ABS (Acrylonitrile Butadiene Styrene) material and preparation method and application thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) material which comprises the following components in parts by weight: 90-95 parts of ABS resin; 4 to 6 parts of anatase titanium dioxide; 0.5 to 1.5 parts of cesium tungstate nano particles; the average particle size of the cesium tungstate nano-particles ranges from 50 nm to 400 nm. The ABS material with high L value and low infrared reflection can be obtained by exploring the particle size of the cesium tungstate nanoparticles and adjusting the content of the anatase titanium dioxide and the cesium tungstate nanoparticles.

Description

Technical Field

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

[0002] A smoke alarm mainly consists of a housing material, a transmitter, a receiver, and a detection chamber. The wavelength of infrared rays is mainly in the range of 800 - 1000 nm or 800 - 1500 nm, which depends on the design of the infrared LED and the receiver used. In this wavelength band, when there are fine particles (such as smoke) in the environment, the smoke particles will scatter the infrared light emitted by the transmitter. According to the Beer-Lambert law I = I0⋅e −αC , as the smoke concentration C increases, the scattered light intensity will increase rapidly, while the intensity of the infrared light passing through the smoke I will decrease exponentially. When it reaches the set threshold, it will alarm. If the housing material reflects infrared light, it will interfere with the normal operation of the detector, thus affecting the detection accuracy of smoke. Currently, to solve this problem, usually the housing will be subjected to light absorption and special texture treatment, which results in a relatively high processing cost, and the coating is often prone to damage, posing a safety hazard, or choosing non-infrared-reflective plastics. However, due to technical reasons, among different colors, black has the lowest reflectivity, so most materials have a black appearance.

[0003] ABS white materials mainly improve the whiteness of the materials by adding white pigments (such as titanium dioxide or zinc sulfide). The refractive index of titanium dioxide or zinc sulfide is between 2.4 and 2.8, and in the visible light band λ = 400 - 750 nm. Most of their particle sizes are controlled at d = 1 / 2 wavelength = 0.2 - 0.36 μm. The control of the refractive index and particle size results in that while they have a reflection effect on visible light, they also have a strong reflection effect on infrared light in the range of 780 - 2000 nm. Therefore, currently, there are few low-infrared-reflective plastics with a high whiteness appearance. In the current field of low-infrared-reflective plastics, the commonly used method is to add black pigments (such as carbon black), dark pigments (such as iron oxide or titanium oxide), or organic compounds (such as phthalocyanine-based, thiodiene-based, naphthalimide-based, or azo-based pigments or dyes). These pigments or dyes mainly effectively absorb infrared light rather than reflect it in plastics. However, dark pigments often bring limitations to the product appearance design, and organic infrared absorbers, such as BASF's "Lumogen", Clariant's "Hostaprint NIR", or Chemours' "Teflon® FEP", have a very high market price, and the product cost is difficult to bear, and their thermal stability and light stability are relatively poor compared with inorganic pigments. Therefore, there are still technical bottlenecks in high-L-value, low-infrared-reflective white ABS materials at present. Summary of the Invention

[0004] The object of the present invention is to provide an ABS material with a high L value and low infrared reflection, as well as its preparation method and application.

[0005] The present invention is achieved by the following technical solutions: An ABS material, by weight, comprises the following components: ABS resin 90 - 95 parts; Anatase titanium dioxide 4 - 6 parts; Cesium tungstate nanoparticles 0.5 - 1.5 parts; The average particle size range of the cesium tungstate nanoparticles is 50 - 400 nm.

[0006] The molecular formula of cesium tungstate is Cs 0.33 WO3.

[0007] The average particle size range of the anatase titanium dioxide is 0.15 - 0.35 microns, preferably 0.2 - 0.3 microns.

[0008] Preferably, the average particle size range of the cesium tungstate nanoparticles is 100 - 200 nm.

[0009] The average particle sizes of the cesium tungstate nanoparticles and the anatase titanium dioxide are measured by a laser particle size analyzer.

