Strong-adhesion environment-friendly solid marking wax for pasture animal marking and preparation method of strong-adhesion environment-friendly solid marking wax

Abstract

The invention discloses strong-adhesion environment-friendly solid marking wax for pasture animal marking and a preparation method of the strong-adhesion environment-friendly solid marking wax. Belongs to the technical field of livestock breeding tools. According to the solid marking wax disclosed by the invention, through the improvement of the composition proportion and the preparation method, the adhesion property of the solid marking wax is effectively improved, the contradiction between adhesion and clearance is effectively coordinated, the stripping force is within a suitable range under the condition that the solid marking wax has high adhesion, and animal fur cannot be damaged. Meanwhile, the solid marking wax disclosed by the invention is high in safety and good in wear resistance, and provides technical support for pasture animal marking.

Description

Technical Field

[0001] This invention relates to the field of livestock farming tools, and more specifically to a strong-adhesion, environmentally friendly solid marking wax for marking animals on ranches and its preparation method. Background Technology

[0002] Ranch animal marking materials are materials specifically designed for marking livestock (such as cattle and sheep). They are primarily used in ranch management to identify and track individual animals. For example, they can distinguish different animals in large ranches; or when ranch animals have health problems, they need to be marked to differentiate between healthy and unhealthy animals that require special care or treatment; in addition, during the breeding season, animals in estrus, mated, or pregnant can be marked separately. Therefore, animal marking is crucial in ranch animal husbandry, especially in large-scale ranch farming.

[0003] However, the following technical problems exist with animal marking materials: Adhesion durability: They are prone to fading or falling off under harsh weather conditions (rain, snow, strong sunlight), or rapid wear due to friction with animal fur. For example, water-soluble markings are easily washed away by rain and have poor durability (adhesion in the wild <72 hours); Safety issues: Some formulations may irritate animal skin, and ingestion by animals may cause health problems. For example, synthetic resin materials can easily cause skin allergies in animals; Environmental issues: Oil-based marking waxes contain mineral oil, which pollutes the soil and is difficult to degrade; Visibility issues: The colors are not bright enough, making them difficult to identify from a distance, and the color rendering is inconsistent on animals of different fur colors; Operability issues: They are inconvenient to use at extreme temperatures (too cold to harden, too hot to soften), and the marking process is time-consuming, making them inefficient for large ranches. For example, conventional waxes are prone to cracking at low temperatures (<5℃) and softening at high temperatures (>40℃); Environmental issues: Some components may not be easily degraded, and residues may pollute the environment; Cost issues: High-quality marking waxes are expensive, and frequent remarking increases usage costs. Among these factors, strong adhesion, safety, and environmental friendliness are the key considerations in the current research and development of animal marker materials, prompting researchers to continuously improve formulations and develop animal marker products with stronger adhesion, safety, and environmental friendliness.

[0004] Therefore, how to provide a strong-adhesion, environmentally friendly solid marking wax for marking ranch animals and its preparation method is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, the present invention provides a strong-adhesion environmentally friendly solid marking wax for marking ranch animals and its preparation method. Through improvements in the formulation and preparation method, the adhesion performance and safety performance of the solid marking wax are significantly improved.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: This strong-adhesion, environmentally friendly solid marking wax for ranch animal marking comprises the following components in parts by weight: 40-60 parts environmentally friendly wax matrix, 18-27 parts hydrogenated castor oil, 2-3 parts erucamide, 7-10 parts rosin glyceryl ester, 3-5 parts petroleum resin, 5-8 parts modified calcium carbonate, 3-5 parts sodium copper chlorophyllin, 2-3 parts nano silica, and 0.5-1 part chitosan.

[0007] Preferably, the strong-adhesion environmentally friendly solid marking wax for marking ranch animals comprises the following components in parts by weight: 45-55 parts environmentally friendly wax matrix, 20-23 parts hydrogenated castor oil, 2-3 parts erucamide, 8-9 parts rosin glycerol ester, 3-4 parts petroleum resin, 6-7 parts modified calcium carbonate, 3-4 parts sodium copper chlorophyllin, 2-2.5 parts nano silica, and 0.5-0.8 parts chitosan.

[0008] Preferably, the environmentally friendly wax matrix comprises natural beeswax, candelilla wax, and microcrystalline wax in a weight ratio of 5-6:1-2:0.3-0.6.

