CN110408165B - Color change additive for manufacturing white or light-colored mark and preparation method thereof - Google Patents

Color change additive for manufacturing white or light-colored mark and preparation method thereof Download PDF

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CN110408165B
CN110408165B CN201910735930.4A CN201910735930A CN110408165B CN 110408165 B CN110408165 B CN 110408165B CN 201910735930 A CN201910735930 A CN 201910735930A CN 110408165 B CN110408165 B CN 110408165B
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ethylene
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propylene
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CN110408165A (en
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周涛
冯金
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K3/08—Metals
    • C08K2003/0806—Silver
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a color change auxiliary agent which comprises the following raw materials in parts by weight: 0.05 to 10.00 parts of laser absorbent, 20.00 to 80.00 parts of thermoplastic polymer and 10.00 to 79.95 parts of carrier polymer; the thermoplastic polymer is polyacrylate resin, polyformaldehyde resin, styrene-acrylonitrile resin, acrylate-styrene resin or ABS resin. The invention further discloses the application of the color change additive in marking on colored polymers. Experiments prove that after the color change additive is added into polymers with different colors in a certain amount, light-color to white marks can be efficiently marked on the polymers with different colors; moreover, the preparation method of the color-changing auxiliary agent disclosed by the invention is simple, easy to operate, safe, environment-friendly and low in energy consumption, is very suitable for industrial large-scale production, and has good economic benefit.

Description

Color change additive for manufacturing white or light-colored mark and preparation method thereof
Technical Field
The invention belongs to the field of polymer material additives, and particularly relates to a color change additive for marking white or light-colored patterns and characters on a colored polymer and a preparation method thereof.
Background
Laser marking is a method of irradiating a material with high-energy laser light to cause carbonization, discoloration, vaporization, foaming, etc. of the surface of the material, thereby leaving a permanent mark. Compared with traditional methods such as ink printing, screen printing, stamping, hot stamping and the like, laser marking has the advantages of high precision, no contact, high efficiency, low cost, cleanness, no pollution and the like, and is gradually becoming a popular marking mode.
In order to achieve laser marking, a laser color-changing assistant is usually added to the material to be marked. However, the current laser marking method can only generate white or light-colored marks on the surface of a black (or black gray, gray) polymer material, and mainly utilizes a laser absorber to absorb laser energy, so that a black polymer matrix generates complex chemical and physical changes under the action of laser to generate white or light-colored marks. For example: chinese patent CN 104804360B discloses an impact resistant ABS resin composition with white laser marking function printed on black matrix, which can only be white marked by laser marking.
However, new application scenarios set forth the need to generate white or light-colored marks on the surface of a polymeric material with a colored substrate (e.g., red, blue, yellow, green, purple, etc. in single colors or in mixed colors) using a laser. The color-changing auxiliary agent in the prior art can only mark black polymers in light color, and cannot mark white or light color of polymers with different colors, so that the application of the color-changing auxiliary agent is greatly limited.
Therefore, there is a need in the art for a laser discoloration aid that can be conveniently used to mark various colored polymers with white or light colors.
Disclosure of Invention
After extensive experimental research and evaluation, the present inventors have unexpectedly discovered a class of color change aids that specifically combines a laser absorber, a thermoplastic polymer, and a carrier polymer to perfectly fulfill the above-mentioned needs.
The invention aims to design and prepare a laser color-changing auxiliary agent, which can endow various colored matrixes (such as single colors or mixed colors of red, blue, yellow, green, purple and the like) with the white or light-colored laser marking capability. The preparation method of the laser color-changing assistant is simple and is suitable for industrial scale production and preparation. It is another object of the present invention to provide specific uses of such laser color change aids.
The invention provides a color change auxiliary agent which comprises the following raw materials in parts by weight: 0.05 to 10.00 parts of laser absorbent, 20.00 to 80.00 parts of thermoplastic polymer and 10.00 to 79.95 parts of carrier polymer;
the thermoplastic polymer is polyacrylate resin, polyformaldehyde resin, styrene-acrylonitrile resin, acrylate-styrene resin or ABS resin.
Further, the color change assistant comprises the following raw materials in parts by weight: 0.05 to 6.50 parts of laser absorbent, 20.00 to 60.00 parts of thermoplastic polymer and 38.00 to 79.95 parts of carrier polymer.
Further, the thermoplastic polymer is selected from one or more than two of polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyformaldehyde, transparent ABS, styrene-acrylonitrile copolymer, styrene-acrylonitrile-acrylate copolymer, methacrylate-styrene copolymer and methacrylate-butadiene-styrene copolymer;
preferably, the thermoplastic polymer is any one or more of homo-polyformaldehyde, co-polyformaldehyde, a styrene-acrylonitrile copolymer, a styrene-acrylonitrile-methyl methacrylate copolymer and polymethyl methacrylate.
