An antibacterial AS masterbatch and its preparation method and an antibacterial PC / ABS alloy

Abstract

The invention discloses an antibacterial AS masterbatch, which comprises the following components by weight: 100 parts of AS resin and carboxylic acid ionomer, wherein the carboxylic acid ionomer accounts for 20-50 parts; 15-40 parts of antibacterial agent; the carboxylic acid ionomer is an ethylene / methacrylic acid copolymer, wherein 25mol%-90mol% of the carboxyl groups in the methacrylic acid unit are neutralized by metal ions. The antibacterial AS masterbatch of the invention is suitable for application in antibacterial PC / ABS alloy, and has the advantages of uniform distribution of antibacterial agent and strong antibacterial property, especially higher retention rate of antibacterial property after heat aging.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to an antibacterial AS masterbatch and a preparation method thereof, and an antibacterial PC / ABS alloy. Background Art

[0002] Polycarbonate (abbreviated as PC resin, bisphenol A type PC) is a highly linear thermoplastic polymer material with flexible carbonate groups and rigid benzene ring groups on the main chain. Such a molecular chain structure gives PC materials good rigidity, heat resistance and excellent notched impact resistance. PC and ABS blends can combine the excellent properties of both. On the one hand, PC / ABS alloy has better heat resistance, impact strength and tensile strength than ABS. On the other hand, its cost and melt viscosity are lower than PC, and its processing performance is better than PC. The sensitivity of its product internal stress and impact strength to product thickness is greatly reduced. It can be used to form large-area or thin-walled long-process products. It is widely used in mechanical parts, electrical components, helmets and automobile bodies, etc., which require both excellent impact resistance and rigidity. Such as automotive interior and exterior parts, home appliances (TVs, telephones, etc.), computers and peripherals, office automation equipment housings, communication equipment and other fields.

[0003] The antibacterial properties of plastic materials are mainly achieved by adding antibacterial agents. However, it is difficult to disperse antibacterial agents in resins. Bacteria can easily breed in places where antibacterial agents are not dispersed. When a certain concentration is reached, bacteria will break through to areas with low antibacterial agent concentrations, resulting in antibacterial failure. Traditional antibacterial masterbatches mainly focus on the compatibility of antibacterial agents in PC / ABS alloy materials, so that antibacterial agents are dispersed in plastics without choice. However, antibacterial agents play a more important role on the surface of plastics. In order to meet antibacterial requirements, traditional antibacterial masterbatches will increase the amount of antibacterial agents used. This will cause some antibacterial agents to aggregate in the material, thereby reducing the toughness of the material. Summary of the invention

[0004] The purpose of the present invention is to overcome the above technical defects and provide an antibacterial AS masterbatch suitable for PC / ABS alloy, so that the alloy has excellent antibacterial properties, especially a higher retention rate of antibacterial properties after thermal aging.

[0005] Another object of the present invention is to provide a method for preparing the antibacterial AS masterbatch and an antibacterial PC / ABS alloy.

[0006] The present invention is achieved through the following technical solutions:

[0007] An antibacterial AS masterbatch, comprising the following components in parts by weight:

[0008] AS resin and carboxylic acid ionomer 100 parts, wherein the carboxylic acid ionomer accounts for 20-50 parts;

[0009] 15-40 parts of antibacterial agent;

[0010] The carboxylic acid-based ionomer is an ethylene / methacrylic acid copolymer, wherein 25 mol% to 90 mol% (molar ratio content) of the carboxyl groups in the methacrylic acid units are neutralized by metal ions.

[0011] Preferably, the AS resin and the carboxylic acid ionomer are 100 parts, wherein the carboxylic acid ionomer accounts for 30-40 parts;

[0012] Preferably, in the carboxylic acid-based ionomer, 30 mol% to 45.1 mol% of the carboxyl groups in the methacrylic acid units are neutralized by metal ions.

[0013] The metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion and potassium ion. The melt index of the carboxylic acid-based ionomer is between 0.5-6 g / 10 min. The test conditions are 190° C. and 2.16 kg.

[0014] Preferably, the metal ion is selected from at least one of zinc ion and magnesium ion.

[0015] The carboxylic acid-based ionomer can be a commercial product or a self-made raw material. In order to more accurately illustrate the innovation of the present invention, the specific implementation of the present invention adopts self-made raw materials.

