Laser color marking composition for black ground color as well as preparation method and application of laser color marking composition

Abstract

The invention provides a polymer composition for laser color marking of black ground color, which is composed of the following components in percentage by weight: 0.1-10% of decoloration microcapsule, 0.01-10% of organic material and the balance of polymer, and the decoloration microcapsule and the organic material are mixed in percentage by weight: 0.1-10% of decoloration microcapsule, 0.01-10% of organic material and the balance of polymer. The invention also provides a preparation method and application of the composition. According to the invention, by utilizing the composition of the laser irradiation polymer, the decoloration microcapsule and the organic material, the existing black ground color can be eliminated in the laser irradiation area, and the patterned colored mark is generated at the same position, so that the polymer with the black ground color can present the bright colored mark under the laser irradiation in a simple, convenient and low-cost manner; therefore, the limitation of the traditional technology is broken through, and a new solution is provided for various applications.

Description

Technical Field

[0001] The invention relates to a laser color marking composition for black background, a preparation method and application thereof, and belongs to the field of polymer materials. Background Art

[0002] Laser marking technology is a technology that uses high-energy laser beams to form permanent marks on the surface of materials. It focuses the laser on the target surface, causing the material to undergo physical or chemical changes under the action of the laser energy, generating information such as logos, text, patterns or QR codes on the surface, thereby achieving product tracking, brand identification, product certification and other purposes.

[0003] At present, the laser marking method for polymers mainly generates white or light-colored marks on the surface of polymer materials with dark backgrounds (black, dark gray or gray), or generates black marks on the surface of polymer materials with light backgrounds. Laser color marking further uses lasers to generate multiple colors of marks on the surface of materials. Different from traditional laser marking (usually black, gray or white), laser color marking can form rich colors such as red, blue and green on the surface of materials.

[0004] At present, the preparation of color markings on metal surfaces is relatively mature. However, there are still many technical challenges in achieving laser color marking of polymers. The main reasons are as follows: polymers have low thermal stability and are easily deformed, burned or melted by the high temperature of the laser, resulting in blurred markings and reduced accuracy. To avoid material damage, both the laser power and the action time need to be precisely controlled. At the same time, laser marking often involves reactions of specific internal components, such as carbonization and oxidation, which makes color marking difficult to achieve. Unlike metals, polymer materials do not have a natural reaction layer on the surface to produce color (such as a metal oxide layer), so they need to rely on additives or special dyes to interact with the laser to generate markings. These additives must be compatible with the polymer matrix and cannot affect its mechanical properties or appearance. For metal materials, color marking usually achieves light interference or diffraction effects by generating specific microstructures on the surface of the material by laser, but on polymer materials, it is very difficult to precisely control and maintain nano or micron-level structures. The surface of polymer materials is relatively soft and is easily deformed after being heated by laser, resulting in unstable microstructures.

[0005] The preparation of white or light-colored marks on the surface of black polymer materials is already quite mature, but colored marks are more visually attractive than single white or light-colored marks. For example: high-end products such as mobile phones and headphones can be marked with colored brand logos, patterns or text on the black shell to enhance recognition; different colored indications or operation areas can be marked on the shell of medical equipment made of black polymer materials to reduce operating errors; and colored markings are made on black automotive interior components to distinguish installation directions, specifications or warning information. However, preparing colored marks on a black background is one of the challenges. Even if a colored pattern is successfully prepared on its surface, the black background can easily cover it up. Simply mixing and curing organic pigments or dye molecules, commonly used black pigments (such as carbon black, graphite, graphene, carbon nanotubes, copper chromium black, iron manganese black, etc.) with polymers, it is impossible to achieve laser color marking of polymer compositions with a black background. This is because when the laser acts on the polymer material, the presence of black pigments can easily lead to the formation of a porous structure on the surface of the black background polymer, thereby producing white / light-colored marks. Even if there is color, it is easily covered by white / light colors and cannot be reflected.

[0006] The Chinese patent application with publication number CN106566068A discloses a polymer composition that can be laser-colored. The patent uses polymers, laser marking powder and temperature-sensitive substances. The heat generated during laser irradiation causes the temperature-sensitive substances to undergo thermal decomposition, oxidation and other reactions at a certain temperature, thereby generating new colors on the surface of black plastic, thus forming color marks. However, the temperature-sensitive substance used in the invention is at least one of the phthalocyanine pigments, and the composition also needs to add expensive specific laser marking powder (such as Merck Iriotec 8835). The process cost is high and it is difficult to apply it in large-scale industrial applications.

[0007] The Chinese patent application with publication number CN109486128A discloses a black plastic paper that can be laser-colored, and its raw materials include plastic material, sodium allyl sulfonate, initiator, black pigment, color pigment, antioxidant, flame retardant, lubricant, and filler that is optionally added or not added. In order to reduce the thermal shrinkage phenomenon caused by local heat absorption of plastic paper during laser marking, the preparation process of black plastic paper is complicated, the types of additives are many, the selection of substrate is demanding, the efficiency of laser marking is low (scanning speed is only 20mm / s), and it cannot be widely used in polymer rubber or elastomer materials.

[0008] The Chinese patent with publication number CN116218033A discloses the use of organic materials in the preparation of color-changeable polymer materials. A specific organic material is added as an additive to a polymer to obtain a color-changeable polymer material, which has an excellent color-change effect. Under the action of a laser, various color marks can be formed on the polymer material, and the obtained color marks are clear, flat and have high contrast. At the same time, the polymer material has a light color and can realize color marking on a light-colored, white or transparent polymer substrate, expanding the application scope of laser color marking. The content disclosed in this patent still cannot solve the problem of laser color marking of black base polymer materials.

[0009] In order to overcome the difficulties of the existing technology in polymer laser color marking, especially color marking of black base polymers, the field is in urgent need of a laser color-changing material with low cost, small amount of additives added, and the ability to produce both a black base color and clear color markings under laser irradiation. Summary of the invention

[0010] The technical solution of the present invention is to provide a laser color marking composition for a black background. Another technical solution of the present invention is to provide a preparation method and use of the composition.

[0011] The present invention provides a polymer composition for laser color marking with a black background, which is composed of a polymer, achromatic microcapsules, and an organic material, wherein the weight percentages of the achromatic microcapsules and the organic material are:

[0012] 0.1-10% of decolorizing microcapsules, 0.01-10% of organic materials; the balance is polymer;

[0013] Wherein, the polymer is selected from polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyurethane, polyester elastomer, polystyrene, styrene-acrylonitrile copolymer, polyethylene naphthalate, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyurethane elastomer, nylon elastomer, styrene-ethylene-butylene-styrene copolymer, styrene-ethylene-isoprene-styrene copolymer, styrene-[ethylene-(ethylene-propylene)]-styrene copolymer, polyester elastomer, chlorinated polyethylene elastomer, polyisobutylene, ethylene-vinyl acetate copolymer, polysulfone, polyimide, cellulose acetate, unsaturated polyester, silicone resin, epoxy resin, phenolic resin, melamine resin, natural rubber, butadiene rubber, styrene-butadiene rubber, silicone rubber, fluororubber, nitrile rubber, butyl rubber, EPDM rubber, any one or a mixture of two or more thereof;

[0014] The organic material is at least one of benzopyran compounds, aniline derivatives, polycyclic quinone compounds, viologen compounds, spiropyran compounds, spirooxazine compounds, fulgide compounds, diarylethene compounds, azobenzene compounds and Schiff base compounds.

