Anti-aging spraying-free ABS material

Abstract

The invention relates to an anti-aging spraying-free ABS (Acrylonitrile Butadiene Styrene) material and belongs to the technical field of spraying-free ABS materials. A sulfydryl modifier is creatively utilized to carry out surface treatment on the pigment, surface sulfydryl is firstly constructed, then cis-1, 2-dimethylol ethylene is used as a bridging agent, unsaturated double bonds of cis-1, 2-dimethylol ethylene and the sulfydryl are subjected to a click reaction, grafting of double-terminal hydroxyl groups is achieved, hexamethylene diisocyanate is added, and the surface sulfydryl modified pigment is prepared. The preparation method comprises the following steps: converting a double-terminal hydroxyl group into a double-terminal isocyanate group based on the action of a hydroxyl group and an isocyanate group, and finally finishing the modification of a polar group and an antioxidant by taking a material prepared from glycollic acid and 2, 2 '-thiobis (4-methyl-6-tert-butylphenol) according to a certain mass ratio as a composite modifier, thereby obtaining the modified pigment. The anti-aging spray-free ABS material is obtained by mixing the modified polypropylene with the lubricant and ABS, extruding and the like in sequence, and not only is good in aesthetic effect, but also is excellent in anti-aging performance.

Description

Technical Field

[0001] The invention belongs to the technical field of spray-free ABS materials, and in particular relates to an anti-aging spray-free ABS material. Background Art

[0002] ABS is a thermoplastic engineering plastic, which refers to a terpolymer of three monomers: acrylonitrile (A), butadiene (B) and styrene (S). Among them, spray-free ABS material refers to ABS with added pigments, which can obtain high gloss, pearlescent and other aesthetic effects similar to those of spraying process without additional spraying process. However, the existing spray-free ABS material still has certain disadvantages that limit its actual application effect. This is because, on the one hand, the pigments added to the spray-free ABS material are mostly inorganic substances, which are not compatible and dispersible with organic plastics, thereby resulting in a decrease in aesthetic effect. On the other hand, the spray-free ABS material is still ABS in essence, which is very susceptible to aging due to oxygen, heat, mechanical and other factors during daily use, resulting in varying degrees of reduction in various performances, which is manifested as yellowing, fading and loss of gloss on a macro scale. Summary of the invention

[0003] In view of the problems existing in the prior art, the purpose of the present invention is to provide an anti-aging spray-free ABS material. The present invention creatively uses a thiol modifier to perform surface treatment on a pigment, first constructs a surface thiol group, then uses cis-1,2-dihydroxymethylethylene as a bridging agent to make its unsaturated double bond click-react with the thiol group to achieve the grafting of double-terminal hydroxyl groups, then adds hexamethylene diisocyanate, and based on the action of hydroxyl and isocyanate groups, converts the double-terminal hydroxyl groups into double-terminal isocyanate groups, and finally uses a material composed of glycolic acid and 2,2′-thiobis(4-methyl-6-tert-butylphenol) in a certain mass ratio as a composite modifier to complete the modification of polar groups and antioxidants, and then obtains a modified pigment, which is mixed with a lubricant and ABS in sequence, extruded, and the like to obtain an anti-aging spray-free ABS material, which not only has good aesthetic effects but also has excellent anti-aging performance.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] An anti-aging spray-free ABS material is prepared from modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer.

[0006] As a preferred technical solution of the present invention, the mass ratio of the modified pigment, the lubricant and the acrylonitrile-butadiene-styrene copolymer is 3.5-4:1:94-95.

[0007] As a preferred technical solution of the present invention, the modified pigment is prepared by the following steps:

[0008] (1) Anhydrous ethanol, deionized water, pigment and thiol modifier are stirred at 60-70° C. for 16-18 hours, filtered, the filter residue is taken, washed with deionized water, and finally vacuum dried at 40-60° C. until constant weight is obtained to obtain a thiol modified pigment;

[0009] (2) mixing dimethyl sulfoxide, thiol-modified pigment, cis-1,2-dihydroxymethylethylene and azobisisobutyronitrile at 80-90° C. for 4-6 hours, filtering, taking the filter residue, washing with deionized water, and finally vacuum drying at 40-60° C. until constant weight, to obtain a double-terminal hydroxyl-modified pigment;

