CN111440428A - Polycarbonate-based laser marking composite material and preparation method thereof - Google Patents
Polycarbonate-based laser marking composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polycarbonate-based laser marking composite material and a preparation method thereof, belonging to the technical field of electronic marking materials. It includes: 80-120 parts of polycarbonate, 20-50 parts of inorganic particles, 30-60 parts of organic toughening agent, 0.1-10 parts of laser absorbent, 10-30 parts of compatibilizer, 3-10 parts of lubricant and 3-10 parts of antioxidant. The invention starts from considering the microstructure design of the polycarbonate, utilizes the permeation toughening, rigid particle toughening mechanism and the irradiation modification principle, selects a component system with proper compatibility with the polycarbonate, and finally constructs a sea-island phase state structure with micro-nano size in the polycarbonate matrix through high-energy ray free radical activation, high-energy ray molecular chain degradation and segmented polymer phase state processing control, and the structure can absorb or dissipate external impact energy through the change of an internal microstructure, thereby inhibiting the failure damage of the material and endowing the material with extremely high toughness, fatigue resistance and laser marking performance.
Description
Technical Field
The invention relates to the technical field of electronic marking materials, in particular to a polycarbonate-based laser marking composite material and a preparation method thereof.
Background
The traditional printing and marking technology usually prints required characters and patterns on the surface of a product, the mode is easy to fall off, fade, wear and damage in the long-term use process, the safety is not high, the anti-counterfeiting effect is not good, the printing process is complicated, the environment and a mold are easily polluted, the finished product is greatly improved, the requirements on anti-counterfeiting are higher and higher along with the updating and upgrading of identification cards, drivers' licenses, passports and other identification cards, the mode of using laser engraving is widely concerned by people, the laser engraving technology permanently marks the surface or the inside of a material to form a text with high definition and contrast, so that the laser engraving technology has extremely important significance on high anti-counterfeiting, and the laser technology becomes one of the best choices for anti-counterfeiting application in occasions with higher safety requirements. For most high polymer materials, the laser light absorption is small, so that the high polymer materials cannot be directly marked by using laser or have poor marking effect, meanwhile, the identification cards need to have fatigue performance requirements reaching tens of thousands of times, and the existing materials cannot simultaneously meet the use requirements of physical properties such as laser marking, high fatigue resistance and the like.
Polycarbonates (PC for short) are high molecular polymers containing carbonate groups in the molecular chain, and are classified into various types, such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester group. Among them, aliphatic and aliphatic-aromatic polycarbonates have limited their use as engineering plastics due to their low mechanical properties. PC is yellowish, rigid and tough, and has good dimensional stability, creep resistance, heat resistance and electrical insulation. The molecule has a symmetrical structure, is simple and regular, has large group volume and is difficult to crystallize, and under general molding conditions, PC has an amorphous structure, and the light transmittance can reach 90%. The ester group in the PC chain is a polar group, so that the moisture absorption and hydrolysis are easy. Meanwhile, the PC chain structure is a rigid and tough material with a flexible carbonate chain and a rigid benzene ring structure and mechanical properties, and can meet the impact or cyclic acting force of low stress. However, in a long cyclic stress environment, the polycarbonate product is easy to generate stress cracking, has a large friction coefficient, no self-lubrication, and low wear resistance and fatigue resistance, and thus has limited wide application in the fields of electronic card base materials, 5G transmission carriers, electronic smart cards and the like.
In order to improve the fatigue resistance and laser marking performance of polycarbonate, toughening particles, a laser absorber and other components are usually added into the polycarbonate and simply mixed, and the toughening particles and the laser absorber are distributed unevenly and agglomerated in such a way, so that the laser marking effect is seriously influenced, and a marking image is unclear. Meanwhile, when the material is subjected to shear stress, the internal stress concentration of the material is easily caused, so that a large number of silver lines are generated and developed to cracks, and particularly, under the action of cyclic stress, the material is easy to lose efficacy and cannot meet the use requirement of the intelligent board card.
Disclosure of Invention
The invention aims to provide a polycarbonate-based laser marking composite material and a preparation method thereof, and aims to solve the problem that the marking effect is influenced by uneven component distribution in the existing polycarbonate-based laser marking material.