Further, the laser absorber is selected from any one or more of metal powder, metal oxide, metal salt, inorganic thin sheet coated by metal oxide, or carbon material;
the metal powder is selected from any one or more than two of silver, iron, copper, tin, tungsten, titanium, chromium, nickel, gold, indium, zinc, antimony, aluminum, magnesium or alloy thereof;
the metal oxide is selected from one or more of antimony trioxide, tin dioxide, titanium dioxide, tin antimony oxide, indium tin oxide, bismuth trioxide, copper oxide, ferroferric oxide, bismuth oxychloride, zinc oxide, molybdenum oxide, ferric oxide, aluminum oxide and magnesium oxide;
the metal salt is selected from one or more than two of copper chromate, calcium silicate, hydroxyl copper phosphate, copper orthophosphate, calcium zirconate, zirconium silicate, barium titanate, calcium titanate, magnesium titanate and strontium titanate;
the inorganic flake coated with the metal oxide is any one or more than two of mica flake coated with the metal oxide, alumina flake coated with the metal oxide, glass flake coated with the metal oxide and ceramic flake coated with the metal oxide;
the carbon material is selected from one or more of graphene, carbon black and carbon nanotubes.
Furthermore, the particle size of the laser absorbent is 10.0 nm-200.0 μm; preferably, the laser absorber has a particle size of 20.0nm to 70.0. mu.m.
Further, the carrier polymer is selected from the group consisting of high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, propylene-octene copolymer, propylene-butene copolymer, ethylene-octene copolymer, ethylene-butene copolymer, ethylene-propylene-octene terpolymer, ethylene-propylene-butene terpolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl ester grafted polyethylene, glycidyl ester grafted polypropylene, maleic anhydride grafted polypropylene, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, ethylene-glycidyl ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, propylene-octene copolymer, propylene-butene copolymer, ethylene-butene copolymer, ethylene-butene-propylene-butene copolymer, ethylene-butene-copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-butene-propylene-copolymer, ethylene-propylene-butene copolymer, ethylene-propylene copolymer, ethylene-propylene copolymer, ethylene-propylene copolymer, ethylene-propylene, Any one or more of ethylene-acrylate-glycidyl methacrylate copolymer, ethylene-acrylate-maleic anhydride copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, SEBS, SEPS and SEEPS.
The invention also provides a method for preparing the color change auxiliary agent, which comprises the following steps: uniformly mixing the laser absorbent, the thermoplastic polymer and the carrier polymer, and then melting, extruding and granulating the obtained mixture to obtain the composite material;
wherein the melt extrusion equipment is an internal mixer or an extruder.
The invention also provides the application of the color change auxiliary agent as a laser color change auxiliary agent in marking white or light-colored characters or patterns on a colored polymer.
Further, the addition amount of the color-changing additive in the colored polymer is 2-60.0 wt.%.
In the present invention, "light color" means various pale white, silvery white, pale gray, silvery, various silvery grays, and the like.
In the present invention, color refers to a single common color such as red, blue, orange, yellow, cyan, green, purple, etc., or various mixed colors of the above colors, and also refers to an illusion color (e.g., a phenomenon of different colors appearing at different viewing angles) generated by various pearlescent pigments. It should be noted that the colors black, grayblack, gray, white, pale gray, and the like do not fall within the scope of the color defined in the present invention.
"ABS-based resin" refers to acrylonitrile-butadiene-styrene copolymer and its derivatives. Including transparent ABS and non-transparent ABS.
"SEBS" is a block copolymer having polystyrene as an end block and hydrogenated polybutadiene obtained by hydrogenating polybutadiene as a middle elastic block.
"SEPS" is a hydrogenated isoprene-styrene block copolymer.
"SEEPS" is a hydrogenated isoprene-hydrogenated butadiene-styrene block copolymer.
The melt extrusion temperature of the materials in the preparation process of the laser color-changing additive is the corresponding melt blending temperature in the common polymer processing, and the extrusion temperature in the preparation process is determined according to the melt temperature of the used polymer.
The laser color-changing assistant of the invention is suitable for various colored matrix polymers, which are obtained by adding coloring agents with different colors into the polymers to color the polymers, such as various inorganic pigments, pearlescent pigments, organic pigments, dyes and the like, and belongs to the common knowledge in the field. Polymers of the above matrix include, but are not limited to, PP, PE, PC, PA6, PA66, SAN, ABS, PS, PBT, PET, PEN, PVC, POM, SEBS, TPU, TPE, and TPV.
The color-changing auxiliary agent disclosed by the invention is suitable for being used at the wavelength of 157nm to 10.Laser between 6 μm; the laser emitting the above wavelength has CO2Laser (10.6 μm), Nd: YAG or Nd: YVO4Lasers (1064, 532, 355 and 266nm), excimer lasers (F)2(157nm), ArF (193nm), KrCl (222nm), KrF (248nm), XeCl (308nm) and XeF (351nm)), a fiber laser, a diode array laser, a diode laser, and the like.
Preferably, pulsed Nd: YAG lasers and pulsed fiber lasers are used, with 1064nm, 532nm and 355nm pulsed lasers being particularly suitable.
