PC / ABS alloy material, preparation method and application thereof

Abstract

The application discloses a PC / ABS alloy material, which comprises the following components: PC resin 20-85 parts; ABS resin 10-75 parts; toughening agent 2-6 parts; LAP activator 4x10 ‑6 ‑1000×10 ‑6 parts; dispersing agent 0.1-0.5 parts; compatibilizer 0.5-2 parts; the LAP activator is selected from any one or several of carbon nanotubes or conductive carbon black; the dispersing agent is selected from any one or several of pentaerythritol stearate, polyester wax or E wax. The PC / ABS alloy material of the application can form a significant difference between the surface after being treated by laser engraving and the surface without laser engraving by adding a trace amount of LAP activator and a certain amount of dispersing agent, and the chemical plating catalyst and metal ions have selectivity during electroplating, so that the plating effect of the material is effectively improved, the problems of plating leakage or overflow are solved, and the material is particularly suitable for the LAP process; and the cold resistance of the material is excellent, and the toughness of the material can be maintained at a high level at low temperature.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a PC / ABS alloy material and a preparation method and application thereof. BACKGROUND

[0002] LAP (LASER ACTIVATED PROCESS, i.e. laser surface activation) is a manufacturing process for making three-dimensional circuit lines on the surface of plastic by laser direct forming and chemical surface nano-treatment. In simple terms, it is to engrave circuit lines on the surface of an injection molded structural part by laser, and then perform chemical plating to form three-dimensional metal circuits, so that the structural part has certain electrical properties. Compared with the maturely applied LDS (LASER DIRECT STRUCTURING, i.e. laser direct structuring) process, the main advantages of LAP technology are that the three-dimensional performance is consistent with that of LDS, but it does not require the use of special laser equipment and LDS laser-induced materials, effectively reducing the cost. In addition, the LDS process requires the addition of metal-activated substances to the material, and the addition of metal substances will cause the mechanical properties of the material to deteriorate, and has a great influence on the color of the material, which can only be made into black, white and gray, and is not suitable for structural parts. LAP technology is suitable for ordinary plastic substrates, including PC, PC / ABS, ABS, etc. Therefore, LAP technology has broad application prospects in the fields of smart phones, automotive electronics, wearable devices, mobile Internet devices, etc.

[0003] PC / ABS alloy material combines the molding properties of ABS (acrylonitrile-butadiene-styrene copolymer) and the mechanical strength, toughness and dimensional stability of PC (polycarbonate). However, the existing PC / ABS material has poor laser roughening effect, and the difference between the surface after laser engraving and the surface without laser engraving is not obvious (especially for products with fine patterns), which causes problems such as poor plating adhesion, plating overflow, plating leakage, etc., and it is difficult to meet the product use requirements, limiting the popularization and application of LAP technology; in addition, PC / ABS material usually has poor cold resistance, and when used in low temperature environments, these products are prone to stress cracking, low impact resistance to notches, poor wear resistance, poor flowability and other shortcomings, and the product reliability is insufficient. Therefore, the present application mainly studies a new PC / ABS material suitable for LAP technology and having good cold resistance, which is of great significance for widening the application of PC / ABS material and promoting the popularization of LAP technology. SUMMARY

[0004] In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present application is to provide a PC / ABS alloy material, which is particularly suitable for the LAP process, has a very good plating effect, can form a metal plating layer with good adhesion, and effectively improves the problems of overplating and underplating; at the same time, the material has excellent cold resistance and can still maintain high toughness at low temperature.

[0005] Another purpose of the present application is to provide a preparation method of the above-mentioned PC / ABS alloy material.

[0006] The present application is realized by the following technical solutions:

[0007] A PC / ABS alloy material, by weight fraction, comprises the following components:

[0008] PC resin 20-85 parts;

[0009] ABS resin 10-75 parts;

[0010] Toughening agent 2-6 parts;

[0011] LAP activator 4x10 -6 -1000x10 -6 parts;

[0012] Dispersing agent 0.1-0.5 parts;

[0013] Compatibility agent 0.5-2 parts;

[0014] Among them, the LAP activator is selected from any one or several of carbon nanotubes or conductive carbon black;

[0015] The dispersing agent is selected from any one or several of pentaerythritol stearate, polyester wax or E wax.

