A heat transfer printing ink, a method for preparing the same and a medical PET material

Abstract

The present application relates to a kind of heat sublimation ink and its preparation method and medical PET material, belong to the technical field of ink.A kind of heat sublimation ink includes the following components: pigment paste, modified polyurethane, surfactant, organic solvent and deionized water.The silver ion polyurethane coating of the PET substrate material surface of the present application, can provide broad-spectrum antibacterial basis by the slow-release effect of silver ion;Outer layer ink containing modified polyurethane further inhibits microbial adhesion and biofilm formation by charge adsorption, interference and destruction of microbial reproduction mechanism, double antibacterial mechanism covers different bacteria, and the antibacterial time efficiency is prolonged;The self-antibacterial property of ink formation layered structure avoids that traditional printing mark area becomes pollution loophole, especially suitable for surgical instrument packaging, reusable consumables and other high-risk infection scenarios.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ink, and relates to a heat sublimation ink and a preparation method thereof and a medical PET material. BACKGROUND

[0002] Although the antibacterial layer (a polyurethane coating containing silver ions) of the medical PET material has basic antibacterial function, the outer layer is formed by directly spraying the heat sublimation ink on the surface of the antibacterial layer. If the ink itself does not contain antibacterial components, the porosity or organic components of the ink may become a breeding ground for microorganisms, especially in a medical environment with high infection risk, a single antibacterial layer cannot completely block the pollution risk of the outer layer. During the use of the material, the ink layer may be partially peeled off due to friction, scratches 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 of microorganisms with the substrate.

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

[0004] The purpose of the present application is to provide a heat sublimation ink and 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 application can provide broad-spectrum antibacterial foundation through the slow release of silver ions. The outer layer containing modified polyurethane further inhibits the attachment of microorganisms and the formation of biofilms through mechanisms such as charge adsorption and interference with microbial reproduction, covering different bacteria with double antibacterial mechanisms and prolonging the antibacterial time. The antibacterial property of the layer structure formed by the ink avoids the traditional printed marking 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 application can be achieved by the following technical solutions:

[0006] A heat sublimation ink comprises the following components in parts by weight: pigment paste 30-40 parts, modified polyurethane 15-18 parts, surfactant 1-3 parts, organic solvent 15-21 parts and deionized water 40-50 parts.

[0007] As a preferred technical solution of the present application, the surfactant is one or more of BYK-019 and BYK-028.

[0008] As a preferred technical solution of the present application, 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.

[0009] As a preferred technical solution of the present application, the surfactant is BYK-019, and the organic solvent is a mixture of 1,3-propanediol, glycerol and triethylene glycol monobutyl ether in a mass ratio of 9:16:3.

[0010] As a preferred technical solution of the present application, the pigment paste is selected from common pigments yellow, orange and orange red, and the surface of the Schiff base compound can adsorb the pigment through hydrogen bonding or coordination, thereby improving the dispersibility.

[0011] As a preferred technical solution of the present application, the pigment paste used in the examples and comparative examples of the present application is pigment yellow 151.

[0012] As a preferred technical solution of the present application, the preparation method of the modified polyurethane comprises the following steps:

[0013] Step A1, vacuum dehydration of polyether glycol, preheating, adding isophorone diisocyanate and catalyst and stirring to obtain a prepolymer;

[0014] Step A2, continuing to stir the prepolymer, dimethylol carboxylic acid and functional filler, mixing uniformly after adding butanediol, cooling, adding triethylamine and deionized water and ultrasonic treatment to obtain the modified polyurethane.

[0015] As a preferred technical solution of the present application, in step A1, the vacuum dehydration is carried out at 105-110℃ under 0.09MPa for 1h; the preheating is heating to 70-75℃; and the stirring time is 1.0-1.5h.

[0016] As a preferred technical scheme of the present application, the mass ratio of the polyether glycol, isophorone diisocyanate and catalyst is 10-15:5-7:0.07-0.08; the polyether glycol is PPG3000; and the catalyst is an organic tin catalyst, dibutyltin dilaurate.

