Sublimation ink, preparation method thereof and medical PET (Polyethylene Terephthalate) material

Abstract

The invention relates to sublimation ink, a preparation method thereof and a medical PET material, and belongs to the technical field of ink. The sublimation ink comprises the following components: pigment color paste, modified polyurethane, a surfactant, an organic solvent and deionized water. The silver ion polyurethane coating on the surface of the PET base material can provide a broad-spectrum antibacterial basis through the slow release effect of silver ions; the ink with the outer layer containing the modified polyurethane further inhibits microbial attachment and biofilm formation through mechanisms such as charge adsorption, interference and destruction of microbial reproduction and the like, different strains are covered with double antibacterial mechanisms, and the antibacterial time efficiency is prolonged; due to the antibacterial property of the layered structure formed by the ink, the pollution loophole of a traditional printing identification area is avoided, and the ink is particularly suitable for high-infection-risk scenes such as surgical instrument packaging and reusable consumables.

Description

Technical Field

[0001] The present invention belongs to the technical field of inks, and relates to a thermal sublimation ink, a preparation method thereof, and a medical PET material. Background Art

[0002] Although the antibacterial layer (a polyurethane coating containing silver ions) of the medical PET material has a basic antibacterial function, since the thermal sublimation ink is directly sprayed on the surface of the antibacterial layer to form an outer layer. If the ink itself does not contain antibacterial components, its porosity or organic components may become a breeding ground for microbial attachment. Especially in a high-infection-risk environment in medical treatment, a single antibacterial layer cannot completely block the risk of outer layer contamination. During the use of the material, the ink layer may be partially peeled off due to friction, scratching, or long-term contact with liquid, exposing the underlying antibacterial layer. If the ink has no antibacterial property, the damaged area may cause infection due to direct contact between microorganisms and the substrate.

[0003] Chitosan is a marine biomass material that has received extensive attention due to its abundant reserves, sustainability, ease of physical or chemical modification, and relatively low and stable cost. However, its application in polyurethane is limited by its high molecular weight and relatively low reactivity. Chitosan oligosaccharide is an antibacterial, biodegradable, hydrophilic, and adhesive polymer. Chitosan oligosaccharide can be modified by acylation, etherification, esterification, crosslinking, graft copolymerization, carboxymethylation, etc. Moreover, due to its low molecular weight and low degree of polymerization, chitosan oligosaccharide also has excellent water solubility, solubility in organic solvents, better antibacterial properties, biocompatibility, etc. In addition, chitosan oligosaccharide contains a large number of functional groups such as hydroxyl and amino groups, which can replace part of the polyol as a raw material for synthesizing polyurethane. Using chitosan oligosaccharide and its derivatives as raw materials for synthesizing polyurethane can not only reduce production costs but also improve the performance of polyurethane materials and increase added value. Summary of the Invention

[0004] The purpose of the present invention is to provide a thermal sublimation ink, a preparation method thereof, and a medical PET material. The silver ion polyurethane coating on the surface of the PET substrate material of the present invention can provide a broad-spectrum antibacterial basis through the slow release of silver ions; the ink containing modified polyurethane in the outer layer further inhibits microbial attachment and biofilm formation through mechanisms such as charge adsorption and interference with the destruction of microbial reproduction. The dual antibacterial mechanisms cover different strains of bacteria, and the antibacterial time effect is extended; the antibacterial property of the ink forming a layered structure itself avoids the traditional printed identification area from becoming a pollution loophole, and is especially suitable for high-infection-risk scenarios such as surgical instrument packaging and reusable consumables.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A sublimation ink comprises the following components by weight parts: 30-40 parts of pigment paste, 15-18 parts of modified polyurethane, 1-3 parts of surfactant, 15-21 parts of organic solvent and 40-50 parts of deionized water.

[0006] As a preferred technical solution of the present invention, the surfactant is one or more of BYK-019 and BYK-028.

[0007] As a preferred technical solution of the present invention, the organic solvent is one or more of 1,3-propanediol, glycerol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, triethylene glycol monobutyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol tert-butyl ether, propylene glycol monoethyl ether and diethylene glycol monomethyl ether.