Experimental results show that the invention discloses a laser color change auxiliary agent, which can be added into polymers of various colored matrixes to efficiently mark white and light colors on the surfaces of the polymers by using laser. The preparation process of the laser color-changing assistant is simple and efficient, is simple and convenient to operate, is safe and environment-friendly, has low energy consumption, and is very suitable for industrial large-scale production.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims. For terms not specifically defined herein, the meanings that would be given to them by a person skilled in the art are to be given in light of the disclosure and the context.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a photograph showing the effect of laser marking on a standard sample prepared in example 7 with a color-changing aid added.
Detailed Description
The starting materials used in the practice of the present invention are all known products and are obtained by purchasing commercially available products.
(1) The device information used by the present invention is as follows:
a double-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 36:1, and the extruder is produced by Nanjing Jennent electromechanical limited company;
injection molding machine, model K-TEC 40, produced by Miracolon International Inc.;
laser marking machine, model MK-GQ10B, fiber pulse laser marking machine, laser maximum power 10W, laser wavelength 1064 nm.
(2) The specific information of the matrix polymer used to prepare the standard panels of the present invention is as follows:
polyethylene (PE): the metallocene petrochemical, TR144, a high density polyethylene;
polypropylene (PP): china petrochemical lanzhou division, T30S;
thermoplastic Polyurethane (TPU): wanhua, 1510;
ABS: taiwan qimei, 747;
nylon 6(PA 6): japan department of Japan, 1013B.
Example 1
Laser light absorber: silver powder, particle diameter (D)50) 0.4 μm;
thermoplastic polymer (b): polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
carrier polymer (b): ethylene-octene copolymers (POE), dupont 8200;
putting 80 parts by weight of polyformaldehyde, 10 parts by weight of silver powder and 10 parts by weight of ethylene-octene copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled between 180 and 230 ℃;
then, adding the obtained laser color-changing assistant into polypropylene resin particles in an amount of 2 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color.
Example 2
Laser light absorber: silver powder, particlesDiameter (D)50) 0.4 μm;
thermoplastic polymer (b): polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
carrier polymer 1: ethylene-octene copolymers (POE), dupont 8200;
carrier polymer 2: ethylene-methyl acrylate-glycidyl methacrylate copolymer, dupont PTW.
Putting 80 parts by weight of polyformaldehyde, 10 parts by weight of silver powder, 7 parts by weight of ethylene-octene copolymer and 3 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled between 180 and 230 ℃;
then, adding the obtained laser color-changing assistant into polypropylene resin particles in an amount of 2 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color.
Example 3
Laser light absorber: silver powder, particle diameter (D)50) 0.4 μm; titanium dioxide, particle diameter (D)50) 0.6 μm;
thermoplastic polymer (b): polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
carrier polymer 1: ethylene-octene copolymers (POE), dupont 8200;
carrier polymer 2: ethylene-methyl acrylate-glycidyl methacrylate copolymer, dupont PTW.
Putting 80 parts by weight of polyformaldehyde, 8 parts by weight of silver powder, 2 parts by weight of titanium dioxide, 7 parts by weight of ethylene-octene copolymer and 3 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled between 180 and 230 ℃;
then, adding the obtained laser color-changing assistant into polypropylene resin particles in an amount of 2 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color.
Example 4
Laser light absorber: indium tin oxide with a particle size (D50) of 10 nm;
thermoplastic polymer (b): styrene-acrylonitrile copolymer (SAN), korean LG 80 HF;
carrier polymer 1: polyethylene (PE), majestic TR144, a high density polyethylene;
placing 20 parts by weight of styrene-acrylonitrile copolymer, 0.05 part by weight of indium tin oxide and 79.95 parts by weight of polyethylene into a high-speed mixer for uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled to be 210-250 ℃;
then, adding the obtained laser color-changing assistant into ABS resin particles by 60 wt%, simultaneously adding 0.3 wt% of solvent blue 70 (dye blue), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and (3) directly carrying out injection molding on the finally obtained blue granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with blue bottom color.
Example 5
Laser light absorber: indium tin oxide with a particle size (D50) of 10 nm;
thermoplastic polymer (b): styrene-acrylonitrile copolymer (SAN), korean LG 80 HF;
carrier polymer 1: polyethylene (PE), majestic TR144, a high density polyethylene;
carrier polymer 2: thermoplastic elastomer SEBS, american kraton G1657.
Placing 20 parts by weight of styrene-acrylonitrile copolymer, 0.05 part by weight of indium tin oxide, 69.95 parts by weight of polyethylene and 10 parts by weight of SEBS into a high-speed mixer for uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled to be 210-250 ℃;
then, adding the obtained laser color-changing assistant into ABS resin particles by 60 wt%, simultaneously adding 0.3 wt% of solvent blue 70 (dye blue), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and (3) directly carrying out injection molding on the finally obtained blue granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with blue bottom color.
