Marking agent and methods of making and using

Abstract

The present disclosure relates to marking agents and plastic bottles having marking agents. An example marking agent can include: 40 to 70 parts of carrier vegetable oil, 1 to 10 parts of endothermic auxiliary agent 1, 10 to 30 parts of endothermic auxiliary agent 2, and 5 to 20 parts of another auxiliary agent. The carrier vegetable oil is epoxidized soybean oil, refined rapeseed oil, pressed peanut oil or a mixture thereof; the endothermic auxiliary agent 1 is titanium nitride, fine carbon black, graphene or a mixture thereof; the endothermic auxiliary agent 2 is zinc oxide; and the other auxiliary agent is an ultraviolet absorber, an antioxidant or a mixture thereof. The marking agent can effectively improve the marking efficiency of plastic bottles while reducing the energy consumption for bottle blowing of plastic bottles during the blowing process, and can improve the printing clarity.

Description

MARKING AGENT AND METHODS OF MAKING AND USINGCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of Chinese Patent Application No. 2023110968658, filed with the China National Intellectual Property Administration (CNIPA) on August 28, 2023, the disclosure of which is incorporated herein in its entirety.TECHNICAL FIELD

[0002] The present disclosure relates to a marking agent, in particular to a marking agent for PET bottles. In addition, the present disclosure further relates to a preparation method and application of the marking agent.BACKGROUND

[0003] Traditional beverage bottle packaging includes three parts: a bottle, a bottle cap and a mark. The mark is a simple sign used to indicate the name, weight, volume, use and other infomiation of an item. However, although the traditional mark form has special functional effects in displaying product information and highlighting product features, it will inevitably cause material loss and increase the cost of screening and separation during the recycling process of beverage bottles.

[0004] Most of the beverage bottles on the market are made of recyclable PET materials, so the recycling and processing of beverage bottles is particularly important. In recent years, many domestic and foreign beverage brands have begun to try to "unmark" their products. The so-called "unmark" means that the body of a beverage bottle no longer has a mark with a brand LOGO and product information, but the main information of the product is directly printed on the bottle by using laser printing or inkjet.

[0005] Although laser marking has certain advantages over the use of marks in the recycling of PET bottles, the technology of laser marking on PET bottles has had limitations so far. No matter what kind of laser is used for mark-free printing, there will be problems such as low printing efficiency, poor contrast, unclear marking content, blurred corners of characters, obvious damageto bottle walls, and rough touch. Also, due to the limitations of the appearance structure of the PET bottle, the content around the mark is almost invisible and it is difficult to clearly present a barcode.

[0006] Patent document CN102070889A discloses a PET resin composition with a laser marking function, which includes polyethylene terephthalate (PET), continuous glass fibers, a toughening agent, carbon black, a nucleating agent, and a laser marking additive, wherein the laser marking additive is produced by DSM Company. The PET resin composition can form a distinct laser mark, such as forming white characters on the surface of black products or forming black characters on the surface of white products. However, the stability and smoothness of the mark are poor, making it difficult to perform efficient laser marking, and the mark cannot be retained for a long time.

[0007] Patent document CN109337356A discloses a laser-markable composition, which contains conversion nanoparticles and a photosensitizer. Under the action of laser, the photosensitizer produces a photothermal effect to bum off a black pigment, leaving the color pigment, thereby fomiing a permanent color mark on the marked workpiece. However, the marking process requires the use of specific conversion nanoparticles, and the process is difficult and not suitable for large-scale industrial production.SUMMARY OF THE DISCLOSURE

[0008] To overcome the above-mentioned defects, the present disclosure provides a marking agent or a composition for making a plastic bottle. By adding only a small amount of the marking agent to a PET base material, the laser marking effect of the PET bottle can be greatly improved while effectively improving the efficiency of mark-free printing. Especially for mark- free printing with more mark content and fewer characters, the printing clarity can be improved. In addition, in the process of bottle blowing using PET base material with the marking agent added, the energy consumption for bottle blowing can be significantly reduced (saving 20% or more), and the appearance of the bottle body is substantially not affected. In addition, an objective of the present disclosure is to provide a method for preparing a marking agent and an application of the marking agent in a PET bottle.

[0009] The marking agent according to the present disclosure (in parts by weight) comprises:40 to 70 parts of carrier vegetable oil,1 to 10 parts of endothermic auxiliary agent 1,10 to 30 parts of endothermic auxiliary agent 2, and5 to 20 parts of another auxiliary agent, wherein the carrier vegetable oil is epoxidized soybean oil, refined rapeseed oil, pressed peanut oil or a mixture thereof; the endothermic auxiliary agent 1 is titanium nitride, fine carbon black, graphene or a mixture thereof; the endothermic auxiliary agent 2 is zinc oxide; and the other auxiliary agent is an ultraviolet absorber, an antioxidant or a mixture thereof.

