Method for fixing a marking composition onto a substrate.

Abstract

The present invention relates to a method for fixing a marking composition onto a substrate by laser irradiation, the marking composition containing at least one colorant, and the method comprising the following steps, namely: - a step (102) of depositing the marking composition onto at least a part of the substrate (4); - a step (104) of fixing a part of the marking composition by moving a laser beam and irradiating at least a part of the marking composition deposited onto the substrate; comprising wherein the power density of the laser beam when in contact with the irradiated marking composition is 32 W / mm 2 to 7.7 kW / mm 2 and the movement of the laser beam is carried out at a speed of 10 m / s -1 to 9.0 m / s -1 measured relative to the substrate, and is characterized in that. 【SELECTED DRAWINGS】Figure 5

Description

Technical Field

[0001] The present invention generally relates to a method for fixing a marking composition on a substrate using a laser.

[0002] More particularly, the present invention relates to a method for fixing a marking composition on a fragile substrate such as an organic substrate derived from plants, an organic substrate derived from animals, a synthetic-derived substrate (including, for example, plastics), a substrate made from cellulose such as cardboard or paper, etc.

[0003] The present invention also relates to a method for fixing a marking composition on a metal or plastic layer of a substrate.

Background Art

[0004] For marking leather products, a hot stamping method is known. This method involves a stamping die that is pressed against the leather to be marked. These methods are practical, but they cannot mark with pigments. In addition, these methods can locally damage the substrate, which may affect its properties such as water resistance, hydrophilicity, or hydrophobicity. Finally, with these methods, the pattern on the substrate cannot be easily customized.

[0005] Laser marking methods are also known for hard substrates selected from, for example, metals, plastics, ceramics, and glass. While this method is practical, it cannot be used for soft or flexible substrates that are fragile because they are easily scratched or damaged by heat. In fact, in these methods, the properties of the laser beam used to irradiate the substrate cause heating exceeding 500°C due to the interaction of light and matter between the laser beam and the substrate. While such properties are suitable for hard substrates such as metals, plastics, ceramics, or glass, they are not suitable for more fragile substrates such as leather, fabrics, and cardboard. This is because the heating of the material induced by this method damages these substrates through a burning engraving phenomenon that causes localized carbonization of the substrate. Such localized carbonization is incompatible with the production of markings in colors other than black and causes substantial localized changes in the properties of the substrate, particularly its behavior in water.

[0006] There are also known methods for marking a metal layer on a substrate. While these methods are practical, they do not adhere the marking composition very well to the metal layer. In addition, the colors obtained on the metal layer are dull, so these methods do not achieve very good color rendering of the colors fixed on the metal layer. These methods are also time-consuming to implement. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The object of the present invention is to correct at least one of the above-mentioned drawbacks and to provide a fixing method suitable for marking marking compositions on different types of substrates, such as brittle ones, particularly those of organic origin, as well as metal and plastic substrates. [Means for solving the problem]

[0008] For this purpose, the present invention provides a method for fixing a marking composition onto a substrate by laser irradiation, wherein the marking composition comprises at least one colorant, and the method comprises the following steps: - A step of depositing a marking composition onto at least a portion of the substrate, - A step of fixing a portion of the marking composition by moving a laser beam and irradiating at least a portion of the marking composition deposited on the substrate, - A step of removing the marking composition that was not irradiated during the fixing step, Includes. According to the present invention, the power density of the laser beam when it comes into contact with the irradiated marking composition is 32 W / mm². 2 ~7.7kW / mm 2 The laser beam movement, when measured relative to the substrate, is 10 millimeters per second to 9.0 meters per second (ms). -1 It is performed at the speed of ).

[0009] In relation to the present invention, the displacement velocity corresponds to the displacement velocity of the substrate being marked, or to the displacement velocity of the laser beam spot on the substrate.

[0010] Power density corresponds to the amount of power passing through a surface per unit area of ​​that surface. Therefore, it represents the amount of power received in a portion (region) of the surface.

[0011] Unlike the hot stamping method, this invention makes it possible to fix various colored pigments onto a fragile substrate without altering them. Such a method is also easy to implement, allowing for the creation of more personalized designs.

[0012] It should be noted that, by combining power density and scanning speed, the present invention makes it possible to limit the amount of power per unit area that the substrate receives during irradiation. Surprisingly, contrary to expectations, this limitation of irradiation does not hinder the optimal adhesion of the marking composition on the fragile substrate.

[0013] By the removal step, the portion of the substrate covered by the marking composition that did not fix during the fixing step can be cleaned.

[0014] In one embodiment, the power density is 60 W / mm 2 ~5 kW / mm 2 and the movement of the laser beam is 0.1 m / s -1 ~9.0 m / s -1 at a speed, thereby further limiting damage to the substrate while achieving a very high marking performance.

[0015] In the present disclosure, the laser beam means an optical beam emitted by a laser or a laser element. The colorant means an agent containing at least one pigment or at least one dye or a combination thereof.

[0016] In one embodiment, the power density is 430 W / mm 2 ~1 kW / mm 2 and the laser beam movement speed is 2500 mm / second to 7000 mm / second. Thus, the method according to the present disclosure is faster while achieving the same performance.

[0017] In one embodiment, the power density is 480 W / mm 2 ~1.1 kW / mm 2 and the laser beam movement speed is 3300 mm / second to 7000 mm / second. Such characteristics can minimize heating of the substrate and thus possible damage thereto.

[0018] In one embodiment, the power density is 480 W / mm 2 ~550 W / mm 2 and the movement speed of the laser beam is 4900 mm / second to 7000 mm / second. Such characteristics can prevent heating from occurring on the substrate. Thus, no change occurs to the substrate (there is no actual damage and the substrate is preserved).

[0019] In a preferred embodiment, the power density is 60 W / mm². 2 ~5kW / mm 2 The laser beam moves at a rate of 0.1 meters per second to 9.0 meters per second (ms). -1 This is done at a speed of ). Due to these characteristics, better results can be obtained while limiting the amount of power received by the substrate.

[0020] In one embodiment, the laser beam is moved at a speed of 0.6 to 9.0 meters per second.

[0021] These characteristics further reduce the exposure of equipment to the laser beam, thus limiting the risk of damaging the substrate and ensuring no impact on the quality of the fixation.

[0022] In one embodiment, the power density of the laser beam when in contact with the irradiated marking composition is 1 kW / mm². 2 ~5kW / mm 2 That is the case.

[0023] These features allow for the use of very fast scanning speeds, thereby reducing method execution time.

[0024] Within the scope of the present invention, displacement of the laser beam with respect to the substrate can be performed by any suitable method, for example, the following displacements, namely: - Displacement of the laser beam (i.e., laser scanning), - Displacement of the substrate, - Combination of laser beam displacement and substrate displacement By at least one of the following.

[0025] In one embodiment, after the removal step, the marking composition covers at least 90 percent of the irradiated substrate.

[0026] In one embodiment, the surface roughness of the substrate is 0 micrometers to 2 millimeters.

[0027] Therefore, this method is effective for various types of substrates, whether smooth or rough.

[0028] In one embodiment, the substrate is either flat or curved.

[0029] In one embodiment, the method includes a step of air-drying the marking composition before the irradiation step, wherein the duration of the drying step is preferably less than 2 minutes.

[0030] In one embodiment, the laser is connected to a focusing device having a certain focal length for focusing the laser beam to a focal point. The substrate is then positioned at the focal point, or at a distance of less than 5 cm, preferably less than 1 cm, from the focal point.

[0031] The combination of beam power and velocity characteristics with such focusing enables effective fixation even on substrates having a flat or non-flat shape. A non-flat substrate refers in particular to a substrate whose surface to be marked is curved, or a substrate whose surface to be marked has both flat and non-flat portions, and / or an irregular surface such as a substrate having concave and convex regions. Therefore, the method is configured to fix the marking composition to, for example, a substrate or portion of the substrate positioned at the focal point when the substrate or portion of the substrate used is flat, or to a substrate or portion of the substrate shifted from the focal point when the substrate or portion of the substrate is curved, i.e., has a non-flat shape.

[0032] In addition, operation outside the focal point can reduce the laser power density in contact with the substrate. Therefore, these features provide an easy-to-implement solution for adhering colorants to fragile substrates without the need to flatten the surface to be marked.

[0033] In one embodiment, fixing is performed on a surface (or surface) of the substrate, including a metal layer, called the marking surface, and the method includes a laser irradiation treatment step of at least one area of ​​the metal layer prior to the deposition step, and the deposition and fixing steps are performed on the treated area of ​​the metal layer.

[0034] In this embodiment, the metal layer can form a markable surface on the substrate.

[0035] In this embodiment, the metal layer is made of the following material, namely, - Metals, such as pure metals (e.g., zinc, aluminum, copper, gold, silver) or treated metals (e.g., anodized aluminum), - Metal alloys (e.g., brass, steel or stainless steel, iron alloys, Zamak-type alloys (alloys of zinc, aluminum, and optionally copper)) It may include at least one layer of at least one of the following.

[0036] Therefore, the marking composition can be fixed onto different metal materials by the method according to the present invention.

[0037] In this embodiment, the metal layer may be coated with a protective layer. The protective layer may include at least one of the following elements: an anodized layer, lacquering (e.g., a layer obtained by ink printing, screen printing, or paint coating), zinc plating, plating, or plasticization (e.g., epoxy type). Hereinafter, when the protective layer includes lacquering, zinc plating, plating, or plasticization, these will be referred to as lacquered metals.

[0038] Therefore, when the fixing method is performed on a metal layer, the method according to the present invention may include a processing step that allows the surface of the metal layer to be deformed or prepared before the deposition and fixing of the marking composition. Such a step, in combination with the properties of the laser used in the fixing step, makes it possible to achieve very good fixing of the marking composition on the metal layer, as well as very good color rendering of the color of this marking composition on the metal layer. In addition, the optical properties of the laser also make it possible to perform the fixing method on a substrate having a metal layer more quickly.

[0039] In this embodiment, a laser emitting a laser beam may be used in the processing step, and the laser beam used in the processing step and the laser beam used in the fixing step may have at least one identical characteristic, which is as follows: - wavelength, - Power density, - Displacement velocity - Number of passes It includes at least one of the following.

[0040] These features make it possible to use the same laser in both the processing and fixing steps, thereby limiting the cost of implementing the method according to the present invention.

[0041] In this embodiment, the processing step may be performed using a laser having a power density less than or equal to (preferably less than) that of the laser used in the fixing step, and the displacement of the laser beam with respect to the substrate at a speed less than or equal to (preferably less than) that of the laser beam displacement used in the fixing step. For example, the power density is 955 W / mm². 2 ~1.9kW / mm 2 Preferably, 955 W / mm 2 ~1.7kW / mm 2 The displacement velocity is 500 mm / s to 1600 mm / s (preferably 500 mm / s to 1500 mm / s).

