CN110606977A - Antibacterial TPU composite foamed bead and preparation method and application thereof - Google Patents
Antibacterial TPU composite foamed bead and preparation method and application thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention discloses an antibacterial TPU composite foaming bead which comprises the following components: an antibacterial TPU composite foamed bead comprises: (1) TPU expanded beads; and (2) spraying the aqueous polyurethane solution containing the nano titanium dioxide silver-loaded inorganic antibacterial agent on the surface of the TPU foamed bead to form an antibacterial coating with the thickness of 10-200 mu m; cleaning and degreasing the surface of the TPU foamed bead by ultrasonic waves and activating the surface by low-temperature plasma; the aqueous polyurethane solution comprises: waterborne polyurethane, a nano titanium dioxide silver-loaded antibacterial agent, a waterborne antioxidant, a waterborne ultraviolet absorber, a waterborne light stabilizer, a crosslinking agent and deionization. The invention has obvious cost advantage, and the nano titanium dioxide silver-carrying antibacterial agent in the surface coating of the TPU composite foaming bead is more uniformly distributed. The invention can be applied to materials requiring antibacterial light buffering in a plurality of fields such as daily life, medical treatment and health, furniture and household appliances.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to an antibacterial TPU composite foamed bead as well as a preparation method and application thereof.
Background
The thermoplastic polyurethane TPU elastomer has the advantages of good rebound resilience, wear resistance, low compression set, low temperature resistance, good mechanical property and the like, is mainly applied to the shoe material industry, and also applied to a plurality of fields such as runways, helmets, logistics packaging materials, new home materials, educational equipment, sporting goods, automotive interiors and the like, and has great development potential.
With the increasing living standard, people's attention on their health is also increasing. The natural world has a large amount of harmful microorganisms which cause great threat to human health, and the prepared antibacterial agent has high antibacterial rate, no toxicity, no harm, excellent durability and stable performance, and is used in the fields of wood, coating, plastics, rubber, food, cosmetics and the like, which is the future development requirement and trend. The rubber and plastic products are common articles in daily life of people, and because frequent use easily causes the breeding of harmful microorganisms, causes the infection of pathogenic microorganisms in the use process of users, and also causes cross infection, the development of antibacterial rubber and plastic materials and products has profound practical application significance.
At present, four antibacterial agents mainly comprise an inorganic antibacterial agent, an organic small-molecule antibacterial agent, a natural antibacterial agent, a high-molecule antibacterial agent and the like, and the antibacterial agents have different advantages and disadvantages and use conditions due to differences in the properties, the antibacterial principle and the like of the antibacterial agent. The organic micromolecule antibacterial agent has the advantages of multiple types, quick sterilization, low cost and the like, but has the defects of poor broad spectrum, poor heat resistance, high toxicity, easy generation of drug resistance, toxic decomposition products and the like, the natural antibacterial agent has high safety, broad spectrum and long effect, but also has poor heat resistance and broad spectrum, short service life and difficult processing, and the macromolecular antibacterial agent has the advantages of high antibacterial efficiency, high speed, low toxicity, good color stability and the like, but has complex preparation process and high preparation cost; the inorganic antibacterial agent mainly comprises a silver antibacterial agent, a titanium photocatalytic antibacterial agent and the like at present, has the advantages of broad antibacterial spectrum, long acting, no drug resistance, low toxicity and the like, particularly has outstanding slow release property and good heat resistance, has great potential in the development of antibacterial agent materials, and is easy to prepare into nano-scale. However, the inorganic antibacterial agent still has the defects of easy color change of silver series, high price, limitation of titanium series by illumination and the like, and the application is limited. The nano titanium dioxide silver-carrying inorganic antibacterial agent is used as a novel composite antibacterial agent, realizes the synergistic antibacterial action of nano titanium dioxide and silver ions, has the functions of sterilization, antivirus and bacterium decomposition under the visible light and ultraviolet light of the nano titanium dioxide, has the functions of strong antibacterial and virus killing of the nano silver without a light source, greatly improves the activity of the silver and reduces the color change through an inorganic anti-tarnish auxiliary agent (nano titanium dioxide), realizes the slow release of the silver ions, and has great superiority.
At present, the problems of high cost, difficult uniform dispersion and the like exist when the nano titanium dioxide silver-loaded antibacterial agent is added into TPU foamed matrix resin.