[0010] In some embodiments, the endothermic auxiliary agent 1 is preferably a mixture of titanium nitride, fine carbon black and graphene.

[0011] In some embodiments, in the endothemric auxiliary agent 1 , preferably, the weight of graphene accounts for more than 10 wt% (weight percentage) of the total weight of the endothermic auxiliary agent 1 ; more preferably, the weight of graphene accounts for 10 to 20 wt% of the total weight of the endothemiic auxiliary agent 1.

[0012] In some embodiments, the ultraviolet absorber is UV234, UV360, UV3638 or a mixture thereof, and the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 9228 or a mixture thereof.

[0013] The method for preparing the marking agent according to the present disclosure comprises the following steps:(1) dispersing the endothermic auxiliary agent 1, the endothermic auxiliary agent 2 and the other auxiliary agent in the carrier vegetable oil according to required amounts, and dispersing them fully and evenly by high-speed stirring to obtain a dispersion; and(2) transferring the dispersion to a grinder, and controlling a particle size of a solid matter included in the dispersion to be within a range of 3 to 5 pm by grinding, thereby obtaining the marking agent.

[0014] In some embodiments, the preparation method further comprises performing quality and performance testing of a finished product of the ground marking agent, and then subpackaging.

[0015] Tn some embodiments, the grinder is a horizontal grinder.

[0016] In some embodiments, the grinding is performed in a ball milling manner.

[0017] According to the present disclosure, an application of the above-mentioned marking agent in a PET bottle is further provided.

[0018] In some embodiments, the PET bottle comprises a PET base material and a marking agent, wherein the contents (by weight percentage) of the components are, respectively;99.80 to 99.95 wt% for the PET base material, and0.05 to 0.20 wt% for the marking agent.

[0019] In some embodiments, the PET base material has an intrinsic viscosity of 0.7 to 0.9 dL / g.

[0020] A method for preparing a PET bottle according to the present disclosure comprises the following steps:(1) drying PET base material particles in a dehumidifying dryer for at least 5 hours;(2) adding a liquid marking agent to the dried PET base material particles according to the aforementioned proportion;(3) injection-molding a preform of a bottle; and(4) heating and blowing the bottle, thereby obtaining a finished PET bottle.

[0021] In the present disclosure, with the vegetable oil being a carrier, two different endothermic auxiliary agents work together as an important component of the marking agent, so that a laser mark is formed through a thermal process during the laser processing of the materials. Here, laser processing is essentially the interaction between laser light and matter. Specifically, when a laser beam is projected onto the surface (or inside) of the matter, part of the energy of the laser beam is reflected, absorbed and / or transmitted, wherein light energy is absorbed in the form of vibration excitation of electrons and atoms, and energy transfer and transmission occur, thereby causing various physical and / or chemical effects and processes.

[0022] The endothermic auxiliary agent 1 used in the present disclosure is titanium nitride, fine carbon black, graphene or a mixture thereof. This endothermic auxiliary agent 1 can effectivelyabsorb heat energy and quickly conduct the heat energy to the inner wall of the bottle preform. The rapid absorption of light facilitates the effect and efficiency of laser marking. The specific working principle is as follows. Near the wavelength of 1100 nanometers, the absorption of PET (polyethylene terephthalate) resin has a weak value, while titanium nitride, fine carbon black, graphene or a mixture thereof can effectively absorb heat energy in the light wavelength range of 1100 nanometers, thereby improving the absorption of heat energy when the bottle preform is heated by a near-infrared lamp before bottle blowing. Moreover, the radiation of near-infrared rays can be effectively increased to compensate for the weak infrared absorption performance of PET itself. Graphene has extremely high thermal conductivity, and its orderly stacked structure can make full use of heat energy during heat conduction. However, pure graphene has problems such as uneven dispersion and interface effect. Therefore, using graphene together with other endothermic materials is a better choice. The inventors of the present disclosure creatively discovered that when the weight of graphene is 10 to 20 wt% of the total weight of the endothermic auxiliary agent 1, the maximum heat absorption efficiency can be achieved without adversely affecting heat conduction due to the interface effect.