[0010] The cesium tungstate nanoparticles can be commercially available products or obtained by self - preparation. The self - preparation method can be, but is not limited to: dispersing cesium hydroxide hydrate and tungsten chloride in benzyl alcohol, with the concentration of the tungsten chloride / benzyl alcohol solution being between 0.013 - 0.017 M, reacting in an autoclave (temperature 190 - 210 °C, reaction time 3 - 5 hours), and then obtaining the raw materials with a specific average particle size through centrifugation, drying, grinding, and screening.

[0011] The present invention does not have a special limitation on the melt flow rate of the ABS resin. Preferably, the melt flow rate range of the ABS resin is 15 - 30 g / 10 min, 230 °C / 2.16 kg. The test standard for the melt flow rate is ASTM D1238.

[0012] By weight, it further comprises 0 - 1.5 parts of an auxiliary agent, and the auxiliary agent is selected from at least one of a dispersant, a silane coupling agent, and an antioxidant; The dispersant is selected from at least one of hyperbranched polyester, polymeric anionic dispersant, and polymeric non - ionic dispersant, preferably hyperbranched polyester; the hyperbranched polyester is selected from at least one of carboxyl - terminated hyperbranched polyester and hydroxyl - terminated hyperbranched polyester, preferably carboxyl - terminated hyperbranched polyester, and can be 0 - 0.6 parts.

[0013] The content of the silane coupling agent can be 0 - 0.1 parts.

[0014] The preparation method of the ABS material of the present invention comprises the following steps: Mix each component evenly according to the ratio, extrude and pelletize through a twin-screw extruder to obtain the ABS material, and the barrel temperature range is 220-250°C.

[0015] The application of the ABS material of the present invention is used for preparing a low-infrared reflection material, such as a smoke detector housing.

[0016] The present invention has the following beneficial effects: First, the use of anatase titanium dioxide can not only obtain a high L value but also reduce the infrared transmittance.

[0017] Second, the synergism of cesium tungstate with a specific average particle size and anatase titanium dioxide with a specific average particle size can reduce the infrared transmittance.

[0018] Third, the further introduction of a dispersant (preferably hyperbranched polyester) improves the steric hindrance effect, is beneficial to the dispersion of nanoparticles, can reduce the electrostatic interaction on the surface of inorganic substances, and thus improves the dispersibility of components.

[0019] The ABS material of the present invention has the advantages of high L value and low infrared reflection. Specific embodiments

[0020] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those of ordinary skill in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0021] The sources of raw materials used in the examples and comparative examples of the present invention are as follows: ABS-1: Purchased from LG of South Korea, grade TR558A, melt flow rate is about 23 g / 10 min, at 230°C, 2.16 kg; ABS-2: Purchased from Toray of Japan, melt flow rate is about 25 g / 10 min, at 230°C, 2.16 kg; The anatase titanium dioxide is purchased from TA-100 of Yantai Titanium Industry Co., Ltd., and raw materials with different average particle sizes are obtained through grinding and screening: Anatase titanium dioxide A: average particle size 0.16 μm; Anatase titanium dioxide B: average particle size 0.20 μm; Anatase titanium dioxide C: average particle size 0.29 μm; Anatase titanium dioxide D: average particle size 0.35 μm; Rutile titanium dioxide: average particle size 0.25 μm, purchased from TianGuang Titanium Dioxide, TIKON 33.