Disclosure of Invention
The invention aims to solve the problems and provide the antibacterial TPU composite foamed bead, the preparation method and the application thereof, and the cost advantage is obvious, and the nano titanium dioxide silver-carrying antibacterial agent in the surface coating of the TPU composite foamed bead is more uniformly distributed.
The purpose of the invention is realized as follows:
the invention discloses an antibacterial TPU composite foaming bead which comprises the following components:
(1) TPU expanded beads; and
(2) spraying the aqueous polyurethane solution containing the nano titanium dioxide silver-loaded inorganic antibacterial agent on the surface of the TPU foaming bead to form an antibacterial coating with the thickness of 10-200 mu m;
cleaning and degreasing the surface of the TPU foamed bead by ultrasonic waves and activating the surface by low-temperature plasma;
the aqueous polyurethane solution comprises: waterborne polyurethane, a nano titanium dioxide silver-loaded antibacterial agent, a waterborne antioxidant, a waterborne ultraviolet absorber, a waterborne light stabilizer, a crosslinking agent and deionization.
The aqueous polyurethane solution in the antibacterial TPU composite foamed bead is carboxyl type thermoplastic aqueous polyurethane emulsion.
The addition amount of the nano titanium dioxide silver-loaded antibacterial agent in the antibacterial TPU composite foamed bead is 0.5-3.0 wt% of the total amount of the antibacterial coating on the surface of the TPU foamed bead, wherein the silver content in the nano titanium dioxide silver-loaded antibacterial agent is not less than 3%, and the titanium content is not less than 30%.
The aqueous antioxidant in the antibacterial TPU composite foamed bead is a dispersion containing hindered phenol antioxidant; the amount of the water-based antioxidant is 0.5 to 5 percent of the solid amount of the water-based polyurethane solution;
the water-based ultraviolet absorbent benzotriazole ultraviolet absorbent has the addition amount of 0.2-3% of the solid content of the water-based polyurethane;
the water-based light stabilizer adopts a light stabilizer containing hindered amine, and the addition amount of the light stabilizer is 0.1-3% of the solid amount of the water-based polyurethane.
The aqueous antioxidant in the antibacterial TPU composite foaming bead is aqueous antioxidant dispersion liquid containing triethylene glycol ether-di (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate.
The cross-linking agent in the antibacterial TPU composite foaming bead is an aziridine type cross-linking agent, the cross-linking agent is used for improving the water resistance of the aqueous polyurethane coating, but the cross-linking degree needs to be controlled, so that the aqueous polyurethane coating coated on the surface of the TPU foaming bead after drying does not lose the thermal bonding capability, and the addition amount of the cross-linking agent is 0.05-2% of the mass percent of the aqueous polyurethane emulsion.
The solid content of the aqueous polyurethane solution containing the nano titanium dioxide silver-carrying antibacterial agent in the antibacterial TPU composite foaming bead is 1-20%.
The proportion of the TPU foamed beads in the antibacterial TPU composite foamed beads is 0.1-0.8 g/cm3。
The invention also provides a preparation method of the antibacterial TPU composite foamed bead, which adopts a spray coating and drying device and at least comprises the following steps:
a drum-shaped rotating drum with an open upper end;
a hot air pipe with an outlet communicated with the interior of the rotary drum and connected with a hot air blowing device outside the rotary drum;
a stirrer installed in the drum for assisting in dispersing the TPU expanded beads; and
the spray gun is used for atomization, and an outlet of the spray gun is positioned in the rotary drum and is connected with a liquid tank outside the rotary drum through a pipeline;
the preparation method of the antibacterial TPU composite foamed bead comprises the following steps:
1) cleaning the surface of the TPU foamed beads by adopting an ultrasonic cleaning process, and drying at 50-100 ℃ after cleaning;
2) processing the surface of the cleaned TPU foamed beads by adopting a low-temperature plasma processing process;
3) uniformly stirring waterborne polyurethane, a nano titanium dioxide silver-loaded antibacterial agent, a waterborne antioxidant, a waterborne titanium dioxide slurry, a cross-linking agent and deionized water, and then matching with ultrasonic dispersion to prepare a waterborne polyurethane solution containing a nano titanium dioxide silver-loaded inorganic antibacterial agent for later use;
4) adding the TPU foamed beads into a rotary drum of the spray drying device, starting the rotary drum to rotate and heat, introducing hot air to dry materials, after the TPU foamed beads are preheated to a set drying temperature of 80-105 ℃, starting a stirrer to assist in dispersing the TPU foamed beads, spraying the aqueous polyurethane spray solution containing the nano titanium dioxide silver-carrying inorganic antibacterial agent prepared in the step 3) on the surfaces of the TPU foamed beads by using a spray gun, continuously heating and drying the TPU foamed beads while intermittently spraying the aqueous polyurethane spray solution containing the nano titanium dioxide silver-carrying inorganic antibacterial agent on the surfaces of the TPU foamed beads for multiple times in the process of uniformly rolling and dispersing the TPU foamed beads until the aqueous polyurethane solution is completely consumed, stopping spraying, finally forming a uniform coating on the surfaces of the TPU foamed beads, and continuously drying until the surface coating of the TPU foamed beads is dried by moisture, and (4) finishing.
