ABS composite material as well as preparation method and application thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) composite material as well as a preparation method and application thereof. The ABS composite material is prepared from the following components in parts by weight: 87 to 99 parts of ABS resin, 0.5 to 5 parts of lanthanide oxide, 0.5 to 5 parts of liquid crystal polymer, 0.1 to 0.5 part of carbon nano tube, nano zinc oxide, organic dye molecules and a carbon-based nano material, the mass ratio of the nano zinc oxide to the organic dye molecules to the carbon-based nano material is (2-4): (3-5): (2-4); the total dosage of the nano zinc oxide, the organic dye molecules and the carbon-based nano material is 3-7 parts. According to the ABS composite material provided by the invention, the time required by laser marking is shortened, the definition of laser marking is improved, and the carbonization or yellowing phenomenon caused by local overheating of the surface of the material is avoided.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of engineering plastics, and more particularly relates to an ABS composite material and a preparation method and application thereof. BACKGROUND

[0002] ABS plastic is an engineering plastic with excellent performance, and is widely used in electronic appliances, automobiles, medical devices, building decoration and other industries. Laser marking technology has been widely used in the field of marking on the surface of ABS plastic products due to its permanent and clear marking effect, high processing flexibility, and no pollution. However, the absorption efficiency of ABS plastic itself for laser energy is limited, and a large amount of heat energy generated during laser irradiation cannot be fully utilized, resulting in obvious loss of laser energy in the actual marking process, affecting the marking efficiency and quality, and specifically showing insufficient marking clarity, slow marking speed, and high energy consumption of laser processing equipment. In addition, when ABS material is irradiated by laser, the surface is easy to carbonize or have uneven color due to local overheating, further affecting the marking effect and aesthetics.

[0003] When using different wavelengths of laser for marking, the existing laser sensitizer has limitations in absorption efficiency for specific wavelengths of laser, resulting in a decrease in laser energy utilization rate at certain wavelengths, which severely limits the use range of ABS material in different laser equipment and application scenarios. In particular, under different wavebands such as ultraviolet laser (200nm-400nm), visible light laser (400nm-700nm) and infrared laser (700nm-10um), the traditional single laser sensitizer cannot achieve efficient absorption of all wavebands, causing problems such as limited selection of laser equipment and poor process adaptability. Therefore, how to develop an ABS material that can have high absorption efficiency for wide-band laser has become a technical problem to be solved. SUMMARY

[0004] In view of the above-mentioned existing technical problems, the primary purpose of the present application is to provide an ABS composite material, which uses a specific combination of laser sensitizers and has excellent absorption efficiency and heat conversion efficiency for multi-band laser energy, thereby improving the efficiency and clarity of laser marking. In addition, the phenomenon of carbonization or yellowing caused by local overheating of the material surface is avoided, and the aesthetics and durability of the marking are significantly improved.

[0005] The second purpose of the present application is to provide a preparation method of the ABS composite material.

[0006] The third purpose of the present application is to provide an ABS composite material comprising a three-layer structure.

[0007] The fourth purpose of the present application is to provide an application of the ABS composite material in automobile parts or electronic products.

[0008] The fifth object of the present application is to provide a laser marking product.

[0009] In order to achieve the above object, the present application is implemented by the following technical scheme: The present application claims an ABS composite material, comprising the following components in parts by weight: ABS resin 87-99 parts, lanthanide oxide 0.5-5 parts, liquid crystal polymer 0.5-5 parts, carbon nanotube 0.1-0.5 parts, nano zinc oxide, organic dye molecule and carbon-based nanomaterial. The mass ratio of the nano zinc oxide, organic dye molecule and carbon-based nanomaterial is 2-4:3-5:2-4. The total amount of the nano zinc oxide, organic dye molecule and carbon-based nanomaterial is 3-7 parts.

[0010] In the present application, the nano zinc oxide, organic dye molecule and carbon-based nanomaterial are added as laser sensitizers in a specific combination. The surface of the nano zinc oxide has abundant defect states and active sites, which can enhance the overall light absorption cross section. The organic dye molecule acts as a photosensitizer and can form an electron transport channel. The high thermal conductivity and large specific surface area of the carbon-based nanomaterial can provide a rapid heat diffusion path.