[0042] In this embodiment, the processing step is the following process, namely, - Anodizing, - Laser ablation, - Laser engraving, - Mechanical ablation It may include at least one of the following.

[0043] In this embodiment, the treated area, after processing, is the following color, i.e., - white - Gray It may have a surface having one of the following characteristics.

[0044] In this embodiment, particularly in the case of a substrate having a colored anodized alumina layer, the processing step can remove at least partially the anodized layer to expose a white or gray alumina layer.

[0045] Therefore, in the present invention, the adhesion of the coloring agent to the metal plate is improved by making the metal plate lighter in color.

[0046] In this embodiment, the surface color of the treated area is determined by the following parameters, namely: - Laser power density, - Displacement velocity of the laser beam, - Number of laser beam passes It may depend on at least one of the following.

[0047] Therefore, it is possible to adjust the above parameters to match the processed area of ​​the desired color.

[0048] In this embodiment, the laser beam may be configured to irradiate the processed area only once during the processing step.

[0049] Needless to say, in one embodiment, fixing is performed on a surface of the substrate, including the metal layer, called the marking surface, and the deposition step can be performed on the marking surface (also called the marking surface). Therefore, in this case, no pretreatment is performed.

[0050] In one embodiment, during the fixing step, the laser is configured to pass over the portion of the marking composition n times, where n is 2 or more.

[0051] These characteristics make it possible to obtain a substrate with the aforementioned advantages while limiting damage to the substrate illuminated by the laser beam.

[0052] In one embodiment, n is 2 to 20, preferably 3 to 10.

[0053] In one embodiment, the number of passes depends on the properties of the substrate. According to the present invention, very good results are obtained when n is 3.

[0054] In one embodiment, the laser used in the fixing step is continuous or pulsed.

[0055] In one embodiment, the laser used in the fixing step and / or processing step is a solid- or gas-based (e.g., CO2) gain-medium laser. In the present invention, a solid-state laser means a laser in which the amplification medium includes a crystal. For example, a solid-state laser may include a laser diode, a YAG laser, or a fiber laser.

[0056] Therefore, the laser used in the fixing and / or processing steps is the following laser, namely, - A YAG laser that emits a laser beam with an emission wavelength of 1064 nanometers. - A CO2 laser that emits a laser beam with an emission wavelength of 10,600 nanometers. - YA laser that emits a laser beam with an emission wavelength of 532 nanometers, - YAG laser that emits a laser beam with an emission wavelength of 355 nanometers It could be at least one of the following.

[0057] Alternatively, or in combination, the laser used in the fixing and / or processing steps may be a square or cube YAG laser emitting a laser beam with an emission wavelength of 100 nm (UV) to 1 μm (far-infrared), for example, 532 nm, 355 nm, or 266 nm.

[0058] Therefore, the method according to the present invention operates with commonly used and widely available lasers, improving the ease of implementation of the method at a reasonable cost.

[0059] In one embodiment, when the laser beam is a YAG laser, the generated laser beam is a pulsed laser beam, and when the laser beam is a CO2 laser, the generated laser beam is a continuous laser beam.

[0060] In one embodiment, the minimum diameter of the beam is, for example, 70 to 120 micrometers when the laser beam is in contact with the substrate.

[0061] In one embodiment, the processing step involves emitting a laser beam with an emission wavelength of 10,600 nanometers and a power output of 955 W / mm². 2 ~1.277kW / mm 2 This can be performed with a CO2 laser having a power density and a travel speed of 500 mm / s to 900 mm / s.

[0062] In one embodiment, the processing step involves emitting a laser beam with an emission wavelength of 355 nanometers and a power output of 1.0 kW / mm². 2 ~1.9kW / mm 2 (Preferably 1.7 kW / mm²) 2 This can be performed with a YAG laser having a power density of ) and a travel speed of 1000 mm / s to 1600 mm / s (preferably 1500 mm / s).

[0063] In one embodiment, the marking composition is - aqueous base, - At least one colorant in an aqueous base Includes.

[0064] Typically, this colorant can be dissolved or may be a mixture of pigments or a mixture of soluble dyes.

[0065] In one embodiment, the colorant or marking composition has photochromic and / or thermal colorchromic properties.

[0066] In this disclosure, “photochromic element” means an element that can change color in response to the intensity of light it receives. Therefore, fluctuations in the intensity of light received cause a change in color. Furthermore, the term “thermochromic element” means an element that can change color in response to temperature. Therefore, fluctuations in the temperature of the environment in which the element is placed cause a change in color.

[0067] In one embodiment, if the colorant contains at least one pigment, each pigment is in the form of particles with a size of 10 nm to 0.1 mm.

[0068] In one embodiment, the amount of aqueous base is 50% to 84% by weight of the marking composition.

[0069] In one embodiment, the amount of colorant is 16% to 50% of the marking composition.

[0070] In one embodiment, the aqueous base is a liquid.

[0071] By using such an aqueous liquid base as a medium for the colorants and particles constituting the marking composition, it becomes possible to obtain a solution that improves the operational ergonomics and stability of this method. In fact, the colorant particles are dispersed in the liquid base.

[0072] In one embodiment, the aqueous base comprises water and an acrylic binder mixed with a short-chain alcohol or a surfactant.

[0073] Such a formulation of the marking composition enhances the uniformity and stability of the suspension constituting the marking composition, while simultaneously improving the adhesion of the colorant to the substrate. Consequently, the quality and lifespan of the markings are improved.

[0074] A binder refers to an emulsion of water and acrylic or vinyl resin.

[0075] In one embodiment, the aqueous base does not contain organic solvents. Therefore, it is possible to avoid the use of flammable organic solvents that are toxic to humans and the environment.

[0076] In one embodiment, the aqueous base contains an organic solvent.

[0077] In this modified embodiment, the coloring agent is in the form of particles with a size of 10 to 50 micrometers.

[0078] These properties improve the fixation of the colorant during the fixing step. In addition, such particle sizes are less dangerous to humans (if inhaled or ingested).

[0079] In one embodiment, at least one colorant is arranged so as not to change color after the fixing step.

[0080] In one embodiment, the coloring agent is - Pigments containing at least one of the following components: metal oxides, metals, metal alloys, and metal alloy oxides. - Inorganic pigments, - Organic pigments - Pigments containing carbonate minerals - Sodium aluminosilicate thiosulfate - Synthetic dyes - natural dyes or a combination of these Selected from.

[0081] In one embodiment, if the colorant is a pigment, the colorant may be in the form of particles.

[0082] In one embodiment, the white inorganic pigment contains TiO2.

[0083] In one embodiment, the inorganic pigment comprises at least one of the following components: a white inorganic pigment, a composite oxide pigment, and a colored natural inorganic pigment.

[0084] In one embodiment, the pigment containing a metal oxide may include a synthetic pigment colored with a metal oxide.

[0085] In one embodiment, the organic pigment may include a TiO2 and / or polyoxymethylene-based thermochromic pigment, such as melamine.

[0086] By using colorants based on inorganic materials, extremely high color quality can be achieved. In addition, this type of colorant has ecological advantages.

[0087] The use of sodium thiosulfate aluminosilicate-based colorants provides non-toxic and inexpensive marking compositions.

[0088] The use of carbonate mineral-based colorants is low-cost and low-toxicity.

[0089] In one embodiment, the metal particles are selected from bronze, gold, silver, copper, aluminum, or a combination thereof.

[0090] Therefore, the method according to the present invention works effectively with precious metals such as gold and silver or bronze-type alloys, thereby enabling the production of high-quality valuable articles.

[0091] In addition, these metal particles allow the substrate to be colored in a variety of colors.

[0092] In one embodiment, the marking composition includes at least one metal oxide particle as a colorant (here, a pigment). For example, the at least one metal oxide particle is one of the following transition metal oxides, i.e., - Titanium oxide - Iron oxide - tin dioxide Selected from.

[0093] These compositions allow us to obtain different colors for marking.

[0094] In one embodiment, the colorant further comprises 38% to 74% by weight of fine particle silicates in the colorant composition.

[0095] In one embodiment, the silicate includes mica.

[0096] Such colorants, especially mica-based colorants, are environmentally friendly and inexpensive. In addition, mica particles improve the adhesion of the colorant to the substrate and absorb some of the beam energy. Therefore, the mica particles limit the heating of the substrate and at the same time increase heat transfer to the colorant particles, which contributes to the quality of the marking.

[0097] In one embodiment, the silicate, preferably mica, has the following properties, namely: - The particle size is k × 10 times larger than the size of other particles in the colorant composition. 3 The value is large by a certain amount, and k is an integer from 1 to 9. - The particle size is between 3.0 μm and 80 μm. It is a particle form having at least one of the following.

[0098] In one embodiment, the marking composition is deposited on a substrate as a layer with a thickness of 10 nanometers to 0.1 millimeters. In one embodiment, the substrate is made of the following material, namely, - metal, - plastic, - synthetics, - Plant-derived organic materials, - Animal-derived organic materials, - Synthetic materials, such as polyurethane, - Cellulose-based materials, such as cardboard or paper, - Woven or nonwoven fabrics that are at least partially organic It includes at least one of the following.

[0099] In the interpretation of the present invention, the organic nature of a material corresponds to the fact that at least a portion of its components or constituents are produced by living organisms, animals, or plants.

[0100] Therefore, this method works perfectly well for fragile substrates such as leather products made from natural, plant-based, or synthetic leather.

[0101] In addition, this method works perfectly well even on harder substrates such as glass, composites, metals, and plastics, where it is known to be difficult to fix stable marking compositions over long periods.

[0102] The present invention also relates to a marking composition that is fixed onto a substrate by laser irradiation, which is, - An aqueous base containing water and a stabilizer, the aqueous base present in the marking composition in a proportion of 50% to 84% by weight, - At least one colorant in the form of particles suspended in an aqueous base, in a proportion of 16% to 50% by weight of the marking composition. Includes.

[0103] A water-based base refers to a base in liquid or paste form.

[0104] This marking composition is intended to be realized within the framework of the method according to the present invention as described above.

[0105] In one embodiment, the marking composition is preferably fixed onto the substrate by the method described above.

[0106] Therefore, the marking composition has properties that allow it to exhibit good adhesion to the substrate while being fixed to the brittle substrate by the method described above.

[0107] The marking composition also has properties that allow it to exhibit good adhesion to the substrate while being fixed to the metal layer of the substrate by the method described above.

[0108] The adhesion of the marking composition to these different substrates remains stable over long periods.

[0109] In one embodiment, the stabilizer comprises a short-chain alcohol or an acrylic resin and a surfactant.

[0110] In one embodiment, the aqueous base contains an organic solvent.

[0111] In one embodiment, each colorant is in the form of particles with a size of 10 nm to 0.1 mm.