[0008] As a preferred technical solution of the present invention, in the examples and comparative examples of the present invention, the surfactant used is BYK-019, and the organic solvent is composed of 1,3-propanediol, glycerol and triethylene glycol monobutyl ether mixed in a mass ratio of 9:16:3.

[0009] As a preferred technical solution of the present invention, the pigment paste is selected from common pigment yellow, pigment orange and pigment red orange. The surface of the Schiff base compound can adsorb the pigment through hydrogen bonding or coordination to improve its dispersibility.

[0010] As a preferred technical solution of the present invention, the pigment paste used in the examples and comparative examples of the present invention is pigment yellow 151.

[0011] As a preferred technical solution of the present invention, the preparation method of the modified polyurethane comprises the following steps: Step A1: Vacuum dehydrate the polyether diol, preheat it, add isophorone diisocyanate and a catalyst and stir to mix to obtain a prepolymer; Step A2: Continue to stir the prepolymer, dimethylol carboxylic acid and functional filler, add butanediol and mix well, then cool down, add triethylamine and deionized water and perform ultrasonic treatment to obtain the modified polyurethane.

[0012] As a preferred technical solution of the present invention, in step A1, the vacuum dehydration is to remove water by vacuum pumping at 105-110°C and 0.09 MPa for 1 h; the preheating is to heat up to 70-75°C; the stirring and mixing time is 1.0-1.5 h.

[0013] As a preferred technical solution of the present invention, the mass ratio of the polyether diol, isophorone diisocyanate and the catalyst is 10-15:5-7:0.07-0.08; the polyether diol is PPG3000; the catalyst is an organotin catalyst, dibutyltin dilaurate.

[0014] As a preferred technical solution of the present invention, in step A2, the continuous stirring is carried out at 60 - 80 °C and 300 - 500 rpm for 1.5 - 2.0 h; the temperature reduction is to reduce the temperature to 35 - 50 °C; the ultrasonic treatment is carried out at a power of 120 - 180 W for 30 - 45 min.

[0015] As a preferred technical solution of the present invention, in step A2, the mass ratio of the prepolymer, dimethylol carboxylic acid, functional filler, butanediol, triethylamine and deionized water is 60 - 70:2.0 - 2.5:2.8 - 3.2:1.6 - 2.4:8 - 10:120 - 130; the dimethylol carboxylic acid is 2,2 - dimethylolbutyric acid.

[0016] As a preferred technical solution of the present invention, the preparation method of the functional filler includes the following steps: S1. Carry out temperature - controlled reflux treatment on fumed silica and nitric acid solution, filter, take the solid matter for washing and drying to obtain pre - prepared silica; S2. Mix the pre - prepared silica, chitosan oligosaccharide and acetic acid solution, carry out ultrasonic dispersion treatment, slowly add the salicylaldehyde derivative solution, heat and stir, filter to remove the supernatant, wash and dry to obtain the product.

[0017] As a preferred technical solution of the present invention, in step S1, the temperature - controlled reflux treatment is carried out at 65 °C for 2 - 3 h; the washing is carried out with deionized water until neutral; the drying is carried out at 80 °C for 8 - 10 h; the dosage ratio of the fumed silica and the nitric acid solution is 10 - 11 g:18 - 21 mL; the concentration of the nitric acid solution is 5 mol / L.

[0018] As a preferred technical solution of the present invention, in step S2, the ultrasonic dispersion treatment is carried out at a power of 200 - 300 W for 20 - 30 min; the heating and stirring is carried out at 45 - 55 °C for 4 - 5 h.

[0019] As a preferred technical solution of the present invention, in step S2, the dosage ratio of the pre - prepared silica, chitosan oligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 15 - 18 g:1.6 - 2.0 g:70 - 80 mL:10 - 11 mL.