[0023] The endothermic auxiliary agent 2 used in the present disclosure is zinc oxide. Zinc oxide, which has a hexagonal wurtzite structure, can generate a concentration difference between holes and electrons at a certain temperature due to the thermal motion of electrons inside the material, thereby generating a thermoelectric potential difference. This is called a pyroelectric effect or a thermoelectric effect. That is, when electrons in a heated object move from a high temperature zone to a low temperature zone along a temperature gradient, the current or charge accumulation phenomenon is generated. When laser marking equipment generates thermoelectric potential by focusing radiation on the above-mentioned endothermic auxiliary agent, a certain thermoelectric effect will be generated, thereby improving the burning carbonization effect on the bottle wall surface during marking, and forming dense and deep burning carbonization traces, so that the effect of laser printing is more prominent and the printed characters are more obvious.

[0024] Endothermic auxiliary agents 1 and 2 work together to further improve the heat conduction and thermal effect during laser marking, achieving higher marking clarity.

[0025] Beneficial effects of the present disclosure:

[0026] 1. In the marking agent according to the present disclosure, titanium nitride, fine carbon black, graphene or a mixture thereof and zinc oxide are used together as endothermic auxiliary agents, which can make full use of the thermal effect occurring during laser marking and enhance the efficiency of laser carbonization and heat conduction. The color rendering effect of the PET bottle with the marking agent added is significantly improved, and the marking content is clearer and more efficient, especially in the comer parts of characters. The marking characters are uniform and beautiful, and the barcodes and QR codes are clear and can all be accurately identified. At a marking speed of 3000 to 8000 mm / s, clear patterns and characters can all be presented.

[0027] 2. The use of the endothermic auxiliary agents in the marking agent according to the present disclosure can also improve the bottle blowing efficiency at the same time, and the energy consumption for bottle blowing is significantly reduced (the maximum endothermic efficiency can exceed 20%), which greatly reduces energy loss and carbon emissions.

[0028] 3. By controlling the content of graphene in the endothermic auxiliary agent 1 according to the present disclosure to 10-20 wt%, the thermal effect of graphene can be maximized. The graphene at the amount of use enables the effect of the marking agent to be effectively exerted without adversely affecting the appearance and performance of the PET bottle due to negative effects such as the interface effect of graphene.

[0029] 4. In the technical solution of the present disclosure, the particle size of the solid matter included in the marking agent is controlled within the range of 3 to 5 pm by means of ball milling, which can ensure the stability of the effect of the marking agent. On the one hand, the resolution clarity of the marking content is improved. On the other hand, the marking content is given a long- lasting smooth effect, and does not fade easily due to external factors such as friction and temperature.BRIEF DESCRIPTION OF DRAWINGS

[0030] FIG. 1 is a schematic diagram of equipment for adding a marking agent to PET particles and related PET bottle preparation equipment.

[0031] FIGS. 2(a) and 2(b) are schematic diagrams showing results of marking PET bottles in the cases where 0.1 wt% of a marking agent is added and where no marking agent is added, respectively.

[0032] FIGS. 3(a) to 3(c) are comparison diagrams of effects of adding Example 1-9 and a blank test bottle at different marking speeds, wherein FIG. 3(a) corresponds to Example 1-3, FIG. 3(b) corresponds to Example 4-6, and FIG. 3(c) corresponds to Example 7-9 and the pure PET bottle.

[0033] List of reference numerals:1001: marking agent adding equipment;1002: marking agent;1003: hopper;1004: premixer;1005: feed port;1006: driving device;1007: injection molding screw.DETAILED DESCRIPTION

[0034] FIG. 1 shows a schematic diagram of equipment for adding a marking agent to PET particles and related PET bottle preparation equipment. In the equipment shown in FIG. 1, the addition of the marking agent 1002 is consistent with a conventional method of adding a liquid additive. That is, plastic particles in a hopper 1003 pass through the marking agent adding equipment 1001 before being fed into an injection molding screw 1007, and quantitative addition is performed through automatic signal control according to an addition amount required for each production cycle, so that effective dispersion and mixing can be performed in the injection molding screw 1007 driven by a driving device 1006. As shown in FIG. 1, a premixer 1004 may also be installed at a feed inlet 1005 of an injection molding machine to enhance stirring and mixing, so that the marking agent and the plastic particles are better mixed, thereby improving the use effect of the marking agent 1002.

[0035] The technical solution according to the present disclosure is clearly and completely described below with reference to embodiments. The embodiments described below are only a part, but not all, of the embodiments of the present disclosure. Based on the embodiments recited in the present disclosure, all other embodiments obtained by those of ordinary skill in the art without any inventive effort should fall within the scope of protection of the present disclosure.