[0112] In one embodiment, the coloring agent is - Pigments containing at least one of the following components: metal oxides, metals, metal alloys, and metal alloy oxides. - Inorganic pigments, - Organic pigments, - Pigments containing carbonate minerals, - Sodium aluminosilicate thiosulfate, - synthetic dyes, - natural dyes, or a combination of these Selected from.

[0113] In one embodiment, the colorant further comprises at least one silicate, preferably mica, in the form of fine particles, in an amount of 38% to 74% by weight in the colorant composition.

[0114] In one embodiment, the silicate, preferably mica, has the following properties, namely: - The particle size is k × 10 times larger than the size of other particles in the colorant composition. 3 Only large, - The particle size is between 3.0 μm and 80 μm. It is a particle form having at least one of the following.

[0115] In one embodiment, each colorant is in the form of particles with a size of 10 nm to 0.2 mm, preferably 10 nm to 0.1 mm.

[0116] Of course, the various features, variations, and embodiments of the present invention can be combined in various ways, as long as they are not contradictory and are not mutually exclusive.

[0117] The present invention also relates to a marking composition comprising at least one colorant and an aqueous base. Such a composition is suitable for fixation onto a substrate by the method described above.

[0118] The following description relating to the accompanying drawings, provided as non-limiting examples, will clarify what the present invention is and how it is carried out. [Brief explanation of the drawing]

[0119] [Figure 1] This is a schematic diagram of one embodiment of a system for applying a marking composition according to the present invention. [Figure 2] This is an example of a deposition apparatus included in a system for fixing a marking composition according to the present invention. [Figure 3] This is a first example of a fixing and / or processing apparatus included in a system for fixing a marking composition according to the present invention. [Figure 4] This is a second example of a fixing and / or processing apparatus included in a system for fixing a marking composition according to the present invention. [Figure 5] This is a first embodiment of a method for adhering a marking composition to a substrate according to the present disclosure. [Figure 6] This is a front view of a flat substrate being irradiated by a fixing device of a system for fixing a marking composition. [Figure 7] This is an example of a curved substrate marked with a marking composition using the fixing method according to the present invention (first or second embodiment). [Figure 8] This is a side view of the substrate according to the present invention. [Figure 9] This is a second embodiment of the method for adhering a marking composition to a substrate according to the present disclosure. [Modes for carrying out the invention]

[0120] system Figure 1 shows a system S for fixing a marking composition 2 onto a substrate 4. System S includes a control unit 50 and a fixing device 10. Optionally, system S also includes a deposit device 20, a cleaning device 60, and a synchronization device 90. In one embodiment, system S optionally includes a processing device 80.

[0121] As shown in Figures 1 and 3, the fixing device 10 includes a frame 11, a laser device 30, and a support 40. The fixing device 10 is connected to a control unit 50 configured to control the fixing device 10.

[0122] The control unit 50 is a computer or any other electronic element that enables the execution of a series of commands and / or calculations. The control unit 50 typically includes a processor, memory, and various input and output interfaces.

[0123] The control unit 50 is configured to receive input data, such as adjustment data, the pattern to be generated, the type of substrate to be used, etc., via input and output interfaces. For this purpose, the control unit 50 is typically connected to a human-machine interface, through which the user can input data, which is then used by the fixing device 10 to fix the marking composition 2 onto the substrate 4.

[0124] The output data consists of commands sent to various elements of system S.

[0125] For the fixing device 10, and especially for the laser device 30, these commands include, for example, adjustment data for the laser device 30 (e.g., operating mode, power, scanning speed, etc.). For the support 40, these data include, for example, the distance from the focal plane of the laser beam.

[0126] As shown in Figure 3, the frame 11 holds the laser device 30 as well as the support 40.

[0127] In this example, the laser apparatus 30 includes a laser 31 configured to irradiate a marking composition 2 placed on a substrate 4, a scanning device 32, and a focusing device 33 including at least one focusing lens 34.

[0128] The laser 31 is positioned to emit a monochromatic beam 35 toward the substrate 4, along the propagation direction toward the substrate 4.

[0129] In Figure 3, the laser beam 35 enters the scanning device 32, which directs the laser beam 35 onto the substrate 4.

[0130] The scanning device 32 is configured to move the laser beam 35 along two directions x and y that intersect the propagation direction of the laser beam 35 on the surface of the substrate 4. Therefore, laser scanning is performed by the scanning device 32. Typically, the scanning device 32 consists of at least two movable mirrors for directing the laser beam 35 onto the substrate 4 and performing spatial scanning of the portion of the substrate to be irradiated, which is defined through input data transmitted to the control unit 50. In this disclosure, the scanning device is typically a high-speed scanning head, such as a Garbo scanner. Therefore, in this embodiment, the movement of the laser beam 35 is performed by the scanning device 32 configured to move the laser beam on the surface 3 of the substrate 4.

[0131] Typically, scanning is performed linearly, which involves scanning each irradiated portion of the substrate surface along a (virtual) line defined on the substrate aligned along the x-axis, and then moving the laser beam 35 along another line by movement along the y-axis to perform a two-dimensional (x,y) scan of the irradiated portion of the substrate. Of course, other movement modes can also be set, such as performing a two-dimensional (x,y) scan by line scanning along the y-axis followed by movement along the x-axis, or vector scanning, which is known to those skilled in the art.

[0132] Here, scanning can be performed on a portion of the substrate.

[0133] In one embodiment, the fixing device 10, particularly the laser, is configured to pass through each irradiated portion of the surface of the substrate 4 n times, where n is an integer of 2 or more. Typically, n corresponds to the number of passes of the laser beam 35 over the irradiated portion of the substrate 4. As mentioned above, in a modified form, n may be equal to 1, in which case only one pass is made.

[0134] In one exemplary embodiment, the portion of the substrate 4's surface has a start point and an end point, which define the portion of the substrate 4 to be irradiated. Therefore, the laser beam 35 is configured to make a first pass over the portion of the substrate 4 defined between the start point and the end point. Once this first pass (i.e., this first iteration) is completed, the laser beam 35 begins irradiating that portion of the substrate by making a second pass over the portion of the substrate defined between the viewpoint and the end point. n passes may be made by the laser beam 35, preferably where n is equal to 3. Typically, the laser beam 35 starts from the position of the end point of the first pass, and therefore can pass through all points of the portion of the substrate 4 to be irradiated, ending at the start point of the first pass. Of course, other embodiments are possible. Alternatively, in the second pass, the laser beam 35 may follow a similar path to the first pass. In this case, the laser beam 35 starts from the start point and ends the irradiation at the end point.

[0135] The laser beam 35 is configured to pass through each point of the irradiated portion of the substrate 4 2 to 40 times, preferably 2 to 20 times, preferably 3 to 10 times (this provides a better balance between energy consumption and marking efficiency). Typically, the number of passes depends on the characteristics of the laser beam 35, for example, the speed and power density of the laser beam 35. This also depends on the type of laser 31 used, the substrate as defined later, particularly the material of the surface 3 illuminated by the laser 35 of the substrate 4, and other factors. For example, in the case of fragile substrates such as animal hides, vegetable leather, and imitation leather, as described later, the number of passes n of the laser beam is, at a power density of 300 W / mm². 2 ~500W / mm 2 The travel speed is 1500 mm / s to 2500 mm / s, and the number of strokes required to fix the marking composition is 1 or more, for example, 5 to 10.

[0136] If three or more passes are programmed, as described above for two passes, even passes can be programmed to start from the same starting point, while odd passes can be programmed to start from the same viewpoint but from a different starting point than the even passes.

[0137] By moving the laser beam 35 across the surface of the substrate 4, controlled by the scanning device 32, multiple patterns, shapes, symbols, designs, and characters can be generated on the surface of the substrate 4. Typically, a desired pattern is input to the control unit 50 in advance, which controls the scanning device 32 to generate the desired shape.

[0138] At the output of the scanning device 32, the laser beam 35 is focused onto the substrate 4 via the focusing device 33. Here, the focusing device 33 therefore has a focal length for focusing the laser beam 35 to a focal point that is included in the focal plane.

[0139] The fixing device 10 also includes positioning means 12 configured to define a mechanical reference frame, such as one or more positioning pins. The substrate 4 has a reference frame that aligns with the mechanical reference frame of the fixing device 10. Therefore, such positioning means make it possible to precisely move and reposition the substrate 4 within the fixing device 10. The positioning means 12 may include one or more positioning pins, a stand, a cradle, etc. In the example shown, the positioning means 12 is positioned on the support of the fixing device. Of course, such means can also be positioned in other locations, such as on the chassis 11. The elements of the fixing device 10 are preferably aligned with the mechanical reference frame of the fixing device 10.

[0140] The fixing device 10 optionally includes a processing device 80 configured to process the metal layer of the substrate 4 by laser irradiation. Such a processing device 80 is used when the substrate 4 has a metal layer on its surface 3 on which it is desired to fix the marking composition 2.

[0141] Typically, metal layers requiring such treatment include at least one of the following materials: metals such as zinc or aluminum, treated metals such as anodized aluminum, or metalloic materials.

[0142] Of course, the apparatus 80 can also be used on metals coated with a protective layer. Typically, the protective layer may include at least one of the following elements: anodizing, lacquering, painting, galvanizing, plating, or plasticization (e.g., epoxy type). When the protective layer includes one of the following elements: lacquering, painting, galvanizing, plating, or plasticization, the metal layer is called a lacquered metal.

[0143] In one embodiment, the processing apparatus 80 and / or laser 30 can be removed (from the fixing device 10). Therefore, in this case, the processing apparatus 80 and / or laser 30 are aligned with the machine reference frame as soon as they are inserted into the fixing device 10.

[0144] As shown in Figure 3, the processing unit 80 is similar to the laser device 30. This means that the processing unit 80 includes all the elements of the aforementioned laser device 30 and operates in the same manner.

[0145] In a preferred embodiment, the processing apparatus 80 and the laser apparatus are separate elements. Therefore, in this preferred embodiment, the laser apparatus 30 is configured to process the metal layer of the substrate 4 and fix the marking composition 2 to the substrate (here, the metal layer of the substrate 4). Thus, in this configuration, one laser apparatus 30 is used to perform two functions. Of course, in a variation of the apparatus 10, there may also be two laser apparatuses 30, namely one for processing the metal layer and one for depositing the marking composition on the metal layer.

[0146] An advantage is that the processing apparatus 80 is configured to pass over the area to be processed in the metal layer of the substrate 4 at least once. This laser pass is performed before fixing the marking composition 2 onto the substrate 4. When processing with the processing apparatus 80, the laser apparatus 30 is configured to fix the marking composition 2 onto the processed area. This means that the laser beam 35 is irradiated only on the portion of the marking composition 2 that is placed on the processed area of ​​the substrate 4. Typically, the area to be processed is included in the input data (i.e., programmed and defined).

