ABS composite material, and preparation method therefor and use thereof

Abstract

The present application relates to an ABS composite material, and a preparation method therefor and a use thereof. The ABS composite material comprises, in parts by weight, the following components: 93-99.6 parts of an ABS resin and 0.18-5 parts of a colorant composition. The colorant composition comprises a combination of a light-transmitting colorant, a light-absorbing colorant, and a light-reflecting colorant. In the present application, by introducing a compound combination of the light-transmitting colorant, the light-absorbing colorant, and the light-reflecting colorant into the ABS composite material, these colorants act synergistically to effectively improve the resistance of the material to aging and discoloration under multi-factor environmental application conditions.

Description

An ABS composite material, its preparation method and application Technical Field

[0001] This application relates to the field of engineering plastics technology, and in particular to an ABS composite material, its preparation method, and its application. Background Technology

[0002] Acrylonitrile-butadiene-styrene copolymer resin, also known as ABS resin, has properties between engineering plastics and general-purpose plastics. It boasts excellent overall mechanical and processing performance, making it widely used in many fields such as electronics, electrical engineering, machinery, and construction. However, due to limitations in its polymer structure and composition, ABS resin also has many defects and shortcomings, requiring modification and improvement.

[0003] Due to its excellent mechanical properties and surface characteristics, ABS resin is often used as the casing material for household appliances, cleaning appliances, and other equipment. Because these devices are used in various environments with complex and variable environmental factors, the ABS material used in these applications experiences varying degrees of aging, resulting in surface yellowing, decreased gloss, and even more serious failures such as cracking and breakage. Currently, research on the aging and discoloration of ABS materials largely focuses on the discoloration performance and improvement of ABS materials with different formulations under various artificial accelerated aging conditions. This research primarily targets resistance to and improvement of single photoaging variables, paying more attention to the color stability of materials under conditions such as photoaging wavelength, irradiation intensity, alternating light and dark environments, and simulated rain spray. While these general artificial accelerated aging conditions can be used to evaluate the material's resistance to photoaging, they often do not correspond well to the color change results under actual usage conditions. The latter is precisely the direction that material application research should focus on.

[0004] Therefore, providing an ABS composite material with excellent aging and discoloration resistance under multi-factor environmental application conditions is of high practical value, expanding the application market of ABS materials. Summary of the Invention

[0005] This application provides an ABS composite material, its preparation method, and its application. By introducing a compound combination of light-transmitting colorants, light-absorbing colorants, and light-reflecting colorants into the ABS composite material, this application effectively improves the material's resistance to aging and discoloration under various environmental conditions.

[0006] In a first aspect, this application provides an ABS composite material, which comprises the following components in parts by weight:

[0007] 93-99.6 parts of ABS resin and 0.18-5 parts of colorant composition;

[0008] The colorant composition comprises a combination of light-transmitting colorants, light-absorbing colorants, and light-reflecting colorants.

[0009] In this application, the ABS resin may be, for example, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, etc.; the colorant composition may be, for example, 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc.

[0010] In this application, when light-reflecting colorants are used alone, due to their own light emission characteristics and the morphological characteristics of inorganic particles, it is difficult to achieve 100% complete reflection, resulting in a certain degree of light leakage. This leads to light scattering on the material surface and inside, accelerating the aging of the material. When used in combination with light-absorbing and light-transmitting colorants, the scattered light can be absorbed, resulting in a synergistic shielding effect against aging light sources. This application, by introducing a compound combination of light-transmitting, light-absorbing, and light-reflecting colorants into ABS composite materials, effectively improves the material's ability to resist aging and discoloration under various environmental conditions through multi-factor synergy.

[0011] Preferably, the ABS resin content in the ABS composite material is 93-99.6% by mass (e.g., 94%, 95%, 96%, 97%, 98%, 99%, etc.).

[0012] Preferably, the colorant composition in the ABS composite material has a mass percentage content of 0.18~5% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.).

[0013] In this application, the ABS resin can be a commercially available product or can be prepared by blending butadiene-grafted SAN copolymer with SAN.

