WO2020224272A1 - 一种高效激光打标料及其制备方法 - Google Patents

一种高效激光打标料及其制备方法 Download PDF

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Publication number
WO2020224272A1
WO2020224272A1 PCT/CN2019/128876 CN2019128876W WO2020224272A1 WO 2020224272 A1 WO2020224272 A1 WO 2020224272A1 CN 2019128876 W CN2019128876 W CN 2019128876W WO 2020224272 A1 WO2020224272 A1 WO 2020224272A1
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Prior art keywords
laser marking
marking material
efficiency laser
zones
antioxidant
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Ceased
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PCT/CN2019/128876
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English (en)
French (fr)
Inventor
缪飞
朱炯
赵学广
管成飞
赵静
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Jiangsu Zhongtian Technology Co Ltd
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Jiangsu Zhongtian Technology Co Ltd
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Priority to EP19928046.2A priority Critical patent/EP3967727B1/en
Publication of WO2020224272A1 publication Critical patent/WO2020224272A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B7/002—Methods
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29B7/88—Adding charges, i.e. additives
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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Definitions

  • the invention belongs to the technical field of materials, and specifically relates to a high-efficiency laser marking material and a preparation method thereof.
  • Black PE material In the cable industry, black PE material has been widely used. Black PE materials generally use traditional ink jet coding, printing wheel printing and other methods for marking, but they all have certain limitations and are difficult to meet production requirements.
  • laser printing technology is energy-saving and environmentally friendly, with high applicability and clear markings.
  • the existing black PE materials using laser printing are prone to defects such as blurred logo, poor contrast, and slow marking speed.
  • defects such as small marks, illegibility, poor contrast, and low marking speed are likely to occur, which cannot meet the needs of industrial production.
  • the technical problem to be solved by the present invention is to provide a high-efficiency laser marking material and a preparation method thereof.
  • the high-efficiency laser marking material provided by the present invention can achieve the goals of high-speed marking, clear marking and high contrast. And it has no effect on the performance of the wire and cable, and the weather resistance is more prominent.
  • the invention provides a high-efficiency laser marking material, which is prepared from raw materials including the following mass percentages:
  • LLDPE resin 20wt% ⁇ 60wt%
  • the laser assistant is 0.3wt% to 1wt%, and the laser assistant is selected from two or more materials of ferroferric oxide, antimony tin oxide and mica copper phosphate;
  • the melt flow rate of the HDPE resin at 190°C and 2.16Kg is not more than 10.0g/10min.
  • the melt flow rate of the LLDPE resin at 190° C. and 2.16 Kg is not more than 2.0 g/10 min.
  • the lubricant is selected from one or more of PE wax, PPA, silicone, PP wax, oleic acid amide, erucamide, stearic acid and EBS.
  • the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 330, antioxidant 168 and antioxidant DLTP.
  • the light stabilizer is selected from one or more of light shielding agents, light absorbers and radical trapping agents.
  • the light shielding agent is selected from carbon black and/or tin oxide
  • the light absorber is selected from UV326 and/or UV531
  • the free radical trapping agent is selected from Chimassorb UV944.
  • the carbon black content in the high-efficiency laser marking material is not more than 2wt%; the melt flow rate of the high-efficiency laser marking material is not more than 2.0 g/10 min.
  • the invention also provides a method for preparing the above-mentioned high-efficiency laser marking material, which includes the following steps:
  • a twin-screw extruder is used for the extrusion granulation, and the processing technology of the twin-screw extruder is: 210 ⁇ 225°C in the first zone, 220-235°C in the second zone, and 230-245°C in the third zone.
  • the screw speed is 280 ⁇ 350r/min, and the water tank temperature is 30 ⁇ 40°C.
  • the present invention provides a high-efficiency laser marking material, which is prepared from raw materials including the following mass percentages: HDPE resin 40wt% ⁇ 80wt%; LLDPE resin 20wt% ⁇ 60wt%; laser aid 0.3 wt%-1wt%, the laser assistant is selected from two or more materials selected from ferroferric oxide, antimony tin oxide and mica copper phosphate; lubricant 0.2wt%-1wt%; antioxidant 0.3wt% ⁇ 0.5wt%; light stabilizer 0.1wt% ⁇ 0.6wt%; black masterbatch 0.5wt% ⁇ 5wt%.
  • the additive amount of the laser assistant and black masterbatch in the formulation system of the high-efficiency laser marking material provided by the present invention plays a leading role in the quality of the printing effect.
  • the mechanical properties of the material have not changed much, but the printing effect is significantly improved.
  • the laser additives can help improve the absorption of the special wavelengths emitted by the laser by the black PE material, so that the polymer surface is carbonized, and through foaming, the white color appears, which is in sharp contrast with the black PE sheath.
  • Figure 1 is a schematic diagram of the cable structure
  • Figure 2 is a schematic diagram of the high-efficiency laser marking material for marking.
