Inorganic-organic composite polymer material capable of realizing laser color change as well as preparation method and application of inorganic-organic composite polymer material

Abstract

The invention belongs to the technical field of polymer laser secondary processing, and particularly relates to an inorganic-organic composite polymer material capable of realizing laser color change as well as a preparation method and application of the inorganic-organic composite polymer material. Specific inorganic materials and organic materials are used as additives to be added into a polymer to obtain the polymer material capable of realizing laser color change. Experiments prove that the polymer material has an excellent color change effect under the action of laser, and can form a color mark with bright color, clear outline, high contrast ratio and flat surface. In addition, the base color of the polymer material is light, and laser color change can be carried out on a white or light-color polymer substrate. The preparation method of the inorganic-organic composite polymer material capable of realizing laser color change is simple and convenient, the operation is easy to control, and the inorganic-organic composite polymer material has the characteristics of safety, environmental protection and low energy consumption, is very suitable for industrial large-scale production, and has remarkable economic benefits.

Description

Technical Field

[0001] This invention belongs to the field of polymer laser secondary processing technology, specifically relating to an inorganic-organic composite polymer material that can change color with laser, its preparation method and application. Background Technology

[0002] Laser marking is a technology that uses high-energy lasers to irradiate the surface of materials, causing changes such as carbonization, discoloration, vaporization, or foaming through photochemical or photothermal reactions, thereby forming permanent marks. Compared with traditional methods such as ink printing, screen printing, gravure printing, and offset printing, laser marking has advantages such as high precision, non-contact operation, ease of operation, and cleanliness, and has broad application prospects.

[0003] However, most current laser color marking technologies are still limited to dark-colored (such as black or dark gray) polymer surfaces. For example, Chinese patent application CN106566068A discloses a polymer composition that achieves color marking by adding laser marking powder and a temperature-sensitive substance, but this composition causes the overall color of the polymer substrate to darken to black or gray; CN109486128A proposes adding black or colored pigments to plastic paper to achieve laser color marking, but the substrate also appears black as a result. Therefore, achieving high-quality color laser marking on white, light-colored, or transparent polymer materials remains a pressing technical challenge that needs to be addressed.

[0004] Chinese patent application CN115895091B discloses a class of inorganic compounds containing tungsten or molybdenum for preparing laser-sensitive color-changing polymer materials. These compounds can generate new colors under laser irradiation, but the colors are very monotonous and far from vibrant, resulting in low practical value. Furthermore, they cannot produce a white polymer substrate, making them unsuitable for white or transparent substrates. Another patent application, CN116218033B, introduces a series of organic photochromic materials (such as azobenzenes, spiroxazines, and polycyclic quinones), which utilize laser-induced photochemical and photothermal effects to produce color changes. However, this technology employs a solution casting process, requiring the solvent to evaporate, resulting in a long production cycle and making it difficult to meet the needs of large-scale industrial production.

[0005] Therefore, there is an urgent need in this field for a novel laser-sensitive color-changing polymer material that is simple to prepare, safe and efficient, and does not introduce obvious background color during the preparation process, so as to realize convenient and efficient laser color marking on white, light-colored or transparent polymer substrates. Summary of the Invention

[0006] The purpose of this invention is to provide an inorganic-organic composite polymer material that can change color via laser, its preparation method, and its application.

[0007] This invention provides an inorganic-organic composite polymer material capable of laser-induced color change, wherein the inorganic-organic composite polymer material is composed of the following components in weight percentage: 0.05wt% to 10.00wt% metal oxide, 0.05wt% to 10.00wt% organic material, and the remainder being polymer;

[0008] The metal oxide is selected from any one or more of the following: aluminum oxide, cerium oxide, barium oxide, magnesium oxide, titanium dioxide, zinc oxide, antimony trioxide, tin oxide, molybdenum trioxide, tungsten trioxide, calcium oxide, zirconium oxide, bismuth trioxide, samarium oxide, yttrium oxide, europium oxide, indium trioxide, antimony tin oxide, zinc aluminum oxide, dysprosium oxide, niobium oxide, lanthanum oxide, and erbium oxide.

[0009] The organic material is selected from at least one of benzopyran compounds, aniline derivatives, polycyclic quinone compounds, spiropyran compounds, spiroxazine compounds, azobenzene compounds, fluorane compounds, and phthalide compounds.

[0010] The polymer has a weight percentage of 80.00 wt% to 99.90 wt%.

[0011] The polymer is selected from any one or more of the following: polyethylene, polypropylene, nylon, polycarbonate, polymethyl methacrylate, polyvinyl alcohol, polyethyl methacrylate, polybutyl methacrylate, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, ethylene-octene copolymer, ethylene-butene copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polystyrene, polyvinyl chloride, polyvinylidene fluoride, polyurethane elastomer, polyester elastomer, styrene-based thermoplastic elastomer, styrene-butadiene copolymer, styrene-methyl methacrylate copolymer, polyisobutylene, ethylene-vinyl acetate copolymer, polysulfone, polyimide, cellulose acetate, unsaturated polyester, silicone resin, epoxy resin, phenolic resin, melamine resin, natural rubber, cis-butadiene rubber, styrene-butadiene rubber, silicone rubber, fluororubber, nitrile rubber, butyl rubber, and ethylene propylene diene monomer (EPDM) rubber.

[0012] Preferably, it is composed of the following components in weight percentage: 0.05 wt% to 5.00 wt% metal oxide, 0.05 wt% to 5.00 wt% organic material, and 90.00 wt% to 99.90 wt% polymer;

[0013] The metal oxide is selected from any one or more of the following: aluminum oxide, cerium oxide, barium oxide, magnesium oxide, titanium dioxide, zinc oxide, antimony trioxide, tin oxide, molybdenum trioxide, tungsten trioxide, calcium oxide, zirconium oxide, bismuth trioxide, samarium oxide, yttrium oxide, europium oxide, indium trioxide, antimony tin oxide, zinc aluminum oxide, dysprosium oxide, niobium oxide, lanthanum oxide, and erbium oxide.