[0015] The decolorizing microcapsule is composed of a shell material and a core material, and has a diameter of 1.5 μm to 15.0 μm;

[0016] Wherein, the weight percentage of the decolorizing microcapsules and organic materials is:

[0017] Organic material 0.01-2%, decolorizing microcapsule 0.1-3%;

[0018] Wherein, the polymer is any one or more of polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET), polyester elastomer (TPEE), styrene-ethylene / propylene copolymer-styrene triblock copolymer (SEPS), styrene-hydrogenated butadiene block copolymer (SEBS), polymethyl methacrylate (PMMA), and polyvinyl chloride (PVC);

[0019] The organic materials are 2-(2-thiophenecarboxamido)benzopyran, 4,4'-bis(hexyloxy)-3-methylazobenzene, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, 4-( At least one of dibenzophenazine)-N,N-diphenylaniline, 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine], 1-hydroxy-2-methylanthraquinone, benzyl viologen, spiro[1,3,3-trimethylindole-chroman], salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzalimidate or 1,9-pyrazoloanthrone;

[0020] Wherein, the weight percentage of the decolorizing microcapsules and organic materials is:

[0021] The polymer is PC, the organic material is at least one of 2-(2-thiophenecarboxamido)benzopyran, 4,4'-bis(hexyloxy)-3-methylazobenzene, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, 4-(dibenzophenazine)-N,N-diphenylaniline, benzyl viologen, spiro[1,3,3-trimethylindole-benzodihydropyran] or 1,9-pyrazoloanthrone, the content of which is 0.02%, and the content of the decolorizing microcapsule is 0.5%;

[0022] The polymer is PC, the organic material is one of 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine] or 1-hydroxy-2-methylanthraquinone, the content is 0.2%, and the content of the decolorizing microcapsule is 0.5%;

[0023] The polymer is PC, the organic material is salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine, the content is 0.2%, and the content of the decolorizing microcapsule is 1%;

[0024] The polymer is TPEE, the organic material is 1-hydroxy-2-methylanthraquinone, the content is 0.02%, and the content of the decolorizing microcapsule is 0.5%;

[0025] The polymer is PP, the organic material is 4,4'-bis(hexyloxy)-3-methylazobenzene, the content is 0.02%, and the content of the color-reducing microcapsule is 0.5%;

[0026] The polymer is PET, the organic material is 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, the content is 0.02%, and the content of the decolorizing microcapsule is 0.5%;

[0027] The polymer is SEPS, the organic material is benzyl viologen, the content is 0.02%, and the content of the color-reducing microcapsules is 0.5%;

[0028] The polymer is SEBS, the organic material is spiro[1,3,3-trimethylindole-chroman], the content is 0.02%, and the content of the color-reducing microcapsule is 0.5%;

[0029] The polymer is PMMA, the organic material is salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine, the content of which is 0.02%, and the content of the decolorizing microcapsule is 0.5%.

[0030] The polymer is PVC, the organic material is (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, the content is 0.02%, and the content of the decolorizing microcapsule is 0.5%.

[0031] The composition is prepared by directly mixing polymer, decolorizing microcapsule and organic material or adding organic solvent to form coating, sheet, plate, rod or film material.

[0032] The present invention provides a method for preparing the polymer composition for laser color marking with a black background, which comprises the following steps:

[0033] The organic material, the decolorizing microcapsule and the polymer are mixed, co-extruded, granulated, injection-molded and frozen to obtain the product; wherein the temperature during the co-extrusion process is 180°C to 270°C; the injection molding temperature is 180°C to 270°C; and the freezing temperature is -20°C to -10°C.

[0034] The present invention also provides a method for preparing the polymer composition for laser color marking with a black background, which comprises the following steps:

[0035] The polymer, the decolorizing microcapsule and the organic material are dissolved in a solvent in sequence to form a membrane material, and the solvent is evaporated to obtain the membrane material;

[0036] The solvent is one or a mixture of two or more of liquid paraffin, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl palmitate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl palmitate, heptane, hexane, cyclohexane, carbon disulfide, dichloromethane, chloroform, xylene, toluene, benzene, chloropropane, ethyl bromide, benzene bromide, dichloroethane, isopropyl ether, nitromethane, methyl acetate, ethyl acetate, butyl acetate, ether, phenol, m-cresol, tert-butanol, ethanol, water, tetrahydrofuran, dioxane, acetone, cyclohexanone, nitrogen-nitrogen dimethylformamide, nitrogen-nitrogen dimethylacetamide or decahydronaphthalene.

[0037] The invention provides use of the composition in preparing laser color marking with a black base color.

[0038] The present invention provides a laser-induced patterned marking method, comprising the following steps:

[0039] The composition is taken, and a laser is used to irradiate the surface of the composition to form an irradiated area, so that the black color of the laser irradiated area can be faded and a color mark can be generated.

[0040] Wherein, the laser is selected from one or a combination of two or more of green laser, ultraviolet laser and excimer laser;

[0041] And / or, the laser is a continuous laser or a pulsed laser;

[0042] And / or, the laser power is 1.0-100W, and the scanning speed of the laser is 1-10000mm / s.

[0043] Preferably, the laser has a wavelength of 192nm to 600nm; further preferably, the wavelength of the laser is 355nm;

[0044] Preferably, the laser power is 2.0-5.0 W, and the scanning speed of the laser is 1000 mm / s; preferably, the laser power is 3.5-4.5 W, the scanning speed of the laser is 1000 mm / s, and the frequency of the laser is 20-100 kHz.

[0045] The present invention utilizes laser irradiation of a composition of polymer, decolorizing microcapsules and organic materials to remove the existing black background in the laser irradiated area and generate patterned color marks at the same location. The polymer with a black background can present bright color marks in a simple, fast and low-cost manner under laser irradiation, thus breaking through the limitations of traditional technologies and providing new solutions for a variety of applications.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] The present invention disperses originally black color-eliminating microcapsules and originally colorless or light-colored organic materials in a solid composition. This black solid composition can eliminate the black background in a simple and quick manner under laser irradiation and present a clear and smooth color mark, thereby breaking through the limitations of traditional technology and providing a new solution for a variety of applications. On the other hand, the present invention realizes the generation of color patterns or text on polymers, and also broadens the application range of polymer resins, rubbers and elastomers. This makes the present invention have very good industrial application prospects. In addition, the method of the present invention is a method for irradiating polymers, color-eliminating microcapsules and organic material compositions with lasers, and then preparing color patterns, texts, and QR codes on their surfaces. It has great application potential in the fields of product tracking, brand identification, product authentication, etc.