[0009] Preferably, the acid value of the rosin glycerol ester is ≤6 mg KOH / g; Preferably, the preparation process of the modified calcium carbonate is as follows: (1) Mix stearic acid and anhydrous ethanol in a weight ratio of 3-5:1-2, place in a water bath at 45-55℃ and stir until completely dissolved, then adjust the pH to 6-7. (2) Select calcium carbonate with a particle size of 1-2.5 μm to remove surface moisture, and then add 3-3.5% of the mass of calcium carbonate to the stearic acid ethanol solution in step (1). After mixing evenly, place it at 105℃ for 10-20 min, then adjust the temperature to 115-125℃, react for 20-25 min, and cool naturally to 60℃ to prepare modified calcium carbonate.

[0010] Another object of the present invention is to provide a method for preparing the above-mentioned strong-adhesion environmentally friendly solid marking wax for marking ranch animals, comprising the following steps: (1) Environmentally friendly wax matrix pretreatment: Place the environmentally friendly wax matrix in a supercritical reactor, adjust the CO2 pressure to 8-10 MPa, the temperature to 35-40℃, maintain the pressure for 1.5-2 hours, and then quickly release it to atmospheric pressure; (2) Gradient coupling of components: A twin-screw extruder is used to perform gradient coupling of polar and non-polar components in different zones, as follows: ① Low temperature zone: After mixing hydrogenated castor oil, erucamide and chitosan according to the formula, place them in the low temperature zone of the twin-screw extruder for mixing treatment until the mixture becomes a viscous paste and forms a flexible network core; ② Medium temperature zone: Add the environmentally friendly wax matrix, sodium copper chlorophyll salt and rosin glycerol ester pretreated in step (1) according to the ratio, and after medium temperature treatment, it is interspersed as a polar component between the flexible network core and the non-polar shell; ③ High-temperature zone: Nano-silica, petroleum resin and modified calcium carbonate are added according to the formula, and after high-temperature treatment, it is used as a non-polar outer shell coating. ④ Mixing output area: The melt is output through the static mixer.

[0011] Preferably, in step (1), the pressure is reduced to atmospheric pressure at a rate of ≥2MPa / s.

[0012] Preferably, in step (2), the temperature of the low-temperature zone is 75-85℃; the temperature of the medium-temperature zone is 105-115℃; the temperature of the high-temperature zone is 125-135℃; and the temperature of the mixed output zone is 95-105℃.

[0013] Preferably, in step (2), ② chlorophyll copper sodium salt is encapsulated, and the specific process is as follows: Chlorophyll copper sodium salt was dissolved in a phosphate buffer solution with a pH of 8 in the dark to prepare a 5% chlorophyllin copper sodium salt solution. Then, β-cyclodextrin was dissolved in ultrapure water at 60℃ until saturation to prepare a saturated β-cyclodextrin solution. Finally, the chlorophyllin copper sodium salt solution was slowly added dropwise to the β-cyclodextrin saturated solution at a volume ratio of 1:4, and the mixture was placed at 40-45℃ and stirred in the dark for 2-3 hours to prepare encapsulated chlorophyllin copper sodium salt.

[0014] Preferably, in step (2), ③ first, nano-silica and petroleum resin are premixed and ground, and then mixed with modified calcium carbonate and subjected to high-temperature treatment.

[0015] Preferably, in step (2), ③ nano-silica is oleophilic nano-silica.

[0016] Another object of the present invention is to provide the application of the above method in the preparation of a strong-adhesion, environmentally friendly solid marking wax for ranch animal marking.

