Application of organic materials in the preparation of color-changing polymer materials

Abstract

The present invention provides the use of organic materials in the preparation of color-changeable polymer materials, and also provides color-changeable polymer materials prepared based on such organic materials and a preparation method thereof, belonging to the technical field of polymer laser processing. The present invention adds a specific organic material as an additive to a polymer to obtain a color-changeable polymer material, and the polymer material 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 and flat with high contrast. At the same time, the polymer material is light in color, and color marks on light-colored, white or transparent polymer substrates can be realized, expanding the application range of laser color marks. In addition, the amount of organic material used in the 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.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer laser processing, and specifically relates to the application of organic materials in the preparation of color-changeable polymer materials, and also relates to color-changeable polymer materials prepared based on such organic materials and a preparation method thereof. Background Art

[0002] Laser marking is a method of using high-energy-density lasers to irradiate the surface of materials to cause chemical reactions such as carbonization, discoloration, and foaming, thereby obtaining a permanent mark with a different color from the substrate. At present, laser marking is mainly used for permanent marking and product anti-counterfeiting. Compared with traditional marking methods such as ink printing, screen printing, embossing, and hot stamping, laser marking is gradually becoming a popular marking method because of its advantages of high processing accuracy, high marking efficiency, simple operation, non-contact, low cost, and cleanliness.

[0003] The current laser marking method mainly generates white or light-colored marks on the surface of dark (black, dark gray or gray) polymer materials, or marks black patterns and text on polymer substrates with light backgrounds. For example: Chinese patent application with publication number CN105504517A discloses the use of graphene as an additive in the preparation of laser-markable polymer materials, which can achieve black marking on the polymer surface; Chinese patent with announcement number CN104804360B discloses an impact-resistant ABS resin composition with the function of printing white markings on a black matrix using laser. There is an increasing demand for using lasers to produce colored (such as red, blue, yellow, green, purple, etc.) marks on the surface of polymer materials. However, it is difficult to perform laser color marking on polymer surfaces. Polymer laser color marking remains a hot spot and difficulty in industry and academia.

[0004] The Chinese patent application with publication number CN106566068A discloses a polymer composition that can be laser-colored. The patent uses polymers, laser marking powders and temperature-sensitive substances. The heat generated during the laser marking process can cause the temperature-sensitive substances to undergo thermal decomposition, oxidation and other reactions at a certain temperature to produce new colors, thereby forming similar color marks on the polymer. The temperature-sensitive substance used in the invention is at least one of the phthalocyanine pigments, and a specific laser marking powder needs to be added to the composition. The process cost is high and it is not suitable for large-scale industrial applications. Moreover, the laser marking powder and phthalocyanine pigments added in the invention are black or dark substances, so the base color of the color-changing polymer composition is black or a darker color. The Chinese patent application with publication number CN109486128A discloses a plastic paper that can be laser-colored, and its preparation raw materials include plastic materials, sodium allyl sulfonate, initiators, black pigments, color pigments, antioxidants, flame retardants, lubricants, and fillers that are optionally added or not added. The composition in the invention needs to add black pigment, so it can only mark color on black substrate, which greatly limits its application in the field of laser color change. In addition, the composition has many ingredients, the process is too complicated, the implementation is difficult, the resource consumption is large, and it is difficult to put into large-scale production.

[0005] The polymer laser color change in the above patent mainly realizes color change by laser on a black or dark base polymer, and the color of the color change depends on the color of the pigment added to the polymer. However, there is no patent literature reporting the use of laser to realize color change on a light-colored, white or transparent polymer base. Therefore, there is an urgent need in the art for a new polymer material capable of laser color change, which can simply and conveniently use laser to perform color marking on a light-colored, white or transparent polymer material. Summary of the invention

[0006] The purpose of the present invention is to provide an application of an organic material in the preparation of a color-changeable polymer material, and at the same time provide a color-changeable polymer material prepared based on the organic material and a preparation method thereof.

[0007] The present invention provides the use of an organic material in preparing a color-changeable polymer material, wherein the organic material is selected from any one or more of benzopyran compounds, azobenzene compounds, diarylethene compounds, fulgide compounds, aniline derivative compounds, spirooxazine compounds, polycyclic quinone compounds, viologen compounds, spiropyran compounds, Schiff base compounds, dianthrone compounds, fluorene compounds, triphenylmethane compounds or cholesteric liquid crystal compounds.