[0048] In the preferred technical solution, the present invention optimizes the types and usage ratios of polymer resins, rubbers and elastomers, decolorizing microcapsules, and organic materials, and optimizes the wavelength, scanning speed, power, pulse frequency and other parameters of the laser. Experiments have shown that under the preferred solution, the composition of the present invention can prepare color marks with bright, full and fine colors, while beyond the preferred solution range of the present invention, the color marks of the composition are not full, not fine, easy to fade or change the base color without laser irradiation.

[0049] Definitions of terms used in the present invention: Unless otherwise stated, the initial definitions provided for groups or terms in this document apply to the groups or terms throughout the specification; for terms that are not specifically defined in this document, the meaning that a person skilled in the art can give them should be given based on the disclosure and context.

[0050] In the present invention, "light color" refers to various white, light white, silvery white, light gray, silver or various silvery grays, etc. "Color" refers to a single common color such as red, blue, yellow, green, purple or various mixed colors of the above colors. It should be noted that dark gray, gray, white, light white, light gray and other colors do not belong to the color category defined in the present invention.

[0051] The present invention adds black decolorizing microcapsules and light-colored organic materials to a polymer to obtain a polymer composition with a black background color that can be color-changed. When the composition is irradiated by laser and generates heat, the black color of the irradiated area is eliminated, and a colorful pattern or text is formed at the same position. Therefore, the present invention is very suitable for information identification, graphic drawing and two-dimensional code writing in black products. In addition, the amount of organic material used in the black laser color-changable polymer composition of the present invention is small, the preparation method is simple, easy to operate, safe, and low in energy consumption, and is very suitable for large-scale industrial production.

[0052] After adding a specific composite organic additive to the polymer, the present invention utilizes the photochemical effect and photothermal effect generated during laser irradiation to cause the decolorizing microcapsules and the organic material to undergo chemical and physical changes simultaneously, fading the black background color and forming a color, thereby generating a color mark. This color change is irreversible, so a stable permanent color change can be formed on the polymer material. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is a diagram of the polymer laser color change effect in Example 16. DETAILED DESCRIPTION

[0054] The raw materials and equipment used in the specific embodiments of the present invention are all known products and are obtained by purchasing commercially available products.

[0055] (1) The equipment information used in the present invention is as follows:

[0056] Twin-screw extruder, screw diameter 35 mm, screw length-diameter ratio 36:1, produced by Nanjing Jieente Electromechanical Co., Ltd.;

[0057] Injection molding machine, Model K-TEC 40, manufactured by Milacron International;

[0058] Adjustable film applicator, model KTQ-II, produced by Shanghai Liangyan Intelligent Technology Co., Ltd.;

[0059] Planar laser marking machine, model MF-EA, pulse laser, maximum laser power 20W, laser wavelength 1064nm;

[0060] Planar laser marking machine, model MUV-ER, pulse laser, maximum laser power 5W, laser wavelength 355nm;

[0061] Planar laser marking machine, model BK-C30, pulse laser, maximum laser power 100W, laser wavelength 9.3μm~10.6μm;

[0062] Planar laser marking machine, model MV-U, pulsed laser, maximum laser power 2W, laser wavelength 192nm;

[0063] Planar laser marking machine, model YK-F20G, pulse laser, maximum laser power 10W, laser wavelength 532nm.

[0064] (2) The specific information of the raw materials used to prepare the composition of the present invention is as follows:

[0065] Polycarbonate (PC): General Electric Company, PC121R;

[0066] Polypropylene (PP): Daqing Petrochemical, T30S;

[0067] Polymethyl methacrylate (PMMA): Degussa, 8NDF21;

[0068] Polyvinyl chloride (PVC): Yibin Tianyuan, SG-3;

[0069] Polyethylene terephthalate (PET): Yuanfang Industrial, C-602;

[0070] Polyamide 66 (PA66): Lanxess, Germany, A30S;

[0071] Polyethylene (PE): Maoming Petrochemical, TR144;

[0072] Polyurethane elastomer (TPU): BASF, Germany, 1185A;

[0073] Polyester elastomer (TPEE): Cologne, Korea, KP3355;

[0074] Styrene-ethylene / propylene copolymer-styrene triblock copolymer (SEPS): Kuraray Co., Ltd., HYBRARTM 7311F;

[0075] Styrene-hydrogenated butadiene block copolymer (SEBS): Sinopec Baling Petrochemical Company, YH-506;

[0076] Color-degrading microcapsules: Dazhan Jiyuan New Material Technology Co., Ltd., EC-1; consists of a shell layer and a core layer, with a diameter of 1.5μm to 15.0μm.

[0077] The color-reducing microcapsules can be purchased commercially or prepared according to the methods reported in the literature, such as: Zhou Xueqin, et al., Study on Thermosensitive Black Reversible Thermochromic Compounds and Their Microencapsulation, Chemical Industry and Engineering, Vol. 34, No. 1, January 2017;

[0078] 2-(2-Thienylamino)benzopyran: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0079] 4,4'-Bis(hexyloxy)-3-methylazobenzene: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0080] 1,2-Bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0081] (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0082] 4-(Dibenzophenazine)-N,N-diphenylaniline: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0083] 1,3-Dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine]: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0084] 1-Hydroxy-2-methylanthraquinone: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0085] Benzyl viologen: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0086] Spiro[1,3,3-trimethylindole-chroman]: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0087] Salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine: Dazhan Jiyuan New Materials Technology Co., Ltd.;

[0088] Dichloromethane: Chengdu Kelong Chemical Co., Ltd., analytical grade.

[0089] Tetrahydrofuran: Chengdu Kelong Chemical Co., Ltd., analytical grade.

[0090] Example 1

[0091] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0092] Color-reducing microcapsules: EC-1;

[0093] Polymer: polycarbonate (PC);

[0094] 99.89 parts by weight of polycarbonate, 0.01 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 0.1 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0095] The composite plate was laser irradiated under the following conditions: the wavelength of the ultraviolet laser was 355 nm, the scanning speed was 1000 mm / s, the laser power was 4.0 W, and the laser frequency was 50 kHz.

[0096] After laser irradiation, visually inspect whether the black background has faded and color markings have been produced in the laser irradiated area. The effects of color markings can be divided into:

[0097] Unable to mark☆

[0098] Laser marking effect is poor★

[0099] Laser marking effect is average★★

[0100] Laser marking effect is good ★★★

[0101] Laser tag works great ★★★★

[0102] Laser marking effect is very good ★★★★★

[0103] In the evaluation of laser marking effect, the more “★” there are, the better the laser marking effect is.

[0104] The laser marking effect is shown in Table 1.

