ABS composite material as well as preparation method and application thereof

Abstract

The invention relates to an ABS (Acrylonitrile Butadiene Styrene) composite material as well as a preparation method and application thereof. The ABS composite material comprises the following components in parts by weight: 93-99.6 parts of ABS resin and 0.18-5 parts of a coloring agent composition, the colorant composition includes a combination of a light transmitting colorant, a light absorbing colorant, and a light reflecting colorant. According to the present invention, the compounding combination of the light transmission coloring agent, the light absorption coloring agent and the light reflection coloring agent is introduced into the ABS composite material, such that the aging discoloration resistance of the material under the multi-factor environmental application condition is effectively improved through the multi-party synergism;

Description

Technical Field

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

[0002] Acrylonitrile-butadiene-styrene copolymer resin, namely ABS resin, has properties between engineering plastics and general plastics, with excellent comprehensive mechanical properties and processing and molding properties, and is widely used in many fields such as electronics and electrical appliances, machinery, and construction. However, limited by its polymer structure and composition, ABS resin also has many defects and deficiencies that need to be modified and improved.

[0003] Due to its excellent mechanical properties and surface characteristics, ABS resin is often used as the outer shell components of household appliances, cleaning appliances and other equipment. Since the usage scenarios of these equipment are not fixed and the environmental factors are complex and variable, the ABS materials used for the outer shell in these application scenarios show varying degrees of aging, such as surface yellowing, decreased gloss, and even more serious failures such as cracking and breakage. At present, the research on the aging and discoloration problems of ABS materials mostly focuses on the discoloration performance and improvement of ABS materials with different formula components under different artificial accelerated aging conditions, and mostly focuses on the resistance and improvement research of a single photoaging variable, paying more attention to the color stability of materials under conditions such as photoaging wavelength, irradiation intensity, light and dark alternation, and simulated rain spraying. These general artificial accelerated aging conditions can be used to evaluate the ranking of the light aging resistance performance of materials themselves, but often have poor correspondence with the color change results under the actual use conditions of the outer shell materials. And the latter is exactly the direction that we should pay more attention to in the research of material applications.

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

[0005] To solve the above technical problems, the present invention provides an ABS composite material, a preparation method thereof, and an application thereof. The present invention effectively improves the ability of the material to resist aging and discoloration under multi-factor environmental application conditions by introducing a compound combination of a light-transmitting colorant, a light-absorbing colorant, and a light-reflecting colorant into the ABS composite material.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides an ABS composite material, and the ABS composite material comprises the following components in parts by weight:

[0008] ABS resin 93 - 99.6 parts

[0009] The colorant composition is 0.18 to 5 parts;

[0010] The colorant composition includes a combination of a light-transmissive colorant, a light-absorbing colorant, and a light-reflective colorant.

[0011] In the present invention, the ABS resin can be, for example, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, etc.; the colorant composition can 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.

[0012] In the present invention, when the light-reflective colorant is used alone, due to its own light-emitting characteristics and the morphological characteristics of the inorganic particles, it is difficult to achieve 100% total reflection, and there is a certain degree of light leakage phenomenon, which will form light scattering on the surface and inside of the material, accelerating the aging of the material; when used in combination with the light-absorbing colorant and the light-transmissive colorant, it can absorb this part of the scattered light, showing the phenomenon of synergistic shielding of the aging light source. The present invention effectively improves the ability of the material to resist aging and discoloration under multi-factor environmental application conditions by introducing a compound combination of a light-transmissive colorant, a light-absorbing colorant, and a light-reflective colorant into the ABS composite material.

[0013] Preferably, the mass percentage content of the ABS resin in the ABS composite material is 93 to 99.6% (for example, it can be 94%, 95%, 96%, 97%, 98%, 99%, etc.).

[0014] Preferably, the mass percentage content of the colorant composition in the ABS composite material is 0.18 to 5% (for example, it can be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.).

[0015] In the present invention, the ABS resin can be selected from commercially available products or prepared by self-mixing a butadiene-grafted SAN copolymer and SAN.

[0016] Preferably, the ABS resin is an ABS resin produced by a two-step process of blending an acrylonitrile-styrene copolymer (AS resin, SAN) with a butadiene-grafted SAN copolymer prepared by emulsion graft polymerization.

[0017] Preferably, the weight content of the acrylonitrile-based structural unit in the ABS resin is 12-35% (for example, it can be 12%, 15%, 20%, 25%, 30%, 35%, etc.), the weight content of the butadiene-based structural unit is 8-35% (for example, it can be 8%, 10%, 15%, 20%, 25%, 30%, 35%, etc.), and the weight content of the styrene-based structural unit is 30-80% (for example, it can be 30%, 40%, 50%, 60%, 70%, 80%, etc.).