[0017] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects: The present invention provides a strong adhesion environmentally friendly solid marking wax for animal marking on ranches. The formulation composition ratio and preparation method have been improved. In the formulation of the present invention, beeswax, candelilla wax and microcrystalline wax are used as environmentally friendly wax matrices, which can provide basic adhesion for the formulation. Moreover, the combination of the three can effectively increase the melting point of the solid wax and improve the crystallization performance. In addition, beeswax and candelilla wax contain long-chain fatty acid esters, which can form van der Waals forces with animal hair. Therefore, the wax matrix composed of the three has stronger adhesion, higher hardness and excellent high temperature stability. In addition, hydrogenated castor oil can enhance the hydrogen bonding force with hair, and the addition of erucamide can effectively improve low temperature ductility (no cracking at -20℃). The combination of hydrogenated castor oil contains hydroxyl groups, which enhances the wettability of polar surfaces. Erucamide, as a lubricant, promotes the spreading and penetration of wax on the hair surface and improves the adhesion performance. Rosin glyceryl ester (low acid value reduces irritation) provides high adhesion, while petroleum resin enhances cohesion and durability, forming a "viscoelastic network." Modified calcium carbonate (stearic acid coated) improves compatibility with the wax matrix, while the rough surface increases the mechanical anchoring effect. Lipophilic nano-silica enhances the coating's rigidity and abrasion resistance through hydrogen bonding between surface silanol groups and the wax matrix. In summary, the improved formulation imparts strong adhesion, low-temperature ductility, and abrasion resistance to the solid wax, and the materials used in this invention are environmentally friendly and pose no safety hazards. Furthermore, in terms of the preparation method, this invention first pre-treats the wax matrix, effectively increasing its specific surface area, promoting the penetration efficiency of rosin glycerol ester in the later stage, improving the penetration and interfacial bonding of subsequent components, enhancing adhesion strength, and reducing the risk of delamination. Then, a gradient coupling optimization process is adopted: In the low-temperature zone, hydrogenated castor oil, erucamide, and chitosan form a "flexible network core," with the amino groups of chitosan combining with the carboxyl groups of the wax matrix to improve toughness and adhesion performance. In the medium-temperature zone, polar components (chlorophyll copper sodium salt capsules and rosin glycerol ester) are interspersed in the flexible core, and β-cyclodextrin encapsulates chlorophyll to prevent high-temperature degradation and slow-release pigments. In the high-temperature zone, nano-silica and petroleum resin are premixed and then coated with modified calcium carbonate through high-temperature melting to form a dense "non-polar shell," enhancing the hydrophobicity and mechanical strength of the coating. After mixing and outputting from the three zones, a "core-shell" structure can be formed, and the adhesion is increased to 4.6 N / cm², which is 60% higher than that of the conventional method. Furthermore, this invention effectively reconciles the contradiction between adhesion and removal, ensuring that the solid marking wax, while possessing high adhesion, has a peeling force within a suitable range and will not damage the animal's fur. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1: A strong-adhesion environmentally friendly solid marking wax for animal marking on ranches, comprising the following components in parts by weight: 40 parts environmentally friendly wax matrix, 18 parts hydrogenated castor oil, 2 parts erucamide, 7 parts rosin glycerol ester, 3 parts petroleum resin, 5 parts modified calcium carbonate, 3 parts sodium copper chlorophyllin, 2 parts nano silica and 0.5 parts chitosan. The environmentally friendly wax matrix comprises natural beeswax, candelilla wax, and microcrystalline wax in a weight ratio of 5:1:0.3; The acid value of the rosin glycerol ester is 6 mg KOH / g; The preparation process of the modified calcium carbonate is as follows: (1) Mix stearic acid and anhydrous ethanol in a weight ratio of 3:1, place in a 45°C water bath and stir until completely dissolved, then adjust the pH to 6; (2) Select calcium carbonate with a particle size of 1 μm to remove surface moisture, and then add 3% of the calcium carbonate mass to the stearic acid ethanol solution in step (1). After mixing evenly, place it at 105℃ for 15 min, then adjust the temperature to 120℃, react for 20 min, and naturally cool to 60℃ to prepare modified calcium carbonate.

[0020] The preparation method of the above-mentioned strong-adhesion environmentally friendly solid marking wax for animal marking on ranches is as follows: (1) Environmentally friendly wax matrix pretreatment: The environmentally friendly wax matrix is ​​placed in a supercritical reactor, the CO2 pressure is adjusted to 8MPa, the temperature is 35℃, and the pressure is maintained for 1.5h. Then, the pressure is rapidly reduced to atmospheric pressure at a rate of 2MPa / s. (2) Gradient coupling of components: A twin-screw extruder is used to perform gradient coupling of polar and non-polar components in different zones, as follows: ① Low temperature zone (80℃): After mixing hydrogenated castor oil, erucamide and chitosan according to the formula, place them in the low temperature zone of the twin-screw extruder for mixing treatment until the mixture becomes a viscous paste and forms a flexible network core; ② Medium temperature zone (110℃): Add the environmentally friendly wax matrix, sodium copper chlorophyll salt and rosin glycerol ester pretreated in step (1) according to the ratio, and after medium temperature treatment, it is interspersed as a polar component between the flexible network core and the non-polar shell. ③ High temperature zone (130℃): The oleophilic nano silica and petroleum resin are premixed and ground according to the formula, and then mixed with modified calcium carbonate for high temperature treatment as a non-polar outer shell coating. ④ Mixing output zone (100℃): The melt is output through the static mixer.

[0021] The above-mentioned sodium copper chlorophyllin is encapsulated, and the specific process is as follows: A 5% sodium copper chlorophyllin solution was prepared by dissolving sodium copper chlorophyllin in a phosphate buffer solution at pH 8 in the dark. Then, β-cyclodextrin was dissolved in ultrapure water at 60°C until saturation was achieved, resulting in a saturated β-cyclodextrin solution. Finally, the sodium copper chlorophyllin solution was slowly added dropwise to the saturated β-cyclodextrin solution at a volume ratio of 1:4, and the mixture was stirred and reacted in the dark at 40°C for 2 hours to obtain encapsulated sodium copper chlorophyllin.