In the preparation method of the antibacterial TPU composite foamed bead, the ultrasonic cleaning process in the step 1) adopts a water-based cleaning agent containing at least one anionic surfactant or nonionic surfactant with the concentration of 1-20%, and the ultrasonic frequency is>20KHz, power density>0.3W/cm2。
In the preparation method of the antibacterial TPU composite foamed bead, the working gas adopted in the low-temperature plasma treatment process in the step 2) is one or a mixture of several of argon, nitrogen, oxygen, ammonia and carbon dioxide, the gas flow is 30-900 sccm, the working pressure is 10-300 Pa, the treatment time is 20 s-10 min, the temperature is 20-130 ℃, and the treatment power is 1500W-12000W.
In the preparation method of the antibacterial TPU composite foamed bead, the rotary drum is arranged on a base, and the installation inclination angle is 30-45 degrees; the outer wall of the drying box is provided with an auxiliary electric heating dryer.
The invention also provides an application of the antibacterial TPU composite foaming bead as in claims 1-13 in a molded body, and the preparation method comprises the following steps: and adding the antibacterial TPU composite foamed beads into a mold of a foamed bead forming machine, heating by adopting steam or microwave, cooling and demolding.
The antibacterial TPU composite foamed bead disclosed by the invention adopts the aqueous polyurethane as a thermal adhesive of the foamed bead, and the preparation process is green and environment-friendly. Compared with the method of adding the antibacterial agent into the foaming matrix resin, the method has obvious cost advantage, and the nano titanium dioxide silver-loaded antibacterial agent in the surface coating of the TPU composite foaming bead is more uniformly distributed. The product of the antibacterial TPU composite foamed bead can be applied to materials requiring antibacterial light buffering in multiple fields of daily life, medical treatment and health, furniture and household appliances and the like.
Drawings
Fig. 1 is a schematic configuration diagram of a spray coating drying apparatus of the present invention.
Detailed Description
The invention discloses an antibacterial TPU composite foaming bead which comprises the following components:
(1) TPU expanded beads; and
(2) spraying the aqueous polyurethane solution containing the nano titanium dioxide silver-loaded inorganic antibacterial agent on the surface of the TPU foaming bead to form an antibacterial coating with the thickness of 10-200 mu m;
the TPU foamed beads can be prepared by adopting an extrusion foaming-underwater granulating method or an in-kettle gas impregnation method, and the surfaces of the TPU foamed beads are subjected to ultrasonic wave surface cleaning and degreasing and low-temperature plasma activation treatment;
the aqueous polyurethane solution comprises: waterborne polyurethane, a nano titanium dioxide silver-loaded antibacterial agent, a waterborne antioxidant, a waterborne ultraviolet absorber, a waterborne light stabilizer, a crosslinking agent and deionization.
Wherein the aqueous polyurethane solution in the antibacterial TPU composite foamed beads is carboxyl type thermoplastic aqueous polyurethane emulsion.
The addition amount of the nano titanium dioxide silver-carrying antibacterial agent in the antibacterial TPU composite foamed bead is 0.5-3.0 wt% of the total amount of the antibacterial coating on the surface of the TPU foamed bead, wherein the silver content in the nano titanium dioxide silver-carrying antibacterial agent is not less than 3%, and the titanium content is not less than 30%.