[0018] Preferably, the weight-average molecular weight of the ABS resin is 94,000-150,000 g / mol (for example, it can be 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.).

[0019] In the present invention, the test method for the weight-average molecular weight of the ABS resin is gel permeation chromatography (GPC), and the mobile phase is tetrahydrofuran.

[0020] The light-transmitting colorant includes any one or a combination of at least two of inorganic colorants with visible light region transmission bands of 380-450 nm, 495-570 nm, 570-590 nm, 590-610 nm, or 610-750 nm. Preferably, it is any one or a combination of at least two of inorganic colorants with visible light region transmission bands of 495-570 nm, 570-590 nm, 590-610 nm, or 610-750 nm.

[0021] Preferably, the inorganic colorant with a visible light region transmission band of 380-450 nm includes any one or a combination of at least two of ultramarine violet, ammonium pyrophosphate manganate, or cobalt phosphate.

[0022] Preferably, the inorganic colorant with a visible light region 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.

[0023] Preferably, the inorganic colorant with a visible light region 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.

[0024] Preferably, the inorganic colorant with a visible light region transmission band of 590-610 nm includes cadmium orange and / or pigment orange 82.

[0025] Preferably, the inorganic colorant with a visible light region transmission band of 610-750 nm includes molybdenum chromate red and / or iron red.

[0026] Preferably, the light-absorbing colorant comprises an inorganic colorant with an absorption band in the visible light region of 380 - 750 nm.

[0027] Preferably, the inorganic colorant with an absorption band in the visible light region of 380 - 750 nm comprises any one or a combination of at least two of carbon black, copper chromite black, or iron chromite black.

[0028] In the present invention, by further defining the light transmission / absorption band of the light transmission / absorbing colorant in the visible light region, the ability of the material to resist aging and discoloration under multi-factor environmental application conditions is effectively improved.

[0029] Preferably, the light-reflecting colorant comprises rutile titanium dioxide.

[0030] Preferably, the D50 particle size of the rutile titanium dioxide is 0.2 - 0.36 μm (for example, 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.).

[0031] In the present invention, if the particle size of the rutile titanium dioxide is too large or too small, the wavelength of the reflected light will shift out of the visible light wavelength range, affecting its reflection effect. When the particle size is within the above-defined range, the effect of improving aging and discoloration is better.

[0032] In the present invention, the refractive index of the rutile titanium dioxide is 2.73.

[0033] Preferably, the mass ratio of the total amount of the light transmission colorant and the light absorption colorant to the amount of the light reflection 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.).

[0034] Preferably, the ABS composite material further comprises 0.2 - 1.5 parts of an antioxidant (for example, it can be 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, etc.).

[0035] Preferably, the antioxidant comprises a hindered phenol antioxidant and / or a phosphite antioxidant.

[0036] Preferably, the ABS composite material further comprises 0.3 - 1.8 parts of a lubricant (for example, it can be 0.3 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, etc.).

[0037] Preferably, the lubricant comprises any one or a combination of at least two of amide lubricants, stearate lubricants, ester lubricants, or silicone lubricants.

[0038] In a second aspect, the present invention provides a method for preparing the ABS composite material according to the first aspect, and the preparation method includes:

[0039] Mixing the components of the ABS composite material, and performing melt extrusion and cooling granulation to obtain the ABS composite material.

[0040] Preferably, the melt extrusion is carried out in a twin-screw extruder.

[0041] Preferably, the temperature of each section of the twin-screw extruder during the melt extrusion is 180-220 °C (for example, it can be 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, etc.), and the screw speed is 200-800 r / min (for example, it can be 200 r / min, 300 r / min, 400 r / min, 500 r / min, 600 r / min, 700 r / min, 800 r / min, etc.).

[0042] In a third aspect, the present invention provides an application of the ABS composite material according to the first aspect in anti-aging and discoloration components.

[0043] Compared with the prior art, the present invention has at least the following beneficial effects:

[0044] (1) By introducing a compound combination of a light-transmitting colorant, a light-absorbing colorant, and a light-reflecting colorant into the ABS composite material, the present invention effectively improves the ability of the material to resist aging and discoloration under multi-factor environmental application conditions through multi-party cooperation.