[0017] As a preferred technical scheme of the present application, in step A2, the continuous stirring is continued at 60-80℃, 300-500rpm for 1.5-2.0h; the cooling is to 35-50℃; and the ultrasonic treatment is at a power of 120-180W for 30-45min.

[0018] As a preferred technical scheme of the present application, 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; and the dimethylol carboxylic acid is 2,2-dimethylol butyric acid.

[0019] As a preferred technical scheme of the present application, the preparation method of the functional filler comprises the following steps:

[0020] S1, the fumed silica is treated by temperature-controlled reflux with a nitric acid solution, filtered, the solid is washed and dried to obtain pre-prepared silica;

[0021] S2, the pre-prepared silica, chitooligosaccharide and acetic acid solution are mixed, ultrasonically dispersed, a salicylaldehyde derivative solution is slowly added, heated and stirred, the supernatant is removed by filtration, washed and dried.

[0022] As a preferred technical scheme of the present application, in step S1, the temperature-controlled reflux treatment is at 65℃ for 2-3h; the washing is with deionized water until neutral; the drying is at 80℃ for 8-10h; the amount ratio of the fumed silica to the nitric acid solution is 10-11g:18-21mL; and the concentration of the nitric acid solution is 5mol / L.

[0023] As a preferred technical scheme of the present application, in step S2, the ultrasonic dispersion treatment is at a power of 200-300W for 20-30min; and the heating and stirring is at 45-55℃ for 4-5h.

[0024] As a preferred technical scheme of the present application, in step S2, the amount ratio of the pre-prepared silica, chitooligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 15-18g:1.6-2.0g:70-80mL:10-11mL.

[0025] As a preferred technical scheme of the present application, the covalent bond is formed by the hydroxyl / amino group of chitosan oligosaccharide in the Schiff base compound and the polyurethane isocyanate, and the silica nanoparticles are used as rigid fillers, so that the adhesion of the ink layer and the antibacterial layer is significantly improved, the delamination or peeling is avoided, the antibacterial performance is improved, and the ink layer material formed still maintains integrity after repeated friction, autoclaving or liquid immersion, and the wear resistance is improved.

[0026] As a preferred technical scheme of the present application, 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.

[0027] As a preferred technical scheme of the present application, in step S2, the salicylaldehyde derivative solution is composed of salicylaldehyde derivatives and anhydrous ethanol at 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 for the ink layer, specifically, the introduction of the fluorinated salicylaldehyde reduces the surface energy, forms a hydrophobic interface, reduces liquid penetration and chemical corrosion, and also inhibits the proliferation of microorganisms in a humid environment, thereby improving the stability of the antibacterial material.

[0028] As a preferred technical scheme of the present application, a medical PET material formed by the above-mentioned thermal sublimation ink, the medical PET material comprises a medical base material, the surface of the medical base material is provided with an antibacterial layer, 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 a PET resin material; and the antibacterial layer is a polyurethane coating containing silver ions.

[0029] As a preferred technical scheme of the present application, a medical PET material formed by the above-mentioned thermal sublimation ink, the medical PET material comprises a medical base material, the surface of the medical base material is provided with an antibacterial layer, 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 a PET resin material; and the antibacterial layer is a polyurethane coating containing silver ions.

[0030] The present application has the following beneficial effects:

[0031] The silver ion polyurethane coating on the surface of the PET substrate material of the present application can provide a broad-spectrum antibacterial basis through the slow-release effect of silver ions (Ag+); the ink containing modified polyurethane on the outer layer further inhibits the adhesion of microorganisms and the formation of biofilms through mechanisms such as charge adsorption, interference and destruction of microbial reproduction, thereby covering different bacteria through double antibacterial mechanisms and prolonging the antibacterial time effect; the self-antibacterial property of the layered structure formed by the ink avoids the traditional printed marking area from becoming a pollution loophole, and is particularly suitable for high-infection-risk scenarios such as surgical instrument packaging and reusable consumables. DETAILED DESCRIPTION

[0032] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined invention purpose, the specific embodiments, structures, features and effects according to the present application are described in detail as follows in combination with examples. Example 1

[0033] A heat sublimation ink includes the following components by weight fraction: pigment paste 30 parts, modified polyurethane 15 parts, surfactant 1 part, organic solvent 15 parts and deionized water 40 parts;