Example 6
Laser light absorber: calcium titanate, particle diameter (D)50) 43 μm;
thermoplastic polymer (b): styrene-acrylonitrile-methyl methacrylate copolymer, german degussel XT polymer 250;
carrier polymer 1: ethylene Vinyl Acetate (EVA), dupont 40W;
putting 60 parts by weight of styrene-acrylonitrile-methyl methacrylate copolymer, 2 parts by weight of calcium titanate and 38 parts by weight of ethylene-vinyl acetate copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled to be 210-235 ℃;
then, adding the obtained laser color-changing assistant into nylon 6 resin particles in an amount of 25 wt%, adding 1 wt% of pigment yellow 184 (inorganic bismuth yellow), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-235 ℃; and (3) directly carrying out injection molding on the obtained lemon yellow granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with the bottom color of lemon yellow.
Example 7
Laser light absorber: calcium titanate, particle diameter (D)50) 43 μm;
thermoplastic polymer (b): styrene-acrylonitrile-methyl methacrylate copolymer, german degussel XT polymer 250;
carrier polymer 1: ethylene Vinyl Acetate (EVA), dupont 40W;
carrier polymer 2: ethylene-acrylic acid copolymer (EAA), dow 3003;
putting 60 parts by weight of styrene-acrylonitrile-methyl methacrylate copolymer, 2 parts by weight of calcium titanate, 19 parts by weight of ethylene-vinyl acetate copolymer and 19 parts by weight of ethylene-acrylic acid copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled to be 210-235 ℃;
then, adding the obtained laser color-changing assistant into nylon 6 resin particles in an amount of 25 wt%, adding 1 wt% of pigment yellow 184 (inorganic bismuth yellow), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-235 ℃; and (3) directly carrying out injection molding on the obtained lemon yellow granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with the bottom color of lemon yellow.
Example 8
Laser light absorber: metal oxide coated mica flakes, Merck Iriotec 8825, Germany, particle size (D)50) Is 10-17 μm;
thermoplastic polymer (b): styrene-acrylonitrile copolymer (SAN), korean LG 80 HF;
carrier polymer 1: polypropylene (PP), medium petrochemical, lanzhou division T30S;
carrier polymer 2: ethylene-acrylic acid copolymer (EAA), dow 3003;
placing 40 parts by weight of styrene-acrylonitrile copolymer, 6 parts by weight of metal oxide coated mica flake, 40 parts by weight of polypropylene and 14 parts by weight of ethylene-acrylic acid copolymer into a high-speed mixer for uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled to be 210-250 ℃;
then, adding the obtained laser color-changing assistant into Thermoplastic Polyurethane (TPU) particles in an amount of 40 wt%, simultaneously adding 0.5 wt% of pigment green 50 (inorganic cobalt green), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and directly injection-molding the finally obtained green granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing the standard sample plate with green ground color.
Example 9
Laser light absorber: graphene, with a lamella thickness of 6.8nm and an average lamella diameter of 86 μm;
thermoplastic polymer (b): polymethyl methacrylate, degussa 8NDF 21;
carrier polymer 1: ethylene-octene copolymers (POE), dupont 8200;
carrier polymer 2: ethylene Vinyl Acetate (EVA), dupont 40W; (ii) a
Putting 30 parts by weight of polymethyl methacrylate, 0.6 part by weight of graphene, 68 parts by weight of ethylene-octene copolymer and 1.4 parts by weight of ethylene-vinyl acetate copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled between 200 ℃ and 230 ℃;
then, adding the obtained laser color-changing assistant into polyethylene particles in an amount of 12 wt%, adding 0.2 wt% of pigment orange 36 (organic orange), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 150-180 ℃; and (3) directly carrying out injection molding on the finally obtained orange granules in an injection molding machine, controlling the injection molding temperature to be 130-160 ℃, and preparing the standard sample plate with orange bottom color.
Example 10
Laser light absorber: graphene, with a lamella thickness of 3.4nm and an average lamella diameter of 53 μm; antimony trioxide, particle size (D50) 5 μm;
thermoplastic polymer (b): styrene-acrylonitrile-methyl methacrylate copolymer, german degussel XT polymer 250;
carrier polymer 1: ethylene-octene copolymers (POE), dupont 8200;
carrier polymer 2: ethylene Vinyl Acetate (EVA), dupont 40W;
placing 30 parts by weight of styrene-acrylonitrile-methyl methacrylate copolymer, 0.5 part by weight of graphene, 6 parts by weight of antimony trioxide, 58 parts by weight of ethylene-octene copolymer and 5.5 parts by weight of ethylene-vinyl acetate copolymer in a high-speed mixer for uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled to be 210-240 ℃;
then, adding the obtained laser color-changing assistant into polyethylene particles by 35 wt%, adding 0.2 wt% of pigment orange 36 (organic orange), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-240 ℃; and (3) directly carrying out injection molding on the finally obtained orange granules in an injection molding machine, controlling the injection molding temperature to be 210-230 ℃, and preparing the standard sample plate with orange bottom color.
Comparative example 1
Laser light absorber: silver powder, particle diameter (D)50) 0.4 μm;
only adding the laser absorber silver powder into polypropylene resin particles in an amount of 0.2 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color. The content of silver powder in the polypropylene resin was exactly the same as in example 1.