[0008] Further, the organic material is selected from 2-(2-thiophenecarboxylic acid amino)benzopyran, 2-phenyl-3-nitro-2H-1-benzopyran, 7-hydroxy-2-oxo-2H-benzopyran-3-carboxylic acid, 2H-1-benzopyran-5-ol, 5-nitrobenzodihydropyran-4-one, 2,3-dihydro-2-phenyl-4-benzopyranone (2,3-dihydro-2-phenyl-4H-1-benzopyran-4-ylidene) hydrazone, 2-[[(benzoylamino)thiocarboxylic acid]amino]-4,7-dihydro-5,5-dimethyl-5H-thieno[2,3-C]pyran-3-carboxylic acid, 4,4'-bis(hexyloxy)-3-methylazobenzene, 4,4'-bis(decyloxy)-3-methylazobenzene, 4 -[Bis(9,9-dimethylfluoren-2-yl)amino]azobenzene, 4,4'-bis(dodecyloxy)-3-methylazobenzene, 1,2,3,4,5,6-hexa-O-[11-[4-(4-hexylbenzylamine)phenoxy]undecanoyl]-D-mannitol, 1,2'-bis(2-chlorophenyl)-tetraphenylbiimidazole and azobenzene, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, 2,3-bis(2,4,5-trimethyl-3-thienyl)maleic anhydride, 2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide, 1,2-bis[2-methylbenzo[b]thien-3-yl]-3,3,4, 4,5,5-hexafluoro-1-cyclopentene, cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethylene, (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, (E)-2-[1-(5-chloro-2-methylthien-3-yl)ethylidene]-3-isopropylidene succinic anhydride, (1-p-methoxyphenyl-2-methyl-5-phenyl)-3-pyrrole-ethylidene (isopropylidene)-succinic anhydride, 4-(dibenzophenazine)-N,N-diphenylaniline, 3-amino-4-cyano-5-methylthiophene-2-carboxylic acid ethyl ester, 3-amino-4'-bromo-2-cyano-[1,1'- Benzene]-4-carboxylic acid ethyl ester, 6-amino-5-cyano-2-methyl-4-phenyl-4H-pyran-3-carboxylic acid ethyl ester, 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine], 5-chloro-1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3-(3H)naphtho[2,1-b](1,4)oxazine], 1,3,3-trimethylindolin-6'-(1-piperidinyl)spirophenophenoxazine, 6'-(dihydroindole-1-yl)-1,3,3-trimethylspiro[dihydroindole-2,3'-naphtho[2,1-B][1,4]oxazine], 1,3,3-trimethylindolenaphthospirooxazine, 1,3,3-Trimethylspiro[indole-2,3'-naphtho[2,1-b][1,4]oxazine]-9'-methacrylate, 1-benzyl-3,3-dimethylspiro[indole-2,3'-naphtho[2,3-f][1,4]benzoxazine], 1-hydroxy-2-methylanthraquinone, 1-morpholine-4-anthraquinone, 1,4-diacetamideanthraquinone, benzyl viologen, N,N'-disubstituted-4,4'-bipyridinium cation salt, 2-(3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indol]-1'-yl)ethylmethacrylate esters, 1',3',3'-trimethyl-6-hydroxyspiro(2H-1-benzopyran-2,2'-indoline), 1,3,3-trimethylindole-β-naphthyldihydrofuran, spiro[1,3,3-trimethylindole-(6'-bromochroman)], spiro[1,3,3-trimethylindole-(8-methoxychroman)], spiro[1,3,3-trimethylindole-chroman], 1`,3`-dihydro-8-methoxy-1`,3`,3`-trimethyl-6-nitrospiro[2H-1-benzopyran-2, 2`-(2H)-indole], spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)], 5-methoxy-1,3,3-trimethyl-6'-nitrospiro[indoline-2,2'-[2H]benzopyran], 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine, R-glycine Schiff base NI(II) complex, 4-aminophenol Schiff base, 1,9-pyrazoloanthrone, 9,10-anthracenedione, benzene Any one or more of anthracene, 1,3,8-trihydroxy-6-methyl-10H-anthracen-9-one, 3-diethylamino-6-methyl-7-phenylaminofluoran, 2-(2-4-dimethylamino)-3-methyl-6-diethylaminofluoran, 3-dibutylamino-6-methyl-7-bromofluoran, 2-(2-chloroanilino)-6-(dibutylamino)fluoran, tris(p-dimethylaminophenyl)methane, 4,4',4"-triaminotriphenylmethane, cholesteryl cinnamate or 5-cholesten-3B-ol-3-hydrocinnamate.

[0009] The present invention also provides a color-changeable polymer composition based on an organic material, which comprises an organic material;

[0010] The organic material is selected from any one or more of benzopyran compounds, azobenzene compounds, diarylethene compounds, fulgide compounds, aniline derivative compounds, spirooxazine compounds, polycyclic quinone compounds, viologen compounds, spiropyran compounds, Schiff base compounds, dianthrone compounds, fluorene compounds, triphenylmethane compounds or cholesteric liquid crystal compounds;