[0016] The PC / ABS alloy material of the present application forms a carbon layer surface after laser engraving and burning by introducing a trace amount of LAP activator, the LAP activator plays a role of conduction inside, so that the surface after laser engraving and the surface without laser engraving have a significant difference in electrical conductivity, so that the metal ions in the electroplating solution selectively enrich on the surface after laser engraving, forming a metal plating layer with good adhesion, effectively preventing the occurrence of underplating or overplating. If the amount of LAP activator added is too much, the electrical conductivity of the material surface increases, which leads to a decrease in the difference in electrical conductivity between the laser engraved surface and the non-laser engraved surface, and the electroplating effect becomes poor.

[0017] Preferably, the LAP activator is selected from conductive carbon black.

[0018] Preferably, the weight fraction of the LAP activator is 10x10 -6 -500x10 -6 parts.

[0019] The carbon nanotube is preferably single-walled carbon nanotube; more preferably, the average length of the carbon nanotube is 2-50 μm. Specifically, the average length of the carbon nanotube can be 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, all of which can achieve the present application.

[0020] The conductive carbon black is preferably acetylene carbon black; more preferably, the average particle size of the conductive carbon black is 10-50 nm. Specifically, the average particle size of the conductive carbon black can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, all of which can achieve the present application.

[0021] The present application adds a certain amount of dispersant, so that the LAP activator can be uniformly dispersed, and the carbon layer formed after the laser carving burning plays a good conduction role in the surface, and achieves good plating effect. Preferably, the dispersant is selected from E wax, which has good compatibility with the LAP activator, and is more conducive to the uniform dispersion of the LAP activator.

[0022] Preferably, the weight ratio of the PC resin to the ABS resin is 1: (1.5-3). More preferably, the weight fraction of the PC resin is 55-85 parts, and the weight fraction of the ABS resin is 10-40 parts.

[0023] The number average molecular weight of the polycarbonate is 17000-30000, preferably 20000-25000.

[0024] The average particle size of the ABS resin is 200 nm-1200 nm, preferably 200 nm-600 nm.

[0025] The toughening agent of the present application is selected from any one or several of the core-shell structure toughening agent with methyl methacrylate or polystyrene acrylonitrile as the shell and acrylate and organic silicon as the core, or the core-shell structure toughening agent with methyl methacrylate as the shell and butadiene styrene as the core. Specifically, the core-shell structure toughening agent with methyl methacrylate as the shell and acrylate and organic silicon as the core includes but is not limited to Mitsubishi S-2001, S-2501, S-2030, S-2100, SX-005; the core-shell structure toughening agent with polystyrene acrylonitrile as the shell and acrylate and organic silicon as the core includes but is not limited to Mitsubishi SRK 200A, SX-006; the core-shell structure toughening agent with methyl methacrylate as the shell and butadiene styrene as the core includes but is not limited to Rohm&Haas 2620, Zhongyuan M-732, Zhongyuan M-711, Akema E920. The addition of the toughening agent can effectively improve the low-temperature toughness of the material, and still maintain good plating effect.

[0026] The compatilizer is selected from styrene grafted maleic anhydride polymers; preferably, the styrene grafted maleic anhydride polymers have a maleic anhydride weight content of 8% to 26%, preferably 16% to 24%.

[0027] The application also provides a preparation method of the PC / ABS alloy material, comprising the following steps: according to the proportion, each component is put into a mixer for mixing for 10-20 minutes; after mixing uniformly, it is placed in a twin-screw extruder for melt extrusion, granulation, and PC / ABS alloy material is prepared; wherein the temperature of the twin-screw extruder is set to 200-260℃.

[0028] The PC / ABS alloy material of the application is particularly suitable for products that need to be processed by the LAP technology, and can be particularly used for preparing automobile antennas or signal transmission components.

[0029] The application has the following beneficial effects:

[0030] The PC / ABS alloy material of the application, by adding a trace amount of LAP activator and a certain amount of dispersant, can form a significant difference between the surface after the laser engraving treatment and the surface without laser engraving, and the chemical plating catalyst and metal ions have selectivity during electroplating, thereby effectively improving the plating effect of the material, solving the problems of plating leakage or overflow, and being particularly suitable for the LAP process; and the material has excellent cold resistance and can still maintain high toughness at low temperature. DETAILED DESCRIPTION

[0031] The application will be described in detail below in combination with specific examples. The following examples will help those skilled in the art to further understand the application, but do not limit the application in any form. It should be pointed out that, for those skilled in the art, without departing from the concept of the application, a number of modifications and improvements can be made. These all belong to the protection scope of the application.

[0032] The raw materials used in the examples and comparative examples of the application are described as follows, but are not limited to these materials:

[0033] PC resin 1: number average molecular weight is 22000, Sanniang 3022PJ of South Korea;

[0034] PC resin 2: number average molecular weight is 17000, FN1700 of Japan Idemitsu;

[0035] ABS resin 1: average particle size is in the range of 200-600nm, ABS PA757 of Chimei.