Comparative example 2
Laser light absorber: silver powder, particle diameter (D)50) 0.4 μm;
thermoplastic polymer (b): polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
putting 80 parts by weight of polyformaldehyde and 10 parts by weight of silver powder into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 180 and 230 ℃;
then, adding the obtained blend into polypropylene resin particles in an amount of 1.8 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color. The contents of the silver powder and the polyoxymethylene in the polypropylene resin were exactly the same as in example 1.
Comparative example 3
Laser light absorber: silver powder, particle diameter (D)50) 0.4 μm;
carrier polymer (b): ethylene-octene copolymers (POE), dupont 8200;
putting 10 parts by weight of silver powder and 10 parts by weight of ethylene-octene copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 180 and 230 ℃;
then, adding the obtained blend into polypropylene resin particles in an amount of 0.4 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color. The contents of the silver powder and the ethylene-octene copolymer in the polypropylene resin were exactly the same as in example 1.
Comparative example 4
Laser light absorber: silver powder, particle diameter (D)50) 0.4 μm;
carrier polymer 1: ethylene-octene copolymers (POE), dupont 8200;
carrier polymer 2: ethylene-methyl acrylate-glycidyl methacrylate copolymer, dupont PTW.
Putting 10 parts by weight of silver powder, 7 parts by weight of ethylene-octene copolymer and 3 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 180 and 230 ℃;
then, adding the obtained blend into polypropylene resin particles in an amount of 0.4 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color. The contents of the silver powder, the ethylene-octene copolymer and the ethylene-methyl acrylate-glycidyl methacrylate copolymer in the polypropylene resin were exactly the same as in example 2.
Comparative example 5
Thermoplastic polymer (b): polyoxymethylene (POM), shenhua MC90, a copolyformaldehyde;
carrier polymer 1: ethylene-octene copolymers (POE), dupont 8200;
carrier polymer 2: ethylene-methyl acrylate-glycidyl methacrylate copolymer, dupont PTW.
Putting 80 parts by weight of polyformaldehyde, 7 parts by weight of ethylene-octene copolymer and 3 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled between 180 and 230 ℃;
then, adding the obtained blend into polypropylene resin particles in an amount of 1.8 wt%, adding 0.1 wt% of pigment red 254 (organic red), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 170-220 ℃; and (3) directly carrying out injection molding on the finally obtained red granules in an injection molding machine, controlling the injection molding temperature to be 180-220 ℃, and preparing the standard sample plate with red bottom color. The contents of polyoxymethylene, ethylene-octene copolymer and ethylene-methyl acrylate-glycidyl methacrylate copolymer in the polypropylene resin were exactly the same as in example 2.
Comparative example 6
Laser light absorber: indium tin oxide with a particle size (D50) of 10 nm;
then, adding the laser absorber indium tin oxide into ABS resin particles in an amount of 0.03 wt%, simultaneously adding 0.3 wt% of solvent blue 70 (dye blue), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and (3) directly carrying out injection molding on the finally obtained blue granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with blue bottom color. The content of indium tin oxide in the ABS resin was exactly the same as in example 4.
Comparative example 7
Laser light absorber: indium tin oxide with a particle size (D50) of 10 nm;
thermoplastic polymer (b): styrene-acrylonitrile copolymer (SAN), korean LG 80 HF;
placing 20 parts by weight of styrene-acrylonitrile copolymer and 0.05 part by weight of indium tin oxide into a high-speed mixer to be uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-250 ℃;
then, adding the obtained blend into ABS resin particles in an amount of 12.03 wt%, adding 0.3 wt% of solvent blue 70 (dye blue), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and (3) directly carrying out injection molding on the finally obtained blue granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with blue bottom color. The contents of indium tin oxide and styrene-acrylonitrile copolymer in the ABS resin were exactly the same as in example 4.
Comparative example 8
Laser light absorber: indium tin oxide with a particle size (D50) of 10 nm;
carrier polymer 1: polyethylene (PE), majestic TR144, a high density polyethylene;
carrier polymer 2: thermoplastic elastomer SEBS, american kraton G1657.
Putting 0.05 weight part of indium tin oxide, 69.95 weight parts of polyethylene and 10 weight parts of SEBS into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-250 ℃;
then, adding the obtained blend into ABS resin particles by 48 wt%, simultaneously adding 0.3 wt% of solvent blue 70 (dye blue), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and (3) directly carrying out injection molding on the finally obtained blue granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with blue bottom color. The contents of indium tin oxide, polyethylene and SEBS in the ABS resin were exactly the same as in example 5.
Comparative example 9
Laser light absorber: calcium titanate, particle diameter (D)50) 43 μm;
adding 0.5 wt% of laser absorbent calcium titanate into nylon 6 resin particles, simultaneously adding 1 wt% of pigment yellow 184 (inorganic bismuth yellow), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-235 ℃; and (3) directly carrying out injection molding on the obtained lemon yellow granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with the bottom color of lemon yellow. The content of calcium titanate in the nylon 6 resin was exactly the same as in example 6.