[0147] The substrate 4 shown in Figure 3 is positioned on a support 40. The support serves to hold the substrate 4 within the fixing device 10. Typically, the substrate 4 can be positioned on a flat support 40. In one embodiment, the support 40 and the frame 11 are formed as separate components. In a modified form, the support 40 is not flat and may have claws that are fixed to a portion of the substrate to hold the substrate 4.

[0148] As shown in Figure 3, distance d separates the surface 3 of the substrate 4 from the focusing device 33. Distance d is defined between a point on the surface 3 of the substrate (located in this case within plane PL1) and a parallel plane PL2 of the focusing device 33. This distance d can be 0 cm to 5 cm from the focal plane. Therefore, typically, plane PL1 is located within the focal plane or in a plane parallel to the focal plane and can be up to 5 cm away from the focal plane, and plane PL2 is parallel to the focal plane.

[0149] In one embodiment, the support 40 is movable. In this case, the support 40 is configured to move in at least one spatial direction. In the example shown in Figure 3, the support 40 is configured to move the substrate 4 along the z-axis parallel to the propagation direction of the laser beam 35. Such a configuration makes it possible to adjust the position of the substrate 4 with respect to the focal point of the laser beam 35. In this example, the distance d is adjusted by moving the support 40. As described above, the substrate 4 can be shifted up to 5 centimeters from the focal plane (by the focusing device 33) or positioned within the focal plane (including the focal point).

[0150] The position of the substrate 4 with respect to the focal point of the laser beam 35 can be adjusted before or during the emission of the laser beam 35. Of course, in other embodiments, the support 40 may also be configured to move the substrate 4 in three spatial dimensions x, y, and z. In this case, the movement of the laser beam 35 with respect to the substrate 4 may be a combination of the movement of the laser beam 35 via the scanning device 32 and the movement of the substrate 4 via the support 40.

[0151] For this purpose, the support 40 may be equipped with an electric motor (not shown), or the position of the support 40 may be adjusted via an adjustment ring to position the support 40 correctly.

[0152] The laser 31 used in the laser device 30 is either a continuous laser 31 or a pulsed laser.

[0153] System S may use different types of lasers, such as a solid-state laser or a CO2 laser with an amplification medium. In this disclosure, the solid amplification medium includes a crystal, such as a neodymium-doped yttrium aluminum garnet crystal known as Nd-YAG or a neodymium-doped yttrium aluminum garnet crystal (Nd:Y3Al2(AlO4)3).

[0154] Preferably, the laser used is configured to emit a laser beam 35 with a power of 0.50 W to 30.0 W.

[0155] In the first embodiment, the solid amplification medium of the laser 31 is an Nd-YAG crystal that emits a laser beam with an emission wavelength of 1,064 nanometers.

[0156] In this embodiment, the laser beam power density is 1.9 kW / mm². 2 ~3.8kW / mm 2 In this case, for example, very good results can be obtained with leather. The emitted laser beam 35 is pulsed with a pulse rate in the range of 1 kHz to 50 kHz. The power of the laser beam emitted to fix the marking composition 2 onto the substrate 4 is 7.5 watts to 15 watts. In this embodiment, the laser beam 35 is configured to scan the surface of the substrate 4 at a scanning speed of 3 m / s to 4.5 m / s. In this embodiment, the laser beam 35 typically has a power of 1.9 W / mm when the laser beam 35 is in contact with the marking composition being irradiated. 2 ~3.8kW / mm 2 It has a laser power density of [value].

[0157] In another embodiment, the laser 31 is a CO2 laser that emits an infrared laser beam with an emission wavelength of 10,600 nanometers.

[0158] Preferably, the CO2 laser 31 operates in pulse mode and emits a laser beam with a power of 25 watts or less, preferably 3 to 25 watts. The pulse rate of the laser beam 35 is 1 kHz to 200 kHz, preferably 1 kHz to 50 kHz. In this embodiment, the beam density of the laser beam 35 is 32 W / mm². 2 ~7.7kW / mm 2 Preferably 60 W / mm 2 ~1.89kW / mm 2 Very good results are obtained when this is the case. In this embodiment, the laser beam 35 is directed across the surface of the substrate 4 at 10 mm.s -1 ~9.0ms -1It is preferably configured to scan at a speed of 0.1 m / s to 9 m / s, and the laser power density when the laser beam 35 is in contact with the marking composition being irradiated is 60 W / mm². 2 ~5kW / mm 2 That is the case.

[0159] In another embodiment, the solid gain medium of the laser 31 is a frequency cube ytterbium-doped yttrium aluminum garnet crystal known as a Yd:YAG laser, which emits a laser beam with an emission wavelength of 355 nanometers.

[0160] In this embodiment, the laser beam power density is 32 W / mm². 2 ~7.7kW / mm 2 Preferably 5.0 W / mm 2 ~60W / mm 2 Very good results are obtained when this is the case. The emitted laser beam 35 is pulsed with a pulse rate of 1 kHz to 50 kHz. The power of the emitted laser beam is 3 to 8 watts, which is typically 5 watts. In this embodiment, the laser beam 35 is configured to scan the surface of the substrate at a scanning speed of 10 mm / s to 150 mm / s, and typically, its laser power density when the laser beam 35 is in contact with the marking composition being irradiated is 60 W / mm². 2 ~5kW / mm 2 That is the case.

[0161] In other embodiments, the laser used is a frequency-squared YAG laser emitting a laser beam with an emission wavelength of 532 nanometers.

[0162] In this embodiment, during the fixing step, the power density of the laser beam is 5.0 W / mm². 2 ~2kW / mm 2 Very good results are obtained when the displacement velocity is between 10 mm / s and 2000 mm / s. Typically, for CICP pigments (mica + TiO2 + SnO2 + Fe2O3), a velocity of 1000 mm / s and a displacement of 1.27 kW / mm² are obtained. 2Very good results are obtained with a power density and 20 laser passes. The emitted laser beam 35 is pulsed with a pulse rate in the range of 1 kHz to 50 kHz. The power of the emitted laser beam is 3 to 8 watts, which is typically 7 watts.

[0163] The diameter of the laser beam 35 when in contact with the surface 3 of the substrate 4 covered with the marking composition is 40 to 120 micrometers, preferably 50 to 120 micrometers.

[0164] The laser beam 35 of system S is thus irradiated onto the marking composition 2, and the marking composition 2 is fixed onto the substrate 4.

[0165] In system S, the unirradiated portion of the marking composition 2 is then removed by cleaning the unirradiated portion.

[0166] In system S, these non-irradiated areas can be cleaned manually using a wiper or sponge moistened with an aqueous solution, or by a cleaning device 60 controlled by the control unit 50. The aqueous solution may contain alcohol or a composition of water and soap. In other variations, the non-irradiated marking composition 2 can be removed with an adhesive, for example, using an adhesive roller.

[0167] The cleaning device 60 may include an ultrasonic system configured to emit sound waves to remove portions of the marking composition 2 that were not irradiated by the laser beam 35. In other examples, the cleaning device 60 may consist of a tool for removing the marking composition that was not irradiated by the laser beam 35 using an aqueous solution, such as a damp sponge or brush, or a movable arm equipped with a spray device or wiper.

[0168] According to this disclosure, different substrates 4 can be marked by the system S described above.

[0169] In particular, the marked substrate 4 may be a fragile substrate.

[0170] Typically, fragile substrates include animal-derived organic substrates such as polyurethane, plasticized leather, artificial leather, and leather (smooth, full-grain). Organic substrates may also include compressed or dried plant-derived substrates called vegetable leather or vegetable skin, such as cardboard, paper, and imitation leather obtained from plants, such as pineapple leather, mango leather, mushroom leather, and tomato leather.

[0171] Other types of substrates can also be marked by the fixing device 10. For example, other substrates that can be marked by the fixing device 10 may include metals, plastics, glass, and synthetic materials. These other substrates are called rigid substrates and will be described in more detail using Figure 9 below.

[0172] In this disclosure, a substrate is referred to as brittle, soft, or weak if its Shore A hardness is 10 to 90, preferably 50 to 90. The deposition properties are improved for substrate 4 having a Shore A hardness of 50 to 90. A soft substrate means a substrate that can be mechanically marked with low-intensity action (less than 10 Newtons), such as a fingernail.

[0173] Conversely, a substrate 4 is considered hard if its Shore A hardness exceeds 90. These hard substrates may require surface treatment by the fixing device 10, as described above.

[0174] In some applications, the base material may be plastic or contain plastic.

[0175] Typically, in this case, the substrate may include at least one of the following plastics: styrene resin (ABS), polyolefin homopolymer (PP), polyester (PETG), polyamide (PA-6), biodegradable plastic (PLA), recycled plastic (PA-6r, PSr, ABSr), acrylic resin (PMMA), polyurethane (PU), or imitation leather.

[0176] If the substrate contains metal, the substrate may contain at least one of the following: a metal alloy such as brass (copper-zinc alloy) or stainless steel (iron-carbon alloy), a metal such as zinc or aluminum, a metal having an oxide layer such as anodized aluminum, or a metal containing a protective layer such as a lacquered metal. Here, the metal may be coated with any of the above-mentioned metal layers. The protective layer may include an anodized layer, lacquering, paint coating, zinc plating, plating, or plasticization (e.g., epoxy type).

[0177] The substrates used may have different thicknesses.

[0178] Furthermore, these substrates may take on various shapes. Typically, the substrates used may be flat or curved.

[0179] The substrate according to this disclosure may have a roughness of 0 micrometers to 2 centimeters. The roughness depends on the substrate 4 to be marked, on which the marking composition 2 is deposited.

[0180] The Shore A hardness of the brittle type of substrate marked by method 100 according to the present invention is preferably 50 to 90.

[0181] In this disclosure, marking composition 2 is - Aqueous base in a proportion of 50% to 84% by weight in the marking composition. - At least one colorant in the form of particles suspended in an aqueous base, in a proportion of 16% to 50% by weight in the marking composition. Includes. Each colorant in marking composition 2 is in the form of particles with a size of 10 nm to 0.1 mm.

[0182] The aqueous base serves as the application vector for marking composition 2.

[0183] The aqueous base contains water and a stabilizer.

[0184] Typically, stabilizers include short-chain water-soluble alcohols or acrylic resins mixed with surfactants.

[0185] When alcohol is used, such aqueous bases help reduce the surface tension of the colorant / water-substrate. The role of alcohol is particularly to accelerate the drying of the marking composition on the surface of the substrate.

[0186] In one embodiment, the aqueous base may include a water-miscible organic solvent. Typically, the organic solvent is selected from acetaldehyde, acetic acid, acetone, acetone nitrile, dimethoxyethane, dimethylformamide, dimethyl sulfoxide (DMSO), dioxane, ethanol, ethylamine, ethylene glycol, glycerol, methanol, propanol, propylene glycol, tetrahydrofuran, and triethylene glycol. Of course, other organic solvents may also be used.

[0187] In preferred embodiments, the aqueous base, particularly the stabilizer, does not contain an organic solvent.