[0036] ABS resin 2: average particle size is in the range of 800-1200nm, ABS 275 of Shanghai Gaoqiao.

[0037] Toughener 1: Core-shell structured toughener with polystyrene acrylonitrile as shell and polyacrylate grafted dimethylsiloxane as core, Mitsubishi SRK 200A;

[0038] Toughener 2: Core-shell structured toughener with methyl methacrylate as shell and polyacrylate grafted dimethylsiloxane as core, Mitsubishi S-2001;

[0039] Toughener 3: Core-shell structured toughener with methyl methacrylate as shell and butadiene styrene as core, Rohm & Haas 2620;

[0040] LAP activator 1: Acetylene carbon black, average particle size 26 nm, Denki Kagaku Denks Black 2;

[0041] LAP activator 2: Acetylene carbon black, average particle size 57 nm, Denki Kagaku Denks Black 1;

[0042] LAP activator 3: Conductive carbon black, average particle size 30 nm, Cabot VXC605;

[0043] LAP activator 4: Single-walled carbon nanotube, average carbon tube length 10 microns, OCSiAl TUBALL™;

[0044] LAP activator 5: Multi-walled carbon nanotube, average carbon tube length 10 microns, Greatwall GT-300;

[0045] Dispersant 1: E wax, Klϋn Licowax E;

[0046] Dispersant 2: Pentaerythritol stearate, Lonza F538;

[0047] Dispersant 3: Polyester wax, Klϋn Liocwax PED 521;

[0048] Compatibilizer 1: Maleic anhydride content 20%, Hua Wen TMSMA-700,

[0049] Compatibilizer 2: Maleic anhydride content 10%, Hua Wen TMHW-320.

[0050] Preparation method of examples and comparative examples:

[0051] According to the proportion of Table 1 / Table 2 / Table 3, each component is put into a mixer and mixed for 10-20 minutes; after being uniformly mixed, it is placed in a twin-screw extruder, melted and extruded, and granulated to prepare a PC / ABS alloy material; wherein the twin-screw extruder includes ten temperature control zones, the temperature control 1-2 zone is 200-250℃, the temperature control 3-4 zone is 220-260℃, the temperature control 5-6 zone is 220-260℃, the temperature control 7-8 zone is 220-260℃, and the temperature control 9-10 zone is 220-260℃.

[0052] Related performance test methods:

[0053] (1) Notched impact strength: tested according to the standard ASTM D256-2010, the sample test thickness is 3.2mm.

[0054] (2) LAP process laser etching plating effect test:

[0055] ①Plating yield: polycarbonate composite material is heated and melted at 220-260℃, injection molded to prepare 100mm×100mm×2mm flat test pieces, after laser etching plating using the LAP process, using Leica microscope to observe whether the surface circuit plating layer has plating leakage or overflow (if the surface etched by laser has no metal layer plated, it is plating leakage; if the edge of the laser etched surface has a plating layer or the non-laser etched surface has plating metal, it is plating overflow), plating leakage or overflow is considered unqualified. The circuit conditions of 100 test pieces in each group are counted to obtain the yield.

[0056] ②Plating layer surface firmness evaluation: using a grid test, after the test piece is laser etched and plated using the LAP process, a 100 grid of 1mm square small grid is cut on the surface of the test piece using a grid knife; the tested small grid area on the surface of the test piece is adhered using 3M adhesive tape, the adhesive tape is firmly adhered to the tested small grid by rubbing the surface of the adhesive tape with a rubber eraser, the adhesive tape is held in the air for a period of time, and is torn off in the direction of the test piece surface at an angle of 60° as much as possible within 0.5-1.0S; the same test is conducted twice for the same example, and the grid layer falling off is observed to evaluate the standard, which is divided into 6 levels from 5B to 0B.