  • the invention provides a high-efficiency laser marking material, which is prepared from raw materials including the following mass percentages:
  • LLDPE resin 20wt% ⁇ 60wt%
  • the laser assistant is 0.3wt% to 1wt%, and the laser assistant is selected from two or more materials of ferroferric oxide, antimony tin oxide and mica copper phosphate;
  • the high-efficiency laser marking material provided by the present invention includes 40 wt% to 80 wt% of HDPE resin, preferably 50 wt% to 70 wt%, and more preferably 55 wt% to 65 wt%.
  • the melt flow rate of the HDPE resin at 190°C and 2.16Kg is not more than 10.0g/10min.
  • the HDPE is selected from one or more mixtures of low-melting index HDPE and high-melting index HDPE resins, and the low-melting index HDPE resin has a melt flow rate of not more than 2.0g/10min at 190°C and 2.16Kg .
  • low melting means that the melt flow rate of the HDPE resin is not greater than 1.0 g/10 min.
  • the HDPE resin of the low melting index is selected from one or more blended materials of 7000F, FB1350, HDPE3363, HDPE00952 and HDPE041.
  • the high melt index HDPE resin has a melt flow rate of not more than 20.0 g/10 min at 190° C. and 2.16 Kg.
  • high melting means that the melt flow rate of HDPE resin is not more than 10.0 g/10 min.
  • the HDPE resin with high melting index is selected from one or more blended materials among HDPE (FMA026), HDPE8008, and HDPE (FMA025).
  • the high-efficiency laser marking material provided by the present invention further includes 20 wt% to 60 wt%, preferably 30 wt% to 50 wt%, and more preferably 35 wt% to 45 wt%.
  • the melt flow rate of the LLDPE resin at 190° C. and 2.16 Kg is not more than 2.0 g/10 min.
  • the melt flow rate of the LLDPE resin is not greater than 1.0 g/10 min.
  • the LLDPE resin mainly includes one or several blended materials of LLDPE7042, LLDPE (FB2230), and LLDPE (FK1820).
  • HDPE resin In order to adapt to various specifications of wires and cables, laser marking materials require very superior processing and extrusion performance.
  • the selection and ratio of HDPE resin and LLDPE resin are very important.
  • HDPE resin in addition to HDPE with low melting index, a certain proportion of HDPE with high melting index plays a role in promoting the processing flow and extrusion performance of the entire formulation system.
  • LLDPE resin chooses bimodal LLDPE with superior processing performance. , And then modified and granulated by lubricant, making the finished product processing performance very superior.
  • the high-efficiency laser marking material provided by the present invention also includes 0.3 wt% to 1 wt% of laser assistant, preferably 0.4 wt% to 0.9 wt%, and more preferably 0.5 wt% to 0.8 wt%.
  • the laser assistant is selected from two or more materials selected from the group consisting of triiron tetroxide, antimony tin oxide and mica copper phosphate.
  • the laser aids mainly include Merck’s Iriotec 8835, Merck’s Iriotec 8815, and Qirun’s laser engraving aid HZ-889A, and Hannuo material laser marking masterbatch 0896-05FT-02. Of two or more blended materials.
  • the laser auxiliary agent can assist in increasing the absorption of the special wavelengths emitted by the laser by the black PE material, so that the polymer surface layer is carbonized and foamed to appear white, which is in sharp contrast with the black PE sheath.
  • the high-efficiency laser marking material provided by the present invention further includes 0.2wt%-1wt% of lubricant, preferably 0.4wt%-0.8wt%, more preferably 0.5wt%-0.7wt%.
  • the lubricant is selected from one or more of PE wax, PPA, silicone, PP wax, oleic acid amide, erucic acid amide, stearic acid and EBS.
  • the lubricant mainly includes one or a mixture of PE wax, PPA, silicone, PP wax, oleic acid amide, erucic acid amide, stearic acid and EBS.
  • the high-efficiency laser marking material provided by the present invention also includes 0.3 wt% to 0.5 wt% of antioxidant, preferably 0.35 wt% to 0.45 wt%, and more preferably 0.37 wt% to 0.0.42 wt%.
  • the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 330, antioxidant 168 and antioxidant DLTP.
  • the high-efficiency laser marking material provided by the present invention further includes a light stabilizer in an amount of 0.1 wt% to 0.6 wt%, preferably 0.2 wt% to 0.5 wt%, and more preferably 0.3 wt% to 0.4 wt%.
  • the light stabilizer is selected from one or more of light shielding agents, light absorbers and radical trapping agents.
  • the light shielding agent is selected from carbon black and/or tin oxide
  • the light absorber is selected from UV326 and/or UV531
  • the free radical trapping agent is selected from Chimassorb UV944.
  • the high-efficiency laser marking material provided by the present invention also includes 0.5 wt% to 5 wt% of black masterbatch, preferably 1.0 wt% to 4.5 wt%, and more preferably 2.0 wt% to 4.0 wt%.
  • the black masterbatch mainly includes one or a blend of Cabot PE2762 and Cabot PE2014.