[0105] Example 2

[0106] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0107] Color-reducing microcapsules: EC-1;

[0108] Polymer: polycarbonate (PC);

[0109] 99.48 parts by weight of polycarbonate, 0.02 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0110] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0111] Example 3

[0112] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0113] Color-reducing microcapsules: EC-1;

[0114] Polymer: polycarbonate (PC);

[0115] 99.45 parts by weight of polycarbonate, 0.05 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0116] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0117] Example 4

[0118] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0119] Color-reducing microcapsules: EC-1;

[0120] Polymer: polycarbonate (PC);

[0121] 98 parts by weight of polycarbonate, 1 part by weight of 2-(2-thiophenecarboxamido)benzopyran, and 1 part by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed material is then added to a twin-screw extruder for co-mixing and extrusion, the extruded material is granulated and then injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the co-mixing and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0122] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0123] Example 5

[0124] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0125] Color-reducing microcapsules: EC-1;

[0126] Polymer: polycarbonate (PC);

[0127] 80 parts by weight of polycarbonate, 10 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 10 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; then the mixture is added to a twin-screw extruder for co-extrusion, the extrudate is granulated and injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the co-extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; the temperature of the freezer is controlled at -20°C to 10°C. The laser irradiation conditions are the same as in Example 1. Visually inspect whether there is fading of the black background and the generation of color marks in the laser irradiated area, and the results are shown in Table 1.

[0128] Example 6

[0129] Organic materials: 4,4'-bis(hexyloxy)-3-methylazobenzene;

[0130] Color-reducing microcapsules: EC-1;

[0131] Polymer: Polypropylene (PP);

[0132] 99.89 parts by weight of polypropylene, 0.01 parts by weight of 4,4'-bis(hexyloxy)-3-methylazobenzene, and 0.1 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 180°C to 230°C; the injection molding temperature is controlled at 180°C to 230°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0133] The composite plate was irradiated with laser under the following conditions: the wavelength of the green laser was 532 nm, the scanning speed was 1000 mm / s, the laser power was 8.0 W, and the laser frequency was 50 kHz.

[0134] The laser irradiated area was visually inspected for fading of the black background and generation of colored marks. The results are shown in Table 1.

[0135] Example 7

[0136] Organic materials: 4,4'-bis(hexyloxy)-3-methylazobenzene;

[0137] Color-reducing microcapsules: EC-1;

[0138] Polymer: Polypropylene (PP);

[0139] 99.48 parts by weight of polypropylene, 0.02 parts by weight of 4,4'-bis(hexyloxy)-3-methylazobenzene, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for co-extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the co-extrusion process is controlled at 180°C to 230°C; the injection molding temperature is controlled at 180°C to 230°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0140] The laser irradiation conditions were the same as those in Example 6. The laser irradiated area was visually inspected for fading of the black background and generation of color marks. The results are shown in Table 1.

[0141] Example 8

[0142] Organic materials: 4,4'-bis(hexyloxy)-3-methylazobenzene;

[0143] Color-reducing microcapsules: EC-1;

[0144] Polymer: Polypropylene (PP);

[0145] 99.0 parts by weight of polypropylene, 0.5 parts by weight of 4,4'-bis(hexyloxy)-3-methylazobenzene, and 0.5 parts by weight of EC-1 are mixed evenly in a high-speed mixer; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 180°C to 230°C; the injection molding temperature is controlled at 180°C to 230°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0146] The laser irradiation conditions were the same as those in Example 6. The laser irradiated area was visually inspected for fading of the black background and generation of color marks. The results are shown in Table 1.

[0147] Example 9

[0148] Organic materials: 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene;

[0149] Color-reducing microcapsules: EC-1;

[0150] Polymer: Polyethylene terephthalate (PET),

[0151] 99.89 parts by weight of polyethylene terephthalate, 0.01 parts by weight of 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, and 0.1 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed material is then added to a twin-screw extruder for blending and extrusion, the extruded material is granulated and then injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 230°C to 270°C; the injection molding temperature is controlled at 230°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0152] The composite plate was irradiated with laser under the following conditions: laser wavelength of 192 nm, scanning speed of 1000 mm / s, laser power of 1.5 W, and laser frequency of 50 kHz.

[0153] The laser irradiated area was visually inspected for fading of the black background and generation of colored marks. The results are shown in Table 1.

[0154] Example 10

[0155] Organic materials: 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene;

[0156] Color-reducing microcapsules: EC-1;

[0157] Polymer: Polyethylene terephthalate (PET),

[0158] 99.48 parts by weight of polyethylene terephthalate, 0.02 parts by weight of 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed material is then added to a twin-screw extruder for blending and extrusion, the extruded material is granulated and then injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 230°C to 270°C; the injection molding temperature is controlled at 230°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0159] The laser irradiation conditions were the same as those in Example 9. The laser irradiated area was visually inspected for fading of the black background and generation of color marks. The results are shown in Table 1.

[0160] Embodiment 11

[0161] Organic materials: 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene;

[0162] Color-reducing microcapsules: EC-1;

[0163] Polymer: Polyethylene terephthalate (PET),

[0164] 99.0 parts by weight of polyethylene terephthalate, 0.5 parts by weight of 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed material is then added to a twin-screw extruder for blending and extrusion, the extruded material is granulated and then injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 230°C to 270°C; the injection molding temperature is controlled at 230°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0165] The laser irradiation conditions were the same as those in Example 9. The laser irradiated area was visually inspected for fading of the black background and generation of color marks. The results are shown in Table 1.

[0166] Example 12

[0167] Organic materials: 1-hydroxy-2-methylanthraquinone;

[0168] Polymer: Thermoplastic polyester (TPEE);

[0169] Color-reducing microcapsules: EC-1;

[0170] 99.89 parts by weight of thermoplastic polyester, 0.01 parts by weight of 1-hydroxy-2-methylanthraquinone, and 0.1 parts by weight of EC-1 were placed in a high-speed mixer and mixed evenly; the mixture was then added to a twin-screw extruder for blending and extrusion, the extrudate was granulated and injection molded into a plate, and then the plate was placed in a refrigerator for freezing. The temperature during the blending and extrusion process was controlled at 180°C to 240°C; the injection molding temperature was controlled at 180°C to 240°C; the temperature of the freezer was controlled at -20°C to 10°C. The laser irradiation conditions were the same as in Example 1. Visually inspect whether there was fading of the black background and generation of color marks in the laser irradiated area, and the results are shown in Table 1.

