Antibacterial antifouling functional adhesive tape and preparation method thereof

Abstract

The invention relates to the technical field of functional adhesive tapes, and discloses an antibacterial antifouling functional adhesive tape and a preparation method thereof.4-dimethylaminophenol, 1-propylene-1, 3-sultone, 1H, 1H, 2H, 2H-perfluorooctylmethyldichlorosilane and the like are used as raw materials, alkenyl organosilicone fluorobetaine is obtained through chemical reaction, the alkenyl organosilicone fluorobetaine and acrylic monomers are subjected to polymerization, and the antibacterial antifouling functional adhesive tape is prepared. And uniformly coating a PET (Polyethylene Terephthalate) film base material with the antibacterial antifouling viscous emulsion to obtain the functional adhesive tape. Zwitterions in the alkenyl organosilicone fluorobetaine inhibit growth and reproduction of bacteria by interfering the normal metabolic process of the bacteria, are introduced into the adhesive tape in a chemical grafting manner, do not migrate and separate out, and have antibacterial durability; in the structure, the continuously arranged perfluoroalkyl long chains and low-surface-energy organic silicon can form a tightly arranged structure on the surface of the adhesive tape, so that the material surface has better hydrophobic performance, and the hydrophobic adhesive tape can be widely applied to various mechanical equipment and electronic products.

Description

Technical Field

[0001] The invention relates to the technical field of functional adhesive tapes, in particular to an antibacterial and antifouling functional adhesive tape and a preparation method thereof. Background Art

[0002] As new electronic components become increasingly miniaturized, high-end, and functional, the performance requirements for electronic tapes are also getting higher and higher. Electronic products have become an indispensable part of modern life. From smartphones, tablets to wearable devices, these products have not only changed our lifestyles, but also have a profound impact on our health and safety. However, as the frequency of use of electronic products increases, bacteria, dust and other pollutants are easily accumulated on their surfaces, which not only affects the aesthetics of the products, but may also pose a potential threat to the health of users. Therefore, it is particularly important to develop an antibacterial and antifouling functional tape for surface protection of electronic products and other mechanical equipment.

[0003] Traditional electronic product surface protection materials, such as plastic films, transparent tapes, etc., can protect products from scratches and impacts to a certain extent, but have obvious deficiencies in antibacterial and antifouling properties. Bacteria and dust are easily accumulated on the surface of these materials and are not easy to clean. After long-term use, they not only affect the appearance of the product, but may also become a medium for the spread of bacteria and viruses, posing a risk to the health of users. Patent No. CN103831221B discloses a method for preparing an antibacterial film, which uses a biaxially oriented polypropylene film or a polyester film as a substrate layer, and applies a nano antibacterial coating on one or both sides of the substrate layer, and obtains an antibacterial film after curing. The active ingredients of the antibacterial coating, nano titanium oxide, nano silver, nano aluminum and their combination are adsorbed on a special porous material. The preparation process of the porous material is complicated and cumbersome. The inorganic nanoparticles that have not been modified are very easy to agglomerate, the antibacterial agent cannot be evenly dispersed, and it does not have self-cleaning ability, so it is difficult to ensure the stable antibacterial and antifouling properties of the product.

[0004] Acrylic pressure-sensitive adhesive is a unique adhesive formed by double bond polymerization. It can achieve firm adhesion in a short time without applying great pressure during use, and can effectively adhere to the surface of system equipment to form an anti-biofilm. However, with the development of science and technology, the performance requirements for pressure-sensitive adhesives are getting higher and higher. The performance of acrylic pressure-sensitive adhesive itself is relatively single and cannot meet the requirements of various industries, so it needs to be modified. The present invention aims to use zwitterionic antibacterial materials and organic silicon fluorine super-hydrophobic materials, and evenly disperse them in a PET film substrate by initiating polymerization to form an antibacterial and anti-fouling layer to prevent dust, bacteria and other pollutants from accumulating on the surface. It is easy to clean and stains can be removed by wiping with a wet cloth. The preparation process is simple. Summary of the invention

[0005] The purpose of the present invention is to solve the problems existing in the above-mentioned prior art and to provide an antibacterial and antifouling functional tape and a preparation method thereof, so as to prevent the accumulation of pollutants such as dust and bacteria on the surface of the tape, which is easy to clean, has a simple preparation process, and has long-lasting and stable antibacterial and antifouling properties.