[0010] (3) stirring toluene, dihydroxy-modified pigment, hexamethylene diisocyanate and dibutyltin dilaurate at 30-40° C. under nitrogen atmosphere for 6-8 h, filtering, taking the filter residue, washing with toluene, and finally vacuum drying at 40-60° C. until constant weight, to obtain a diisocyanate-modified pigment;

[0011] (4) dimethylformamide, bi-terminal isocyanate modified pigment, composite modifier and dibutyltin dilaurate are stirred and mixed at 65-80° C. under nitrogen atmosphere for 6-8 h, filtered, and the filter residue is washed with deionized water, and finally vacuum dried at 40-60° C. until constant weight, and the preparation is completed.

[0012] Furthermore, in step (1), the mass ratio of the anhydrous ethanol, the deionized water, the pigment and the thiol modifier is 100:1:3-4:0.8-1.

[0013] Furthermore, the pigment in step (1) is at least one of aluminum pigment, titanium dioxide and zinc sulfide.

[0014] Furthermore, the mercapto modifier in step (1) is γ-mercaptopropyltrimethoxysilane.

[0015] Furthermore, in step (2), the mass ratio of the dimethyl sulfoxide, the mercapto-modified pigment, the cis-1,2-dihydroxymethylethylene and the azobisisobutyronitrile is 100:3-4:1-1.5:0.5.

[0016] Furthermore, in step (3), the mass ratio of the toluene, the dihydroxy-modified pigment, the hexamethylene diisocyanate and the dibutyltin dilaurate is 100:3-4:8:0.5.

[0017] Furthermore, in step (4), the mass ratio of the dimethylformamide, the double-ended isocyanate-modified pigment, the composite modifier and the dibutyltin dilaurate is 100:3-4:8:0.5.

[0018] Furthermore, the composite modifier in step (4) comprises glycolic acid and 2,2′-thiobis(4-methyl-6-tert-butylphenol); the mass ratio of the glycolic acid to the 2,2′-thiobis(4-methyl-6-tert-butylphenol) is 1:3-3.2.

[0019] As a preferred technical solution of the present invention, the lubricant is ethylene bisoleamide.

[0020] A method for preparing an anti-aging spray-free ABS material, the preparation method comprising the following steps:

[0021] The modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer are mixed, then extruded by a twin-screw extruder, water-cooled and cut into particles, and finally vacuum dried at 60-70° C. until constant weight, and the preparation is completed; the extrusion temperature of the twin-screw extruder is 200-220° C.; the screw speed of the twin-screw extruder is 300-500 rpm.

[0022] Beneficial effects of the present invention:

[0023] (1) The present invention creatively utilizes a thiol modifier to perform surface treatment on a pigment, first constructs a surface thiol group, then uses cis-1,2-dihydroxymethylethylene as a bridging agent to cause a click reaction between its unsaturated double bond and the thiol group to achieve the grafting of double-terminal hydroxyl groups, then adds hexamethylene diisocyanate to convert the double-terminal hydroxyl groups into double-terminal isocyanate groups based on the action of hydroxyl groups and isocyanate groups, and finally uses a material composed of glycolic acid and 2,2′-thiobis(4-methyl-6-tert-butylphenol) in a certain mass ratio as a composite modifier to complete the modification of polar groups and antioxidants, and then obtains a modified pigment, which is mixed with a lubricant and ABS in sequence, extruded, and other operations to obtain an anti-aging and spray-free ABS material, which not only has a good aesthetic effect but also has excellent anti-aging performance.