The technical scheme for solving the technical problems is as follows:
a polycarbonate-based laser-marked composite material comprising: 80-120 parts of polycarbonate, 20-50 parts of inorganic particles, 30-60 parts of organic toughening agent, 0.1-10 parts of laser absorbent, 10-30 parts of compatibilizer, 3-10 parts of lubricant and 3-10 parts of antioxidant.
Further, in a preferred embodiment of the present invention, the aliphatic polycarbonate includes: one or more of an aliphatic-aromatic polycarbonate, a bisphenol a type polycarbonate, or a graft-modified polycarbonate.
The group for grafting and modifying the polycarbonate is acrylamide, acrylic acid, ester group, alkyl lithium, alkyl boron, vinyl, maleic anhydride, acrylonitrile, MMA grafting, carbonyl or epoxy anhydride.
Further, in a preferred embodiment of the present invention, the inorganic particles include one or more of talc, mica, whiskers, titanium dioxide, graphene, or carbon nanotubes, and the particle size of the inorganic particles is in a micrometer scale to a nanometer scale, the size distribution of the inorganic particles conforms to a normal distribution, and the kurtosis is less than 3.
Further, in a preferred embodiment of the present invention, the toughening agent includes: one or more of MBS, SEBS, ABS, polysiloxane, POE, PE, PS, rubber, PE or polyurethane, and the molecular weight is more than 10 ten thousand.
Further, in a preferred embodiment of the present invention, the laser beam absorber includes: one or more of metal powder, metal oxide, metal complex or metal complex, the particle size of which is 10nm-10 μm; wherein the metal powder includes: one or more of copper, iron, titanium, zinc, aluminum, magnesium, gold, silver, or alloys thereof; the metal oxide includes: one or more of iron oxide, copper oxide, vanadium trioxide, antimony trioxide, zinc oxide, magnesium oxide or titanium oxide; the metal complex includes: one or more of copper tetrammine sulfate, platinum diammine dichloride, potassium trichloroplatinate, xanthate, hematite, prussian blue or metal carbonyl compounds.
Further, in a preferred embodiment of the present invention, the compatibilizer comprises: one or more of silicone, E wax, silane coupling agent, titanate coupling agent, higher fatty acid, fatty acid soap or molybdenum disulfide; the above lubricant: one or more of silicone, polyvinyl alcohol, cellulose acetate, fluoroplastics, fatty acids, fatty acid soaps, paraffin wax, or ethylene glycol.
Further, in a preferred embodiment of the present invention, the antioxidant comprises: monophenol antioxidant BHT, monophenol antioxidant 2246, bisphenol A antioxidant, polyphenol antioxidant 1010, polyphenol antioxidant 1076, phosphite antioxidant, antioxidant 168[ tris (1, 4-di-tert-butylphenyl) phosphite ], antioxidant 626[ bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphate ], antioxidant 618[ bis (octadecyl) pentaerythritol diphosphite ], thio antioxidant, thiobisphenol antioxidant or thioether-type phenol antioxidant.
The preparation method of the polycarbonate-based laser marking composite material comprises the following steps:
(1) drying the components in the proportion for 5-12h at 50-120 ℃ to obtain the dried component with the water content of 0.03-0.06%;
(2) the dried inorganic particles, the compatibilizer and the lubricant are stirred and mixed uniformly at the temperature of 100-120 ℃ at 50-150r/min and then are mixed uniformly at the temperature of 150-300 r/min;
(3) adding the dried organic toughening agent and the laser absorbent into the mixed material in the step (2), stirring and mixing uniformly at the temperature of 100-120 ℃, and marking as a material 1;
(4) stirring and mixing the dried part of polycarbonate and the antioxidant uniformly at the temperature of 100-120 ℃, and marking as a material 2;
(5) respectively carrying out irradiation treatment on the material 1 and the material 2;
(6) mixing the material 1 and the material 2 after the irradiation treatment at the temperature of 100-120 ℃, stirring and mixing uniformly, and marking as a material 3;
(7) and stirring and mixing the rest polycarbonate and the material 3, conveying the mixture into a double-screw extruder through a conveying device, wherein the temperatures of all sections of the extruder are respectively 150 ℃, 230 ℃, 245 ℃, 250 ℃, 265 ℃ and 250 ℃, the speed of a main machine of the extruder is 600r/min, and drying the mixture after extrusion granulation to obtain the polycarbonate-based laser marking composite material.