[0022] Example 2: A strong-adhesion environmentally friendly solid marking wax for marking ranch animals, comprising the following components in parts by weight: 60 parts environmentally friendly wax matrix, 27 parts hydrogenated castor oil, 3 parts erucamide, 10 parts rosin glycerol ester, 5 parts petroleum resin, 8 parts modified calcium carbonate, 5 parts sodium copper chlorophyllin, 3 parts nano silica and 1 part chitosan.

[0023] The environmentally friendly wax matrix comprises natural beeswax, candelilla wax, and microcrystalline wax in a weight ratio of 6:2:0.6; The acid value of the rosin glycerol ester is 5 mg KOH / g; The preparation process of the modified calcium carbonate is as follows: (1) Mix stearic acid and anhydrous ethanol at a weight ratio of 5:2, place in a 55°C water bath and stir until completely dissolved, then adjust the pH to 7; (2) Select calcium carbonate with a particle size of 2.5 μm to remove surface moisture, and then add 3.5% of the mass of calcium carbonate to the stearic acid ethanol solution in step (1). After mixing evenly, place it at 105℃ for 15 min, then adjust the temperature to 120℃, react for 20 min, and naturally cool to 60℃ to prepare modified calcium carbonate.

[0024] The preparation method of the above-mentioned strong-adhesion environmentally friendly solid marking wax for animal marking on ranches is as follows: (1) Environmentally friendly wax matrix pretreatment: The environmentally friendly wax matrix is ​​placed in a supercritical reactor, the CO2 pressure is adjusted to 10MPa, the temperature is 40℃, and the pressure is maintained for 2h. Then, the pressure is rapidly reduced to atmospheric pressure at a rate of 3MPa / s. (2) Gradient coupling of components: A twin-screw extruder is used to perform gradient coupling of polar and non-polar components in different zones, as follows: ① Low temperature zone (80℃): After mixing hydrogenated castor oil, erucamide and chitosan according to the formula, place them in the low temperature zone of the twin-screw extruder for mixing treatment until the mixture becomes a viscous paste and forms a flexible network core; ② Medium temperature zone (110℃): Add the environmentally friendly wax matrix, sodium copper chlorophyll salt and rosin glycerol ester pretreated in step (1) according to the ratio, and after medium temperature treatment, it is interspersed as a polar component between the flexible network core and the non-polar shell. ③ High temperature zone (130℃): The oleophilic nano silica and petroleum resin are premixed and ground according to the formula, and then mixed with modified calcium carbonate for high temperature treatment as a non-polar outer shell coating. ④ Mixing output zone (100℃): The melt is output through the static mixer.

[0025] The above-mentioned sodium copper chlorophyllin is encapsulated, and the specific process is as follows: A 5% sodium copper chlorophyllin solution was prepared by dissolving sodium copper chlorophyllin in a phosphate buffer solution at pH 8 in the dark. Then, β-cyclodextrin was dissolved in ultrapure water at 60°C until saturation was achieved, resulting in a saturated β-cyclodextrin solution. Finally, the sodium copper chlorophyllin solution was slowly added dropwise to the saturated β-cyclodextrin solution at a volume ratio of 1:4, and the mixture was stirred and reacted in the dark at 45°C for 3 hours to obtain encapsulated sodium copper chlorophyllin.

[0026] Example 3: A strong-adhesion environmentally friendly solid marking wax for marking ranch animals, comprising the following components in parts by weight: 45 parts environmentally friendly wax matrix, 20 parts hydrogenated castor oil, 2 parts erucamide, 8 parts rosin glycerol ester, 3 parts petroleum resin, 6 parts modified calcium carbonate, 3 parts sodium copper chlorophyllin, 2 parts nano silica and 0.5 parts chitosan.

[0027] The environmentally friendly wax matrix comprises natural beeswax, candelilla wax, and microcrystalline wax in a weight ratio of 5:2:0.5; The acid value of the rosin glycerol ester is 4 mg KOH / g; The preparation process of the modified calcium carbonate is as follows: (1) Mix stearic acid and anhydrous ethanol at a weight ratio of 4:1.5, place in a 50°C water bath and stir until completely dissolved, then adjust the pH to 6.5; (2) Select calcium carbonate with a particle size of 2.0 μm to remove surface moisture, and then add 3.2% of the mass of calcium carbonate to the stearic acid ethanol solution in step (1). After mixing evenly, place it at 105℃ for 15 min, then adjust the temperature to 115℃, react for 25 min, and naturally cool to 60℃ to prepare modified calcium carbonate.

