WO2022001766A1 - 一种红外光激发碳化助剂及其制备方法和应用 - Google Patents

一种红外光激发碳化助剂及其制备方法和应用 Download PDF

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Publication number
WO2022001766A1
WO2022001766A1 PCT/CN2021/101712 CN2021101712W WO2022001766A1 WO 2022001766 A1 WO2022001766 A1 WO 2022001766A1 CN 2021101712 W CN2021101712 W CN 2021101712W WO 2022001766 A1 WO2022001766 A1 WO 2022001766A1
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Prior art keywords
infrared light
excited
parts
carbonization
oxide
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PCT/CN2021/101712
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English (en)
French (fr)
Inventor
杨优其
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中山市芸浩科技有限公司
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Publication of WO2022001766A1 publication Critical patent/WO2022001766A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/70—Auxiliary operations or equipment
    • B23K26/702—Auxiliary equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/30—Organic material
    • B23K2103/42—Plastics

Definitions

  • the invention relates to the technical field of an infrared light-excited carbonization auxiliary, and more particularly, to an infrared-light-excited carbonization auxiliary and a preparation method and application thereof.
  • Laser engraving refers to the change of the shape or performance of the sample caused by the action of the laser beam on the material. It is a high-power density spot formed by focusing the laser beam. In a few microseconds, the temperature of the spot area rises to the melting point or even the boiling point of the material. The irradiated material immediately melts and vaporizes, ablates, or reaches its ignition point.
  • Laser marking changes color on the plastic surface through the excitation of laser energy, white or light-colored products become black when marked, and black or dark-colored products become white when marked.
  • Laser marking additives can help plastic products better absorb laser light, so as to achieve better laser color rendering effect.
  • the advantages of laser marking no contact, no ink, difficult to counterfeit, fast, no surface pretreatment, marking can be minimized, flexible surface and design, most plastics cannot be marked well, because they do not absorb laser light, laser marking additives can absorb The laser energy is then converted into thermal energy.
  • the research on the ideal laser marking additive in the prior art still has the problem of marking contrast chromatic aberration contrast. Therefore, it is necessary to develop a laser marking additive that can produce relatively excellent chromatic aberration contrast in the process of laser marking.
  • the first aspect of the present invention provides an infrared light-excited carbonization auxiliary, in terms of weight percentage, the raw materials at least comprise: 0.01-0.15 parts of metal powder, 35-55 parts of metal oxide, 15 -30 parts semi-aromatic polyamide, 2-4 parts compatibilizer, 20-35 parts carrier resin.
  • the average particle size of the metal powder in the present invention is 1-10 ⁇ m.
  • the metal oxide in the present invention includes at least one of tin dioxide, antimony trioxide, antimony tin oxide, aluminum oxide, zinc oxide, titanium oxide, and copper oxide.
  • the metal oxides in the present invention also include rare earth oxides; the added amount of the rare earth oxides is 0.1-0.5% by weight of antimony trioxide.
  • the rare earth oxide in the present invention includes at least one of neodymium oxide, lanthanum oxide, niobium oxide, cerium oxide, and ytterbium oxide.
  • the semi-aromatic polyamide in the present invention includes at least one of PA6T, PA12T, PA9T, PA10T, PA4T, and PA46.
  • the semi-aromatic polyamide in the present invention is a mixture of PA6T and PA12T; the weight ratio of PA6T and PA12T is 1:(0.5-3.5).
  • the carrier resin in the present invention includes at least one of LDPE, PP, and HDPE; the melt flow rate of the LDPE is 24-70 g/10min.
  • the second aspect of the present invention provides a method for preparing the described infrared light-excited carbonization auxiliary, the steps at least comprising: (1) blending, melt-extruding metal powder, metal oxide and semi-aromatic polyamide Pelletizing to obtain the initial mixed material particles; (2) blending the initial mixed material particles, the compatibilizer and the carrier resin to melt, extrude and granulate.
  • a third aspect of the present invention provides an application of the infrared light-excited carbonization auxiliary, which is applied to infrared light marking of plastic materials.
  • the present invention has the following excellent beneficial effects:
  • the present invention provides an infrared light-excited carbonization auxiliary, which is mainly used for laser engraving on the plastic surface for marking.
  • thermoplastic carrier resins are mixed and compounded, and the prepared infrared light-excited carbonization additives can be applied to different types of polymer matrix materials, such as PP, PE, PET, PS, PVC, PC and other plastics. It can form a very obvious color difference contrast, which can not change the color and characteristics of the product, absorb enough laser light to raise the local temperature to burn or foam the plastic, and improve the effect of marking, especially when applied to PP polyolefin resin, the color difference contrast is the best .