[0011] Preferably, the organic material is selected from 2-(2-thienylamino)benzopyran, 2-phenyl-3-nitro-2H-1-benzopyran, 7-hydroxy-2-oxo-2H-benzopyran-3-carboxylic acid, 2H-1-benzopyran-5-ol, 5-nitrobenzodihydropyran-4-one, 2,3-dihydro-2-phenyl-4-benzopyranone (2,3-dihydro-2-phenyl-4H-1-benzopyran-4-ylidene) hydrazone, 2-[[(benzoylamino)thiocarboxyl]amino]-4,7-dihydro-5,5-dimethyl-5H-thieno[2,3-C]pyran-3-carboxylic acid, 4,4'-bis(hexyloxy)-3-methylazobenzene, 4,4'-bis(decyloxy)-3-methylazobenzene, 4- [Bis(9,9-dimethylfluoren-2-yl)amino]azobenzene, 4,4'-bis(dodecyloxy)-3-methylazobenzene, 1,2,3,4,5,6-hexa-O-[11-[4-(4-hexylbenzylamine)phenoxy]undecanoyl]-D-mannitol, 1,2'-bis(2-chlorophenyl)-tetraphenylbiimidazole and azobenzene, 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, 2,3-bis(2,4,5-trimethyl-3-thienyl)maleic anhydride, 2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide, 1,2-bis[2-methylbenzo[b]thien-3-yl]-3,3,4, 4,5,5-hexafluoro-1-cyclopentene, cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethylene, (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione, (E)-2-[1-(5-chloro-2-methylthien-3-yl)ethylidene]-3-isopropylidene succinic anhydride, (1-p-methoxyphenyl-2-methyl-5-phenyl)-3-pyrrole-ethylidene (isopropylidene)-succinic anhydride, 4-(dibenzophenazine)-N,N-diphenylaniline, 3-amino-4-cyano-5-methylthiophene-2-carboxylic acid ethyl ester, 3-amino-4'-bromo-2-cyano-[1,1'- Benzene]-4-carboxylic acid ethyl ester, 6-amino-5-cyano-2-methyl-4-phenyl-4H-pyran-3-carboxylic acid ethyl ester, 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine], 5-chloro-1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3-(3H)naphtho[2,1-b](1,4)oxazine], 1,3,3-trimethylindolin-6'-(1-piperidinyl)spirophenophenoxazine, 6'-(dihydroindole-1-yl)-1,3,3-trimethylspiro[dihydroindole-2,3'-naphtho[2,1-B][1,4]oxazine], 1,3,3-trimethylindolenaphthospirooxazine, 1,3,3-Trimethylspiro[indole-2,3'-naphtho[2,1-b][1,4]oxazine]-9'-methacrylate, 1-benzyl-3,3-dimethylspiro[indole-2,3'-naphtho[2,3-f][1,4]benzoxazine], 1-hydroxy-2-methylanthraquinone, 1-morpholine-4-anthraquinone, 1,4-diacetamideanthraquinone, benzyl viologen, N,N'-disubstituted-4,4'-bipyridinium cation salt, 2-(3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indol]-1'-yl)ethylmethacrylate esters, 1',3',3'-trimethyl-6-hydroxyspiro(2H-1-benzopyran-2,2'-indoline), 1,3,3-trimethylindole-β-naphthyldihydrofuran, spiro[1,3,3-trimethylindole-(6'-bromochroman)], spiro[1,3,3-trimethylindole-(8-methoxychroman)], spiro[1,3,3-trimethylindole-chroman], 1`,3`-dihydro-8-methoxy-1`,3`,3`-trimethyl-6-nitrospiro[2H-1-benzopyran-2, 2`-(2H)-indole], spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)], 5-methoxy-1,3,3-trimethyl-6'-nitrospiro[indoline-2,2'-[2H]benzopyran], 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, salicylaldehyde Schiff base N-(p-benzoic acid)-2-hydroxybenzyl imine, R-glycine Schiff base NI(II) complex, 4-aminophenol Schiff base, 1,9-pyrazoloanthrone, 9,10-anthracenedione, benzene Any one or more of anthracene, 1,3,8-trihydroxy-6-methyl-10H-anthracen-9-one, 3-diethylamino-6-methyl-7-phenylaminofluoran, 2-(2-4-dimethylamino)-3-methyl-6-diethylaminofluoran, 3-dibutylamino-6-methyl-7-bromofluoran, 2-(2-chloroanilino)-6-(dibutylamino)fluoran, tris(p-dimethylaminophenyl)methane, 4,4',4"-triaminotriphenylmethane, cholesteryl cinnamate or 5-cholesten-3B-ol-3-hydrocinnamate.

[0012] Further, the weight percentage of the organic material is 0.001wt% to 10wt%;

[0013] Preferably, the weight percentage of the organic material is 0.005wt% to 10wt%;

[0014] More preferably, the weight percentage of the organic material is 0.005 wt % to 5 wt %.

[0015] Furthermore, the aforementioned color-changeable polymer composition is composed of the following components in weight percentage: 0.001wt% to 10wt% of organic material, 90wt% to 99.999wt% of polymer;

[0016] Preferably, it is composed of the following components in weight percentage: 0.005wt% to 10wt% of organic material, 90wt% to 99.995wt% of polymer;

[0017] More preferably, it is composed of the following components in weight percentage: 0.005wt% to 5wt% of organic material, and 95wt% to 99.995wt% of polymer.