The aqueous antioxidant in the antibacterial TPU composite foamed bead is a dispersion containing hindered phenol antioxidant; the amount of the water-based antioxidant is 0.5 to 5 percent of the solid amount of the water-based polyurethane solution;
the water-based ultraviolet absorbent benzotriazole ultraviolet absorbent has the addition amount of 0.2-3% of the solid content of the water-based polyurethane;
the water-based light stabilizer adopts a light stabilizer containing hindered amine, and the addition amount of the light stabilizer is 0.1-3% of the solid amount of the water-based polyurethane.
The water-based antioxidant in the antibacterial TPU composite foaming bead is a water-based antioxidant dispersion liquid containing triethylene glycol ether-di (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate.
The cross-linking agent in the antibacterial TPU composite foaming bead adopts an aziridine type cross-linking agent, the cross-linking agent is used for improving the water resistance of the aqueous polyurethane coating, but the cross-linking degree needs to be controlled, so that the aqueous polyurethane coating coated on the surface of the TPU foaming bead after drying does not lose the thermal bonding capability, and the addition amount of the cross-linking agent is 0.05-2% of the mass percentage of the aqueous polyurethane emulsion;
the solid content of the aqueous polyurethane solution containing the nano titanium dioxide silver-carrying antibacterial agent in the antibacterial TPU composite foaming bead is 1-20%.
The specific gravity of the TPU foamed beads in the antibacterial TPU composite foamed beads is 0.1-0.8 g/cm3。
The preparation method of the antibacterial TPU composite foamed bead comprises the following steps:
1) cleaning the surface of the TPU foamed beads by adopting an ultrasonic cleaning process, and drying at 50-100 ℃ after cleaning;
2) processing the surface of the cleaned TPU foamed beads by adopting a low-temperature plasma processing process;
3) uniformly stirring waterborne polyurethane, a nano titanium dioxide silver-loaded antibacterial agent, a waterborne antioxidant, a waterborne titanium dioxide slurry, a cross-linking agent and deionized water, and then matching with ultrasonic dispersion to prepare a waterborne polyurethane solution containing a nano titanium dioxide silver-loaded inorganic antibacterial agent for later use;
4) adding TPU foamed beads into a drum-shaped rotary drum 1 of a spray drying device, starting the rotary drum 1 to rotate and heat, introducing hot air to dry materials, after the TPU foamed beads are preheated to a set drying temperature of 80-105 ℃, starting a stirrer 3 for assisting in dispersing the beads, which is arranged in the rotary drum, spraying the aqueous polyurethane spray solution containing the nano titanium dioxide silver-carrying inorganic antibacterial agent, which is prepared in the step 3), on the surfaces of the TPU foamed beads by using a spray gun 4 with an atomization effect, so that in the process of uniformly rolling and dispersing the TPU foamed beads in the rotary drum 1, the surfaces of the TPU foamed beads are continuously heated and dried while being repeatedly and discontinuously sprayed with the aqueous polyurethane spray solution containing the nano titanium dioxide silver-carrying inorganic antibacterial agent, until the aqueous polyurethane solution is completely consumed, stopping spraying, finally forming an even coating on the surfaces of the TPU foamed beads, and continuously drying until the surface coating of the TPU foamed beads is dried in moisture, and (4) finishing.
Preferably, the ultrasonic cleaning process in the step 1) adopts a water-based cleaning agent containing at least one anionic surfactant or nonionic surfactant with the concentration of 1-20%, and the ultrasonic frequency is>20KHz, power density>0.3W/cm2。
Preferably, the working gas adopted by the low-temperature plasma treatment process in the step 2) is one or a mixture of several of argon, nitrogen, oxygen, ammonia and carbon dioxide, the gas flow is 30-900 sccm, the working pressure is 10-300 Pa, the treatment time is 20 s-10 min, the temperature is 20-130 ℃, and the treatment power is 1500-12000W.
Preferably, as shown in fig. 1, step 4) is implemented using a spray coating drying apparatus comprising:
a rotating drum 1 with an opening at the upper end, wherein the rotating drum 1 is arranged on a base 11;
a hot air pipe 2 with an outlet communicated with the interior of the rotary drum 1 and connected with a hot air blowing device 21 outside the rotary drum 1;
an agitator 3 installed in the drum 1 for assisting in dispersing the TPU expanded beads; and
a spray gun 4 with an outlet positioned in the rotating drum 1 and connected with a liquid tank outside the rotating drum 1 through a pipeline for atomization.