  • a first aspect of the present invention provides an infrared light-excited carbonization auxiliary, in terms of weight percentage, the raw materials at least comprise: 0.01-0.15 parts of metal powder, 35-55 parts of metal oxide, 15-30 parts of semi-aromatic polymer Amide, 2-4 parts compatibilizer, 20-35 parts carrier resin.
  • the infrared light-excited carbonization assistant in terms of weight percentage, the raw material at least comprises: 0.03-0.10 parts of metal powder, 40-50 parts of metal oxide, 20-25 parts of semi-aromatic polyamide , 2.5-3.5 parts of compatibilizer, 25-30 parts of carrier resin.
  • the infrared light-excited carbonization assistant by weight percentage, the raw material at least comprises: 0.05 parts of metal powder, 46 parts of metal oxide, 22 parts of semi-aromatic polyamide, 3 parts of compatibility agent, 28 parts of carrier resin.
  • the average particle size of the metal powder is 1-10 ⁇ m.
  • the average particle size of the metal powder is 5 ⁇ m.
  • the metal powder includes at least one of aluminum powder, zinc powder, copper powder, iron powder, and silver powder.
  • the metal powder is aluminum powder.
  • the metal oxide includes at least one of tin dioxide, antimony trioxide, antimony tin oxide, aluminum oxide, zinc oxide, titanium oxide, and copper oxide.
  • the metal oxide is antimony trioxide.
  • the average particle size of the antimony trioxide is 0.1-1.5 ⁇ m.
  • the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide further includes rare earth oxide; the added amount of the rare earth oxide is 0.1-0.5% by weight of antimony trioxide.
  • the rare earth oxide is added in an amount of 0.2% by weight of antimony trioxide.
  • the rare earth oxide includes at least one of neodymium oxide, lanthanum oxide, niobium oxide, cerium oxide, and ytterbium oxide.
  • the rare earth oxide is neodymium oxide.
  • the average particle size of the neodymium oxide is 1-50 nm.
  • the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide includes at least one of PA6T, PA12T, PA9T, PA10T, PA4T, PA46.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of the PA6T and PA12T is 1:(0.5-3.5).
  • the weight ratio of the PA6T and PA12T is 1:(1-3). In some more preferred embodiments, the weight ratio of the PA6T and PA12T is 1:2.
  • the purchasers of the PA6T and PA12T are not particularly limited, and are preferably purchased from Solvay Investments Co., Ltd.
  • the present invention provides an infrared light-excited carbonization aid, wherein the inventor finds that the use of semi-aromatic polyamide as the matrix resin, and the use of a specific amount of metal powder can be beneficial to increase the color difference contrast after laser marking. It was found that especially the use of low-density polyethylene with high melt index as the carrier, and the addition of two rare earth oxides and antimony trioxide can further improve the contrast effect of marking color difference. The invention unexpectedly found that, especially for the combination of PA6T and PA12T.
  • the semi-aromatic polyamide has the best marking effect.
  • the invention unexpectedly found that the infrared light-excited carbonization assistant prepared by the present invention is more suitable for the marking of polypropylene polyolefin as the matrix material.
  • the carrier resin includes at least one of LDPE, PP, and HDPE; the melt flow rate of the LDPE is 24-70 g/10min.
  • the carrier resin is LDPE; the melt flow rate of the LDPE is 24-70 g/10min.
  • the melt flow rate of the LDPE is 60-70 g/10min.
  • the melt flow rate of the LDPE is 70 g/10 min.
  • the source of the LDPE brand in the present invention is not particularly limited.
  • the LDPE is LotreneMG70, SINPOLENEFRN1982, LDPE (low density polyethylene) 1965-T/Dutch DSM, LDPE (low density polyethylene) LD9150/Australia At least one of Qenos; more preferably, the LDPE is LotreneMG70.
  • the test conditions for the melt flow rate were 190°C/2.16kg.
  • the compatibilizer is a maleic anhydride grafted polyolefin.
  • the compatibilizer is at least one of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene; more preferably, the compatibilizer is maleic anhydride grafted polyethylene.
  • the graft ratio of the maleic anhydride-grafted polyethylene is 0.5-1.5%; more preferably, the graft ratio of the maleic anhydride-grafted polyethylene is 1%.
  • the purchase source of the maleic anhydride-grafted polyethylene in the present invention is not particularly limited.
