CN111117195A - Low-internal-stress electroplating-grade PC/ABS alloy material and preparation method thereof - Google Patents
Low-internal-stress electroplating-grade PC/ABS alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electroplating-grade PC/ABS alloy with low internal stress and high toughness and a preparation method thereof. The PC/ABS alloy material comprises the following components in parts by weight: 45-75 parts of PC resin, 20-50 parts of ABS resin, 5-20 parts of TPU resin, 1-2 parts of hydrophilic modifier, 3-5 parts of compatilizer and 0.3-1 part of antioxidant. By adding the TPU resin, the melt flow property of the PC/ABS alloy is improved, and the residual stress generated in the injection molding process is reduced; and because the TPU has the characteristics of high elasticity, easy coarsening and the like, the problem that the PC/ABS is difficult to coarsen is effectively solved, and the defect that the toughness is greatly reduced after electroplating is overcome. The preparation method mainly comprises two steps of mixing and melt extrusion of materials, and the process is simple and efficient and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to an electroplating-grade PC/ABS alloy material and a preparation method thereof.
Background
The PC/ABS has the characteristics of excellent toughness, dimensional stability, oil resistance, cold resistance, heat resistance and the like, is an engineering plastic with excellent comprehensive performance, and is widely applied to the fields of electronic products, household appliances, automobile accessories and the like. Among the PC/ABS alloys, PC provides high heat resistance and high rigidity to the alloy, and ABS provides good fluidity and notch toughness to the alloy. For electroplating PC/ABS, the ABS content is low, so that butadiene components which can be etched away in the roughening process are less, and the formed physical anchoring points are reduced, so that the bonding force of a plating layer is reduced, and even the plating leakage phenomenon occurs.
The TPU is a thermoplastic elastomer with good fluidity, and the structure of the TPU is mainly divided into a soft section and a hard section, wherein the hard section brings the characteristics of excellent weather resistance, corrosion resistance, fluidity and the like to the TPU, and the soft section provides good elasticity and low-temperature toughness to the TPU. Compared with elastomers such as butadiene high rubber powder and acrylates, the TPU has higher melt fluidity while keeping good toughness, and can reduce residual stress in the product processing process; the TPU in the same process can also provide more physical anchoring points for the PC/ABS in the coarsening process so as to ensure the electroplating bonding force of the material.
Through searching, the following related patents are found:
CN106751390A discloses an electroplating PC/ABS alloy material and a preparation method thereof, wherein the electroplating PC/ABS alloy material comprises the following components in parts by mass: 30-80 parts of PC resin, 20-70 parts of ABS resin, 1-30 parts of heat-conducting filler, 0.1-1 part of filler pretreating agent and 1-5 parts of compatibilization toughening agent, wherein the heat-conducting filler is any one or combination of more of graphite, carbon fiber and carbon black. The good electroplating performance is provided for PC/ABS by utilizing the heat conduction and the electric conductivity of the filler. However, the addition of the filler can reduce the fluidity of PC/ABS, which is not favorable for eliminating the internal stress generated in the molding process.
CN102532852A discloses an electroplating PC/ABS alloy and a preparation method thereof, wherein the alloy comprises the following components in parts by weight: the anti-oxidation agent comprises, by weight, 30-70 parts of PC, 30-70 parts of ABS, 1-5 parts of sodium silicate and 0.1-1 part of an antioxidant. The pits generated during coarsening are increased by adding the micromolecule easily-soluble sodium silicate, and the small molecule easily-soluble sodium silicate is used as a physical binding point to increase the electroplating binding force. However, the pits provided by the small-molecule sodium silicate can reduce the toughness of the PC/ABS, and further can increase the notch sensitivity of the PC/ABS, so that the material becomes brittle.
The PC/ABS alloy prepared by the two methods has flowability, toughness and electroplating performance which cannot be obtained simultaneously. The method of the invention uses the high-strength and high-fluidity TPU, and increases the fluidity and the electroplating bonding force of PC/ABS while ensuring the toughness. The PC/ABS alloy has excellent toughness, high flowability, high electroplating binding force and less surface defects of electroplated products.
Disclosure of Invention
The invention aims to overcome the defects of stress striking, poor electroplating binding force and the like of the existing electroplating PC/ABS material, and provides the electroplating PC/ABS alloy material with simple processing technology, high fluidity and low internal stress.
In order to achieve the above object, the technical solution of the present invention is as follows:
a low-internal-stress electroplating-grade PC/ABS alloy material comprises the following components in parts by weight:
in the low internal stress plating grade PC/ABS alloy material:
the PC resin is PC synthesized by a phosgene method, and the Melt Flow Rate (MFR) of the PC resin is 10-25 g/10min (260 ℃, 5 kg).