Comparative example 10
Laser light absorber: calcium titanate, particle diameter (D)50) 43 μm;
thermoplastic polymer (b): styrene-acrylonitrile-methyl methacrylate copolymer, german degussel XT polymer 250;
putting 60 parts by weight of styrene-acrylonitrile-methyl methacrylate copolymer and 2 parts by weight of calcium titanate into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-235 ℃;
then, adding the obtained blend into nylon 6 resin particles in an amount of 15.5 wt%, adding 1 wt% of pigment yellow 184 (inorganic bismuth yellow), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-235 ℃; and (3) directly carrying out injection molding on the obtained lemon yellow granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with the bottom color of lemon yellow. The contents of calcium titanate and styrene-acrylonitrile-methyl methacrylate copolymer in the nylon 6 resin were exactly the same as in example 6.
Comparative example 11
Laser light absorber: calcium titanate, particle diameter (D)50) 43 μm;
carrier polymer 1: ethylene Vinyl Acetate (EVA), dupont 40W;
carrier polymer 2: ethylene-acrylic acid copolymer (EAA), dow 3003;
2 parts by weight of calcium titanate, 19 parts by weight of ethylene-vinyl acetate copolymer and 19 parts by weight of ethylene-acrylic acid copolymer are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-235 ℃;
then, adding the obtained blend into nylon 6 resin particles by 10 wt%, simultaneously adding 1 wt% of pigment yellow 184 (inorganic bismuth yellow), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-235 ℃; and (3) directly carrying out injection molding on the obtained lemon yellow granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with the bottom color of lemon yellow. The contents of calcium titanate, ethylene-vinyl acetate copolymer and ethylene-acrylic acid copolymer in the nylon 6 resin were exactly the same as in example 7.
Comparative example 12
Thermoplastic polymer (b): styrene-acrylonitrile-methyl methacrylate copolymer, german degussel XT polymer 250;
carrier polymer 1: ethylene Vinyl Acetate (EVA), dupont 40W;
carrier polymer 2: ethylene-acrylic acid copolymer (EAA), dow 3003;
putting 60 parts by weight of styrene-acrylonitrile-methyl methacrylate copolymer, 19 parts by weight of ethylene-vinyl acetate copolymer and 19 parts by weight of ethylene-acrylic acid copolymer into a high-speed mixer, and uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the laser color change additive. The temperature in the blending extrusion processing process is controlled to be 210-235 ℃;
then, adding the obtained laser color-changing assistant into nylon 6 resin particles in an amount of 24.5 wt%, adding 1 wt% of pigment yellow 184 (inorganic bismuth yellow), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-235 ℃; and (3) directly carrying out injection molding on the obtained lemon yellow granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing a standard sample plate with the bottom color of lemon yellow. The contents of styrene-acrylonitrile-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer and ethylene-acrylic acid copolymer in the nylon 6 resin were exactly the same as in example 7.
Comparative example 13
Laser light absorber: metal oxide coated mica flakes, Merck Iriotec 8825, Germany, particle size (D)50) Is 10-17 μm;
adding Iriotec 8825 in an amount of 2.4 wt% into Thermoplastic Polyurethane (TPU) particles, adding 0.5 wt% of pigment green 50 (inorganic cobalt green), blending by a double-screw extruder, and granulating at an extrusion temperature of 220-250 ℃; and directly injection-molding the finally obtained green granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing the standard sample plate with green ground color. The content of Iriotec 8825 in the Thermoplastic Polyurethane (TPU) was exactly the same as in example 8.
Comparative example 14
Laser light absorber: metal oxide coated mica flakes, Merck Iriotec 8825, Germany, particle size (D)50) Is 10-17 μm;
thermoplastic polymer (b): styrene-acrylonitrile copolymer (SAN), korean LG 80 HF;
placing 40 parts by weight of styrene-acrylonitrile copolymer and 6 parts by weight of metal oxide coated mica flakes into a high-speed mixer to be uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-250 ℃;
then, adding the obtained blend into Thermoplastic Polyurethane (TPU) particles in an amount of 18.4 wt%, adding 0.5 wt% of pigment green 50 (inorganic cobalt green), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and directly injection-molding the finally obtained green granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing the standard sample plate with green ground color. The content of Iriotec 8825 and styrene-acrylonitrile copolymer in the Thermoplastic Polyurethane (TPU) was exactly the same as in example 8.
Comparative example 15
Laser light absorber: metal oxide coated mica flakes, Merck Iriotec 8825, Germany, particle size (D)50) Is 10-17 μm;
carrier polymer 1: polypropylene (PP), medium petrochemical, lanzhou division T30S;
carrier polymer 2: ethylene-acrylic acid copolymer (EAA), dow 3003;
6 parts by weight of metal oxide-coated mica flakes, 40 parts by weight of polypropylene and 14 parts by weight of ethylene-acrylic acid copolymer are placed in a high-speed mixer and uniformly mixed; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-250 ℃;
then, adding the obtained blend into Thermoplastic Polyurethane (TPU) particles in an amount of 24 wt%, adding 0.5 wt% of pigment green 50 (inorganic cobalt green), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 220-250 ℃; and directly injection-molding the finally obtained green granules in an injection molding machine, controlling the injection molding temperature to be 220-240 ℃, and preparing the standard sample plate with green ground color. The content of Iriotec 8825, polypropylene, and ethylene acrylic acid copolymer in the Thermoplastic Polyurethane (TPU) was exactly the same as in example 8.