[0034] The preparation method of the modified polyurethane includes the following steps:

[0035] Step A1, vacuum drying of polyether glycol at 105℃, 0.09MPa for 1h, heating to 70℃, adding isophorone diisocyanate and dibutyltin dilaurate and stirring for 1.0h to obtain a prepolymer; the mass ratio of the polyether glycol, isophorone diisocyanate and dibutyltin dilaurate is 10:5:0.07; the polyether glycol is PPG3000;

[0036] Step A2, continue stirring the prepolymer, dimethylol carboxylic acid and functional filler at 60℃, 300rpm for 1.5h, mix uniformly with butanediol, cool to 35℃, add triethylamine and deionized water and ultrasonic treat at 120W power for 30min to obtain a modified polyurethane; the mass ratio of the 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-dimethylol butyric acid;

[0037] The preparation method of the functional filler includes the following steps:

[0038] S1, reflux treatment of fumed silica and nitric acid solution at 65℃ for 2h, filtration, washing the solid with deionized water to neutral, drying at 80℃ for 8h to obtain a pre-prepared silica; the dosage ratio of the fumed silica and the nitric acid solution is 10g:18mL; the concentration of the nitric acid solution is 5mol / L;

[0039] S2, the pre-prepared silica, chitosan oligosaccharide and acetic acid solution are mixed, and a salicylaldehyde derivative solution is slowly added under ultrasonic treatment at a power of 200 W for 20 min, and then stirred at 45℃ for 4 h, the supernatant is removed by filtration, and the filter is washed with anhydrous ethanol for 3 times, and dried at 90℃ until the weight is constant, to obtain the product; the weight ratio of the pre-prepared silica, chitosan oligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 15g:1.6g:70mL:10mL; the molecular weight of the chitosan oligosaccharide is 2500Da; the mass fraction of the acetic acid solution is 1%; the salicylaldehyde derivative solution is composed of salicylaldehyde derivative and anhydrous ethanol with a mass ratio of 1:10; the salicylaldehyde derivative is 4-fluorosalicylaldehyde;

[0040] A preparation method of a thermal dye sublimation ink comprises the following steps: sequentially adding pigment paste, organic solvent, modified polyurethane and surfactant in deionized water under stirring at a rotation speed of 400 rpm, grinding and treating with zirconium beads with a particle size of 0.3 mm at a rotation speed of 1500 rpm for 4 h, and filtering through a microporous filter membrane with a pore size of 0.45 μm to obtain the thermal dye sublimation ink. Example 2

[0041] A thermal dye sublimation ink comprises the following components in parts by weight: pigment paste 35 parts, modified polyurethane 16 parts, surfactant 2 parts, organic solvent 18 parts and deionized water 45 parts.

[0042] The preparation method of the modified polyurethane comprises the following steps:

[0043] Step A1, polyether glycol is vacuumed at 108℃ and 0.09MPa for 1h to remove water, heated and warmed to 72℃, and then isophorone diisocyanate and dibutyltin dilaurate are added and stirred and mixed for 1.2h to obtain a prepolymer; the mass ratio of the polyether glycol, isophorone diisocyanate and dibutyltin dilaurate is 12:6:0.075; the polyether glycol is PPG3000;

[0044] Step A2, the prepolymer, dimethylol carboxylic acid and functional filler are continuously stirred at 70℃ and 400 rpm for 1.8h, and then butanediol is added and mixed, the temperature is lowered to 42℃, and then triethylamine and deionized water are added and treated under ultrasonic treatment at a power of 150 W for 38 min to obtain the modified polyurethane; the mass ratio of the 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;

[0045] The preparation method of the functional filler comprises the following steps:

[0046] S1, fumed silica and nitric acid solution were refluxed at 65℃ for 2.5h, filtered, the solid was washed with deionized water until neutral, and dried at 80℃ for 9h to obtain the pre-silica; the amount ratio of fumed silica and nitric acid solution was 10.5g:20mL; the concentration of the nitric acid solution was 5mol / L;