In the step (1) of the preparation method, all the components are dried firstly, so that the water content is reduced, and the polycarbonate can be prevented from being degraded due to high water content in the subsequent operation of the material. At the same time, the polycarbonate resin also contains a proper amount of water, thereby promoting the chain scission of the polycarbonate and improving the fatigue resistance of the polycarbonate.
In the step (2), the compatilizer, the inorganic particles and the lubricant are separately sheared and mixed, the size distribution of the adopted inorganic particles conforms to normal distribution, the kurtosis is less than 3, the particles in the range have uniform particle size distribution and are not easy to agglomerate, and the particles can be well mixed with the compatilizer and the lubricant uniformly, so that the rigidity and the strength of the composite material are improved. The components are favorably rubbed among respective particles to reach an ideal dispersion state, the temperature of the components can be quickly raised by the friction to provide a basic condition for the next reaction, the lubricant can further promote the inorganic particles to reach micro-nano dispersion and form on the particle surfaces, and simultaneously, the reactive groups (such as anhydride, amino or carboxyl) on the compatilizer react with the reactive groups on the inorganic particle surfaces to treat the inorganic particle surfaces, thereby increasing the compatibility of the rest toughening agents and the polycarbonate.
In the step (3), a toughening agent and a laser absorber are added, the molecular weight of the adopted organic solubilizer is large, a large number of branched structures exist on the molecular structure of the organic solubilizer, and a certain cross-linked but incompletely cross-linked structure also exists, when the organic solubilizer is mixed with the polyacetate, the branched structures can improve the compatibility with the polyacetate, and meanwhile, the cross-linked structures can also improve the toughness of the polyacetate. Through differential high-speed shearing and stirring, the temperature is controlled, the toughening agent generates mechanochemical chain scission under the action of shearing force, the compatibility of the toughening agent and the component in the step (2) is increased, the laser absorber is well dispersed on the surfaces of the toughening agent and inorganic particles, and the subsequent laser marking performance is improved.
In the step (4), the antioxidant is stirred and mixed with the polycarbonate to promote the antioxidant to be uniformly dispersed on the surface of the polycarbonate, so that the polycarbonate is prevented from being excessively degraded by high-energy rays in the irradiation process (step 5), and the degradation degree of the polycarbonate in the thermal processing process is protected.
In the step (5), the materials 1 and 2 are respectively subjected to irradiation treatment to promote the molecular chains of the components to be broken to generate active free radicals, the generated low molecular chain components are further improved in the flexibility of chain segments under the action of high-energy rays, and energy is transferred through a molecular chain motion absorbent during cyclic stress bending, so that the material has high fatigue resistance.
In the step (6), the material 1 and the material 2 after the irradiation treatment are subjected to high-speed differential stirring, and due to the existence of active free radicals between the components, a certain micro chemical reaction can be generated on the surfaces of component particles, so that the compatibility between the whole systems is further improved.
In steps 2-4 and 6 of the preparation method, the specific mixing temperature is selected according to different raw materials in the mixing process, so that the surface reaction of each component is promoted under the temperature condition, the compatibility of each component is promoted, the dispersibility of each component is improved, and the toughness and the fatigue resistance of the final composite material are improved.
In the step (7), all the components are extruded by an extruder, in the screw, a micro-area chemical grafting reaction is further generated among the components under the action of high-speed shearing of the screw and the high-energy rays to promote inorganic particles, a toughening agent and a laser absorbent to achieve micro-nano dispersion, and then the components are extruded, granulated and dried. The polycarbonate composite material with ultrahigh fatigue resistance and excellent laser marking is prepared through the hierarchical physical-level dispersion and the controllable chemical reaction in the process, and the polycarbonate composite material has the advantages of ultrahigh fatigue resistance and high toughness even when high-content inorganic particles are added.