  • the maleic anhydride-grafted polyethylene is purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name is CMG5904.
  • the second aspect of the present invention provides a method for preparing the described infrared light-excited carbonization auxiliary, the steps at least comprising: (1) blending, melt-extruding metal powder, metal oxide and semi-aromatic polyamide Pelletizing to obtain the initial mixed material particles; (2) blending the initial mixed material particles, the compatibilizer and the carrier resin to melt, extrude and granulate.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 290-320°C; preferably, the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 290-320°C; preferably, the processing temperature in the step (2) is 310°C.
  • a third aspect of the present invention provides an application of the infrared light-excited carbonization auxiliary, which is applied to infrared light marking of plastic materials.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 5 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.2% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of the PA6T and PA12T is 1:2.
  • the PA6T and PA12T were purchased from Solvay Investment Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 70 g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least include: 0.03 parts of metal powder, 40 parts of metal oxides, 20 parts of semi-aromatic polyamide, 2.5 parts of compatibilizer, and 25 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 1 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.1 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.1% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 20 nm.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of PA6T and PA12T is 1:1.
  • the PA6T and PA12T were purchased from Solvay Investment Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 60 g/10min
  • the LDPE is SINPOLENEFRN1982.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 0.5%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.1 part of metal powder, 50 parts of metal oxide, 25 parts of semi-aromatic polyamide, 3.5 parts of compatibilizer, and 30 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 10 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 1.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.5% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 50 nm.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of the PA6T and PA12T is 1:3.
  • the PA6T and PA12T were purchased from Solvay Investment Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 65g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1.5%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the brand name is CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated to obtain.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 5 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.2% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide was PA6T; the PA6T was purchased from Solvay Investments Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 70 g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization assistant in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 5 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.2% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide is PA12T, and PA12T was purchased from Solvay Investments Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 70 g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 5 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.2% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of the PA6T and PA12T is 5:1.
  • the PA6T and PA12T were purchased from Solvay Investment Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 70 g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 5 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.2% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide is a mixture of PA6T and PA66; the weight ratio of the PA6T and PA66 is 1:2.
  • the PA6T and PA66 were purchased from Solvay Investment Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 70 g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated to obtain.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 5 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of the PA6T and PA12T is 1:2.
  • the PA6T and PA12T were purchased from Solvay Investment Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 70 g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 50 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.2% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of the PA6T and PA12T is 1:2.
  • the PA6T and PA12T were purchased from Solvay Investment Co., Ltd.
  • the carrier resin is LDPE
  • the melt flow rate of the LDPE is 70 g/10min
  • the LDPE is LotreneMG70.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the trade name was CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • An infrared light-excited carbonization auxiliary in terms of weight percentage, the raw materials at least comprise: 0.05 parts of metal powder, 46 parts of metal oxides, 22 parts of semi-aromatic polyamide, 3 parts of compatibilizer, and 28 parts of carrier resin.
  • the metal powder is aluminum powder, and the average particle size of the metal powder is 5 ⁇ m.
  • the metal oxide is antimony trioxide, and the average particle size of the antimony trioxide is 0.5 ⁇ m.
  • the metal oxide also includes rare earth oxide; the added amount of the rare earth oxide is 0.2% by weight of antimony trioxide.
  • the rare earth oxide is neodymium oxide, and the average particle size of the neodymium oxide is 40 nm.
  • the semi-aromatic polyamide is a mixture of PA6T and PA12T; the weight ratio of the PA6T and PA12T is 1:2.
  • the PA6T and PA12T were purchased from Solvay Investment Co., Ltd.
  • Described carrier resin is HDPE, and the melt flow rate of described HDPE is 66g/10min, 190 °C/2.16kg, and described HDPE is HDPE (high density polyethylene) DMDA-8965NT7/Dow DuPont.
  • the compatibilizer is maleic anhydride grafted polyethylene, and the graft ratio is 1%.
  • the maleic anhydride grafted polyethylene was purchased from Jiayirong Compatibilizer Jiangsu Co., Ltd., and the brand name is CMG5904.
  • the preparation method of the infrared light-excited carbonization auxiliary includes at least the following steps: (1) blending metal powder, metal oxide, and semi-aromatic polyamide for melt extrusion and granulation to obtain primary mixed material particles; (2) ) The initial compound particles, the compatibilizer and the carrier resin are blended, melted, extruded and granulated, that is, obtained.
  • the processing equipment in the steps (1) and (2) is a twin-screw extrusion granulator with a screw diameter of 30 mm.