[0014] The organic material is selected from 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane, 2'-chloro-6'-(diethylamino)spiro[isobenzofuran-1(3H),9'-(9H)oxanthracene]-3-one, 3,3-bis(N-octyl-2-methylindole)phthalic acid lactone, 3-(4-dimethylaminophenyl)-3-(1-butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide, 9(9H)oxanthracene-2-carboxylic acid-6-(di- 3-(1,2-dimethyl-3-indolyl)-3-[4-diethylamino-2-methylphenyl]phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-aza-2-benzo[C]furanone, 9-[ethyl(3-methylbutyl)amino]-spiro[12H-benzo[a]oxanthracene-12,1'(3'H)-isobenzofuran]-3'-one, 6'-( Dihydroindol-1-yl)-1,3,3-trimethylspiro[dihydroindol-2,3'-naphtho[2,1-B][1,4]oxazine], 1,3-dimethyl-6-diethylaminofluorane, 3',6'-dimethoxyfluorane, 4-methoxy-2-methyl-diphenylamine, 1,3,3-trimethylindololin-6'-(1-piperidinyl)spirophenoxazine, 3-(N-ethyl-4-toluidine)-6-methyl-7-anilinefluorane, 3,3-bis(4-dimethylaminophenyl) 6-Dimethylaminophthalide, 2-(2',4'-dimethylphenylamino-3-methyl-6-diethylaminofluorane, 6'-(diethylamino)-1',2'-benzofluorane, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-b]pyridin-5(7H)-one, 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H), 9'-[9H] x[Ton]-2'-carboxylic acid ethyl ester, N,N-dimethyl-4-[2-[2-(octoxy)phenyl]-6-phenyl-4-pyridyl]-aniline, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 2-(2-thiophenecarboxylamino)benzopyran, 2-phenyl-3-nitro-2H-1-benzopyran, 2'-(dibenzylamino)-6'-(diethylamino)fluorane, 7-hydroxy-2-oxo-2H-benzopyran-3-carboxylic acid, 2H-1-benzopyran-5-ol, 5-nitrobenzodihydropyran-4-one, 1,3,3-trimethylindolenaphthospirazine, 1,3,3-trimethylspirocyclic [indole-2,3'-naphtho[2,1-b][1,4]oxazine]-9'-methacrylate, 1,3,8-trihydroxy The following are any one or more of the following: 6-methyl-10H-anthrafen-9-one, 3-diethylamino-6-methyl-7-phenylaminofluorane, 2-(2-4-dimethylamino)-3-methyl-6-diethylaminofluorane, 3-dibutylamino-6-methyl-7-bromofluorane, tris(p-dimethylaminophenyl)methane, 6-(N-ethyl-4-toluidine)-2-methylfluorane, 4,4',4”-triaminotriphenylmethane, 4-hydroxy-4-isopropoxydiphenyl sulfone, 3-(3-methylureo)phenyl-4-methylbenzenesulfonate, (1-p-methoxyphenyl-2-methyl-5-phenyl)-3-pyrrole-ethide (isopropylidene)-succinic anhydride, and 3,4-di[1-(2,5-dimethyl-3-furanyl)ethide]-3,4-dihydrofuran-2,5-dione;

[0015] Preferably, the organic material is selected from 3-(N-ethyl-4-toluidine)-6-methyl-7-anilinofluorane, 3,3-bis(N-octyl-2-methylindole)phthalic acid lactone, 3-(4-dimethylaminophenyl)-3-(1-butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide, 3-(1,2-dimethyl-3-indole)-3-[4-diethylamino-2-methylphenyl]phthalide, 9-[ethyl(3-methylbutyl)amino]-spiro[12H-benzo[a]oxanthracene-12,1'(3'H)-isobenzofuran]-3'-one, 3',6'-dimethoxyfluorane, 2-(2',4'-dimethylphenylamino) 3-Methyl-6-diethylaminofluorane, 6'-(diethylamino)-1',2'-benzofluorane, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-b]pyridin-5(7H)-one, N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridyl]-aniline, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 2'-(dibenzylamino)-6'-(diethylamino)fluorane, 6-(N-ethyl-4-toluidine)-2-methylfluorane, or any two or more thereof;

[0016] The polymer is selected from any one or more of polyethylene, polypropylene, nylon, polycarbonate, polymethyl methacrylate, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polystyrene, polyurethane elastomer, and polyester elastomer.

[0017] It is composed of the following components by weight percentage: 0.4% 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane, 0.5% cerium dioxide, and 99.1% polyethylene; or, 2% 6'-(diethylamino)-1',2'-benzofluorane, 0.2%-0.4% barium oxide, and 97.6%-97.8% polycarbonate; or, 0.4% 3-(4-dimethylaminophenyl)-3-(1-butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide, 0.4% titanium dioxide, and 99.8% polyurethane; or,

[0018] 3,3-Bis(N-octyl-2-methylindole)phthalic acid lactone 0.4%, tin dioxide 0.2%, polypropylene 99.4%; or 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indole-3-yl)furano[3,4-B]pyridine-5(7H)-one 0.3%, cerium dioxide 0.5%, polyethylene terephthalate 99.2%; or,

[0019] 3% 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-B]pyridin-5(7H)-one, 2% molybdenum trioxide, 95% polyethylene terephthalate; or,

[0020] 3',6'-Dimethoxyfluorane 0.2%, tungsten trioxide 0.2%-1%, polybutylene terephthalate 98.8%-99.6%; or

[0021] 3,3-Di(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide 1%, calcium oxide 0.5%, ABS 98.5%; or, 9-[ethyl(3-methylbutyl)amino]-spiro[12H-benzo[a]oxanthracene-12,1'(3'H)-isobenzofuran]-3'-one 0.3%, zirconium oxide 0.3%, polymethyl methacrylate 99.4%; or,

[0022] 2-(2',4'-dimethylphenylamino-3-methyl-6-diethylaminofluorane 0.3%, bismuth trioxide 0.5%, nylon 66 99.2%; or,

[0023] 2'-(dibenzylamino)-6'-(diethylamino)fluorane 2%, samarium oxide 0.4%, polystyrene 97.6%;

[0024] 0.4% 3-(1,2-dimethyl-3-indolyl)-3-[4-diethylamino-2-methylphenyl]phthalide, 0.2% or 2% yttrium oxide, and 97.6% or 99.4% polyester elastomer;

[0025] 1% 6-(N-ethyl-4-toluidine)-2-methylfluorane, 0.5% europium oxide, 98.5% polyoxymethylene; or

[0026] N,N-Dimethyl-4-[2-[2-(octoxy)phenyl]-6-phenyl-4-pyridyl]-aniline 0.05%, indium trioxide 1%, polyurethane 98.95%; or

[0027] 0.2% 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane, 0.05% antimony tin oxide, 99.75% polyethylene; or

[0028] 6'-(diethylamino)-1',2'-benzofluorane 0.1%, zinc alumina 0.08%, polycarbonate 99.82%; or

[0029] 3-(4-Dimethylaminophenyl)-3-(1-Butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide 0.4%, dysprosium oxide 0.2%, polyurethane 99.4%; or

[0030] 3,3-bis(N-octyl-2-methylindole)phthalic acid lactone 0.1%, niobium oxide 1%, polypropylene 98.90%; or 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indole-3-yl)furano[3,4-B]pyridin-5(7H)-one 0.3%, lanthanum oxide 2.5%, polyethylene terephthalate 97.2%; or 3',6'-dimethoxyfluorane 0.2%, erbium oxide 3%, polybutylene terephthalate 96.8%.

[0031] The average particle size of the metal oxide is 0.01 μm to 10.00 μm.

[0032] This invention also provides a method for preparing a laser-sensitive color-changing inorganic-organic composite polymer material, which includes the following steps:

[0033] a. Take metal oxides, organic materials and polymers, mix them evenly to obtain a mixture;

[0034] b. Take the mixture obtained in step a, melt-blend it, and granulate it to obtain the final product.

[0035] This invention also provides the use of a laser-sensitive inorganic-organic composite polymer material in the preparation of laser color markings.

[0036] The inorganic-organic composite polymer material provided by this invention is suitable for laser color marking with wavelengths between 157 nm and 10.6 μm. Lasers emitting these wavelengths include CO2 lasers (10.6 μm), Nd:YAG lasers (1064, 532, 355, and 266 nm), Nd:YVO4 lasers (1064, 532, 355, and 266 nm), excimer lasers (F2 (157 nm), ArF (193 nm), KrCl (222 nm), KrF (248 nm), XeCl (308 nm), and XeF (351 nm)), fiber lasers, diode array lasers, and diode lasers, etc.

[0037] Preferably, pulsed Nd:YAG lasers and pulsed fiber lasers are used, with pulsed lasers of 1064 nm, 532 nm and 355 nm being particularly suitable.