The invention starts from considering the microstructure design of the polycarbonate, utilizes the permeation toughening, rigid particle toughening mechanism and irradiation modification principle, selects a component system with proper compatibility with the polycarbonate, finally, a sea-island phase state structure with micro-nano size formed on a polycarbonate base is constructed through high-energy ray free radical activation and segmented polymer phase state processing control, the structure is that inorganic particles and a toughening agent are independently dispersed in the polycarbonate in micron order, wherein the low molecular compatilizer is attached to the surface of the inorganic particles, and generates heat when the inorganic particles are subjected to repeated cyclic bending, the activity (flexibility) of the small molecules is increased, so that the fatigue property of the material is improved, and the chain breaking of the polycarbonate molecules caused by the fatigue can be always realized by the structure, meanwhile, when the silver lines are generated in the material, the silver lines can be prevented from expanding to cracks, so that the material is protected from being damaged. This structure is when receiving stress, accessible molecular chain motion and intermolecular friction absorbed energy to improve the toughness and the fatigue resistance of material, when receiving cyclic stress, the motion of molecular chain produces the internal friction and can make the looks put up the micro-district and produce the microphase liquid district, and this liquid pool size is less than critical dimension, and the effect of toughening is very showing, can the limited crack of preventing sprouting, reduces the inside micro-region accumulated damage of material, thereby improves polycarbonate fatigue resistance by a wide margin. Meanwhile, the structural material can meet the requirement of laser marking, has the advantages of short laser marking time, good colorability, high color saturation and the like, and can be applied to the aspects of certificates, visual anti-counterfeiting, 5G radio frequency devices, electronics and the like.
Further, in a preferred embodiment of the present invention, the step of irradiation treatment in the step (5) includes: packing the material 1 into a box, and placing the box into a cobalt-60 irradiation source to perform irradiation under the total irradiation dose of 10-50 kGy; and (4) packing the material 2 into a cobalt-60 radiation source, and performing radiation under the total radiation dose of 5-30 kGy.
In the step (5) of the invention, gamma rays (gamma rays) generated by cobalt-60 have strong penetrating power and high energy and can cause reactions among corresponding systems, and the total dose is selected mainly according to the characteristics and the reaction degree of the systems, and the material 1 needs to be irradiated more when the reaction degree is high; material 2 requires only a small amount of molecular chain scission, so a low dose was chosen.
Further, in a preferred embodiment of the present invention, in the step (7), an ultrasonic vibration device and an EB electron beam device are installed at the head of the twin-screw extruder, wherein the laser powder contains surface double bonds, and the laser powder is dispersed into particles of 20-100nm by in-situ vibration, and is uniformly contacted with and distributed in the extruded granules.
The invention has the following beneficial effects:
1. the invention starts from considering the microstructure design of the polycarbonate, utilizes the permeation toughening, rigid particle toughening mechanism and the irradiation modification principle, selects a component system with proper compatibility with the polycarbonate, and finally constructs a sea-island phase state structure with micro-nano size in the polycarbonate matrix through high-energy ray free radical activation, high-energy ray molecular chain degradation and segmented polymer phase state processing control, when the structure is stressed, the structure can absorb energy through molecular chain movement and intermolecular friction, thereby improving the toughness and fatigue resistance of the material, when the structure is subjected to cyclic stress, the movement of the molecular chain generates internal friction to enable a phase raising micro area to generate a micro-phase liquid area, the size of the liquid pool is smaller than a critical size, the toughening effect is extremely obvious, cracks can be prevented from growing in a limited way, the accumulated damage of the microscopic area in the material is reduced, thereby greatly improving the fatigue resistance of the polycarbonate by 10-50 ten thousand times, meanwhile, the notch impact of the cantilever beam is as high as 50-150KJ/m2. Meanwhile, the structural material can meet the requirement of laser marking, has the advantages of short laser marking time, good colorability, high color saturation and the like, and can be applied to the aspects of certificates, visual anti-counterfeiting, 5G radio frequency devices and the like.
2. Through the activation of high-energy ray free radicals, the degradation of high-energy ray molecular chains and the processing control of segmented polymer phase states, a sea-island phase state structure with micro-nano size formed in a polycarbonate matrix is finally constructed, and when the structure is stressed, energy can be absorbed through molecular chain movement and intermolecular friction, so that the toughness and fatigue resistance of the material are improved,when the material is subjected to cyclic stress, the movement of the molecular chain generates internal friction to enable the phase raising micro area to generate a micro-phase liquid area, the size of the liquid pool is smaller than the critical size, the toughening effect is extremely obvious, crack initiation can be limited and the accumulated damage of the microscopic area in the material is reduced, so that the fatigue resistance of the polycarbonate is greatly improved by 10-50 ten thousand times, and meanwhile, the impact of the cantilever beam notch is as high as 50-150KJ/m2. The structure can absorb or dissipate external impact energy through the change of the internal microstructure, thereby inhibiting the failure of the material due to damage and endowing the material with extremely high toughness and fatigue resistance.