[0036] Synthesis Example 1, preparation of marking agent 1:

[0037] (1) Disperse 3 parts of titanium nitride, 1 part of fine carbon black, 1 part of graphene, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0038] (2) Transfer the dispersion to a grinder, such as a clean horizontal grinder; control the particle size of the solid matter included in the dispersion within the range of 3 to 5 pm by means of grinding, such as ball milling; and then perform quality and performance testing of the ground finished product, and subpackage the finished product after passing the test to obtain marking agent 1.

[0039] Synthesis Example 2, preparation of marking agent 2:

[0040] (1) Disperse 4 parts of titanium nitride, 1 part of graphene, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0041] (2) Transfer the dispersion to a grinder, and control the particle size of the solid matter included in the dispersion within the range of 3 to 5 pm by grinding; and then perform quality and performance testing of the finished product, and subpackage the finished product after passing the test to obtain marking agent 2.

[0042] Synthesis Example 3, preparation of marking agent 3:

[0043] (1) Disperse 4 parts of fine carbon black, 1 part of graphene, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0044] (2) Transfer the dispersion to a grinder, and control the particle size of the solid matter included in the dispersion within the range of 3 to 5 pm by grinding; and then perform quality and performance testing of the finished product, and subpackage the finished product after passing the test to obtain marking agent 3.

[0045] Synthesis Example 4, preparation of marking agent 4:

[0046] (1) Disperse 4 parts of titanium nitride, 1 part of fine carbon black, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0047] (2) Transfer the dispersion to a grinder, and control the particle size of the solid matter included in the dispersion within the range of 3 to 5 pm by grinding; and then perform quality and performance testing of the finished product, and subpackage the finished product after passing the test to obtain marking agent 4.

[0048] Synthesis Example 5, preparation of marking agent 5:

[0049] (1) Disperse 3 parts of titanium nitride, 1 part of fine carbon black, 2 parts of graphene, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0050] (2) Transfer the dispersion to a grinder, and control the particle size of the solid matter included in the dispersion within the range of 3 to 5 pm by grinding; and then perform quality and performance testing of the finished product, and subpackage the finished product after passing the test to obtain marking agent 5.

[0051] Synthesis Example 6, preparation of marking agent 6:

[0052] (1) Disperse 3 parts of titanium nitride, 1 part of fine carbon black, 0.3 parts of graphene, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0053] (2) Transfer the dispersion to a grinder, and control the particle size of the solid matter included in the dispersion within the range of 3 to 5 pm by grinding; and then perform quality andperformance testing of the finished product, and subpackage the finished product after passing the test to obtain marking agent 6.

[0054] Synthesis Example 7, preparation of marking agent 7:

[0055] (1) Disperse 3 parts of titanium nitride, 1 part of fine carbon black, 1 part of graphene, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0056] (2) Transfer the dispersion to a grinder, and control the particle size of the solid matter included in the dispersion within the range of 6 to 8 pin by grinding; and then perform quality and performance testing of the finished product, and subpackage the finished product after passing the test to obtain marking agent 7.

[0057] Synthesis Example 8, preparation of marking agent 8:

[0058] (1) Disperse 3 parts of titanium nitride, 1 part of fine carbon black, 1 part of graphene, 20 parts of zinc oxide, and 5 parts of UV absorber UV3638 in 60 parts of epoxidized soybean oil, and disperse them fully and evenly by high-speed stirring at a stirring speed of 1000 rpm to obtain a dispersion.

[0059] (2) Transfer the dispersion to a grinder, and carrying out simple grinding to obtain a finished product with the particle size of the solid matter within the range of 8 to 10 pm; and then perform quality and performance testing of the finished product, and subpackage the finished product after passing the test to obtain marking agent 8.Example 1

[0060] In this example, marking agent 1 and a PET base material are selected. PET base material particles are dried in a dehumidifying dryer for at least 5 hours, and liquid marking agent 1 is added to the dried PET base material particles at an addition ratio of 0.1 wt%. The intrinsic viscosity of the PET base material particles is 0.8 dL / g. A bottle preform is injection molded and heated for bottle blowing to obtain a PET bottle according to this Example 1.

[0061] Laser marking of the PET bottle according to this Example 1 includes the following steps: focusing a laser on the bottle body to be laser marked; and performing corresponding routescanning according to a required mark, and causing the surface of the bottle body through which the scanning route passes to change color due to the radiation of laser light of a specific wavelength emitted by the laser, thereby forming a mark. In this example, the scanning speed is set to 4000 mm / s, and laser marking equipment is selected as a fiber laser marking machine HANS20Y (20 W) of Shenzhen Han's Laser.Examples 2 to 8

[0062] In Examples 2 to 8, marking agent 1 in Example 1 is replaced with marking agents 2 to 8, respectively, and the other process steps remain the same as those in Example 1, thereby preparing corresponding PET bottles, and performing laser marking of the PET bottles according to these examples.