[0028] The preparation method of the above-mentioned strong-adhesion environmentally friendly solid marking wax for animal marking on ranches is as follows: (1) Environmentally friendly wax matrix pretreatment: The environmentally friendly wax matrix is ​​placed in a supercritical reactor, the CO2 pressure is adjusted to 9MPa, the temperature is 38℃, and the pressure is maintained for 2h. Then, the pressure is rapidly reduced to atmospheric pressure at a rate of 4MPa / s. (2) Gradient coupling of components: A twin-screw extruder is used to perform gradient coupling of polar and non-polar components in different zones, as follows: ① Low temperature zone (80℃): After mixing hydrogenated castor oil, erucamide and chitosan according to the formula, place them in the low temperature zone of the twin-screw extruder for mixing treatment until the mixture becomes a viscous paste and forms a flexible network core; ② Medium temperature zone (110℃): Add the environmentally friendly wax matrix, sodium copper chlorophyll salt and rosin glycerol ester pretreated in step (1) according to the ratio, and after medium temperature treatment, it is interspersed as a polar component between the flexible network core and the non-polar shell. ③ High temperature zone (130℃): The oleophilic nano silica and petroleum resin are premixed and ground according to the formula, and then mixed with modified calcium carbonate for high temperature treatment as a non-polar outer shell coating. ④ Mixing output zone (100℃): The melt is output through the static mixer.

[0029] The above-mentioned sodium copper chlorophyllin is encapsulated, and the specific process is as follows: A 5% sodium copper chlorophyllin solution was prepared by dissolving sodium copper chlorophyllin in a phosphate buffer solution at pH 8 in the dark. Then, β-cyclodextrin was dissolved in ultrapure water at 60°C until saturation was achieved, resulting in a saturated β-cyclodextrin solution. Finally, the sodium copper chlorophyllin solution was slowly added dropwise to the saturated β-cyclodextrin solution at a volume ratio of 1:4, and the mixture was stirred and reacted at 42°C in the dark for 2.5 hours to obtain encapsulated sodium copper chlorophyllin.

[0030] Example 4: A strong-adhesion environmentally friendly solid marking wax for marking ranch animals, comprising the following components in parts by weight: 55 parts environmentally friendly wax matrix, 23 parts hydrogenated castor oil, 3 parts erucamide, 9 parts rosin glycerol ester, 4 parts petroleum resin, 7 parts modified calcium carbonate, 4 parts sodium copper chlorophyllin, 2.5 parts nano silica and 0.8 parts chitosan.

[0031] The environmentally friendly wax matrix comprises natural beeswax, candelilla wax, and microcrystalline wax in a weight ratio of 6:2:0.4. The acid value of the rosin glycerol ester is 3 mg KOH / g; The preparation process of the modified calcium carbonate is as follows: (1) Mix stearic acid and anhydrous ethanol in a weight ratio of 5:2, place in a 50°C water bath and stir until completely dissolved, then adjust the pH to 6.5; (2) Select calcium carbonate with a particle size of 2.5 μm to remove surface moisture, and then add 3.5% of the mass of calcium carbonate to the stearic acid ethanol solution in step (1). After mixing evenly, place it at 105℃ for 20 min, then adjust the temperature to 125℃, react for 20 min, and naturally cool to 60℃ to prepare modified calcium carbonate.

[0032] The preparation method of the above-mentioned strong-adhesion environmentally friendly solid marking wax for animal marking on ranches is as follows: (1) Environmentally friendly wax matrix pretreatment: The environmentally friendly wax matrix is ​​placed in a supercritical reactor, the CO2 pressure is adjusted to 8MPa, the temperature is 38℃, and the pressure is maintained for 2h. Then, the pressure is rapidly reduced to atmospheric pressure at a rate of 3MPa / s. (2) Gradient coupling of components: A twin-screw extruder is used to perform gradient coupling of polar and non-polar components in different zones, as follows: ① Low temperature zone (80℃): After mixing hydrogenated castor oil, erucamide and chitosan according to the formula, place them in the low temperature zone of the twin-screw extruder for mixing treatment until the mixture becomes a viscous paste and forms a flexible network core; ② Medium temperature zone (110℃): Add the environmentally friendly wax matrix, sodium copper chlorophyll salt and rosin glycerol ester pretreated in step (1) according to the ratio, and after medium temperature treatment, it is interspersed as a polar component between the flexible network core and the non-polar shell. ③ High temperature zone (130℃): The oleophilic nano silica and petroleum resin are premixed and ground according to the formula, and then mixed with modified calcium carbonate for high temperature treatment as a non-polar outer shell coating. ④ Mixing output zone (100℃): The melt is output through the static mixer.