The TPU is a polyester type, the MFR is 60-120 g/10min (230 ℃, 5kg), the optimal content range is 5-20 parts, when the TPU is less than 5 parts, the fluidity of the PC/ABS alloy is not obviously improved, the effect of eliminating internal stress cannot be achieved, and when the TPU content is more than 20 parts, the material is excessively easy to coarsen, so that the surface strength of the electroplated PC/ABS alloy is reduced, and the defects of surface wrinkles and the like can be generated.
The hydrophilic modifier is PVA resin, the polymerization degree of the PVA resin is 1700, the alcoholysis degree of the PVA resin is 88, when the alcoholysis degree is too high, the hydrophilicity of the PVA is enhanced, and the PVA needs to be fully dried before electroplating to remove moisture.
The compatilizer is one or more of maleic anhydride grafted acrylonitrile-butadiene-styrene (ABS-g-MAH), styrene maleic anhydride copolymer (SMA) and methyl methacrylate-methyl acrylate copolymer (MMA-MA).
The antioxidant is one or two of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and tri [2, 4-di-tert-butylphenyl ] phosphite ester (antioxidant 168).
The invention also discloses a preparation method of the PC/ABS alloy, which comprises the following steps:
(1) weighing the components according to the formula of the PC/ABS alloy material as defined in any one of claims 1 to 6. The material needs to be dried before extrusion molding, the PC is dried at the temperature of 100-110 ℃ for 4-6 hours, the ABS is dried at the temperature of 80-90 ℃ for 4-6 hours, and the TPU is dried at the temperature of 60-80 ℃ for 4-6 hours.
(2) And (2) uniformly mixing the materials in the step (1) by a high-speed mixer. Then pouring the mixture into a double-screw extruder, and carrying out melt extrusion, traction, cutting and granulation to obtain the PC/ABS alloy particles.
(3) And performing injection molding on the obtained PC/ABS alloy material to obtain a standard sample strip for performance test, and performing injection molding to obtain a high-gloss plate for electroplating verification.
The rotating speed of the high-speed mixer in the step (2) is 500-1000 rpm, the mixing temperature is 20-50 ℃, and the mixing time is 3-5 min. The screw extruder is a double-screw extruder, and the temperature of each zone is 220-250 ℃.
The injection molding machine in the step (3) is a horizontal injection molding machine, and the temperature of each zone is 220 ℃ and 240 ℃.
Compared with the prior art, the invention has the advantages and positive effects that:
(1) according to the invention, the auxiliaries such as PC, ABS, TPU, antioxidant and the like are fully mixed and generate synergistic effect by a melt extrusion method, so that the PC/ABS alloy material is endowed with excellent toughness and processing fluidity.
(2) According to the invention, by adding the TPU elastomer, the toughness and the electroplating coarsening performance of the alloy are improved on the premise of ensuring the fluidity. And the hydrophilic polyvinyl alcohol with polyhydroxy is added, so that the hydrophilicity of the surface of PC/ABS is enhanced, the roughening liquid can more easily infiltrate the surface, and the roughening is more uniform. The electroplating effect of the PC/ABS alloy material is improved by increasing the number of coarsening binding points and improving the hydrophilicity of the material.
(3) The preparation method of the PC/ABS alloy material is simple, continuous in production process, high in production efficiency and suitable for industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of the article of the present invention after etching with roughening solution.
Detailed Description
For better understanding of the present invention, the present invention is described below with reference to specific examples, but the present invention is not limited to the following examples, and the descriptions of the examples are only for assisting understanding of the method of the present invention and the core concept thereof.
The embodiment of the invention adopts the following raw materials: PC selects 1201-22 produced by LG chemistry, ABS selects Taiwan Qimei PA727, TPU resin selects German Bayer 9395A, hydrophilic modifier PVA selects medium petrochemical 1788 (100 mesh powder), compatilizer selects commercially available SMA, antioxidant selects commercially available 1010.
Example 1:
drying PC at the temperature of 100-110 ℃ for 4-6 h, drying ABS at the temperature of 80-90 ℃ for 4-6 h, and drying TPU at the temperature of 60-80 ℃ for 4-6 h.
Weighing the following raw materials in parts by weight: 50 parts of PC resin, 45 parts of ABS resin, 5 parts of TPU resin, 1 part of hydrophilic modifier, 3 parts of compatilizer and 0.5 part of antioxidant. And (2) putting the raw materials prepared according to the parts by weight into a high-speed mixer, mixing for 3-5 minutes, putting the fully mixed materials into a double-screw extruder, performing melt extrusion, wherein the set temperature of the double-screw extruder is 220-250 ℃, the head temperature is 240 ℃, the screw rotating speed is 500rpm, and performing traction, cutting and granulation to obtain the electroplating-grade PC/ABS alloy material. The MFR is 25.69g/10min, the contact angle is 81.6 degrees, and the notch impact strength after electroplating is 45.3kJ/m2The grid marking experiment is 4B, and the electroplating yield is 80%.