  • the additive amount of the laser assistant and the black masterbatch in the formula system plays a leading role in the quality of the printing effect.
  • the mechanical properties of the material do not change much, but the printing effect is significantly improved.
  • antioxidants in order to ensure good weather resistance and long service life, the addition of antioxidants, light stabilizers and black color masterbatch play a role in light shielding agent, light absorption, and free radical capture, ensuring the outdoor use time of the finished cable .
  • the high-efficiency laser marking material contains a certain amount of carbon black, and the source of the carbon black is the carbon black and/or black masterbatch in the light stabilizer in the formula, and the carbon black content in the product is not more than 2wt% .
  • the melt flow rate of the high-efficiency laser marking material provided by the present invention is not greater than 2.0 g/10 min.
  • the melt flow rate of the high-efficiency laser marking material is not greater than 2.0 g/10 min.
  • the invention also provides a method for preparing the above-mentioned high-efficiency laser marking material, which includes the following steps:
  • the present invention firstly mixes HDPE resin and LLDPE resin.
  • the present invention does not have any special restrictions on the mixing method, as long as the mixing method is well known to those skilled in the art. In the present invention, it is preferable to mix according to the following method:
  • the batch of mixed resin is placed in a discharge bin, and then the batch of mixed resin is placed in a high-speed mixer through automatic weighing.
  • the mixture is extruded and pelletized to obtain high-efficiency laser marking materials.
  • a twin-screw extruder is used for the extrusion granulation, and the processing technology of the twin-screw extruder is: 210 ⁇ 225°C in the first zone, 220 ⁇ 235°C in the second zone, and 230 ⁇ 235 in the third zone. 245°C, four zone 240 ⁇ 255°C, five zone 220 ⁇ 235°C, six zone 230 ⁇ 245°C, seven zone 225 ⁇ 245°C, eight zone 220 ⁇ 235°C, nine zone 215 ⁇ 230°C, ten zone 195 ⁇ 210 °C; screw speed 280 ⁇ 350r/min, water tank temperature 30 ⁇ 40°C.
  • the high-efficiency laser marking material is used on the surface of a cable made of black PE material, wherein the present invention does not have any special restrictions on the structure and specifications of the cable.
  • a cable with a black PE sheath on the surface well known to those skilled in the art is sufficient.
  • the cable includes a black PE sheath, a filler wire and a loose tube arranged inside the black PE sheath, and the loose tube is filled with optical fibers.
  • FIG. 2 is a schematic diagram of the high-efficiency laser marking material when marking.
  • the laser additives can help increase the absorption of the special wavelengths emitted by the laser by the black PE material, so that the polymer surface layer is carbonized, and through foaming, a white color appears, which is in sharp contrast with the black PE sheath.
  • the high-efficiency laser marking material provided by the invention is suitable for wires and cables of various specifications, with clear printing effect, high contrast and high production efficiency.
  • the material has superior performance, good weather resistance and long service life.
  • the additive amount of laser additives and black masterbatch in the formula system plays a leading role in the quality of the printing effect.
  • the content of laser additives increases and the content of carbon black decreases, the mechanical properties of the material do not change much, but the printing effect is significantly improved.
  • HDPE resin in addition to HDPE with low melting index, a certain proportion of HDPE with high melting index plays a role in promoting the processing flow and extrusion performance of the entire formulation system.
  • LLDPE resin selects bimodal LLDPE with processing performance. After the lubricant is modified and granulated, the processing performance of the finished product is very superior.
  • antioxidants In order to ensure good weather resistance and long service life, the addition of antioxidants, light stabilizers and black color masterbatch play a role in light shielding agent, light absorption, and free radical capture, ensuring the finished cable's outdoor use time.
  • the HDPE resin in Table 1 contains low-melting index HDPE resin whose melt flow rate is not more than 1.0g/10min, selected from one or more blended materials among 7000F, FB1350, HDPE3363, HDPE00952 and HDPE041; high-melting index
  • the melt flow rate of HDPE resin is not more than 10.0g/10min, and it is selected from one or more blended materials among HDPE (FMA026), HDPE8008, and HDPE (FMA025).
  • the melt flow rate of LLDPE resin is not more than 1.0g/10min, and it is selected from one or more blended materials among LLDPE7042, LLDPE (FB2230) and LLDPE (FK1820).
  • the laser assistant in the laser assistant is Heqirun HZ-889A.
  • Example 2 Example 3
  • Example 4 HDPE 60 40 80 75 LLDPE 40 60 20 25 Laser additives 0.1 0.4 0.5 0.8 Lubricant 0.3 0.35 0.5 0.4 Antioxidant 0.3 0.4 0.3 0.5 Light stabilizer 0.4 0.4 0.4 0.4 Black masterbatch 2 1 3 1
  • the first step according to the proportion designed in the formula system, weigh the HDPE resin and LLDPE resin by the corresponding weight, and put them into the batch mixing equipment for up and down reciprocating mixing.