[0063] The marking effect according to Examples 1 to 8 is shown by reference numeral 1, wherein whether lines in marked areas are smooth and clear and whether characters are complete and smooth is evaluated by visual inspection.Table 1

[0064] The above test results clearly show that under the same marking conditions, compared with the bottle without the marking agent, by adding the marking agent according to the present disclosure, the marking content is clearer, the printed characters are more uniform and beautiful, especially the corner parts of the characters, and even with a smaller font, the characters are clear and beautiful, as shown in the left sub-figure of FIG. 2 in the drawings (wherein 0.1 wt% of the marking agent 1 is added). It can better highlight the quality and beauty of the product logo, and the barcodes are clear and can be identified. In particular, according to Table 1 above, it can be clearly seen that the marking agent with an appropriate amount of graphene has excellent performance in terms of clarity, smoothness and marking effect. However, the pure PET bottle without the marking agent according to the present disclosure added is obviously relatively blurred in marking, the text content or patterns around the mark are almost invisible, and the barcodes are hardly presented clearly, as shown in the right sub-figure of FIG. 2 of the drawings (wherein no marking agent is added).

[0065] In addition, the addition of the marking agent further improves the marking efficiency while improving the marking effect. To observe and compare the marking efficiency more intuitively, PET bottles manufactured according to Examples 1 to 8 of the present disclosure and a blank test bottle (i.e., a pure PET bottle without a marking agent added) were selected for laser marking tests at marking rates of 3000 mm / s to 8000 mm / s, respectively. The marking results are shown in FIGS. 3(a) to 3(c), wherein bottles 1 to 8 correspond to Examples 1 to 8, respectively, and Example bottle 9 corresponds to the blank test bottle.

[0066] The experimental results show that the PET bottle with the marking agent according to the present disclosure added can still present clear characters and patterns even when the marking rate reaches 8000 mm / s. However, the marking of pure PET bottles without a marking agent added can only keep the characters and patterns relatively clear at a marking speed of 3000 mm / s, and as the marking rate is further increased, the marking results are completely unacceptable.

[0067] In addition, the inventors also discovered that in the process of bottle blowing, the energy consumption when the PET base material with the marking agent according to the present disclosure added is used for blowing bottles is significantly reduced compared with when the PET base material without a marking agent added is used, and the appearance of the bottle body is substantially not adversely affected. In view of this, the following method is used for verification: in the process of heating a bottle preform, the rated power of a heating lamp box in a preform feeding section, a stabilization section and a heat dispersion section of an oven is adjusted, and the total power change of a bottle blowing machine is checked in a relatively stable heating and bottle blowing state. The comparison of the energy consumption for bottle blowing of PET bottles according to Examples 1 to 8 and the blank test bottle is shown in Table 2 below:Table 2

[0068] The test results show that when the PET base material with 0.1 wt% of the marking agent added is used for bottle blowing, the energy consumption can be reduced by more than 20% at most, and the energy consumption of manufacturing the PET bottle according to Example 1 is reduced by 27% compared with the energy consumption of manufacturing the pure PET bottle. The main reason for this result is that under the joint action of titanium nitride, fine carbon black, graphene and zinc oxide in the endothermic auxiliary agents, the heat absorption effect of the PET base material has been improved as a whole, thereby improving the heat absorption efficiency. In particular, with the help of the ultra-high thermal conductivity of graphene, the joint action of graphene, titanium nitride and fine carbon black enables the system's heat energy absorption efficiency to be maximized, thereby bringing about a significant reduction in the energy consumption of bottle blowing.

[0069] Only a part of the embodiments according to the present disclosure are enumerated above, and are not intended to limit the present disclosure to the scope of these enumerated embodiments. In fact, any modifications, equivalent replacements, improvements, etc., made without deviating from the spirit and principle of the present disclosure should be included in the scope of protection of the present disclosure.