[0006] The present invention is achieved through the following technical solutions:

[0007] A method for preparing an antibacterial and antifouling functional adhesive tape is carried out according to the following steps:

[0008] Step (1), under a nitrogen atmosphere, add butyl acrylate, methyl methacrylate, acrylic acid and deionized water to a reaction bottle equipped with a dropping funnel, stir at a temperature of 80-95° C. and a rotation speed of 800-1000 r / min for 5-15 minutes to obtain a pre-emulsion, first take 1 / 4 of the pre-emulsion and add 1 / 3 of the initiator, stir at 75-85° C. for 20-40 minutes, and then add the remaining 3 / 4 of the pre-emulsion, 2 / 3 of the initiator and the structural formula The mixture is stirred for 3-8 hours, cooled to room temperature, and aqueous ammonia is added to adjust the pH to 8-9. The mixture is filtered to obtain an antibacterial and antifouling viscous emulsion.

[0009] Step (2), laying a PET substrate film on a flat and smooth glass plate, fixing both ends, pouring an antibacterial and antifouling viscous emulsion on one end of the film, and slowly pushing it from one end to the other end with a scraper to evenly coat the emulsion on the film, placing it at room temperature for 30-50 minutes, drying it in a constant temperature drying oven, and after cooling, sticking a release paper on the adhesive surface, transferring it with both sides of the PET substrate film by composite roller pressing, and obtaining an antibacterial and antifouling functional adhesive tape after slitting.

[0010] Preferably, the initiator in step (1) is any one of dibenzoyl peroxide, azobisisobutyronitrile or isopropylbenzene hydroperoxide.

[0011] Preferably, in step (1), butyl acrylate:methyl methacrylate:acrylic acid:dibenzoyl peroxide:alkenyl organosilicon fluorobetaine=100g:30-45g:5-10g:0.5-0.8g:3-15g.

[0012] Preferably, the coating thickness in step (2) is 20-40 μm.

[0013] Preferably, the preparation method of alkenyl organosilicon fluorobetaine in step (1) is carried out according to the following steps:

[0014] Step S1: In a nitrogen atmosphere, 4-dimethylaminophenol and acetone are added to a reaction flask, and after stirring evenly, 1-propylene 1,3-sultone is added, and the reaction is stirred. After the reaction is completed, the mixture is cooled to room temperature, filtered, and recrystallized from acetonitrile to obtain alkenyl betaine phenol. The preparation reaction formula is as follows:

[0015]

[0016] Step S2, under nitrogen atmosphere, add alkenyl betaine type phenol and N, N-dimethylformamide to the reaction flask, stir evenly, add 1H, 1H, 2H, 2H-perfluorooctylmethyldichlorosilane and pyridine, stir and react, after the reaction is completed, cool to room temperature, extract with ethyl acetate and deionize, concentrate the organic phase, and distill under reduced pressure (0.3KPa, 2mmHg) to obtain alkenyl organosilicon fluorobetaine. The preparation reaction formula is as follows:

[0017]

[0018] Preferably, in step S1, the ratio of 4-dimethylaminophenol to 1-propylene 1,3-sultone is 1 mol:(1.3-1.5) mol.

[0019] Preferably, in step S1, the reaction temperature is 45-60° C. and the reaction time is 24-48 h.

[0020] Preferably, in step S2, the ratio of alkenyl betaine phenol, 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and pyridine is 1 mol:(1.05-1.2) mol:(1.3-1.8) mol.

[0021] Preferably, in step S2, the reaction temperature is 80-100° C. and the reaction time is 5-12 h.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The invention uses 4-dimethylaminophenol, 1-propylene 1,3-sultone and 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane as raw materials, obtains alkenyl organosilicon fluorobetaine through chemical reaction, and initiates polymerization with acrylic monomers to obtain antibacterial and antifouling viscous emulsion, which is evenly coated on a PET film substrate to obtain an antibacterial and antifouling functional adhesive tape.