[0011] During laser irradiation, a cascade energy transfer effect occurs between the three components: the laser energy is first absorbed efficiently by the composite interface, then the energy is rapidly redistributed through the intermolecular energy resonance transfer mechanism, and finally uniform heat diffusion is achieved through the thermal conduction network of the carbon-based nanomaterial. This not only improves the overall laser energy utilization efficiency, but also avoids local overheating, ensuring the consistency of the marking quality.

[0012] In the present application, the nano zinc oxide, organic dye molecule and carbon-based nanomaterial are used as laser sensitizers in a specific combination, and are matched with the ABS resin, lanthanide oxide, liquid crystal polymer and carbon nanotube in the system. They have excellent absorption efficiency and thermal conversion efficiency for multi-band laser energy, thereby shortening the time required for laser marking. In addition, the clarity of laser marking is also improved, and the carbonization or yellowing phenomenon caused by local overheating on the material surface is avoided.

[0013] Specifically, in the ABS resin, the content of acrylonitrile is 18-28%, the content of butadiene is 5-15%, and the content of styrene is 60-75% by weight percentage.

[0014] Specifically, the ABS resin can be 87 parts, 89 parts, 91 parts, 93 parts, 95 parts, 97 parts, 98 parts, or an interval range formed by any of the above values, and the application is not limited to this. Specifically, the lanthanide oxide can be 0.8 parts, 1.3 parts, 1.5 parts, 1.8 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3.3 parts, 3.5 parts, 3.8 parts, 4.3 parts, 4.5 parts, 4.8 parts, or an interval range formed by any of the above values, and the application is not limited to this. The liquid crystal polymer can be 0.8 parts, 1.3 parts, 1.5 parts, 1.8 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3.3 parts, 3.5 parts, 3.8 parts, 4.3 parts, 4.5 parts, 4.8 parts, or an interval range formed by any of the above values, and the application is not limited to this. The carbon nanotube or surface treatment agent can be 0.05 parts, 0.08 parts, 0.15 parts, 0.18 parts, 0.23 parts, 0.25 parts, 0.28 parts, 0.33 parts, 0.35 parts, 0.38 parts, 0.43 parts, 0.45 parts, 0.48 parts, or an interval range formed by any of the above values, and the application is not limited to this. The laser sensitizer can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or an interval range formed by any of the above values, and the application is not limited to this.

[0015] Specifically, the mass percentage of the ABS resin in the ABS composite material is not less than 82.3%.

[0016] Specifically, the mass ratio of the nano-zinc oxide, the organic dye molecule, and the carbon-based nanomaterial can be 2:3:2, 2:3:3, 2:3:4, 3:4:3, 3:4:4, 4:3:4, 4:4:2, 4:4:5, or an interval range formed by any of the above values, and the application is not limited to this.

[0017] Specifically, the melt flow rate of the ABS resin under the condition of 200℃, 5kg is 0.5-10g / 10min. Specifically, the melt flow rate of the ABS resin under the condition of 200℃, 5kg is 2-5g / 10min. Specifically, the test method of the melt flow rate of the ABS resin is ASTM D1238.

[0018] Preferably, the organic dye molecule is selected from at least one of cyanine dyes, azo dyes, phthalocyanine dyes, rhodamine B, malachite green, and anthocyanins.

[0019] Preferably, the cyanine dyes include, but are not limited to, indocyanine green (ICG), trimethine cyanine dye (Cy3), pentamethine cyanine dye (Cy5), heptamethine cyanine dye (Cy7), and other cyanine dyes. Preferably, the azo dyes include, but are not limited to, methyl orange, congo red, Sudan red, disperse orange, disperse red, and the like. Preferably, the phthalocyanine dyes include, but are not limited to, copper phthalocyanine (copper phthalocyanine blue), zinc phthalocyanine, iron phthalocyanine, and other metal phthalocyanine compounds.

[0020] Preferably, the carbon-based nanomaterial is selected from at least one of carbon nanotubes, graphene, or carbon black.

[0021] Preferably, the average particle size of the nano-zinc oxide is 10-150 nm; further preferably, the average particle size of the nano-zinc oxide is 15-120 nm; more preferably, the average particle size of the nano-zinc oxide is 20-100 nm. Specifically, the test method for the average particle size of the nano-zinc oxide is dynamic light scattering method.