[0047] S2, the pre-silica, chitooligosaccharide and acetic acid solution were mixed, and ultrasonic treatment was carried out at 250W for 25min, then salicylaldehyde derivative solution was slowly added and stirred at 50℃ for 4.5h, the supernatant was removed by filtration, and the solid was washed with anhydrous ethanol for 3 times, and dried at 90℃ until constant weight to obtain the product; the amount ratio of the pre-silica, chitooligosaccharide, acetic acid solution and salicylaldehyde derivative solution was 16g:1.8g:75mL:10.5mL; the molecular weight of the chitooligosaccharide was 2750Da; the mass fraction of the acetic acid solution was 1%; the salicylaldehyde derivative solution was composed of salicylaldehyde derivative and anhydrous ethanol with a mass ratio of 1:10; the salicylaldehyde derivative was 4-fluorosalicylaldehyde;

[0048] A preparation method of a thermal dye sublimation ink comprises the following steps: sequentially adding pigment paste, organic solvent, modified polyurethane and surfactant in deionized water under stirring at a rotation speed of 400rpm, grinding with zirconium beads of 0.3mm in size at a rotation speed of 1650rpm for 4h, and filtering through a 0.45μm microporous filter membrane to obtain the thermal dye sublimation ink. Example 3

[0049] A thermal dye sublimation ink comprises the following components by weight fraction: pigment paste 40 parts, modified polyurethane 18 parts, surfactant 3 parts, organic solvent 21 parts and deionized water 50 parts.

[0050] The preparation method of the modified polyurethane comprises the following steps:

[0051] Step A1, polyether glycol was vacuumed at 110℃ and 0.09MPa for 1h to remove water, heated and warmed to 75℃, then isophorone diisocyanate and dibutyltin dilaurate were added and stirred and mixed for 1.5h to obtain a prepolymer; the mass ratio of polyether glycol, isophorone diisocyanate and dibutyltin dilaurate was 15:7:0.08; the polyether glycol was PPG3000;

[0052] Step A2, continue stirring the prepolymer, dimethylol carboxylic acid and functional filler at 80℃, 500rpm for 2.0h, add butanediol, mix well, cool to 50℃, add triethylamine and deionized water, ultrasonic treatment at 180W power for 45min, to obtain modified polyurethane; the mass ratio of the 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;

[0053] The preparation method of the functional filler comprises the following steps:

[0054] S1, reflux the fumed silica and nitric acid solution at 65℃ for 3h, filter, wash the solid with deionized water until neutral, dry at 80℃ for 10h, to obtain pre-prepared silica; the use amount ratio of the fumed silica and nitric acid solution is 11g:21mL; the concentration of the nitric acid solution is 5mol / L;

[0055] S2, mix the pre-prepared silica, chitooligosaccharide and acetic acid solution, ultrasonic at 300W power for 30min, slowly add the salicylaldehyde derivative solution, stir at 55℃ for 5h, filter off the supernatant, rinse with anhydrous ethanol for 3 times, dry at 90℃ until constant weight, to obtain the product; the use amount ratio of the pre-prepared silica, chitooligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 18g:2.0g:80mL:11mL; the molecular weight of the chitooligosaccharide is 3000Da; the mass fraction of the acetic acid solution is 1%; the salicylaldehyde derivative solution is composed of salicylaldehyde derivative and anhydrous ethanol according to the mass ratio of 1:10; the salicylaldehyde derivative is 4-fluorosalicylaldehyde;

[0056] A preparation method of a thermal dye sublimation ink comprises the following steps: under the stirring condition of 400rpm, sequentially add pigment paste, organic solvent, modified polyurethane and surfactant in deionized water and stir to mix uniformly, use zirconium beads with a particle size of 0.3mm to grind at a speed of 1800rpm for 4h, filter through a 0.45μm microporous filter membrane to obtain the thermal dye sublimation ink.

[0057] Comparative Example 1

[0058] Comparative Example 1 is different from Example 3 in that the step A1 of Comparative Example 1 uses diphenylmethane diisocyanate instead of isophorone diisocyanate, and the rest is the same.

[0059] Comparative Example 2

[0060] Comparative Example 2 is different from Example 3 in that the dimethylol carboxylic acid of Step A2 of Comparative Example 2 is 2,2-dimethylol propionic acid, and the rest is the same.