[0024] The quaternary ammonium salt cations in alkenyl organosilicon fluorobetaine can interact with the negative charge of the bacterial cell membrane through the positive charge they carry, adsorb and penetrate the cell membrane, destroy the permeability of the cell membrane, and cause the leakage of intracellular substances; the negative charge of the sulfonic acid anion can produce electrostatic repulsion with the negative charge on the bacterial surface, and at the same time can penetrate into the bacterial cell membrane, interact with the phospholipid molecules on the cell membrane, and destroy the integrity of the cell membrane; zwitterions have synergistic antibacterial effects, and further inhibit the growth and reproduction of bacteria by interfering with the normal metabolic process of bacteria, such as inhibiting enzyme activity and affecting protein synthesis. In addition, alkenyl organosilicon fluorobetaine is introduced into the tape by chemical grafting, will not migrate or precipitate, and has antibacterial persistence.

[0025] The continuously arranged perfluoroalkyl long chains and low surface energy organosilicon in alkenyl organosilicon fluorobetaine can form a tightly arranged structure on the surface of the tape, which can effectively reduce the contact area between liquid and solid, reduce the adsorption of liquid, and thus reduce the wettability of the material surface; after the organosilicon and fluorine are combined, the outer layer of the tape is covered with hydrophobic silicon-fluorine groups, so that the surface of the material has lower surface energy and better hydrophobic properties; the "micro-nano structure" of the functional tape with superhydrophobic structure captures the air layer, so that bacteria or other pollutants are isolated from the tape, and the contact area is reduced, so that it has good antifouling properties. The functional tape prepared by the present invention not only has excellent antibacterial and antifouling properties, but also has good mechanical properties, can be applied to various mechanical equipment and electronic products, and has wide applicability. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Unless otherwise specified, the raw materials and reagents used in this application are commercially available or can be prepared by known methods.

[0028] 4-Dimethylaminophenol, CAS number is 619-60-3.

[0029] 1-Propene 1,3-sultone, CAS number is 21806-61-1.

[0030] 1H,1H,2H,2H-Perfluorooctylmethyldichlorosilane, CAS number is 73609-36-6.

[0031] Example 1

[0032] (1) Under a nitrogen atmosphere, 85 mmol of 4-dimethylaminophenol and 680 mL of acetone were added to a reaction flask, and after stirring, 119 mmol of 1-propylene 1,3-sultone was added, and the mixture was reacted at 55° C. for 32 h. The mixture was cooled to room temperature, filtered, and recrystallized from acetonitrile to obtain alkenyl betaine phenol.

[0033] (2) Under nitrogen atmosphere, 75 mmol of alkenyl betaine-type phenol and 900 mL of N,N-dimethylformamide were added to a reaction flask, and after stirring, 84 mmol of 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and 120 mmol of pyridine were added, and the mixture was reacted at 90 °C for 8 h. The mixture was cooled to room temperature, extracted with ethyl acetate and deionized water, and the organic phase was concentrated and distilled under reduced pressure (0.3 KPa, 2 mmHg) to obtain alkenyl organosilicon fluorobetaine.

[0034] (3) Under nitrogen atmosphere, 100 g of butyl acrylate, 35 g of methyl methacrylate, 8 g of acrylic acid and 750 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at 85 ° C. and 900 r / min for 10 min to obtain a pre-emulsion. First, 1 / 4 of the pre-emulsion was added with 0.2 g of dibenzoyl peroxide, and stirred at 80 ° C. for 30 min. Then, the remaining 3 / 4 of the pre-emulsion, 0.4 g of dibenzoyl peroxide and 3 g of alkenyl organosilicon fluorobetaine were added, and stirring was continued for 5 h. The mixture was cooled to room temperature, ammonia water was added, the pH was adjusted to 9, and filtered to obtain an antibacterial and antifouling viscous emulsion.

[0035] (4) The PET substrate film is laid on a flat and smooth glass plate and fixed at both ends. The antibacterial and antifouling viscous emulsion is poured on one end of the film and slowly pushed from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 20 μm. The film is placed at room temperature for 40 minutes and dried in a constant temperature drying oven. After cooling, the release paper is attached to the adhesive surface and transferred by composite roller pressing with both sides of the PET substrate film. After slitting, the antibacterial and antifouling functional tape is obtained.

[0036] Example 2

[0037] (1) Under a nitrogen atmosphere, 150 mmol of 4-dimethylaminophenol and 750 mL of acetone were added to a reaction flask, and after stirring, 195 mmol of 1-propylene 1,3-sultone was added, and the mixture was reacted at 60° C. for 24 h. The mixture was cooled to room temperature, filtered, and recrystallized from acetonitrile to obtain alkenyl betaine phenol.