3. The molecular chain structure of the matrix material and the auxiliary agents such as the laser absorbent and the like is activated by the high-energy rays to form a certain chemical chain structure, so that the compatibility between the laser absorbent and the resin matrix is improved, and the good dispersion of the laser absorbent is promoted. The structural material can meet the requirement of laser marking, and has the advantages of short laser marking time, good colorability, high color saturation and the like.
4. The preparation process is efficient and convenient, and the product can be widely popularized and applied to the fields of electronic card base materials, electronic smart cards, visual anti-counterfeiting devices, 5G radio frequency devices and the like due to high fatigue resistance and excellent strength and toughness.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an optical microscope image with ultra-depth of field of a polycarbonate-based laser marking composite prepared in example 2 of the present invention;
FIG. 2 is an optical microscope image with ultra-depth of field of a polycarbonate-based laser marking material prepared in comparative example 4 of the present invention;
wherein the purple dots represent the laser powder in the film.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
the polycarbonate-based laser marking composite of the present embodiment includes: 80 parts of bisphenol A polycarbonate, 20 parts of mica, 30 parts of MBS, 0.1 part of potassium trichloroplatinate, 10 parts of silane coupling agent, 3 parts of fatty acid soap, 1010 (1) parts of polyphenol antioxidant and 1076 (2) parts of polyphenol antioxidant. Wherein mica is 0.1 μm
The preparation method of the polycarbonate-based laser marking composite material comprises the following steps:
(1) drying the components in the proportion for 5 hours at 50 ℃ to obtain the dried component with the water content of 0.03%;
(2) stirring the dried inorganic particles, the compatibilizer and the lubricant at 100 ℃ for 2min at 50r/min, and then stirring at 150r/min for 3min to mix uniformly;
(3) adding the dried organic toughening agent and the laser absorbent into the mixed material in the step (2), stirring at the temperature of 100 ℃ at 150r/min for 5min, uniformly mixing, and marking as a material 1;
(4) stirring and uniformly mixing the dried part of polycarbonate and the antioxidant at the temperature of 100 ℃ at a speed of 100r/min for 5min, and marking as a material 2;
(5) respectively carrying out irradiation treatment on the material 1 and the material 2;
(6) mixing the material 1 and the material 2 after the irradiation treatment at 100 ℃ and stirring at 300r/min for 5min to mix evenly, and marking as a material 3;
(7) and stirring and mixing the rest polycarbonate and the material 3, conveying the mixture into a double-screw extruder through a conveying device, wherein the temperatures of all sections of the extruder are respectively 150 ℃, 230 ℃, 245 ℃, 250 ℃, 265 ℃ and 250 ℃, the speed of a main extruder is 300r/min, and drying the extruded and granulated mixture to obtain the polycarbonate-based laser marking composite material.
Wherein the step of irradiation treatment in step (5) comprises: packing the material 1 into a box, putting the box into a cobalt-60 irradiation source, and irradiating under the total irradiation dose of 10 kGy; and (4) packing the material 2, putting the material into a cobalt-60 radiation source, and performing radiation under the total radiation dose of 5 kGy.
And (7) mounting an ultrasonic vibration device and an EB electron beam device at the head of the double-screw extruder, wherein the ultrasonic vibration device and the EB electron beam device both contain laser powder with surface double bonds, and the laser powder is dispersed into particles of 20nm through in-situ vibration and is uniformly contacted with and distributed on extruded granules.
Example 2:
the polycarbonate-based laser marking composite of the present embodiment includes: 100 parts of bisphenol A polycarbonate, 35 parts of titanium dioxide, 45 parts of ABS, 8 parts of copper tetraammine sulfate, 20 parts of silane coupling agent, 30 parts of silicone, 7 parts of paraffin and 7 parts of thiobisphenol antioxidant, wherein the particle size of the titanium dioxide is 0.1 micron.