  • the processing temperature in the step (1) is 300°C.
  • the processing temperature in the step (2) is 310°C.
  • Example 10 The infrared light-excited carbonization assistant prepared in Example 1-Example 10 was added to the polyolefin resin in an addition amount of 2wt%.
  • the types of the polyolefin resin were PP and LDPE respectively, and 1wt% of titanium dioxide was added to make a board.
  • a 20-watt fiber laser machine was used for the marking test, and the fiber laser marking machine was purchased from Shenzhen Tiance Laser Technology Co., Ltd.
  • the polypropylene was purchased from 1120D of Formosa Plastics Polypropylene (Ningbo) Co., Ltd.; the LDPE was purchased from LDPE (low density polyethylene) 16P/Mitsui Chemicals.
  • the preparation method is as follows: using a plastic bag to weigh the infrared light-excited carbonization assistant, titanium dioxide, and polypropylene; mixing by hand evenly; cleaning the injection molding machine, adding the mixed materials into the injection molding machine, and setting the injection molding temperature to 220° C. ;
  • Marking graphics one-dimensional code, marking power: 75%, marking speed: 3000mm/s, marking frequency: 30KHz, filling: 0.05.
  • the product form, marking effect and color influence of the produced black lettering laser particles are tested.
  • the quality testing method and standard of the black lettering laser particles are shown in Table 1, and the evaluation criteria are shown in Table 2.
  • the particle color test is to add 1% of particles and 1% of titanium dioxide (Kronos 2450) to the PP material (specifically 5090t).
  • Example 3 injection molding, and the L value is required to be more than 93, and the higher the value, the better; the test results are shown in Table 3, wherein the infrared light-excited carbonization additives of Example 1-Example 3 and Example 6-Example 10 are prepared
  • the particle appearance and color of the particles are in line with the standard; the infrared light-excited carbonization assistants of Examples 4 to 5 can meet the requirements of use by increasing the addition amount.
  • the particles prepared by the infrared light-excited carbonization assistants of the examples in Table 3 have an apparent diameter of about 2 mm and a length of about 3.5 mm.
  • Example Contrast marking effect particle appearance Particle color L value Example 1 (PP) 5 stars Standards compliant 94.32 Example 1 (LDPE) 4 stars Standards compliant 93.25 Example 2 5 stars Standards compliant 93.56 Example 3 5 stars Standards compliant 94.62 Example 4 3 stars Standards compliant 94.32 Example 5 3 stars Standards compliant 93.85 Example 6 4 stars Standards compliant 92.95 Example 7 4 stars Standards compliant 93.89 Example 8 4 stars Standards compliant 94.63 Example 9 4 stars Standards compliant 93.32 Example 10 4 stars Standards compliant 93.85