  • Step 2 Put the mixed batch of resin into the discharge bin automatically.
  • the third step put a certain amount of batch mixed resin into the high-speed mixer by automatic weighing.
  • Step 4 Put the weighed laser additives, lubricants, antioxidants, light stabilizers, and black masterbatch into the high-speed mixer.
  • the fifth step After mixing in a high-speed mixer for 60 seconds, the materials are uniformly mixed and fed into the twin-screw extruder for extrusion and granulation.
  • the twin-screw extrusion process is: 210°C in the first zone, 220°C in the second zone, 230°C in the third zone, 240°C in the fourth zone, 235°C in the fifth zone, 230°C in the sixth zone, 225°C in the seventh zone, 220°C in the eight zone, and in the nine zone 215°C, ten zones 210°C, screw speed 280r/min, water tank temperature 35°C. Get high-efficiency laser marking material.
  • Step 6 Clean, cool, dry, weigh, and pack the high-efficiency laser marking material after pelletizing.
  • Example 2 Example 3
  • Example 4 Cable pulling speed m/min 70m/min 60m/min 90m/min 100m/min Apparent performance The surface is smoother and brighter General surface Smooth and shiny surface Smooth and shiny surface Printing effect Clearer general Clear Clear Clear
  • Example 2 Example 3
  • Example 4 Cable pulling speed m/min 50m/min 40m/min 55m/min 60m/min Apparent performance The surface is smoother and brighter General surface Smooth and shiny surface Smooth and shiny surface Printing effect Clearer general Clear Clear Clear
  • Examples 4,4-1,4-2,4-3 in Table 7 are selected from the mixture of Iriotec 8835 and Iriotec 8815 with a mass ratio of 4:1;
  • Example 4-4 does not add laser additives ;
  • Example 4-5 selects the laser aid for Heqirun laser carving aid HZ-889A;
  • Example 4-3 For small wire diameter wires and cables (outer diameter ⁇ 2.5mm), under the condition of cable formation with a line speed of 60-100 m/min, the printing effect of Example 4-3 is superior, and the font is clearer. Under the test conditions of steel needle (4N, 100 times), wool felt (10N, 300 times) and rubbing with alcohol, the printing effect of Example 4-3 was more difficult to remove the printing effect, and the retention effect was more prominent. However, in Example 4-4, the printing effect is blurred without adding laser additives, and the fonts can be easily wiped and removed; Example 4-5 selects the light additives and Qirun laser engraving additives HZ-889A, and its printing effect Relatively clear, the font is not easy to wipe off. The specific results are shown in Table 9