[0038] More preferably, the laser energy is 0.5 to 8 W; and / or, the laser frequency is 10 to 100 kHz; and / or, the laser marking speed is 400 to 4000 mm / s.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] This invention provides a color-changing polymer material based on a composition of metal oxides and organic materials. The invention uses specific metal oxides and organic materials as additives in a polymer to obtain a polymer material suitable for color marking. Under laser irradiation, color marks with clear outlines, smooth surfaces, and high contrast can be formed on the surface of this material. Simultaneously, the polymer has a light color, making it suitable for color marking on white, light-colored, or transparent polymer substrates, thus expanding its application range. Furthermore, the metal oxides and organic materials in this polymer material are commercially available, and the material preparation is simple, safe, and easy to operate, facilitating large-scale production and application, and demonstrating promising application prospects.

[0041] Obviously, based on the above description of the present invention, and according to ordinary technical knowledge and common practice in the art, various other modifications, substitutions, or alterations can be made without departing from the basic technical concept of the present invention. For terms not specifically defined herein, their meanings should be given according to the disclosed content and context, as would be possible for those skilled in the art.

[0042] The following detailed embodiments further illustrate the above-described content of the present invention. However, this should not be construed as limiting the scope of the present invention to the following examples. All technologies implemented based on the above-described content of the present invention fall within the scope of the present invention. Attached Figure Description

[0043] Figure 1 This is a photograph of the polymer laser marking effect in Example 14. Detailed Implementation

[0044] In the specific embodiments of the present invention, the raw materials and equipment used are all known products, obtained by purchasing commercially available products.

[0045] (1) The equipment information used in this invention is as follows:

[0046] (2) Twin-screw extruder, model SHJ 25, screw diameter 50mm, screw length-to-diameter ratio 40:1, manufactured by Nanjing J&T Electromechanical Co., Ltd.

[0047] Injection molding machine, model MA600, manufactured by Haitian Machinery Co., Ltd.

[0048] Laser marking machine, model MUV-ER, pulsed fiber laser marking machine, maximum laser power 10W, laser wavelength 355nm.

[0049] Laser marking machine, model MF-EA, pulsed fiber laser marking machine, with a maximum laser power of 20W, a laser wavelength of 1064nm, and equipped with a high-speed digital galvanometer;

[0050] The laser marking machine, model YK-F20G, is a pulsed fiber laser marking machine with a maximum laser power of 10W and a laser wavelength of 532nm. It is equipped with a high-speed digital galvanometer.

[0051] The laser marking machine, model AUT-FQCW-266, is a single-mode continuous laser marking machine with a maximum laser power of 3W and a laser wavelength of 266nm. It is equipped with a high-speed digital galvanometer.

[0052] (2) The specific information of the polymer used in this invention to prepare the standard sample is as follows:

[0053] Metal oxides: Aluminum oxide: Particle size (D) 50 The particle size is 0.03-0.70 μm; Cerium dioxide: particle size (D 50 The particle size is 3 μm; Barium oxide: particle size (D 50 The particle size is 0.2 μm; magnesium oxide: particle size (D 50 The particle size is 5.0 μm; titanium dioxide: particle size (D 50 The particle size is 0.02-0.10 μm; Zinc oxide: particle size (D) 50 The particle size is 4 μm; Antimony trioxide: particle size (D 50 The particle size is 1 μm; Tin dioxide: particle size (D 50 The particle size is 10 μm; molybdenum trioxide: particle size (D 50 The particle size is 4 μm; Tungsten trioxide: particle size (D 50 The particle size is 0.02 μm; calcium oxide: particle size (D 50 The particle size is 0.5 μm; Zirconia: particle size (D 50 The particle size is 0.03 μm; Bismuth trioxide: particle size (D 50 The particle size is 6 μm; samarium oxide: particle size (D 50 The particle size is 0.06 μm; Yttrium oxide: particle size (D 50 The particle size is 10 μm; europium oxide: particle size (D 50 The particle size is 0.8 μm; Indium trioxide: particle size (D 50 The particle size is 5 μm; antimony tin oxide: particle size (D 50 The particle size is 0.06 μm; Zinc alumina: particle size (D 50 The particle size is 4 μm; dysprosium oxide: particle size (D 50 The particle size is 0.2 μm; niobium oxide: particle size (D 50 The particle size is 0.5 μm; Lanthanum oxide: particle size (D 50 The particle size is 0.02 μm; Erbium oxide: particle size (D 50 The value is 0.6 μm;

[0054] Organic materials: Maclean's reagent platform, analytical grade;

[0055] Polyethylene (PE): Maoming Petrochemical, TR144;

[0056] Polypropylene (PP): Sinopec Lanzhou Branch, T30S;

[0057] Polycarbonate: General Electric Company, PC121R;

[0058] Polystyrene: Dushan Petrochemical, GPPS-500;

[0059] Polyurethane: Bayer, Germany, 9385;

[0060] Acrylonitrile-butadiene-styrene (ABS): Chi Mei Corporation (Taiwan), PA757;

[0061] Polymethyl methacrylate (PMMA): Evonik Degussa, 8803;

[0062] Polyethylene terephthalate: Far Eastern Textile Industry, CB-602;

[0063] Polybutylene terephthalate: BASF, Germany, PBTB4500;

[0064] Nylon 66: Lanxess, Germany, A30S;

[0065] Polyester elastomer: KP3355, from Kolon, South Korea.

[0066] Example 1

[0067] First, 99.75g of polyethylene resin, 0.05g of inorganic material additive aluminum oxide powder (average particle size 0.03μm), and 0.2g of organic material additive 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature is 160℃ to obtain a polymer material that can change color with laser.

[0068] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 160℃.

[0069] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 50kHz. The color change effect is shown in Table 1.

[0070] Example 2

[0071] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the amount of aluminum powder added to the polyethylene resin was 0.2 wt%. Other conditions were the same as in Example 1. The color-changing effect is shown in Table 1.

[0072] Example 3

[0073] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the amount of aluminum oxide powder added to the polyethylene resin was 1 wt%, and the other conditions were the same as in Example 1. The color-changing effect is shown in Table 1.

[0074] Example 4

[0075] First, 99.50g of polyethylene resin, 0.10g of inorganic material additive cerium dioxide powder (average particle size of 3μm), and 0.40g of organic material additive 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature is 160℃, which yields a polymer material that can change color with laser.

[0076] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 160℃.

[0077] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 1064nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 50kHz. The color change effect is shown in Table 1.

[0078] Example 5

[0079] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the amount of cerium dioxide powder added to the polyethylene resin was 0.5 wt%. Other conditions were the same as in Example 4. The color-changing effect is shown in Table 1.

[0080] Example 6

[0081] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the amount of cerium dioxide powder added to the polyethylene resin was 3 wt%, and the other conditions were the same as in Example 4. The color-changing effect is shown in Table 1.

[0082] Example 7

[0083] First, 99.82g of polycarbonate resin, 0.08g of inorganic material additive barium oxide powder (average particle size of 0.2μm), and 0.10g of organic material additive 6'-(diethylamino)-1',2'-benzofluorane are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature is 260℃ to obtain a polymer material that can change color with laser.

[0084] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at an injection temperature of 270℃.

[0085] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 40kHz. The color change effect is shown in Table 1.

[0086] Example 8

[0087] The polymer laser color-changing composition was prepared according to the method of Example 7, except that the amount of barium oxide added to the polycarbonate resin was 0.2 wt%, and the other conditions were the same as in Example 7. The color-changing effect is shown in Table 1.

[0088] Example 9

[0089] The polymer laser color-changing composition was prepared according to the method of Example 7, except that the amount of barium oxide added to the polycarbonate resin was 0.4 wt%, and the other conditions were the same as in Example 7. The color-changing effect is shown in Table 1.