[0020] As a preferred technical solution of the present invention, in the present invention, chitosan oligosaccharide in the Schiff base compound forms a covalent bond connection with polyurethane isocyanate through hydroxyl / amino group. At the same time, the silica nanoparticles act as rigid fillers, significantly improving the adhesion between the ink layer and the antibacterial layer, avoiding delamination or peeling. While improving the antibacterial performance, the ink layer material formed remains intact after repeated friction, autoclaving or liquid immersion, and the wear resistance is improved.

[0021] As a preferred technical solution of the present invention, in step S2, the molecular weight of the chitosan oligosaccharide is 2500-3000 Da; the mass fraction of the acetic acid solution is 1%, and the solvent is deionized water.

[0022] As a preferred technical solution of the present invention, in step S2, the salicylaldehyde derivative solution is composed of a salicylaldehyde derivative and absolute ethanol in a mass ratio of 1:10; the salicylaldehyde derivative is one or both of 4-fluorosalicylaldehyde and 5-fluorosalicylaldehyde; the fluorinated salicylaldehyde can form a hydrophobic barrier in the performance ink layer. Specifically, the introduction of fluorinated salicylaldehyde reduces the surface energy, forms a hydrophobic interface, reduces liquid penetration and chemical corrosion, and at the same time inhibits the proliferation of microorganisms in a humid environment, and also improves the stability of the antibacterial material.

[0023] As a preferred technical solution of the present invention, a medical PET material formed by using the thermal sublimation ink as described above, the medical PET material includes a medical matrix material, an antibacterial layer is provided on the surface of the medical matrix material, and the thermal sublimation ink is sprayed on the surface of the antibacterial layer and forms the layered structure after drying; the medical matrix material is made of a PET resin material; the antibacterial layer is a polyurethane coating containing silver ions.

[0024] As a preferred technical solution of the present invention, a medical PET material formed by using the thermal sublimation ink as described above, the medical PET material includes a medical matrix material, an antibacterial layer is provided on the surface of the medical matrix material, and the thermal sublimation ink is sprayed on the surface of the antibacterial layer and forms the layered structure after drying; the medical matrix material is made of a PET resin material; the antibacterial layer is a polyurethane coating containing silver ions.

[0025] Advantages of the present invention: The silver ion polyurethane coating on the surface of the PET base material of the present invention can provide a broad-spectrum antibacterial basis through the slow release of silver ions (Ag⁺); the ink containing modified polyurethane in the outer layer further inhibits the attachment of microorganisms and the formation of biofilms through mechanisms such as charge adsorption and interference with the destruction of microbial reproduction. The dual antibacterial mechanisms cover different bacterial species, and the antibacterial time effect is extended; the antibacterial property of the ink forming the layered structure itself avoids the traditional printed identification area from becoming a pollution loophole, and is particularly suitable for high-infection-risk scenarios such as surgical instrument packaging and reusable consumables. Detailed implementation manners

[0026] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following combines examples to detail the specific implementation manners, structures, features and their effects according to the present invention. Example 1