  • the high-efficiency laser marking material provided by the invention is suitable for wires and cables of various specifications, with clear printing effect, high contrast and high production efficiency.
  • the material has superior performance, good weather resistance and long service life.

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Abstract

本发明提供了一种高效激光打标料，本发明提供的高效激光打标料的配方体系中激光助剂和黑色色母粒的添加量对印字效果的好坏起到主导作用，随着激光助剂含量的增加和炭黑含量的减少，其材料的机械性能变化不大，但是印字效果明显提高。另外，激光助剂可以辅助提高黑色PE材料吸收激光器发射的特殊的波长，使得聚合物表层炭化，并且通过发泡，从而出现白色，与黑色的PE护套形成鲜明的对比。

Description

一种高效激光打标料及其制备方法 技术领域
本发明属于材料技术领域，具体涉及一种高效激光打标料及其制备方法。
背景技术
在线缆行业，黑色PE材料得到了广泛的应用。黑色PE材料一般采用传统的油墨喷码、印字轮印字等方式来进行标识，但是均存在一定的局限性，难以满足生产要求。
而激光印刷技术，相对于传统印刷方式，节能环保，适用性高，标识清晰。但采用激光印字过程中，现有的黑色PE材料采用激光印字容易出现了标识模糊，对比度差，标记速度慢等缺陷。特别在外径小、壁厚薄的小规格线缆印刷中容易出现标识小、模糊不清、对比度差、标记速度低等缺陷，无法满足工业化生产需求。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种高效激光打标料及其制备方法，本发明提供的高效激光打标料能够实现高速标记，标识清晰，对比度高的目标。且对电线电缆的性能没有影响，同时耐候性能也更加突出。
本发明提供了一种高效激光打标料，由包括以下质量百分比的原料制备而成：
HDPE树脂              40wt％～80wt％；
LLDPE树脂             20wt％～60wt％；
激光助剂              0.3wt％～1wt％，所述激光助剂选自四氧化三铁、氧化锑锡和云母磷酸铜中的两种或两种以上材料；
Figure PCTCN2019128876-appb-000001
Figure PCTCN2019128876-appb-000002
上述各组分之和为100wt％。
优选的，所述HDPE树脂在190℃、2.16Kg下，熔体流动速率不大于10.0g/10min。
优选的，所述LLDPE树脂在190℃、2.16Kg下，熔体流动速率不大于2.0g/10min。
优选的，所述润滑剂选自PE蜡、PPA、硅酮、PP蜡、油酸酰胺、芥酸酰胺、硬脂酸和EBS中的一种或多种。
优选的，所述抗氧剂选自抗氧剂1010、抗氧剂1076、抗氧剂330、抗氧剂168和抗氧剂DLTP中的一种或多种。
优选的，所述光稳定剂选自光屏蔽剂、光吸收剂和自由基捕获剂中的一种或多种。
优选的，所述光屏蔽剂选自炭黑和/或氧化锡，所述光吸收剂选自UV326和/或UV531，所述自由基捕获剂选自Chimassorb UV944。
优选的，所述高效激光打标料中炭黑含量不大于2wt％；所述高效激光打标料的熔体流动速率不大于2.0g/10min。
本发明还提供了一种上述高效激光打标料的制备方法，包括以下步骤：
A)将HDPE树脂和LLDPE树脂混合后再加入激光助剂、润滑剂、抗氧剂、光稳定剂和黑色色母粒进行混合，得到混合料；
B)将所述混合料挤出造粒，得到高效激光打标料。
优选的，所述挤出造粒选用双螺杆挤出机，双螺杆挤出机挤出造粒的加工工艺为：一区210～225℃、二区220～235℃、三区230～245℃、四区240～255℃、五区220～235℃、六区230～245℃、七区225～245℃、八区220～235℃、九区215～230℃、十区195～210℃；螺杆转速280～350r/min，水槽温度30～40℃。
与现有技术相比，本发明提供了一种高效激光打标料，由包括以下质量百分比的原料制备而成：HDPE树脂40wt％～80wt％；LLDPE树脂20wt％～60wt％；激光助剂0.3wt％～1wt％，所述激光助剂选自四氧化三铁、氧化锑锡和云母磷酸铜中的两种或两种以上材料；润滑剂0.2wt％～1wt％；抗氧剂0.3wt％～0.5wt％；光稳定剂0.1wt％～0.6wt％；黑色色母粒0.5wt％～5wt％。本发明提供的高效激光打标料的配方体系中激光助剂和黑色色母粒的添加量对印 字效果的好坏起到主导作用，随着激光助剂含量的增加和炭黑含量的减少，其材料的机械性能变化不大，但是印字效果明显提高。另外，激光助剂可以辅助提高黑色PE材料吸收激光器发射的特殊的波长，使得聚合物表层炭化，并且通过发泡，从而出现白色，与黑色的PE护套形成鲜明的对比。