[0024] (2) The present invention creatively prepares a modified pigment, which is mixed with a lubricant and ABS in sequence, extruded, and other operations to obtain an anti-aging spray-free ABS material, which not only has good aesthetic effects, but also has excellent anti-aging properties. On the one hand, the modified pigment is transformed from an inorganic interface to an organic interface, which to a certain extent promotes its compatibility and dispersibility with ABS, and can obtain better aesthetic effects. On the other hand, since the organic interface of the modified pigment is modified by 2,2′-thiobis(4-methyl-6-tert-butylphenol) antioxidant, it can also give the prepared spray-free ABS material excellent anti-aging properties. Thanks to the relatively lower mobility of the pigment, the modified pigment of the present invention can well overcome the migration problem of the small molecule 2,2′-thiobis(4-methyl-6-tert-butylphenol) antioxidant, greatly reduce physical loss, and achieve long-term anti-aging. In addition, based on the fact that the acrylonitrile monomer in ABS has a strongly polar nitrile group, while the butadiene monomer and the styrene monomer are both non-polar compounds, for this reason, the present invention also adds a certain amount of glycolic acid in the preparation process of the modified pigment for modification, completes the modification of the polar group, and correspondingly further promotes the compatibility of the modified pigment with ABS, and better exerts the aesthetic and anti-aging effects. DETAILED DESCRIPTION

[0025] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0026] The sources of raw materials are as follows: acrylonitrile-butadiene-styrene copolymer was purchased from LG Chemical, brand HI-121H; aluminum pigment was purchased from Hefei Xuyang Aluminum Pigment Co., Ltd., model M-1620, D 50 The particle size is 16 μm; titanium dioxide was purchased from Shanghai Lingrui Chemical Co., Ltd., model number is titanium dioxide A101.

[0027] Example 1

[0028] An anti-aging spray-free ABS material is prepared from modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer.

[0029] The mass ratio of the modified pigment, the lubricant and the acrylonitrile-butadiene-styrene copolymer is 3.5:1:94.

[0030] The modified pigment is prepared by the following steps:

[0031] (1) Anhydrous ethanol, deionized water, pigment and thiol modifier are stirred and mixed at 60° C. for 16 h, filtered, the filter residue is taken, washed with deionized water, and finally vacuum dried at 40° C. until constant weight is obtained to obtain a thiol modified pigment;

[0032] (2) dimethyl sulfoxide, thiol-modified pigment, cis-1,2-dihydroxymethylethylene and azobisisobutyronitrile were stirred and mixed at 80° C. for 4 h, filtered, the filter residue was taken, washed with deionized water, and finally vacuum dried at 40° C. until constant weight was obtained to obtain a double-terminal hydroxyl-modified pigment;

[0033] (3) stirring toluene, a dihydroxy-modified pigment, hexamethylene diisocyanate and dibutyltin dilaurate at 30° C. under a nitrogen atmosphere for 6 h, filtering, taking the filter residue, washing with toluene, and finally vacuum drying at 40° C. until constant weight, to obtain a diisocyanate-modified pigment;

[0034] (4) Dimethylformamide, bi-terminal isocyanate-modified pigment, composite modifier and dibutyltin dilaurate are stirred and mixed at 65° C. for 6 h under a nitrogen atmosphere, filtered, and the filter residue is washed with deionized water, and finally vacuum dried at 40° C. until constant weight, and the preparation is completed.

[0035] The mass ratio of the anhydrous ethanol, the deionized water, the pigment and the thiol modifier in step (1) is 100:1:3:0.8.

[0036] The pigments in step (1) are aluminum pigment and titanium dioxide; the mass ratio of the aluminum pigment to the titanium dioxide is 1:1.5.

[0037] The mercapto modifier in step (1) is γ-mercaptopropyltrimethoxysilane.

[0038] In step (2), the mass ratio of the dimethyl sulfoxide, the mercapto-modified pigment, the cis-1,2-dihydroxymethylethylene and the azobisisobutyronitrile is 100:3:1:0.5.

[0039] In step (3), the mass ratio of the toluene, the dihydroxy-modified pigment, the hexamethylene diisocyanate and the dibutyltin dilaurate is 100:3:8:0.5.

[0040] In step (4), the mass ratio of the dimethylformamide, the double-ended isocyanate-modified pigment, the composite modifier and the dibutyltin dilaurate is 100:3:8:0.5.

[0041] The composite modifier in step (4) includes glycolic acid and 2,2′-thiobis(4-methyl-6-tert-butylphenol); the mass ratio of the glycolic acid to the 2,2′-thiobis(4-methyl-6-tert-butylphenol) is 1:3.

[0042] The lubricant is ethylene bisoleamide.