[0022] Preferably, the average particle size of the carbon-based nanomaterial is 30-200 nm. Specifically, the test method for the average particle size of the carbon-based nanomaterial is field emission scanning electron microscopy.

[0023] Preferably, the liquid crystal polymer is selected from at least one of polycarbonate PC-based liquid crystal polymer, polyamide-based liquid crystal polymer, and polyester-based liquid crystal polymer. More specifically, the polyester-based liquid crystal polymer includes, but is not limited to, polyethylene terephthalate, polybutylene terephthalate, and polyarylate, and the like.

[0024] Preferably, the lanthanide oxide is selected from trivalent lanthanide oxide. More specifically, the trivalent lanthanide oxide includes, but is not limited to, lanthanum trioxide. More specifically, the average particle size of the lanthanide oxide is 50-500 nm. The test method for the average particle size of the lanthanide oxide is laser particle size analyzer.

[0025] Preferably, the carbon nanotube is selected from at least one of (a) to (d) as follows: (a) the carbon nanotube is at least one of single-walled carbon nanotube and multi-walled carbon nanotube; (b) the average outer diameter of the carbon nanotube is 10-50 nm; (c) the length of the carbon nanotube is 0.5-10 μm; (d) the melt flow rate of the ABS resin under the condition of 200 °C and 5 kg is 0.5-10 g / 10 min.

[0026] Preferably, the ABS composite further includes 0-0.5 parts of a surface treatment agent; further preferably, 0.01-0.5 parts of a surface treatment agent.

[0027] Preferably, the surface treatment agent is at least one of stearic acid, silane coupling agent, boric acid.

[0028] Further, the present application claims to protect an ABS composite material comprising a three-layer structure, the three-layer structure being a bottom layer, a middle layer and a top layer; The bottom layer comprises carbon-based nanomaterial, ABS resin, lanthanide oxide, liquid crystal polymer; The middle layer comprises organic dye molecules, ABS resin, lanthanide oxide; The top layer comprises nano-zinc oxide, carbon nanotube, ABS resin, liquid crystal polymer.

[0029] Preferably, an ABS composite material comprising a three-layer structure, comprising the following components: ABS resin 87-99 parts, lanthanide oxide 0.5-5 parts, liquid crystal polymer 0.5-5 parts, carbon nanotube 0.1-0.5 parts, nano-zinc oxide, organic dye molecules and carbon-based nanomaterial; The mass ratio of the nano-zinc oxide, organic dye molecules and carbon-based nanomaterial is 2-4:3-5:2-4; The total amount of the nano-zinc oxide, organic dye molecules and carbon-based nanomaterial is 3-7 parts; In terms of mass percentage, wherein, The bottom layer comprises: carbon-based nanomaterial, 20-40% ABS resin, 30-40% lanthanide oxide, 30-50% liquid crystal polymer; The middle layer comprises: organic dye molecules, 20-50% ABS resin, 60-70% lanthanide oxide; The top layer comprises: nano-zinc oxide, carbon nanotube, 10-60% ABS resin, 50-70% liquid crystal polymer.

[0030] Further, the present application claims to protect a preparation method of an ABS composite material, comprising the following steps: (1) The nano-zinc oxide, organic dye molecules and carbon-based nanomaterial are respectively surface treated with a surface treatment agent; (2) Layer-by-layer compounding: The surface-treated carbon-based nanomaterial, part of the ABS resin, part of the lanthanide oxide and part of the liquid crystal polymer are mixed to form a bottom layer mixture; The surface-treated organic dye molecules, part of the ABS resin and the remaining lanthanide oxide are mixed to form a middle layer mixture; The surface-treated nano-zinc oxide, part of the ABS resin, carbon nanotube and the remaining liquid crystal polymer are mixed to form a top layer mixture; (3) melt-extruding the bottom layer mixture, the middle layer mixture and the top layer mixture through a multi-layer co-extrusion die to form the ABS composite material.

[0031] Preferably, the specific operation in step (1) is: mixing the nano-zinc oxide, the organic dye molecule and the carbon-based nanomaterial with the surface treatment agent solution respectively and ultrasonic dispersing.

[0032] Preferably, in step (1), the power of the ultrasonic is 200-500 W and the frequency is 20-100 kHz.