Preferably, the installation inclination angle of the rotary drum 1 is 30-45 degrees;
preferably, the drum 1 is a drum-type stainless steel drum;
preferably, an auxiliary electric heating dryer is installed on the outer wall of the rotary drum 1;
the invention also provides a forming body of the antibacterial TPU composite foaming bead, and the preparation method comprises the following steps:
and adding the antibacterial TPU composite foamed beads into a mold of a foamed bead forming machine, heating by adopting steam or microwave, cooling, and demolding to obtain the antibacterial TPU composite foamed bead forming body. The surface of the white TPU foaming bead and the external aqueous polyurethane coating are softened in a steam or microwave heating mode, molecular chains of interfaces between the white TPU foaming bead and the aqueous polyurethane coating and between the aqueous polyurethane coatings are mutually diffused to form firmer adhesion, so that a foam product with good rebound resilience, compression resistance and buffering performance is obtained, and the surface of a formed body has a good and durable antibacterial effect and a certain mildew-proof effect.
The present invention will be further described with reference to examples 1 to 2.
Example 1
The specific gravity of the product prepared by the in-kettle gas immersion method is 0.11g/cm3White TPU expanded beads.
1) Firstly, grease and dirt on the surface of white TPU foamed beads are removed, rinsed and dried at 50-100 ℃ by utilizing an ultrasonic cleaning process, and a cleaning solution is a water-based cleaning solution containing 10% of surfactant 6501Liquid, ultrasonic frequency 25KHz, power density 0.35W/cm2；
2) Then carrying out low-temperature plasma treatment on the surface of the treated white TPU foamed beads, wherein the working gas is nitrogen, the working gas pressure is 100Pa, and the temperature is 80 ℃;
3) preparing carboxyl type aqueous polyurethane solution containing nano titanium dioxide silver-loaded inorganic antibacterial agent with solid content of 10%, which comprises the following steps:
a. the addition amount of the nano titanium dioxide silver-loaded inorganic antibacterial agent is 1.5 wt% of the total solid amount of the aqueous polyurethane spray solution;
b. selecting an aqueous antioxidant dispersion liquid containing triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS NO:36443-68-2), wherein the amount of the aqueous antioxidant is 2% of the solid content of the aqueous polyurethane solution;
c. the aqueous ultraviolet absorbent adopts UV-1130, and the addition amount of the aqueous ultraviolet absorbent is 2 percent of the solid amount of the aqueous polyurethane solution;
d. the waterborne light stabilizer adopts UV-292, and the addition amount of the waterborne light stabilizer is 1.5 percent of the solid amount of the waterborne polyurethane solution;
e. the cross-linking agent adopts aziridine cross-linking agent SAC-100, and the addition amount of the aziridine cross-linking agent is 0.2 percent of the mass of the aqueous polyurethane liquid; (ii) a
4) Adding the white TPU expanded beads treated in the step 2) into a spray coating drying device (shown in the attached figure 1), setting the hot air temperature to be 100 ℃, setting the solid content of the aqueous polyurethane solution containing the nano titanium dioxide silver-loaded inorganic antibacterial agent prepared in the step 3) to be 28% of the content of the white TPU expanded beads, and obtaining the antibacterial TPU composite expanded beads with the specific gravity of about 0.14g/cm3；
5) And (3) putting the prepared antibacterial TPU composite foamed bead into a mold, heating by adopting steam, cooling, and demolding to obtain an antibacterial TPU composite foamed bead molded body.
Through tests, the coating of the TPU foamed bead forming body containing the thin graphene permanent antistatic coating is uniform, the TPU foamed bead forming body can pass a water resistance test of 60 ℃, the relative humidity is 95% for seven days, the TPU foamed bead forming body can not fade after being wiped by external force, and the surface antibacterial rate is as follows: 99.23 percent of escherichia coli, 99.57 percent of staphylococcus aureus and 98.63 percent of penicillium.
Example 2
The specific gravity of the product prepared by the in-kettle gas immersion method is 0.11g/cm3White TPU expanded beads.