[0022] Cesium tungstate nanoparticles A-1: average particle size 56 nm, self-made; Cesium tungstate nanoparticles A-2: average particle size 110 nm, self-made; Cesium tungstate nanoparticles A-3: average particle size 193 nm, self-made; Cesium tungstate nanoparticles A-4: average particle size 387 nm, self-made; Cesium tungstate nanoparticles A-5: average particle size 31 nm, self-made; Cesium tungstate nanoparticles A-6: average particle size 662 nm, self-made; Cesium tungstate nanoparticles B: average particle size 220 nm, purchased from SS-CW20 of Xinzhongda New Materials Co., Ltd.; Antimony tin oxide: nano ATO, Jiangsu Tianxing New Materials, average particle size 210 nm; Antimony indium oxide: nano indium tin oxide (ITO), Luofei Nano Technology 120 nm; Carboxyl-terminated hyperbranched polyester A: Hyper C100, Wuhan Hyperbranched Resin Technology Co., Ltd.; Carboxyl-terminated hyperbranched polyester B: HyPer C201, Wuhan Hyperbranched Resin Technology Co., Ltd.; Hydroxyl-terminated hyperbranched polyester: HyPer H301, Wuhan Hyperbranched Resin Technology Co., Ltd.; Other dispersant A: polymer anionic dispersant, TDL-ND1, Jiangsu Tianxing New Materials; Other dispersant B: polymer non-ionic dispersant, TDL-ND2, Jiangsu Tianxing New Materials; Antioxidant: Irganox 1010, Irganox 168, purchased from Ciba; Preparation method of ABS materials in examples and comparative examples: According to the ratio, mix each component evenly, and extrude and pelletize through a twin-screw extruder to obtain ABS materials, and the barrel temperature range is 220 - 250 °C.

[0023] Each test method: (1) L value: Inject the ABS resin prepared in the present invention into a color plate with a length of 10 cm, a width of 5 cm, and a thickness of 2 mm. The injection temperature is 230 - 250 °C. Test the L value of the color plate. The test equipment is X-Rite spectrophotometer 7000A, and the test is based on GB / T3979-2008.

[0024] (2) Infrared reflection: The ABS resin prepared according to the present invention was injection molded into a color plate with a length of 10 cm, a width of 5 cm, and a thickness of 2 mm. The injection temperature was 230 - 250 °C. The infrared reflectance of the color plate was tested using the LAMBDA 1050+ from PerkinElmer, and the test was based on ISO 26723:2020.

[0025] Table 1: Weight parts of each component of ABS materials in Examples 1 - 7 and test results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 ABS-1 90 92 92 92 92 92 ABS-2 95 Anatase Titanium Dioxide A 6 5 4 5 Anatase Titanium Dioxide B 5 Anatase Titanium Dioxide C 5 Anatase Titanium Dioxide D 5 Cesium Tungstate Nanoparticle A-1 0.5 1.0 1.5 1.0 1.0 1.0 1.0 Carboxyl-Terminated Hyperbranched Polyester A 0.2 0.1 0.6 0.1 0.1 0.1 Carboxyl-Terminated Hyperbranched Polyester B 0.1 Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 L value 94.4 93.7 92.8 93.9 94.1 93.8 93.5 R (780~2000nm) 48.8 26.3 16.3 25.5 25.8 26.5 26.9 R (800~1500nm) 56.7 31.7 21.7 29.1 30.3 31.4 31.3 It can be seen from Examples 2 / 4 / 5 / 6 that when anatase titanium dioxide with a preferred average particle size is used, the near-infrared reflectance is lower.

[0026] Table 2: Weight parts of each component of ABS materials in Examples 8 - 12 and test results Example 8 Example 9 Example 10 Example 11 Example 12 ABS-1 92 90 90 90 90 Anatase Titanium Dioxide A 5 6 6 6 6 Cesium Tungstate Nanoparticle A-1 1.0 Cesium Tungstate Nanoparticle A-2 0.5 Cesium Tungstate Nanoparticle A-3 0.5 Cesium Tungstate Nanoparticle A-4 0.5 Cesium Tungstate Nanoparticle B 0.5 Carboxyl-Terminated Hyperbranched Polyester A 0.2 0.2 0.2 0.2 Hydroxyl-Terminated Hyperbranched Polyester 0.1 Antioxidant 0.2 0.2 0.2 0.2 0.2 L value 93.8 94.2 94.7 94.6 94.5 R (780~2000nm) 30.5 34.2 37.6 43.5 39.4 R (800~1500nm) 35.7 39.5 43.0 51.4 41.6 Table 3: Weight parts of each component of ABS materials in Examples 13 - 15 and test results Example 13 Example 14 Example 15 ABS-1 92 92 92 Anatase Titanium Dioxide A 5 5 5 Cesium Tungstate Nanoparticle A-1 1.0 1.0 1.0 Other Dispersant A 0.1 Other Dispersant B 0.1 Antioxidant 0.2 0.2 0.2 L value 93.2 93.6 93.4 R (780~2000nm) 35.3 33.1 32.8 R (800~1500nm) 40.3 37.4 36.6 It can be seen from Examples 2 / 7 / 8 / 13 / 14 / 15 that the dispersant can significantly reduce the R value. Hyperbranched polyester is preferred, and hyperbranched polyester with terminal carboxyl groups is more preferred.