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Abstract

一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.01-0.15份金属粉，35-55份金属氧化物，15-30份半芳香族聚酰胺，2-4份相容剂，20-35份载体树脂；制备得到的红外光激发碳化助剂能够适用于不同种类的聚合物基体材料，都能够形成非常明显的色彩对比度，可以不改变制品颜色和特性、吸收足够的激光来升高局部温度使塑料烧焦或发泡，提高标识的效果，尤其是应用于PP树脂时的色差对比度最为优异。

Description

一种红外光激发碳化助剂及其制备方法和应用
本申请要求于2020年07月01日提交中国专利局、申请号为CN202010630685.3、发明名称为“一种红外光激发碳化助剂及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及红外光激发碳化助剂的技术领域，具体的更涉及一种红外光激发碳化助剂及其制备方法和应用。
背景技术
在塑料表面进行标示，传统的方法就是印刷，但成本高，不环保，容易擦掉。激光雕刻指用激光束作用在材料上引起样品形状或性能的改变，是利用激光束聚焦形成的高功率密度光斑，在数微秒的时间内，光斑区的温度升高到材料熔点甚至沸点，使被照射处的材料迅即熔化和汽化、烧蚀或达到燃点。当激光束沿着设定路径移动时，光子与材料不断相互作用，同时借与光束同轴的高速气流吹除熔融物质，并起冷却作用，从而获得所需要的形状。激光标识在塑料表面通过激光能量的激发作用使之变色，白色或者浅色制品打标变黑色，黑色或者深色制品打标变白色。激光标识助剂就是可以帮助塑料制品更好地吸收激光，从而达到更好的激光显色效果。激光标识的好处：不接触、无油墨、难于伪造、快速、表面无需预处理、标识可以最小化、表面和设计灵活，大部分塑料不能很好标识，因为本身不吸收激光，激光标识添加剂能吸收激光能，然后转化为热能。但是现有技术中对于其理想激光标识添加剂的研究仍旧会存在标识对比色差对比度问题出现，因此需要研发一种激光标识添加剂能够在激光标识的过程中产生较为优异色差对比度。
发明内容
为了解决上述的技术问题，本发明的第一个方面提供了一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.01-0.15份金属粉，35-55 份金属氧化物，15-30份半芳香族聚酰胺，2-4份相容剂，20-35份载体树脂。
作为一种优选的技术方案，本发明中所述金属粉的平均粒径为1-10μm。
作为一种优选的技术方案，本发明中所述金属氧化物包括二氧化锡、三氧化二锑、氧化锡锑、氧化铝、氧化锌、氧化钛、氧化铜中的至少一种。
作为一种优选的技术方案，本发明中所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.1-0.5％。
作为一种优选的技术方案，本发明中所述稀土氧化物包括氧化钕、氧化镧、氧化铌、氧化铈、氧化镱中的至少一种。
作为一种优选的技术方案，本发明中所述半芳香族聚酰胺包括PA6T、PA12T、PA9T、PA10T、PA4T、PA46中的至少一种。
作为一种优选的技术方案，本发明中所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：(0.5-3.5)。
作为一种优选的技术方案，本发明中所述载体树脂包括LDPE、PP、HDPE中的至少一种；所述LDPE的熔体流动速率为24-70g/10min。
本发明的第二个方面提供了一种所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。
本发明的第三个方面提供了一种所述的红外光激发碳化助剂的应用，应用于塑料材料的红外光标识。
与现有技术相比，本发明具有如下优异的有益效果：
本发明提供了一种红外光激发碳化助剂，主要是用于激光在塑料表面进行雕刻进行标识的作用，本发明中，采用特殊种类复合金属氧化物、金属粉与特定半芳香族聚酰胺混合物、热塑性载体树脂之间进行混合复配，制备得到的红外光激发碳化助剂能够适用于不同种类的聚合物基体材料，比如PP、PE、PET、PS、PVC、PC等各种塑料，都能够形成非常明显的色差对比度，可以不改变制品颜色和特性、吸收足够的激光来升高局部温 度使塑料烧焦或发泡，提高标识的效果尤其是应用于PP聚烯烃树脂时的色差对比度最为优异。
具体实施方式
下面结合具体实施方式对本发明提供技术方案中的技术特征作进一步清楚、完整的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本技术领域技术人员可以理解，除非另外定义，这里使用的所有术语(包括技术术语和科学术语)具有与本发明所属领域中的普通技术人员的一般理解相同的意义。还应该理解的是，诸如通用字典中定义的那些术语应该被理解为具有与现有技术的上下文中的意义一致的意义，并且除非像这里一样定义，不会用理想化或过于正式的含义来解释。
本发明中的词语“优选的”、“优选地”、“更优选的”等是指，在某些情况下可提供某些有益效果的本发明实施方案。然而，在相同的情况下或其他情况下，其他实施方案也可能是优选的。此外，对一个或多个优选实施方案的表述并不暗示其他实施方案不可用，也并非旨在将其他实施方案排除在本发明的范围之外。
本发明的第一个方面提供了一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.01-0.15份金属粉，35-55份金属氧化物，15-30份半芳香族聚酰胺，2-4份相容剂，20-35份载体树脂。
在一些优选的实施方式中，所述红外光激发碳化助剂，按重量百分比计，原料至少包含：0.03-0.10份金属粉，40-50份金属氧化物，20-25份半芳香族聚酰胺，2.5-3.5份相容剂，25-30份载体树脂。
在一些更优选的实施方式中，所述红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
金属粉
在一些实施方式中，所述金属粉的平均粒径为1-10μm。
在一些优选的实施方式中，所述金属粉的平均粒径为5μm。
在一些实施方式中，所述金属粉包括铝粉、锌粉、铜粉、铁粉、银粉中的至少一种。
在一些优选的实施方式中，所述金属粉为铝粉。
金属氧化物
在一些实施方式中，所述金属氧化物包括二氧化锡、三氧化二锑、氧化锡锑、氧化铝、氧化锌、氧化钛、氧化铜中的至少一种。
在一些优选的实施方式中，所述金属氧化物为三氧化二锑。
在一些实施方式中，所述三氧化二锑的平均粒径为0.1-1.5μm。
在一些优选的实施方式中，所述三氧化二锑的平均粒径为0.5μm。
