillers and/or pigments, especially inorganic pigments such as titanium dioxide. In carrying out the invention, inorganic or organic pigments or polymer-soluble dyes can be used alone or in mixtures, with or without pigment additives if desired. Can be done. The only caveat with these pigments is that they must be compatible with the plastic film used. Suitable pigment additives include fatty acids, typically having at least 12 carbon atoms, such as stearic acid or behenic acid, as well as magnesium stearate,
Zinc stearate. Amides, salts or esters of these acids such as aluminum stearate or magnesium behenate, as well as tri(01-C4)
Quaternary ammonium compounds such as alkylbenzylammonium salts, waxes such as polyethylene wax, resin acids such as abietic acid, rosin soaps, hydrogenated or dimerized gins, Ctt to C1. Examples include paraffin disulfonic acid or alkylphenol. Preferred colorants of the present invention include inorganic color pigments and azo,
Metal complex salts of azomethine or methine dyes and azo,
The organic pigments are azomethine, methine, anthraquinone, phthalocyanine, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, or pyrrolopyrrole.

Most preferred in carrying out the present invention are heat-resistant coloring components.

Typical examples of coloring components used in the method of the present invention are f
R-phthalocyanine, acetoacetarylide, β-oxynaphthoarylide and 3-methyl-1-phenylvirazol-5-one mono- and disuazo pigments, metal salts of sulfonated α-phenylazo β-oxy-3-naphthoic acid , nickel, cobalt or copper complex pigments, and anthraquinone-based polymer-soluble heat-resistant dyes. The amount of coloring component contained in the lacquer film of the present invention is 0.01 to 15% by weight based on the dry film. If the plastic object is colored, preferably from 1 to 8% by weight, the colored marking will be a combination of the color of the coloring component of the invention and the color present on the plastic object. The lacquer film may also be natural or synthetic and in both cases may be prepared from the material in dissolved form as a film former or binder.
The lacquer film can be made from modified natural materials such as cellulose derivatives, such as nitrocellulose, acetylcellulose, cellulose probionate, cellulose acetobutyrate, ethylcellulose. or cellulose esters or cellulose ethers, such as mixtures of gore;
Polyvinyl acetals such as polyvinyl acetate, polyvinyl propionate, polyvinyl alcohol, polyvinyl butyral, polyacrylates and polymethacrylates, preferably polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polybutyl acrylate and polyisobutyl acrylate; mixtures of polyvinylpyrrolidone, polyamides, polyvinyl copolymers such as polyvinyl chloride and polyvinyl acetate, alcohol-soluble resins such as shellac; and urea-formaldehyde resins, drying oils such as linseed oil, phenolic resins, resins. This lacquer film can be selected from modified phenolic resins, maleic resins, alkyd resins, ketone resins, polyurethanes, epoxy resins, polyesters and starch derivatives such as dextrins.6 This lacquer film is made from materials that are in the form of monomers,
For example, 14 can also be produced from free S radical-curable acrylate monomers. Preferred film-forming materials for the method of the invention are nitrocellulose, ethylcellulose, cellulose probionate, cellulose acetobutyrate, polyvinyl butyral, polyacrylates and polymethacrylates, vinyl chloride-vinyl acetate copolymers, polyvinyl alcohol, polyesters, polyurethanes. Or epoxy resin.

The plastic object can be prepared in a known manner, for example in the form of a masterbatch, by extruding the necessary ingredients, such as organic materials and usual additives. It can be prepared by mixing it into the base material using a roll mill, mixer or attritor. The material obtained is then brought into the desired final shape by known methods, such as calendering, molding, extrusion, coating, casting or by means of an injection molding machine. In order to create non-brittle molded products or to reduce the brittleness of molded products,
It is often desirable to mix plasticizers with organic materials before processing. Suitable plasticizers are, for example, esters of phosphoric acid, phthalic acid or sevalenic acid. The plasticizer can be mixed with the polymer before or after mixing the coloring component.