[0090] Example 10

[0091] First, 97.95g of polycarbonate resin, 0.05g of inorganic material additive magnesium oxide powder (average particle size of 0.2μm), and 2.00g of organic material additive 6'-(diethylamino)-1',2'-benzofluorane are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature is 260℃ to obtain a polymer material that can change color with laser.

[0092] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 260℃.

[0093] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 532nm, marking speed of 1000mm / s, laser energy of 2.5W, and laser frequency of 40kHz. The color change effect is shown in Table 1.

[0094] Example 11

[0095] The polymer laser color-changing composition was prepared according to the method of Example 10, except that the amount of magnesium oxide powder added to polycarbonate was 0.5 wt%, and the other conditions were the same as in Example 10. The color-changing effect is shown in Table 1.

[0096] Example 12

[0097] The polymer laser color-changing composition was prepared according to the method of Example 10, except that the amount of magnesium oxide powder added to polycarbonate was 1 wt%, and the other conditions were the same as in Example 10. The color-changing effect is shown in Table 1.

[0098] Example 13

[0099] First, 99.40g of polyurethane resin, 0.20g of inorganic material additive titanium dioxide powder (average particle size 0.02μm), and 0.40g of organic material additive 3-(4-dimethylaminophenyl)-3-(1-butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 190℃ to obtain a laser-sensitive color-changing polymer material.

[0100] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 190℃.

[0101] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 5W, and laser frequency 80kHz. The color change effect is shown in Table 1.

[0102] Example 14

[0103] The polymer laser color-changing composition was prepared according to the method of Example 13, except that the amount of titanium dioxide powder added to the polyurethane resin was 0.4 wt%, and the other conditions were the same as in Example 13. The color-changing effect is shown in Table 1.

[0104] Example 15

[0105] The polymer laser color-changing composition was prepared according to the method of Example 13, except that the amount of titanium dioxide powder added to the polyurethane resin was 2 wt%, and the other conditions were the same as in Example 13. The color-changing effect is shown in Table 1.

[0106] Example 16

[0107] First, 95.95g of polyurethane resin, 0.05g of inorganic material additive zinc oxide powder (average particle size of 4μm), and 4.00g of organic material additive 3-(4-dimethylaminophenyl)-3-(1-butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 190℃ to obtain a laser-sensitive color-changing polymer material.

[0108] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 190℃.

[0109] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 1064nm, marking speed 1000mm / s, laser energy 5W, and laser frequency 80kHz. The color change effect is shown in Table 1.

[0110] Example 17

[0111] The polymer laser color-changing composition was prepared according to the method of Example 16, except that the amount of zinc oxide added to the polyurethane was 0.5 wt%. Other conditions were the same as in Example 16, and the color-changing effect is shown in Table 1.

[0112] Example 18

[0113] The polymer laser color-changing composition was prepared according to the method of Example 16, except that the amount of zinc oxide added to the polyurethane was 2 wt%, and the other conditions were the same as in Example 16. The color-changing effect is shown in Table 1.

[0114] Example 19

[0115] First, 99.84g of polypropylene resin, 0.06g of antimony trioxide powder (average particle size 1μm) and 0.10g of 3,3-bis(N-octyl-2-methylindole) phthalic acid lactone were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 190℃ to obtain a laser-sensitive color-changing polymer material.

[0116] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 190℃.

[0117] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 4W, and laser frequency 90kHz. The color change effect is shown in Table 1.

[0118] Example 20

[0119] The polymer laser color-changing composition was prepared according to the method of Example 19, except that the amount of antimony trioxide added to polypropylene was 0.6 wt%. Other conditions were the same as in Example 19, and the color-changing effect is shown in Table 1.

[0120] Example 21

[0121] The polymer laser color-changing composition was prepared according to the method of Example 19, except that the amount of antimony trioxide added to polypropylene was 0.6 wt%. All other conditions were the same as in Example 19, and the color-changing effect is shown in Table 1.

[0122] Example 22

[0123] First, 99.55g of polypropylene resin, 0.05g of inorganic material additive tin dioxide powder (average particle size of 1μm), and 0.40g of organic material additive 3,3-bis(N-octyl-2-methylindole) phthalic acid lactone were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 190℃, which yielded a polymer material that could change color with laser.

[0124] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 190℃.

[0125] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 532nm, marking speed of 1000mm / s, laser energy of 4W, and laser frequency of 90kHz. The color change effect is shown in Table 1.

[0126] Example 23

[0127] The polymer laser color-changing composition was prepared according to the method of Example 22, except that the amount of inorganic material additive tin dioxide powder added to polypropylene was 0.2 wt%. Other conditions were the same as in Example 22. The color-changing effect is shown in Table 1.

[0128] Example 24

[0129] The polymer laser color-changing composition was prepared according to the method of Example 22, except that the amount of inorganic material additive tin dioxide powder added to polypropylene was 2wt%, and the other conditions were the same as in Example 22. The color-changing effect is shown in Table 1.

[0130] Example 25

[0131] First, 99.65g of polyethylene terephthalate resin, 0.05g of inorganic material additive cerium dioxide powder (average particle size of 0.3μm), and 0.30g of organic material additive 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-B]pyridine-5(7H)-one were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 240℃ to obtain a laser-sensitive color-changing polymer material.

[0132] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 250°C.

[0133] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 266nm, marking speed of 1000mm / s, laser energy of 3W, and laser frequency of 30kHz. The color change effect is shown in Table 1.

[0134] Example 26

[0135] The polymer laser color-changing composition was prepared according to the method of Example 25, except that the amount of cerium dioxide powder added to polyethylene terephthalate resin was 0.5 wt%, and the other conditions were the same as in Example 25. The color-changing effect is shown in Table 1.

[0136] Example 27

[0137] The polymer laser color-changing composition was prepared according to the method of Example 25, except that the amount of cerium dioxide powder added to polyethylene terephthalate resin was 2.5 wt%, and the other conditions were the same as in Example 25. The color-changing effect is shown in Table 1.

[0138] Example 28

[0139] First, 96.95g of polyethylene terephthalate resin, 0.05g of molybdenum trioxide powder (average particle size 0.02μm) and 3.00g of 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-B]pyridine-5(7H)-one were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 240℃ to obtain a laser-sensitive color-changing polymer material.

[0140] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 250°C.

[0141] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 1064nm, marking speed 1000mm / s, laser energy 3W, and laser frequency 30kHz. The color change effect is shown in Table 1.

[0142] Example 29

[0143] The polymer laser color-changing composition was prepared according to the method of Example 28, except that the amount of molybdenum trioxide powder added to polyethylene terephthalate resin was 0.2 wt%, and the other conditions were the same as in Example 28. The color-changing effect is shown in Table 1.

[0144] Example 30

[0145] The polymer laser color-changing composition was prepared according to the method of Example 28, except that the amount of molybdenum trioxide powder added to polyethylene terephthalate resin was 2wt%, and the other conditions were the same as in Example 28. The color-changing effect is shown in Table 1.

[0146] Example 31

[0147] First, 99.60g of polybutylene terephthalate resin, 0.20g of inorganic material additive tungsten trioxide powder (average particle size 0.02μm), and 0.20g of organic material additive 3',6'-dimethoxyfluorane are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 265℃ to obtain a laser-sensitive color-changing polymer material.

[0148] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at an injection temperature of 270℃.