在一些实施方式中，所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.1-0.5％。
在一些优选的实施方式中，所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
在一些实施方式中，所述稀土氧化物包括氧化钕、氧化镧、氧化铌、氧化铈、氧化镱中的至少一种。
在一些优选的实施方式中，所述稀土氧化物为氧化钕。
在一些实施方式中，所述氧化钕的平均粒径为1-50nm。
在一些优选的实施方式中，所述氧化钕的平均粒径为40nm。
半芳香族聚酰胺
在一些实施方式中，所述半芳香族聚酰胺包括PA6T、PA12T、PA9T、PA10T、PA4T、PA46中的至少一种。
在一些实施方式中，所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：(0.5-3.5)。
在一些优选的实施方式中，所述PA6T、PA12T的重量比为1：(1-3)。在一些更优选的实施方式中，所述PA6T、PA12T的重量比为1：2。
在本发明中，所述的PA6T、PA12T的购买厂家不做特殊的限定，优选的购买自索尔维投资有限公司。
本发明中提供了一种红外光激发碳化助剂，其中发明人发现采用半芳香族聚酰胺为基体树脂，以及复配使用特定用量的金属粉可以有利于增加激光打标后的色差对比度，申请人发现尤其是选用高熔融指数的低密度聚乙烯作为载体，并加入两种稀土氧化物和三氧化二锑之后可以进一步提高打标色差对比效果，发明意外发现，尤其针对于PA6T、PA12T组合的半芳香族聚酰胺时打标效果最佳，发明人认为可能是由于，PA6T亚甲基柔性链比较短，形成结晶趋势较差，利于粒径小、分布均匀、比表面积大、高表面活性的纳米氧化钕增强对激光的吸收性能，而PA12T具有较长的亚甲基柔性长链，使得大分子容易形成有序排列的结晶趋势，两种不同的PA6T、PA12T半芳香族聚酰胺在打标后利于得到较好的打标色差对比效果。
此外发明意外发现，本发明制备的红外光激发碳化助剂，更适用于聚丙烯聚烯烃为基质材料的打标。
载体树脂
在一些实施方式中，所述载体树脂包括LDPE、PP、HDPE中的至少一种；所述LDPE的熔体流动速率为24-70g/10min。
在一些优选的实施方式中，所述载体树脂为LDPE；所述LDPE的熔体流动速率为24-70g/10min。
在一些更优选的实施方式中，所述LDPE的熔体流动速率为60-70g/10min。
在一些更优选的实施方式中，所述LDPE的熔体流动速率为70g/10min。
本发明中所述LDPE的牌号来源不做特殊的限定，优选的，所述LDPE为LotreneMG70、SINPOLENEFRN1982、LDPE(低密度聚乙烯)1965-T/荷兰DSM、LDPE(低密度聚乙烯)LD9150/澳大利亚Qenos中的至少一种；更优选的，所述LDPE为LotreneMG70。
所述熔体流动速率的测试条件为190℃/2.16kg。
相容剂
在一些实施方式中，所述相容剂为马来酸酐接枝聚烯烃。
在一些优选的实施方式中，所述相容剂为马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯中的至少一种；更优选的，所述相容剂为马来酸酐接枝聚乙烯。
在一些实施方式中，所述马来酸酐接枝聚乙烯的接枝率为0.5-1.5％；更优选的，所述马来酸酐接枝聚乙烯的接枝率为1％。
本发明中所述马来酸酐接枝聚乙烯的购买来源不做特殊的限定，优选的，所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
本发明的第二个方面提供了一种所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。
在一些实施方式中，所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
在一些实施方式中，所述步骤(1)中的加工温度为290-320℃；优选的，所述步骤(1)中的加工温度为300℃。
在一些实施方式中，所述步骤(2)中的加工温度为290-320℃；优选的，所述步骤(2)中的加工温度为310℃。
本发明的第三个方面提供了一种所述的红外光激发碳化助剂的应用，应用于塑料材料的红外光标识。
为了更好的理解上述技术方案，下面将结合具体的实施方式对上述技术方案进行详细的说明。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。另外，如果没有其它说明，所用原料都是市售的。
实施例1
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为5μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为40nm。
所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：2。所述PA6T、PA12T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为70g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例2
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.03份金属粉，40份金属氧化物，20份半芳香族聚酰胺，2.5份相容剂，25份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为1μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.1μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.1％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为20nm。
所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：1。所述PA6T、PA12T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为60g/10min，LDPE为SINPOLENEFRN1982。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为0.5％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例3