1) Firstly, grease and dirt on the surface of white TPU foamed beads are removed, rinsed and dried at 50-100 ℃ by utilizing an ultrasonic cleaning process, wherein the cleaning liquid is a water-based cleaning liquid containing 10% of a surfactant 6501, the ultrasonic frequency is 25KHz, and the power density is 0.35W/cm2；
2) Then carrying out low-temperature plasma treatment on the surface of the treated white TPU foamed beads, wherein the working gas is nitrogen, the working gas pressure is 100Pa, and the temperature is 80 ℃;
3) preparing carboxyl type aqueous polyurethane solution containing nano titanium dioxide silver-loaded inorganic antibacterial agent with solid content of 10%, which comprises the following steps:
a. the addition amount of the nano titanium dioxide silver-loaded inorganic antibacterial agent is 3.0 wt% of the total solid amount of the aqueous polyurethane spray solution;
b. selecting an aqueous antioxidant dispersion liquid containing triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS NO:36443-68-2), wherein the amount of the aqueous antioxidant is 2% of the solid content of the aqueous polyurethane solution;
c. the aqueous ultraviolet absorbent adopts UV-1130, and the addition amount of the aqueous ultraviolet absorbent is 2 percent of the solid amount of the aqueous polyurethane solution;
d. the waterborne light stabilizer adopts UV-292, and the addition amount of the waterborne light stabilizer is 1.5 percent of the solid amount of the waterborne polyurethane solution;
e. the cross-linking agent adopts aziridine cross-linking agent SAC-100, and the addition amount of the aziridine cross-linking agent is 0.2 percent of the mass of the aqueous polyurethane liquid; (ii) a
4) Adding the white TPU expanded beads treated in the step 2) into a spray coating drying device (shown in the attached figure 1), setting the hot air temperature to be 100 ℃, setting the solid content of the aqueous polyurethane solution containing the nano titanium dioxide silver-loaded inorganic antibacterial agent prepared in the step 3) to be 36 percent of the content of the white TPU expanded beads, and obtaining the antibacterial TPU composite expanded beads with the specific gravity of about 0.16g/cm3；
5) And (3) putting the prepared antibacterial TPU composite foamed bead into a mold, heating by adopting steam, cooling, and demolding to obtain an antibacterial TPU composite foamed bead molded body.
Through tests, the coating of the TPU foamed bead forming body containing the thin graphene permanent antistatic coating is uniform, the TPU foamed bead forming body can pass a water resistance test of 60 ℃, the relative humidity is 95% for seven days, the TPU foamed bead forming body can not fade after being wiped by external force, and the surface antibacterial rate is as follows: 100.00 percent of escherichia coli, 100.00 percent of staphylococcus aureus and 100.00 percent of penicillium.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (10)
1. An antimicrobial TPU composite expanded bead, characterized in that it comprises:
(1) TPU expanded beads; and
(2) spraying the aqueous polyurethane solution containing the nano titanium dioxide silver-loaded inorganic antibacterial agent on the surface of the TPU foaming bead to form an antibacterial coating with the thickness of 10-200 mu m;
cleaning and degreasing the surface of the TPU foamed bead by ultrasonic waves and activating the surface by low-temperature plasma;
the aqueous polyurethane solution comprises: waterborne polyurethane, a nano titanium dioxide silver-loaded antibacterial agent, a waterborne antioxidant, a waterborne ultraviolet absorber, a waterborne light stabilizer, a crosslinking agent and deionization.
2. The antimicrobial TPU composite foamed bead of claim 1, wherein the aqueous polyurethane solution is a carboxyl-type thermoplastic aqueous polyurethane emulsion;
the water-based antioxidant is a dispersion liquid containing hindered phenol antioxidants;
the water-based ultraviolet absorbent is a benzotriazole ultraviolet absorbent;
the water-based light stabilizer adopts a light stabilizer containing hindered amine;
the water-based light stabilizer adopts a light stabilizer containing hindered amine;
the cross-linking agent is an aziridine type cross-linking agent.