[0014] Preferably, the ABS resin is an ABS resin produced by a two-step process of emulsion graft polymerization of butadiene-grafted SAN copolymer and acrylonitrile-styrene copolymer (AS resin, SAN).

[0015] Preferably, the ABS resin contains 12-35% by weight of acrylonitrile-based structural units (e.g., 12%, 15%, 20%, 25%, 30%, 35%, etc.), 8-35% by weight of butadiene-based structural units (e.g., 8%, 10%, 15%, 20%, 25%, 30%, 35%, etc.), and 30-80% by weight of styrene-based structural units (e.g., 30%, 40%, 50%, 60%, 70%, 80%, etc.).

[0016] Preferably, the weight-average molecular weight of the ABS resin is 94,000-150,000 g / mol (e.g., 94,000 g / mol, 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol, 140,000 g / mol, 150,000 g / mol, etc.).

[0017] In this application, the weight-average molecular weight of ABS resin is determined by gel permeation chromatography (GPC), and the mobile phase is tetrahydrofuran.

[0018] The light-transmitting colorant includes any one or a combination of at least two inorganic colorants with a visible light transmission band of 380~450 nm, 495~570 nm, 570~590 nm, 590~610 nm or 610~750 nm, preferably any one or a combination of at least two inorganic colorants with a visible light transmission band of 495~570 nm, 570~590 nm, 590~610 nm or 610~750 nm.

[0019] Preferably, the inorganic colorant with a visible light transmission band of 380~450 nm includes any one or a combination of at least two of ultramarine violet, manganese ammonium pyrophosphate, or cobalt phosphate.

[0020] Preferably, the inorganic colorant with a visible light transmission band of 495~570 nm includes any one or a combination of at least two of chromium oxide green, cobalt titanium green, or cobalt chromium green.

[0021] Preferably, the inorganic colorant with a visible light transmission band of 570-590 nm includes any one or a combination of at least two of chrome yellow, cadmium yellow, iron yellow, titanium nickel yellow, or bismuth vanadate yellow.

[0022] Preferably, the inorganic colorant with a visible light transmission band of 590~610 nm includes cadmium orange and / or pigment orange 82.

[0023] Preferably, the inorganic colorant with a visible light transmission band of 610~750 nm includes molybdenum chromium red and / or iron oxide red.

[0024] Preferably, the light-absorbing colorant includes an inorganic colorant with an absorption band of 380-750 nm in the visible light region.

[0025] Preferably, the inorganic colorant with a visible light absorption band of 380~750 nm includes any one or a combination of at least two of carbon black, copper chromium black, or iron chromium black.

[0026] In this application, by further limiting the visible light transmission / absorption band of the light-transmitting / absorbing colorant, the material's ability to resist aging and discoloration under multi-factor environmental application conditions is effectively improved.

[0027] Preferably, the light-reflecting colorant comprises rutile titanium dioxide.

[0028] Preferably, the D50 particle size of the rutile titanium dioxide is 0.2~0.36 μm (e.g., it can be 0.2 μm, 0.22 μm, 0.25 μm, 0.28 μm, 0.3 μm, 0.32 μm, 0.34 μm, 0.36 μm, etc.).

[0029] In this application, if the particle size of rutile titanium dioxide is too large or too small, the wavelength of the reflected light will deviate from the wavelength range of visible light, affecting its reflection effect. When the particle size is within the above-mentioned limit range, the effect of improving aging and discoloration is better.

[0030] In this application, the refractive index of the rutile titanium dioxide is 2.73.

[0031] Preferably, the mass ratio of the total amount of light-transmitting colorant and light-absorbing colorant to the amount of light-reflecting colorant is (1:2)-(1:10) (for example, it can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.).

[0032] Preferably, the ABS composite material further includes 0.2 to 1.5 parts of antioxidant (e.g., 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, etc.).

[0033] Preferably, the antioxidant includes hindered phenolic antioxidants and / or phosphite antioxidants.

[0034] Preferably, the ABS composite material further includes 0.3 to 1.8 parts of lubricant (e.g., 0.3 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, etc.).