Further modifiers can be added to the organic plastic material depending on the end use. Modifiers include, for example, kaolin,
My power, feldspar, volasnite, aluminum silicate,
Fillers such as barium sulfate, calcium sulfate, chalk, calcite and dolomite, as well as light stabilizers, antioxidants, flaming agents, heat stabilizers, processing aids commonly used in glass fiber or plastics processing and known to those skilled in the art. It is a drug. The lacquer film is applied to the plastic object in a known manner, for example by applying printing ink by letterpress, intaglio, lithographic or screen printing methods. That is, for example, film-forming materials and coloring components,
Furthermore, if necessary, film additives may be added, such as a common organic solvent (joint organic solvent).
t) or finely dispersed or dissolved in a solvent mixture. The procedure involves dispersing or dissolving the individual components or several components together, and finally combining all the components. The homogeneous colored film material is then applied to the object to be marked by one of the above-described printing methods and the resulting film is dried, typically having a thickness of 5 to 50 micrometers. , this film is marked by the method of the present invention. This film can be applied to plastic objects such as
It can be applied by coating, rolling, dipping, squirting or brushing. It is advantageous to use this film to coat only a portion of the object, that is to say only the surface area required depending on the type and size of the marking. ? High energy sources such as continuous lasers are used for marking. This operation involves applying an energy source to the surface of the material to be marked, depending on the form of the graphical symbol to be applied, and focusing the energy source so as to cause a contrast marking in the irradiated area, if necessary. Including matching. Preferably, the marking device irradiates a laser beam perpendicularly to the surface of the object to be marked. Laser sources include, for example, continuously pumped or continuous wave lasers based on CW Nd:YAG lasers or CW ion lasers (Ar, Kr) with frequency multipliers, or emitting visible light directly or with frequency multipliers. Examples include high-capacity pulsed semiconductor lasers and gas lasers such as CO2 lasers. It is advantageous to use an intensity of between 0.1 kilowatt and 1 megawatt per lcm". Preferably, a continuous CO2 laser or an argon ion laser is used in the visible region of the spectrum. The following table shows that the present invention A number of commercially available lasers are listed which are suitable for carrying out the process. In the method according to the invention, marking is carried out, for example, by a continuous CO2 laser at an intensity of about 4 watts. The laser has its parameters, e.g. If the pulse duration can be easily adjusted, it can best be adapted to the requirements of the object to be marked.

The best wavelength selected for irradiation is one such that the film or object to be marked or colored component absorbs more than half of the laser radiation in a layer approximately 50 microns thick. Softening should be understood to mean the state in which a plastic material becomes soft, as well as the state in which the material melts. Three different laser marking methods are suitable for implementing the present invention. These are the mask method, linear marking method, and dot matrix method. The latter two methods (dynamic focusing method)
In , any . Preferably, it is combined with a laser deflection system so that objects can be marked with digits, letters and special symbols, for example with computer programs.