[0038] (2) Under nitrogen atmosphere, 135 mmol of alkenyl betaine-type phenol and 1080 mL of N,N-dimethylformamide were added to the reaction flask, and after stirring, 147.75 mmol of 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and 175.5 mmol of pyridine were added, and the mixture was reacted at 100 °C for 5 h. The mixture was cooled to room temperature, extracted with ethyl acetate and deionized water, and the organic phase was concentrated and distilled under reduced pressure (0.3 KPa, 2 mmHg) to obtain alkenyl organosilicon fluorobetaine.

[0039] (3) Under nitrogen atmosphere, 100 g of butyl acrylate, 30 g of methyl methacrylate, 5 g of acrylic acid and 600 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at 95 °C and 1000 r / min for 5 min to obtain a pre-emulsion. 0.3 g of azobisisobutyronitrile was added to 1 / 4 of the pre-emulsion, and the mixture was stirred at 85 °C for 20 min. Then, the remaining 3 / 4 of the pre-emulsion, 0.5 g of azobisisobutyronitrile and 6 g of alkenyl organosilicon fluorobetaine were added, and stirring was continued for 3 h. The mixture was cooled to room temperature, ammonia water was added, the pH was adjusted to 8, and the mixture was filtered to obtain an antibacterial and antifouling viscous emulsion.

[0040] (4) The PET substrate film is laid on a flat and smooth glass plate and fixed at both ends. The antibacterial and antifouling viscous emulsion is poured on one end of the film and slowly pushed from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 25 μm. The film is placed at room temperature for 30 minutes and dried in a constant temperature drying oven. After cooling, the release paper is attached to the adhesive surface and rolled on both sides of the PET substrate film. After slitting, the antibacterial and antifouling functional tape is obtained.

[0041] Example 3

[0042] (1) Under a nitrogen atmosphere, 40 mmol of 4-dimethylaminophenol and 400 mL of acetone were added to a reaction flask, and after stirring, 60 mmol of 1-propylene 1,3-sultone was added, and the mixture was reacted at 45° C. for 48 h. The mixture was cooled to room temperature, filtered, and recrystallized from acetonitrile to obtain alkenyl betaine phenol.

[0043] (2) Under nitrogen atmosphere, 32 mmol of alkenyl betaine-type phenol and 480 mL of N,N-dimethylformamide were added to the reaction flask, and after stirring, 38.4 mmol of 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and 57.6 mmol of pyridine were added, and the mixture was reacted at 80 °C for 12 h. The mixture was cooled to room temperature, extracted with ethyl acetate and deionized water, and the organic phase was concentrated and distilled under reduced pressure (0.3 KPa, 2 mmHg) to obtain alkenyl organosilicon fluorobetaine.

[0044] (3) Under nitrogen atmosphere, 100 g of butyl acrylate, 45 g of methyl methacrylate, 10 g of acrylic acid and 800 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at 80 ° C. and 800 r / min for 15 min to obtain a pre-emulsion. 0.3 g of cumene hydroperoxide was added to 1 / 4 of the pre-emulsion, and the mixture was stirred at 75 ° C. for 40 min. Then, the remaining 3 / 4 of the pre-emulsion, 0.4 g of cumene hydroperoxide and 9 g of alkenyl organosilicon fluorobetaine were added, and stirring was continued for 8 h. The mixture was cooled to room temperature, ammonia water was added, the pH was adjusted to 9, and the mixture was filtered to obtain an antibacterial and antifouling viscous emulsion.

[0045] (4) The PET substrate film is laid on a flat and smooth glass plate and fixed at both ends. The antibacterial and antifouling viscous emulsion is poured on one end of the film and slowly pushed from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 30 μm. The film is placed at room temperature for 50 min and dried in a constant temperature drying oven. After cooling, a release paper is attached to the adhesive surface and rolled on both sides of the PET substrate film. After slitting, an antibacterial and antifouling functional tape is obtained.

[0046] Example 4

[0047] (1) Under a nitrogen atmosphere, 90 mmol of 4-dimethylaminophenol and 675 mL of acetone were added to a reaction flask, and after stirring, 135 mmol of 1-propylene 1,3-sultone was added, and the mixture was reacted at 50° C. for 40 h. The mixture was cooled to room temperature, filtered, and recrystallized from acetonitrile to obtain alkenyl betaine phenol.