[0188] For example, if the stabilizer is a water-soluble short-chain alcohol, the short-chain alcohol may contain C2-C3 groups or it may be methanol.

[0189] When the stabilizers are acrylic resin and surfactant, the acrylic resin mixed with water is involved in the fixing method of the colorant.

[0190] In this case, the surfactant can be selected from anionic surfactants, cationic surfactants, nonionic surfactants such as esters, amphoteric surfactants, polymer surfactants, or biosurfactants belonging to one of these classifications.

[0191] The surfactant used depends on the colorant that will be used in the marking composition.

[0192] Colorants are - Pigments containing at least one of the following elements: metal oxides, metals, metal alloys, and metal alloy oxides. - Inorganic pigments, - Organic pigments, - Carbonate mineral pigments, - Sodium aluminosilicate thiosulfate, - Synthetic dyes - natural dyes It may be selected from or a mixture of the colorants listed above.

[0193] Typically, when a colorant contains a pigment, the pigment may be in the form of particles.

[0194] For example, if the colorant (here, the pigment of the colorant) contains particles of at least one metal, these particles are selected from bronze, gold, and silver.

[0195] As mentioned above, the colorant can be a mixture of several different pigment particles.

[0196] For this purpose, in one embodiment, the colorant further comprises at least one silicate, preferably mica, which is present in a proportion of 38% to 74% by weight in the colorant composition.

[0197] Typically, when a silicate contains or is mica, the mica particles may be coated with one or more metal oxide particles.

[0198] At least one metal oxide particle is a transition metal oxide, namely, - Titanium oxide, - Participating railway enthusiasts, - tin dioxide Selected from.

[0199] In one embodiment, the colorant or marking composition has photochromic and / or thermal colorchromic properties.

[0200] The following detailed examples illustrate various colorants of the marking composition 2 used in method 100 described later. In particular, in these examples, the colorant comprises at least one pigment in the form of particles. [Examples]

[0201] Example 1 In this embodiment, the colorant comprises a pigment in the form of particles. The particles are bronze particles made from a copper-tin alloy known to those skilled in the art. The particle size of the bronze particles is 10 nanometers to 20 μm. The bronze particles are mixed in an aqueous base containing water and short-chain alcohol, but remain undissolved. For example, the bronze particles are present in 16.6% by weight in the marking composition 2, the isopropanol of the aqueous base is present in 16.6% by weight in the marking composition 2, and the water of the aqueous base is present in 66.6% by weight in the marking composition 2. This composition is then applied to a substrate by hand or via a deposition apparatus 20. The color obtained with this marking composition is typically gold.

[0202] Example 2 In this embodiment, the colorant contains a pigment comprising carbon particles and iron oxide particles (Fe2O3). The particle size of the carbon particles is 10 nanometers to 100 μm. A black color can be obtained with such a colorant. The iron oxide particles are mixed in an aqueous base containing water and short-chain alcohol, but remain undissolved. For example, the colorant is present in 16.6% by weight in marking composition 2, the isopropanol of the aqueous base is present in 16.6% by weight in marking composition 2, and the water of the aqueous base is present in 66.6% by weight in marking composition 2. This composition is then applied to the substrate by hand or via the deposition apparatus 20.

[0203] Example 3 In this embodiment, the colorant comprises a pigment comprising synthetic or natural mica particles associated with (and thus coated with) particles of a precious metal selected from gold to obtain a golden / golden color or silver to obtain a silvery color.

[0204] In this embodiment, the mica particles are 1000 times larger than the silver or gold particles. Typically, the particle size of the mica particles is on the order of micrometers, while the particle size of the gold or silver particles is on the order of tens or hundreds of nanometers. The mica particles are present in the colorant composition at a proportion of 80-99% by weight. These particles are mixed with the aqueous base described above.

[0205] For example, the coloring agent is present in 16.6% by weight of the marking composition 2, the isopropanol aqueous base is present in 16.6% by weight of the marking composition 2, and the water aqueous base is present in 66.6% by weight of the marking composition 2. This composition is then applied to the substrate by hand or via the deposition device 20.

[0206] Example 4 In this embodiment, the aqueous base comprises an acrylic binder and a surfactant. Typically, in this embodiment, the colorant is present in 30% by weight of the marking composition 2, the acrylic binder is present in 64% by weight of the marking composition 2, and the surfactant is present in 66.6% by weight of the marking composition 2. The surfactant may include sodium lauryl sulfoacetate.

[0207] The colorants include pigments containing synthetic or natural mica mixed with metal oxide particles.

[0208] Mica particles are present in the colorant composition at a proportion of 38-74% by weight. The remaining portion of the colorant composition consists of particles of at least one metal oxide. In this example, the particle size of the mica particles is 3.8 μm-74 μm.

[0209] Different compositions of colorants are also possible.

[0210] Case 1: The colorant of the marking composition contains mica particles, titanium dioxide (TiO2) particles, tin dioxide (SnO2) particles, and iron oxide (Fe2O3) particles, each with a particle size of 10 to 60 micrometers. For example, mica particles are present in the colorant composition at 66% to 74% by weight, TiO2 particles at 15% to 19% by weight, Fe2O3 particles at 11% to 15% by weight, and SnO2 particles at less than 1% by weight. The colorant is mixed with the aforementioned aqueous base to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is gold / golden.

[0211] Case 2: In this example, the colorant of the marking composition comprises mica particles, titanium dioxide (TiO2) particles, and iron oxide (Fe2O3) particles, each with a particle size of 10 to 60 micrometers. This colorant is mixed with the aforementioned aqueous base to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is gold / golden.

[0212] Case 3: In this example, the colorant of the marking composition contains mica particles and iron oxide (Fe2O3) particles with a particle size of 5 nanometers to 23 nanometers. This colorant is mixed with the aforementioned aqueous base to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is gold / golden.

[0213] Case 4: In this example, the colorant of the marking composition contains mica particles and titanium dioxide (TiO2) particles with a particle size of 10 to 60 nanometers. This colorant is mixed with the aforementioned aqueous base to obtain marking composition 2. In this example, the color of marking composition 2 when irradiated on a substrate is white.

[0214] Case 5: The colorant of the marking composition contains mica particles and iron(III) oxide particles (Fe2O3). This colorant is mixed with the aqueous base as described above to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is green.

[0215] Case 6: The colorant of the marking composition contains mica particles present at 69% to 73% by weight in the colorant composition, and titanium dioxide particles present at 26% to 30% by weight in the colorant composition. This colorant is mixed with the aqueous base as described above to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is gray.

[0216] Case 7: The colorant of the marking composition contains mica particles, iron oxide particles, and tin dioxide (SnO2) particles. This colorant is mixed with the aqueous base as described above to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is yellow.

[0217] Case 8: The colorant of the marking composition contains mica particles, iron oxide particles, and titanium dioxide (TiO2) particles. This colorant is mixed with the aqueous base as described above to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is orange.

[0218] Case 9: The colorant of the marking composition contains mica particles, iron oxide particles, SnO2 particles, and TiO2 particles. This colorant is mixed with the aqueous base as described above to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is purple.

[0219] Case 10: The colorant of the marking composition contains mica particles, TiO2 particles, and Fe2O3 particles. This colorant is mixed with the aqueous base as described above to obtain marking composition 2. According to this example, the color of marking composition 2 when irradiated on a substrate is black.

[0220] Case 11: The colorant of the marking composition contains mica particles and Fe2O3 particles. This colorant is mixed with the aqueous base as described above to obtain the marking composition 2. According to this example, the color of the marking composition 2 irradiated on the substrate is red.

[0221] The colorant of this example is shown to be mixed with an aqueous composition containing an acrylic binder and a surfactant, but in an alternative embodiment, the colorant may be mixed in an aqueous base containing a short-chain alcohol as shown in the previous examples.

[0222] Example 5 In one embodiment, the colorant comprises a pigment containing at least one of the following particles, namely, - Ceramic enamel particles made of silicon, - Particle bundles, - Alumina particles or a combination thereof The color of such a colorant is gray. Typically, the colorant is 16.6% by weight in the marking composition 2, the isopropanol of the aqueous base is 16.6% by weight in the marking composition 2, and the water of the aqueous base is present at 66.6% by weight in the marking composition 2.

[0223]

[0224] Example 6: In this example, the colorant contains a pigment containing aluminum oxide coated with titanium dioxide and also contains tin oxide. The particles of the colorant are 5 μm to 60 μm in this example, and here 5 μm to 30 μm. With such a colorant, blue can be obtained. The aluminum oxide particles are mixed in an aqueous base containing an acrylic binder and a surfactant. For example, the colorant is present in the marking composition 2 in an amount of 30% by weight, and the aqueous base is present in an amount of 66% by weight of the marking composition. In this example, the aqueous base contains an acrylic binder in an amount of 60% by weight in the marking composition 2, and the surfactant is present in an amount of 6% by weight in the marking composition 2. Then, the composition is applied to the substrate by hand or via the deposition device .

[0225] To perform the marking according to the present invention, the marking composition 2 must be deposited on the surface 3 of the substrate positioned to face the laser beam 35, and this deposition can be carried out in various ways.

[0226] In the present disclosure, the marking composition 2 can be deposited manually on the substrate 4, for example, using a brush. In this case, the thickness of the deposited marking composition 2 can be less than 1 mm, preferably 0.01 mm to 0.1 mm.

[0227] In one variant, the marking composition can be deposited automatically via a deposition device 20. For this purpose, the deposition device 20 is controlled by a control unit 50.

[0228] Typically, the deposition device 20 can include a tool, for example, a movable arm provided with a brush configured to deposit the marking composition on the surface 3 of the substrate 4. The deposition of the marking composition 2 is preferably carried out in a linear manner on the substrate 4.

[0229] In the variant shown in Figure 2, the deposition device 20 uses an application rod according to a technique known by the English name Rod Coater. As shown in Figure 2, the deposition device 20 includes, in this example, a movable cylindrical rod 21 covered with a wire 22 wound so as to form a coil around the rod 21. In Figure 2, the substrate 4 is placed on a support 40. A part of the marking composition 2 is deposited at a certain position P on the surface 3 of the substrate 4, for example, by spraying. When the rod 21 is rotated (moved) in the direction 6, the marking composition 2 can be deposited on the substrate 4 in the direction 6.

[0230] The thickness of the marking composition 2 depends on the thickness of the wire 22 used. The moving speed of the rod 21 is controlled by the control unit 50. This is typically a value between 2 and 15 m / min.

[0231] In this disclosure, the deposition apparatus 20 is configured such that the thickness of the marking composition 2 is 10 μm to 20 mm, for example, 10 μm to 100 μm.

[0232] Figure 4 shows a second example of the fixing device 70. Only the differences from Figure 3 will be explained.

[0233] In this example, the fixing device 70 includes a frame 11, a laser device 30 including a laser 31 that emits a laser beam 35, a focusing device 33 including a focusing lens 34, and a support 40.