[0018] Further, the polymer is selected from any one or more of 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 thermoplastic elastomer, styrene-butadiene copolymer, styrene-methacrylate copolymer, 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, and EPDM rubber;

[0019] Preferably, the polymer is selected from polymethyl methacrylate, polystyrene, polycarbonate, polyurethane elastomer, acrylonitrile-butadiene-styrene copolymer, polyvinyl alcohol, polyvinyl chloride, polyvinylidene fluoride, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, nylon 6, styrene-butadiene-styrene copolymer.

[0020] The present invention also provides a method for preparing the aforementioned color-changeable polymer composition, which comprises the following steps:

[0021] a. dissolving the polymer in a solvent to obtain a polymer solution;

[0022] b. dissolving the organic material in the polymer solution, casting into a film, and volatilizing the solvent to obtain;

[0023] Preferably, the concentration of the polymer solution is 0.1wt% to 60wt%;

[0024] More preferably, the concentration of the polymer solution is 1 wt% to 50 wt%.

[0025] Further, the solvent is selected from any one 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.

[0026] The present invention also provides the use of the aforementioned color-changeable polymer composition in the preparation of laser color marking.

[0027] The present invention also provides a laser color mark, which is a color pattern or text produced by irradiating the aforementioned color-changeable polymer composition with laser;

[0028] Preferably, the laser is emitted by a CO2 laser, a Nd:YAG laser, a Nd:YVO4 laser, an excimer laser, a fiber laser, a diode array laser or a diode laser; the wavelength of the laser is 157nm to 10.6μm;

[0029] More preferably, the laser is emitted by a pulsed Nd:YAG laser or a pulsed fiber laser; the wavelength of the laser is 1064nm, 532nm or 355nm;

[0030] Further preferably, the laser energy is 0.5-8 W; and / or, the laser frequency is 10-100 kHz; and / or, the laser marking speed is 400-4000 mm / s.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The present invention provides a color-changeable polymer material prepared based on organic materials. The present invention adds a specific organic material as an additive to a polymer to obtain a color-changeable polymer material, and the polymer material 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 a high contrast. At the same time, the polymer material is light in color, and color marks on light-colored, white or transparent polymer substrates can be achieved, expanding the application range of laser color markings. In addition, the amount of organic material used in the 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, and 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.

[0033] After adding specific organic materials to the polymer, the present invention utilizes the photochemical effect and photothermal effect generated during the laser marking process to cause chemical changes in the organic material, thereby generating a new color. This color change is irreversible, so a stable permanent color change can be formed on the polymer material.

[0034] Obviously, according to the above contents of the present invention, in accordance with common technical knowledge and customary means in the art, without departing from the above basic technical ideas of the present invention, other various forms of modification, replacement or change may be made.

[0035] The above contents of the present invention are further described in detail below through specific implementation methods in the form of embodiments. However, this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above contents of the present invention belong to the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a diagram of the polymer laser color change effect in Example 3. DETAILED DESCRIPTION

[0037] 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.

[0038] (1) The equipment information used in the present invention is as follows:

[0039] Laser marking machine, model MUV-ER, pulse fiber laser marking machine, laser maximum power 10W, laser wavelength 355nm.

[0040] (2) The specific information of the polymer used to prepare the standard sample of the present invention is as follows:

[0041] Organic materials: Aladdin reagent platform; Solvents: Chengdu Kelong Chemical Co., Ltd., AR; Polyethylene (PE): Maoming Petrochemical, TR144; Polypropylene (PP): Sinopec Lanzhou Branch, T30S; Polymethyl methacrylate (PMMA): Evonik Degussa, Germany, 8803; Polystyrene: Duzishan Petrochemical, GPPS-500; Acrylonitrile-butadiene-styrene (ABS): Chimei, Taiwan, China, PA757; Styrene-butadiene-styrene (SBS): Duzishan Petrochemical, T171; Nylon 6: Lanxess, Germany, A30S; Polyethylene terephthalate: Far Eastern Textile Industry, CB-602; Polybutylene terephthalate: BASF, Germany, PBTB4500; Polycarbonate: General Electric Company, USA, PC121R; Polyurethane: Bayer, Germany, 9385; Polyvinyl alcohol: Changchun, Taiwan, China, BP-24; Polyvinyl chloride: Formosa Plastics, S80; Polyvinylidene fluoride: Solvay Chemical, USA, 6008.

[0042] Example 1

[0043] First, polycarbonate is dissolved in dichloromethane solvent to prepare a solution with a concentration of 20wt%. After it is completely dissolved, a benzopyran compound 2-(2-thiophenecarboxamido)benzopyran is added to the polymer solution at 0.007wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0044] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2.5 W, the laser frequency was 70 kHz, and the color change effect was shown in Table 1.