[0070] The following numbered clauses define further embodiments of the present disclosure:NUMBERED CLAUSES1. A marking agent comprising:40 to 70 parts by weight of a carrier vegetable oil,1 to 10 parts by weight of a first endothermic auxiliary agent,10 to 30 parts by weight of a second endothermic auxiliary agent, and5 to 20 parts by weight of a third auxiliary agent, wherein the carrier vegetable oil is selected from the group consisting of epoxidized soybean oil, refined rapeseed oil, pressed peanut oil, and any combination thereof; the first endothermic auxiliary agent is selected from the group consisting of titanium nitride, fine carbonblack, graphene, and any combination thereof; the second endothermic auxiliary agent is zinc oxide; and the third auxiliary agent is selected from the group consisting of an ultraviolet absorber, an antioxidant, and a mixture thereof.2. The marking agent according to clause 1, wherein the first endothermic auxiliary agent is a mixture of titanium nitride, fine carbon black and graphene.3. The marking agent according to any one of clauses 1 and 2, wherein a weight of graphene accounts for 10 wt% or more of a total weight of the first endothermic auxiliary agent.4. The marking agent according to any one of claims 1-3, wherein a weight of graphene accounts for 10 to 20 wt% of the total weight of the first endothermic auxiliary agent.5. The marking agent according to any one of clauses 1-4, wherein the ultraviolet absorber is selected from the group consisting of UV234, UV360, UV3638, and any combination thereof, and the antioxidant is selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 9228, and any combination thereof.6. The marking agent according to any one of clauses 1-5, wherein the marking agent having solids with a particle size within a range of 3 to 5 pm.7. A method for preparing a marking agent, the method comprising: dispersing a first endothermic auxiliary agent, a second endothermic auxiliary agent, and a third auxiliary agent in a carrier vegetable oil by stirring to obtain a dispersion,; and grinding the dispersion in a grinder to obtain the marking agent having solids with a particle size within a range of 3 to 5 pm, wherein the carrier vegetable oil is in 40 to 70 parts by weight, the first endothermic auxiliary agent is in 1 to 10 parts by weight, the second endothermic auxiliary agent is in 10 to 30 parts by weight, and the third auxiliary agent is in 5 to 20 parts by weight, the carrier vegetable oil is selected from the group consisting of epoxidized soybean oil, refined rapeseed oil, pressed peanut oil, and any combination thereof; the first endothermic auxiliary agent is selected from the group consisting of titanium nitride, fine carbon black, graphene, and any combination thereof; the second endothermic auxiliary agent is zinc oxide; andthe third auxiliary agent is selected from the group consisting of an ultraviolet absorber, an antioxidant, and a mixture thereof.8. The method according to clause 7, further comprising: performing quality and performance testing of the grinded marking agent; and packaging the marking agent.9. The method according to any one of clauses 7-8, wherein the grinder is a horizontal grinder.10. The method according to any one of clauses 7-9, wherein the grinding is ball milling.11. The method according to any one of clauses 7-10, wherein the first endothermic auxiliary agent is a mixture of titanium nitride, fine carbon black and graphene.12. The method according to any one of clauses 7-11, wherein a weight of graphene accounts for 10 wt% or more of a total weight of the first endothermic auxiliary agent.13. The method according to any one of clauses 7-12, wherein a weight of graphene accounts for 10 to 20 wt% of the total weight of the first endothermic auxiliary agent.14. The method according to any one of clauses 7-13, wherein the ultraviolet absorber is selected from the group consisting of UV234, UV360, UV3638, and any combination thereof, and the antioxidant is selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 9228, and any combination thereof.15. A plastic bottle comprising: a plastic base material; and a marking agent, the marking agent comprising: a carrier vegetable oil in 40 to 70 parts by weight, relative to total parts by weight of the marking agent, a first endothermic auxiliary agent in 1 to 10 parts by weight, relative to the total parts by weight of the marking agent,a second endothermic auxiliary agent in 10 to 30 parts by weight, relative to the total parts by weight of the marking agent, and a third auxiliary agent in 5 to 20 parts by weight, relative to the total parts by weight of the marking agent, wherein the carrier vegetable oil is selected from the group consisting of epoxidized soybean oil, refined rapeseed oil, pressed peanut oil, and any combination