[0149] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 266nm, marking speed of 1000mm / s, laser energy of 5W, and laser frequency of 90kHz. The color change effect is shown in Table 1.

[0150] Example 32

[0151] The polymer laser color-changing composition was prepared according to the method of Example 31, except that the amount of tungsten trioxide powder added to polybutylene terephthalate was 1 wt%, and the other conditions were the same as in Example 31. The color-changing effect is shown in Table 1.

[0152] Example 33

[0153] The polymer laser color-changing composition was prepared according to the method of Example 31, except that the amount of tungsten trioxide powder added to polybutylene terephthalate was 3 wt%, and the other conditions were the same as in Example 31. The color-changing effect is shown in Table 1.

[0154] Example 34

[0155] First, 98.94g of ABS resin, 0.06g of inorganic material additive calcium oxide powder (average particle size of 0.5μm), and 1.00g of organic material additive 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature is 210℃, which yields a polymer material that can change color with laser.

[0156] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 210℃.

[0157] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 532nm, marking speed of 1000mm / s, laser energy of 2W, and laser frequency of 30kHz. The color change effect is shown in Table 1.

[0158] Example 35

[0159] The polymer laser color-changing composition was prepared according to the method of Example 34, except that the amount of calcium oxide powder added to the ABS resin was 0.4 wt%, and the other conditions were the same as in Example 34. The color-changing effect is shown in Table 1.

[0160] Example 36

[0161] The polymer laser color-changing composition was prepared according to the method of Example 34, except that the amount of calcium oxide powder added to the ABS resin was 0.4 wt%, and the other conditions were the same as in Example 34. The color-changing effect is shown in Table 1.

[0162] Example 37

[0163] First, 99.45g of polymethyl methacrylate resin, 0.05g of inorganic material additive zirconium oxide powder (average particle size of 0.03μm), and 0.50g of organic material additive 9-[ethyl(3-methylbutyl)amino]-spiro[12H-benzo[a]oxanthracene-12,1'(3'H)-isobenzofuran]-3'-one were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 240℃ to obtain a laser-sensitive color-changing polymer material.

[0164] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 240℃.

[0165] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 3W, and laser frequency 30kHz. The color change effect is shown in Table 1.

[0166] Example 38

[0167] The polymer laser color-changing composition was prepared according to the method of Example 37, except that the amount of zirconium oxide powder added to polymethyl methacrylate was 0.3 wt%, and the other conditions were the same as in Example 37. The color-changing effect is shown in Table 1.

[0168] Example 39

[0169] The polymer laser color-changing composition was prepared according to the method of Example 37, except that the amount of zirconium oxide powder added to polymethyl methacrylate was 1.5 wt%, and the other conditions were the same as in Example 37. The color-changing effect is shown in Table 1.

[0170] Example 40

[0171] First, 99.60g of nylon 66 resin, 0.10g of molybdenum-doped bismuth trioxide powder (average particle size of 6μm) and 0.30g of organic additive 2-(2',4'-dimethylphenylamino-3-methyl-6-diethylaminofluorane) were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 230℃ to obtain a laser-sensitive color-changing polymer material.

[0172] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 240℃.

[0173] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 1064nm, marking speed 1000mm / s, laser energy 3.5W, and laser frequency 70kHz. The color change effect is shown in Table 1.

[0174] Example 41

[0175] The polymer laser color-changing composition was prepared according to the method of Example 40, except that the amount of bismuth trioxide powder added to nylon 66 resin was 0.5 wt%, and the other conditions were the same as in Example 40. The color-changing effect is shown in Table 1.

[0176] Example 42

[0177] The polymer laser color-changing composition was prepared according to the method of Example 40, except that the amount of bismuth trioxide powder added to nylon 66 resin was 2wt%, and the other conditions were the same as in Example 40. The color-changing effect is shown in Table 1.

[0178] Example 43

[0179] First, 97.92g of polystyrene resin, 0.08g of samarium oxide powder (average particle size 0.06μm) and 2.00g of 2'-(dibenzylamino)-6'-(diethylamino)fluorane were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 210℃ to obtain a laser-sensitive color-changing polymer material.

[0180] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 210℃.

[0181] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 4W, and laser frequency 80kHz. The color change effect is shown in Table 1.

[0182] Example 44

[0183] The polymer laser color-changing composition was prepared according to the method of Example 43, except that the amount of samarium oxide powder added to polystyrene was 0.4 wt%. Other conditions were the same as in Example 46. The color-changing effect is shown in Table 1.

[0184] Example 45

[0185] The polymer laser color-changing composition was prepared according to the method of Example 43, except that the amount of samarium oxide powder added to polystyrene was 3 wt%, and the other conditions were the same as in Example 46. The color-changing effect is shown in Table 1.

[0186] Example 46

[0187] First, 99.40g of polyester elastomer resin, 0.20g of inorganic additive yttrium oxide powder (average particle size of 10μm), and 0.40g of organic additive 3-(1,2-dimethyl-3-indolyl)-3-[4-diethylamino-2-methylphenyl]phthalide are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 190℃ to obtain a laser-sensitive color-changing polymer material.

[0188] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 190℃.

[0189] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 532nm, marking speed of 1000mm / s, laser energy of 4W, and laser frequency of 60kHz. The color change effect is shown in Table 1.

[0190] Example 47

[0191] The polymer laser color-changing composition was prepared according to the method of Example 46, except that the amount of yttrium oxide powder added to the polyester elastomer resin was 1 wt%, and the other conditions were the same as in Example 46. The color-changing effect is shown in Table 1.

[0192] Example 48

[0193] The polymer laser color-changing composition was prepared according to the method of Example 46, except that the amount of yttrium oxide powder added to the polyester elastomer resin was 2 wt%, and the other conditions were the same as in Example 46. The color-changing effect is shown in Table 1.

[0194] Example 49

[0195] First, 98.50g of polyoxymethylene resin, 0.50g of europium oxide powder (average particle size of 0.8μm) and 1.00g of 6-(N-ethyl-4-toluidine)-2-methylfluorane were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 200℃ to obtain a laser-sensitive color-changing polymer material.

[0196] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 205℃.

[0197] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 3W, and laser frequency 50kHz. The color change effect is shown in Table 1.

[0198] Example 50

[0199] The polymer laser color-changing composition was prepared according to the method of Example 49, except that the amount of europium oxide powder added to the polyoxymethylene resin was 2 wt%, and the other conditions were the same as in Example 49. The color-changing effect is shown in Table 1.

[0200] Example 51

[0201] The polymer laser color-changing composition was prepared according to the method of Example 49, except that the amount of europium oxide powder added to the polyoxymethylene resin was 4 wt%, and the other conditions were the same as in Example 49. The color-changing effect is shown in Table 1.

[0202] Example 52

[0203] First, 99.90g of polyurethane resin, 0.05g of inorganic material additive indium trioxide powder (average particle size of 5μm), and 0.05g of organic material additive N,N-dimethyl-4-[2-[2-(octoxy)phenyl]-6-phenyl-4-pyridyl]-aniline are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 190℃ to obtain a laser-sensitive color-changing polymer material.

[0204] Then, the prepared laser-sensitive color-changing polymer material is injection molded into a standard sample using an injection molding machine at a temperature of 190℃.

[0205] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 1064nm, marking speed 1000mm / s, laser energy 5W, and laser frequency 80kHz. The color change effect is shown in Table 1.

[0206] Example 53

[0207] The polymer laser color-changing composition was prepared according to the method of Example 52, except that the amount of indium trioxide powder added to the polyurethane resin was 0.4 wt%. Other conditions were the same as in Example 52. The color-changing effect is shown in Table 1.