[0043] A method for preparing an anti-aging spray-free ABS material, the preparation method comprising the following steps:

[0044] The modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer are mixed, then extruded by a twin-screw extruder, water-cooled and cut into particles, and finally vacuum dried at 60° C. until constant weight, and the preparation is completed; the extrusion temperature of the twin-screw extruder is 200° C.; the screw speed of the twin-screw extruder is 300 rpm.

[0045] Example 2

[0046] An anti-aging spray-free ABS material is prepared from modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer.

[0047] The mass ratio of the modified pigment, the lubricant and the acrylonitrile-butadiene-styrene copolymer is 4:1:95.

[0048] The modified pigment is prepared by the following steps:

[0049] (1) Anhydrous ethanol, deionized water, pigment and thiol modifier are stirred and mixed at 70° C. for 18 h, filtered, the filter residue is taken, washed with deionized water, and finally vacuum dried at 60° C. until constant weight is obtained to obtain a thiol modified pigment;

[0050] (2) dimethyl sulfoxide, thiol-modified pigment, cis-1,2-dihydroxymethylethylene and azobisisobutyronitrile were stirred and mixed at 90° C. for 6 h, filtered, the filter residue was taken, washed with deionized water, and finally vacuum dried at 60° C. until constant weight was obtained to obtain a double-terminal hydroxyl-modified pigment;

[0051] (3) stirring toluene, a dihydroxy-modified pigment, hexamethylene diisocyanate and dibutyltin dilaurate at 40° C. for 8 h under a nitrogen atmosphere, filtering, taking the filter residue, washing with toluene, and finally vacuum drying at 60° C. until constant weight, to obtain a diisocyanate-modified pigment;

[0052] (4) Dimethylformamide, bi-terminal isocyanate-modified pigment, composite modifier and dibutyltin dilaurate are stirred and mixed at 80° C. for 8 h under a nitrogen atmosphere, filtered, and the filter residue is washed with deionized water, and finally vacuum dried at 60° C. until constant weight, and the preparation is completed.

[0053] The mass ratio of the anhydrous ethanol, the deionized water, the pigment and the thiol modifier in step (1) is 100:1:4:1.

[0054] The pigments in step (1) are aluminum pigment and titanium dioxide; the mass ratio of the aluminum pigment to the titanium dioxide is 1:1.5.

[0055] The mercapto modifier in step (1) is γ-mercaptopropyltrimethoxysilane.

[0056] In step (2), the mass ratio of the dimethyl sulfoxide, the mercapto-modified pigment, the cis-1,2-dihydroxymethylethylene and the azobisisobutyronitrile is 100:4:1.5:0.5.

[0057] In step (3), the mass ratio of the toluene, the dihydroxy-modified pigment, the hexamethylene diisocyanate and the dibutyltin dilaurate is 100:4:8:0.5.

[0058] In step (4), the mass ratio of the dimethylformamide, the double-ended isocyanate-modified pigment, the composite modifier and the dibutyltin dilaurate is 100:4:8:0.5.

[0059] The composite modifier in step (4) includes glycolic acid and 2,2′-thiobis(4-methyl-6-tert-butylphenol); the mass ratio of the glycolic acid to the 2,2′-thiobis(4-methyl-6-tert-butylphenol) is 1:3.2.

[0060] The lubricant is ethylene bisoleamide.

[0061] A method for preparing an anti-aging spray-free ABS material, the preparation method comprising the following steps:

[0062] The modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer are mixed, then extruded by a twin-screw extruder, water-cooled and cut into particles, and finally vacuum dried at 70°C until constant weight, and the preparation is completed; the extrusion temperature of the twin-screw extruder is 220°C; the screw speed of the twin-screw extruder is 500rpm.

[0063] Example 3

[0064] An anti-aging spray-free ABS material is prepared from modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer.

[0065] The mass ratio of the modified pigment, the lubricant and the acrylonitrile-butadiene-styrene copolymer is 3.8:1:94.5.

