Infrared-transmissive flame-retardant ABS composite material, preparation method and application thereof

Abstract

The application discloses an infrared-transmitting flame-retardant ABS composite material and a preparation method and application thereof. The ABS composite material comprises MABS resin, PMMA resin and a flame retardant, wherein the flame retardant comprises low-molecular bromine flame retardant and liquid phosphate ester in a mass ratio of (4-15):1. The ABS composite material can further comprise ultraviolet absorber, light stabilizer and antibacterial and mildew-proof agent. The ABS composite material of the application takes MABS resin and PMMA resin as a matrix, controls the proportion of the two, improves infrared transmittance and scratch resistance, adopts a compound system of bromine flame retardant and liquid phosphate ester to improve the flame-retardant effect of the system and reduce the decrease of infrared transmittance of the material, simultaneously adds specific ultraviolet absorber and light stabilizer to improve weather resistance, so that the ABS composite material can be applied to long-term high-temperature and high-humidity environment, and adds antibacterial and mildew-proof agent to provide antibacterial and mildew-proof performance and reduce the influence on infrared transmittance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ABS material, more particularly, to an infrared-transmissive flame-retardant ABS composite material and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of green and healthy smart home, the performance requirements of intelligent control panel materials of intelligent household appliances, bathroom products and the like are higher and higher. ABS resin is a ternary graft copolymer of acrylonitrile-butadiene-styrene, has a mechanical property of rigid and tough balance, excellent chemical resistance and dimensional stability, and is easy to process and shape. The transparent ABS resin (MABS) also has good infrared transmissivity and can be used for intelligent control panel materials. However, the MABS itself has a low oxygen index, is flammable, and the surface hardness of its product is low, the pencil hardness is only at the level of 2B-B, and the scratch resistance is poor, which fails to meet the requirements of intelligent control panel materials.

[0003] The MABS resin before modification is a high-transparency material, but after flame-retardant modification, it usually becomes a non-transparent material and the infrared transmissivity is significantly reduced, so it is difficult to simultaneously consider the infrared transmissivity, flame retardancy and scratch resistance. Patent CN103289294A proposes a transparent flame-retardant ABS material, which introduces an environmentally-friendly bromine-based flame retardant, an antimony-based flame-retardant synergist, a phosphorus-based flame-retardant synergist and a toughening agent in the transparent ABS resin matrix, so that after flame-retardant modification, the material still has high transparency and good mechanical properties and weather resistance. However, the light transmittance can only reach 45-78% when the flame retardancy is V-2 or above, and the scratch resistance needs to be improved.

[0004] In addition, as an appearance part, the control panel has high requirements for the weather resistance of the material, especially in some use scenarios where light is directly irradiated indoors or outdoors, the yellowing resistance of the material has a great influence on the service life. At the same time, with the rapid development of green and healthy smart home, the demand for antibacterial and mildew-proof is increasing in some use scenarios of household appliances, bathroom products and the like, and it is worth discussing and researching how to make the material have weather resistance and antibacterial and mildew-proof function while ensuring infrared transmissivity and scratch resistance. SUMMARY

[0005] The present application aims to overcome the defects and deficiencies that the existing flame-retardant ABS cannot simultaneously consider infrared transmissivity, flame retardancy and scratch resistance, and provide an ABS composite material.

[0006] Another object of the present application is to provide a preparation method of the ABS composite material.

[0007] Another object of the present application is to provide an application of the ABS composite material in preparing a control panel material.

[0008] The above object of the present application is achieved by the following technical solutions.

[0009] The present application protects an ABS composite material, which comprises the following components in parts by mass:

[0010] MABS resin 50-70 parts,

[0011] PMMA resin 20-30 parts,

[0012] Flame retardant 10-15 parts,

[0013] The flame retardant comprises low-molecular bromine-based flame retardant and liquid phosphoric acid ester in a mass ratio of (4-15):1.