The preparation method of the polycarbonate-based laser marking composite material comprises the following steps:
(1) drying the components in the proportion for 8 hours at the temperature of 80 ℃ to obtain the dried component with the water content of 0.04 percent;
(2) stirring the dried inorganic particles, the compatibilizer and the lubricant at the temperature of 110 ℃ for 2min at 100r/min, and then stirring at 200r/min for 3min to mix uniformly;
(3) adding the dried organic toughening agent and the laser absorbent into the mixed material in the step (2), stirring at the temperature of 110 ℃ for 5min at 150r/min, uniformly mixing, and marking as a material 1;
(4) stirring and uniformly mixing the dried part of polycarbonate and the antioxidant at the temperature of 110 ℃ at 100r/min for 5min, and marking as a material 2;
(5) respectively carrying out irradiation treatment on the material 1 and the material 2;
(6) mixing the material 1 and the material 2 after the irradiation treatment at 110 ℃ and stirring at 300r/min for 5min to mix evenly, and marking as a material 3;
(7) and stirring and mixing the rest polycarbonate and the material 3, conveying the mixture into a double-screw extruder through a conveying device, wherein the temperatures of all sections of the extruder are respectively 150 ℃, 230 ℃, 245 ℃, 250 ℃, 265 ℃ and 250 ℃, the speed of a main extruder is 450r/min, and drying the extruded and granulated mixture to obtain the polycarbonate-based laser marking composite material.
Wherein the step of irradiation treatment in step (5) comprises: packing the material 1 into a box, putting the box into a cobalt-60 irradiation source, and irradiating under the total irradiation dose of 30 kGy; and (4) packing the material 2, putting the material into a cobalt-60 radiation source, and performing radiation under the total radiation dose of 15 kGy.
And (7) mounting an ultrasonic vibration device and an EB electron beam device at the head of the double-screw extruder, wherein the ultrasonic vibration device and the EB electron beam device both contain laser powder with surface double bonds, and the laser powder is dispersed into particles of 50nm through in-situ vibration and is uniformly contacted with and distributed on extruded granules.
Example 3:
the polycarbonate-based laser marking composite of the present embodiment includes: 95 parts of bisphenol A polycarbonate, 25 parts of aliphatic polycarbonate, 49 parts of mica, 1 part of carbon nano tube, 60 parts of polyurethane, 25 parts of silane coupling agent, 35 parts of silicone, 10 parts of paraffin, 5 parts of vanadium trioxide, 5 parts of titanium oxide and 10 parts of bisphenol A antioxidant. Wherein mica is 0.1 micrometer, the inner diameter of the carbon nanotube is 1-2 nanometers, the outer diameter is 3-4 nanometers, and the length is 50 micrometers.
The preparation method of the polycarbonate-based laser marking composite material comprises the following steps:
(1) drying the components in the proportion for 12h at 120 ℃ to obtain the dried component with the water content of 0.06%;
(2) stirring the dried inorganic particles, the compatibilizer and the lubricant at 120 ℃ for 2min at 150r/min, and then stirring at 300r/min for 3min to mix uniformly;
(3) adding the dried organic toughening agent and the laser absorbent into the mixed material in the step (2), stirring at the temperature of 120 ℃ at 150r/min for 5min, uniformly mixing, and marking as a material 1;
(4) stirring and mixing the dried part of polycarbonate and the antioxidant uniformly at the temperature of 120 ℃, and marking as a material 2;
(5) respectively carrying out irradiation treatment on the material 1 and the material 2;
(6) mixing the material 1 and the material 2 after the irradiation treatment at 120 ℃ and stirring at 300r/min for 5min to mix evenly, and marking as a material 3;
(7) and stirring and mixing the rest polycarbonate and the material 3, conveying the mixture into a double-screw extruder through a conveying device, wherein the temperatures of all sections of the extruder are respectively 150 ℃, 230 ℃, 245 ℃, 250 ℃, 265 ℃ and 250 ℃, the speed of a main extruder is 600r/min, and drying the extruded and granulated mixture to obtain the polycarbonate-based laser marking composite material.
Wherein the step of irradiation treatment in step (5) comprises: packing the material 1 into a box, putting the box into a cobalt-60 irradiation source, and irradiating under the total irradiation dose of 50 kGy; and (4) packing the material 2, putting the material into a cobalt-60 radiation source, and performing radiation under the total radiation dose of 30 kGy.