Example 2:
the difference from the embodiment 1 is that:
weighing the following raw materials in parts by weight: 50 parts of PC resin, 45 parts of ABS resin, 5 parts of TPU resin, 1 part of hydrophilic modifier, 3 parts of compatilizer and 0.5 part of antioxidant. The MFR is 25.8g/10min, the contact angle is 79.4 degrees, and the notch impact strength after electroplating is 44.8kJ/m2The grid marking experiment is 4B, and the electroplating yield is 84%.
Example 3:
the difference from the embodiment 1 is that:
weighing the following raw materials in parts by weight: 50 parts of PC resin, 45 parts of ABS resin, 5 parts of TPU resin, 2 parts of hydrophilic modifier, 3 parts of compatilizer and 0.5 part of antioxidant. The MFR was 27.1g/10min, the contact angle was 72.3 degrees, and the notched impact strength after plating was 46.4kJ/m2The grid marking experiment is 5B, and the electroplating yield is 86%.
Example 4:
the difference from the embodiment 1 is that:
weighing the following raw materials in parts by weight: 70 parts of PC resin, 25 parts of ABS resin, 5 parts of TPU resin, 2 parts of hydrophilic modifier, 3 parts of compatilizer and 0.5 part of antioxidant. The MFR was 20.4g/10min, the contact angle was 63.1 °, and the notched impact strength after plating was 37.5kJ/m2The grid marking experiment is 4B, and the electroplating yield is 77%.
Example 5:
the difference from the embodiment 1 is that:
weighing the following raw materials in parts by weight: 70 parts of PC resin, 20 parts of ABS resin, 10 parts of TPU resin, 2 parts of hydrophilic modifier, 3 parts of compatilizer and 0.5 part of antioxidant. The MFR was 23.1g/10min, the contact angle was 62.6 °, and the notched impact strength after plating was 45.3kJ/m2The grid marking experiment is 5B, and the electroplating yield is 84%.
Example 6:
the difference from the embodiment 1 is that:
weighing the following raw materials in parts by weight: 70 parts of PC resin, 10 parts of ABS resin, 20 parts of TPU resin, 2 parts of hydrophilic modifier, 3 parts of compatilizer and 0.5 part of antioxidant. The MFR was 27.9g/10min, the contact angle was 61.8 °, and the notched impact strength after plating was 56.9kJ/m2The grid marking experiment is 5B, and the electroplating yield is 87%.
Comparative example 1:
drying PC at the temperature of 100-110 ℃ for 4-6 h, drying ABS at the temperature of 80-90 ℃ for 4-6 h, and drying TPU at the temperature of 60-80 ℃ for 4-6 h.
Weighing the following raw materials in parts by weight: 50 parts of PC resin, 45 parts of ABS resin, 3 parts of compatilizer and 0.5 part of antioxidant. And (2) putting the raw materials prepared according to the parts by weight into a high-speed mixer, mixing for 3-5 minutes, putting the fully mixed materials into a double-screw extruder, performing melt extrusion, wherein the set temperature of the double-screw extruder is 220-250 ℃, the head temperature is 240 ℃, the screw rotating speed is 500rpm, and performing traction, cutting and granulation to obtain the electroplating-grade PC/ABS alloy material. The MFR was 24.1g/10min, the contact angle was 89.2 °, and the notched impact strength after plating was 39.7kJ/m2The grid marking experiment is 3B, and the electroplating yield is 75%.
Comparative example 2:
drying PC at the temperature of 100-110 ℃ for 4-6 h, drying ABS at the temperature of 80-90 ℃ for 4-6 h, and drying TPU at the temperature of 60-80 ℃ for 4-6 h.
Weighing the following raw materials in parts by weight: 70 parts of PC resin, 30 parts of ABS resin, 2 parts of hydrophilic modifier, 3 parts of compatilizer and 0.5 part of antioxidant. And (2) putting the raw materials prepared according to the parts by weight into a high-speed mixer, mixing for 3-5 minutes, putting the fully mixed materials into a double-screw extruder, performing melt extrusion, wherein the set temperature of the double-screw extruder is 220-250 ℃, the head temperature is 240 ℃, the screw rotating speed is 500rpm, and performing traction, cutting and granulation to obtain the electroplating-grade PC/ABS alloy material. The MFR is 18.5g/10min, the contact angle is 85.4 degrees, and the notch impact strength after electroplating is 31.9kJ/m2The grid marking experiment is 2B, and the electroplating yield is 71 percent.