[0014] The ABS composite material of the present application takes MABS resin and PMMA resin as the matrix and controls the ratio of the two to improve the infrared transmittance and scratch resistance; the use of the combination of bromine-based flame retardant and liquid phosphoric acid ester improves the flame-retardant effect of the system, the liquid phosphoric acid ester can improve the flame-retardant stability of the bromine-based flame retardant and increase the flowability of the material, so that the material is easier to be extinguished by dripping, and under the synergistic effect of the bromine-based flame retardant and the liquid phosphoric acid ester, the V-2 level or above flame retardancy can be achieved at a lower amount of the flame retardant, thereby reducing the loss of the infrared transmittance of the material caused by the addition of the flame retardant.

[0015] It should be noted that the ratio of the components is particularly important, increasing the content of PMMA resin can improve the infrared transmittance and scratch resistance, but to some extent, it affects the impact strength and flame retardant performance; and too high content of the flame retardant is beneficial to improving the heat resistance, but it affects the infrared transmittance; the present application optimizes the content of each component to achieve that the ABS composite material can simultaneously consider the infrared transmittance, flame retardancy and scratch resistance.

[0016] In addition, the low-molecular flame retardant has good compatibility with the ABS system and stable physical and chemical properties, compared with the high-molecular weight polymer flame retardant, it can avoid precipitation in a long-term high-temperature and high-humidity environment, which affects the infrared transmittance and flame retardancy of the material.

[0017] The low-molecular flame retardant in the present application refers to a flame retardant with a relative molecular mass of less than 1200; preferably, the low-molecular bromine-based flame retardant is selected from at least one of brominated triazine or tetrabromobisphenol A.

[0018] In some embodiments, the liquid phosphoric acid ester is at least one of bisphenol A-bis(diphenyl phosphate) (BDP), triethyl phosphate (TEP) or tris(2,3-dichloropropyl) phosphate (TCPP); preferably bisphenol A-bis(diphenyl phosphate).

[0019] Preferably, the mass ratio of low molecular weight bromine-based flame retardant to liquid phosphate ester in the flame retardant is (5-14):1, more preferably (5-13):1.

[0020] In some embodiments, the MABS resin content that enables the present invention to achieve its objective can be 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, or 70 parts.

[0021] In some embodiments, the PMMA resin content that enables the achievement of the present invention can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, or 30 parts.

[0022] In some embodiments, the flame retardant content that enables the achievement of the present invention can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts.

[0023] Both conventional MABS and PMMA resins can be used in this invention.

[0024] Preferably, the MABS resin has a haze of less than 4% (ASTM D1003) at a thickness of 2 mm and a transparency of more than 85% (ASTM D1003) at a thickness of 2 mm; more preferably, the haze is 0-2% and the transparency is 88-92%.

[0025] Preferably, the PMMA resin has a haze of less than 1% (ASTM D1003) at a thickness of 2 mm and a transparency of more than 90% (ASTM D1003) at a thickness of 2 mm; more preferably, the haze is 0-0.5% and the transparency is 90-94%.

[0026] In some embodiments, the MABS resin has a melt flow rate (ASTM D1238) of 6–23 g / 10 min at 220°C and 10 kg.

[0027] In some embodiments, the PMMA resin has a melt flow rate (ASTM D1238) of 8–17 g / 10 min at 230°C and 3.8 kg.

[0028] The ABS composite material further includes:

[0029] 0.3-0.7 parts UV absorber, 0.3-0.7 parts light stabilizer, and 0.6-1.2 parts transparent antibacterial and antifungal agent;

[0030] The transparent antibacterial and antifungal agent is a zolinone compound and / or a chitin compound.

[0031] The ABS composite material of this invention employs a compound system of brominated flame retardants and liquid phosphate esters to achieve a flame retardancy rating of V-2 or higher, while maintaining a low amount of flame retardant added, thus providing room for further material improvement. Adding specific amounts of UV absorbers and light stabilizers enhances weather resistance, enabling its application in long-term high-temperature and high-humidity environments; simultaneously, the addition of specific antibacterial and antifungal agents provides antibacterial and antifungal properties without significantly affecting the material's infrared transmittance and scratch resistance.