[0061] Comparative Example 3

[0062] Comparative Example 3 is different from Example 3 in that Comparative Example 3 does not perform Step S1. Step S2 uses fumed silica instead of pre-made silica, and the rest is consistent.

[0063] Comparative Example 4

[0064] Comparative Example 4 is different from Example 3 in that Comparative Example 4 does not use chitosan oligosaccharide in Step S2, and the rest is consistent.

[0065] Comparative Example 5

[0066] Comparative Example 5 is different from Example 3 in that Comparative Example 5 uses salicylaldehyde instead of salicylaldehyde derivative in Step S2, and the rest is consistent.

[0067] Comparative Example 6

[0068] Comparative Example 6 is different from Example 3 in that Comparative Example 6 does not use salicylaldehyde derivative in Step S2, and the rest is consistent.

[0069] Examples 1-3 and Comparative Examples 1-6 are respectively tested for the following properties.

[0070] The antibacterial effect of the ink is qualitatively tested by the inhibition zone method, and the bacteria used are Staphylococcus aureus and Escherichia coli. The antibacterial rate is tested for 48 hours, and the test results are shown in Table 1.

[0071] Table 1 (antibacterial rate test results)

[0072]

[0073] From the test results in Table 1, it can be seen that Examples 1-3 and Comparative Examples 1-6 have very high antibacterial rates on Staphylococcus aureus and Escherichia coli microorganisms.

[0074] The adhesion test is performed according to the provisions of GB / T9286; the sample is treated by 1 millimeter grid method, and the test results are shown in Table 2.

[0075] Table 2 (adhesion test results)

[0076]

[0077] From the test results in Table 2, it can be seen that Examples 1-3 and Comparative Examples 1-6 have significantly better adhesion effect on the substrate than Comparative Examples 1-6, and have excellent scratch resistance.

[0078] The application adopts dimethylol butyric acid, which is easier to melt in polyol and hot water than dimethylol propionic acid, and has better hydrophilicity, and the interaction between the carboxyl group of dimethylol propionic acid and the hydroxyl group on the functional filler is reduced when only part of the dimethylol propionic acid is dissolved in the system, so that the dispersibility of the functional filler in the polyurethane system is reduced, and the reaction of dimethylol propionic acid as a chain extender is incomplete, the crosslinking density of the polyurethane material is reduced, and the mechanical properties and antibacterial properties of the ink layer are both reduced; diphenyl methane diisocyanate contains multiple benzene ring structures, which has large steric hindrance, limits the flowability of the functional filler in the system, affects the uniformity of the antibacterial functional filler, and the crosslinking degree of the polyurethane is reduced, so that the performance is also reduced.

[0079] The application activates the surface hydroxyl group by nitric acid pickling and oxidation of fumed silica, improves the purity, dispersibility and reactivity of the fumed silica as a slow-release carrier, and more hydroxyl groups are beneficial to the organic coating effect of chitosan oligosaccharide and salicylaldehyde derivative; the Schiff base compound formed by chitosan oligosaccharide and fluorinated salicylaldehyde can effectively coat the silica, increase the dispersibility of the silica in the polyurethane, and the Schiff base structure can also adsorb the organic pigment in the pigment paste, so that the organic pigment is not easy to migrate, and the mechanical properties of the ink layer are also improved; in addition, the amino and hydroxyl groups on the chitosan oligosaccharide can form a chemical bond combined molecular crosslinking network in the polyurethane, effectively improving the mechanical properties and antibacterial properties of the ink layer, and the phenolic hydroxyl group on the fluorinated salicylaldehyde can interact with the dimethylol butyric acid through hydrogen bond, further increasing the dispersibility of the silica; the application also uses the rigid benzene ring of the fluorinated salicylaldehyde to form a rigid chain on the chitosan oligosaccharide, increasing the mechanical properties of the ink, and the introduction of the hydrophobic benzene ring structure and fluorine element can increase the contact between the antibacterial Schiff base compound and the microorganism and destroy the structure of the microorganism, further improving the antibacterial properties of the material.