[0048] (2) Under nitrogen atmosphere, 100 mmol of alkenyl betaine-type phenol and 1250 mL of N,N-dimethylformamide were added to a reaction flask, and after stirring, 110 mmol of 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and 155 mmol of pyridine were added, and the mixture was reacted at 95 °C for 10 h. The mixture was cooled to room temperature, extracted with ethyl acetate and deionized water, and the organic phase was concentrated and distilled under reduced pressure (0.3 KPa, 2 mmHg) to obtain alkenyl organosilicon fluorobetaine.

[0049] (3) Under nitrogen atmosphere, 100 g of butyl acrylate, 40 g of methyl methacrylate, 7 g of acrylic acid and 650 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at 90 ° C. and 950 r / min for 8 min to obtain a pre-emulsion. First, 1 / 4 of the pre-emulsion was added with 0.15 g of dibenzoyl peroxide, and the mixture was stirred at 80 ° C. for 35 min. Then, the remaining 3 / 4 of the pre-emulsion, 0.45 g of dibenzoyl peroxide and 12 g of alkenyl organosilicon fluorobetaine were added, and stirring was continued for 4 h. The mixture was cooled to room temperature, ammonia water was added, the pH was adjusted to 9, and the mixture was filtered to obtain an antibacterial and antifouling viscous emulsion.

[0050] (4) The PET substrate film is laid on a flat and smooth glass plate and fixed at both ends. The antibacterial and antifouling viscous emulsion is poured on one end of the film and slowly pushed from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 35 μm. The film is placed at room temperature for 45 minutes and dried in a constant temperature drying oven. After cooling, the release paper is attached to the adhesive surface and transferred by composite roller pressing with both sides of the PET substrate film. After slitting, the antibacterial and antifouling functional tape is obtained.

[0051] Example 5

[0052] (1) Under a nitrogen atmosphere, 50 mmol of 4-dimethylaminophenol and 425 mL of acetone were added to a reaction flask, and after stirring, 72.5 mmol of 1-propylene 1,3-sultone was added, and the mixture was reacted at 50° C. for 48 h. The mixture was cooled to room temperature, filtered, and recrystallized from acetonitrile to obtain alkenyl betaine phenol.

[0053] (2) Under nitrogen atmosphere, 40 mmol of alkenyl betaine-type phenol and 500 mL of N,N-dimethylformamide were added to the reaction flask, and after stirring, 46 mmol of 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and 66 mmol of pyridine were added, and the mixture was reacted at 100 °C for 12 h. The mixture was cooled to room temperature, extracted with ethyl acetate and deionized water, and the organic phase was concentrated and distilled under reduced pressure (0.3 KPa, 2 mmHg) to obtain alkenyl organosilicon fluorobetaine.

[0054] (3) Under nitrogen atmosphere, 100 g of butyl acrylate, 45 g of methyl methacrylate, 5 g of acrylic acid and 720 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at 95 °C and 900 r / min for 12 min to obtain a pre-emulsion. 0.2 g of azobisisobutyronitrile was added to 1 / 4 of the pre-emulsion, and the mixture was stirred at 85 °C for 25 min. Then, the remaining 3 / 4 of the pre-emulsion, 0.4 g of azobisisobutyronitrile and 15 g of alkenyl organosilicon fluorobetaine were added, and stirring was continued for 8 h. The mixture was cooled to room temperature, ammonia water was added, the pH was adjusted to 8, and the mixture was filtered to obtain an antibacterial and antifouling viscous emulsion.

[0055] (4) The PET substrate film is laid on a flat and smooth glass plate and fixed at both ends. The antibacterial and antifouling viscous emulsion is poured on one end of the film and slowly pushed from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 40 μm. The film is placed at room temperature for 50 min and dried in a constant temperature drying oven. After cooling, a release paper is attached to the adhesive surface and rolled on both sides of the PET substrate film. After slitting, an antibacterial and antifouling functional tape is obtained.