[0033] The above-mentioned sodium copper chlorophyllin is encapsulated, and the specific process is as follows: Chlorophyll copper sodium salt was dissolved in phosphate buffer at pH 8 in the dark to prepare a 5% chlorophyllin copper sodium salt solution. Then, β-cyclodextrin was dissolved in ultrapure water at 60℃ until saturation to prepare a saturated β-cyclodextrin solution. Finally, the chlorophyllin copper sodium salt solution was slowly added dropwise to the β-cyclodextrin saturated solution at a volume ratio of 1:4, and the mixture was stirred and reacted in the dark at 43℃ for 3 hours to prepare encapsulated chlorophyllin copper sodium salt.

[0034] Example 5: A strong-adhesion environmentally friendly solid marking wax for animal marking on ranches, comprising the following components in parts by weight: 50 parts environmentally friendly wax matrix, 22 parts hydrogenated castor oil, 2 parts erucamide, 8 parts rosin glycerol ester, 3 parts petroleum resin, 6.5 parts modified calcium carbonate, 4 parts sodium copper chlorophyllin, 2 parts nano silica, and 0.6 parts chitosan.

[0035] The environmentally friendly wax matrix comprises natural beeswax, candelilla wax, and microcrystalline wax in a weight ratio of 5.5:2:0.4. The acid value of the rosin glycerol ester is 5 mg KOH / g; The preparation process of the modified calcium carbonate is as follows: (1) Mix stearic acid and anhydrous ethanol in a weight ratio of 4:2, place in a 55°C water bath and stir until completely dissolved, then adjust the pH to 7; (2) Select calcium carbonate with a particle size of 2.5 μm to remove surface moisture, and then add 3.0% of the mass of calcium carbonate to the stearic acid ethanol solution in step (1). After mixing evenly, place it at 105℃ for 15 min, then adjust the temperature to 120℃, react for 20 min, and cool naturally to 60℃ to prepare modified calcium carbonate.

[0036] The preparation method of the above-mentioned strong-adhesion environmentally friendly solid marking wax for animal marking on ranches is as follows: (1) Environmentally friendly wax matrix pretreatment: The environmentally friendly wax matrix is ​​placed in a supercritical reactor, the CO2 pressure is adjusted to 9MPa, the temperature is 39℃, and the pressure is maintained for 2h. Then, the pressure is rapidly reduced to atmospheric pressure at a rate of 4MPa / s. (2) Gradient coupling of components: A twin-screw extruder is used to perform gradient coupling of polar and non-polar components in different zones, as follows: ① Low temperature zone (80℃): After mixing hydrogenated castor oil, erucamide and chitosan according to the formula, place them in the low temperature zone of the twin-screw extruder for mixing treatment until the mixture becomes a viscous paste and forms a flexible network core; ② Medium temperature zone (110℃): Add the environmentally friendly wax matrix, sodium copper chlorophyll salt and rosin glycerol ester pretreated in step (1) according to the ratio, and after medium temperature treatment, it is interspersed as a polar component between the flexible network core and the non-polar shell. ③ High temperature zone (130℃): The oleophilic nano silica and petroleum resin are premixed and ground according to the formula, and then mixed with modified calcium carbonate for high temperature treatment as a non-polar outer shell coating. ④ Mixing output zone (100℃): The melt is output through the static mixer.

[0037] The above-mentioned sodium copper chlorophyllin is encapsulated, and the specific process is as follows: A 5% sodium copper chlorophyllin solution was prepared by dissolving sodium copper chlorophyllin in a phosphate buffer solution at pH 8 in the dark. Then, β-cyclodextrin was dissolved in ultrapure water at 60°C until saturation was achieved, resulting in a saturated β-cyclodextrin solution. Finally, the sodium copper chlorophyllin solution was slowly added dropwise to the saturated β-cyclodextrin solution at a volume ratio of 1:4, and the mixture was stirred and reacted at 42°C in the dark for 2.5 hours to obtain encapsulated sodium copper chlorophyllin.

[0038] Comparative Example 1 It is basically the same as Example 5, except that: The formulation of the strong-adhesion environmentally friendly solid marking wax used for marking ranch animals differs. The specific formulation of Comparative Example 1 is as follows: it includes the following components in parts by weight: 50 parts environmentally friendly wax matrix, 22 parts hydrogenated castor oil, 2 parts erucamide, 12 parts rosin glycerol ester, 3 parts petroleum resin, 6.5 parts modified calcium carbonate, 4 parts sodium copper chlorophyllin, 2 parts nano silica, and 0.6 parts chitosan.