[0045] Example 2

[0046] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 1, except that the benzopyran compound accounted for 0.07wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 1. The color-changing effects are shown in Table 1.

[0047] Example 3

[0048] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 1, except that the benzopyran compound accounted for 0.2 wt % of the total amount of the final color-changing composition. Other conditions were the same as those of Example 1. The color-changing effects are shown in Table 1.

[0049] Example 4

[0050] First, polyurethane is dissolved in tetrahydrofuran solvent to prepare a solution with a concentration of 15wt%. After it is completely dissolved, an azobenzene compound 4,4'-bis(hexyloxy)-3-methylazobenzene is added to the polymer solution at 0.05wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changeable composition based on organic materials is obtained.

[0051] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 90 kHz, and the color change effect was shown in Table 1.

[0052] Example 5

[0053] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 4, except that the azobenzene compound accounted for 0.5wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 4. The color-changing effects are shown in Table 1.

[0054] Example 6

[0055] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 4, except that the azobenzene compound accounted for 1wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 4. The color-changing effects are shown in Table 1.

[0056] Example 7

[0057] First, ABS is dissolved in toluene solvent to prepare a solution with a concentration of 30wt%. After it is completely dissolved, the diarylethene compound 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene is added to the polymer solution at 0.02wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0058] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 50 kHz, and the color change effect was shown in Table 1.

[0059] Example 8

[0060] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 7, except that the diarylethene compound accounted for 0.8wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 7. The color-changing effects are shown in Table 1.

[0061] Example 9

[0062] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 7, except that the diarylethene compound accounted for 2wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 7. The color-changing effects are shown in Table 1.

[0063] Example 10

[0064] First, polyvinyl alcohol is dissolved in an aqueous solvent to prepare a solution with a concentration of 20wt%. After it is completely dissolved, a fulgide compound (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furanyl)ethylidene]dihydro-2,5-furandione is added to the polymer solution at 0.005wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0065] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 80 kHz, and the color change effect was shown in Table 1.

[0066] Embodiment 11

[0067] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 10, except that the fulgide compound accounted for 0.05wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 10. The color-changing effects are shown in Table 1.

[0068] Example 12

[0069] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 10, except that the fulgide compound accounted for 0.5wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 10. The color-changing effects are shown in Table 1.

[0070] Embodiment 13

[0071] First, polyvinyl chloride is dissolved in cyclohexanone solvent to prepare a solution with a concentration of 10wt%. After it is completely dissolved, an aniline derivative compound 4-(dibenzophenazine)-N,N-diphenylaniline is added to the polymer solution at 0.06wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0072] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3.5 W, the laser frequency was 70 kHz, and the color change effect was shown in Table 1.

[0073] Embodiment 14

[0074] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 13, except that the aniline derivative compound accounted for 0.6wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 13. The color-changing effects are shown in Table 1.

[0075] Embodiment 15

[0076] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 13, except that the aniline derivative compound accounted for 1wt% of the total amount of the final color-changing composition. Other conditions were the same as those of Example 13. The color-changing effects are shown in Table 1.

[0077] Example 16

[0078] First, a polystyrene resin is dissolved in a xylene solvent to prepare a solution with a concentration of 25 wt%. After the polystyrene resin is completely dissolved, a spirooxazine compound 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3`-[3H]phenanthro[9,10-B](1,4)oxazine] is added to the polymer solution at 0.08 wt% of the total amount of the final color-changeable composition, and the mixture is stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changeable composition based on an organic material is obtained.

[0079] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 1.5 W, the laser frequency was 30 kHz, and the color change effect was shown in Table 1.

[0080] Embodiment 17

[0081] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 16, with the only difference that the spirooxazine compound accounted for 0.2 wt % of the total amount of the final color-changing composition. Other conditions were the same as those of Example 16. The color-changing effects are shown in Table 1.

[0082] Embodiment 18

[0083] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 16, except that the spirooxazine compound accounted for 0.5wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 16. The color-changing effects are shown in Table 1.

[0084] Embodiment 19

[0085] First, polyvinylidene fluoride is dissolved in a nitrogen-nitrogen dimethylformamide solvent to prepare a solution with a concentration of 5wt%. After it is completely dissolved, the polycyclic quinone compound 1-hydroxy-2-methylanthraquinone is added to the polymer solution at 0.007wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0086] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 20 kHz, and the color change effect was shown in Table 1.

[0087] Embodiment 20

[0088] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 19, with the only difference that the polycyclic quinone compound accounted for 0.07wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 19. The color-changing effects are shown in Table 1.

[0089] Embodiment 21

[0090] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 19, with the only difference that the polycyclic quinone compound accounted for 0.7wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 19. The color-changing effects are shown in Table 1.

[0091] Embodiment 22

[0092] First, polyethylene is dissolved in decahydronaphthalene solvent to prepare a solution with a concentration of 15wt%. After it is completely dissolved, benzyl viologen, a viologen compound, is added to the polymer solution at 0.03wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent evaporates, a polymer laser color-changing composition based on organic materials is obtained.