[0033] Preferably, in step (1), the concentration of the surface treatment agent in the surface treatment agent solution is 1-10 wt%.

[0034] Preferably, in the bottom layer mixture of step (2), 20-40% ABS resin is contained, and / or 30-40% lanthanide oxide is contained, and / or 30-50% liquid crystal polymer is contained.

[0035] Preferably, in the middle layer mixture of step (2), 20-50% ABS resin is contained, and / or 60-70% lanthanide oxide is contained.

[0036] Preferably, in the top layer mixture of step (2), 10-60% ABS resin is contained, and / or 50-70% liquid crystal polymer is contained.

[0037] Preferably, in step (2), ultrasonic-assisted mixing and dispersing is adopted.

[0038] Preferably, in step (2), the power of the ultrasonic is 400-1000 W, the frequency is 80-200 kHz, and the power density is 0.5-1.5 W / cm 3 .

[0039] Preferably, in step (3), the temperature of the melt-extrusion is 180-240℃.

[0040] Preferably, in step (3), a twin-screw extruder is adopted for melt-extrusion. More specifically, the length-diameter ratio of the twin-screw extruder is 30-40:1.

[0041] Preferably, in step (3), the thickness ratio of the layers formed by the bottom layer mixture, the middle layer mixture and the top layer mixture is 1-3:2-4:1-3.

[0042] Further, the present application claims the application of the ABS composite material in automobile parts or electronic products. More specifically, the automobile parts or electronic products include but are not limited to instrument panels, center consoles, door interior panels, steering wheel assemblies, electronic product housings, etc.

[0043] Further, the present application claims a kind of laser marking product, the ABS composite material described above is carried out laser marking and is prepared after generating laser mark.

[0044] Compared with prior art, the present application has the following beneficial effects: In the present application, the laser sensitizing agent of the specific combination of nano-zinc oxide, organic dye molecules and carbon-based nanomaterials, in combination with ABS resin, lanthanide oxide, liquid crystal polymer, carbon nanotube in the system, has excellent absorption efficiency and heat conversion efficiency for multi-band laser energy, thereby shortening the time required for laser marking; In addition, the clarity of laser marking is also improved, and the carbonization or yellowing phenomenon caused by local overheating of the material surface is avoided. DETAILED DESCRIPTION

[0045] The present application is further illustrated in conjunction with the specification and specific examples, but the examples do not limit the present application in any form. Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the technical field.

[0046] ABS resin: ABS resin 1, melt flow rate at 200 DEG C, 5 kg condition is 3g / 10min, ABS 758, Taiwan Qimei.

[0047] ABS resin 2, melt flow rate at 200 DEG C, 5 kg condition is 2.5g / 10min, PA-747, Taiwan Qimei.

[0048] Nano-zinc oxide: Nano-zinc oxide 1, average particle size is 20nm, ZnO-20, Sigma Aldrich.

[0049] Nano-zinc oxide 2, average particle size is 50nm, ZnO-50, Aladdin Industry.

[0050] Nano-zinc oxide 3, average particle size is 70nm, ZnO-70, Sigma Aldrich.

[0051] Nano-zinc oxide 4, average particle size is 100nm, ZnO-100, Aladdin Industry.

[0052] Organic dye molecules: Organic dye molecules 1, Rhodamine B, RhB-1, Sigma Aldrich.

[0053] Organic dye molecules 2, Malachite Green, MG-1, Aladdin Industry.

[0054] Organic dye molecules 3, Phthalocyanine Blue 15:3, PB15:3, BASF.

[0055] Organic dye molecule 4, methyl orange, MO-1, Sigma Aldrich.

[0056] Organic dye molecule 5, cyanine, CY-1, Aldrich.

[0057] Carbon-based nanomaterials: Carbon-based nanomaterial 1, carbon nanotube, average outer diameter 30 nm, CNT-30, Beijing Defang Nanometer.

[0058] Carbon-based nanomaterial 2, graphene, average particle size 150 nm, GR-150, Ningbo Mexi Technology.

[0059] Carbon-based nanomaterial 3, carbon black, average particle size 120 nm, CB-120, Cabot Corporation.

[0060] Lanthanide oxide, lanthanum trioxide, purity ≥ 99.9%, average particle size 200 nm, Aldrich.