[0171] Example 13

[0172] Organic materials: 1-hydroxy-2-methylanthraquinone;

[0173] Polymer: Thermoplastic polyester (TPEE);

[0174] Color-reducing microcapsules: EC-1;

[0175] 99.48 parts by weight of thermoplastic polyester, 0.02 parts by weight of 1-hydroxy-2-methylanthraquinone, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed material is then added to a twin-screw extruder for blending and extrusion, the extruded material is granulated and then injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 180°C to 240°C; the injection molding temperature is controlled at 180°C to 240°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0176] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0177] Embodiment 14

[0178] Organic materials: 1-hydroxy-2-methylanthraquinone;

[0179] Polymer: Thermoplastic polyester (TPEE);

[0180] Color-reducing microcapsules: EC-1;

[0181] 99.45 parts by weight of thermoplastic polyester, 0.05 parts by weight of 1-hydroxy-2-methylanthraquinone, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed material is then added to a twin-screw extruder for blending and extrusion, the extruded material is granulated and then injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 180°C to 240°C; the injection molding temperature is controlled at 180°C to 240°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0182] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0183] Embodiment 15

[0184] Organic materials: benzyl viologen;

[0185] Polymer: SEPS;

[0186] Color-reducing microcapsules: EC-1;

[0187] 99.89 parts by weight of SEPS, 0.01 parts by weight of benzyl viologen, and 0.1 parts by weight of EC-1 are mixed evenly in a high-speed mixer; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 180°C to 230°C; the injection molding temperature is controlled at 180°C to 230°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0188] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0189] Example 16

[0190] Organic materials: benzyl viologen;

[0191] Polymer: SEPS;

[0192] Color-reducing microcapsules: EC-1;

[0193] 99.48 parts by weight of SEPS, 0.02 parts by weight of benzyl viologen, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 180°C to 230°C; the injection molding temperature is controlled at 180°C to 230°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0194] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0195] Embodiment 17

[0196] Organic materials: benzyl viologen;

[0197] Polymer: SEPS;

[0198] Color-reducing microcapsules: EC-1;

[0199] 96.5 parts by weight of SEPS, 1.5 parts by weight of benzyl viologen, and 2.0 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 180°C to 230°C; the injection molding temperature is controlled at 180°C to 230°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0200] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0201] Embodiment 18

[0202] Organic materials: Spiro[1,3,3-trimethylindole-chroman];

[0203] Polymer: SEBS;

[0204] Color-reducing microcapsules: EC-1;

[0205] 99.89 parts by weight of SEBS, 0.01 parts by weight of spiro[1,3,3-trimethylindole-chroman], and 0.1 parts by weight of EC-1 are mixed evenly in a high-speed mixer; the mixed materials are then added to a twin-screw extruder for co-extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are put into a refrigerator for freezing. The temperature during the co-extrusion process is controlled at 180°C to 240°C; the injection molding temperature is controlled at 180°C to 240°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0206] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0207] Embodiment 19

[0208] Organic materials: Spiro[1,3,3-trimethylindole-chroman];

[0209] Polymer: SEBS;

[0210] Color-reducing microcapsules: EC-1;

[0211] 99.48 parts by weight of SEBS, 0.02 parts by weight of spiro[1,3,3-trimethylindole-chroman], and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for co-extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the co-extrusion process is controlled at 180°C to 240°C; the injection molding temperature is controlled at 180°C to 240°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0212] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0213] Embodiment 20

[0214] Organic materials: Spiro[1,3,3-trimethylindole-chroman];

[0215] Polymer: SEBS;

[0216] Color-reducing microcapsules: EC-1;

[0217] 95.0 parts by weight of SEBS, 2.0 parts by weight of spiro[1,3,3-trimethylindole-chroman], and 3.0 parts by weight of EC-1 were placed in a high-speed mixer and mixed evenly; the mixed materials were then added to a twin-screw extruder for co-extrusion, the extrudates were granulated and injection molded into plates, and the plates were then placed in a refrigerator for freezing. The temperature during the co-extrusion process was controlled at 180°C to 240°C; the injection molding temperature was controlled at 180°C to 240°C; the temperature of the freezer was controlled at -20°C to 10°C. The laser irradiation conditions were the same as in Example 1. Visually inspect whether the black background color faded and the color mark was generated in the laser irradiated area, and the results are shown in Table 1.

[0218] Embodiment 21

[0219] Organic materials: 4,4'-bis(hexyloxy)-3-methylazobenzene;

[0220] Polymer: polycarbonate (PC);

[0221] Color-reducing microcapsules: EC-1;

[0222] 99.48 parts by weight of polycarbonate, 0.02 parts by weight of 4,4'-bis(hexyloxy)-3-methylazobenzene, and 0.5 parts by weight of EC-1 are mixed evenly in a high-speed mixer; the mixed materials are then added to a twin-screw extruder for co-extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are put into a refrigerator for freezing. The temperature during the co-extrusion process is controlled at 250℃~270℃; the injection molding temperature is controlled at 250℃~270℃; and the temperature of the freezer is controlled at -20℃~10℃.

[0223] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0224] Embodiment 22

[0225] Organic materials: 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene;

[0226] Polymer: polycarbonate (PC);

[0227] Color-reducing microcapsules: EC-1;

[0228] 99.48 parts by weight of polycarbonate, 0.02 parts by weight of 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, and 0.5 parts by weight of EC-1 are mixed evenly in a high-speed mixer; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0229] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0230] Embodiment 23

[0231] Organic materials: (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione;

[0232] Polymer: polycarbonate (PC);

[0233] Color-reducing microcapsules: EC-1;

[0234] 99.48 parts by weight of polycarbonate, 0.02 parts by weight of (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylene]dihydro-2,5-furandione, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0235] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0236] Embodiment 24

[0237] Organic materials: 4-(dibenzophenazine)-N,N-diphenylaniline;

[0238] Polymer: polycarbonate (PC);

[0239] Color-reducing microcapsules: EC-1;

[0240] 99.48 parts by weight of polycarbonate, 0.02 parts by weight of 4-(dibenzophenazine)-N,N-diphenylaniline, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for co-extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the co-extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0241] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0242] Embodiment 25

[0243] Organic materials: 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine];

[0244] Polymer: polycarbonate (PC);

[0245] Color-reducing microcapsules: EC-1;

[0246] 99.3 parts by weight of polycarbonate, 0.2 parts by weight of 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine], and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0247] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0248] Embodiment 26

[0249] Organic materials: 1-hydroxy-2-methylanthraquinone;

[0250] Polymer: polycarbonate (PC);

[0251] Color-reducing microcapsules: EC-1;

[0252] 99.3 parts by weight of polycarbonate, 0.2 parts by weight of 1-hydroxy-2-methylanthraquinone, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for co-mixing and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the co-mixing and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0253] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0254] Embodiment 27

[0255] Organic materials: benzyl viologen;

[0256] Polymer: polycarbonate (PC);

[0257] Color-reducing microcapsules: EC-1;

[0258] 99.48 parts by weight of polycarbonate, 0.02 parts by weight of benzyl viologen, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0259] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0260] Embodiment 28

[0261] Organic materials: Spiro[1,3,3-trimethylindole-chroman];

[0262] Polymer: polycarbonate (PC);

[0263] Color-reducing microcapsules: EC-1;

[0264] 99.48 parts by weight of polycarbonate, 0.02 parts by weight of spiro[1,3,3-trimethylindole-chroman], and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0265] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0266] Embodiment 29

[0267] Organic materials: salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine;

[0268] Polymer: polycarbonate (PC);

[0269] Color-reducing microcapsules: EC-1;

[0270] 98.8 parts by weight of polycarbonate, 0.2 parts by weight of salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine, and 1.0 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed material is then added to a twin-screw extruder for co-extrusion, the extruded material is granulated and then injection molded into a plate, and then the plate is placed in a refrigerator for freezing. The temperature during the co-extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0271] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0272] Embodiment 30

[0273] Organic materials: salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine;

[0274] Polymer: polymethyl methacrylate (PMMA);

[0275] Color-reducing microcapsules: EC-1;

[0276] 99.79 parts by weight of polymethyl methacrylate was dissolved in 700 parts by weight of dichloromethane solution. After it was completely dissolved, 0.2 parts by weight of EC-1 and 0.01 parts by weight of salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine were weighed and added thereto. The mixture was stirred at room temperature for 4 hours, and then the mixture was made into a film material using an adjustable film applicator. After the solvent evaporated, the film was irradiated with laser under the following conditions: the wavelength of the ultraviolet laser was 355nm, the marking speed was 1000mm / s, the laser power was 4W, and the laser frequency was 50kHz.

