CN109880276B - High-speed laser marking PBT/ABS composite material, and preparation method and application thereof - Google Patents
High-speed laser marking PBT/ABS composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of laser marking of bicolor keycaps, in particular to a PBT/ABS composite material marked by high-speed laser, a preparation method and application thereof, wherein the composite material comprises the following raw materials: PBT resin, ABS resin, compatilizer, antioxidant, laser assistant, opacifier, odor absorbent and functional synergistic assistant. The composite material has the advantages of high laser marking speed, good marking effect, high mechanical strength, oil resistance, good wear resistance and suitability for bicolor keycaps.
Description
Technical Field
The invention relates to the technical field of laser marking of bicolor keycaps, in particular to a PBT/ABS composite material marked by high-speed laser, a preparation method and application thereof.
Background
Letters or numbers are displayed on keycaps of the keyboard, the traditional marking mode is an ink printing technology, although the keys can be marked, when the keyboard is used for a period of time, the colors of the numbers and the letters on the keyboard can be gradually lightened, and when the keyboard is used for typing for a long time, fingers can be blackened, so that great trouble is brought to people. The cost of ink printing is also high and the environment is polluted. Therefore, manufacturers choose to mark key caps of the keyboard by using a laser marking machine in order to solve the problems, the existing laser marking key caps have long processing time, dark shadows are easy to appear on the key caps after marking, and the phenomenon of oiling is easy to appear after the key caps are used for a long time.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the high-speed laser marking PBT/ABS composite material which has the advantages of high laser marking speed, good marking effect, high mechanical strength, oil resistance and good wear resistance and is suitable for the double-color keycaps.
The second purpose of the invention is to provide a preparation method of the high-speed laser marking PBT/ABS composite material, which has the advantages of simple operation, convenient control, high production efficiency and low production cost and can be used for large-scale production.
The invention also aims to provide the application of the high-speed laser marking PBT/ABS composite material, the composite material is applied to the double-color keycaps, the marking effect is clear, no shadow is presented, the outline of the marking of the double-color keycaps is clearer under the bright effect, the bonding performance with the key base of the ABS keyboard is strong, and the double-color keycaps and the key base of the ABS keyboard are not easy to fall off and separate.
One of the purposes of the invention is realized by the following technical scheme: a high-speed laser marking PBT/ABS composite material comprises the following raw materials in parts by weight:
the high-speed laser marking PBT/ABS composite material takes PBT resin (namely polybutylene terephthalate) and ABS resin (namely acrylonitrile-butadiene-styrene copolymer) as main materials, and is mixed with a compatilizer, an antioxidant, a laser assistant, an opacifier, a smell absorbent and a functional synergistic assistant according to specific weight parts, so that the prepared composite material has the advantages of high laser marking speed, good marking effect, high mechanical strength, oil resistance and good wear resistance, and is suitable for bicolor keycaps. The PBT resin and the ABS resin have synergistic effect, the PBT resin improves the oil resistance and the wear resistance, makes up for the low wear resistance of the ABS resin, prevents the ABS resin from producing oil, improves the product quality, plays a role in viscosity regulation in the system, avoids the flash when the composite material is applied to keycaps to be processed into films due to the low melt viscosity of the PBT, and reduces the processing difficulty; compared with nylon, the PBT resin has high heat resistance, good toughness and low water absorption, can effectively avoid the phenomenon of product size expansion after absorbing water, and has strong electrical insulation property; the compatilizer and the antioxidant act together, so that poor system stability and reduced mechanical performance caused by mixing of the laser assistant, the opacifier and the functional synergistic assistant in the composite material are avoided; the added odor absorbent has high compatibility with PBT resin and ABS resin, can eliminate the peculiar smell of the PBT resin and the ABS resin, avoids discomfort caused by the peculiar smell absorbed by a human body when the human body uses the double-color keycap prepared from the composite material, and improves the product quality.
Preferably, the PBT resin has an intrinsic viscosity of 0.7-1.2dL/g and a terminal carboxyl group concentration of 0.1-18 mu eq/g.