[0027] A sublimation ink comprises the following components by weight parts: 30 parts of pigment paste, 15 parts of modified polyurethane, 1 part of surfactant, 15 parts of organic solvent and 40 parts of deionized water; Among them, the preparation method of the modified polyurethane comprises the following steps: Step A1: Vacuum dehydrate polyether diol at 105 °C and 0.09 MPa for 1 h, heat up to 70 °C, add isophorone diisocyanate and dibutyltin dilaurate and stir and mix for 1.0 h to obtain a prepolymer; the mass ratio of polyether diol, isophorone diisocyanate and dibutyltin dilaurate is 10:5:0.07; the polyether diol is PPG3000; Step A2: Continue to stir the prepolymer, dimethylol carboxylic acid and functional filler at 60 °C and 300 rpm for 1.5 h, add butanediol and mix evenly, cool down to 35 °C, add triethylamine and deionized water and perform ultrasonic treatment at a power of 120 W for 30 min to obtain modified polyurethane; the mass ratio of prepolymer, dimethylol carboxylic acid, functional filler, butanediol, triethylamine and deionized water is 60:2.0:2.8:1.6:8:120; the dimethylol carboxylic acid is 2,2-dimethylolbutyric acid; The preparation method of the functional filler comprises the following steps: S1: Reflux and treat fumed silica and nitric acid solution at 65 °C for 2 h, filter, take the solid matter and wash it with deionized water until neutral, and dry it at 80 °C for 8 h to obtain prefabricated silica; the dosage ratio of fumed silica and nitric acid solution is 10 g:18 mL; the concentration of the nitric acid solution is 5 mol / L; S2: Mix the prefabricated silica, chitosan oligosaccharide and acetic acid solution, perform ultrasonic treatment at a power of 200 W for 20 min, slowly add the salicylaldehyde derivative solution and stir at 45 °C for 4 h, filter off the supernatant, rinse it with absolute ethanol 3 times, and dry it at 90 °C to constant weight to obtain it; the dosage ratio of prefabricated silica, chitosan oligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 15 g:1.6 g:70 mL:10 mL; the molecular weight of chitosan oligosaccharide is 2500 Da; the mass fraction of the acetic acid solution is 1%; the salicylaldehyde derivative solution is composed of salicylaldehyde derivative and absolute ethanol according to a mass ratio of 1:10; the salicylaldehyde derivative is 4-fluorosalicylaldehyde; A preparation method of sublimation ink comprises the following steps: Under the condition of stirring at a speed of 400 rpm, sequentially add pigment paste, organic solvent, modified polyurethane and surfactant into deionized water and stir and mix evenly, use zirconium beads with a particle size of 0.3 mm to grind at a speed of 1500 rpm for 4 h, and filter through a 0.45 μm microporous filter membrane to obtain sublimation ink. Example 2

[0028] A sublimation ink comprises the following components by weight parts: 35 parts of pigment paste, 16 parts of modified polyurethane, 2 parts of surfactant, 18 parts of organic solvent, and 45 parts of deionized water; Among them, the preparation method of the modified polyurethane includes the following steps: Step A1: Vacuum dehydrate polyether diol at 108°C and 0.09 MPa for 1 h, heat up to 72°C, add isophorone diisocyanate and dibutyltin dilaurate, and stir and mix for 1.2 h to obtain a prepolymer; the mass ratio of polyether diol, isophorone diisocyanate, and dibutyltin dilaurate is 12:6:0.075; the polyether diol is PPG3000; Step A2: Continue to stir the prepolymer, dimethylol carboxylic acid, and functional filler at 70°C and 400 rpm for 1.8 h, add butanediol and mix evenly, cool down to 42°C, add triethylamine and deionized water, and perform ultrasonic treatment at a power of 150 W for 38 min to obtain modified polyurethane; the mass ratio of prepolymer, dimethylol carboxylic acid, functional filler, butanediol, triethylamine, and deionized water is 65:2.2:3:2:9:125; the dimethylol carboxylic acid is 2,2-dimethylol butyric acid; The preparation method of the functional filler includes the following steps: S1: Reflux treat fumed silica and nitric acid solution at 65°C for 2.5 h, filter, wash the solid matter with deionized water until neutral, and dry at 80°C for 9 h to obtain prefabricated silica; the dosage ratio of fumed silica and nitric acid solution is 10.5 g:20 mL; the concentration of the nitric acid solution is 5 mol / L; S2: Mix the prefabricated silica, chitosan oligosaccharide, and acetic acid solution, perform ultrasonic treatment at a power of 250 W for 25 min, slowly add the salicylaldehyde derivative solution, and stir at 50°C for 4.5 h, filter off the supernatant, wash 3 times with absolute ethanol, and dry at 90°C to constant weight to obtain it; the dosage ratio of prefabricated silica, chitosan oligosaccharide, acetic acid solution, and salicylaldehyde derivative solution is 16 g:1.8 g:75 mL:10.5 mL; the molecular weight of chitosan oligosaccharide is 2750 Da; the mass fraction of the acetic acid solution is 1%; the salicylaldehyde derivative solution is composed of salicylaldehyde derivative and absolute ethanol in a mass ratio of 1:10; the salicylaldehyde derivative is 4-fluorosalicylaldehyde; A preparation method of a sublimation ink includes the following steps: Under the stirring condition of 400 rpm, sequentially add pigment paste, organic solvent, modified polyurethane, and surfactant to deionized water, stir and mix evenly, use zirconium beads with a particle size of 0.3 mm to grind at a speed of 1650 rpm for 4 h, and filter through a 0.45 μm microporous membrane to obtain sublimation ink. Example 3