[0277] The laser irradiated area was visually inspected for fading of the black background and generation of colored marks. The results are shown in Table 1.

[0278] Embodiment 31

[0279] Organic materials: salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine;

[0280] Polymer: polymethyl methacrylate (PMMA);

[0281] Color-reducing microcapsules: EC-1;

[0282] 99.48 parts by weight of polymethyl methacrylate was dissolved in 700 parts by weight of dichloromethane solution. After the solution was completely dissolved, 0.5 parts by weight of EC-1 and 0.02 parts by weight of salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine were weighed and added thereto. The mixture was stirred at room temperature for 4 hours, and then the mixture was made into a film material using an adjustable film applicator. After the solvent evaporated, laser irradiation was performed under the same laser irradiation conditions as in Example 30.

[0283] The laser irradiated area was visually inspected for fading of the black background and generation of colored marks. The results are shown in Table 1.

[0284] Embodiment 32

[0285] Organic materials: salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine;

[0286] Polymer: polymethyl methacrylate (PMMA);

[0287] Color-reducing microcapsules: EC-1;

[0288] 96.5 parts by weight of polymethyl methacrylate was dissolved in 700 parts by weight of dichloromethane solution. After the solution was completely dissolved, 3.0 parts by weight of EC-1 and 0.5 parts by weight of salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine were weighed and added thereto. The mixture was stirred at room temperature for 4 hours, and then the mixture was made into a film material using an adjustable film applicator. After the solvent evaporated, laser irradiation was performed under the same laser irradiation conditions as in Example 30.

[0289] The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of colored marks. The results are shown in Table 1.

[0290] Embodiment 33

[0291] Organic materials: (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione;

[0292] Polymer: polyvinyl chloride (PVC);

[0293] Color-reducing microcapsules: EC-1;

[0294] 99.79 parts by weight of polyvinyl chloride was dissolved in 700 parts by weight of tetrahydrofuran solution. After all the polyvinyl chloride was dissolved, 0.2 parts by weight of EC-1 and 0.01 parts by weight of salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine were added thereto. The mixture was stirred at room temperature for 3-5 hours. Then, the mixture was made into a film material using an adjustable film applicator.

[0295] After the solvent evaporates, the composite plate is irradiated with laser under the following conditions: the wavelength of the green laser is 532 nm, the scanning speed is 1000 mm / s, the laser power is 8.0 W, and the laser frequency is 50 kHz.

[0296] The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of colored marks. The results are shown in Table 1.

[0297] Embodiment 34

[0298] Organic materials: (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione;

[0299] Polymer: polyvinyl chloride (PVC);

[0300] Color-reducing microcapsules: EC-1;

[0301] 99.3 parts by weight of polyvinyl chloride was dissolved in 700 parts by weight of tetrahydrofuran solution. After the solution was completely dissolved, 0.5 parts by weight of EC-1 and 0.2 parts by weight of salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine were added thereto, stirred at room temperature for 3-5 hours, and then the mixture was made into a film material using an adjustable film applicator. After the solvent evaporated, laser irradiation was performed under the same laser irradiation conditions as in Example 33.

[0302] The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of colored marks. The results are shown in Table 1.

[0303] Embodiment 35

[0304] Organic materials: (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione;

[0305] Polymer: polyvinyl chloride (PVC);

[0306] Color-reducing microcapsules: EC-1;

[0307] 83.5 parts by weight of polyvinyl chloride was dissolved in 700 parts by weight of tetrahydrofuran solution. After the solution was completely dissolved, 9.5 parts by weight of EC-1 and 7.0 parts by weight of salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine were weighed and added thereto. The mixture was stirred at room temperature for 3-5 hours, and then the mixture was made into a film material using an adjustable film applicator. After the solvent evaporated, laser irradiation was performed under the same laser irradiation conditions as in Example 33.

[0308] The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of colored marks. The results are shown in Table 1.

[0309] Comparative Example 1

[0310] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0311] Color-reducing microcapsules: EC-1;

[0312] Polymer: polycarbonate (PC);

[0313] 86.98 parts by weight of polycarbonate, 0.02 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 13 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for co-mixing and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the co-mixing and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0314] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0315] Comparative Example 2

[0316] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0317] Color-reducing microcapsules: EC-1;

[0318] Polymer: polycarbonate (PC);

[0319] 88.98 parts by weight of polycarbonate, 0.02 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 11 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0320] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0321] Comparative Example 3

[0322] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0323] Color-reducing microcapsules: EC-1;

[0324] Polymer: polycarbonate (PC);

[0325] 99.93 parts by weight of polycarbonate, 0.02 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 0.05 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0326] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0327] Comparative Example 4

[0328] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0329] Color-reducing microcapsules: EC-1;

[0330] Polymer: polycarbonate (PC);

[0331] 86.5 parts by weight of polycarbonate, 13 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0332] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0333] Comparative Example 5

[0334] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0335] Color-reducing microcapsules: EC-1;

[0336] Polymer: polycarbonate (PC);

[0337] 88.5 parts by weight of polycarbonate, 11 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0338] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0339] Comparative Example 6

[0340] Organic materials: 2-(2-thiophenecarboxamido)benzopyran;

[0341] Color-reducing microcapsules: EC-1;

[0342] Polymer: polycarbonate (PC);

[0343] 99.495 parts by weight of polycarbonate, 0.005 parts by weight of 2-(2-thiophenecarboxamido)benzopyran, and 0.5 parts by weight of EC-1 are placed in a high-speed mixer and mixed evenly; the mixed materials are then added to a twin-screw extruder for blending and extrusion, the extruded materials are granulated and then injection molded into plates, and then the plates are placed in a refrigerator for freezing. The temperature during the blending and extrusion process is controlled at 250°C to 270°C; the injection molding temperature is controlled at 250°C to 270°C; and the temperature of the freezer is controlled at -20°C to 10°C.

[0344] The laser irradiation conditions were the same as those in Example 1. The laser irradiated area was visually inspected to see if there was any fading of the black background and generation of color marks. The results are shown in Table 1.