[0056] Comparative Example 1

[0057] (1) Under a nitrogen atmosphere, 100 g of butyl acrylate, 35 g of methyl methacrylate, 8 g of acrylic acid and 750 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at a temperature of 85° C. and a rotation speed of 900 r / min for 10 min to obtain a pre-emulsion. First, 0.2 g of dibenzoyl peroxide was added dropwise to 1 / 4 of the pre-emulsion, and the mixture was stirred at 80° C. for 30 min. Then, the remaining 3 / 4 of the pre-emulsion, 0.4 g of dibenzoyl peroxide and 3 g of alkenyl betaine phenol (prepared in Example 1) were added, and stirring was continued for 5 h. The mixture was cooled to room temperature, ammonia water was added, the pH was adjusted to 9, and the mixture was filtered to obtain an antibacterial viscous emulsion.

[0058] (2) The PET substrate film is laid on a flat and smooth glass plate and fixed at both ends. The antibacterial viscous emulsion is poured on one end of the film and slowly pushed from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 20 μm. The film is placed at room temperature for 40 minutes and dried in a constant temperature drying oven. After cooling, the release paper is attached to the adhesive surface and rolled and transferred with the two sides of the PET substrate film. The antibacterial functional tape is obtained after slitting.

[0059] Comparative Example 2

[0060] (1) Under nitrogen atmosphere, 75 mmol of 4-vinylphenol (structural formula: CAS No. 2628-17-3) and 900 mL of N, N-dimethylformamide, stir evenly, add 84 mmol of 1H, 1H, 2H, 2H-perfluorooctylmethyldichlorosilane and 120 mmol of pyridine, react at 90 ° C for 8 hours, cool to room temperature, extract with ethyl acetate and deionized water, concentrate the organic phase, and distill under reduced pressure (0.3 KPa, 2 mmHg) to obtain an alkenyl organosilicone fluorine intermediate.

[0061] (2) In a nitrogen atmosphere, 100 g of butyl acrylate, 35 g of methyl methacrylate, 8 g of acrylic acid and 750 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at a temperature of 85° C. and a rotation speed of 900 r / min for 10 min to obtain a pre-emulsion. 0.2 g of dibenzoyl peroxide was added dropwise to 1 / 4 of the pre-emulsion, and the mixture was stirred at 80° C. for 30 min. Then, the remaining 3 / 4 of the pre-emulsion, 0.4 g of dibenzoyl peroxide and 3 g of an alkenyl organosilicon fluoride intermediate (structural formula: ), continue stirring for 5 h, cool to room temperature, add ammonia water, adjust the pH to 9, filter, and obtain an antifouling viscous emulsion.

[0062] (3) The PET substrate film is laid on a flat and smooth glass plate and fixed at both ends. The antifouling viscous emulsion is poured on one end of the film and slowly pushed from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 20 μm. The film is placed at room temperature for 40 minutes and dried in a constant temperature drying oven. After cooling, the release paper is attached to the adhesive surface and transferred by composite roller pressing with both sides of the PET substrate film. After slitting, the antifouling functional tape is obtained.

[0063] Comparative Example 3

[0064] (1) Under nitrogen atmosphere, 100 g of butyl acrylate, 35 g of methyl methacrylate, 8 g of acrylic acid and 750 mL of deionized water were added to a reaction bottle equipped with a dropping funnel, and the mixture was stirred at 85° C. and 900 r / min for 10 min to obtain a pre-emulsion. 0.2 g of dibenzoyl peroxide was added dropwise to 1 / 4 of the pre-emulsion, and the mixture was stirred at 80° C. for 30 min. Then, the remaining 3 / 4 of the pre-emulsion and 0.4 g of dibenzoyl peroxide were added, and the mixture was stirred for 5 h. The mixture was cooled to room temperature, and aqueous ammonia was added to adjust the pH to 9. The mixture was filtered to obtain a viscous emulsion.

[0065] (2) Spread the PET substrate film on a flat and smooth glass plate and fix both ends. Pour the viscous emulsion on one end of the film and slowly push it from one end to the other end with a scraper to evenly coat the emulsion on the film. The coating thickness is 20 μm. Place the film at room temperature for 40 minutes and dry it in a constant temperature drying oven. After cooling, stick the release paper on the adhesive surface and transfer it with the two sides of the PET substrate film by rolling. After slitting, a functional tape is obtained.