[0029] A sublimation ink comprises the following components by weight parts: 40 parts of pigment paste, 18 parts of modified polyurethane, 3 parts of surfactant, 21 parts of organic solvent and 50 parts of deionized water; Among them, the preparation method of the modified polyurethane comprises the following steps: Step A1: Vacuum dehydrate polyether diol at 110°C and 0.09 MPa for 1 h, heat up to 75°C, add isophorone diisocyanate and dibutyltin dilaurate and stir and mix for 1.5 h to obtain a prepolymer; the mass ratio of polyether diol, isophorone diisocyanate and dibutyltin dilaurate is 15:7:0.08; the polyether diol is PPG3000; Step A2: Continue to stir the prepolymer, dimethylol carboxylic acid and functional filler at 80°C and 500 rpm for 2.0 h, add butanediol and mix evenly, cool down to 50°C, add triethylamine and deionized water and perform ultrasonic treatment at a power of 180 W for 45 min to obtain modified polyurethane; the mass ratio of prepolymer, dimethylol carboxylic acid, functional filler, butanediol, triethylamine and deionized water is 70:2.5:3.2:2.4:10:130; the dimethylol carboxylic acid is 2,2-dimethylol butyric acid; The preparation method of the functional filler comprises the following steps: S1: Reflux and treat fumed silica and nitric acid solution at 65°C for 3 h, filter, wash the solid matter with deionized water until neutral, and dry at 80°C for 10 h to obtain prefabricated silica; the dosage ratio of fumed silica and nitric acid solution is 11 g:21 mL; the concentration of the nitric acid solution is 5 mol / L; S2: Mix the prefabricated silica, chitosan oligosaccharide and acetic acid solution, perform ultrasonic treatment at a power of 300 W for 30 min, slowly add the salicylaldehyde derivative solution and stir at 55°C for 5 h, filter off the supernatant, rinse with absolute ethanol 3 times, and dry at 90°C to constant weight to obtain it; the dosage ratio of prefabricated silica, chitosan oligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 18 g:2.0 g:80 mL:11 mL; the molecular weight of chitosan oligosaccharide is 3000 Da; the mass fraction of the acetic acid solution is 1%; the salicylaldehyde derivative solution is composed of salicylaldehyde derivative and absolute ethanol according to a mass ratio of 1:10; the salicylaldehyde derivative is 4-fluorosalicylaldehyde; A preparation method of a sublimation ink comprises the following steps: Under the condition of stirring at a speed of 400 rpm, sequentially add pigment paste, organic solvent, modified polyurethane and surfactant to deionized water and stir and mix evenly, use zirconium beads with a particle size of 0.3 mm to grind at a speed of 1800 rpm for 4 h, and filter through a 0.45 μm microporous filter membrane to obtain sublimation ink.

[0030] Comparative Example 1 Compared with Example 3, the difference in Comparative Example 1 is that diphenylmethane diisocyanate is used instead of isophorone diisocyanate in step A1 of Comparative Example 1, and the rest are the same.

[0031] Comparative Example 2 Compared with Example 3, the difference in Comparative Example 2 is that the dihydroxymethyl carboxylic acid in step A2 of Comparative Example 2 is 2,2-dihydroxymethylpropionic acid, and the rest are the same.

[0032] Comparative Example 3 Compared with Example 3, the difference in Comparative Example 3 is that step S1 is not carried out. In step S2, fumed silica is used instead of prefabricated silica, and the rest are the same.

[0033] Comparative Example 4 Compared with Example 3, the difference in Comparative Example 4 is that chitosan oligosaccharide is not used in step S2 of Comparative Example 4, and the rest are the same.

[0034] Comparative Example 5 Compared with Example 3, the difference in Comparative Example 5 is that salicylaldehyde is used instead of salicylaldehyde derivative in step S2 of Comparative Example 5, and the rest are the same.