The intrinsic viscosity of the PBT resin is controlled to be 0.7-1.2dL/g, and meanwhile, the PBT resin with the terminal carboxyl concentration of 0.1-18 mu eq/g is selected, so that the processing flowability and toughness of the composite material are improved, the processing is facilitated, and the reduction of the molecular weight of the PBT resin and the reduction of mechanical properties caused by hydrolysis in the process of using the PBT resin under moist heat are avoided; if the intrinsic viscosity is higher than 1.2dL/g, the problems of poor flowing, poor filling and the like of the composite material in a forming die are easily caused, the processing difficulty is increased, the energy consumption is increased, and the smoothness of the prepared keycap is extremely poor and the keycap is easy to scrap. If the intrinsic viscosity is lower than 0.7dL/g, even if the ABS resin is added, the composite material still has flash when being applied to keycaps to process films because the melt viscosity of the PBT resin is too low.
Preferably, the compatilizer is at least one of PE-G-MAH, MBS and POE-G-GMA.
The molecular structure of the PBT resin is changed by adopting the compatilizer, and the flexible chain segment is introduced to play a toughening effect, so that the product performance is more stable, the toughening effect is excellent, and the high impact resistance is shown at low addition level; more preferably, the compatilizer is PE-G-MAH, MBS and POE-G-GMA in a weight ratio of 1-2: 1-2: 5, the grafting rate of the POE-G-GMA is 1 to 1.2 percent, the adhesive force between the PBT resin and the ABS resin is improved, the system stability is improved, the mechanical property and the processing fluidity can be improved, the processing defect of the product is reduced, and the processing is facilitated. The PE-G-MAH is maleic anhydride grafted polyethylene; MBS is a terpolymer of methyl methacrylate (M), butadiene (B) and styrene (S); POE-G-GMA is glycidyl methacrylate grafted ethylene-octene copolymer.
Preferably, the antioxidant is antioxidant 1010 and/or antioxidant S9228; the opacifier is titanium dioxide and/or lithopone.
The composite material can achieve the effects of aging resistance and color change by adopting the antioxidant, and the decomposition resistance time of the composite material is prolonged. More preferably, the antioxidant is antioxidant 1010 and antioxidant S9228, and the weight ratio of the antioxidant to the antioxidant is 1: 2-3, not only can prevent the antioxidant from decomposing due to high temperature in the preparation process of the composite material and not reaching the antioxidant effect, but also can reduce the thermal decomposition of the composite material in the extrusion process, reduce the micromolecule precipitation of the material in the process and improve the surface smoothness.
Adopt above-mentioned light-shading agent can provide the shading effect to the double-colored key cap of goods, can make double-colored key cap mark again and be in under the bright light effect profile more clear and light transmissivity strong. More preferably, the titanium dioxide is rutile type titanium dioxide.
Preferably, the laser auxiliary agent is at least one of tin oxide, antimony oxide, neodymium oxide, bismuth oxide and zirconium phosphate.
The composite material is easy to mark by adopting the laser auxiliary agent, the marking definition is higher, no shadow is generated after marking, the definition of character outlines is high, and compared with the common titanium oxide and copper phosphate, the laser auxiliary agent adopted by the invention has the advantages of higher marking speed and better marking effect. More preferably, the laser auxiliary agent can be prepared by mixing at least two of tin oxide, antimony oxide, neodymium oxide, bismuth oxide and zirconium phosphate in different proportions, so that multicolor laser marking such as white carving black, black carving white, black carving gold and the like can be realized, and the product selectivity is improved.
Preferably, the odor absorbent is degussel TEGO Sorb PY 88 TQ.