[0234] In this example, the fixing device 70 does not include a scanning device.

[0235] Here, the support 40 is a movable support 40 configured to move in three spatial directions x, y, and z, as described in the previous example. Therefore, in this embodiment, the movement of the laser 35 is achieved by the movement of the substrate 4.

[0236] Firstly, the distance between the substrate 4 and the focusing device 33 is adjusted by moving the support 40 along the z-axis to position the substrate at a desired distance from the focal point of the focusing device. This distance can be adjusted before the emission of the laser beam 35 or during laser irradiation.

[0237] Then, the laser beam 35 at the output of the focusing device 33 moves over the substrate 4 via a movable support 40 that moves in two spatial directions x and y. Typically, the movement of the support 40 is linear. The support 40 moves along a (virtual) line along the x-axis, and then moves along the other line by moving along the y-axis, resulting in the relative movement of the laser beam 35 with respect to the substrate 4. Through the two-dimensional (x, y) movement of the support 40, the laser beam 35 is irradiated onto the target portion of the substrate to obtain the desired pattern.

[0238] For this purpose, the fixing device 70 may include a synchronization device 90 for synchronizing the movement of the substrate 4 with respect to the laser beam 35. In this case, the synchronization device 90 is controlled by a control unit 50.

[0239] Method A first example of method 100 for fixing a marking composition onto a substrate will be described with reference to FIGS. 5 to 8. The marking composition 2 used is as described above, which is a marking composition suitable for being fixed onto the substrate by method 100 (or 200 to be described later).

[0240] The method shown in FIG. 5 is executed by the system S shown in FIG. 1.

[0241] Method 100 includes a step 102 of depositing the marking composition 2 on at least a part of the substrate 4. In this example, the substrate 4 is granular polyurethane with an average particle size of 35 μm.

[0242] As described above, this deposition onto the substrate 4 can be carried out manually, for example using a brush, or automatically via the aforementioned deposition device 20. If the deposition of the marking composition 2 is carried out outside the fixing devices 10, 70, the substrate 4 is fixed to the mechanical reference frame of the fixing devices 10, 70, for example using the positioning means 12 of the fixing devices 10, 70.

[0243] When the marking composition 2 is fixed onto the substrate, here particularly onto the surface 3 of the substrate, method 100 optionally includes a step 103 of dyeing the marking composition 2.

[0244] The dyeing step 103 depends on the marking composition 2 used.

[0245] Typically, the dyeing step 103 is carried out in an open space. The dyeing time depends on the materials of the marking composition 2 and the substrate 4. In the presented example, the dyeing time is less than 2 minutes.

[0246] Method 100 then includes a step 104 in which a portion of the marking composition 2 is fixed by laser irradiation. The fixing step 104 is performed by a fixing device 10 shown in Figure 3 or a fixing device 70 shown in Figure 4, in particular by a laser device 30 of the fixing devices 10 and 70 that emits a laser beam 35. As shown in Figure 5, the laser beam 35 is irradiated onto a point or spot 36 on the substrate 4, where the diameter of the laser beam 35 on the surface 3 of the substrate 4 is 90 μm. The laser beam 35 is then moved over the surface 3 of the substrate 4 to obtain a desired pattern on the surface 3 of the substrate 4.

[0247] As described above, the movement of the laser beam 35 can be performed using the scanning device 32 shown in Figure 3, by moving the substrate 4 by the movable support 40, or by a combination of the two movements described above. By moving the scanning device 32 and / or the substrate 4 along the x and y axes, the laser beam 35 can be directed to a desired position on the surface 3 of the substrate 4.

[0248] Typically, during the fixing step 104, the power density of the laser beam 35 when in contact with the irradiated marking composition 2 is 32 W / mm². 2 ~7.7kW / mm 2 Preferably 60 W / mm 2 ~5kW / mm 2 The laser beam movement, when measured relative to the substrate, is 10 mm.s. -1 ~9.0ms -1 Preferably 0.10 ms -1 ~9.0ms -1 It will be executed at this speed.

[0249] In one embodiment, the color of the colorant remains the same (before and after laser fixing). However, in a certain modification, the colorant may contain a thermochromic pigment that changes color when exposed to laser irradiation.

[0250] Method 100 optionally includes a step 106 to remove the marking composition that was not irradiated in the fixing step 104.

[0251] Typically, the removal step 106 can be performed manually or via the cleaning device 60, as described above.

[0252] The removal step 106 allows for the removal of portions of the marking composition 2 that were not irradiated by the laser beam 35 in the fixing step 104.

[0253] As can be seen in Figure 5, the substrate 4 obtained after the removal step 106 is marked with gold markings. In this example, nine gold patterns 16 measuring 3 mm x 3 mm are marked on the substrate 4. Apart from the patterns 16, the substrate 4 has unmarked portions 17. This means that the laser beam 35 was not irradiated onto these portions 17 during the fixing step 104.

[0254] The marking composition 2 irradiated with the laser beam 35 does not change color (does not stain) between the deposition step 102 and the fixing step 104.

[0255] Figure 7 shows an example of a substrate 4 obtained after applying method 100 to the substrate 4.

[0256] The substrate 4 shown in Figure 6 is a silver-plated leather with an average roughness of 35 μm and has two parts: a first part 14 that is not covered with the marking composition and a second part 15 that is covered with the marking composition 2 during the deposition step 102. In this example, the first part 14 and the second part 15 of the substrate 4 were irradiated with the aforementioned CO2 laser beam during the fixing step 104 (the irradiation of the first and second parts was performed with the same laser parameters).

[0257] Here, the laser beam 35 was irradiated onto portions P1, P2, P3, and P4 of the first portion 14 and portions P5, P6, P7, and P8 of the second portion 15 of the substrate 4.

[0258] As shown in Figure 6, the substrate 4 has no marks in sections P1, P2, P3, and P4, while sections P5, P6, P7, and P8 are marked on the surface 3 of the substrate 4 with a pattern of 18 golden squares measuring 5 mm x 5 mm. In the second section 15, all of sections P5, P6, P, and P8 of the substrate 4 are covered with the marking composition 2, which is fixed to the substrate 4. Therefore, the laser beam 35 does not mark or damage the first section 14 of the substrate 4, although it is irradiated there.

[0259] Typically, the marking composition 2 for portions P5, P6, P7, and P8 covers at least 90 percent of the irradiated portions P5, P6, P7, and P8 of the substrate 4.

[0260] Coverage refers to the ratio of the effective irradiated surface to the effective marked surface (i.e., the surface of the marking composition that is stained or colored, in this case fixed to the substrate 4) after performing Method 100. In this example, each portion P5, P6, P7, and P8 corresponds to the effective irradiated surface of the second portion 15 of the substrate 4. Here, for each portion P5, P6, P7, and P8, the effective marked surface is obtained by comparing the effective irradiated surface (in this case, the surface of portions P5, P6, P7, and P8) with the proportion of the unirradiated substrate in each portion P5, P6, P7, and P8.

[0261] Figure 7 shows an example of a bottle or portable container B made of cylindrical synthetic leather or artificial leather (polyurethane). As shown in Figure 7, a gold pattern M is marked on the surface 3 of the base material 4 of the box B. This pattern M was marked using the method 100 described above.

[0262] Typically, in method 100, the bottle M is positioned relative to the light concentrator 33 before the fixing step 104, in this case after or during the drying step 103.

[0263] The distance d separating the substrate surface 4 from the portable container B and the focusing device 33 was adjusted to match the shape of bottle B. In method 100, marking can be performed on substrates positioned up to 5 cm from the focal plane, so even if the substrate is curved, it is not necessary to adjust the distance d during the fixing step 104. In fact, this 5 cm allows for the adaptation of the shape and curvature of the substrate being marked during the fixing step.

[0264] Method 100 typically involves a substrate, particularly the surface 3 of the substrate 4, that comes into contact with the laser beam 35 during the fixing step, having the following elements: - Plant-derived organic materials, - Animal-derived organic materials, - Synthetic materials - Cellulose-derived materials, - metal materials, - Plastic materials, - composite materials, - Some mixtures or combinations of the above Used when it includes at least one of the following.

[0265] Animal-derived organic materials include leather (e.g., leather from mammals such as cows, leather from vertebrates such as fish, or snakeskin). Plant-derived organic materials include various types of vegetable leather (e.g., mango peel, pineapple peel, mushroom skin, mushroom mycelium, etc.).

[0266] Plastic materials also include synthetic leathers such as imitation leather.

[0267] Here, we will describe examples of implementing Method 100 on various substrates.

[0268] The results shown below were obtained for flat surfaces with an average roughness of less than 2 cm, preferably 50 mm, and preferably less than 1 mm. The colorants presented are used in the marking composition described above, namely, the marking composition comprises 50% to 84% by weight of an aqueous base (water + short-chain alcohol or acrylic binder mixed with a surfactant) and 16% to 50% by weight of at least one colorant (as described below).

[0269] For example, Table 1 shows an example of applying Method 100 to a substrate having a surface 3, including the aforementioned fragile materials (leather, imitation leather, vegetable skin).

[0270] The colorants used include at least one of the aforementioned elements.

[0271] [Table 1]

[0272] The lasers used, as listed in Table 1, are the same as those described above (in the section on equipment), and were obtained in one pass (n is equal to 1) or multiple passes (n is 2 or more) of the laser beam during the fixing step.

[0273] For these results, the power density of the laser beam used was 32 W / mm². 2 ~7.7kW / mm 2 The displacement velocity is 10 mm / sec to 9 m / sec.

[0274] One of its advantages is its power density of 300W / mm². 2 ~500W / mm 2 When the travel speed is 1500 to 2500 mm / second and the number of passes is 2 or more, preferably 3 to 10, preferably 5 to 10, better marking results are obtained while limiting damage to the substrate.

[0275] Table 2 shows an example of performing Method 100 on a substrate including a surface containing a (non-brittle) plastic material, the plastic material being irradiated during the fixing step.

[0276] The results shown below were obtained when the average roughness was less than 2.00 cm, preferably less than 0.50 cm, and preferably less than 1.00 mm.

[0277] Suitable plastic materials (polymers) for marking by Method 100 include at least one of the following plastics: styrene resin (ABS), polyolefin homopolymer (PP), polyester (PETG), polyamide (PA-6), biodegradable plastic (PLA), recycled plastic (PA-6r, PSr, ABSr), and acrylic resin (PMMA).

[0278] For example, Figure 2 shows an example of applying Method 100 to a substrate having a surface containing a plastic material, which is marked by Method 100.

[0279] [Table 2]

[0280] The solid-gain medium lasers used, as listed in Table 2, are the same as those described above (in the section on equipment), and were obtained in one or more passes of the laser beam in fixing step 104.

[0281] For these results, for example, the power intensity of the laser beam used for at least one pass of the laser beam was 32 W / mm². 2 ~7.7kW / mm 2 The displacement velocity is 10 mm / s to 9 m / s.