附图说明
图1为线缆的结构示意图；
图2为所述高效激光打标料进行打标时的原理图。
具体实施方式
本发明提供了一种高效激光打标料，由包括以下质量百分比的原料制备而成：
HDPE树脂              40wt％～80wt％；
LLDPE树脂             20wt％～60wt％；
激光助剂              0.3wt％～1wt％，所述激光助剂选自四氧化三铁、氧化锑锡和云母磷酸铜中的两种或两种以上材料；
Figure PCTCN2019128876-appb-000003
本发明提供的高效激光打标料包括40wt％～80wt％的HDPE树脂，优选为50wt％～70wt％，进一步优选为55wt％～65wt％。在本发明中，所述HDPE树脂在190℃、2.16Kg下，熔体流动速率不大于10.0g/10min。
所述HDPE选自低熔指HDPE和高熔指的HDPE树脂中的一种或多种混合物，所述低熔指HDPE树脂在190℃、2.16Kg下，熔体流动速率不大于2.0g/10min。优选的，低熔指HDPE树脂的熔体流动速率不大于1.0g/10min。所述低熔指的HDPE树脂选自7000F、FB1350、HDPE3363、HDPE00952和HDPE041中的一种或几种共混材料。所述高熔指的HDPE树脂在190℃、2.16Kg下，熔体流动速率不大于20.0g/10min。优选的，高熔指HDPE树脂的熔体流动速率不大于10.0g/10min。所述高熔指的HDPE树脂选自HDPE (FMA026)、HDPE8008、HDPE(FMA025)中的一种或几种共混材料。
本发明提供的高效激光打标料还包括20wt％～60wt％，优选为30wt％～50wt％，进一步优选为35wt％～45wt％。所述LLDPE树脂在190℃、2.16Kg下，熔体流动速率不大于2.0g/10min。优选的，LLDPE树脂的熔体流动速率不大于1.0g/10min。所述LLDPE树脂主要包括LLDPE7042、LLDPE(FB2230)、LLDPE(FK1820)中的一种或几种共混材料。
为了适应各种规格的电线电缆，激光打标材料需要非常优越的加工挤出性能，在本发明中，HDPE树脂和LLDPE的树脂选择与配比至关重要。在HDPE树脂的选择中，除了低熔指的HDPE之外，一定比例的高熔指HDPE对整个配方体系的加工流动挤出性能起着促进作用，同时LLDPE树脂选择加工性能更加优越的双峰LLDPE，再经过润滑剂通过改性造粒，使得成品的加工性能非常优越。
本发明提供的高效激光打标料还包括0.3wt％～1wt％的激光助剂，优选为0.4wt％～0.9wt％，进一步优选为0.5wt％～0.8wt％。所述激光助剂选自四氧化三铁、氧化锑锡和云母磷酸铜中的两种或两种以上材料。在本发明中，所述激光助剂主要包括默克的Iriotec 8835、默克的Iriotec 8815、和琦润的镭雕助剂HZ-889A、汉诺材料激光打标母粒0896-05FT-02中的两种或几种共混材料。
所述激光助剂可以辅助提高黑色PE材料吸收激光器发射的特殊的波长，使得聚合物表层炭化，并且通过发泡，从而出现白色，与黑色的PE护套形成鲜明的对比。
本发明提供的高效激光打标料还包括0.2wt％～1wt％的润滑剂，优选为0.4wt％～0.8wt％，进一步优选为0.5wt％～0.7wt％。所述润滑剂选自PE蜡、PPA、硅酮、PP蜡、油酸酰胺、芥酸酰胺、硬脂酸和EBS中的一种或多种。在本发明中，所述润滑剂主要包括PE蜡、PPA、硅酮、PP蜡、油酸酰胺、芥酸酰胺、硬脂酸和EBS中一种或几种的混合物。
本发明提供的高效激光打标料还包括0.3wt％～0.5wt％的抗氧剂，优选为0.35wt％～0.45wt％，进一步优选为0.37wt％～0.0.42wt％。所述抗氧剂选自抗氧剂1010、抗氧剂1076、抗氧剂330、抗氧剂168和抗氧剂DLTP中的一种或多种。
本发明提供的高效激光打标料还包括0.1wt％～0.6wt％的光稳定剂，优选 为0.2wt％～0.5wt％，进一步优选为0.3wt％～0.4wt％。所述光稳定剂选自光屏蔽剂、光吸收剂和自由基捕获剂中的一种或多种。所述光屏蔽剂选自炭黑和/或氧化锡，所述光吸收剂选自UV326和/或UV531、自由基捕获剂选自Chimassorb UV944。
本发明提供的高效激光打标料还包括0.5wt％～5wt％的黑色色母粒，优选为1.0wt％～4.5wt％，进一步优选为2.0wt％～4.0wt％。所述黑色色母粒主要包括卡博特的PE2762、卡博特的PE2014中一种或两种的共混物。
在本发明中，配方体系中激光助剂和黑色色母粒的添加量对印字效果的好坏起到主导作用。随着激光助剂含量的增加和炭黑含量的减少，其材料的机械性能变化不大，但是印字效果明显提高。
另外，为了保证耐候性能好，且使用寿命长，抗氧剂、光稳定剂和黑色色母的添加，起到了光屏蔽剂、光吸收、自由基捕获的能力，保证了成品缆在室外使用时间。
所述高效激光打标料中含有一定量的炭黑，所述炭黑的来源为配方中光稳定剂中的炭黑和/或黑色色母粒，折算成产品中炭黑含量不大于2wt％。
本发明提供的高效激光打标料的熔体流动速率不大于2.0g/10min，优选的，所述高效激光打标料的熔体流动速率不大于2.0g/10min。
本发明还提供了一种上述高效激光打标料的制备方法，包括以下步骤：