[0093] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2.5 W, the laser frequency was 60 kHz, and the color change effect was shown in Table 1.

[0094] Embodiment 23

[0095] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 22, with the only difference being that the viologen compound accounted for 0.5 wt % of the total amount of the final color-changing composition. Other conditions were the same as those of Example 22. The color-changing effects are shown in Table 1.

[0096] Embodiment 24

[0097] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 22, with the only difference that the viologen compound accounted for 2wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 22. The color-changing effect is shown in Table 1.

[0098] Embodiment 25

[0099] First, polymethyl methacrylate resin is dissolved in chloroform solvent to prepare a solution with a concentration of 10wt%. After it is completely dissolved, spiropyran compound spiro[1,3,3-trimethylindole-chroman] is added to the polymer solution at 0.005wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changeable composition based on organic materials is obtained.

[0100] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 60 kHz, and the color change effect was shown in Table 1.

[0101] Embodiment 26

[0102] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 25, with the only difference that the spiropyran compound accounted for 0.05wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 25. The color-changing effects are shown in Table 1.

[0103] Embodiment 27

[0104] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 25, with the only difference that the spiropyran compound accounted for 0.5wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 25. The color-changing effects are shown in Table 1.

[0105] Embodiment 28

[0106] First, polypropylene is dissolved in toluene solvent to prepare a solution with a concentration of 20wt%. After it is completely dissolved, the Schiff base compound salicylaldehyde Schiff base N-(parabenzoic acid)-2-hydroxybenzyl imine is added to the polymer solution at 0.005wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0107] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 90 kHz, and the color change effect was shown in Table 1.

[0108] Embodiment 29

[0109] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 28, with the only difference being that the Schiff base compound accounted for 0.1 wt % of the total amount of the final color-changing composition. Other conditions were the same as those of Example 28. The color-changing effects are shown in Table 1.

[0110] Embodiment 30

[0111] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 28, with the only difference being that the Schiff base compound accounted for 2 wt % of the total amount of the final color-changing composition. Other conditions were the same as those of Example 28. The color-changing effects are shown in Table 1.

[0112] Embodiment 31

[0113] First, polyethylene terephthalate is dissolved in m-cresol solvent to prepare a solution with a concentration of 35wt%. After it is completely dissolved, the dianthrone compound 1,9-pyrazoloanthrone is added to the polymer solution at 0.01wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0114] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 1.5 W, the laser frequency was 20 kHz, and the color change effect was shown in Table 1.

[0115] Embodiment 32

[0116] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 31, with the only difference that the dianthrone compound accounted for 0.1wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 31. The color-changing effect is shown in Table 1.

[0117] Embodiment 33

[0118] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 31, with the only difference that the dianthrone compound accounted for 1wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 31. The color-changing effect is shown in Table 1.

[0119] Embodiment 34

[0120] First, polybutylene terephthalate is dissolved in phenol solvent to prepare a solution with a concentration of 30wt%. After it is completely dissolved, the fluorene compound 3-diethylamino-6-methyl-7-phenylaminofluorane is added to the polymer solution at 0.04wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0121] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 40 kHz, and the color change effect was shown in Table 1.

[0122] Embodiment 35

[0123] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 34, with the only difference that the fluorescent hydrocarbon compound accounted for 0.4wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 34. The color-changing effect is shown in Table 1.

[0124] Embodiment 36

[0125] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 34, the only difference being that the fluorescent hydrocarbon compound accounted for 1wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 34. The color-changing effects are shown in Table 1.

[0126] Embodiment 37

[0127] First, nylon 6 is dissolved in a nitrogen-nitrogen dimethylformamide solvent to prepare a solution with a concentration of 10wt%. After it is completely dissolved, a triphenylmethane compound tris(p-dimethylaminophenyl)methane is added to the polymer solution at 0.005wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution is cast into a mold to form a film. After the solvent is evaporated, a polymer laser color-changing composition based on organic materials is obtained.

[0128] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 50 kHz, and the color change effect was shown in Table 1.

[0129] Embodiment 38

[0130] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 37, with the only difference being that the triphenylmethane compound accounted for 0.1wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 37. The color-changing effects are shown in Table 1.

[0131] Embodiment 39

[0132] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 37, with the only difference being that the triphenylmethane compound accounted for 0.2 wt % of the total amount of the final color-changing composition. Other conditions were the same as those of Example 37. The color-changing effects are shown in Table 1.

[0133] Embodiment 40

[0134] First, SBS was dissolved in cyclohexane solvent to prepare a solution with a concentration of 50wt%. After it was completely dissolved, cholesteric liquid crystal compound cholesteryl cinnamate was added to the polymer solution at 0.03wt% of the total amount of the final color-changeable composition, and stirred for 1 hour. Then, the composition solution was cast into a mold to form a film. After the solvent evaporated, a polymer laser color-changeable composition based on organic materials was obtained.