The odor absorbent has strong temperature resistance, and avoids the decomposition of the composite material due to high temperature in the processing or molding process; the durability of the odor removal is high, and the odor removal agent can react with active gas small molecules under normal conditions to ensure that the active gas small molecules are not volatilized to the surrounding environment any more; on the other hand, the odor absorbent promotes the dispersion and the diffusion of micromolecule gas in the processing process, reduces the exhaust amount to the welding mark position, is favorable for the smooth discharge of the micromolecule gas from the exhaust position in the processing process, avoids the occurrence of light shadow on the composite material caused by high air pressure formed by accumulation of the micromolecule gas in the exhaust position, is favorable for the composite material to present a high-light and high-brightness surface, discharges the micromolecule gas in the processing process, reduces the content of the micromolecule gas in the prepared composite material, and reduces the working load of the odor absorbent and the consumption of active groups by adding low VOC content of PBT resin, ABS resin and additives, thereby having better odor eliminating effect.
Preferably, the functional synergist comprises an antibacterial agent and a toner.
More preferably, the functional synergistic auxiliary agent is an antibacterial agent and a toner, and the weight parts of the antibacterial agent and the toner are 0.5-1: 0.5-1, and the antibacterial agent is nano silver ions and/or nano zinc oxide. The keyboard is contacted by a human body for a long time, so that bacteria are easy to breed, and the keyboard is not good for the health of the human body; the nano silver ion and/or nano zinc oxide antibacterial agent is added, so that escherichia coli and staphylococcus aureus can be killed efficiently, the antibacterial rate reaches 99%, and meanwhile, the nano zinc oxide antibacterial agent has good compatibility and stability with a PBT/ABS system and does not affect the surface effect of the keycap.
The second purpose of the invention is realized by the following technical scheme: the preparation method of the high-speed laser marking PBT/ABS composite material comprises the following steps:
(A1) weighing PBT resin, ABS resin, compatilizer, antioxidant, laser assistant, opacifier, odor absorbent and functional synergistic assistant according to the weight parts for later use;
(A2) premixing the PBT resin and the ABS resin with diffusion oil in a high-speed mixer for 1-3min, then blending with other raw materials for 1-3min, discharging, and performing extrusion granulation by a double-screw extruder to obtain the high-speed laser marking PBT/ABS composite material.
The preparation method of the high-speed laser marking PBT/ABS composite material has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production. In the step (A2), the PBT resin and the ABS resin are premixed with the diffusion oil to promote the adhesion between the PBT resin and the ABS resin, improve the uniformity, improve the surface smoothness of the composite material and improve the film release property.
Preferably, in the step (a2), the processing temperature of each section of the twin-screw extruder from the feeding section is respectively: 190 ℃ at 170-.
According to the invention, the temperature of each zone in the extrusion equipment is controlled, so that the prepared composite material has excellent mechanical properties, and is free from yellowing and foaming, smooth in surface and high in glossiness. When the temperature in each zone is too high, the effect of the antioxidant and odor absorbent is affected, so that the melting temperature is controlled to be lower than 250 ℃.
The third purpose of the invention is realized by the following technical scheme: the high-speed laser marking PBT/ABS composite material is applied to a bicolor keycap. Compared with the keycaps manufactured by the traditional ink printing technology, the double-color keycap is integrally distributed and injection molded by PBT and ABS composite materials and manufactured by adopting a high-speed laser marking technology, is more environment-friendly and lower in cost, has permanent color-fastness of the mark, has a clear marking effect, presents no shadow, has a clear outline under the bright effect of the marking of the double-color keycap, is strong in associativity with the key base of the ABS keyboard, and is not easy to fall off and separate from the key base of the ABS keyboard.
The invention has the beneficial effects that: the high-speed laser marking PBT/ABS composite material has the advantages of high laser marking speed, good marking effect, high mechanical strength, oil resistance and good wear resistance, and is suitable for bicolor keycaps.
The preparation method of the high-speed laser marking PBT/ABS composite material has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
According to the application of the high-speed laser marking PBT/ABS composite material, the composite material is applied to the double-color keycaps, the marking effect is clear, no dark shadow is presented, the outline of the marking of the double-color keycaps is clearer under the bright effect, the bonding performance with the ABS keyboard key base is strong, and the double-color keycaps are not easy to fall off and separate from the ABS keyboard key base.