[0016] The preparation method of the carboxylic acid-based ionomer is as follows: according to the calculated neutralization degree ratio, ethylene-methacrylic acid and Zn(CH3COO)2·2H2O (or sodium hydroxide, potassium hydroxide, magnesium hydroxide) are uniformly mixed and then extruded into granules through a twin-screw extruder, the screw temperature is 150-170°C, and the speed range is 150-350 r / min.

[0017] The antibacterial agent is selected from at least one of quaternary ammonium salt antibacterial agents, copper ion antibacterial agents, zinc ion antibacterial agents, and silver ion antibacterial agents;

[0018] Preferably, the antibacterial agent is selected from at least one of a copper ion antibacterial agent, a zinc ion antibacterial agent, and a silver ion antibacterial agent;

[0019] More preferably, the antibacterial agent is selected from at least one of a zinc ion antibacterial agent and a silver ion antibacterial agent.

[0020] Further preferably, when the antibacterial agent is selected from zinc ion antibacterial agents, the metal ion that neutralizes the carboxylic acid group is selected from zinc ions.

[0021] Preferably, when a zinc ion antibacterial agent is selected and the metal ions in the carboxylic acid-based ionomer are also zinc ions, the antibacterial property can be further improved.

[0022] The quaternary ammonium salt antibacterial agent is selected from one or more of monoalkyl quaternary ammonium salt antibacterial agents, dialkyl quaternary ammonium salt antibacterial agents, organosilicon quaternary ammonium salt antibacterial agents, organic fluorine quaternary ammonium salt antibacterial agents, and organic chloride quaternary ammonium salt antibacterial agents;

[0023] The copper ion antibacterial agent is selected from a non-carrier type copper ion antibacterial agent or a carrier type copper ion antibacterial agent;

[0024] The zinc ion antibacterial agent is selected from a non-carrier type zinc ion antibacterial agent or a carrier type zinc ion antibacterial agent;

[0025] The silver ion antibacterial agent is selected from a non-carrier type silver ion antibacterial agent or a carrier type silver ion antibacterial agent;

[0026] The carrier can be a zirconium phosphate carrier, a silica gel carrier, a glass carrier, a zeolite carrier, a nano-ceramic carrier, etc.

[0027] The AN content in the AS resin is 21-35wt%; preferably, the AN content in the AS resin is 26-30wt%, which has a better antibacterial effect.

[0028] AN refers to acrylonitrile monomer.

[0029] In order to improve the antistatic masterbatch and obtain other properties, a certain amount of additives can be selectively added. By weight, 0-2 parts of additives are also included; the additives are selected from at least one of antioxidants and lubricants. The lubricant can be a pentaerythritol lubricant, a stearate lubricant, etc., and the antioxidant can be a hindered phenol antioxidant or a hindered amine antioxidant.

[0030] The preparation method of the antibacterial AS masterbatch of the present invention comprises the following steps: according to the proportion, the carboxylic acid-based ionomer, AS resin and antibacterial agent are uniformly mixed and then extruded into granules by a twin-screw extruder, the screw temperature is 200-270°C, and the speed range is 180-500 r / min.

[0031] An antibacterial PC / ABS alloy comprises the following components in parts by weight:

[0032] 30-70 parts of PC resin;

[0033] ABS resin 30-70 parts;

[0034] The antibacterial AS masterbatch of the present invention is 10-50 parts.

[0035] The present invention has the following beneficial effects:

[0036] In order to solve the problem of uneven dispersion of antibacterial agents in a multiphase system of PC / ABS, the present invention provides an antibacterial masterbatch, which selects ionic antibacterial agents. First, it is utilized that ionic antibacterial agents (especially metal ions) have good dispersion in carboxylic acid ionomers of carboxylic acid ion groups. Second, since the compatibility of carboxylic acid ionomers with ABS resin is poor, the addition of AS resin can improve the compatibility of carboxylic acid ionomers and ABS so that they tend to be on the surface of ABS resin. Third, the carboxylic acid ionomers have a certain compatibility with PC resin and are more inclined to be dispersed on the surface of PC resin. Therefore, after the antibacterial masterbatch of the present invention is applied to PC / ABS alloy, the antibacterial agent can be evenly and densely dispersed on the surface of PC / ABS alloy, thereby solving the problem of difference in antibacterial properties at different positions of the alloy.