[0282] Suitable metallic materials for marking by Method 100 include metals coated with a protective layer, such as an anodized layer (e.g., anodized aluminum) or a lacquer layer, and referred to as lacquered metals as described above. Various colorants can be used in the marking compositions used in Method 100 for marking anodized metals or lacquered metals (marking on the surface 43). These colorants include, as listed in Tables 1 and 2, at least one of the following: organic pigments, white inorganic pigments, colored CICP inorganic pigments, colored synthetic pigments made from metal oxides, colored natural inorganic pigments, synthetic dyes, and colorants based on base dyes and natural dyes. In this case, the laser used in the fixing step is preferably a CO2 laser that emits light at 10,600 nm, has a certain power density, and is used at the same speed as described above (in the case of Table 2).

[0283] Therefore, it should be understood that the above-mentioned substrate may also have other material layers, for example, other material layers that are not treated by Method 100 (i.e., none of the steps of Method 100 are performed on these layers).

[0284] Next, another example of method 200 in this disclosure will be described with reference to Figures 8 and 9. Method 200 shown in Figure 9 is performed by the system S shown in Figure 1. Only the differences from method 100 described with reference to Figures 5, 6, and 7 will be described.

[0285] Figure 8 shows a side view of the substrate 42 that has been prepared to be marked by method 200. Of course, as mentioned above, the substrate shown in Figure 8 can also be marked by method 100 in the example described above.

[0286] The base material 42 may be of any type. Typically, the base material 42 used in method 200 is one of the following materials, namely: - metal, - Plastic, - Glass, - Ceramic, - stone, - Brick, - composite materials, - Plant-derived organic materials, - Animal-derived organic materials, - Synthetic materials, - Cellulose-derived materials at least one of the following, Or a mixture or combination of several layers of the above materials. Includes.

[0287] Therefore, the substrate 42 may include a brittle material such as those listed in method 100, or a material having a higher hardness coefficient (i.e., a Shore A hardness coefficient of 80 or higher).

[0288] In this embodiment, the substrate 42 has a surface 43 including a metal layer 44. The surface 43 is also called the marking surface 43.

[0289] For example, the metal layer 44 is made of the following materials, namely, - metal, - Metal alloys at least one layer Or it includes a mixture or combination of several layers of the above materials.

[0290] The substrate 42 may include other layers 41 formed of other materials. In the example shown in Figure 9, the substrate 42 is formed of a single material, which is a single 5 mm thick layer of anodized aluminum.

[0291] The substrate 42 shown in Figure 8 is positioned in the fixing device 10 shown in Figure 3 or the fixing device 70 shown in Figure 4, and is marked with the marking composition 2 via the steps of method 200 described later. For this purpose, the substrate 42 is positioned with respect to the mechanical reference frame of the fixing devices 10 and 70.

[0292] Unlike method 100 shown in Figure 5, method 200 includes a laser irradiation treatment step 202 for the metal layer 44 prior to the deposition step 102.

[0293] Typically, processing step 202 is performed by the processing apparatus 80 shown in Figures 3 and 4.

[0294] To promote miniaturization and cost reduction, the processing apparatus 80 is similar to the fixing apparatus 30 described above. Typically, processing step 202 is performed by a laser apparatus 30 that emits a laser beam onto the metal layer 44 of the substrate 42. As shown in Figure 9, the laser beam has a beam diameter of 90 μm and can irradiate or illuminate the surface of the metal layer 44.

[0295] In processing step 202, the laser beam can be moved over the surface of the metal layer 44, typically by laser scanning using a Garbo head 32 as shown in Figure 3, or by moving the substrate as shown in Figure 4. Moving the laser beam locally causes surface treatment of the metal layer 44, in particular, a chemical change on the surface of the metal layer 44 or a physical change of the metal layer, depending on the substrate. The area scanned by the laser beam 35 therefore forms a treated area 45 on the metal layer 44.

[0296] In processing step 202, the processed region 45 can be obtained by a single pass of the laser beam over the metal layer 44. Of course, in a variation of method 200, the laser beam may pass over the metal layer 44 multiple times. However, these additional passes will increase energy consumption.

[0297] In this example, during processing step 202, the laser beam moves across the surface of the metal layer 44 to form a desired shape pattern. This desired shape is programmed, for example, in the input data, or is defined by default by the system S. The default shape may be a rectangle, square, circle, or ellipse. As shown in Figure 9, the processed area 45 is broken down into a circular pattern with a diameter of 5 mm. Of course, as mentioned above, other shapes can also be obtained depending on the movement of the laser during processing step 202. Typically, the processed area 45 may have a shape relating to one or more personalized patterns (e.g., a logo, name, sequence of words, sequence of letters, image, etc.). Thus, the processed area 45 can be broken down into separate, distinct parts on the surface 43 of the metal layer 44.

[0298] For example, if a CO2 laser emits light at 10,600 nm, the power density is 955 W / mm². 2 ~1.27kW / mm 2 This is possible, and the speed can be between 500 mm / second and 900 mm / second.

[0299] For example, if a YAG laser emits light at 355 nm, the power density is 1 kW / mm². 2 ~1.9kW / mm 2 (Preferably 1.7 kW / mm²) 2 ) can be such that the speed can be 1000 mm / s to 1600 mm / s (preferably 1500 mm / s).

[0300] In this example, the treated area 45 of the metal layer 44 (here, a circular pattern) has a surface color that distinguishes it from the area not treated by the laser beam (i.e., the area of ​​the metal layer 44 that was not irradiated by the laser beam). The treated area 45 may, in a favorable embodiment, be white or grayscale. The color of the treated area 45 depends particularly on the characteristics of the laser beam, e.g., the laser beam's travel speed and / or power density. This also depends on the material of the metal layer 44. Therefore, in method 200, the grayscale level of the treated area 45 can be selected by adjusting the laser illumination parameters, e.g., by adjusting the number of passes and / or power density and / or travel speed.

[0301] Typically, in method 200, when the metal layer 44 (especially the marking surface) is made of anodized aluminum, the processing step is performed using, for example, a CO2 laser at 955 W / mm². 2 ~1.27kW / mm 2 A power density and a laser beam travel speed of 500 mm / sec to 900 mm / sec can be used. These parameters allow for better results in fixing the marking composition while limiting the energy consumption of Method 200.

[0302] In method 200, the color of the treated area 45 may affect the adhesion performance of the marking composition 2. For example, in the case of anodized aluminum, it is preferable that the treated area 45 remains gray in color to facilitate adhesion of the marking composition during the fixing step 206. Thus, adhesion is easier and more stable over the long term. In addition, the final color rendering of the colorants of the marking composition on the metal layer 44 is improved.

[0303] At the end of processing step 202, a processed area 45 is obtained on the surface of the metal layer 44.

[0304] Method 200 then includes a step 204 of depositing the marking composition, which in this example is similar to the deposit step 102 of Method 100. Here, in particular, depositing the marking composition 2 is performed by the depositing apparatus 20 shown in Figure 2, or by manual means, for example, using a brush. If, as previously stated, it is necessary to move the substrate for depositing and then reposition it in the same location, in Method 200 the substrate 4 is aligned with the same mechanical reference frame of the fixing apparatus 10, 70 by the positioning means 12.

[0305] In the deposition step 204, the deposition apparatus 20 deposits a layer of the marking composition 2 on the treated area 45 of the metal layer 44. The marking composition may also cover the untreated area of ​​the metal layer 44. As the substrate 42 is moved during deposition, the substrate is then repositioned in the fixing apparatus 10, 70 and aligned with the mechanical reference frame of the fixing apparatus 10, 70.

[0306] In method 200 shown in Figure 9, the marking composition 2 comprises an aqueous base and at least one colorant, as described above. The aqueous base may therefore comprise water and a short-chain alcohol or an acrylic binder mixed with a surfactant.

[0307] An advantage is that the colorant (in particle form) of the marking composition 2 is made to be fixed onto the treated area 45. Such a colorant comprises silicate particles coated with metal oxide particles or silicate particles coated with at least one noble metal particle. The silicate particles are selected from mica. If the silicate particles contain mica or are mica, the colorant used in the marking composition may be the colorant described in Example 3 above, which comprises a colorant composed of mica particles coated with at least one noble metal particle, or the colorant described in Example 4 above, which comprises a colorant composed of mica particles coated with at least one metal oxide particle.

[0308] In other embodiments, the colorant comprises particles of at least one metal alloy or at least one transition metal. Therefore, the colorant may be the same as that of Example 1, Example 5, or Example 6.

[0309] In other variations, the colorant contains at least one carbonate mineral particle. Therefore, the colorant may be similar to that of Example 2 described above.

[0310] In other variants, the coloring agent contains sodium aluminosilicate thiosulfate particles.

[0311] In other embodiments, the colorant comprises a pigment containing particles of at least one inorganic material as described above, for example, particles of Cu2(CO3)(OH)2) or mica-TiO2-SnO2-Fe2O3 (Table 1 or Table 2).

[0312] In other variations, the colorant comprises a pigment containing particles of at least one organic material. The organic material may include a polyoxymethylene-melamine-based material.

[0313] In one variant, the colorant or marking composition has photochromic and / or thermal color-changing properties that do not change by the steps of Method 200, particularly during step 206 in which the colorant is fixed or step 208 in which it is removed.

[0314] If the colorant has photochromic properties, such a colorant may be the same as the colorant described in Example 7 below.

[0315] Example 7 In this Example 7, the coloring agent is - 21.0%~24.0% polyoxymethylene maramine particles, - 1.3% to 1.8% blue light-shifting pigment - 62.0%~68.0% mineral oil • 7.5% to 9.5% maleate polymer Monomethylstyrene maleic anhydride containing This is a coloring agent composition containing [a specific ingredient].

[0316] If the coloring agent has thermal discoloration properties, such a coloring agent may be the same as the coloring agent described in Example 8 below.

[0317] Example 8 In this example 8, the coloring agent is - 19.0% to 27.2% polyoxymethylene melamine particles (known by the English name "polyoxymethylene melamine") - 5.8%~7.2% styrene maleic anhydride monomethyl maleate polymer particles (known in English as "styrene maleic anhydride monomethyl maleate polymer") - 2.0%~4.2% ODB-II particles (2'-anilino-6'-(dibutylamino)-3'-methyl-3H-spiro[2-benzofuran-1,9'-xanthene]-3-one), - 0.3% to -0.7% black DCF particles (known as "Black DCF" in English), - 45.6%~47.5% ethyl stearate particles (known by the English name "ethyl stearate") - 15.2% to 15.8% methyl palmitate particles (known by the English name "methyl palmitate") It is a colorant composition containing [the specified ingredient].

[0318] Following the deposition step 204, method 200 optionally includes a drying step 205. The drying step 205 is the same as the drying step 103 described in method 100.