[0045] (2) The ABS composite material provided by the present invention still has excellent anti-aging and discoloration performance under multi-factor environmental application conditions, can be used indoors for a long time under different lighting source conditions, and can also be stored for a long time under high-temperature and high-humidity conditions such as long-distance sea transportation without color change; it can be used for electrical equipment components in high-humidity environmental conditions in low-latitude regions, and can also be used for other application components and products with high requirements for heat and humidity aging resistance, and can completely replace the application market of traditional ABS materials. Specific Embodiments

[0046] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0047] The sources of the materials used in the following examples and comparative examples are as follows:

[0048] A. Matrix resin

[0049] The ABS resin is obtained through the following synthesis process:

[0050] (1) Preparation of ABS grafted rubber powder: After putting butadiene monomer, emulsifier, polymerization initiator and water into the emulsion polymerization kettle for reaction, butadiene latex is prepared; after the butadiene latex is degassed and pH adjusted, it is sent into the graft polymerization kettle, and then styrene, acrylonitrile, emulsifier, redox agent and molecular weight regulator are added for reaction, and then through coagulation kettle coagulation, dehydration, washing and air flow drying, ABS grafted rubber powder is obtained;

[0051] (2) Preparation of SAN resin: After putting styrene and acrylonitrile monomers into the polymerization kettle for reaction, after devolatilization treatment, extrusion granulation and air drying are carried out to obtain SAN resin;

[0052] (3) Mix and granulate the obtained ABS grafted rubber powder and SAN resin to obtain ABS resin.

[0053] By adjusting the synthesis parameters and feeding ratios, ABS resins with different specifications and properties can be prepared. The main ones used in this invention are as follows:

[0054] ABS-1: The weight content of the structural unit based on acrylonitrile is 22%, the weight content of the structural unit based on butadiene is 20%, and the weight content of the structural unit based on styrene is 58%; the weight average molecular weight is 145000 g / mol;

[0055] ABS-2: The weight content of the structural unit based on acrylonitrile is 23%, the weight content of the structural unit based on butadiene is 26%, and the weight content of the structural unit based on styrene is 51%; the weight average molecular weight is 95000 g / mol;

[0056] ABS-3: The weight content of the structural unit based on acrylonitrile is 20%, the weight content of the structural unit based on butadiene is 23%, and the weight content of the structural unit based on styrene is 57%; the weight average molecular weight is 116000 g / mol;

[0057] ABS-4: The weight content of the structural unit based on acrylonitrile is 21%, the weight content of the structural unit based on butadiene is 15%, and the weight content of the structural unit based on styrene is 64%; the weight average molecular weight is 148000 g / mol.

[0058] B. Light reflection colorant

[0059] B-1: R-104, D50 particle size 0.2 μm, Chemours Titanium Technologies, refractive index 2.73;

[0060] B-2: R-900, D50 particle size 0.36 μm, Chemours Titanium Technologies, refractive index 2.73;

[0061] B-3: R-960, D50 particle size 0.5 μm, Chemours Titanium Technologies, refractive index 2.73;

[0062] C. Light absorption colorants

[0063] C-1: Furnace black, M717, Cabot, visible light absorption band 380 - 750 nm, particle size 22 nm;

[0064] D. Light transmission colorants

[0065] D-1: Ultramarine violet, V10, Rubitherm, visible light transmission band 380 - 450 nm;

[0066] D-2: Cobalt titanate green, P-600, Korea Heliant, visible light transmission band 495 - 570 nm;

[0067] D-3: Chrome yellow, I3920GA, Runba, visible light absorption band 570 - 590 nm;

[0068] D-4: Cadmium orange, PO20, Hunan Kele, visible light absorption band 590 - 610 nm;

[0069] D-5: Iron oxide red, Sicotrans Red K2915, BASF, visible light absorption band 610 - 750 nm;

[0070] D-6: Ultramarine blue, GP-58, Rubitherm, visible light absorption band 450 - 495 nm;

[0071] E. Antioxidants:

[0072] E-1: Hindered phenol antioxidant, pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], commercially available;

[0073] E-2: Phosphite antioxidant, tris(2,4-di-tert-butylphenyl) phosphite, commercially available;

[0074] F. Lubricants

[0075] F-1: Ethylene bisstearamide, commercially available;

[0076] G. UV absorbers

[0077] 2-(2-Hydroxy-5-methylphenyl) benzotriazole, commercially available.

[0078] Examples 1 - 12, Comparative Examples 1 - 4

[0079] The above examples and comparative examples respectively provide an ABS composite material, and its composition and weight parts are shown in Table 1.

[0080] The preparation methods of the ABS composites in the above examples and comparative examples are as follows:

[0081] Put each component into a mixer and mix at a speed of 1000 r / min for 5 min, then put it into a twin-screw extruder. Set the temperatures of the first and second sections to 180 - 220 °C for each section, the temperatures of the third to ninth sections to 200 °C, and the die head temperature to 220 °C. The set range of the screw speed is 350 r / min. After melt blending through a co-rotating twin-screw extruder, water-cooled strand pelletizing is carried out to obtain the said ABS composite.