[0061] Liquid crystal polymer, liquid crystal polyester, Zenite LCP6000, DuPont.

[0062] Carbon nanotube 1, single-walled carbon nanotube, average outer diameter 15 nm, length 0.5-10 μm, TNIS2, Beijing Defang Nanometer Company.

[0063] Carbon nanotube 2, multi-walled carbon nanotube, average outer diameter 30 nm, length 0.5-10 μm, TNIM4, Beijing Defang Nanometer Company.

[0064] Surface treatment agent, stearic acid, Merck.

[0065] Unless otherwise specified, each component used in each parallel example and comparative example is the same commercially available product.

[0066] Examples 1-16 A method for preparing an ABS composite material, comprising the following steps: (1) Laser sensitizer pretreatment: According to the proportioning requirements in Tables 1 to 3, nano-zinc oxide, organic dye molecules, and carbon-based nanomaterials were placed in a stearic acid solution for ultrasonic dispersion treatment. The stearic acid solution used anhydrous ethanol as a solvent, the stearic acid concentration was 3.5 wt%, the ultrasonic dispersion power was 300 W, the frequency was 40 kHz, the treatment time was 45 minutes, and after ultrasonic treatment, the nano-zinc oxide, organic dye molecules, and carbon-based nanomaterials were filtered and dried to obtain surface-modified nano-zinc oxide, organic dye molecules, and carbon-based nanomaterials.

[0067] (2) Layer-by-layer composite mixing: different sensitizers were dispersed in the ABS matrix in a layer-by-layer composite manner, and the specific steps were as follows: Bottom layer preparation: the surface treated carbon-based nanomaterial, 30% ABS resin, 30% lanthanide oxide and 40% liquid crystal polymer were mixed uniformly in a high-speed mixer to obtain the bottom layer mixture.

[0068] Middle layer preparation: the surface treated organic dye molecules, 40% ABS resin and 70% lanthanide oxide were mixed uniformly to obtain the middle layer mixture.

[0069] Top layer preparation: the surface treated nano-zinc oxide, 30% ABS resin, carbon nanotubes and 60% liquid crystal polymer were mixed uniformly to obtain the top layer mixture.

[0070] (3) Ultrasonic-assisted mixing: the bottom layer mixture, the middle layer mixture and the top layer mixture were respectively subjected to ultrasonic-assisted mixing. An ultrasonic generator (frequency of 100 kHz, power of 500 W, power density of 0.8 W / cm 3 ) was started, and mechanical stirring was carried out under ultrasonic assistance at a stirring speed of 200 rpm for 75 minutes. Every 15 minutes of treatment was stopped for 2 minutes to prevent excessive heating. The whole process was carried out under nitrogen protection to prevent material oxidation. The uniformly dispersed bottom layer mixture, the middle layer mixture and the top layer mixture were obtained respectively.

[0071] (4) Melt extrusion granulation: the treated bottom layer mixture, the middle layer mixture and the top layer mixture were respectively subjected to layer-by-layer composite melt extrusion through a double-screw extruder of a multi-layer co-extrusion die. The length-diameter ratio of the double-screw extruder was 36:1, and the screw diameter was 40 mm. The extruder temperature was controlled in sections: the feeding section temperature was 180℃, the compression section temperature was 200℃, the homogenization section temperature was 220℃, and the die temperature was 210℃. The screw rotation speed was 150 rpm, and the traction speed was 8 m / min. The three layers of materials were simultaneously extruded and compounded through the multi-layer co-extrusion die to form a multi-layer structure, and the thickness ratio of each layer was bottom layer: middle layer: top layer = 2:3:2. After extrusion, the material was cooled to below 60℃ by water, and then granulated by a granulator to prepare pelletized ABS modified material with a three-layer composite structure and a diameter of about 3 mm. The whole extrusion process was carried out under nitrogen protection.

[0072] (5) Injection molding: the pellets obtained in step (4) were subjected to injection molding through an injection molding machine, and the injection molding temperature was set to 220℃, and the mold temperature was 75℃ to prepare ABS plastic parts.

[0073] Table 1

[0074] Table 2

[0075] Table 3

[0076] Comparative Examples 1-7 The weight parts of raw materials used in the following comparative examples are shown in Table 4. The preparation method refers to the preparation method of Example 1 described above.