Comparative example 16
Laser light absorber: graphene, with a lamella thickness of 3.4nm and an average lamella diameter of 53 μm; antimony trioxide, particle size (D50) 5 μm;
adding 0.175 wt% of graphene and 2.1 wt% of antimony trioxide into polyethylene particles, adding 0.2 wt% of pigment orange 36 (organic orange), blending by a double-screw extruder, granulating, and extruding at the temperature of 210-240 ℃; and (3) directly carrying out injection molding on the finally obtained orange granules in an injection molding machine, controlling the injection molding temperature to be 210-230 ℃, and preparing the standard sample plate with orange bottom color. The contents of graphene and antimony trioxide in the polyethylene resin were exactly the same as in example 10.
Comparative example 17
Laser light absorber: graphene, with a lamella thickness of 3.4nm and an average lamella diameter of 53 μm; antimony trioxide, particle size (D50) 5 μm;
thermoplastic polymer (b): styrene-acrylonitrile-methyl methacrylate copolymer, german degussel XT polymer 250;
placing 30 parts by weight of styrene-acrylonitrile-methyl methacrylate copolymer, 0.5 part by weight of graphene and 6 parts by weight of antimony trioxide in a high-speed mixer for uniform mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-240 ℃;
then, adding 12.775 wt% of the obtained blend into polyethylene particles, simultaneously adding 0.2 wt% of pigment orange 36 (organic orange), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-240 ℃; and (3) directly carrying out injection molding on the finally obtained orange granules in an injection molding machine, controlling the injection molding temperature to be 210-230 ℃, and preparing the standard sample plate with orange bottom color. The contents of graphene, antimony trioxide and styrene-acrylonitrile-methyl methacrylate copolymer in the polyethylene resin were exactly the same as in example 10.
Comparative example 18
Laser light absorber: graphene, with a lamella thickness of 3.4nm and an average lamella diameter of 53 μm; antimony trioxide, particle size (D50) 5 μm;
carrier polymer 1: ethylene-octene copolymers (POE), dupont 8200;
carrier polymer 2: ethylene Vinyl Acetate (EVA), dupont 40W;
placing 0.5 part by weight of graphene, 6 parts by weight of antimony trioxide, 58 parts by weight of ethylene-octene copolymer and 5.5 parts by weight of ethylene-vinyl acetate copolymer in a high-speed mixer for uniformly mixing; and adding the mixed materials into a double-screw extruder, blending, extruding and granulating to obtain the blend. The temperature in the blending extrusion processing process is controlled to be 210-240 ℃;
then, adding the obtained blend into polyethylene particles in an amount of 24.5 wt%, adding 0.2 wt% of pigment orange 36 (organic orange), blending by a double-screw extruder, and granulating, wherein the extrusion temperature is 210-240 ℃; and (3) directly carrying out injection molding on the finally obtained orange granules in an injection molding machine, controlling the injection molding temperature to be 210-230 ℃, and preparing the standard sample plate with orange bottom color. The contents of graphene, antimony trioxide, ethylene-octene copolymer and ethylene-vinyl acetate copolymer in the polyethylene resin were exactly the same as in example 10.
The beneficial effects of the laser color change assistant of the invention are demonstrated by the following experimental examples.
Experimental example 1 laser marking Effect test
1. Experimental methods
The standard samples prepared in all examples and comparative examples were evaluated for laser marking using the following conditions. The laser scanning speed is 1000mm/s, the laser energy is 10W, and the laser frequency is 100 kHz.
The formula composition of all examples and comparative examples is shown in table 1, and the amount of each component in table 1 is calculated by weight; the laser marking effect is shown in table 2.
The evaluation criteria for laser effect were as follows:
Figure BDA0002162159910000151
in the evaluation of the laser light marking effect, the larger the number of "+" indicates the better the laser light marking effect.
TABLE 1 formulation composition
Figure BDA0002162159910000161
Figure BDA0002162159910000171
Figure BDA0002162159910000181
Figure BDA0002162159910000191
Figure BDA0002162159910000201
TABLE 2 evaluation results of laser marking effect
Figure BDA0002162159910000202
Figure BDA0002162159910000211
Figure BDA0002162159910000221
2. Results of the experiment
The evaluation results of the light-colored laser marking are shown in Table 2. It can be seen that by adding the laser color change additive of the present invention to the matrix polymer, highly effective light-colored or white marks can be achieved on various different colored polymers, with marking effects much better than the templates prepared in comparative examples 1-18. Especially, examples 5 to 8 are best marked by laser light coloring. It is shown that the laser color-changing assistant obtained under the combined action of the laser absorber, the thermoplastic polymer and the carrier polymer of the invention can obtain excellent light color or white marking effect.