[0037] The presence of carboxylic acid-based ionomers can also protect the antimicrobial agent from oxidation and precipitation, resulting in less decrease in antimicrobial properties after thermal aging. DETAILED DESCRIPTION

[0038] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0039] The sources of raw materials used in the present invention are as follows:

[0040] AS resin A: AN content is 30 wt%, brand Luran DN50, manufacturer: Benling Chemical;

[0041] AS resin B: AN content is 26wt%, brand SAN NF2200 AK, manufacturer is Formosa Chemical Corporation;

[0042] AS resin C: AN content is 21wt%, brand SAN 310 N TR, manufacturer is Kumho, South Korea;

[0043] AS resin D: AN content is 35 wt%, brand SAN 350 N, manufacturer is Kumho, South Korea;

[0044] Carboxylic acid ionomer A: 39.9 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 2.1 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0045] Carboxylic acid ionomer B: 30 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 1.8 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0046] Carboxylic acid ionomer C: 45.1 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 4.5 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0047] Carboxylic acid ionomer D: 26.5 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 2.4 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0048] Carboxylic acid ionomer E: 77.9 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 2.3 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0049] Carboxylic acid ionomer F: 89.9 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 2.6 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0050] Carboxylic acid ionomer G: 45.1 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by magnesium metal ions, the melt index is between 3.2 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0051] Carboxylic acid ionomer H: 45.1 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by sodium metal ions, the melt index is between 1.9 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0052] Carboxylic acid ionomer I: 45.1 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by potassium metal ions, the melt index is between 2.0 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0053] Carboxylic acid ionomer J: 20 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 3.3 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0054] Carboxylic acid ionomer K: 95 mol% of the carboxyl groups in the methacrylic acid unit are neutralized by zinc metal ions, the melt index is between 2.2 g / 10 min, the test conditions are 190 ° C, 2.16 kg, homemade;

[0055] Antimicrobial agent A: Silver ion antimicrobial agent, B 103, manufacturer Langyi New Materials, carrier is glass

[0056] Antibacterial agent B: copper ion antibacterial agent, B 403, manufacturer Langyi New Materials, carrier is glass;

[0057] Antimicrobial agent C: zinc ion antimicrobial agent, B 203, manufacturer Langyi New Materials, carrier is glass;

[0058] Antimicrobial agent D: monoalkyl quaternary ammonium salt antimicrobial agent, QPAV, Kerui Chemical.

[0059] Polycarbonate resin: PC WY-106BR, monomers are bisphenol A (BPA) and diphenyl carbonate (DPC), commercially available;

[0060] ABS: Chimei, ABS PA-757;

[0061] Embodiment and comparative example Preparation method of antibacterial AS masterbatch: According to the ratio, carboxylic acid-based ionomer, AS resin and antibacterial agent are uniformly mixed and then extruded into granules by a twin-screw extruder, the screw temperature is 200-270° C., and the speed range is 250 r / min.

[0062] Embodiment and comparative example Preparation method of antibacterial PC / ABS alloy: According to the ratio, antibacterial AS masterbatch, polycarbonate resin and ABS resin are uniformly mixed, and then extruded into granules by a twin-screw extruder, and the screw temperature is set to 210-260°C and the speed is 250 r / min.

[0063] Various test methods:

[0064] (1) Antibacterial rate: tested in accordance with standard GB21551.2-2010, film method; the fungus is Staphylococcus aureus.

[0065] (2) Antibacterial retention rate after thermal aging: After baking in a hot oxygen oven at 80℃ for 48 hours, the test was carried out in accordance with standard GB21551.2-2010, using the film method. Antibacterial retention rate after thermal aging = initial antibacterial rate / antibacterial rate after thermal aging.

[0066] Table 1: A1-7 antibacterial AS masterbatch (parts by weight)

[0067] A1 A2 A3 A4 A5 A6 A7 AS Resin A 50 80 70 60 AS resin B 50 AS Resin C 50 AS Resin D 50 Carboxylate Ionomer A 50 50 50 50 20 30 40 Antimicrobial Agent A 25 25 25 25 15 25 40

[0068] Table 2: A8-15 antibacterial AS masterbatch (parts by weight)