[0345] Comparative Example 7

[0346] A black laser color-changeable polymer composition was prepared by referring to the method of Example 2, except that the achromatic microcapsules were not added. Other conditions were the same as those of Example 2. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0347] Comparative Example 8

[0348] A black laser color-changeable polymer composition was prepared by referring to the method of Example 2, except that no organic material was added. Other conditions were the same as in Example 2. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0349] Comparative Example 9

[0350] A black laser color-changeable polymer composition was prepared by referring to the method of Example 2, except that no organic material and achromatic microcapsules were added. Other conditions were the same as in Example 2. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0351] Comparative Example 10

[0352] A black laser color-changeable polymer composition was prepared by referring to the method of Example 7, except that the achromatic microcapsules were not added. Other conditions were the same as those of Example 7. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0353] Comparative Example 11

[0354] A black laser color-changeable polymer composition was prepared by referring to the method of Example 7, except that no organic material was added. Other conditions were the same as those of Example 7. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0355] Comparative Example 12

[0356] A black laser color-changeable polymer composition was prepared by referring to the method of Example 7, except that no organic material and achromatic microcapsules were added. Other conditions were the same as in Example 7. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0357] Comparative Example 13

[0358] A black laser color-changeable polymer composition was prepared by referring to the method of Example 10, except that the achromatic microcapsules were not added. Other conditions were the same as those of Example 10. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0359] Comparative Example 14

[0360] A black laser color-changeable polymer composition was prepared by referring to the method of Example 10, except that no organic material was added. Other conditions were the same as those of Example 10. The laser irradiated area was visually inspected to see whether color marks were produced. The results are shown in Table 1.

[0361] Comparative Example 15

[0362] A black laser color-changeable polymer composition was prepared by referring to the method of Example 10, except that no organic material and achromatic microcapsules were added. Other conditions were the same as in Example 10. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0363] Comparative Example 16

[0364] A black laser color-changeable polymer composition was prepared by referring to the method of Example 23, except that the laser wavelength used was 1064 nm. Other conditions were the same as those of Example 23. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0365] Comparative Example 17

[0366] A black laser color-changeable polymer composition was prepared by referring to the method of Example 24, except that the laser wavelength used was 10.6 μm. Other conditions were the same as those of Example 24. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0367] Comparative Example 18

[0368] A black laser color-changeable polymer composition was prepared by referring to the method of Example 25, except that the laser wavelength used was 9.3 μm. Other conditions were the same as those of Example 25. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0369] Comparative Example 19

[0370] A black laser color-changeable polymer composition was prepared by referring to the method of Example 13, except that the achromatic microcapsules were not added. Other conditions were the same as those of Example 13. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0371] Comparative Example 20

[0372] A black laser color-changeable polymer composition was prepared by referring to the method of Example 13, except that no organic material was added. Other conditions were the same as those of Example 13. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0373] Comparative Example 21

[0374] A black laser color-changeable polymer composition was prepared by referring to the method of Example 13, except that no organic material and decolorizing microcapsules were added. Other conditions were the same as in Example 13. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0375] Comparative Example 22

[0376] A black laser color-changeable polymer composition was prepared by referring to the method of Example 16, except that the achromatic microcapsules were not added. Other conditions were the same as those of Example 16. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0377] Comparative Example 23

[0378] A black laser color-changeable polymer composition was prepared by referring to the method of Example 16, except that no organic material was added. Other conditions were the same as in Example 16. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0379] Comparative Example 24

[0380] A black laser color-changeable polymer composition was prepared by referring to the method of Example 16, except that no organic material and achromatic microcapsules were added. Other conditions were the same as in Example 16. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0381] Comparative Example 25

[0382] A black laser color-changeable polymer composition was prepared by referring to the method of Example 19, except that the achromatic microcapsules were not added. Other conditions were the same as in Example 19. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0383] Comparative Example 26

[0384] A black laser color-changeable polymer composition was prepared by referring to the method of Example 19, except that no organic material was added. Other conditions were the same as in Example 19. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0385] Comparative Example 27

[0386] A black laser color-changeable polymer composition was prepared by referring to the method of Example 19, except that no organic material and achromatic microcapsules were added. Other conditions were the same as in Example 19. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0387] Comparative Example 28

[0388] A black laser color-changeable polymer composition was prepared by referring to the method of Example 31, except that no achromatic microcapsules were added. Other conditions were the same as in Example 31. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0389] Comparative Example 29

[0390] A black laser color-changeable polymer composition was prepared by referring to the method of Example 31, except that no organic material was added. Other conditions were the same as in Example 31. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0391] Comparative Example 30

[0392] A black laser color-changeable polymer composition was prepared by referring to the method of Example 31, except that no organic material and achromatic microcapsules were added. Other conditions were the same as in Example 31. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0393] Comparative Example 31

[0394] A black laser color-changeable polymer composition was prepared by referring to the method of Example 34, except that no achromatic microcapsules were added. Other conditions were the same as in Example 34. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0395] Comparative Example 32

[0396] A black laser color-changeable polymer composition was prepared by referring to the method of Example 34, except that no organic material was added. Other conditions were the same as in Example 34. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0397] Comparative Example 33

[0398] A black laser color-changeable polymer composition was prepared by referring to the method of Example 34, except that no organic material and achromatic microcapsules were added. Other conditions were the same as in Example 34. The laser irradiated area was visually inspected to see whether there was fading of the black background and generation of color marks. The results are shown in Table 1.

[0399] Table 1. Laser color change effect

[0400]

[0401]

[0402]

[0403]

[0404]

[0405] The above results show that the polymer without adding the specific composite organic additive of the present invention or only adding a single additive cannot achieve the black background fading and color change effects. After adding the specific composite organic additive of the present invention to the polymer, a very excellent color marking can be achieved on the black polymer. At the same time, it can be seen from Examples 1-5 and Comparative Examples 1-6 that compared with the use of the color-eliminating microcapsules less than 0.1wt% and greater than 10wt%, the use of the color-eliminating microcapsules is between 0.1wt% and 10wt%, and the base color of the polymer can be well maintained in black; compared with the use of organic materials less than 0.01wt% and greater than 10wt%, the use of organic materials is between 0.01wt% and 10wt%, and the polymer has a better color marking effect. It can be seen from Examples 1-11 and Comparative Examples 16-18 that compared with lasers with wavelengths of 1064nm, 9.3μm and 10.6μm, the color marking effect of lasers with wavelengths of 192nm to 600nm is good. In addition, when the organic material provided by the present invention is used in an amount as low as 0.02 wt %, the laser color change effect of the obtained polymer is very good, and it is very suitable for industrial production and application.

[0406] The polymer prepared based on the organic material provided by the present invention can be marked with various colors and has a very wide range of applications.

[0407] In summary, the present invention provides a black laser color-changeable polymer composition. The present invention adds a specific composite organic additive as an additive to the polymer to obtain a color-changeable black polymer material. The polymer material has an excellent color-change effect. Under the action of a laser, various color marks can be formed on the black polymer material. The obtained color marks are clear, flat, and have a high contrast. At the same time, the polymer material has a black base color, which can realize color marking on a black polymer substrate, expanding the application scope of laser color marking. In addition, the amount of organic material used in the laser color-changeable polymer material of the present invention is small, and the preparation method is simple, easy to operate, safe, and low in energy consumption, which is very suitable for large-scale industrial production. The present invention broadens the application field of polymer laser color change and has good application prospects.