And (7) mounting an ultrasonic vibration device and an EB electron beam device at the head of the double-screw extruder, wherein the ultrasonic vibration device and the EB electron beam device both contain laser powder with surface double bonds, and the laser powder is dispersed into particles of 100nm through in-situ vibration and is uniformly contacted with and distributed on extruded granules.
Example 4:
the polycarbonate-based laser marking composite of the present embodiment includes: 90 parts of bisphenol A polycarbonate, 10 parts of aliphatic polycarbonate, 15 parts of titanium dioxide, 25 parts of mica, 40 parts of rubber, 15 parts of a silane coupling agent, 3 parts of molybdenum disulfide, 5 parts of hematite and 5 parts of phosphite ester antioxidant, and 5 parts of fatty acid soap. Wherein the particle size of the titanium dioxide is 0.1 micron, and the particle size of the mica is 0.1 micron.
The preparation method of the polycarbonate-based laser marking composite material of the present example is identical to that of example 1.
Comparative example 1
The polycarbonate-based laser marking material of the present comparative example includes: 100 parts of bisphenol A polycarbonate and 8 parts of copper tetraammine sulfate. The preparation method of the polycarbonate-based laser marking material of the comparative example was the same as that of example 2.
Comparative example 2
The polycarbonate-based laser marking material of the present comparative example includes: 100 parts of bisphenol A polycarbonate, 35 parts of titanium dioxide and 8 parts of copper tetraammine sulfate, wherein the particle size of the titanium dioxide is 0.1 micron. The preparation method of the polycarbonate-based laser marking material of the comparative example was the same as that of example 2.
Comparative example 3
The polycarbonate-based laser marking material of the present comparative example includes: 100 parts of bisphenol A polycarbonate, 45 parts of ABS, 35 parts of titanium dioxide and 8 parts of copper tetraammine sulfate, wherein the particle size of the titanium dioxide is 0.1 micron. The preparation method of the polycarbonate-based laser marking material of the comparative example was the same as that of example 2.
Comparative example 4
The polycarbonate-based laser marking material of this comparative example was identical to that of example 2 except that the preparation method was different, and the irradiation treatment of step (5) was reduced in this comparative example.
The performance tests of the polycarbonate-based laser marking materials prepared in the examples 1-4 and the comparative examples 1-4 are carried out according to the standards of GB/T9341-2008 for detecting bending performance, GB/T21189-2007 for detecting impact performance, GB/T1040.2-2006 for detecting tensile strength and GB/T1688-2008 for detecting fatigue performance, and the results are as follows:
TABLE 1 tables of results of tests on product properties obtained in examples 1 to 4 and comparative examples 1 to 4
As can be seen from the above table, the invention has excellent bending strength, impact toughness, high fatigue resistance and laser marking performance.
The polycarbonate-based laser marking materials prepared in example 2 and comparative example 4 were subjected to the super-depth-of-field optical microscope scanning test, and the results are shown in fig. 1 and 2.
As can be seen from fig. 1, after the polycarbonate-based laser marking material in example 2 is subjected to irradiation treatment and laser powder treatment, the laser powder is dispersed more uniformly and has better compatibility with polycarbonate, so that the dispersion, agglomeration and component interface compatibility of the laser powder are greatly improved, and the material performance and the laser marking performance are greatly improved. As can be seen from fig. 2, the polycarbonate-based laser marking material in example 2 has agglomeration, distinct component interfaces, and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A polycarbonate-based laser-marked composite, comprising: 80-120 parts of polycarbonate, 20-50 parts of inorganic particles, 30-60 parts of organic toughening agent, 0.1-10 parts of laser absorbent, 10-30 parts of compatibilizer, 3-10 parts of lubricant and 3-10 parts of antioxidant.
2. The polycarbonate-based laser marking composite material according to claim 1, wherein the aliphatic polycarbonate comprises: one or more of an aliphatic-aromatic polycarbonate, a bisphenol a type polycarbonate, and a graft-modified polycarbonate.
3. The polycarbonate-based laser marking composite material according to claim 1, wherein the inorganic particles comprise one or more of talc, mica, whiskers, titanium dioxide, graphene, and carbon nanotubes, and have a particle size ranging from micro-scale to nano-scale, a size distribution conforming to a normal distribution, and a kurtosis of less than 3.