[0032] In some embodiments, the ultraviolet absorber is at least one of benzotriazole compounds, triazine compounds, or benzophenone compounds; preferably, it is a benzotriazole compound.

[0033] In some embodiments, the light stabilizer is a hindered amine compound and / or a hydroquinone compound. A hindered amine compound is preferred.

[0034] In some embodiments, the mixture also includes 0.2-1 parts of antioxidant and 0.2-1 parts of processing aid.

[0035] Preferably, the antioxidant comprises a hindered amine primary antioxidant, or a combination of a hindered amine primary antioxidant and a phosphite secondary antioxidant.

[0036] The processing aids include, but are not limited to, lubricants, dispersants, white mineral oil, and coupling agents, or a mixture of one or more of these.

[0037] A method for preparing an ABS composite material involves uniformly mixing the raw material components in the specified amounts, then melt-blending and extruding to obtain the ABS composite material.

[0038] This invention protects the application of an ABS composite material in the manufacture of control panels.

[0039] Compared with the prior art, the beneficial effects of the present invention are:

[0040] This invention provides an ABS composite material with MABS resin and PMMA resin as the matrix, and controls the ratio of the two to improve infrared transmittance and scratch resistance. The flame retardant effect of the system is improved by compounding brominated flame retardants and liquid phosphate esters. The liquid phosphate ester can improve the flame retardant stability of brominated flame retardants, increase the fluidity of the material, and make the material easier to drip and extinguish. Under the synergistic effect of brominated flame retardants and liquid phosphate esters, flame retardancy of V-2 level or higher can be achieved with a low amount of flame retardant added, thereby reducing the loss of infrared transmittance of the material due to the addition of flame retardants.

[0041] The ABS composite material of the present invention also has good weather resistance and antibacterial and mildew-proof properties, and can take into account the infrared transmittance, flame retardancy and scratch resistance of the material, and can be used as control panel material for home appliances, bathroom products and other products. Detailed Implementation

[0042] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0043] The raw materials used in the following examples and comparative examples are as follows:

[0044] MABS resin:

[0045] MABS1#: MABS TR557, LG Chem; at 220°C and 10kg, the melt flow rate (ASTM D1238) is 21g / 10min, the transparency (ASTM D1003) is 90%, and the haze (ASTM D1003) is 2%.

[0046] MABS2#: MABS TR551, LG Chem; at 220°C and 10kg, the melt flow rate (ASTM D1238) is 8g / 10min, the transparency (ASTM D1003) is 90%, and the haze (ASTM D1003) is 1.9%.

[0047] PMMA resin:

[0048] PMMA1#: PMMA LG, Sumitomo Chemical Singapore Pte. Ltd.; at 230°C and 3.8 kg, the melt flow rate (ASTM D1238) is 10 g / 10 min, the transparency (ASTM D1003) is 92%, and the haze (ASTM D1003) is 0.5%.

[0049] PMMA 2#: PMMA LG2, Sumitomo Chemical Singapore Pte. Ltd.; at 230°C and 3.8 kg, the melt flow rate (ASTM D1238) is 15 g / 10 min, the transparency (ASTM D1003) is 92%, and the haze (ASTM D1003) is 0.5%.

[0050] Flame retardant:

[0051] Bromine-based flame retardant #1: Bromotriazine, FR-245, Israel Chemicals.

[0052] Bromine-based flame retardant #2: Tetrabromobisphenol A, FR-1524, Israel Chemicals.

[0053] Brominated flame retardant #3: Brominated epoxy resin, F-3014, Israel Chemicals.

[0054] Liquid phosphate ester: WSFR-BDP-N2, Zhejiang Wansheng Technology Co., Ltd.

[0055] Solid phosphate ester: WSFR-PX-220, Zhejiang Wansheng Technology Co., Ltd.