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.1份金属粉，50份金属氧化物，25份半芳香族聚酰胺，3.5份相容剂，30份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为10μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为1.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.5％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为50nm。
所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：3。所述PA6T、PA12T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为65g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1.5％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒， 即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例4
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为5μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为40nm。
所述半芳香族聚酰胺为PA6T；所述PA6T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为70g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例5
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份 载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为5μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为40nm。
所述半芳香族聚酰胺为PA12T，PA12T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为70g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例6
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为5μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为40nm。
所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为5：1。所述PA6T、PA12T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为70g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例7
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为5μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为40nm。
所述半芳香族聚酰胺为PA6T、PA66的混合物；所述PA6T、PA66的重量比为1：2。所述PA6T、PA66购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为70g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒， 即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例8
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为5μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：2。所述PA6T、PA12T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为70g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例9
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为50μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为40nm。
所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：2。所述PA6T、PA12T购买自索尔维投资有限公司。
所述载体树脂为LDPE，所述LDPE的熔体流动速率为70g/10min，LDPE为LotreneMG70。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
实施例10
一种红外光激发碳化助剂，按重量百分比计，原料至少包含：0.05份金属粉，46份金属氧化物，22份半芳香族聚酰胺，3份相容剂，28份载体树脂。
所述金属粉为铝粉，所述金属粉的平均粒径为5μm。
所述金属氧化物为三氧化二锑，所述三氧化二锑的平均粒径为0.5μm。
所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.2％。
所述稀土氧化物为氧化钕，所述氧化钕的平均粒径为40nm。
所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：2。所述PA6T、PA12T购买自索尔维投资有限公司。
所述载体树脂为HDPE，所述HDPE的熔体流动速率为66g/10min，190℃/2.16kg，所述HDPE为HDPE(高密度聚乙烯)DMDA-8965NT7/陶氏 杜邦。
所述相容剂为马来酸酐接枝聚乙烯，接枝率为1％。所述马来酸酐接枝聚乙烯购买自佳易容相容剂江苏有限公司，牌号为CMG5904。
所述的红外光激发碳化助剂的制备方法，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。所述步骤(1)、(2)中加工设备为螺杆直径为30mm的双螺杆挤出造粒机。