4. The polycarbonate-based laser marked composite material according to claim 1, wherein the toughening agent comprises: one or more of MBS, SEBS, ABS, polysiloxane, POE, PE, PS, rubber, PE and polyurethane, and the molecular weight of the polyurethane is more than 10 ten thousand.
5. The polycarbonate-based laser marking composite as claimed in claim 1, wherein the laser absorber comprises: one or more of metal powder, metal oxide, metal complex or metal complex, the particle size of which is 10nm-10 μm; wherein the metal powder includes: one or more of copper, iron, titanium, zinc, aluminum, magnesium, gold, silver, and alloys thereof; the metal oxide includes: one or more of iron oxide, copper oxide, vanadium trioxide, antimony trioxide, zinc oxide, magnesium oxide and titanium oxide; the metal complex includes: one or more of copper tetrammine sulfate, platinum diammine dichloride, potassium trichloroplatinate, xanthate, hematite, prussian blue or metal carbonyl compounds.
6. The polycarbonate-based laser-marked composite material according to claim 1, wherein the compatibilizer comprises: one or more of silicone, E wax, silane coupling agent, titanate coupling agent, higher fatty acid, fatty acid soap and molybdenum disulfide; the lubricant is: one or more of silicone, polyvinyl alcohol, cellulose acetate, fluoroplastics, fatty acids, fatty acid soaps, paraffin wax, and ethylene glycol.
7. The polycarbonate-based laser marking composite as claimed in claim 1, wherein the antioxidant comprises: monophenol antioxidant BHT, monophenol antioxidant 2246, bisphenol A antioxidant, polyphenol antioxidant 1010, polyphenol antioxidant 1076, phosphite antioxidant, antioxidant 168[ tris (1, 4-di-tert-butylphenyl) phosphite ], antioxidant 626[ bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphate ], antioxidant 618[ bis (octadecyl) pentaerythritol diphosphite ], thio antioxidant, thiobisphenol antioxidant and thioether-type phenol antioxidant.
8. Method for the preparation of a polycarbonate-based laser marking composite according to any of the claims 1 to 7, characterized in that it comprises the following steps:
(1) drying the components in the proportion for 5-12h at 50-120 ℃ to obtain the dried component with the water content of 0.03-0.06%;
(2) the dried inorganic particles, the compatibilizer and the lubricant are stirred and mixed uniformly at the temperature of 100-120 ℃ at 50-150r/min and then are mixed uniformly at the temperature of 150-300 r/min;
(3) adding the dried organic toughening agent and the laser absorbent into the mixed material in the step (2), stirring and mixing uniformly at the temperature of 100-120 ℃, and marking as a material 1;
(4) stirring and mixing the dried part of polycarbonate and the antioxidant uniformly at the temperature of 100-120 ℃, and marking as a material 2;
(5) respectively carrying out irradiation treatment on the material 1 and the material 2;
(6) mixing the material 1 and the material 2 after the irradiation treatment at the temperature of 100-120 ℃, stirring and mixing uniformly, and marking as a material 3;
(7) and stirring and mixing the rest polycarbonate and the material 3, conveying the mixture into a double-screw extruder through a conveying device, wherein the temperatures of all sections of the extruder are respectively 150 ℃, 230 ℃, 245 ℃, 250 ℃, 265 ℃ and 250 ℃, the speed of a main machine of the extruder is 600r/min, and drying the mixture after extrusion granulation to obtain the polycarbonate-based laser marking composite material.
9. The method for preparing a polycarbonate-based laser marking composite material according to claim 8, wherein the step of irradiation treatment in the step (5) comprises: packing the material 1 into a box, and placing the box into a cobalt-60 irradiation source to perform irradiation under the total irradiation dose of 10-50 kGy; and (4) packing the material 2 into a cobalt-60 radiation source, and performing radiation under the total radiation dose of 5-30 kGy.
10. The method for preparing the polycarbonate-based laser marking composite material as claimed in claim 8, wherein the step (7) is that an ultrasonic vibration device and an EB electron beam device are arranged at the head of the twin-screw extruder, wherein the laser powder with surface double bonds is dispersed into particles of 20-100nm through in-situ vibration and is uniformly contacted with and distributed in the extruded granules.
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