[0057] 5B level: no falling off at the cutout and its edge, and at the intersection of the grid;

[0058] 4B level: partial falling off at the cutout intersection or edge, 0

[0059] 3B level: partial falling off at the cutout intersection or edge, 5%< falling off area of the grid area ≤15%;

[0060] 2B grade: partial flaking at the intersection of the cuts or edges, and / or partial grid flaking, 15% < grid area flaking ≤ 35%;

[0061] 1B grade: partial flaking at the intersection of the cuts or edges, and / or partial grid flaking, 35% < grid area flaking ≤ 65%;

[0062] 0B grade: partial flaking at the intersection of the cuts or edges, and / or partial grid flaking, grid area flaking > 65%;

[0063] Table 1: allocation ratio of each component (by weight parts) and performance test results of Examples 1-8

[0064]

[0065] Table 2: allocation ratio of each component (by weight parts) and performance test results of Examples 9-17

[0066]

[0067] Table 3: allocation ratio of each component (by weight parts) and performance test results of Comparative Examples 1-6

[0068]

[0069] From the above results, it can be seen that the PC / ABS alloy material of the present application, by adding a trace amount of LAP activator and a certain amount of dispersant, through the introduction of trace amount of LAP activator and dispersant, the material is particularly suitable for LAP process, has very good plating effect, the adhesion of the plating layer is good, and effectively reduces the problems of overflow plating and missing plating; at the same time, the material has excellent cold resistance and still maintains high toughness at low temperature.

[0070] Comparative Example 1: the LAP activator is added in excess, the conductive performance of the material surface is increased, which leads to the reduction of the difference in conductive performance between the laser engraved surface and the non-laser engraved surface, the plating effect is poor, and the problems of missing plating and overflow plating are prone to occur.

[0071] Comparative Example 2: the material surface without adding LAP activator is difficult to be plated.

[0072] Comparative Example 3: without adding dispersant, the LAP activator is difficult to disperse uniformly, and the plating effect is poor.

[0073] Comparative Example 4: without adding a compatibilizer, the material has poor low-temperature toughness and poor plating effect.

[0074] Comparative Examples 5 / 6: without adding a toughening agent, the material has poor low-temperature toughness; and too much toughening agent will affect the plating effect.

Claims

1. A PC / ABS alloy material, characterized by, By weight parts, including the following components: PC resin 55-85 parts; ABS resin 10-40 parts; Toughening agent 2-6 parts; LAP activator 4 x 10 -6 -1000 x 10 -6 parts; Dispersant 0.1-0.5 parts; Compatibility agent 0.5-2 parts; The LAP activator is selected from any one or several of carbon nanotubes or conductive carbon black; The dispersant is selected from any one or several of pentaerythritol stearate, polyester wax or E wax.

2. The PC / ABS alloy material according to claim 1, characterized in that, The PC resin has a number average molecular weight of 17000-30000.

3. The PC / ABS alloy material according to claim 1, characterized in that, The PC resin has a number average molecular weight of 20000-25000.

4. The PC / ABS alloy material according to claim 1, characterized in that, The average particle size of the ABS resin is 200nm-1200nm.

5. The PC / ABS alloy material according to claim 1, characterized in that, The average particle size of the ABS resin is 200nm-600nm.

6. The PC / ABS alloy material according to claim 1, characterized in that, The weight fraction of the LAP activator is 10 x 10 -6 -500 x 10 -6 parts.

7. The PC / ABS alloy material according to claim 1, characterized in that, The carbon nanotubes are selected from single-walled carbon nanotubes.

8. The PC / ABS alloy material according to claim 1, characterized in that, The average length of the carbon nanotubes is 2-50μm.

9. The PC / ABS alloy material according to claim 1, characterized in that, The conductive carbon black is selected from acetylene carbon black.

10. The PC / ABS alloy material according to claim 1, characterized in that, The average particle size of the conductive carbon black is 10-50nm.

11. The PC / ABS alloy material according to claim 1, characterized in that, The LAP activator is selected from conductive carbon black; the dispersant is selected from E wax.

12. The PC / ABS alloy material according to claim 1, characterized in that, The toughening agent is selected from any one or several of core-shell structure toughening agents with methyl methacrylate or polystyrene acrylonitrile as the shell, with acrylate and organosilicon as the core, or core-shell structure toughening agents with methyl methacrylate as the shell and butadiene styrene as the core.

13. The PC / ABS alloy material according to claim 1, characterized in that, The compatibility agent is selected from styrene grafted maleic anhydride polymers.

14. The PC / ABS alloy material according to claim 13, characterized in that, The styrene grafted maleic anhydride polymer has a maleic anhydride weight content of 8%-26%.

15. The PC / ABS alloy material according to claim 13, characterized in that, The styrene grafted maleic anhydride polymer has a maleic anhydride weight content of 16%-24%.

16. The method of producing a PC / ABS alloy material according to any one of claims 1 to 15, characterized in that, The method comprises the following steps: according to the ratio, each component is put into a mixer and mixed for 10-20 minutes; after uniform mixing, it is placed in a twin-screw extruder, melted and extruded, granulated, and PC / ABS alloy material is prepared; wherein the temperature of the twin-screw extruder is set to 200-260℃.

Images