[0135] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 4 W, the laser frequency was 80 kHz, and the color change effect was shown in Table 1.

[0136] Embodiment 41

[0137] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 40, with the only difference that the cholesteric liquid crystal compound accounted for 0.3wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 40. The color-changing effects are shown in Table 1.

[0138] Embodiment 42

[0139] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 40, with the only difference that the cholesteric liquid crystal compound accounted for 3wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 40. The color-changing effects are shown in Table 1.

[0140] Embodiment 43

[0141] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 40, with the only difference that the cholesteric liquid crystal compound accounted for 5wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 40. The color-changing effects are shown in Table 1.

[0142] Embodiment 44

[0143] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 40, with the only difference that the cholesteric liquid crystal compound accounted for 10wt% of the total amount of the final color-changing composition. Other conditions were the same as in Example 40. The color-changing effect is shown in Table 1.

[0144] Comparative Example 1

[0145] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 1, except that the benzopyran compound 2-(2-thiophenecarboxamido)benzopyran accounted for 0.001 wt % of the total amount of the final color-changing composition.

[0146] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2.5 W, the laser frequency was 70 kHz, and the color change effect was shown in Table 1.

[0147] Comparative Example 2

[0148] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 1, except that the benzopyran compound 2-(2-thiophenecarboxamido)benzopyran accounted for 15 wt % of the total amount of the final color-changing composition.

[0149] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2.5 W, the laser frequency was 70 kHz, and the color change effect was shown in Table 1.

[0150] Comparative Example 3

[0151] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 1, except that the benzopyran compound 2-(2-thiophenecarboxamido)benzopyran accounted for 20 wt % of the total amount of the final color-changing composition.

[0152] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2.5 W, the laser frequency was 70 kHz, and the color change effect was shown in Table 1.

[0153] Comparative Example 4

[0154] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 4, except that the azobenzene compound 4,4'-bis(hexyloxy)-3-methylazobenzene accounted for 0.002 wt% of the total amount of the final color-changing composition.

[0155] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 90 kHz, and the color change effect was shown in Table 1.

[0156] Comparative Example 5

[0157] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 7, except that the diarylethene compound 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene accounted for 0.0025wt% of the total amount of the final color-changing composition.

[0158] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 50 kHz, and the color change effect was shown in Table 1.

[0159] Comparative Example 6

[0160] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 1, except that no organic material was added to the polycarbonate.

[0161] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2.5 W, the laser frequency was 70 kHz, and the color change effect was shown in Table 1.

[0162] Comparative Example 7

[0163] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 4, except that no organic material was added to the polyurethane.

[0164] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 90 kHz, and the color change effect was shown in Table 1.

[0165] Comparative Example 8

[0166] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 7, except that no organic material was added to ABS.

[0167] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 50 kHz, and the color change effect was shown in Table 1.

[0168] Comparative Example 9

[0169] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 10, except that no organic material was added to the polyvinyl alcohol.

[0170] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 80 kHz, and the color change effect was shown in Table 1.

[0171] Comparative Example 10

[0172] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 13, except that no organic material was added to the polyvinyl chloride.

[0173] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3.5 W, the laser frequency was 70 kHz, and the color change effect was shown in Table 1.

[0174] Comparative Example 11

[0175] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 16, except that no organic material was added to the polystyrene.

[0176] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 1.5 W, the laser frequency was 30 kHz, and the color change effect was shown in Table 1.

[0177] Comparative Example 12

[0178] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 19, except that no organic material was added to the polyvinylidene fluoride.

[0179] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 20 kHz, and the color change effect was shown in Table 1.

[0180] Comparative Example 13

[0181] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 22, except that no organic material was added to the polyethylene.

[0182] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2.5 W, the laser frequency was 60 kHz, and the color change effect was shown in Table 1.

[0183] Comparative Example 14

[0184] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 25, except that no organic material was added to the polymethyl methacrylate.

[0185] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 60 kHz, and the color change effect was shown in Table 1.

[0186] Comparative Example 15

[0187] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 28, except that no organic material was added to the polypropylene.

[0188] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 90 kHz, and the color change effect was shown in Table 1.

[0189] Comparative Example 16

[0190] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 31, except that no organic material was added to the polyethylene terephthalate.

[0191] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 1.5 W, the laser frequency was 20 kHz, and the color change effect was shown in Table 1.

[0192] Comparative Example 17

[0193] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 34, except that no organic material was added to polybutylene terephthalate.

[0194] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 2 W, the laser frequency was 40 kHz, and the color change effect was shown in Table 1.

[0195] Comparative Example 18

[0196] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 37, except that no organic material was added to nylon 6.

[0197] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 3 W, the laser frequency was 50 kHz, and the color change effect was shown in Table 1.

[0198] Comparative Example 19

[0199] A polymer laser color-changing composition based on organic materials was prepared by referring to the method of Example 40, except that no organic material was added to the SBS.