[0066] The modified pigment is prepared by the following steps:

[0067] (1) Anhydrous ethanol, deionized water, pigment and thiol modifier are stirred and mixed at 65° C. for 17 h, filtered, the filter residue is taken, washed with deionized water, and finally vacuum dried at 50° C. until constant weight is obtained to obtain a thiol modified pigment;

[0068] (2) dimethyl sulfoxide, thiol-modified pigment, cis-1,2-dihydroxymethylethylene and azobisisobutyronitrile were stirred and mixed at 85° C. for 5 h, filtered, the filter residue was taken, washed with deionized water, and finally vacuum dried at 50° C. until constant weight was obtained to obtain a double-terminal hydroxyl-modified pigment;

[0069] (3) stirring toluene, a dihydroxy-modified pigment, hexamethylene diisocyanate and dibutyltin dilaurate at 35° C. under a nitrogen atmosphere for 7 h, filtering, taking the filter residue, washing with toluene, and finally vacuum drying at 50° C. until constant weight, to obtain a diisocyanate-modified pigment;

[0070] (4) Dimethylformamide, bi-terminal isocyanate-modified pigment, composite modifier and dibutyltin dilaurate are stirred and mixed at 70° C. for 7 h under a nitrogen atmosphere, filtered, and the filter residue is washed with deionized water, and finally vacuum dried at 50° C. until constant weight, and the preparation is completed.

[0071] The mass ratio of the anhydrous ethanol, the deionized water, the pigment and the thiol modifier in step (1) is 100:1:3.5:0.9.

[0072] The pigments in step (1) are aluminum pigment and titanium dioxide; the mass ratio of the aluminum pigment to the titanium dioxide is 1:1.5.

[0073] The mercapto modifier in step (1) is γ-mercaptopropyltrimethoxysilane.

[0074] In step (2), the mass ratio of the dimethyl sulfoxide, the mercapto-modified pigment, the cis-1,2-dihydroxymethylethylene and the azobisisobutyronitrile is 100:3.5:1.3:0.5.

[0075] In step (3), the mass ratio of the toluene, the dihydroxy-modified pigment, the hexamethylene diisocyanate and the dibutyltin dilaurate is 100:3.7:8:0.5.

[0076] In step (4), the mass ratio of the dimethylformamide, the double-ended isocyanate-modified pigment, the composite modifier and the dibutyltin dilaurate is 100:3.5:8:0.5.

[0077] The composite modifier in step (4) includes glycolic acid and 2,2′-thiobis(4-methyl-6-tert-butylphenol); the mass ratio of the glycolic acid to the 2,2′-thiobis(4-methyl-6-tert-butylphenol) is 1:3.1.

[0078] The lubricant is ethylene bisoleamide.

[0079] A method for preparing an anti-aging spray-free ABS material, the preparation method comprising the following steps:

[0080] The modified pigment, lubricant and acrylonitrile-butadiene-styrene copolymer are mixed, then extruded by a twin-screw extruder, water-cooled and cut into particles, and finally vacuum dried at 65° C. until constant weight, and the preparation is completed; the extrusion temperature of the twin-screw extruder is 210° C.; the screw speed of the twin-screw extruder is 400 rpm.

[0081] Comparative Example 1

[0082] On the basis of Example 3, glycolic acid was replaced by an equal weight of 2,2′-thiobis(4-methyl-6-tert-butylphenol), and the rest remained unchanged.

[0083] Comparative Example 2

[0084] Based on Example 3, 2,2′-thiobis(4-methyl-6-tert-butylphenol) was replaced by an equal weight of glycolic acid, and the rest remained unchanged.

[0085] Comparative Example 3

[0086] On the basis of Example 3, step (2), step (3) and step (4) are not performed, and step (1) is changed to mixing aluminum pigment, titanium dioxide and 2,2′-thiobis(4-methyl-6-tert-butylphenol) in a mass ratio of 1:1.5:1, and the preparation is completed; the rest remain unchanged.

[0087] Test Example 1

[0088] Performance Test:

[0089] The anti-aging spray-free ABS materials prepared in Example 3 and Comparative Examples 1-3 were respectively injection molded into samples with a specification of 10 cm*10 cm*3 mm, wherein the injection molding temperature was 230°C.

[0090] Gloss test: The gloss of the above samples was tested using a gloss meter (60 degree angle, 6 random tests, taking the average, rounding to one decimal place).

[0091] Aging test: Place the above samples in air at 60°C for 100 hours, and then repeat the above gloss test.

[0092] Migration resistance test: The above samples were placed in a nitrogen atmosphere at room temperature and away from light for 180 days, then washed with deionized water, vacuum dried at 25°C until constant weight, and finally repeated the above aging test.