[0077] Table 4

[0078] Test Example (1) A unified multi-wavelength laser marking device was used, including an ultraviolet laser (355 nm), a visible light laser (532 nm), and an infrared laser (1064 nm). The sample materials of each example and comparative example were marked under the same laser power (20 W), the same scanning speed (1000 mm / s), and the same marking pattern (a circle with a diameter of 20 mm). The laser irradiation time of each waveband was 15 seconds, and the next waveband was switched after an interval of 5 seconds.

[0079] (2) The whiteness of the marked area was detected using a whiteness tester (domestic ZBD type whiteness tester), and the clarity of the marking was evaluated by the improvement amplitude of the whiteness value.

[0080] The whiteness value was calculated according to the GB / T 3979-2008 standard, and the calculation formula was: W=Y+800(xn-x)+1700(yn-y), where W was the whiteness value, Y was the tristimulus value, xn and yn were the color coordinates of the standard illuminant, and x and y were the color coordinates of the sample.

[0081] Whiteness value evaluation standard: ≥85 was excellent, 75-84 was good, 65-74 was general, 50-64 was relatively poor, and <50 was very poor.

[0082] (3) An infrared thermal imager (model FLIR T540) was used to monitor the surface temperature distribution of the material during the laser marking process in real time, to observe whether there were local overheating or carbonization phenomena.

[0083] Surface carbonization evaluation grading standard: 1st grade was no obvious carbonization phenomenon, the surface was smooth and smooth; 2nd grade was slight carbonization, with local light color change; 3rd grade was moderate carbonization, with obvious discoloration but no obvious concave-convex; 4th grade was severe carbonization, with obvious concave-convex and dark spots on the surface; and 5th grade was complete carbonization, with serious surface damage and obvious concave.

[0084] (4) A timing device was used to record the time (in seconds) required to complete the marking under the same pattern size, to compare the laser processing efficiency of each sample.

[0085] The test data is shown in Table 5 below.

[0086] Table 5

[0087] The present application provides an ABS composite material, as shown in Table 5, the whiteness of the ABS composite material provided by the present application after laser marking is greater than or equal to 87.8, the surface carbonization condition can reach level 2 or above, and the time required for marking is less than or equal to 10.8 seconds.

[0088] As can be seen from Example 1 and Comparative Examples 1-3, when the nano-zinc oxide, the organic dye molecules or the carbon-based nanomaterials are missing in the ABS composite material, it is difficult to achieve the technical effects of the present application, the whiteness significantly decreases, the surface carbonization condition significantly deteriorates, and the time required for laser marking significantly increases.

[0089] As can be seen from Example 1 and Comparative Examples 4-5, the nano-zinc oxide, the organic dye molecules and the carbon-based nanomaterials in the ABS composite material need to be in a specific ratio to achieve excellent technical effects.

[0090] As can be seen from Example 1 and Comparative Example 6, the lack of lanthanide oxides leads to a decrease in crystallinity and poor thermal stability, resulting in a significant decrease in the whiteness of the ABS composite material, a significant deterioration in the surface carbonization condition, and a significant increase in the time required for laser marking.

[0091] As can be seen from Example 1 and Comparative Example 7, the lack of liquid crystal polymers leads to a high glass transition temperature and poor processing performance, uneven distribution of laser energy, and thus a significant decrease in the whiteness of the ABS composite material, a significant deterioration in the surface carbonization condition, and a significant increase in the time required for laser marking.

[0092] The foregoing examples are illustrative only and are presented to explain some features of the method of the present application. The appended claims are intended to claim the broadest possible range of the present application and the examples presented herein are intended to be illustrative of the true experimental results obtained by the applicant. Thus, it is the intention of the applicant that the appended claims not be limited by the selection of examples of features that illustrate the present application. Some numerical ranges in the claims are intended to include sub-ranges within the range, and the ranges are intended to be interpreted as if the ranges were expressly written out individually, to the maximum extent allowed by the express language of the claims.

Claims

1. An ABS composite material, characterized by, The ABS resin, the lanthanide oxide, the liquid crystal polymer, the carbon nanotube, the nano zinc oxide, the organic dye molecule and the carbon-based nanomaterial are in a mass ratio of 87-99:0.5-5:0.5-5:0.1-0.5:0.1-0.5:0.1-0.