[0208] Example 54

[0209] The polymer laser color-changing composition was prepared according to the method of Example 52, except that the amount of indium trioxide powder added to the polyurethane resin was 1 wt%, and the other conditions were the same as in Example 52. The color-changing effect is shown in Table 1.

[0210] Example 55

[0211] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the inorganic material was replaced with 0.05 wt% antimony tin oxide (average particle size of 0.06 μm). Other conditions were the same as in Example 1. The color-changing effect is shown in Table 1.

[0212] Example 56

[0213] The polymer laser color-changing composition was prepared according to the method of Example 7, except that the inorganic material was replaced with 0.08 wt% zinc alumina (average particle size of 4 μm). Other conditions were the same as in Example 7. The color-changing effect is shown in Table 1.

[0214] Example 57

[0215] The polymer laser color-changing composition was prepared according to the method of Example 13, except that the inorganic material was replaced with 0.2 wt% dysprosium oxide (average particle size of 0.2 μm). Other conditions were the same as in Example 13. The color-changing effect is shown in Table 1.

[0216] Example 58

[0217] The polymer laser color-changing composition was prepared according to the method of Example 21, except that the inorganic material was replaced with 1 wt% niobium oxide (average particle size of 0.5 μm). Other conditions were the same as in Example 21. The color-changing effect is shown in Table 1.

[0218] Example 59

[0219] The polymer laser color-changing composition was prepared according to the method of Example 27, except that the inorganic material was replaced with 2.5 wt% lanthanum oxide (average particle size of 0.02 μm). Other conditions were the same as in Example 27. The color-changing effect is shown in Table 1.

[0220] Example 60

[0221] The polymer laser color-changing composition was prepared according to the method of Example 33, except that the inorganic material was replaced with 3 wt% erbium oxide (average particle size of 0.6 μm). Other conditions were the same as in Example 33. The color-changing effect is shown in Table 1.

[0222] Comparative Example 1

[0223] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the amount of aluminum oxide powder added to polyethylene was 0.01 wt%.

[0224] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 50kHz. The color change effect is shown in Table 1.

[0225] Comparative Example 2

[0226] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the amount of aluminum oxide powder added to polyethylene was 10 wt%.

[0227] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 50kHz. The color change effect is shown in Table 1.

[0228] Comparative Example 3

[0229] The polymer laser color-changing composition was prepared according to the method of Example 1, except that the amount of aluminum oxide powder added to polyethylene was 20 wt%.

[0230] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 50kHz. The color change effect is shown in Table 1.

[0231] Comparative Example 4

[0232] The polymer laser color-changing composition was prepared according to the method of Example 7, except that the amount of organic material additive 6'-(diethylamino)-1',2'-benzofluorane added to the polycarbonate was 0.01 wt%.

[0233] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 1064nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 40kHz. The color change effect is shown in Table 1.

[0234] Comparative Example 5

[0235] The polymer laser color-changing composition was prepared according to the method of Example 7, except that the amount of organic material additive 6'-(diethylamino)-1',2'-benzofluorane added to the polycarbonate was 15wt%.

[0236] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 40kHz. The color change effect is shown in Table 1.

[0237] Comparative Example 6

[0238] The polymer laser color-changing composition was prepared according to the method of Example 7, except that the amount of organic material additive 6'-(diethylamino)-1',2'-benzofluorane added to the polycarbonate was 20wt%.

[0239] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 40kHz. The color change effect is shown in Table 1.

[0240] Comparative Example 7

[0241] The polymer laser color-changing composition was prepared according to the method of Example 13, except that no metal oxides were added to the polyurethane.

[0242] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 5W, and laser frequency 80kHz. The color change effect is shown in Table 1.

[0243] Comparative Example 8

[0244] The polymer laser color-changing composition was prepared according to the method of Example 13, except that no organic materials were added to the polyurethane.

[0245] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 5W, and laser frequency 80kHz. The color change effect is shown in Table 1.

[0246] Comparative Example 9

[0247] The polymer laser color-changing composition was prepared according to the method of Example 19, except that no metal oxides were added to the polypropylene.

[0248] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 4W, and laser frequency 90kHz. The color change effect is shown in Table 1.

[0249] Comparative Example 10

[0250] The polymer laser color-changing composition was prepared according to the method of Example 19, except that no organic materials were added to the polypropylene.

[0251] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 4W, and laser frequency 90kHz. The color change effect is shown in Table 1.

[0252] Comparative Example 11

[0253] The polymer laser color-changing composition was prepared according to the method of Example 25, except that no metal oxide was added to the polyethylene terephthalate.

[0254] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 266nm, marking speed of 1000mm / s, laser energy of 5W, and laser frequency of 90kHz. The color change effect is shown in Table 1.

[0255] Comparative Example 12

[0256] The polymer laser color-changing composition is based on the method of Example 25, except that no organic materials are added to the polyethylene terephthalate.

[0257] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 266nm, marking speed of 1000mm / s, laser energy of 5W, and laser frequency of 90kHz. The color change effect is shown in Table 1.

[0258] Comparative Example 13

[0259] The polymer laser color-changing composition was prepared according to the method of Example 31, except that no metal oxide was added to the polybutylene terephthalate.

[0260] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 266nm, marking speed of 1000mm / s, laser energy of 2W, and laser frequency of 30kHz. The color change effect is shown in Table 1.

[0261] Comparative Example 14

[0262] The polymer laser color-changing composition was prepared according to the method of Example 31, except that no organic materials were added to the polybutylene terephthalate.

[0263] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 266nm, marking speed of 1000mm / s, laser energy of 2W, and laser frequency of 30kHz. The color change effect is shown in Table 1.

[0264] Comparative Example 15

[0265] The polymer laser color-changing composition was prepared according to the method of Example 34, except that no metal oxide was added to the polymer-p-ABS.

[0266] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 532nm, marking speed of 1000mm / s, laser energy of 3W, and laser frequency of 30kHz. The color change effect is shown in Table 1.

[0267] Comparative Example 16

[0268] The polymer laser color-changing composition was prepared according to the method of Example 34, except that no organic materials were added to the ABS.

[0269] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 532nm, marking speed of 1000mm / s, laser energy of 3W, and laser frequency of 30kHz. The color change effect is shown in Table 1.

[0270] Comparative Example 17

[0271] The polymer laser color-changing composition was prepared according to the method of Example 37, except that no metal oxide was added to the polymethyl methacrylate.

[0272] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 3.5W, and laser frequency 70kHz. The color change effect is shown in Table 1.

[0273] Comparative Example 18

[0274] The polymer laser color-changing composition was prepared according to the method of Example 37, except that no organic materials were added to the polymethyl methacrylate.

[0275] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 3.5W, and laser frequency 70kHz. The color change effect is shown in Table 1.

[0276] Comparative Example 19

[0277] The polymer laser color-changing composition was prepared according to the method of Example 40, except that no organic materials were added to the polymethyl methacrylate.

[0278] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 1064nm, marking speed of 1000mm / s, laser energy of 4W, and laser frequency of 80kHz. The color change effect is shown in Table 1.

[0279] Comparative Example 20

[0280] The polymer laser color-changing composition was prepared according to the method of Example 40, except that no organic materials were added to the nylon 66.

[0281] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 1064nm, marking speed of 1000mm / s, laser energy of 4W, and laser frequency of 80kHz. The color change effect is shown in Table 1.