In summary, the present invention selects a specific thermoplastic polymer, combines a laser absorber, a thermoplastic polymer, and a carrier polymer at a specific ratio to obtain a laser discoloration aid, and after the discoloration aid is added to polymers of various colored substrates, white and light color marking can be efficiently performed on the surface thereof by laser. The preparation process of the laser color-changing assistant is simple and efficient, is simple and convenient to operate, is safe and environment-friendly, has low energy consumption, and is very suitable for industrial large-scale production.

Claims (12)

1. A color-changing additive, characterized in that: the color change auxiliary agent is prepared from the following raw materials in parts by weight: 0.05 to 10.00 parts of laser absorbent, 20.00 to 80.00 parts of thermoplastic polymer and 10.00 to 79.95 parts of carrier polymer;
the thermoplastic polymer is polyacrylate resin, polyformaldehyde resin, styrene-acrylonitrile resin, acrylate-styrene resin or ABS resin.
2. The color-changing aid according to claim 1, wherein: the color change auxiliary agent is prepared from the following raw materials in parts by weight: 0.05 to 6.50 parts of laser absorbent, 20.00 to 60.00 parts of thermoplastic polymer and 38.00 to 79.95 parts of carrier polymer.
3. The color-changing aid according to claim 1, wherein: the thermoplastic polymer is selected from one or more of polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyformaldehyde, ABS, styrene-acrylonitrile copolymer, styrene-acrylonitrile-acrylate copolymer, methacrylate-styrene copolymer and methacrylate-butadiene-styrene copolymer.
4. The color-changing aid of claim 3, wherein: the thermoplastic polymer is any one or more than two of homo-polyformaldehyde, co-polyformaldehyde, a styrene-acrylonitrile copolymer, a styrene-acrylonitrile-methyl methacrylate copolymer or polymethyl methacrylate.
5. The color-changing aid of claim 3, wherein: the ABS is transparent ABS.
6. The color-changing aid according to any one of claims 1 to 5, wherein: the laser absorbent is selected from one or more of metal powder, metal oxide, metal salt, inorganic thin sheet coated by metal oxide, or carbon material;
the metal powder is selected from any one or more than two of silver, iron, copper, tin, tungsten, titanium, chromium, nickel, gold, indium, zinc, antimony, aluminum, magnesium or alloy thereof;
the metal oxide is selected from one or more of antimony trioxide, tin dioxide, titanium dioxide, tin antimony oxide, indium tin oxide, bismuth trioxide, copper oxide, ferroferric oxide, bismuth oxychloride, zinc oxide, molybdenum oxide, ferric oxide, aluminum oxide and magnesium oxide;
the metal salt is selected from one or more than two of copper chromate, calcium silicate, hydroxyl copper phosphate, copper orthophosphate, calcium zirconate, zirconium silicate, barium titanate, calcium titanate, magnesium titanate and strontium titanate;
the inorganic flake coated with the metal oxide is any one or more than two of mica flake coated with the metal oxide, alumina flake coated with the metal oxide, glass flake coated with the metal oxide and ceramic flake coated with the metal oxide;
the carbon material is selected from one or more of graphene, carbon black and carbon nanotubes.
7. The color-changing aid of claim 6, wherein: the particle size of the laser absorbent is 10.0 nm-200.0 mu m.
8. The color-changing aid of claim 7, wherein: the particle size of the laser absorbent is 20.0 nm-70.0 μm.
9. The color-changing aid according to any one of claims 1 to 5, wherein: the carrier polymer is selected from high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, propylene-octene copolymer, propylene-butene copolymer, ethylene-octene copolymer, ethylene-butene copolymer, ethylene-propylene-octene terpolymer, ethylene-propylene-butene terpolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, glycidyl ester grafted polypropylene, maleic anhydride grafted polypropylene, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, ethylene-glycidyl ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester-glycidyl methacrylate copolymer, polyethylene-propylene-butene copolymer, ethylene-propylene-butylene terpolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, glycidyl ester grafted polypropylene, maleic anhydride copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, ethylene-glycidyl ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester-methacrylic acid copolymer, ethylene-propylene-butylene copolymer, ethylene-propylene-butylene-propylene-terpolymer, ethylene-propylene-copolymer, ethylene-propylene-copolymer, ethylene-propylene-copolymer, ethylene-propylene-, One or more of ethylene-acrylate-maleic anhydride copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, SEBS, SEPS and SEEPS.
10. A method for preparing the color-change assistant according to any one of claims 1 to 9, wherein: the method comprises the following steps: uniformly mixing the laser absorbent, the thermoplastic polymer and the carrier polymer, and then melting, extruding and granulating the obtained mixture to obtain the composite material;
wherein the melt extrusion equipment is an internal mixer or an extruder.
11. Use of the colour-change additive according to any one of claims 1 to 9 as a laser colour-change additive for marking white or light-coloured text or patterns on coloured polymers.
12. Use of a colour-change additive according to claim 11, characterized in that: the addition amount of the color-changing additive in the colored polymer is 2-60.0 wt.%.
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