[0200] The prepared polymer film was marked under the following conditions: the laser marking equipment was a pulse fiber laser marking machine, the laser wavelength was 355 nm, the marking speed was 1000 mm / s, the laser energy was 4 W, the laser frequency was 80 kHz, and the color change effect was shown in Table 1.

[0201] The evaluation of laser color change effect is as follows:

[0202]

[0203] In the laser color change effect evaluation level, the more “+” there are, the better the laser color change effect is.

[0204] The laser color change effects of the above-mentioned Examples 1 to 44 and Comparative Examples 1 to 19 are shown in Table 1.

[0205] Table 1. Laser color change effect

[0206]

[0207]

[0208]

[0209]

[0210] The above results show that: the polymer without adding the specific organic material of the present invention cannot achieve the color change effect (Comparative Examples 6-19); after adding the specific organic material of the present invention to the polymer, the polymer can have a very excellent color change effect, and achieve a very excellent color marking on the polymer; at the same time, it can be seen from Comparative Examples 1-5 that compared with the use amount of organic material less than 0.005wt% and greater than 10wt%, the use amount of organic material is between 0.005wt% and 10wt%, and the color change effect of the polymer is better. In addition, when the organic material provided by the present invention is used in an amount as low as 0.005wt%, the laser color change effect of the obtained polymer is very good, which is very suitable for industrial production and application.

[0211] 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.

[0212] In summary, the present invention provides a color-changeable polymer material prepared based on organic materials. The present invention adds a specific organic material as an additive to a polymer to obtain a color-changeable polymer material, and the polymer material 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 a high contrast. At the same time, the polymer material is light in color, and color marks on light-colored, white or transparent polymer substrates can be achieved, which expands the application range of laser color marks. In addition, the amount of organic material used in the 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. Use of a color-changing polymer composition based on organic materials in the preparation of laser color marking; The polymer composition is composed of the following components in weight percentage: Organic materials 0.005wt%~10wt%, polymers 90wt%~99.995wt%; The organic material is selected from 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, 1,3-dihydro Any one or more of -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-hydroxybenzyl imine, 1,9-pyrazoloanthrone, 3-diethylamino-6-methyl-7-phenylaminofluoran, tris(p-dimethylaminophenyl)methane or cholesteryl cinnamate; The color-changing polymer composition will produce irreversible permanent color change after being irradiated with laser; the wavelength of the laser is 355nm.

2. The use according to claim 1, characterized in that: It is composed of the following components in weight percentage: 0.005wt%~5wt% of organic material and 95wt%~99.995wt% of polymer.

3. The use according to claim 2, characterized in that: The polymer is selected from any one or more of 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 thermoplastic elastomer, styrene-methacrylate copolymer, polyisobutylene, ethylene-vinyl acetate copolymer, polysulfone, polyimide, cellulose acetate, unsaturated polyester, silicone resin, epoxy resin, phenolic resin, melamine resin, natural rubber, butadiene rubber, silicone rubber, fluororubber, nitrile rubber, butyl rubber, and EPDM rubber.

4. The use according to claim 3, characterized in that: The styrene-based thermoplastic elastomer is selected from styrene-butadiene copolymer.

5. The use according to claim 3, characterized in that: The polymer is selected from polymethyl methacrylate, polystyrene, polycarbonate, polyurethane elastomer, acrylonitrile-butadiene-styrene copolymer, polyvinyl alcohol, polyvinyl chloride, polyvinylidene fluoride, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, nylon 6, styrene-butadiene-styrene copolymer.

6. The use according to any one of claims 1 to 5, characterized in that: The method for preparing the color-changing polymer composition comprises the following steps: a. dissolving the polymer in a solvent to obtain a polymer solution; b. Dissolve the organic material in the polymer solution, cast it into a film, and evaporate the solvent to obtain the product.

7. The use according to claim 6, characterized in that: The concentration of the polymer solution is 0.1wt%~60wt%.

8. The use according to claim 7, characterized in that: The concentration of the polymer solution is 1 wt% to 50 wt%.

9. The use according to claim 6, characterized in that: The solvent is selected from any one 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.

10. A laser color marking, characterized in that: The invention relates to an irreversible permanent color pattern or text produced by irradiating the color-changing polymer composition described in any one of claims 1 to 9 with laser; the wavelength of the laser is 355nm.

11. The laser color marking according to claim 10, characterized in that: The laser light is emitted by a Nd:YAG laser, a Nd:YVO4 laser, an excimer laser, a fiber laser, a diode array laser or a diode laser.

12. The laser color marking according to claim 11, characterized in that: The laser is emitted by a pulsed Nd:YAG laser or a pulsed fiber laser; the wavelength of the laser is 355 nm.

13. The laser color marking according to claim 12, characterized in that: The laser energy is 0.5-8W; and / or the laser frequency is 10-100kHz; and / or the laser marking speed is 400-4000mm / s.

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