[0282] Comparative Example 21

[0283] The polymer laser color-changing composition was prepared according to the method of Example 43, except that no metal oxides and organic materials were added to the polystyrene.

[0284] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 4W, and laser frequency 60kHz. The color change effect is shown in Table 1.

[0285] Comparative Example 22

[0286] The polymer laser color-changing composition was prepared according to the method of Example 46, except that no metal oxides and organic materials were added to the polyester elastomer.

[0287] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength of 532nm, marking speed of 1000mm / s, laser energy of 3W, and laser frequency of 50kHz. The color change effect is shown in Table 1.

[0288] Comparative Example 23

[0289] A polymer laser color-changing composition based on organic materials was prepared according to the method of Example 49, except that no metal oxides and organic materials were added to the polyoxymethylene.

[0290] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 355nm, marking speed 1000mm / s, laser energy 5W, and laser frequency 80kHz. The color change effect is shown in Table 1.

[0291] Comparative Example 24

[0292] The polymer laser color-changing composition was prepared according to the method of Example 52, except that no metal oxides and organic materials were added to the polyurethane.

[0293] The prepared standard sample was marked using a pulsed fiber laser marking machine. The marking parameters were as follows: laser wavelength 1064nm, marking speed 1000mm / s, laser energy 2.5W, and laser frequency 50kHz. The color change effect is shown in Table 1.

[0294] The evaluation of the laser color-changing effect is as follows:

[0295]

[0296] In the evaluation level of laser color-changing effect, the more "+" signs there are, the better the laser color-changing effect.

[0297] Table 1 Laser Color Change Effect

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305] 2. Experimental Results

[0306] The color change results show that adding the specific metal oxides and organic materials of this invention to a white or light-colored polymer substrate can enable the polymer to exhibit excellent color change effects under laser irradiation.

[0307] Comparing the marking effects of Examples 1, 7 and Comparative Examples 1-6, it was found that the laser color marking effect was poor when the ratio of organic materials / metal oxides was outside the range provided by the invention.

[0308] Comparing the marking effects of Examples 13, 19, 25, 31, 34, 37, 40 and Comparative Examples 7-20, it was found that the inorganic-organic composite color-changing additive composition prepared in this invention can significantly improve the laser color marking effect compared with using metal oxides or organic materials alone.

[0309] Comparing the marking effects of Examples 43, 46, 49, 52 and Comparative Examples 21-24, it was found that, compared with not using organic materials and metal oxides, using the inorganic-organic composite color-changing composition prepared by the present invention can enable polymer materials to obtain excellent color-changing effects.

[0310] In summary, this invention provides a color-changing polymer composition for laser irradiation. This invention incorporates specific metal oxides and organic materials as additives into a polymer to obtain a color-changing polymer material. Experiments have shown that this polymer material exhibits excellent color-changing effects under laser irradiation, forming clear, flat, and high-contrast color markings. Furthermore, this polymer material has a light color, enabling color marking on white or light-colored polymer substrates. Moreover, the preparation method of the color-changing polymer disclosed in this invention is simple, easy to operate, safe, environmentally friendly, and energy-efficient, making it highly suitable for large-scale industrial production and offering significant economic benefits.

Claims

1. A laser-sensitive color-changing inorganic-organic composite polymer material, characterized in that: The inorganic-organic composite polymer material is composed of the following components in weight percentage: 0.05wt% to 10.00wt% metal oxides, 0.05wt% to 10.00wt% organic materials, and the remainder being polymers; The metal oxide is selected from any one or more of the following: aluminum oxide, cerium oxide, barium oxide, magnesium oxide, titanium dioxide, zinc oxide, antimony trioxide, tin oxide, molybdenum trioxide, tungsten trioxide, calcium oxide, zirconium oxide, bismuth trioxide, samarium oxide, yttrium oxide, europium oxide, indium trioxide, antimony tin oxide, zinc aluminum oxide, dysprosium oxide, niobium oxide, lanthanum oxide, and erbium oxide. The organic material is selected from at least one of benzopyran compounds, aniline derivatives, polycyclic quinone compounds, spiropyran compounds, spiroxazine compounds, azobenzene compounds, fluorane compounds, and phthalide compounds.

2. The laser-sensitive color-changing inorganic-organic composite polymer material according to claim 1, characterized in that: The polymer has a weight percentage of 80.00 wt% to 99.90 wt%. The polymer is selected from any one or more of the following: polyethylene, polypropylene, nylon, polycarbonate, polymethyl methacrylate, polyvinyl alcohol, polyethyl methacrylate, polybutyl methacrylate, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, ethylene-octene copolymer, ethylene-butene copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polystyrene, polyvinyl chloride, polyvinylidene fluoride, polyurethane elastomer, polyester elastomer, styrene-based thermoplastic elastomer, styrene-butadiene copolymer, styrene-methyl methacrylate copolymer, polyisobutylene, ethylene-vinyl acetate copolymer, polysulfone, polyimide, cellulose acetate, unsaturated polyester, silicone resin, epoxy resin, phenolic resin, melamine resin, natural rubber, cis-butadiene rubber, styrene-butadiene rubber, silicone rubber, fluororubber, nitrile rubber, butyl rubber, and ethylene propylene diene monomer (EPDM) rubber.