[0056] Nitrogen-based flame retardant: Melamine cyanurate (MCA), Sichuan Fine Chemical Research and Design Institute.

[0057] UV absorber 1#: Benzotriazole UV absorber, RIASORB UV-234, RIASORB Corporation.

[0058] UV absorber #2: Triazine UV absorber, UV-1577, BASF.

[0059] Light stabilizer 1#: Hindered amine light stabilizer, RIASORB UV-770DF, RIASORB Corporation.

[0060] Light stabilizer 2#: Hydroquinone-based light stabilizer, 2,5-ditert-butylhydroquinone (DBH), Wuhan Kanos Technology Co., Ltd.

[0061] Antibacterial and antifungal agent 1#: Organic transparent antibacterial and antifungal agent (azolinone class), JDGKP-007DG, Jinda Nanotechnology (Xiamen) Co., Ltd.

[0062] Antibacterial and antifungal agent #2: Chitosan-based organic transparent antibacterial and antifungal agent, KEPUYIN J160, Guangdong Kepuyin Biotechnology Co., Ltd.

[0063] Antibacterial and antifungal agent #3: Silver-plated glass antibacterial agent, IONPURE PZA, Ishizuka Glass Co., Ltd.

[0064] Antioxidants: RIANOX 1010 and RIANOX 168 in a mass ratio of 1:2, from Rianon Corporation.

[0065] Processing aids: EBS B50, PT.CMS CHEMICAL INDONESIA.

[0066] The ABS composite materials used in the following examples and comparative examples include the following steps:

[0067] The raw materials are mixed evenly, melt-blended, extruded and granulated to obtain the ABS composite material.

[0068] The melt blending process is carried out using a twin-screw extruder with an extrusion temperature of 180℃~225℃, a rotation speed of 200rpm~350rpm, and a feeding speed of 220kg / h~400kg / h.

[0069] Examples 1-14

[0070] This embodiment provides a series of ABS composite materials, the raw material composition of which is shown in Table 1.

[0071] Table 1. Raw material components (parts by mass) for Examples 1-14

[0072]

[0073] Comparative Examples 1-10

[0074] This embodiment provides a series of ABS composite materials, the raw material composition of which is shown in Table 2.

[0075] Table 2. Raw material composition (parts by mass) for Comparative Examples 1–10

[0076]

[0077] Performance testing

[0078] The ABS composite materials of Examples 1-14 and Comparative Examples 1-10 were subjected to the following tests, and the results are shown in Tables 3-4.

[0079] Infrared transmittance: A 70mm × 40mm × 3mm square injection molded sample was prepared from ABS composite material.

[0080] Tested using a TU-1810PC UV-Vis-IR spectrophotometer.

[0081] Transparency: Tested according to standard ASTM D1003.

[0082] Haze: Tested according to standard ASTM D1003.

[0083] Scratch resistance: The scratch resistance was evaluated using a color fastness tester for rubbing. The test sample was rubbed back and forth with gauze 500 times, and the depth of the scratches was observed under a Leica microscope at 200x magnification. The shallower the scratch, the better, and the deeper the scratch, the worse. The evaluation grades were: worst --, poor --, average 0, good +, best ++.

[0084] Pencil hardness: Tested according to ASTM D3363 standard; the method is as follows: A 70mm × 40mm × 3mm square injection-molded sample is placed on a fixed horizontal surface. A pencil is held at a 45° angle to the coating (pointing in the opposite direction to the tester) and pushed away from the tester, drawing a line 6.5mm long. This process begins with the hardest pencil and continues until the pencil no longer scratches the sample surface; the corresponding pencil hardness is the sample pencil hardness.

[0085] Xenon lamp aging: According to standard ISO 4892-2 method A cycle 1: Filter: daylight filter, 102 min illumination + 18 min spray irradiance: 0.51 W / (·nm)@340nm; Black panel temperature: 63℃; Chamber temperature:

[0086] 44℃; Relative humidity: 50%.