所述步骤(1)中的加工温度为300℃。所述步骤(2)中的加工温度为310℃。
性能测试
将实施例1-实施例10制备的红外光激发碳化助剂，按2wt％的添加量加入到聚烯烃树脂中，聚烯烃树脂的种类分别为PP、LDPE中，加入1wt％钛白粉，制作板片，然后使用20瓦光纤激光机进行打标测试，光纤激光打标机购自深圳天策激光科技有限公司。聚丙烯购买自台塑聚丙烯(宁波)有限公司的1120D；所述LDPE购买自LDPE(低密度聚乙烯)16P/三井化学。
制备方法为：用塑料袋称取红外光激发碳化助剂，钛白粉，聚丙烯；手摇混合均匀；将注塑机清洗干净，将混合好的材料加入到注塑机中，注塑温度设置为220℃；
打标图形：一维码，打标功率：75％，打标速度：3000mm/s，打标频率：30KHz，填充：0.05。
对所生产打黑字激光颗粒的产品形态，打标效果，颜色影响进行检验打黑字激光颗粒品质检测方法和标准。其中，检测设备、仪器如表1所示，评估标准如表2所示，其中，粒子颜色的测试是在PP材料(具体为5090t)中添加1％的粒子和1％的钛白粉(Kronos 2450)，注塑打板，L值要求93以上，值越高越好；检测结果如表3所示，其中实施例1-实施例3以及实施例6-实施例10的红外光激发碳化助剂制备的粒子外观、粒子颜色都符合标准；实施例4-实施例5的红外光激发碳化助剂可以通过提高添 加量来满足使用要求。表3中各实施例的红外光激发碳化助剂制备的粒子外观直径约2mm，长度约3.5mm。
表1检测设备/仪器
检测设备和仪器 制造厂商 设备仪器/规格 编号
注塑机 震德塑料机械有限公司 80吨 J80M3V
光纤激光打标机 深圳天策激光科技有限公司 20瓦特 TC-YLP
分光测色仪 深圳市威福光电科技有限公司 便携立式 WN700D
电子称   2000g/0.01g  
表2评估标准
Figure PCTCN2021101712-appb-000001
表3检测结果
实施例 对比度打标效果 粒子外观 粒子颜色L值
实施例1(PP) 5星 符合标准 94.32
实施例1(LDPE) 4星 符合标准 93.25
实施例2 5星 符合标准 93.56
实施例3 5星 符合标准 94.62
实施例4 3星 符合标准 94.32
实施例5 3星 符合标准 93.85
实施例6 4星 符合标准 92.95
实施例7 4星 符合标准 93.89
实施例8 4星 符合标准 94.63
实施例9 4星 符合标准 93.32
实施例10 4星 符合标准 93.85
以上所述仅是本发明的较佳实施例而已，并非是对发明作其他形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或更改为等同变化的等效实施例，但凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改，等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (20)

  1. 一种红外光激发碳化助剂，其特征在于，按重量百分比计，原料至少包含：0.01-0.15份金属粉，35-55份金属氧化物，15-30份半芳香族聚酰胺，2-4份相容剂，20-35份载体树脂。
  2. 如权利要求1所述的红外光激发碳化助剂，其特征在于，原料至少包含：0.03-0.10份金属粉，40-50份金属氧化物，20-25份半芳香族聚酰胺，2.5-3.5份相容剂，25-30份载体树脂。
  3. 如权利要求1所述的红外光激发碳化助剂，其特征在于，所述金属粉的平均粒径为1-10μm。
  4. 如权利要求1所述的红外光激发碳化助剂，其特征在于，所述金属氧化物包括二氧化锡、三氧化二锑、氧化锡锑、氧化铝、氧化锌、氧化钛、氧化铜中的至少一种。
  5. 如权利要求4所述的红外光激发碳化助剂，其特征在于，所述三氧化二锑的平均粒径为0.1-1.5μm。
  6. 如权利要求4所述的红外光激发碳化助剂，其特征在于，所述金属氧化物还包括稀土氧化物；所述稀土氧化物的加入量为三氧化二锑重量的0.1-0.5％。
  7. 如权利要求6所述的红外光激发碳化助剂，其特征在于，所述稀土氧化物包括氧化钕、氧化镧、氧化铌、氧化铈、氧化镱中的至少一种。
  8. 如权利要求7所述的红外光激发碳化助剂，其特征在于，所述氧化钕的平均粒径为1-50nm。
  9. 如权利要求1所述的红外光激发碳化助剂，其特征在于，所述半芳香族聚酰胺包括PA6T、PA12T、PA9T、PA10T、PA4T、PA46中的至少一种。
  10. 如权利要求9所述的红外光激发碳化助剂，其特征在于，所述半芳香族聚酰胺为PA6T、PA12T的混合物；所述PA6T、PA12T的重量比为1：(0.5-3.5)。
  11. 如权利要求1所述的红外光激发碳化助剂，其特征在于，所述载 体树脂包括LDPE、PP、HDPE中的至少一种；所述LDPE的熔体流动速率为24-70g/10min。
  12. 如权利要求11所述的红外光激发碳化助剂，其特征在于，所述熔体流动速率的测试条件为190℃/2.16kg。
  13. 如权利要求1所述的红外光激发碳化助剂，其特征在于，所述相容剂为马来酸酐接枝聚烯烃。
  14. 如权利要求13所述的红外激发碳化助剂，其特征在于，所述相容剂为马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯中的至少一种。
  15. 如权利要求14所述的红外光激发碳化助剂，其特征在于，所述马来酸酐接枝聚乙烯的接枝率为0.5-1.5％。
  16. 一种如权利要求1-15任一项所述的红外光激发碳化助剂的制备方法，其特征在于，步骤至少包括：(1)将金属粉、金属氧化物、半芳香族聚酰胺进行共混熔融挤出造粒，得到初混合料粒子；(2)将初混合料粒子、相容剂、载体树脂进行共混熔融挤出造粒，即得。
  17. 如权利要求16所述的红外光激发碳化助剂的制备方法，其特征在于，所述步骤(1)中的加工温度为290-320℃，所述步骤(2)中的加工温度为290-320℃。
  18. 一种如权利要求1-17任一项所述的红外光激发碳化助剂的应用，其特征在于，应用于塑料材料的红外光标识。
  19. 根据权利要求18所述的应用，其特征在于，所述塑料材料为聚烯烃。
  20. 根据权利要求19所述的应用，其特征在于，所述聚烯烃为聚丙烯。
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CN114790308B (zh) * 2021-05-18 2023-09-22 中山市芸浩科技有限公司 一种激光标识碳化组合物及其制备方法和应用
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