A)将HDPE树脂和LLDPE树脂混合后再加入激光助剂、润滑剂、抗氧剂、光稳定剂和黑色色母粒进行混合，得到混合料；
B)将所述混合料挤出造粒，得到高效激光打标料。
本发明首先将HDPE树脂和LLDPE树脂进行混合，本发明对所述混合方法并没有特殊限制，本领域技术人员公知的混合方法即可。在本发明中，优选按照如下方法进行混合：
将HDPE树脂和LLDPE树脂投入至批混设备中上下往复循环式混合，得到批混好的树脂；
将所述批混好的树脂置于放料仓中，然后通过自动计量称，将批混好的树脂置于高速混合机中。
接着，将称量好的激光助剂、润滑剂、抗氧剂、光稳定剂、黑色色母粒投入到高速混合机中。
然后，开始高速混合机混合60s～300s使原料均匀混合，得到混合料。
随后，将混合料挤出造粒，得到高效激光打标料。
在本发明中，所述挤出造粒选用双螺杆挤出机，双螺杆挤出机挤出造粒的加工工艺为：一区210～225℃、二区220～235℃、三区230～245℃、四区240～255℃、五区220～235℃、六区230～245℃、七区225～245℃、八区220～235℃、九区215～230℃、十区195～210℃；螺杆转速280～350r/min，水槽温度30～40℃。
最后，将切粒后的高效激光打标料进行清洁、冷却、干燥、称重和包装。
在本发明中，所述高效激光打标料用于黑色PE材料制备的线缆表面，其中，本发明对所述线缆的结构和规格并没有特殊限制。本领域技术人员公知的表面为黑色PE护套的线缆即可。
参见图1，图1为线缆的结构示意图。在本发明中，所述线缆包括黑色PE护套以及设置于所述黑色PE护套内部的填充线和松套管，所述松套管内部填充有光纤。
所述高效激光打标料进行打标时，其打标原理参见图2，图2为所述高效激光打标料进行打标时的原理图。其中，激光助剂可以辅助提高黑色PE材料吸收激光器发射的特殊的波长，使得聚合物表层炭化，并且通过发泡，从而出现白色，与黑色的PE护套形成鲜明的对比。
本发明提供的高效激光打标料适用各种规格的电线电缆，印字效果清晰，对比度高且生产效率高。材料性能优越，耐候性能好，且使用寿命长。
就印字效果清晰来说，配方体系中激光助剂和黑色色母粒的添加量对印字效果的好坏起到主导作用。随着激光助剂含量的增加和炭黑含量的减少，其材料的机械性能变化不大，但是印字效果明显提高。
就适用各种规格的电线电缆，且材料性能优越，对材料进行了详细的描述。要适应各种规格的电线电缆，表明材料需要非常优越的加工挤出性能，为此在配方体系中，HDPE树脂和LLDPE的树脂选择与配比至关重要。在HDPE树脂的选择中，除了低熔指的HDPE之外，一定比例的高熔指HDPE对整个配方体系的加工流动挤出性能起着促进作用，同时LLDPE树脂选择加工性能的双峰LLDPE，再经过润滑剂通过改性造粒，使得成品的加工性能非常优越。
同时为了保证耐候性能好，且使用寿命长，抗氧剂、光稳定剂和黑色色母的添加，起到了光屏蔽剂、光吸收、自由基捕获的能力，保证了成品缆在室外使用时间。
为了进一步理解本发明，下面结合实施例对本发明提供的高效激光打标料以及制备方法进行说明，本发明的保护范围不受以下实施例的限制。
实施例1～4
1、配方种类和用量分别见表1和表2
表1配方种类
Figure PCTCN2019128876-appb-000004
Figure PCTCN2019128876-appb-000005
注：表1中HDPE树脂包含低熔指HDPE树脂其熔体流动速率不大于1.0g/10min，选自7000F、FB1350、HDPE3363、HDPE00952和HDPE041中的一种或几种共混材料；高熔指HDPE树脂的熔体流动速率不大于10.0g/10min，选自HDPE(FMA026)、HDPE8008、HDPE(FMA025)中的一种或几种共混材料。LLDPE树脂其熔体流动速率不大于1.0g/10min，选自LLDPE7042、LLDPE(FB2230)、LLDPE(FK1820)中的一种或几种共混材料。激光助剂中的镭雕助剂为和琦润HZ-889A。
表2配方用量(单位：kg)
  实施例1 实施例2 实施例3 实施例4
HDPE 60 40 80 75
LLDPE 40 60 20 25
激光助剂 0.1 0.4 0.5 0.8
润滑剂 0.3 0.35 0.5 0.4
抗氧剂 0.3 0.4 0.3 0.5
光稳定剂 0.4 0.4 0.4 0.4
黑色色母粒 2 1 3 1
2、制备工艺
第一步：按照配方体系中设计的比例，将HDPE树脂和LLDPE树脂称取相应的重量，投入到批混设备中进行上下往复循环式混合。
第二步：将批混好的树脂自动投入到放料仓中。
第三步：通过自动计量称放入一定量的批混好树脂到高速混合机中。
第四步：将称取好的激光助剂、润滑剂、抗氧剂、光稳定剂、黑色色母 粒投入到高速混合机中。
第五步：在高速混合机中混合60s后，使材料均和混合投入双螺杆挤出机中挤出造粒。
双螺杆挤出加工工艺为：一区210℃、二区220℃、三区230℃、四区240℃、五区235℃、六区230℃、七区225℃、八区220℃、九区215℃、十区210℃，螺杆转速280r/min，水槽温度35℃。即得到高效激光打标料。
第六步：将切粒后的高效激光打标料进行清洁、冷却、干燥、称重、包装。
3、性能检测
(1)对实施例1～4制备得到的高效激光打标料的成缆性能进行对比表征，结果如表3所示。
表3高效激光打标料的成缆性能
Figure PCTCN2019128876-appb-000006
(2)对实施例1～4制备得到的高效激光打标料对于小线径电线电缆(外径≤2.5mm)的激光打印效果进行对比表征，结果如表4所示。