[0080] The above is only a preferred embodiment of the application, and does not limit the application in any form, although the application has been disclosed as above, however, it is not intended to limit the application, any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the application, and any indirect modification, equivalent change and modification of the above embodiments according to the technical essence of the application are still within the scope of the technical solution of the application.

Claims

1. A heat sublimation ink, characterized by, By weight parts including the following components: pigment paste 30-40 parts, modified polyurethane 15-18 parts, surfactant 1-3 parts, organic solvent 15-21 parts and deionized water 40-50 parts; The preparation method of the modified polyurethane comprises the following steps: Step A1, vacuum dehydration of polyether glycol, preheating, adding isophorone diisocyanate and catalyst stirring mixing, getting prepolymer; Step A2, continue stirring the prepolymer, dimethylol carboxylic acid and functional filler, after mixing with butanediol, cooling, adding triethylamine and deionized water ultrasonic treatment, getting modified polyurethane; the dimethylol carboxylic acid is 2, 2-dimethylol butyric acid; The preparation method of the functional filler comprises the following steps: S1, temperature control reflux treatment of fumed silica and nitric acid solution, filtration, washing, drying, getting pre-prepared silica; the amount ratio of fumed silica and nitric acid solution is 10-11g:18-21mL; S2, mixing pre-prepared silica, chitooligosaccharide and acetic acid solution, ultrasonic dispersion treatment, slowly adding salicylaldehyde derivative solution, heating stirring, filtering out supernatant, washing, drying, getting it; the salicylaldehyde derivative solution is composed of salicylaldehyde derivative and anhydrous ethanol according to the mass ratio of 1:10; the salicylaldehyde derivative is one or two of 4-fluorosalicylaldehyde and 5-fluorosalicylaldehyde; the amount ratio of pre-prepared silica, chitooligosaccharide, acetic acid solution and salicylaldehyde derivative solution is 15-18g:1.6-2.0g:70-80mL:10-11mL.

2. The sublimation ink according to claim 1, characterized by: In step A1, the vacuum dehydration is vacuum dehydration at 105-110℃, 0.09MPa for 1h; the preheating is heating to 70-75℃; the stirring mixing time is 1.0-1.5h; the mass ratio of polyether glycol, isophorone diisocyanate and catalyst is 10-15:5-7:0.07-0.08; the polyether glycol is PPG3000; the catalyst is organic tin catalyst.

3. The dye-sublimation ink according to claim 1, characterized by: In step A2, the continue stirring is continue stirring at 60-80℃, 300-500rpm for 1.5-2.0h; the cooling is cooling to 35-50℃; the ultrasonic treatment is ultrasonic treatment at 120-180W power for 30-45min.

4. The dye-sublimation ink according to claim 1, characterized by: In step A2, the mass ratio of 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。 5. The dye-sublimation ink according to claim 1, wherein: In step S1, the temperature control reflux treatment is reflux treatment at 65℃ for 2-3h; the washing is washing with deionized water until neutral; the drying is drying at 80℃ for 8-10h; the concentration of nitric acid solution is 5mol / L.

6. The dye-sublimation ink according to claim 1, wherein: In step S2, the ultrasonic dispersion treatment is ultrasonic dispersion treatment at 200-300W power for 20-30min; the heating stirring is stirring at 45-55℃ for 4-5h.

7. The dye-sublimation ink according to claim 1, wherein: In step S2, the molecular weight of chitooligosaccharide is 2500-3000Da; the mass fraction of acetic acid solution is 1%.

8. A method of preparing a dye-sublimation ink as claimed in any one of claims 1 to 7, characterized in that, The preparation method comprises the following steps: adding pigment paste, organic solvent, modified polyurethane and surfactant in deionized water under stirring condition, stirring and mixing uniformly, and then grinding, and filtering through a 0.45-micron microporous filter membrane to obtain the thermal sublimation ink.

9. A medical PET material formed using the sublimation ink according to any one of claims 1 to 7, characterized by: The medical PET material comprises a medical base material, the surface of the medical base material is provided with an antibacterial layer, the thermal sublimation ink is sprayed on the surface of the antibacterial layer, and a layered structure is formed after drying; the medical base material is made of a PET resin material; and the antibacterial layer is a polyurethane coating layer containing silver ions.

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