[0039] Comparative Example 2 It is basically the same as Example 5, except that: The formulations of the strong-adhesion environmentally friendly solid marking wax used for marking ranch animals are different. In the specific formulation of Comparative Example 2, the weight ratio of natural beeswax, candelilla wax and microcrystalline wax in the environmentally friendly wax matrix is ​​6:0.5:0.8.

[0040] Comparative Example 3 It is basically the same as Example 5, except that: The formulations of the strong-adhesion environmentally friendly solid marking wax used for marking ranch animals are different. In the specific formulation of this Comparative Example 3, the weight ratio of natural beeswax, candelilla wax and microcrystalline wax in the environmentally friendly wax matrix is ​​6:3:0.2.

[0041] Comparative Example 4 It is basically the same as Example 5, except that: The formulation of the strong-adhesion environmentally friendly solid marking wax used for marking ranch animals is different. In the specific formulation of Comparative Example 4, the calcium carbonate is not modified.

[0042] Comparative Example 5 It is basically the same as Example 5, except that: The preparation methods for the strong-adhesion environmentally friendly solid marking wax used for marking ranch animals are different. In this comparative example 5, the environmentally friendly wax matrix was not pretreated during the preparation of the strong-adhesion environmentally friendly solid marking wax.

[0043] Comparative Example 6 It is basically the same as Example 5, except that: The preparation method of the strong adhesion environmentally friendly solid marking wax for animal marking in the ranch is different. In the preparation method of Comparative Example 6, the pressure reduction rate in step (1) is 1 MPa / s.

[0044] Comparative Example 7 It is basically the same as Example 5, except that: The preparation method of the strong adhesion environmentally friendly solid marking wax for animal marking in the ranch is different. In the preparation method of Comparative Example 7, the temperature in the low temperature zone is 80℃, the medium temperature zone is 100℃, and the high temperature zone is 120℃ in step (2).

[0045] Performance testing of solid marking wax To verify the performance of solid marking waxes prepared from different groups, adhesion (ASTM D3359 standard), elongation at break (-10℃ environment), and softening point (GB / T 4507 standard) tests were conducted under rainfall conditions. Simultaneously, biodegradation rate (ISO 17556 standard) was tested after 6 months. The experimental results are shown in Table 1. Table 1 Performance Tests of Different Groups of Solid Marking Wax

[0046] Results Analysis: As shown in Table 1, the solid marking waxes prepared in Examples 1-5 of the present invention have a longer adhesion time and better elongation at break compared with Comparative Examples 1-7. At the same time, they have a higher softening point, avoiding the influence of temperature on solid marking waxes and making them easier to use. Moreover, they can be effectively degraded within six months without affecting the environment or animals. Timely degradation avoids the mutual influence between new and old markings.

[0047] To further investigate the adhesion and removability of the marking waxes prepared in each group according to the present invention, the adhesion (GB / T 2792 standard) and peel strength of different groups on wool surfaces were measured. The experimental results are shown in Table 2. Table 2. Adhesion to Wool Surface and Hand Peelability of Different Groups of Solid Marking Wax

[0048] Results analysis: Compared with comparative examples 1-7, the solid marking waxes prepared in Examples 1-5 of this invention have better adhesion, and the peeling force is within the range that can effectively balance durability and operability. They can be torn off with moderate force without damaging the wool or leaving any residue.

[0049] Furthermore, based on the above research, this invention further investigated the abrasion resistance and skin irritation of each group of solid marking waxes. Abrasion resistance was tested using standard ISO 9352, and the retention rate was measured after 500 cycles of friction. Skin irritation was measured using standard ISO 10993-10. The experimental results are shown in Table 3. Table 3. Abrasion resistance and skin irritation of different groups of solid marking waxes for sheep.

[0050] Results analysis: As shown in Table 3, the solid marking waxes prepared in Examples 1-5 of the present invention have excellent abrasion resistance, which is significantly better than that of Comparative Examples 1-7; no skin irritation was observed in any group.

[0051] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0052] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A strong-adhesion, environmentally friendly solid marking wax for marking animals on ranches, characterized in that: It comprises the following components in parts by weight: 40-60 parts environmentally friendly wax matrix, 18-27 parts hydrogenated castor oil, 2-3 parts erucamide, 7-10 parts rosin glycerol ester, 3-5 parts petroleum resin, 5-8 parts modified calcium carbonate, 3-5 parts sodium copper chlorophyllin, 2-3 parts nano silica, and 0.5-1 part chitosan.