[0093] Table 1. Performance test results

[0094] Gloss test Aging test Migration resistance test Example 3 89.3GU 85.8GU 84.2GU Comparative Example 1 86.1GU 83.0GU 81.2GU Comparative Example 2 89.6GU 76.4GU 74.9GU Comparative Example 3 83.8GU 80.4GU 76.3GU

[0095] From the comparison of Test Example 1, Example 3 and Comparative Examples 1-3, it can be seen that the anti-aging spray-free ABS material prepared by the present invention can ensure both good aesthetic effect and excellent anti-aging performance. At the same time, even after being placed, the glossiness still decreases less, which indirectly indicates that the migration resistance is also strong.

[0096] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. An anti-aging spray-free ABS material, characterized by: The anti-aging spray-free ABS material is prepared from modified pigments, lubricants and acrylonitrile-butadiene-styrene copolymer.

2. The anti-aging spray-free ABS material according to claim 1, characterized in that: The mass ratio of the modified pigment, the lubricant and the acrylonitrile-butadiene-styrene copolymer is 3.5-4:1:94-95.

3. The anti-aging spray-free ABS material according to claim 1, characterized in that: The modified pigment is prepared by the following steps: (1) Anhydrous ethanol, deionized water, pigment and thiol modifier are stirred at 60-70° C. for 16-18 hours, filtered, the filter residue is taken, washed with deionized water, and finally vacuum dried at 40-60° C. until constant weight is obtained to obtain a thiol modified pigment; (2) mixing dimethyl sulfoxide, thiol-modified pigment, cis-1,2-dihydroxymethylethylene and azobisisobutyronitrile at 80-90° C. for 4-6 hours, filtering, taking the filter residue, washing with deionized water, and finally vacuum drying at 40-60° C. until constant weight, to obtain a double-terminal hydroxyl-modified pigment; (3) stirring toluene, dihydroxy-modified pigment, hexamethylene diisocyanate and dibutyltin dilaurate at 30-40° C. under nitrogen atmosphere for 6-8 h, filtering, taking the filter residue, washing with toluene, and finally vacuum drying at 40-60° C. until constant weight, to obtain a diisocyanate-modified pigment; (4) dimethylformamide, bi-terminal isocyanate modified pigment, composite modifier and dibutyltin dilaurate are stirred and mixed at 65-80° C. under nitrogen atmosphere for 6-8 h, filtered, and the filter residue is washed with deionized water, and finally vacuum dried at 40-60° C. until constant weight, and the preparation is completed.

4. The anti-aging spray-free ABS material according to claim 3, characterized in that: The mass ratio of the anhydrous ethanol, the deionized water, the pigment and the thiol modifier in step (1) is 100:1:3-4:0.8-1.

5. The anti-aging spray-free ABS material according to claim 3, characterized in that: The pigment in step (1) is at least one of aluminum pigment, titanium dioxide and zinc sulfide.

6. The anti-aging spray-free ABS material according to claim 3, characterized in that: The mercapto modifier in step (1) is γ-mercaptopropyltrimethoxysilane.

7. The anti-aging spray-free ABS material according to claim 3, characterized in that: In step (2), the mass ratio of the dimethyl sulfoxide, the mercapto-modified pigment, the cis-1,2-dihydroxymethylethylene and the azobisisobutyronitrile is 100:3-4:1-1.5:0.

5.

8. The anti-aging spray-free ABS material according to claim 3, characterized in that: In step (3), the mass ratio of the toluene, the dihydroxy-modified pigment, the hexamethylene diisocyanate and the dibutyltin dilaurate is 100:3-4:8:0.

5.

9. The anti-aging spray-free ABS material according to claim 3, characterized in that: In step (4), the mass ratio of the dimethylformamide, the double-ended isocyanate-modified pigment, the composite modifier and the dibutyltin dilaurate is 100:3-4:8:0.

5.

10. The anti-aging spray-free ABS material according to claim 3, characterized in that: The composite modifier in step (4) comprises glycolic acid and 2,2′-thiobis(4-methyl-6-tert-butylphenol); the mass ratio of the glycolic acid to the 2,2′-thiobis(4-methyl-6-tert-butylphenol) is 1:3-3.2.