[0035] Preferably, the lubricant includes any one or a combination of at least two of amide lubricants, stearate lubricants, ester lubricants, or silicone lubricants.

[0036] Secondly, this application provides a method for preparing the ABS composite material according to the first aspect, the method comprising:

[0037] The components of the ABS composite material are mixed, melt-extruded, cooled and granulated to obtain the ABS composite material.

[0038] Preferably, the melt extrusion is carried out in a twin-screw extruder.

[0039] Preferably, the temperature of each section of the twin-screw extruder during melt extrusion is 180~220℃ (e.g., 180℃, 190℃, 200℃, 210℃, 220℃, etc.), and the screw speed is 200~800 r / min (e.g., 200 r / min, 300 r / min, 400 r / min, 500 r / min, 600 r / min, 700 r / min, 800 r / min, etc.).

[0040] Thirdly, this application provides an application of the ABS composite material according to the first aspect in aging-resistant and color-changing components.

[0041] Compared with the prior art, this application has at least the following beneficial effects:

[0042] (1) This application introduces a combination of light-transmitting colorant, light-absorbing colorant and light-reflecting colorant into ABS composite material, which effectively improves the material’s ability to resist aging and discoloration under multi-factor environmental application conditions.

[0043] (2) The ABS composite material provided in this application still has excellent aging and discoloration resistance under multi-factor environmental application conditions. It can be used indoors for a long time under different lighting conditions, and can also be stored for a long time under high temperature and high humidity conditions such as long-distance sea transport without color change. It can be used for electrical equipment parts under high humidity conditions in low latitude areas, and can also be used for other application parts and products with high resistance to humid heat aging. It can completely replace the application market of traditional ABS materials. Detailed Implementation

[0044] To facilitate understanding of this application, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of this application.

[0045] The sources of materials used in the following embodiments and comparative examples are as follows:

[0046] A. Matrix resin

[0047] ABS resin is obtained through the following synthesis process:

[0048] (1) Preparation of ABS grafted rubber powder: Butadiene monomer, emulsifier, polymerization initiator and water are added to the emulsion polymerization kettle to react and prepare butadiene latex; after degassing and pH adjustment, butadiene latex is sent to the grafting polymerization kettle, and styrene, acrylonitrile, emulsifier, redox agent and molecular weight regulator are added to react. After coagulation, dehydration, washing and air drying in the coagulation kettle, ABS grafted rubber powder is obtained.

[0049] (2) Preparation of SAN resin: After styrene and acrylonitrile monomers are added to the polymerization reactor for reaction, after devolatilization treatment, they are extruded, granulated and air-dried to obtain SAN resin.

[0050] (3) The obtained ABS grafted adhesive powder and SAN resin are mixed and granulated to obtain ABS resin.

[0051] By adjusting the synthesis parameters and feed ratios, ABS resins with different specifications and properties can be prepared. The main types used in this application are as follows:

[0052] ABS-1: The weight content of acrylonitrile-based structural units is 22%, the weight content of butadiene-based structural units is 20%, and the weight content of styrene-based structural units is 58%; the weight average molecular weight is 145,000 g / mol.

[0053] ABS-2: The weight content of acrylonitrile-based structural units is 23%, the weight content of butadiene-based structural units is 26%, and the weight content of styrene-based structural units is 51%; the weight average molecular weight is 95,000 g / mol.

[0054] ABS-3: The weight content of acrylonitrile-based structural units is 20%, the weight content of butadiene-based structural units is 23%, and the weight content of styrene-based structural units is 57%; the weight average molecular weight is 116,000 g / mol.

[0055] ABS-4: The weight content of acrylonitrile-based structural units is 21%, the weight content of butadiene-based structural units is 15%, and the weight content of styrene-based structural units is 64%; the weight average molecular weight is 148,000 g / mol.