[0069] A8 A9 A10 A11 A12 A13 A14 A15 AS Resin A 70 70 70 70 70 70 70 70 Carboxylic acid ionomer B 30 Carboxylic acid ionomer C 30 Carboxylic acid ionomer D 30 Carboxylic acid ionomer E 30 Carboxylate Ionomer F 30 Carboxylate Ionomer G 30 Carboxylic acid ionomer H 30 Carboxylate Ionomer I 30 Antimicrobial Agent A 25 25 25 25 25 25 25 25

[0070] Table 3: A16-19 antibacterial AS masterbatch (parts by weight)

[0071] A16 A17 A18 A19 AS Resin A 70 70 70 70 Carboxylate Ionomer A 30 30 30 Carboxylate Ionomer G 30 Antimicrobial Agent B 25 Antimicrobial Agent C 25 25 Antimicrobial Agent D 25

[0072] Table 4: B antibacterial AS masterbatch (parts by weight)

[0073] B1 B2 B3 B4 B5 B6 AS Resin A 100 90 40 70 70 Carboxylate Ionomer A 10 60 100 Carboxylic acid ionomer J 30 Carboxylic acid ionomer K 30 Antimicrobial Agent A 25 25 25 25 25 25

[0074] Table 5: Antibacterial PC / ABS alloys of Examples and Comparative Examples (parts by weight) and test results

[0075] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polycarbonate 60 60 60 60 60 60 60 ABS 40 40 40 40 40 40 40 Antibacterial AS Masterbatch A1 A2 A3 A4 A5 A6 A7 Antibacterial AS masterbatch, 1 part 30 30 30 30 30 30 30 Antibacterial rate, % 98.0 97.8 94.1 95.2 84.4 96.1 98.6 Antibacterial retention rate, % 98.7 99.6 96.6 97.4 96.4 98.9 99.6

[0076] It can be seen from Examples 1-4 that the AS resin preferably has an AN content of 26-30wt% for better antibacterial effect.

[0077] It can be seen from Examples 1 / 5 / 6 / 7 that the content of the AS resin is preferably 60-70 parts and the content of the carboxylic acid ionomer is preferably 30-40 parts.

[0078] Table 5: Antibacterial PC / ABS alloys of Examples and Comparative Examples (parts by weight) and test results

[0079] Example 8 Example 9 Example 10 Embodiment 11 Example 12 Example 13 Embodiment 14 Embodiment 15 Polycarbonate 60 60 60 60 60 60 60 60 ABS 40 40 40 40 40 40 40 40 Antibacterial AS Masterbatch A8 A9 A10 A11 A12 A13 A14 A15 Antibacterial AS masterbatch, 1 part 30 30 30 30 30 30 30 30 Antibacterial rate, % 96.8 95.9 92.1 91.3 90.0 93.6 92.6 91.4 Antibacterial retention rate, % 95.4 95.1 93.4 93.9 93.1 96.5 94.7 93.4

[0080] As can be seen from Examples 6 / 8-15, it is preferred that the carboxyl group ionomer is one in which 30 mol% to 45.1 mol% of the carboxyl groups in the methacrylic acid units are neutralized by metal ions, and the metal ions are preferably magnesium and zinc.

[0081] Table 5: Antibacterial PC / ABS alloys of Examples and Comparative Examples (parts by weight) and test results

[0082] Example 16 Embodiment 17 Embodiment 18 Embodiment 19 Polycarbonate 60 60 60 60 ABS 40 40 40 40 Antibacterial AS Masterbatch A16 A17 A18 A19 Antibacterial AS masterbatch, 1 part 30 30 30 30 Antibacterial rate, % 93.4 99.2 90.8 95.6 Antibacterial retention rate, % 94.5 99.8 89.6 96.4

[0083] It can be seen from Examples 6 / 16-19 that the antibacterial agent is preferably a zinc ion antibacterial agent or a silver ion antibacterial agent; specifically, it can be seen from Examples 17 / 19 that when the carboxylic acid-based ionomer is neutralized with zinc ions, the antibacterial property of the zinc ion antibacterial agent can be improved.

[0084] Table 5 continued:

[0085] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Polycarbonate 60 60 60 60 60 60 ABS 40 40 40 40 40 40 Antibacterial AS Masterbatch B1 B2 B3 B4 B5 B6 Antibacterial AS masterbatch, 1 part 30 30 30 30 30 30 Antibacterial rate, % 63.1 66.4 65.6 61.9 69 65.7 Antibacterial retention rate, % 79.6 84.1 87.4 85.3 84.9 83.1

[0086] It can be seen from Comparative Examples 1-4 that the ratio of AS / carboxylic acid-based ionomer in the antibacterial AS masterbatch will significantly affect the antibacterial properties of the antibacterial AS masterbatch after it is applied to polycarbonate / ABS alloy.