The choice of laser system is made depending on the marking method adopted for its capacity. High capacity is preferable for mask exposure. For marking that requires dynamic focusing, medium to low capacity is preferred. Deflection of the beam is accomplished by galvo-mirrors.
) or polygon-scann
ers), e.g. sono-optical (aeous+
to-optically). It can be done holographically. Dynamic focus allows for extremely flexible marking because the marks are created electronically. Dissolving the film in the unmarked areas is carried out in a manner known per se, for example using a solvent or solvent mixture in which the lacquer film is easily dissolved, but the plastic object is not. For example, in the case of polyacrylate films containing carboxyl groups, aqueous alkaline solutions or water-alcoholic alkaline solutions can also be used. Suitable solvents include aromatic hydrocarbons such as methanol, ethanol, n-probanol, isopropanol, butanol, petroleum ether, toluene, and ketones such as cyclohexane, acetone, methyl ethyl ketone and methyl isobutyl ketone.
Included are ethyl acetate, butyl acetate, tetrahydrofuran, glycol esters and ethers and aliphatic hydrocarbons such as n-hebutane, n-octane, n-decane and n-dodecane, as well as mixtures of these solvents. ．． A wide range of markings can be obtained by the method of the present invention. Examples of these include variable text programming of numerical symbols by text input using a video display unit, text programming of standard symbols or monograms as well as special symbols such as initials or inscriptions, identification marks, abbreviations, and repeating data. (recurring data), continuous article number printing, input of measurable variables, input of memorized programs, linear markings or decorations. A wide range of plastic objects such as moldings, planks, sheets and films can also be marked using the method of the invention. Examples of such objects include ribbons, plates,
tubes and profiles, locks and plastic-coated electronic components. Typical applications include marking of circuits, printed circuit boards, printed circuits, active and passive electronic components, encapsulated high voltage transformers, electrical outlets, cast products, precision mechanical parts, watchmaking industry, automotive parts, keyboards, etc. markings on operating knobs, electronic components, cables, tubes, sheets and films, and credit cards and identification cards.

The method of the invention can produce color-contrasting markings of any combination that are indelible and therefore abrasion resistant and scratch resistant. The markings obtained according to the invention are also corrosion resistant, dimensionally stable, non-deformable and have light fastness, heat fastness and weather fastness.
It is easy to read and the outline (periphery) is clear. Furthermore, the mechanical and physical properties of the marked object, such as mechanical strength and chemical resistance, are hardly impaired. The depth of the marking part depends on the material being marked, but is usually less than 1 mm, often less than 0-2 mrn. Therefore, it is possible to create markings that are detectable with the naked eye and of sufficient thickness that do not impair the mechanical properties of the workpiece. In the examples below, parts are parts by weight, unless otherwise stated. Examples 1-3 (Marking of Polyester) (A) Acrylic lacquer was dissolved in Dowanol" PM (2-methoxyethanol). (equivalent to 46% acrylate solution) Prepare the colored layer.This acrylic lacquer consists of: cyclohexyl methacrylate 40 g butyl acrylate 80 g methacrylic acid
It consisted of a mixture of 40 g of acrylic acid polymerized in a mixture of 30 ml of methylcellulose and 300 mQ of methyl ethyl ketone at 80°C for 30 hours. 30 g of this solution and 1.5 g of each of the following pigments are thoroughly mixed at 50° C. for 3 hours using a magnetic stirrer. Each air-drying pigmented lacquer was applied to a 2 mm thick thermoplastic plate [Crastin
■) S600. Ciba Geigy polyester] was coated with an applicator to a wet film thickness of 12 micrometers and dried at 50°C for 1 hour.

Pigment used: Cromophtal ■ Scarlet RN (manufactured by Ciba Geigy: C*I.Pigment Red
166) Chromophthal Green GFN (Ciba Geigy: C.I. Pigment Green 7) Microlith (Microlith@) Blue 4G-vA
(Ciba Geigy: C.I.Pigment Blu
Pigment colorant containing 15=3 of polyacrylic acid and polyacrylic acid) (B) Vector marking device [Greta
Argon laser beam (514 nm, output 0.5 W) using g@)6210] [lens diameter 200 mm]
is focused and guided under computer control over the thermoplastic coated surface at a speed of 25 mm/s to create the marking. (C) After marking, remove the plastic plate with an alkaline aqueous solution (Na.C0) until the colored film is completely removed from the non-marking areas.
, 1% and ethanol 1%) (i.e., treat non-irradiated areas). A distinct decorative marking with the original hue of the pigment (scarlet, green or blue) is produced on the white surface of the substrate. This marking is resistant to moderate mechanical stress and mild solvents (alcohol). The procedure described in Examples 1 to 3 was followed except that a transparent polycarbonate plate was coated instead of a Krastin plate. Marking and development were performed in the same manner as in Examples 1-3. Similar colored markings obtained on transparent materials can be observed either on transparency or in transmitted light.