thereof; the first endothermic auxiliary agent is selected from the group consisting of titanium nitride, fine carbon black, graphene, and any combination thereof; the second endothermic auxiliary agent is zinc oxide; and the third auxiliary agent is selected from the group consisting of an ultraviolet absorber, an antioxidant, and a mixture thereof.16. The plastic bottle according to clause 15, wherein the first endothermic auxiliary agent is a mixture of titanium nitride, fine carbon black and graphene.17. The plastic bottle according to any one of clauses 15-16, wherein a weight of graphene accounts for 10 to 20 wt% of the total weight of the first endothermic auxiliary agent.18. The plastic bottle according to any one of clauses 15-17, wherein, based on a total weight of the plastic bottle, the plastic base material is 99.80 wt% to 99.95 wt%, and the marking agent is 0.05 wt% to 0.20 wt%.19. The plastic bottle according to any one of clauses 15-18, wherein the plastic base material is PET base material.20. The plastic bottle according to any one of clauses 15-19, wherein the plastic base material has an intrinsic viscosity of 0.7 to 0.9 dL / g.21. The plastic bottle according to any one of clauses 15-20, wherein the marking agent has solids with a particle size within a range of 3 to 5 pm.22. The plastic bottle according to any one of clauses 15-21, further comprising: a laser mark on a portion of the plastic bottle, wherein the laser mark comprises a carbonized plastic base material formed by applying laser radiation on the portion of the plasticbottle, wherein the marking agent included in the portion upon laser radiation causes carbonization of the plastic base material included in the portion to form the laser mark.23. A method for preparing a plastic bottle, the method comprising: drying a plastic base material comprising plastic particles in a dehumidifying dryer; adding a marking agent to the dried plastic base material particles to obtain a mixture; subjecting the mixture to injection-molding to obtain a preform of the plastic bottle; and heating and blowing the preform to obtain the plastic bottle, wherein the marking agent comprises: a carrier vegetable oil in 40 to 70 parts by weight, relative to total parts by weight of the marking agent, a first endothermic auxiliary agent in 1 to 10 parts by weight, relative to the total parts by weight of the marking agent, a second endothermic auxiliary agent in 10 to 30 parts by weight, relative to the total parts by weight of the marking agent, and a third auxiliary agent in 5 to 20 parts by weight, relative to the total parts by weight of the marking agent, wherein the carrier vegetable oil is selected from the group consisting of epoxidized soybean oil, refined rapeseed oil, pressed peanut oil, and any combination thereof; the first endothermic auxiliary agent is selected from the group consisting of titanium nitride, fine carbon black, graphene, and any combination thereof; the second endothermic auxiliary agent is zinc oxide; and the third auxiliary agent is selected from the group consisting of an ultraviolet absorber, an antioxidant, and a mixture thereof.24. The method according to clause 23, further comprising: applying laser radiation on a portion of the plastic bottle to cause the marking agent included in the portion to carbonize the plastic base material included in the portion and form a laser mark comprising a carbonized plastic base material.25. The method according to any one of clauses 23-24, wherein the first endothermic auxiliary agent is a mixture of titanium nitride, fine carbon black and graphene.26. The method according to any one of clauses 23-25, wherein a weight of graphene accounts for 10 wt% or more of a total weight of the first endothermic auxiliary agent.27. The method according to any one of clauses 23-26, wherein a weight of graphene accounts for 10 to 20 wt% of the total weight of the first endothermic auxiliary agent. 28. The method according to any one of clauses 23-27, wherein the ultraviolet absorber is selected from the group consisting of UV234, UV360, UV3638, and any combination thereof, and the antioxidant is selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 9228, and any combination thereof.29. The method according to any one of clauses 23-28, wherein, based on a total weight of the plastic bottle, the plastic base material is 99.80 wt% to 99.95 wt%, and the marking agent is 0.05 wt% to 0.20 wt%.30. The method according to any one of clauses 23-29, wherein the marking agent has solids with a particle size within a range of 3 to 5 pm.31. The method according to any one of clauses 23-30, wherein the plastic base material is PET base material.32. The method according to any one of clauses 23-31, wherein the plastic base material has an intrinsic viscosity of 0.7 to 0.9 dL / g.