[0035] Comparative Example 6 Compared with Example 3, the difference in Comparative Example 6 is that salicylaldehyde derivative is not used in step S2 of Comparative Example 6, and the rest are the same.

[0036] Examples 1-3 and Comparative Examples 1-6 were respectively subjected to the following performance tests.

[0037] The antibacterial effect of the ink was qualitatively examined by the inhibition zone method. The bacterial strains used were Staphylococcus aureus and Escherichia coli, and the inhibition rate was tested for 48 h. The test results are shown in Table 1; Table 1 (Inhibition rate test results)

[0038] As can be seen from the test results in Table 1, compared with Comparative Examples 1-6, the ink prepared by the present invention has a very high inhibition rate against Staphylococcus aureus and Escherichia coli microorganisms.

[0039] The adhesion test was carried out according to the provisions of GB / T9286; the sample was treated by the 1-mm cross-cut method, and the test results are shown in Table 2.

[0040] Table 2 (Adhesion test results)

[0041] From the test results in Table 2, it can be seen that compared with Comparative Examples 1-6, the adhesion of the ink prepared by the present invention to the substrate is significantly better than that of Comparative Examples 1-6, and it has excellent scratch-resistant mechanical properties.

[0042] Through comparative analysis, it can be known that the dimethylolbutyric acid used in the present invention is more soluble in polyols and hot water than dimethylolpropionic acid, and it also has better hydrophilicity. When only part of the dimethylolpropionic acid is dissolved in the system, the interaction force between its carboxyl group and the hydroxyl group on the functional filler decreases, resulting in a decrease in the dispersibility of the functional filler in the polyurethane system. Moreover, when dimethylolpropionic acid is used as a chain extender, the reaction is incomplete, and the crosslinking density of the polyurethane material decreases, leading to a decrease in both the mechanical properties and antibacterial properties of the ink layer; diphenylmethane diisocyanate contains multiple benzene ring structures compared with isophorone diisocyanate, and its steric hindrance is large, which limits the fluidity of the functional filler in the system, affects the uniformity of the antibacterial functional filler, and the crosslinking degree of the polyurethane decreases, resulting in a decrease in its performance.

[0043] In the present invention, nitric acid is used to carry out acid leaching and oxidation on fumed silica to activate the surface hydroxyl groups, improve its purity, dispersibility and reaction activity as a sustained-release carrier. More hydroxyl groups are beneficial to the organic coating effect of chitosan oligosaccharide and salicylaldehyde derivatives. The Schiff base compound formed by chitosan oligosaccharide and fluorinated salicylaldehyde can effectively coat silica, increasing the dispersibility of silica in polyurethane. At the same time, the Schiff base structure can also adsorb the organic pigments in the pigment paste, making the organic pigments not easy to migrate and also improving the mechanical properties of the ink layer; in addition, the amino and hydroxyl groups on chitosan oligosaccharide can form a molecular crosslinking network through chemical bond binding in polyurethane, effectively improving the mechanical properties and antibacterial properties of the ink layer. The phenolic hydroxyl group on fluorinated salicylaldehyde can interact with dimethylolbutyric acid through hydrogen bonds, further increasing the dispersibility of silica. The present invention also utilizes the rigid benzene ring of fluorinated salicylaldehyde to form a rigid chain on chitosan oligosaccharide, increasing the mechanical properties of the ink. At the same time, the introduction of the hydrophobic benzene ring structure and fluorine element can increase the contact between the antibacterial Schiff base compound and microorganisms and destroy their structure, further improving the antibacterial properties of the material.