J main continuous wave C○2 laser (wavelength 10.6 micrometers)
Examples except [strength 3 to 4 W; marking speed 100 mm/sec]]. Produce a plastic plate according to 3. The marking is obtained by the hue of the pigment used on a white background. The following plastic material is processed into a plate with dimensions of 3 x 8 cm (length x width) and thickness of 2 mm by a method well known to those skilled in the art. Example ■: Polypropylene sinona (Simona■)P
P-Devu [Siw+ona GmbH
, West Germany] Example ■: Polycarbonate Lexan (General Electric Plastics) Example M: ABs transparent, Terluran@ 8 7 7 M [Basfu (
BASF)] Example IV: ABS white, (Tie, included), Telluran 877M [BASF] Example V: P
MMA Plexiglas (Bayer) Example VI: PMMA white, Plexiglas (
Bayer) Example ■: PVC gray, Trobidur (Trov
idur@ ) E N [ Dynamite Nobel (D
Example ■: PVC white, Trobidur ET (Dynamit Nobel) Example W: PVC transparent, Trobidur ET (Dynamit Nobel) Example X: PBTP natural color, Crustin ■5600 (
Example XI: PBTP Orange, Cadmopur (Cadm
opur@) Orange 0.3% Crastin ■S
600 Example
Clasten @ S600 with 3% Example x■: Boryamide, RLLsa
n@8esno) P 4 0 The following colored lacquer,
Prepare to coat the sample plate mentioned above. 1. Polyvinyl butyral Mobital (Movita)
A solution of 2 g of B 6 O T (Hoechst) dissolved in 18 mQ of ethanol and 4% (based on the weight of the polymer) of one of the following pigments are thoroughly mixed.

(a) Microlith ■Blue-40-WA (C.I.74 160) (b) Irgalith (Irgalith@) Blue GL
SM (C.I.7 4 1 6 0) (c) Microlith Red 2 B-WA (C.I.
．． Pigmant Red 2 2 1)2. Polymethyl methacrylate elvacite (Elvacite@
) 2043 (Dupont) 3 g dissolved in 20 mQ of ethanol and 4% of one of the following dyes are mixed until the dye is completely dissolved.

(a) Fil.ester Red 2973-A (Andraquinone derivative, Ciba Geigy) (b) Orasat@Ero-〇〇S (C
．． I, 5 8 8 4 0) (c) Orasol@ Red 3GL (
C. I. Solvent Red 130)3. Polycarbonate Luvican M170
Blue-40-WA (C
．． I. 74.160) and mix thoroughly.

Dowkonin (
Additives commercially available from D ov-Cowning)
Wetting agent No. 29 can be added to the lacquers of Example 1 and Examples 2(a)-(c) at 0.5%. Next, the lacquer described above was applied with an applicator to a rectangular flat plate made of the plastic material of Examples E to XII described above so that the thickness of the undried film was 100 micrometers. The coated board is marked with letters 2-4 mm high according to Example 1 and then a rectangle with dimensions 4 x 20 mm (length x width) is delineated using an argon laser and a CO2 laser.

Marking with argon laser was done according to Example IB.
O. Laser marks follow Examples 7-9. The test conditions and results are summarized in Table 1.

The numbers listed in the last column of the table represent visual evaluations and should be interpreted as follows. The rating takes into account three factors: color contrast, relief formation and hue of the marking. The grading numbers are: 4: Very good on all three factors; 3: Very good on at least two factors; 2: Good on at least two factors; 1: Good on at least one factor.