[0056] B. Light-reflecting colorant

[0057] B-1: R-104, D50 particle size 0.2 μm, Chemours Titanium Dioxide Technology, refractive index 2.73;

[0058] B-2: R-900, D50 particle size 0.36 μm, Chemours Titanium Dioxide Technology, refractive index 2.73;

[0059] B-3: R-960, D50 particle size 0.5 μm, Chemours Titanium Dioxide Technology, refractive index 2.73;

[0060] C. Light-absorbing colorants

[0061] C-1: Furnace black, M717, Cabot, with a visible light absorption band of 380-750 nm and a particle size of 22 nm;

[0062] D. Light-transmitting colorant

[0063] D-1: Ultraviolet, V10, New Balance, visible light transmission band is 380-450 nm;

[0064] D-2: Cobalt titanium green, P-600, from Hylian, South Korea, with a visible light transmission band of 495-570 nm;

[0065] D-3: Chrome Yellow, I3920GA, Runba, absorption band in the visible light region is 570-590 nm;

[0066] D-4: Cadmium Orange, PO20, Hunan Kelai, absorption band in the visible light region is 590-610 nm;

[0067] D-5: Iron Red, Sicotrans Red K2915, BASF, absorption band in the visible light region is 610-750 nm;

[0068] D-6: Ultramarine Blue, GP-58, Neobilite, absorption band in the visible light region is 450-495 nm;

[0069] E. Antioxidants:

[0070] E-1: Hindered phenolic antioxidant, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], commercially available;

[0071] E-2: Phosphite antioxidant, tris[2,4-di-tert-butylphenyl] phosphite, commercially available;

[0072] F. Lubricant

[0073] F-1: Ethylene bis-stearamide, commercially available;

[0074] G. Ultraviolet absorber

[0075] 2-(2-hydroxy-5-methylphenyl)benzotriazole, commercially available.

[0076] Examples 1-12, Comparative Examples 1-4

[0077] The above embodiments and comparative examples each provide an ABS composite material, the composition and weight parts of which are shown in Table 1.

[0078] The preparation methods of the ABS composite materials in the above embodiments and comparative examples are as follows:

[0079] Each component was fed into a mixer and mixed at 1000 r / min for 5 min. Then it was fed into a twin-screw extruder. The temperature of the first and second stages was set to 180℃, the temperature of the third to ninth stages was set to 200℃, the die temperature was set to 220℃, and the screw speed was set to 350 r / min. After melt blending in a co-rotating twin-screw extruder, the mixture was water-cooled, stretched, and pelletized to obtain the ABS composite material.

[0080] The ABS composite materials provided in Examples 1-12 and Comparative Examples 1-4 were dried and injection molded into 80 mm × 50 mm × 2 mm samples. The samples were then subjected to aging tests to determine color changes under the following conditions:

[0081] Phase 1: Using a window glass filter, controlling the wavelength to 420 nm and the irradiance to 0.56 W / m². 2 The humidity inside the chamber was 50%, the temperature inside the chamber was 38℃, and the temperature on the blackboard was 43℃. After drying and irradiating under these conditions for 60 hours, the process was moved to stage 2 for continued aging.

[0082] Phase 2: In a light-proof oven, set the oven temperature to 80℃ and the humidity to 90%, and age under these conditions for 60 hours before taking it out for testing;

[0083] Sample Testing: Following the testing standard ASTM D2244-2015, the L, a, and b scales of the samples before and after aging treatment were measured using a spectrophotometer. The color difference was calculated using the following formula. :

[0084]

[0085] in This represents the value of the sample before aging treatment. This indicates the value of the sample after aging treatment.

[0086] The test method used in this application takes into account multiple aging variables, and the evaluation system is closer to actual use conditions. The results obtained using this test method are shown in Tables 1 and 2.

[0087]

[0088]

[0089] Note: / indicates that the component is not present.

[0090] The test results show that:

[0091] (1) As can be seen from Examples 1 to 12, the present application introduces a colorant composition in ABS composite material that combines light-transmitting colorant, light-absorbing colorant and light-reflecting colorant, which has excellent anti-aging and color-changing ability and the color difference is controlled within 2.0.