[0082] The ABS composites provided in Examples 1 - 12 and Comparative Examples 1 - 4 are dried and injection molded into samples with dimensions of 80 mm * 50 mm * 2 mm. The samples are subjected to aging tests for color change under the following conditions:

[0083] Stage 1: Use a window glass filter to control the wavelength at 420 nm, the irradiance at 0.56 W / m 2 , the humidity inside the box at 50%, the box temperature at 38 °C, and the blackboard temperature at 43 °C. After drying and irradiating for 60 h under these conditions, transfer to Stage 2 for continued aging;

[0084] Stage 2: In a light-shielded oven, set the box temperature at 80 °C and the humidity at 90%. After aging treatment for 60 h under these conditions, take out for testing;

[0085] Sample testing: According to the test standard ASTM D2244 - 2015, use a spectrophotometer to measure the L, a, b scales of the samples before and after aging treatment, and calculate the color difference through the following formula

[0086]

[0087] where represents the value of the sample before aging treatment, represents the value of the sample after aging treatment.

[0088] The test method adopted in the present invention takes into account multiple aging variables. This evaluation system is closer to the actual use conditions. The results obtained by using this test method are shown in Tables 1 - 2.

[0089] Table 1

[0090]

[0091]

[0092] Table 2

[0093]

[0094]

[0095] Note: " / " indicates that the component is not included.

[0096] It can be concluded from the test results that:

[0097] (1) It can be seen from Examples 1 to 12 that by introducing a colorant composition in which a light-transmitting colorant, a light-absorbing colorant, and a light-reflecting colorant are used in combination into the ABS composite material, the present invention has excellent anti-aging discoloration ability, and the color difference is controlled within 2.0.

[0098] (2) It can be seen from the comparison between Example 1 and Examples 8 to 9 that when the dosage of the colorant composition is too small in the present invention, the color difference increases and the anti-discoloration ability of the material becomes poor; when the dosage is too large, the color difference increases and the anti-color change ability of the material becomes poor; it can be seen from the comparison between Example 1 and Example 10 that when the particle size of the light-reflecting colorant is too large, the anti-aging discoloration ability becomes poor; it can be seen from the comparison between Example 1 and Examples 11 to 12 that by optimizing the absorption band of the light-transmitting colorant, the anti-aging discoloration ability of the material can be improved.

[0099] (3) It can be seen from the comparison between Example 1 and Comparative Examples 1 to 3 that when any one of the light-transmitting colorant, the light-absorbing colorant, or the light-reflecting colorant is missing in the colorant composition, the anti-aging discoloration ability of the material becomes poor; it can be seen from the comparison between Example 1 and Comparative Example 4 that when the light-absorbing colorant is replaced by an ultraviolet absorber, the anti-aging discoloration ability of the material becomes poor.

[0100] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention 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 technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

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

2. The ABS composite material according to claim 1, characterized in that: The weight content of the structural unit based on acrylonitrile in the ABS resin is 12-35%, the weight content of the structural unit based on butadiene is 8-35%, and the weight content of the structural unit based on styrene is 30-80%; Preferably, the weight average molecular weight of the ABS resin is 94000-150000 g / mol.

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

4. The ABS composite material according to claim 1, characterized in that: The light absorbing colorant includes an inorganic colorant having an absorption band of 380-750nm in the visible light region; Preferably, the inorganic colorant having an absorption band of 380 to 750 nm in the visible light region includes any one of carbon black, copper chrome black or iron chrome black, or a combination of at least two of them.

5. The ABS composite material according to claim 1, characterized in that: The light-reflecting colorant includes rutile titanium dioxide; Preferably, the D50 particle size of the rutile titanium dioxide is 0.2-0.36 μm.

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

7. The ABS composite material according to claim 1, characterized in that: The ABS composite material also includes 0.2 to 1.5 parts of antioxidant; Preferably, the antioxidant comprises a hindered phenol antioxidant and / or a phosphite antioxidant.

8. The ABS composite material according to claim 1, characterized in that: The ABS composite material also includes 0.3 to 1.8 parts of lubricant; Preferably, the lubricant includes any one of an amide lubricant, a stearate lubricant, an ester lubricant or a silicone lubricant, or a combination of at least two of them.

9. A method for preparing the ABS composite material according to any one of claims 1 to 8, characterized in that: The preparation method comprises: The components of the ABS composite material are mixed, melt-extruded, cooled and granulated to obtain the ABS composite material.

10. Use of the ABS composite material according to any one of claims 1 to 8 in ageing-resistant discoloration parts.

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