No. table ”””Ichiju] Material L

Claims (1)

[Claims] 1. (a) At least one object to be marked is
(b) after said film has dried, directing a laser beam onto the surface of the coated object according to the desired marking shape; (c) irradiate the film with a continuously excited laser such that the film and the object surface directly adjacent thereto are softened in the irradiated area and the colored component penetrates into the surface of the plastic object; and (c) the remaining non-irradiated residue. A method for laser colored marking of plastic objects of a desired shape, comprising dissolving a film with a solvent to leave a visible color contrast marking in the irradiated area of said plastic object. 2. The method according to claim 1, comprising using a CO_2 laser or an argon laser in the visible region of the spectrum as continuous laser. 3. The material of the plastic object is selected from the group consisting of polyolefin, polyvinyl ester, polyacrylate and polymethacrylate, polyester, polyamide, polyimide, polycarbonate, polyurethane, polyether, polyacetal, phenolic resin, aminoplast or epoxy resin. ,
The method according to claim 1. 4. The method according to claim 1, wherein the colored component absorbs in the visible region. 5. The method according to claim 1, wherein the coloring component is an inorganic or organic pigment or a polymer-soluble dye. 6. The inorganic pigment is a white pigment, a colored metal oxide, Berlin blue, lead chromate, lead sulfochromate, bismuth vanadate, molybdenum orange, molybdenum red, metal sulfide or zirconium silicate,
6. The method according to claim 5, wherein the material is carbon black or graphite. 7. The organic pigment is an azo pigment, an azomethine pigment, a methine pigment, an anthraquinone pigment, an indanthrone pigment, a pyranthrone pigment, a flavanthrone pigment,
Claims that the pigment is a benzanthrone pigment, a phthalocyanine pigment, a perinone pigment, a perylene pigment, a dioxazine pigment, a thioindigo pigment, an isoindoline pigment, an isoindolinone pigment, a quinacridone pigment, a pyrrolopyrrole pigment or a quinophthalone pigment, or a metal complex salt or metal salt of an azo compound. 5. The method described in 5. 8. The coloring component is an inorganic colored pigment, or a metal complex salt of an azo dye, an azomethine dye, or a methine dye, or an azomethine pigment, a methine pigment, an anthraquinone pigment, a phthalocyanine pigment, a perylene pigment, a dioxazine pigment, a thioindigo pigment, an isoindoline pigment, 6. The method according to claim 5, wherein the pigment is an isoindolinone pigment, a quinacridone pigment or a pyrrolopyrrole pigment. 9. The polymer-soluble dye is an anthraquinone-based disperse dye, a metal complex salt of an azo dye, a coumarin-based, a naphthalimide-based, a pyrazoline-based, an acridine-based,
2. The method according to claim 1, wherein the dye is a xanthene-based, thioxanthene-based, oxazine-based, thiazine-based or benzene-based fluorescent dye. 10. Claim 1, wherein the amount of the coloring component used is 0.01 to 15% by weight based on the dry film.
Method described. 11. The lacquer film may contain cellulose derivatives, polyvinyl acetate, polyvinyl propionate, polyvinyl alcohol, polyvinyl acetal, polyacrylate or polymethacrylate, polyvinylpyrrolidone, polyamide, polyvinyl copolymer, alcohol-soluble resin, urea/formaldehyde resin , drying oil,
Phenolic resin, resin-modified phenolic resin, maleic acid resin, alkyd resin, ketone resin, polyurethane,
2. The method of claim 1, wherein the method is made from epoxy resin, polyester or starch derivatives. 12. The lacquer film may contain nitrocellulose, ethylcellulose, cellulose propionate, cellulose acetobutyrate, polyvinyl butyral, polyacrylate or polymethacrylate, vinyl chloride/vinyl acetate copolymer, polyvinyl alcohol,
12. The method of claim 11, wherein the material is made from polyester, polyurethane or epoxy resin. 13. The method according to claim 1, wherein the non-irradiated residual film is dissolved and removed using an alkaline aqueous solution or an aqueous alcohol-alkaline solution. 14. A material marked by the method of claim 1.