[0087] Flame retardancy performance: UL94 flame retardancy test standard, test sample thickness is 1.5mm.

[0088] Antibacterial rate: Standard GB / T 31402-2015 Surface antibacterial performance test, strain type: Staphylococcus aureus.

[0089] Table 3

[0090]

[0091] Table 4

[0092]

[0093]

[0094] The results show that the ABS composite material of the present invention has high infrared transmittance, good transparency, strong scratch resistance, high flame retardancy, and good weather resistance and antibacterial properties. Its infrared transmittance is above 82%, transparency is above 80%, haze is below 15%, scratch resistance is above + level, pencil hardness reaches HB, 500h xenon lamp aging ΔE ≤ 2.0, flame retardancy rating reaches V-2 level, and antibacterial rate is above 95%.

[0095] Compared to Example 1, the PMMA content in the ABS composite material of Comparative Example 1 is too high. Its infrared transmittance and scratch resistance are improved, but its flame retardant properties are significantly reduced, resulting in the material failing to reach the V-2 rating.

[0096] Compared to Example 1, Comparative Example 2, which uses a polymeric brominated flame retardant, exhibits a significant decrease in infrared transmittance and transparency, and a significant increase in haze. Comparative Example 3, which uses a solid phosphate ester instead of a liquid phosphate ester, results in a slight decrease in infrared transmittance and transparency, and an increase in haze. In Comparative Examples 4 and 5, when brominated flame retardants or liquid phosphate esters are used alone, relatively high amounts are required to achieve a V-2 flame retardancy rating, leading to a decrease in infrared transmittance and transparency, and an increase in haze. In Comparative Example 6, the ratio of low-molecular-weight brominated flame retardant to liquid phosphate ester is too high, resulting in a failure to achieve a V-2 flame retardancy rating. In Comparative Example 7, using an equal amount of nitrogen-based flame retardant, a V-2 flame retardancy rating is not achieved, and infrared transmittance and transparency decrease significantly, while haze increases.

[0097] Compared to Example 1, when the antibacterial and antifungal agent in Comparative Example 8 was made of silver-impregnated glass, the haze of the material increased significantly. In Comparative Example 9, when the content of antibacterial and antifungal agent increased, its infrared transmittance and transparency decreased.

[0098] Compared to Example 1, Comparative Example 10 had excessively high levels of UV absorber and light stabilizer. Although its resistance to xenon lamp aging was improved, its transparency decreased and its haze increased.

[0099] The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the implementation of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. An ABS composite material, characterized by, The ABS composite material comprises the following components by mass: MABS resin 50-70 parts, PMMA resin 20-30 parts, Flame retardant 10-15 parts, UV absorber 0.3-0.7 parts, Light stabilizer 0.3-0.7 parts, Transparent antibacterial and mildew-proof agent 0.6-1.2 parts; The transparent antibacterial and mildew-proof agent is a compound of oxazinone and / or chitin; The flame retardant comprises a low-molecular bromine-based flame retardant and a liquid phosphoric acid ester in a mass ratio of (4-15):1; The low-molecular bromine-based flame retardant is at least one selected from brominated triazine and tetrabromobisphenol A; The UV absorber is at least one selected from benzotriazole, triazine and benzophenone; and the light stabilizer is a hindered amine compound and / or hydroquinone.

2. The ABS composite of claim 1, wherein, The MABS resin has a melt flow rate of 6-23 g / 10 min at 220°C under a load of 10 kg.

3. The ABS composite of claim 1, wherein, The PMMA resin has a melt flow rate of 8-17 g / 10 min at 230°C under a load of 3.8 kg.

4. The ABS composite of claim 1, wherein, The MABS resin has a transparency of more than 85% and a haze of less than 4% at a thickness of 2 mm.

5. A process for the production of the ABS composite according to any one of claims 1 to 4, characterized in that The ABS composite material is obtained by uniformly mixing the components in the formula amount and melt blending and extruding.

6. Use of the ABS composite material of any one of claims 1-4 in the preparation of a control panel.

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