表4小线径电线电缆(外径≤2.5mm)的激光打印效果比较
  实施例1 实施例2 实施例3 实施例4
线缆牵引速度m/min 70m/min 60m/min 90m/min 100m/min
表观性能 表面较光滑光亮 表面一般 表面光滑光亮 表面光滑光亮
印字效果 较清晰 一般 清晰 清晰
(3)对实施例1～4制备得到的高效激光打标料对于一般线径电线电缆(外径 ≥3.0mm)的激光打印效果进行对比表征，结果如表5所示。
表5一般线径电线电缆(外径≥3.0mm)的激光打印效果比较
  实施例1 实施例2 实施例3 实施例4
线缆牵引速度m/min 50m/min 40m/min 55m/min 60m/min
表观性能 表面较光滑光亮 表面一般 表面光滑光亮 表面光滑光亮
印字效果 较清晰 一般 清晰 清晰
(4)对电线电缆擦拭效果进行检测，结果见表6
表6电线电缆擦拭效果
Figure PCTCN2019128876-appb-000007
实施例5
以实施例4的配方和制备方法为基础，改变原料的用量或改变激光助剂，其他条件不变，进行高效激光打标料的制备，配方具体用量见表7
表7配方用量
Figure PCTCN2019128876-appb-000008
注：表7中实施例4,4-1,4-2,4-3激光助剂选自Iriotec8835、Iriotec8815以质量比为4:1的配比混合物；实施例4-4不添加激光助剂；实施例4-5选用激光助剂为和琦润镭雕助剂HZ-889A；
对上述高效激光打标料的性能进行检测，结果见表8
表8高效激光打标料的成缆性能
Figure PCTCN2019128876-appb-000009
由表8可知，配方用量的改变，产品的机械性能基本没有太大变化。
但是对于小线径电线电缆(外径≤2.5mm)，在线速度为60～100m/min的成缆条件下，实施例4-3的印字效果更加优越，其字体更加清晰。在钢针(4N，100次)、羊毛毡(10N，300次)和酒精擦拭的试验条件下，实施例4-3其印字更不易去除印字效果，保留效果更加突出。而实施例4-4在不添加激光助剂的情况下，印字效果模糊，且字体易被擦拭去除；实施例4-5选用光助剂和琦润镭雕助剂HZ-889A，其印字效果相对清晰，字体不易被擦拭去除。具体结果见表9
表9
Figure PCTCN2019128876-appb-000010
Figure PCTCN2019128876-appb-000011
Figure PCTCN2019128876-appb-000012
本发明提供的高效激光打标料适用各种规格的电线电缆，印字效果清晰，对比度高且生产效率高。材料性能优越，耐候性能好，且使用寿命长。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种高效激光打标料，其特征在于，由包括以下质量百分比的原料制备而成：
    HDPE树脂              40wt％～80wt％；
    LLDPE树脂             20wt％～60wt％；
    激光助剂              0.3wt％～1wt％，所述激光助剂选自四氧化三铁、氧化锑锡和云母磷酸铜中的两种或两种以上材料；
    Figure PCTCN2019128876-appb-100001
    上述各组分之和为100wt％。
  2. 根据权利要求1所述的高效激光打标料，其特征在于，所述HDPE树脂在190℃、2.16Kg下，熔体流动速率不大于10.0g/10min。
  3. 根据权利要求1所述的高效激光打标料，其特征在于，所述LLDPE树脂在190℃、2.16Kg下，熔体流动速率不大于2.0g/10min。
  4. 根据权利要求1所述的高效激光打标料，其特征在于，所述润滑剂选自PE蜡、PPA、硅酮、PP蜡、油酸酰胺、芥酸酰胺、硬脂酸和EBS中的一种或多种。
  5. 根据权利要求1所述的高效激光打标料，其特征在于，所述抗氧剂选自抗氧剂1010、抗氧剂1076、抗氧剂330、抗氧剂168和抗氧剂DLTP中的一种或多种。
  6. 根据权利要求1所述的高效激光打标料，其特征在于，所述光稳定剂选自光屏蔽剂、光吸收剂和自由基捕获剂中的一种或多种。
  7. 根据权利要求6所述的高效激光打标料，其特征在于，所述光屏蔽剂选自炭黑和/或氧化锡，所述光吸收剂选自UV326和/或UV531，所述自由基捕获剂选自Chimassorb UV944。
  8. 根据权利要求1所述的高效激光打标料，其特征在于，所述高效激光打标料中炭黑含量不大于2wt％；所述高效激光打标料的熔 体流动速率不大于2.0g/10min。
  9. 一种如权利要求1～8任意一项所述的高效激光打标料的制备方法，其特征在于，包括以下步骤：
    A)将HDPE树脂和LLDPE树脂混合后再加入激光助剂、润滑剂、抗氧剂、光稳定剂和黑色色母粒进行混合，得到混合料；
    B)将所述混合料挤出造粒，得到高效激光打标料。
  10. 根据权利要求9所述的制备方法，其特征在于，所述挤出造粒选用双螺杆挤出机，双螺杆挤出机挤出造粒的加工工艺为：一区210～225℃、二区220～235℃、三区230～245℃、四区240～255℃、五区220～235℃、六区230～245℃、七区225～245℃、八区220～235℃、九区215～230℃、十区195～210℃；螺杆转速280～350r/min，水槽温度30～40℃。
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