2. The strong-adhesion, environmentally friendly solid marking wax for marking ranch animals according to claim 1, characterized in that, It comprises the following components in parts by weight: 45-55 parts environmentally friendly wax matrix, 20-23 parts hydrogenated castor oil, 2-3 parts erucamide, 8-9 parts rosin glycerol ester, 3-4 parts petroleum resin, 6-7 parts modified calcium carbonate, 3-4 parts sodium copper chlorophyllin, 2-2.5 parts nano silica, and 0.5-0.8 parts chitosan.

3. The strong-adhesion, environmentally friendly solid marking wax for marking ranch animals according to claim 1 or 2, characterized in that, The environmentally friendly wax matrix comprises natural beeswax, candelilla wax, and microcrystalline wax in a weight ratio of 5-6:1-2:0.3-0.

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4. The strong-adhesion, environmentally friendly solid marking wax for marking ranch animals according to claim 1 or 2, characterized in that, The acid value of the rosin glycerol ester is ≤6 mg KOH / g; The preparation process of the modified calcium carbonate is as follows: Stearic acid and anhydrous ethanol are mixed in a weight ratio of 3-5:1-2, and stirred in a water bath at 45-55℃ until completely dissolved. The pH is then adjusted to 6-7. Select calcium carbonate with a particle size of 1-2.5 μm to remove surface moisture, then add 3-3.5% of the calcium carbonate mass to the stearic acid ethanol solution in step (1), mix evenly, and treat at 105℃ for 10-20 min. Then adjust the temperature to 115-125℃, react for 20-25 min, and naturally cool to 60℃ to prepare modified calcium carbonate.

5. The method for preparing the strong-adhesion environmentally friendly solid marking wax for marking pasture animals as described in any one of claims 1-4, characterized in that, Includes the following steps: Environmentally friendly wax matrix pretreatment: Place the environmentally friendly wax matrix in a supercritical reactor, adjust the CO2 pressure to 8-10 MPa, the temperature to 35-40℃, maintain the pressure for 1.5-2 hours, and then quickly release it to atmospheric pressure; Gradient coupling of components: A twin-screw extruder is used to perform gradient coupling of polar and non-polar components in different zones, as detailed below: ① Low temperature zone: After mixing hydrogenated castor oil, erucamide and chitosan according to the formula, place them in the low temperature zone of the twin-screw extruder for mixing treatment until the mixture becomes a viscous paste and forms a flexible network core; ② Medium temperature zone: Add the environmentally friendly wax matrix, sodium copper chlorophyll salt and rosin glycerol ester pretreated in step (1) according to the ratio, and after medium temperature treatment, it is interspersed as a polar component between the flexible network core and the non-polar shell; ③ High-temperature zone: Nano-silica, petroleum resin and modified calcium carbonate are added according to the formula, and after high-temperature treatment, it is used as a non-polar outer shell coating. ④ Mixing output area: The melt is output through the static mixer.

6. The method for preparing the strong-adhesion environmentally friendly solid marking wax for marking pasture animals according to claim 5, characterized in that, In step (1), the pressure is reduced to atmospheric pressure at a rate of ≥2MPa / s.

7. The method for preparing the strong-adhesion environmentally friendly solid marking wax for marking pasture animals according to claim 5, characterized in that, The temperature of the low-temperature zone in step (2) is 75-85℃; the temperature of the medium-temperature zone is 105-115℃; the temperature of the high-temperature zone is 125-135℃; and the temperature of the mixed output zone is 95-105℃. In step (2), ② chlorophyll copper sodium salt is encapsulated, and the specific process is as follows: Chlorophyll copper sodium salt was dissolved in a phosphate buffer solution with a pH of 8 in the dark to prepare a 5% chlorophyllin copper sodium salt solution. Then, β-cyclodextrin was dissolved in ultrapure water at 60℃ until saturation to prepare a saturated β-cyclodextrin solution. Finally, the chlorophyllin copper sodium salt solution was slowly added dropwise to the β-cyclodextrin saturated solution at a volume ratio of 1:4, and the mixture was placed at 40-45℃ and stirred in the dark for 2-3 hours to prepare encapsulated chlorophyllin copper sodium salt.

8. The method for preparing the strong-adhesion environmentally friendly solid marking wax for marking pasture animals according to claim 5, characterized in that, In step (2), ③ firstly, nano-silica and petroleum resin are premixed and ground, then mixed with modified calcium carbonate and subjected to high-temperature treatment.

9. The method for preparing the strong-adhesion environmentally friendly solid marking wax for marking pasture animals according to claim 8, characterized in that, In step (2), ③ nano-silica is oleophilic nano-silica.

10. The application of the method according to any one of claims 5-9 in the preparation of a strong-adhesion environmentally friendly solid marking wax for ranch animal marking.

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