[0319] Method 200 includes a step 206 in which the marking composition 2 is fixed by moving a laser beam 35 over a surface of the substrate covered with the marking composition 2. In this example, the fixing step 206 of Method 200 is the same as the fixing step 104 of Method 100. Therefore, in the fixing step 206, the laser device 30 emits a laser beam 35 which moves along the surface of the metal layer 44 covered with the marking composition 2. Thus, in this step 206, the marking composition 2 is fixed onto the treated area 45 of the metal layer 44 by illuminating or irradiating the treated area 45 with the laser beam 35. As previously stated, the surface of the substrate irradiated with the laser beam 25 may be positioned at the focal point or offset from the focal point (preferably up to 5 cm).

[0320] An advantage of method 200 is that the laser beam 35 is programmed to move only over the treated area 45 of the substrate 42 in order to fix the marking composition to the treated area. Therefore, in the fixing step 206, the laser beam 35 follows a similar movement to the laser beam movement in the processing step 202. Thus, in the example shown in the figure, the laser beam 35 emitted in the fixing step 206 is irradiated only over the treated area 45.

[0321] Preferably, in fixing step 206, the laser beam 35 irradiates the treated area 45 by passing over the entire treated area 45 once, i.e., by irradiating the entire surface of the treated area 45. In this first pass, the laser beam 35 has a power density of 60 W / mm² when in contact with the marking composition 2 covering the treated area 45, similar to method 100. 2 ~5kW / mm 2 The movement was measured relative to the substrate 42 at 0.1 ms. -1 ~0.9ms -1 It is done at this speed.

[0322] After this first pass, the laser beam 35 irradiates the processed area 45 at least a second time by passing over the entire processed area 45 again. In this second pass, the laser beam 35 follows a similar movement to the first pass, that is, it starts from the same starting point and ends at the same ending point, or starts from the ending point of the previous pass and returns to the starting point of the previous pass, or follows a different movement, passing only over the portion of the marking composition 2 that was irradiated by the laser beam 35 in the first pass. In addition, the irradiation parameters, in this case the laser beam's movement speed and power density, are preferably the same for the first pass and the next pass. Of course, these irradiation parameters can also be changed by programming a movement speed that is faster or slower than that used in the first pass, for example.

[0323] Preferably, the laser beam 35 can pass over the treated area 45 2 to 20 times, preferably 3 to 10 times. In the example shown in the figure, the laser beam 35 passes over the treated area 45 3 times during the fixing step 104.

[0324] If the processing step 202 and the fixing step 206 are performed by two different removable devices, the processing step 202 and / or the fixing step 206 include aligning the processing device 80 and / or the laser device 30 using the positioning means 12 before performing these steps.

[0325] Method 200 optionally includes a step 208 to remove the marking composition 2 that was not irradiated in the fixing step 206.

[0326] The removal step 208 can be performed manually or via the cleaning device 60, as described above.

[0327] As can be seen from Figure 8, the metal layer 44 of the substrate 42 includes color marking only on the treated area 45. Therefore, in this example, a color pattern is obtained on the metal layer 44 according to method 200. The rest of the substrate 42 is not marked (or dyed or colored) by the marking composition 2.

[0328] Therefore, in the removal step 208, the unirradiated portion of the marking composition 2 in the fixing step 206 and / or the portion of the marking composition that was irradiated in the fixing step 206 but is not on the treated area 45 of the metal layer 44 is removed. A colored pattern 24 is obtained on the surface of the metal layer 44.

[0329] Therefore, the marking composition 2 can be fixed onto the substrate 42 having the metal layer 44 by method 200. As described above, the marking composition 2 can use various colorants of different kinds to stain (or color) the metal layer 44 to a desired color.

[0330] Table 3 shows the results for a substrate 42 having a metal layer 44 with regions colored (i.e., marked) in different colors by performing the method 200 described above.

[0331] In this example, fixing step 206 emits light at 355 nm, and its power density is typically 32 W / mm². 2 ~208W / mm 2 This can be performed with a laser beam. The laser beam travel speed for these two steps is 50 mm.s per pass of the laser beam over the surface of the substrate to be marked. -1 ~500mm.s -1 That was the case.

[0332] [Table 3]

[0333] Table 4 shows the results for a substrate 42 having a metal layer 44 with regions colored (i.e., marked) in different colors by performing the method 200 described above.

[0334] In this example, fixing step 206 emits light at 10,600 nm and has a power density of 60 W / mm². 2 ~5kW / mm 2 This can be performed using a CO2 laser beam. The laser beam travel speed for these two steps is 0.1 ms for 1 to 20 passes of the laser beam. -1 ~9.0ms -1 That was the case.

[0335] [Table 4]

[0336] Next, an example of a substrate having a metal surface to be marked by method 200 will be described.

[0337] A metal layer suitable for marking by Method 200 includes at least one of the following materials: pure metals such as zinc, aluminum, copper, gold, and silver; treated (oxidized) metals such as anodized aluminum; brass or steel or stainless steel (also known as stainless steel); iron alloys; and metal alloys such as Zamak-type alloys (alloys of zinc, aluminum, and optionally copper). Of course, in one embodiment, the metal layer may be covered with a protective layer as described above.

[0338] The results obtained below were obtained on flat substrates with an average roughness of less than 2.00 cm. The marking compositions used were the same as those used in Tables 1 and 2 above.

[0339] The fixing step has a power density of 32W / mm². 2 ~7.7kW / mm 2 The measured speed relative to the substrate is 10 mm.s -1 ~9.0ms -1It was performed using one of the following lasers. As an advantageous point, the processing step has a power density of 955 W / mm 2 ~1.277 kW / mm 2 and a travel speed of 500 mm / s -1 ~900 mm / s -1 and better results are obtained in the case of a CO2 laser that emits at 10,600 nm with a pass number n of 1.

[0340]

Table 5

[0341]

Table 6

[0342] The solid gain medium laser described in this Table 5 is the same as that described above (in the section on the apparatus) and was obtained with one pass of the laser beam in the fixing step 206 or multiple passes of the laser beam in the fixing step 206.

[0343] Modified type The present invention is not limited to any way to the described and illustrated embodiments, and those skilled in the art will be able to provide any modified type according to the present invention.

Claims

1. A method for fixing a marking composition (2) onto a substrate (4, 42) by laser irradiation, wherein the marking composition (2) comprises at least one coloring agent, and the method comprises the following steps, namely, - Step (102, 204) of depositing the marking composition (2) onto at least a portion of the substrate (4, 42), - A step (104, 206) to fix a portion of the marking composition (2) by moving the laser beam (35) and irradiating at least a portion of the marking composition (2) deposited on the substrate (4, 42), - Steps (106, 208) to remove the marking composition (2) that was not irradiated during the fixing steps (104, 206), In a method including, The power density of the laser beam (35) when it comes into contact with the irradiated marking composition (2) is 32 W / mm². ２ ~7.7 kW / mm ２ Furthermore, the movement of the laser beam, measured relative to the substrate, is 10 mm.s. －１ ~9.0 m. s －１ A method characterized by being performed at a certain speed.

2. The aforementioned power density is 60 W / mm². ２ ~5kW / mm ２ Furthermore, the movement of the laser beam is 0.1 m. s. －１ ~9.0 m. s －１ The method according to claim 1, characterized in that it is performed at a speed of [speed].

3. The method according to claim 1 or 2, characterized in that the fixing step is performed on a surface of the substrate (3, 43) including a metal layer, hereinafter referred to as the marking surface, and includes a laser irradiation treatment step (202) of at least one region of the metal layer (44) prior to the deposition steps (102, 204), and the deposition step (204) and fixing step (206) are performed on the treated region (45) of the metal layer (44).

4. In the processing step (202), a laser emitting a laser beam is used, and the laser beam used in the processing step (202) and the laser beam used in the fixing step (206) have at least one identical characteristic, and this at least one characteristic is the following element, namely, - wavelength, - Power density, - Movement speed The method according to claim 3, characterized by including at least one of the following.

5. The processed area (45) is the following color, namely, - white, - Grayscale color The method according to any one of claims 3 to 4, characterized in that it has a surface having one of the following.

6. The aforementioned substrates (4, 42) consist of the following elements, namely, - metal, - plastic, - Composite materials - Plant-derived organic materials, - Animal-derived organic materials, - Synthetic materials - Cellulose-derived materials - Several mixtures or combinations of the above materials The method according to any one of claims 1 to 5, characterized in that it includes at least one of the following.

7. The method according to any one of claims 1 to 6, characterized in that, during the fixing step (104, 206), the laser is configured to pass over the portion of the marking composition (2) n times, where n is 2 or more.

8. The method according to any one of claims 1 to 7, characterized in that the roughness of the substrate (4, 42) is 0 micrometers to 2 centimeters.

9. The method according to any one of claims 1 to 8, characterized in that the laser (31) is connected to a focusing device (33) having a focal length for focusing the laser beam (35) to a focal point, and the substrates (4, 42) are installed at the focal point or at a distance of 5 cm or less from the focal point.

10. The laser (31) used in the fixing step (104, 206) is the following laser, namely, - A YAG laser that emits a laser beam with an emission wavelength of 1064 nanometers. - A CO laser that emits a laser beam with an emission wavelength of 10,600 nanometers ２ laser - A squared YAG laser that emits a laser beam with an emission wavelength of 532 nanometers. - A cubed YAG laser that emits a laser beam at an emission wavelength of 355 nanometers. The method according to any one of claims 1 to 9, characterized by comprising at least one of the following.

11. When the laser beam is a YAG laser, the generated laser beam (31) is a pulsed laser beam (31), and the laser beam is CO ２ The method according to claim 10, characterized in that, in the case of a laser, the generated laser beam (31) is a continuous laser beam (31).

12. The marking composition (2) is - Aqueous base, - At least one coloring agent in the aqueous base The method according to any one of claims 1 to 11, characterized by including

13. The method according to claim 12, characterized in that the aqueous base comprises water and an acrylic binder mixed with a short-chain alcohol or a surfactant.

14. The aforementioned coloring agent is - Pigments comprising at least one of the following elements: metal oxides, metals, metal alloys, and metal alloy oxides. - Inorganic pigments, - Organic pigments, - Pigments containing carbonate minerals, - Sodium aluminosilicate thiosulfate, - Synthetic dyes - natural dyes, or a combination of these The method according to any one of claims 12 to 13, characterized in that it is selected from among.

15. The method according to claim 14, characterized in that the coloring agent further comprises a silicate in the form of particles, present in an amount of 38% to 74% by weight in the composition of the coloring agent.

16. The method according to any one of claims 1 to 15, characterized in that the thickness of the marking composition (2) fixed on the substrate (4, 42) is 10 nanometers to 0.1 millimeters.

17. The method according to any one of claims 1 to 16, characterized in that the coloring agent comprises at least one pigment, and each pigment is in the form of particles with a particle size of 10 nm to 0.2 mm.

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