[0092] (2) By comparing Examples 1 and 8-9, it can be seen that when the amount of colorant composition used in this application is too small, the color difference increases and the material’s resistance to discoloration decreases; when the amount used is too large, the color difference increases and the material’s resistance to discoloration decreases; by comparing Examples 1 and 10, it can be seen that when the particle size of the light-reflecting colorant is too large, the resistance to aging and discoloration decreases; by comparing Examples 1 and 11-12, it can be seen that by optimizing the absorption band of the light-transmitting colorant, the material’s resistance to aging and discoloration can be improved.

[0093] (3) By comparing Example 1 and Comparative Examples 1 to 3, it can be seen that when any one of the light-transmitting colorant, light-absorbing colorant or light-reflecting colorant is missing in the colorant composition, the material’s anti-aging and color-changing ability deteriorates; by comparing Example 1 and Comparative Example 4, it can be seen that when the light-absorbing colorant is replaced with an ultraviolet absorber, the material’s anti-aging and color-changing ability deteriorates.

[0094] The applicant declares that the above description is only a specific implementation of this application, but the protection scope of this application is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application fall within the protection and disclosure scope of this application.

Claims

1. An ABS composite material, comprising the following components in parts by weight: 93-99.6 parts of ABS resin and 0.18-5 parts of colorant composition; The colorant composition comprises a combination of light-transmitting colorants, light-absorbing colorants, and light-reflecting colorants.

2. The ABS composite material according to claim 1, wherein, The ABS resin contains 12-35% by weight of acrylonitrile-based structural units, 8-35% by weight of butadiene-based structural units, and 30-80% by weight of styrene-based structural units.

3. The ABS composite material according to claim 1, wherein, The weight-average molecular weight of the ABS resin is 94,000-150,000 g / mol.

4. The ABS composite material according to claim 1, wherein, The light-transmitting colorant includes any one or a combination of at least two inorganic colorants with visible light transmission bands of 380~450 nm, 495~570 nm, 570~590 nm, 590~610 nm or 610~750 nm. Preferably, the inorganic colorant with a visible light transmission band of 380~450 nm includes any one or a combination of at least two of ultramarine violet, manganese ammonium pyrophosphate, or cobalt phosphate. Preferably, the inorganic colorant with a visible light transmission band of 495~570 nm includes any one or a combination of at least two of chromium oxide green, cobalt titanium green, or cobalt chromium green; Preferably, the inorganic colorant with a visible light transmission band of 570~590 nm includes any one or a combination of at least two of chrome yellow, cadmium yellow, iron yellow, titanium nickel yellow, or bismuth vanadate yellow. Preferably, the inorganic colorant with a visible light transmission band of 590~610 nm includes cadmium orange and / or pigment orange 82. Preferably, the inorganic colorant with a visible light transmission band of 610~750 nm includes molybdenum chromium red and / or iron oxide red.

5. The ABS composite material according to claim 1, wherein, The light-absorbing colorant includes an inorganic colorant with an absorption band of 380-750 nm in the visible light region; Preferably, the inorganic colorant with a visible light absorption band of 380~750 nm includes any one or a combination of at least two of carbon black, copper chromium black, or iron chromium black.

6. The ABS composite material according to claim 1, wherein, The light-reflecting colorant includes rutile titanium dioxide; Preferably, the D50 particle size of the rutile titanium dioxide is 0.2~0.36 μm.

7. The ABS composite material according to claim 1, wherein, The mass ratio of the total amount of light-transmitting colorant and light-absorbing colorant to the amount of light-reflecting colorant is (1:2)-(1:10).

8. The ABS composite material according to claim 1, wherein, The ABS composite material also includes 0.2 to 1.5 parts of antioxidant; Preferably, the antioxidant includes hindered phenolic antioxidants and / or phosphite antioxidants.

9. The ABS composite material according to claim 1, wherein, The ABS composite material also includes 0.3 to 1.8 parts of lubricant; Preferably, the lubricant includes any one or a combination of at least two of amide lubricants, stearate lubricants, ester lubricants, or silicone lubricants.

10. A method for preparing an ABS composite material according to any one of claims 1 to 9, comprising: The components of the ABS composite material are mixed, melt-extruded, cooled and granulated to obtain the ABS composite material.

11. The application of an ABS composite material according to any one of claims 1 to 9 in aging-resistant and color-changing components.

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