[0027] It can be seen from Examples 1 / 9 - 12 that when the particle size of cesium tungstate nanoparticles is preferred, the near-infrared reflectance is significantly lower.

[0028] Table 4: Weight parts of each component of ABS materials in Comparative Examples and test results Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 ABS-1 90 90 90 90 90 90 Anatase Titanium Dioxide A 6 6 8 6 6 Rutile Titanium Dioxide 6 Cesium Tungstate Nanoparticle A-1 0.5 0.5 Cesium Tungstate Nanoparticle A-5 0.5 Cesium Tungstate Nanoparticle A-6 0.5 Antimony Tin Oxide 0.5 Antimony Indium Oxide 0.5 Carboxyl-Terminated Hyperbranched Polyester A 0.2 0.2 0.2 0.2 0.2 0.2 Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 L value 90.8 93.1 93.7 95.1 90.1 90.5 R (780~2000nm) 57.5 62.1 56.6 62.8 62.5 67.7 R (800~1500nm) 66.7 75.7 67.3 71.3 75.5 79.5 It can be seen from Comparative Example 1 that when rutile titanium dioxide is selected, the R value is too high.

[0029] It can be seen from Comparative Examples 2 - 3 that when the particle size of cesium tungstate is not within the scope of the present invention, the R value is too high, indicating that the average particle size of cesium tungstate significantly affects the near-infrared light reflection.

[0030] It can be seen from Comparative Example 4 that when the content of anatase titanium dioxide is too high, even if it is only 2 parts more than that in Example 1, the R value will also increase significantly.

[0031] It can be seen from Comparative Examples 5 / 6 that when other types of near-infrared reflection materials are selected, their reflection effects are not good and the L value is also low.

Claims

1. An ABS material, characterized in that, By weight, it comprises the following components: 90 - 95 parts of ABS resin; 4 - 6 parts of anatase titanium dioxide; 0.5 - 1.5 parts of cesium tungstate nanoparticles; The average particle size range of the cesium tungstate nanoparticles is 50 - 400 nm.

2. The ABS material according to claim 1, wherein The average particle size range of the anatase titanium dioxide is 0.15 - 0.35 microns.

3. The ABS material according to claim 2, wherein The average particle size range of the anatase titanium dioxide is 0.2 - 0.3 microns.

4. The ABS material according to claim 1, characterized in that, The average particle size range of the cesium tungstate nanoparticles is 100 - 200 nm.

5. The ABS material according to claim 1, wherein The melt flow rate range of the ABS resin is 15 - 30 g / 10 min, 230 °C / 2.16 kg.

6. The ABS material according to claim 1, wherein By weight, it further comprises 0 - 1.5 parts of an auxiliary agent, and the auxiliary agent is selected from at least one of a dispersant, a silane coupling agent, and an antioxidant.

7. The ABS material according to claim 6, wherein The dispersant is selected from at least one of hyperbranched polyester, polymeric anionic dispersant, and polymeric nonionic dispersant, preferably hyperbranched polyester; the hyperbranched polyester is selected from at least one of carboxyl - terminated hyperbranched polyester and hydroxyl - terminated hyperbranched polyester, and preferably, the hyperbranched polyester is carboxyl - terminated hyperbranched polyester.

8. The preparation method of the ABS material according to any one of claims 1-7, characterized in that It includes the following steps: Mix each component evenly according to the ratio, and extrude and pelletize through a twin - screw extruder to obtain the ABS material.

9. Use of the ABS material according to any one of claims 1-7, characterized in that, It is used for preparing a low - infrared - reflection material.