[0044] The above are only the preferred embodiments of the present invention, and there is no any form of limitation to the present invention. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or equivalent changes and modifications within the scope of the technical solution of the present invention. However, as long as it does not depart from the technical solution content of the present invention, any indirect modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A thermal sublimation ink, characterized in that: The following components are included by weight: 30-40 parts of pigment paste, 15-18 parts of modified polyurethane, 1-3 parts of surfactant, 15-21 parts of organic solvent and 40-50 parts of deionized water; Wherein, the preparation method of the modified polyurethane comprises the following steps: Step A1, vacuum dehydrating the polyether diol, preheating, adding isophorone diisocyanate and a catalyst, stirring and mixing, to obtain a prepolymer; Step A2, continue stirring the prepolymer, dihydroxymethyl carboxylic acid and functional filler, add butanediol and mix well, then cool down, add triethylamine and deionized water for ultrasonic treatment, and obtain modified polyurethane.

2. A thermal sublimation ink according to claim 1, characterized in that: In step A1, the vacuum dehydration is to remove water by vacuuming at 105-110° C. and 0.09 MPa for 1 hour; the preheating is to heat to 70-75° C.; the stirring and mixing time is 1.0-1.5 hours; the mass ratio of the polyether diol, isophorone diisocyanate and the catalyst is 10-15:5-7:0.07-0.08; the polyether diol is PPG3000; and the catalyst is an organic tin catalyst.

3. The thermal sublimation ink according to claim 1, characterized in that: In step A2, the continued stirring is continued stirring at 60-80° C. and 300-500 rpm for 1.5-2.0 h; the cooling is cooling to 35-50° C.; and the ultrasonic treatment is ultrasonic treatment at a power of 120-180 W for 30-45 min.

4. The thermal sublimation ink according to claim 1, characterized in that: In step A2, the mass ratio of the prepolymer, dihydroxymethyl carboxylic acid, functional filler, butanediol, triethylamine and deionized water is 60-70: 2.0-2.5:2.8-3.2:1.6-2.4:8-10:120-130; the dihydroxymethyl carboxylic acid is 2,2-dihydroxymethyl butyric acid.

5. The thermal sublimation ink according to claim 1, characterized in that: The preparation method of the functional filler comprises the following steps: S1, reflux the fumed silica and nitric acid solution under controlled temperature, filter, wash and dry the solid to obtain prefabricated silica; S2. Mix the prefabricated silicon dioxide, chitosan oligosaccharide and acetic acid solution, perform ultrasonic dispersion treatment, slowly add the salicylaldehyde derivative solution, heat and stir, filter to remove the supernatant, wash and dry to obtain.

6. A thermal sublimation ink according to claim 5, characterized in that: In step S1, the temperature-controlled reflux treatment is reflux treatment at 65°C for 2-3h; the washing is washing with deionized water until neutral; the drying is drying at 80°C for 8-10h; the usage ratio of the fumed silica and the nitric acid solution is 10-11g:18-21mL; the concentration of the nitric acid solution is 5mol / L.

7. The thermal sublimation ink according to claim 5, characterized in that: In step S2, the ultrasonic dispersion treatment is 200-300W power ultrasound for 20-30min; the heating stirring is stirring at 45-55°C for 4-5h; the dosage ratio of the prefabricated silica, chitosan oligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 15-18g:1.6-2.0g:70-80mL:10-11mL.

8. The thermal sublimation ink according to claim 5, characterized in that: In step S2, the molecular weight of the chitosan oligosaccharide is 2500-3000Da; the mass fraction of the acetic acid solution is 1%; the salicylaldehyde derivative solution is composed of salicylaldehyde derivative and anhydrous ethanol in a mass ratio of 1:10; the salicylaldehyde derivative is one or both of 4-fluorosalicylaldehyde and 5-fluorosalicylaldehyde.

9. A method for preparing a thermal sublimation ink according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: adding pigment paste, organic solvent, modified polyurethane and surfactant into deionized water in sequence under stirring conditions, stirring and mixing evenly, grinding, and filtering through a 0.45 μm microporous filter membrane to obtain thermal sublimation ink.

10. A medical PET material formed by using the thermal sublimation ink according to any one of claims 1 to 8, characterized in that: The medical PET material comprises a medical base material, an antibacterial layer is provided on the surface of the medical base material, the thermal sublimation ink is sprayed on the surface of the antibacterial layer and forms the layered structure after drying; the medical base material is made of PET resin material; the antibacterial layer is a polyurethane coating containing silver ions.

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