Drawings
FIG. 1 is a bright effect diagram of the application of embodiment 1 of the present invention to a two-color keycap;
FIG. 2 is a graph of the effect of the light applied to a two-color keycap in comparative example 1;
FIG. 3 is an effect diagram of the application of embodiment 4 of the present invention to a two-color keycap;
FIG. 4 is a diagram showing the effect of comparative example 1 applied to a two-color keycap.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
Example 1
A high-speed laser marking PBT/ABS composite material comprises the following raw materials in parts by weight:
the PBT resin has an intrinsic viscosity of 1dL/g and a terminal carboxyl group concentration of 9 mu eq/g.
The compatilizer is PE-G-MAH, MBS and POE-G-GMA, and the weight ratio is 1.5: 1.5: 5, and the grafting rate of the POE-G-GMA is 1.1 percent.
The antioxidant is an antioxidant 1010 and an antioxidant S9228, and the weight ratio of the antioxidant to the antioxidant is 1: 2.5 is compounded; the opacifier is rutile titanium dioxide.
The laser auxiliary agent is tin oxide.
The odor absorbent is degussel TEGO Sorb PY 88 TQ.
The functional synergistic auxiliary agent is prepared from the following components in parts by weight: 0.5-1, and the antibacterial agent is nano silver ions.
The preparation method of the high-speed laser marking PBT/ABS composite material comprises the following steps:
(A1) weighing PBT resin, ABS resin, compatilizer, antioxidant, laser assistant, opacifier, odor absorbent and functional synergistic assistant according to the weight parts for later use;
(A2) premixing the PBT resin and the ABS resin with diffusion oil in a high-speed mixer for 2min, then blending the premixed PBT resin and the ABS resin with other raw materials for 2min, discharging, and extruding and granulating by a double-screw extruder to obtain the high-speed laser marking PBT/ABS composite material.
In the step (A2), the processing temperatures of the twin-screw extruder in the sections from the feeding section are respectively as follows: 180 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ of head temperature and 360r/min of screw rotation speed.
The high-speed laser marking PBT/ABS composite material is applied to the bicolor keycaps.
Example 2
A high-speed laser marking PBT/ABS composite material comprises the following raw materials in parts by weight:
the PBT resin had an intrinsic viscosity of 0.7dL/g and a terminal carboxyl group concentration of 0.1. mu. eq/g.
The compatilizer is PE-G-MAH, MBS and POE-G-GMA, and the weight ratio of the PE-G-MAH to the MBS is 1: 1: 5, and the grafting rate of the POE-G-GMA is 1 percent.
The antioxidant is an antioxidant 1010 and an antioxidant S9228, and the weight ratio of the antioxidant to the antioxidant is 1: 2, compounding; the opacifier is lithopone.
The laser auxiliary agent is neodymium oxide.
The odor absorbent is degussel TEGO Sorb PY 88 TQ.
The functional synergistic auxiliary agent is prepared from the following components in parts by weight: 0.5, and the antibacterial agent is nano zinc oxide.
The preparation method of the high-speed laser marking PBT/ABS composite material comprises the following steps:
(A1) weighing PBT resin, ABS resin, compatilizer, antioxidant, laser assistant, opacifier, odor absorbent and functional synergistic assistant according to the weight parts for later use;
(A2) premixing the PBT resin and the ABS resin with diffusion oil in a high-speed mixer for 1min, then blending the premixed PBT resin and the ABS resin with other raw materials for 1min, discharging, and extruding and granulating by a double-screw extruder to obtain the high-speed laser marking PBT/ABS composite material.
In the step (A2), the processing temperatures of the twin-screw extruder in the sections from the feeding section are respectively as follows: 170 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ of head temperature and 320r/min of screw rotation speed.
The high-speed laser marking PBT/ABS composite material is applied to the bicolor keycaps.
Example 3
A high-speed laser marking PBT/ABS composite material comprises the following raw materials in parts by weight:
the PBT resin has an intrinsic viscosity of 1.2dL/g and a terminal carboxyl group concentration of 18 mu eq/g.