The impact strength test of the invention was carried out in accordance with ISO-179-1eA with a pendulum energy of 4J. The melt flow rate performance test was carried out according to ISO 1133 at a temperature of 260 ℃ and a load of 5 kg. Electroplating, roughening and etching, adopting a commonly used sulfuric acid-chromic acid system roughening solution for etching, spraying gold on the surface of an etched sample, observing by using a scanning electron microscope, and testing by a Baige experiment according to DIN EN ISO 2409.
As can be seen from the performance comparison of the embodiments 1-3 and the comparative example 1, the hydrophilicity of PC/ABS can be obviously improved by adding the hydrophilic modifier PVA, so that the substrate and the electroplating solution can be conveniently and fully contacted, the electroplating binding force of the matrix is improved, and the electroplating yield of the workpiece is improved.
As can be seen from the comparison of the performances of the examples 4-6 and the comparative example 2, the addition of TPU resins with different contents can obviously improve the melt flow rate of PC/ABS so as to reduce the internal stress of the product, and the notch impact strength of the product is improved after electroplating, so that the notch sensitivity of the PC/ABS after electroplating is improved. As can be seen from the comparison of the etching performances of FIG. 1, examples 3 to 4 and comparative example 1, the addition of the TPU increases the etching points of the base material and increases the bonding force between the coating and the product.
Claims (9)
2. the low internal stress plated grade PC/ABS alloy material according to claim 1, wherein: the PC resin is PC synthesized by a phosgene method, the Melt Flow Rate (MFR) of the PC resin is 10-25 g/10min, the temperature is 260 ℃ and the weight is 5 kg.
3. The low internal stress plated grade PC/ABS alloy material according to claim 1, wherein: the TPU is polyester type, and the MFR of the TPU is 60-120 g/10min, 230 ℃ and 5 kg.
4. The low internal stress plated grade PC/ABS alloy material according to claim 1, wherein: the hydrophilic modifier is PVA resin, the polymerization degree of the PVA resin is 1700, the alcoholysis degree of the PVA resin is 88, when the alcoholysis degree is too high, the hydrophilicity of the PVA is enhanced, and the PVA needs to be fully dried before electroplating to remove moisture.
5. The low internal stress plated grade PC/ABS alloy material according to claim 1, wherein: the compatilizer is one or more of maleic anhydride grafted acrylonitrile-butadiene-styrene (ABS-g-MAH), styrene maleic anhydride copolymer (SMA) and methyl methacrylate-methyl acrylate copolymer (MMA-MA).
6. The low internal stress plating grade PC/ABS alloy material as claimed in claim 1, wherein the antioxidant is one or two of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168).
7. The method for preparing the low internal stress plating grade PC/ABS alloy material according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) weighing the components according to the formula of the PC/ABS alloy material as defined in any one of claims 1 to 6. The material needs to be dried before extrusion molding, the PC is dried at the temperature of 100-110 ℃ for 4-6 h, the ABS is dried at the temperature of 80-90 ℃ for 4-6 h, and the TPU is dried at the temperature of 60-80 ℃ for 4-6 h;
(2) and (2) uniformly mixing the materials in the step (1) by a high-speed mixer. Then pouring the mixture into a double-screw extruder, and performing melt extrusion, traction, cutting and granulation to obtain the PC/ABS alloy particles;
(3) and performing injection molding on the obtained PC/ABS alloy material to obtain a standard sample strip for performance test, and performing injection molding to obtain a high-gloss plate for electroplating verification.
8. The method for preparing the low internal stress plating grade PC/ABS alloy material according to claim 7, characterized in that: the rotating speed of the high-speed mixer in the step (2) is 500-1000 rpm, the mixing temperature is 20-50 ℃, and the mixing time is 3-5 min; the screw extruder is a double-screw extruder, and the temperature of each zone is 220-250 ℃.
9. The method for preparing the low internal stress plating grade PC/ABS alloy material according to claim 7, characterized in that: the injection molding machine in the step (3) is a horizontal injection molding machine, and the temperature of each zone is 220 ℃ and 240 ℃.
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Cited By (1)
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CN111205589A (en) * | 2019-11-28 | 2020-05-29 | 上海普利特复合材料股份有限公司 | Stress cracking resistant high-fluidity electroplating-grade ABS/PBT alloy material and preparation method thereof |
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CN111205589B (en) * | 2019-11-28 | 2022-06-28 | 上海普利特复合材料股份有限公司 | Stress-cracking-resistant high-fluidity electroplating-grade ABS/PBT alloy material and preparation method thereof |
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