5. The mass ratio of the nano zinc oxide, the organic dye molecule and the carbon-based nanomaterial is 2-4:3-5:2-4. The total amount of the nano zinc oxide, the organic dye molecule and the carbon-based nanomaterial is 3-7 parts.

2. The ABS composite of claim 1, wherein, The organic dye molecule is at least one of cyanine dyes, azo dyes, phthalocyanine dyes, rhodamine B, malachite green and anthocyanins.

3. The ABS composite of claim 1, wherein, The carbon-based nanomaterial is at least one of carbon nanotubes, graphene or carbon black.

4. The ABS composite of claim 1, wherein, The average particle size of the nano zinc oxide is 10-150 nm; and / or The average particle size of the carbon-based nanomaterial is 30-200 nm.

5. The ABS composite according to any one of claims 1 to 4, characterized in that, At least one of the following (a)-(d) is selected: (a) The liquid crystal polymer is at least one of polycarbonate PC liquid crystal polymers, polyamide liquid crystal polymers and polyester liquid crystal polymers; (b) The lanthanide oxide is a trivalent lanthanide oxide; (c) The ABS composite further comprises a surface treatment agent; the surface treatment agent is at least one of stearic acid, silane coupling agent and boric acid; (d) The melt flow rate of the ABS resin at 200°C and 5kg is 0.5-10 g / 10 min.

6. An ABS composite comprising a three-layer structure, characterized in that, The three-layer structure comprises a bottom layer, a middle layer and a top layer; The bottom layer comprises the carbon-based nanomaterial, the ABS resin, the lanthanide oxide and the liquid crystal polymer; The middle layer comprises the organic dye molecule, the ABS resin and the lanthanide oxide; The top layer comprises the nano zinc oxide, the carbon nanotube, the ABS resin and the liquid crystal polymer.

7. The ABS composite comprising a three-layer structure according to claim 6, characterized in that, The ABS resin, the lanthanide oxide, the liquid crystal polymer, the carbon nanotube, the nano zinc oxide, the organic dye molecule and the carbon-based nanomaterial are in a mass ratio of 87-99:0.5-5:0.5-5:0.1-0.5:0.1-0.5:0.1-0.

5. The mass ratio of the nano zinc oxide, the organic dye molecule and the carbon-based nanomaterial is 2-4:3-5:2-4. The total amount of the nano zinc oxide, the organic dye molecule and the carbon-based nanomaterial is 3-7 parts. In terms of mass percentage, The bottom layer comprises: the carbon-based nanomaterial, 20-40% ABS resin, 30-40% lanthanide oxide and 30-50% liquid crystal polymer; The middle layer comprises: the organic dye molecule, 20-50% ABS resin and 60-70% lanthanide oxide; The top layer comprises: the nano zinc oxide, the carbon nanotube, 10-60% ABS resin and 50-70% liquid crystal polymer.

8. Process for the production of the ABS composite according to any one of claims 1 to 5 or according to any one of claims 6 to 7, characterized in that, The method comprises the following steps: (1) The nano zinc oxide, the organic dye molecule and the carbon-based nanomaterial are respectively surface-treated with a surface treatment agent; (2) Layer-by-layer compounding: The surface-treated carbon-based nanomaterial, part of the ABS resin, part of the lanthanide oxide and part of the liquid crystal polymer are mixed to form a bottom layer mixture; The surface-treated organic dye molecule, part of the ABS resin and the remaining lanthanide oxide are mixed to form a middle layer mixture; and The surface-treated carbon-based nanomaterial, part of the ABS resin, part of the lanthanide oxide and part of the liquid crystal polymer are mixed to form a bottom layer mixture. mixing the surface-treated nano-zinc oxide, part of the ABS resin, carbon nanotubes and the rest of the liquid crystal polymer to form a top layer mixture; (3) melting and extruding the bottom layer mixture, the middle layer mixture and the top layer mixture through a multi-layer co-extrusion die to form the ABS composite material.

9. Use of the ABS composite material according to any one of claims 1-5 or the ABS composite material according to any one of claims 6-7 in automobile parts or electronic products.

10. A laser-marked article, characterized in that, Prepared by laser marking after laser marking using the ABS composite material according to any one of claims 1-5 or the ABS composite material according to any one of claims 6-7.

Images