The compatilizer is PE-G-MAH, MBS and POE-G-GMA, and the weight ratio of the PE-G-MAH to the MBS to the POE-G-GMA is 2: 2: 5, and the grafting rate of the POE-G-GMA is 1.2 percent.
The antioxidant is an antioxidant 1010 and an antioxidant S9228, and the weight ratio of the antioxidant to the antioxidant is 1: 3, compounding; the opacifier is formed by mixing titanium dioxide and lithopone in equal proportion.
The laser auxiliary agent is zirconium phosphate.
The odor absorbent is degussel TEGO Sorb PY 88 TQ.
The functional synergistic auxiliary agent is prepared from the following components in parts by weight: 1, mixing the antibacterial agent with nano silver ions and nano zinc oxide in equal proportion.
The preparation method of the high-speed laser marking PBT/ABS composite material comprises the following steps:
(A1) weighing PBT resin, ABS resin, compatilizer, antioxidant, laser assistant, opacifier, odor absorbent and functional synergistic assistant according to the weight parts for later use;
(A2) premixing the PBT resin and the ABS resin with diffusion oil in a high-speed mixer for 3min, then blending the premixed PBT resin and the ABS resin with other raw materials for 3min, discharging, and extruding and granulating by a double-screw extruder to obtain the high-speed laser marking PBT/ABS composite material.
In the step (A2), the processing temperatures of the twin-screw extruder in the sections from the feeding section are respectively as follows: 190 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, a head temperature of 250 deg.C, and a screw rotation speed of 400 r/min.
The high-speed laser marking PBT/ABS composite material is applied to the bicolor keycaps.
Example 4
A high-speed laser marking PBT/ABS composite material comprises the following raw materials in parts by weight:
the PBT resin has an intrinsic viscosity of 0.8dL/g and a terminal carboxyl group concentration of 4. mu. eq/g.
The compatilizer is POE-G-GMA, and the grafting rate of the POE-G-GMA is 1-1.2%.
The antioxidant is 1010; the opacifier is lithopone.
The laser auxiliary agent is formed by mixing tin oxide, bismuth oxide and zirconium phosphate in equal proportion.
The odor absorbent is degussel TEGO Sorb PY 88 TQ.
The functional synergistic auxiliary agent is prepared from the following components in parts by weight: 0.6, and the antibacterial agent is nano silver ions.
The preparation method of the high-speed laser marking PBT/ABS composite material comprises the following steps:
(A1) weighing PBT resin, ABS resin, compatilizer, antioxidant, laser assistant, opacifier, odor absorbent and functional synergistic assistant according to the weight parts for later use;
(A2) and premixing the PBT resin and the ABS resin with diffusion oil in a high-speed mixer for 2.5min, then blending with other raw materials for 1.5min, discharging, and performing extrusion granulation by a double-screw extruder to obtain the high-speed laser marking PBT/ABS composite material.
In the step (A2), the processing temperatures of the twin-screw extruder in the sections from the feeding section are respectively as follows: 175 ℃, 195 ℃, 205 ℃, 215 ℃, 225 ℃, 230 ℃, 240 ℃ of head temperature and 380r/min of screw rotation speed.
The high-speed laser marking PBT/ABS composite material is applied to the bicolor keycaps.
Comparative example 1
This comparative example differs from example 1 in that:
a laser marking PA6/ABS composite material comprises the following raw materials in parts by weight:
the laser adjuvant, opacifier, odor absorber and functional builder were the same as in example 1.
The preparation method of the laser marking PA6/ABS composite material is the same as that of the embodiment 1.
Comparative example 2
This comparative example differs from example 1 in that: the compatilizer is PE-G-ST.
Example 5 Performance testing
(I) The composite materials prepared in the embodiment 1 and the comparative example 1 are integrally distributed and injected into keycaps, then the laser marking is adopted to prepare double-color keycaps containing letters, and the two-color keycaps are assembled into a keyboard and then displayed under bright light and compared with each other, wherein the effect graphs are shown in figures 1-2. From the comparison of fig. 1-2, it is clear that the letter of fig. 1 contains no shadow, has good marking effect and clear outline, while the letter B of fig. 2 contains a shadow, has poor effect.