Claims

WHAT IS CLAIMED IS:

1. A marking agent comprising:40 to 70 parts by weight of a carrier vegetable oil;1 to 10 parts by weight of a first endothermic auxiliary agent;10 to 30 parts by weight of a second endothermic auxiliary agent; and5 to 20 parts by weight of a third auxiliary agent, wherein the carrier vegetable oil is selected from the group consisting of epoxidized soybean oil, refined rapeseed oil, pressed peanut oil, and any combination thereof; the first endothermic auxiliary agent is selected from the group consisting of titanium nitride, fine carbon black, graphene, and any combination thereof; the second endothermic auxiliary agent is zinc oxide; and the third auxiliary agent is selected from the group consisting of an ultraviolet absorber, an antioxidant, and a mixture thereof.

2. The marking agent according to claim 1, wherein the first endothermic auxiliary agent is a mixture of titanium nitride, fine carbon black and graphene.

3. The marking agent according to claim 2, wherein a weight of graphene accounts for 10 wt% or more of a total weight of the first endothermic auxiliary agent.

4. The marking agent according to claim 3, wherein the weight of graphene accounts for 10 to 20 wt% of the total weight of the first endothermic auxiliary agent.

5. The marking agent according claim 1, wherein the ultraviolet absorber is selected from the group consisting of UV234, UV360, UV3638, and any combination thereof, and the antioxidant is selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 9228, and any combination thereof.

6. A method for preparing a marking agent, the method comprising: dispersing 1 to 10 parts by weight of a first endothermic auxiliary agent, 10 to 30 parts by weight of a second endothermic auxiliary agent, and 5 to 20 parts by weight of a third auxiliary agent in 40 to 70 parts by weight of a carrier vegetable oil by stirring to obtain a dispersion; andgrinding the dispersion in a grinder to obtain the marking agent, the marking agent having solids with a particle size in a range of 3 pm to 5 pm.

7. The method according to claim 6, further comprising: performing quality and performance testing of the grinded marking agent; and packaging the marking agent.

8. The method according to claim 6, wherein the grinder is a horizontal grinder.

9. The method according to claim 6, wherein the grinding is ball milling.

10. A plastic bottle comprising: a plastic base material; and a marking agent, the marking agent comprising: a carrier vegetable oil in 40 to 70 parts by weight of the marking agent, a first endothermic auxiliary agent in 1 to 10 parts by weight of the marking agent, a second endothermic auxiliary agent in 10 to 30 parts by weight of the marking agent, and a third auxiliary agent in 5 to 20 parts by weight of the marking agent, wherein the carrier vegetable oil is selected from the group consisting of epoxidized soybean oil, refined rapeseed oil, pressed peanut oil, and any combination thereof; the first endothermic auxiliary agent is selected from the group consisting of titanium nitride, fine carbon black, graphene, and any combination thereof; the second endothermic auxiliary agent is zinc oxide; and the third auxiliary agent is selected from the group consisting of an ultraviolet absorber, an antioxidant, and a mixture thereof.

11. The plastic bottle according to claim 10, wherein the first endothermic auxiliary agent is a mixture of titanium nitride, fine carbon black, and graphene.

12. The plastic bottle according to claim 10, wherein a weight of graphene accounts for 10 to 20 wt% of the total weight of the first endothermic auxiliary agent.

13. The plastic bottle according to claim 10, wherein, based on a total weight of the plastic bottle, the plastic base material is 99.80 wt% to 99.95 wt%, and the marking agent is 0.05 wt% to 0.20 wt%.

14. The plastic bottle according to claim 10, wherein the plastic base material is PET base material.

15. The plastic bottle according to claim 14, wherein the PET base material has an intrinsic viscosity of 0.7 to 0.9 dL / g.

16. The plastic bottle according to claim 10, further comprising: a laser mark on a portion of the plastic bottle, wherein the laser mark comprises a carbonized plastic base material formed by applying laser radiation on the portion of the plastic bottle, wherein the marking agent included in the portion upon laser radiation causes carbonization of the plastic base material included in the portion to form the laser mark.

17. A method for preparing a plastic bottle, the method comprising: drying a plastic base material comprising plastic particles in a dehumidifying dryer for at least 5 hours; adding a marking agent to the dried plastic base material particles to obtain a mixture; subjecting the mixture to injection-molding to obtain a preform; and heating and blowing the preform to obtain the plastic bottle, wherein the marking agent comprises: a carrier vegetable oil in 40 to 70 parts by weight of the marking agent, a first endothermic auxiliary agent in 1 to 10 parts by weight of the marking agent, a second endothermic auxiliary agent in 10 to 30 parts by weight of the marking agent, and a third auxiliary agent in 5 to 20 parts by weight of the marking agent, wherein the carrier vegetable oil is selected from the group consisting of epoxidized soybean oil, refined rapeseed oil, pressed peanut oil, and any combinationthereof; the first endothermic auxiliary agent is selected from the group consisting of titanium nitride, fine carbon black, graphene, and any combination thereof; the second endothermic auxiliary agent is zinc oxide; and the third auxiliary agent is selected from the group consisting of an ultraviolet absorber, an antioxidant, and a mixture thereof.

18. The method according to claim 17, further comprising: applying laser radiation on a portion of the plastic bottle to cause the marking agent included in the portion to carbonize the plastic base material included in the portion and form a laser mark comprising a carbonized plastic base material.

19. The method according to claim 17, wherein, based on a total weight of the mixture, the plastic base material is 99.80 wt% to 99.95 wt%, and the marking agent is 0.05 wt% to 0.20 wt%.

20. The method according to claim 17, wherein the plastic base material is PET base material.

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