Claims

1. A polymer composition for laser color marking with a black background, characterized in that: It is composed of polymer, decolorizing microcapsule and organic material, wherein the weight percentage of decolorizing microcapsule and organic material is: 0.1-10% of decolorizing microcapsules, 0.01-10% of organic materials, and the balance is polymer; Wherein, the polymer is selected from polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyurethane, polyester elastomer, polystyrene, styrene-acrylonitrile copolymer, polyethylene naphthalate, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyurethane elastomer, nylon elastomer, styrene-ethylene-butylene-styrene copolymer, styrene-ethylene-isoprene-styrene copolymer, styrene-[ethylene-(ethylene-propylene)]-styrene copolymer, polyester elastomer, chlorinated polyethylene elastomer, polyisobutylene, ethylene-vinyl acetate copolymer, polysulfone, polyimide, cellulose acetate, unsaturated polyester, silicone resin, epoxy resin, phenolic resin, melamine resin, natural rubber, butadiene rubber, styrene-butadiene rubber, silicone rubber, fluororubber, nitrile rubber, butyl rubber, EPDM rubber, any one or a mixture of two or more thereof; The organic material is at least one of benzopyran compounds, aniline derivatives, polycyclic quinone compounds, viologen compounds, spiropyran compounds, spirooxazine compounds, fulgide compounds, diarylethene compounds, azobenzene compounds, and Schiff base compounds; The laser wavelength used in the laser marking is 192nm-600nm.

2. The polymer composition for laser color marking with a black background according to claim 1, characterized in that: The weight percentage of the decolorizing microcapsules and organic materials is: Organic material 0.01-2%, decolorizing microcapsule 0.1-3%; Wherein, the polymer is any one or more of polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET), polyester elastomer (TPEE), styrene-ethylene / propylene copolymer-styrene triblock copolymer (SEPS), styrene-hydrogenated butadiene block copolymer (SEBS), polymethyl methacrylate (PMMA), and polyvinyl chloride (PVC); The organic materials are 2-(2-thiophenecarboxamido)benzopyran, 4,4'-bis(hexyloxy)-3-methylazobenzene, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, 4-( At least one of dibenzophenazine)-N,N-diphenylaniline, 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine], 1-hydroxy-2-methylanthraquinone, benzyl viologen, spiro[1,3,3-trimethylindole-chroman], salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzalimidate or 1,9-pyrazoloanthrone.

3. The polymer composition for laser color marking with a black background according to claim 1 or 2, characterized in that: The weight percentage of the decolorizing microcapsules and organic materials is: The polymer is PC, the organic material is at least one of 2-(2-thiophenecarboxamido)benzopyran, 4,4'-bis(hexyloxy)-3-methylazobenzene, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, 4-(dibenzophenazine)-N,N-diphenylaniline, benzyl viologen, spiro[1,3,3-trimethylindole-benzodihydropyran] or 1,9-pyrazoloanthrone, the content of which is 0.02%, and the content of the decolorizing microcapsule is 0.5%; The polymer is PC, the organic material is one of 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine] or 1-hydroxy-2-methylanthraquinone, the content is 0.2%, and the content of the decolorizing microcapsule is 0.5%; The polymer is PC, the organic material is salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine, the content is 0.2%, and the content of the decolorizing microcapsule is 1%; The polymer is PP, the organic material is 4,4'-bis(hexyloxy)-3-methylazobenzene, the content is 0.02%, and the content of the color-reducing microcapsule is 0.5%; The polymer is PET, the organic material is 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, the content is 0.02%, and the content of the decolorizing microcapsule is 0.5%; The polymer is TPEE, the organic material is 1-hydroxy-2-methylanthraquinone, the content is 0.02%, and the content of the decolorizing microcapsule is 0.5%; The polymer is SEPS, the organic material is benzyl viologen, the content is 0.02%, and the content of the color-reducing microcapsules is 0.5%; The polymer is SEBS, the organic material is spiro[1,3,3-trimethylindole-chroman], the content is 0.02%, and the content of the color-reducing microcapsule is 0.5%; The polymer is PMMA, the organic material is salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine, the content of which is 0.02%, and the content of the decolorizing microcapsule is 0.5%. The polymer is PVC, the organic material is (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, the content is 0.02%, and the content of the decolorizing microcapsule is 0.5%.

4. The polymer composition for laser color marking with a black background according to any one of claims 1 to 3, characterized in that: The composition is prepared by directly mixing polymer, decolorizing microcapsule and organic material or adding organic solvent to form coating, sheet, plate, rod or film material.

5. A method for preparing a polymer composition for laser color marking with a black background as claimed in any one of claims 1 to 4, characterized in that: It includes the following steps: The organic material, the decolorizing microcapsule and the polymer are mixed, co-extruded, granulated, injection-molded and frozen to obtain the product; wherein the temperature during the co-extrusion process is 180°C to 270°C; the injection molding temperature is 180°C to 270°C; and the freezing temperature is -20°C to -10°C.

6. A method for preparing a polymer composition for laser color marking with a black background according to any one of claims 1 to 4, characterized in that: It includes the following steps: The polymer, the decolorizing microcapsule and the organic material are dissolved in a solvent in sequence to form a membrane material, and the solvent is evaporated to obtain the membrane material; The solvent is one or a mixture of two or more of liquid paraffin, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl palmitate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl palmitate, heptane, hexane, cyclohexane, carbon disulfide, dichloromethane, chloroform, xylene, toluene, benzene, chloropropane, ethyl bromide, benzene bromide, dichloroethane, isopropyl ether, nitromethane, methyl acetate, ethyl acetate, butyl acetate, ether, phenol, m-cresol, tert-butanol, ethanol, water, tetrahydrofuran, dioxane, acetone, cyclohexanone, nitrogen-nitrogen dimethylformamide, nitrogen-nitrogen dimethylacetamide or decahydronaphthalene.

7. Use of the composition according to any one of claims 1 to 4 in preparing laser color marking with a black base color.

8. A laser-induced patterned marking method, characterized in that: The steps include: Take the composition according to any one of claims 1 to 4, and irradiate the surface of the composition with laser to form an irradiated area, so that the black color of the laser irradiated area can be faded and a color mark can be produced.

9. The patterned marking method according to claim 8, characterized in that: The laser is selected from one or a combination of two or more of green laser, ultraviolet laser and excimer laser; And / or, the laser is a continuous laser or a pulsed laser; And / or, the laser power is 1.0-100W, and the scanning speed of the laser is 1-10000mm / s.

10. The patterned marking method according to claim 9, characterized in that: The laser has a wavelength of 192nm to 600nm; preferably, the wavelength of the laser is 355nm; The laser power is 2.0-5.0W, and the scanning speed of the laser is 1000mm / s; preferably, the laser power is 3.5-4.5W, the scanning speed of the laser is 1000mm / s, and the frequency of the laser is 20-100kHz.

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