(II) the composite materials prepared in the embodiment 4 and the comparative example 1 are integrally distributed and injected into keycaps, then laser marking is adopted to prepare double-color keycaps containing letters, the two-color keycaps are assembled into a keyboard, the letters are observed and compared, the effect graph of the embodiment 4 is shown in figure 3, and the effect graph of the comparative example 1 is shown in figure 4. By comparing fig. 3-4, it is clear that the letter D in fig. 3 is closed and clear in outline, while the letter D in fig. 4 is open and poor in marking effect.
(III) taking the composite materials prepared in the examples 1-4 and the comparative examples 1-2, and testing the tensile strength of the composite materials by using an ASTM-D638 test standard, wherein the tensile strength is measured in MPa; the notched impact strength was measured in KJ/m units using the ASTM-D6110 test standard2(ii) a The flexural modulus, in MPa, was tested using ASTM-D790 test standard; the melt index was measured using ASTM-D1238 test standard in g/10 min; the double-colored key cap of moulding plastics into with the integrative distribution of combined material, adopt laser marking machine again to make with 6000mm/s the mark speed of beating and contain the double-colored key cap of alphabetical, observe the outward appearance of beating mark department and the outward appearance of key cap, whether observe the key cap and beat oil and record after 30d stew under the 50 ℃ condition, the result is as shown in following table 1:
TABLE 1
As can be seen from the above table 1, compared with the comparative example 1, the tensile strength of the example 1 has little influence, but the gap impact strength is greatly different, and the keycap surface of the example 1 is smooth and clean, the marking contour is clear, no shadow is generated, the marking speed of 6000mm/s is realized, the marking efficiency is high, and the anti-oiling effect is good. Compared with the comparative example 2, the specific compatilizers in the embodiment 1 are compounded with each other according to the specific proportion, so that the keycap surface is obvious in smooth and clean effect.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (2)
1. A high-speed laser marking PBT/ABS composite material is characterized in that: the feed comprises the following raw materials in parts by weight:
the PBT resin has the intrinsic viscosity of 0.7-1.2dL/g and the concentration of terminal carboxyl is 0.1-18 mu eq/g;
the compatilizer is PE-G-MAH, MBS and POE-G-GMA, and the weight ratio of the PE-G-MAH to the MBS is 1-2: 1-2: 5, compounding;
the antioxidant is antioxidant 1010 and/or antioxidant S9228; the opacifier is titanium dioxide and/or lithopone;
the laser auxiliary agent is at least one of tin oxide, antimony oxide, neodymium oxide, bismuth oxide and zirconium phosphate;
the odor absorbent is degos TEGO Sorb PY 88 TQ;
the functional synergistic auxiliary comprises an antibacterial agent and toner;
the functional synergistic auxiliary agent is prepared from the following components in parts by weight: 0.5-1, wherein the antibacterial agent is nano silver ions and/or nano zinc oxide;
the preparation method of the high-speed laser marking PBT/ABS composite material comprises the following steps:
(A1) weighing PBT resin, ABS resin, compatilizer, antioxidant, laser assistant, opacifier, odor absorbent and functional synergistic assistant according to the weight parts for later use;
(A2) premixing the PBT resin and the ABS resin with diffusion oil in a high-speed mixer for 1-3min, then blending with other raw materials for 1-3min, discharging, and performing extrusion granulation by a double-screw extruder to obtain the high-speed laser marking PBT/ABS composite material;
in the step (A2), the processing temperatures of the twin-screw extruder in the sections from the feeding section are respectively as follows: 190 ℃ at 170-.
2. The application of the high-speed laser marking PBT/ABS composite material as claimed in claim 1, wherein: the high-speed laser marking PBT/ABS composite material is applied to a bicolor keycap.
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