3. The laser-sensitive color-changing inorganic-organic composite polymer material according to claim 1 or 2, characterized in that: It is composed of the following components by weight percentage: metal oxides 0.05wt% to 5.00wt%, organic materials 0.05wt% to 5.00wt%, and polymers 90.00wt% to 99.90wt%. The metal oxide is selected from any one or more of the following: aluminum oxide, cerium oxide, barium oxide, magnesium oxide, titanium dioxide, zinc oxide, antimony trioxide, tin oxide, molybdenum trioxide, tungsten trioxide, calcium oxide, zirconium oxide, bismuth trioxide, samarium oxide, yttrium oxide, europium oxide, indium trioxide, antimony tin oxide, zinc aluminum oxide, dysprosium oxide, niobium oxide, lanthanum oxide, and erbium oxide. The organic material is selected from 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane, 2'-chloro-6'-(diethylamino)spiro[isobenzofuran-1(3H),9'-(9H)oxanthracene]-3-one, 3,3-bis(N-octyl-2-methylindole)phthalic acid lactone, 3-(4-dimethylaminophenyl)-3-(1-butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide, 9(9H)oxanthracene-2-carboxylic acid-6-(di- 3-(1,2-dimethyl-3-indolyl)-3-[4-diethylamino-2-methylphenyl]phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-aza-2-benzo[C]furanone, 9-[ethyl(3-methylbutyl)amino]-spiro[12H-benzo[a]oxanthracene-12,1'(3'H)-isobenzofuran]-3'-one, 6'-( Dihydroindol-1-yl)-1,3,3-trimethylspiro[dihydroindol-2,3'-naphtho[2,1-B][1,4]oxazine], 1,3-dimethyl-6-diethylaminofluorane, 3',6'-dimethoxyfluorane, 4-methoxy-2-methyl-diphenylamine, 1,3,3-trimethylindololin-6'-(1-piperidinyl)spirophenoxazine, 3-(N-ethyl-4-toluidine)-6-methyl-7-anilinefluorane, 3,3-bis(4-dimethylaminophenyl) 6-Dimethylaminophthalide, 2-(2',4'-dimethylphenylamino-3-methyl-6-diethylaminofluorane, 6'-(diethylamino)-1',2'-benzofluorane, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-b]pyridin-5(7H)-one, 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H), 9'-[9H] x [Ton]-2'-carboxylic acid ethyl ester, N,N-dimethyl-4-[2-[2-(octoxy)phenyl]-6-phenyl-4-pyridyl]-aniline, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 2-(2-thiophenecarboxylamino)benzopyran, 2-phenyl-3-nitro-2H-1-benzopyran, 2'-(dibenzylamino)-6'-(diethylamino)fluorane, 7-hydroxy-2-oxo-2H-benzopyran-3-carboxylic acid, 2H-1-benzopyran-5-ol, 5-nitrobenzodihydropyran-4-one, 1,3,3-trimethylindolenaphthospiroxazine, 1,3,3-trimethylspirocyclic [indole-2,3'-naphtho[2,1-b][1,4]oxazine]-9'-methacrylate, 1,3,8-trihydroxy The following are any one or more of the following: 6-methyl-10H-anthrafen-9-one, 3-diethylamino-6-methyl-7-phenylaminofluorane, 2-(2-4-dimethylamino)-3-methyl-6-diethylaminofluorane, 3-dibutylamino-6-methyl-7-bromofluorane, tris(p-dimethylaminophenyl)methane, 6-(N-ethyl-4-toluidine)-2-methylfluorane, 4,4',4”-triaminotriphenylmethane, 4-hydroxy-4-isopropoxydiphenyl sulfone, 3-(3-methylureo)phenyl-4-methylbenzenesulfonate, (1-p-methoxyphenyl-2-methyl-5-phenyl)-3-pyrrole-ethide (isopropylidene)-succinic anhydride, and 3,4-di[1-(2,5-dimethyl-3-furanyl)ethide]-3,4-dihydrofuran-2,5-dione; Preferably, the organic material is selected from 3-(N-ethyl-4-toluidine)-6-methyl-7-anilinofluorane, 3,3-bis(N-octyl-2-methylindole)phthalic acid lactone, 3-(4-dimethylaminophenyl)-3-(1-butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide, 3-(1,2-dimethyl-3-indole)-3-[4-diethylamino-2-methylphenyl]phthalide, 9-[ethyl(3-methylbutyl)amino]-spiro[12H-benzo[a]oxanthracene-12,1'(3'H)-isobenzofuran]-3'-one, 3',6'-dimethoxyfluorane, 2-(2',4'-dimethylphenylamino) 3-Methyl-6-diethylaminofluorane, 6'-(diethylamino)-1',2'-benzofluorane, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-b]pyridin-5(7H)-one, N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridyl]-aniline, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 2'-(dibenzylamino)-6'-(diethylamino)fluorane, 6-(N-ethyl-4-toluidine)-2-methylfluorane, or any two or more thereof; The polymer is selected from any one or more of polyethylene, polypropylene, nylon, polycarbonate, polymethyl methacrylate, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polystyrene, polyurethane elastomer, and polyester elastomer.

4. The laser-sensitive color-changing inorganic-organic composite polymer material according to claim 3, characterized in that: It is composed of the following components by weight percentage: 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane 0.4%, cerium dioxide 0.5%, polyethylene 99.1%; or, 6'-(diethylamino)-1',2'-benzofluorane 2%, barium oxide 0.2%-0.4%, polycarbonate 97.6%-97.8%; or, 3-(4-Dimethylaminophenyl)-3-(1-Butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide 0.4%, titanium dioxide 0.4%, polyurethane 99.8%; or, 3,3-Bis(N-octyl-2-methylindole) phthalic acid 0.4%, tin dioxide 0.2%, polypropylene 99.4%; or 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-B]pyridin-5(7H)-one 0.3%, cerium dioxide 0.5%, polyethylene terephthalate 99.2%; or, 3% 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furano[3,4-B]pyridin-5(7H)-one, 2% molybdenum trioxide, 95% polyethylene terephthalate; or, 3',6'-Dimethoxyfluorane 0.2%, tungsten trioxide 0.2%-1%, polybutylene terephthalate 98.8%-99.6%; or 3,3-Di(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide 1%, calcium oxide 0.5%, ABS 98.5%; or, 9-[ethyl(3-methylbutyl)amino]-spiro[12H-benzo[a]oxanthracene-12,1'(3'H)-isobenzofuran]-3'-one 0.3%, zirconium oxide 0.3%, polymethyl methacrylate 99.4%; or, 2-(2',4'-dimethylphenylamino-3-methyl-6-diethylaminofluorane 0.3%, bismuth trioxide 0.5%, nylon 6699.2%; or, 2'-(dibenzylamino)-6'-(diethylamino)fluorane 2%, samarium oxide 0.4%, polystyrene 97.6%; 0.4% 3-(1,2-dimethyl-3-indolyl)-3-[4-diethylamino-2-methylphenyl]phthalide, 0.2% or 2% yttrium oxide, and 97.6% or 99.4% polyester elastomer; 1% 6-(N-ethyl-4-toluidine)-2-methylfluorane, 0.5% europium oxide, 98.5% polyoxymethylene; or N,N-Dimethyl-4-[2-[2-(octoxy)phenyl]-6-phenyl-4-pyridyl]-aniline 0.05%, indium trioxide 1%, polyurethane 98.95%; or 0.2% 3-(N-ethyl-4-toluidine)-6-methyl-7-aniline fluorane, 0.05% antimony tin oxide, 99.75% polyethylene; or 6'-(diethylamino)-1',2'-benzofluorane 0.1%, zinc alumina 0.08%, polycarbonate 99.82%; or 3-(4-Dimethylaminophenyl)-3-(1-Butyl-2-methyl-indole-3-yl)-6-dimethylaminophthalide 0.4%, dysprosium oxide 0.2%, polyurethane 99.4%; or 3,3-Bis(N-octyl-2-methylindole)phthalic acid lactone 0.1%, niobium oxide 1%, polypropylene 98.90%; or 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indole-3-yl)furano[3,4-B]pyridin-5(7H)-one 0.3%, lanthanum oxide 2.5%, polyethylene terephthalate 97.2%; or 3',6'-Dimethoxyfluorane 0.2%, Erbium oxide 3%, Polybutylene terephthalate 96.8%.

5. The laser-sensitive color-changing inorganic-organic composite polymer material according to any one of claims 1-4, characterized in that: The average particle size of the metal oxide is 0.01 μm to 10.00 μm.

6. The method for preparing the laser-sensitive color-changing inorganic-organic composite polymer material according to any one of claims 1-5, characterized in that: It includes the following steps: a. Take metal oxides, organic materials and polymers, mix them evenly to obtain a mixture; b. Take the mixture obtained in step a, melt-blend it, and granulate it to obtain the final product.

7. The use of the laser-sensitive color-changing inorganic-organic composite polymer material according to any one of claims 1 to 5 in the preparation of laser color markers.

8. A laser color marking, characterized in that: It is a colored pattern or text produced by irradiating the laser-sensitive inorganic-organic composite polymer material as described in any one of claims 1 to 5 with a laser.

9. The laser color marking according to claim 8, characterized in that: The laser is emitted by a CO2 laser, an Nd:YAG laser, an Nd:YVO4 laser, an excimer laser, a fiber laser, a diode array laser, or a diode laser; the wavelength of the laser is 157 nm to 10.6 μm. Preferably, the laser is emitted by a pulsed Nd:YAG laser or a pulsed fiber laser; the wavelength of the laser is 1064nm, 532nm, 355nm or 266nm.

10. The laser color marking according to claim 9, characterized in that: The laser energy is 0.5 to 8 W; and / or the laser frequency is 10 to 100 kHz; and / or the laser marking speed is 400 to 4000 mm / s.

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