3. The antibacterial TPU composite foamed bead as claimed in claim 1 or 2, wherein the nano titanium dioxide silver-carrying antibacterial agent is added in an amount of 0.5 wt% to 3.0 wt% based on the total amount of the antibacterial coating on the surface of the TPU foamed bead, wherein the nano titanium dioxide silver-carrying antibacterial agent has a silver content of not less than 3% and a titanium content of not less than 30%;
the amount of the water-based antioxidant is 0.5 to 5 percent of the solid amount of the water-based polyurethane solution;
the addition amount of the aqueous ultraviolet absorbent is 0.2-3% of the solid content of the aqueous polyurethane;
the addition amount of the water-based light stabilizer is 0.1-3% of the solid amount of the water-based polyurethane;
the addition amount of the cross-linking agent is 0.05-2% of the mass percent of the waterborne polyurethane emulsion;
the solid content of the aqueous polyurethane solution containing the nano titanium dioxide silver-loaded antibacterial agent is 1-20 percent;
the TPU foamed bead has a specific gravity of 0.1-0.8 g/cm3。
4. The antimicrobial TPU composite foam beads of claim 2, wherein the aqueous antioxidant is an aqueous antioxidant dispersion comprising triethylene glycol ether-bis (3-t-butyl-4-hydroxy-5-methylphenyl) propionate.
5. The method of claim 1, wherein the spray coating and drying apparatus is used for the preparation of the antibacterial TPU composite expanded beads, and the method comprises:
a drum-shaped rotating drum with an open upper end;
a hot air pipe with an outlet communicated with the interior of the rotary drum and connected with a hot air blowing device outside the rotary drum;
an agitator mounted within the drum for assisting in dispersing the TPU expanded beads; and
the spray gun is used for atomization, and an outlet of the spray gun is positioned in the rotary drum and is connected with a liquid tank outside the rotary drum through a pipeline; the preparation method of the antibacterial TPU composite foamed bead comprises the following steps:
1) cleaning the surface of the TPU foamed beads by adopting an ultrasonic cleaning process, and drying at 50-100 ℃ after cleaning;
2) processing the surface of the cleaned TPU foamed beads by adopting a low-temperature plasma processing process;
3) uniformly stirring waterborne polyurethane, a nano titanium dioxide silver-loaded antibacterial agent, a waterborne antioxidant, a waterborne titanium dioxide slurry, a cross-linking agent and deionized water, and then matching with ultrasonic dispersion to prepare a waterborne polyurethane solution containing a nano titanium dioxide silver-loaded inorganic antibacterial agent for later use;
4) adding the TPU foamed beads into a rotary drum of the spray drying device, starting the rotary drum to rotate and heat, introducing hot air to dry materials, after the TPU foamed beads are preheated to a set drying temperature of 80-105 ℃, starting a stirrer to assist in dispersing the TPU foamed beads, spraying the aqueous polyurethane spray solution containing the nano titanium dioxide silver-carrying inorganic antibacterial agent prepared in the step 3) on the surfaces of the TPU foamed beads by using a spray gun, continuously heating and drying the TPU foamed beads while intermittently spraying the aqueous polyurethane spray solution containing the nano titanium dioxide silver-carrying inorganic antibacterial agent on the surfaces of the TPU foamed beads for multiple times in the process of uniformly rolling and dispersing the TPU foamed beads until the aqueous polyurethane solution is completely consumed, stopping spraying, finally forming a uniform coating on the surfaces of the TPU foamed beads, and continuously drying until the surface coating of the TPU foamed beads is dried by moisture, and (4) finishing.
6. The method for preparing the antibacterial TPU composite foamed bead as claimed in claim 5, wherein the ultrasonic cleaning process in step 1) adopts a water-based cleaning agent containing at least one anionic surfactant or nonionic surfactant with a concentration of 1-20%, and the ultrasonic frequency is set to be within the range of>20KHz, power density>0.3W/cm2。
7. The preparation method of the antibacterial TPU composite foamed bead as claimed in claim 5, wherein the working gas adopted in the low-temperature plasma treatment process in step 2) is one or a mixture of several gases of argon, nitrogen, oxygen, ammonia and carbon dioxide, the gas flow is 30-900 sccm, the working pressure is 10-300 Pa, the treatment time is 20 s-10 min, the temperature is 20-130 ℃, and the treatment power is 1500W-12000W.
8. The method for preparing antibacterial TPU composite expanded beads according to claim 5, wherein the rotary drum is mounted on a base with a mounting inclination angle of 30 to 45 °; the outer wall of the drying box is provided with an auxiliary electric heating dryer.
9. A molded article of the antibacterial TPU composite expanded beads as claimed in claims 1 to 8.
10. A method for preparing a molded body of the antibacterial TPU composite expanded bead as set forth in claim 9, characterized by comprising the steps of: and adding the antibacterial TPU composite foamed beads into a mold of a foamed bead forming machine, heating by adopting steam or microwave, cooling, and demolding.
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