[0087] It can be seen from Comparative Examples 5 / 6 that if the amount of methacrylic acid units in the carboxylic acid-based ionomers neutralized by metal ions is too low or too high, the antibacterial property will be significantly reduced.

Claims

1. An antibacterial AS masterbatch, characterized in that: By weight, it includes the following components: AS resin and carboxylic acid ionomer 100 parts, wherein the carboxylic acid ionomer accounts for 20-50 parts; 15-40 parts of antibacterial agent; The carboxylic acid-based ionomer is an ethylene / methacrylic acid copolymer, and 25 mol% to 90 mol% of the carboxyl groups in the methacrylic acid units are neutralized by metal ions; The antibacterial agent is selected from at least one of quaternary ammonium salt antibacterial agents, copper ion antibacterial agents, zinc ion antibacterial agents and silver ion antibacterial agents.

2. The antibacterial AS masterbatch according to claim 1, characterized in that: AS resin and carboxylic acid ionomer 100 parts, wherein the carboxylic acid ionomer accounts for 30-40 parts; 30 mol%-45.1 mol% of the carboxyl groups in the methacrylic acid units of the carboxylic acid ionomer are neutralized by metal ions.

3. The antibacterial AS masterbatch according to claim 1, characterized in that: The metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion and potassium ion. The melt index of the carboxylic acid-based ionomer is between 0.5-6 g / 10 min. The test conditions are 190° C. and 2.16 kg.

4. The antibacterial AS masterbatch according to claim 1, characterized in that: The metal ions are selected from at least one of zinc ions and magnesium ions.

5. The antibacterial AS masterbatch according to claim 1, characterized in that: The antibacterial agent is selected from at least one of a copper ion antibacterial agent, a zinc ion antibacterial agent and a silver ion antibacterial agent.

6. The antibacterial AS masterbatch according to claim 5, characterized in that: The antibacterial agent is selected from at least one of a zinc ion antibacterial agent and a silver ion antibacterial agent.

7. The antibacterial AS masterbatch according to claim 6, characterized in that: When the antimicrobial agent is selected from zinc ion antimicrobial agents, the metal ion of the carboxylic acid group ionomer is selected from zinc ion.

8. The antibacterial AS masterbatch according to claim 1, characterized in that: The quaternary ammonium salt antibacterial agent is selected from one or more of monoalkyl quaternary ammonium salt antibacterial agents, dialkyl quaternary ammonium salt antibacterial agents, silicone quaternary ammonium salt antibacterial agents, organic fluorine quaternary ammonium salt antibacterial agents, and organic chloride quaternary ammonium salt antibacterial agents; the copper ion antibacterial agent is selected from non-carrier type copper ion antibacterial agents or carrier type copper ion antibacterial agents; the zinc ion antibacterial agent is selected from non-carrier type zinc ion antibacterial agents or carrier type zinc ion antibacterial agents; the silver ion antibacterial agent is selected from non-carrier type silver ion antibacterial agents or carrier type silver ion antibacterial agents.

9. The antibacterial AS masterbatch according to claim 1, characterized in that: In the AS resin, the AN content is 21-35wt%.

10. The antibacterial AS masterbatch according to claim 9, characterized in that: The AN content in the AS resin is 26-30wt%.

11. The antibacterial AS masterbatch according to claim 10, characterized in that: By weight, the invention also includes 0-2 parts of auxiliary agents; the auxiliary agents are selected from at least one of antioxidants and lubricants.

12. The method for preparing the antibacterial AS masterbatch according to any one of claims 1 to 11, characterized in that: The method comprises the following steps: according to the proportion, the carboxylic acid-based ionomer, AS resin and antibacterial agent are uniformly mixed and then extruded into granules through a twin-screw extruder, the screw temperature is 200-270°C, and the speed range is 180-500 r / min.

13. An antibacterial PC / ABS alloy, characterized in that: By weight, it includes the following components: 30-70 parts of PC resin; ABS resin 30-70 parts; 10-50 parts of the antibacterial AS masterbatch according to any one of claims 1-11.