[0066] Antibacterial performance test: The test strains (Staphylococcus aureus, Escherichia coli, Candida albicans) were inoculated into liquid culture medium and cultured in a shaking incubator at 37°C for 24 h. 1 mL of bacteria with a concentration of 10 8 CFU / mL of bacterial suspension, the functional tapes prepared in the embodiments and comparative examples were cut and placed in the bacterial suspension, cultured at 37°C for 24 h, colony counted, and the antibacterial rate was calculated. The antibacterial rate = (BC) / B×100%, where C is the number of bacteria in the experimental group after culture, and B is the number of bacteria in the blank group. The functional tape of comparative example 3 was used as the blank group.

[0067] Table 1 Antibacterial performance test

[0068]

[0069] Escherichia coli is a Gram-negative bacterium, Staphylococcus aureus is a Gram-positive bacterium, and Candida albicans is a fungus. It can be seen from the test results in the above table that with the increase of the content of alkenyl organosilicon fluorobetaine in the antibacterial and antifouling adhesive emulsion, the antibacterial performance of the functional tape against different bacteria is gradually enhanced. This is because the quaternary ammonium salt cation interacts with the negative charge of the bacterial cell membrane through the positive charge it carries, adsorbs and penetrates the cell membrane, destroys the permeability of the cell membrane, and causes the leakage of intracellular substances; the negative charge of the sulfonic acid anion can interact with the negative charge on the surface of the bacteria. The electric charge produces electrostatic repulsion and can penetrate into the bacterial cell membrane, interact with the phospholipid molecules on the cell membrane, and destroy the integrity of the cell membrane; zwitterions have synergistic antibacterial effects and further inhibit the growth and reproduction of bacteria by interfering with the normal metabolic process of bacteria, such as inhibiting the activity of enzymes and affecting protein synthesis. In addition, alkenyl organosilicon fluorobetaine is introduced into the tape by chemical grafting, and will not migrate or precipitate, and has antibacterial persistence; Comparative Examples 2 and 3 do not contain zwitterionic antibacterial groups and do not have antibacterial properties.

[0070] Hydrophobic performance test: The hydrophilic and hydrophobic properties are determined by testing the contact angle of the functional tape surface. The water contact angle is tested at room temperature using a surface tension meter, and the volume of the test droplet is 5μL. The rolling angle of the droplet is measured by lifting the tape from 0° to a higher angle until the droplet rolls off the surface.

[0071] Table 2 Hydrophobic performance test

[0072] Contact angle (°) Roll angle (°) Example 1 118.5 16.0 Example 2 127.6 12.1 Example 3 135.8 7.3 Example 4 147.0 3.2 Example 5 150.1 2.7 Comparative Example 1 76.3 28.4 Comparative Example 2 120.5 15.8 Comparative Example 3 75.2 30.1

[0073] It can be seen from the test results in the above table that with the increase of the content of alkenyl organosilicon fluorobetaine in the antibacterial and antifouling viscous emulsion, the hydrophobic properties of the functional tape are gradually enhanced. The contact angle in Example 5 reaches 150.1° and the rolling angle is 2.7°, showing super-hydrophobic properties. The super-hydrophobicity of the material surface provides a guarantee for its excellent self-cleaning performance. This is because the continuously arranged perfluoroalkyl long chains and low-surface-energy organosilicon in alkenyl organosilicon fluorobetaine can form a tightly arranged structure on the surface of the tape, which can effectively reduce the contact area between liquid and solid, reduce the adsorption of liquid, and thus reduce the wettability of the material surface. After the combination of organosilicon and fluorine, the outer layer of the tape is covered with hydrophobic silicon-fluorine groups, which makes the surface of the material have lower surface energy and better hydrophobic properties; the air layer captured by the "micro-nano structure" of the functional tape with a super-hydrophobic structure isolates bacteria or other pollutants from the tape, reduces the contact area, and thus has good anti-fouling properties.

[0074] Peel strength test: According to GB2792-1998 standard, the prepared functional tape was cut into standard specimens with a width of 25 mm, and the release paper was peeled off and attached to a standard stainless steel plate. After being pressed back and forth twice using a standard 5 kg roller machine, the plate was left for 10 minutes, and then tested using a universal tensile testing machine at a peeling speed of 300 mm / min.

[0075] Table 3 Peel strength test

[0076] Peel strength (gf / 25mm) Example 1 810 Example 2 950 Example 3 1090 Example 4 1200 Example 5 1250 Comparative Example 1 710 Comparative Example 2 800 Comparative Example 3 590

[0077] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent application. It should be pointed out that, for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application; the methods used in the present application are conventional methods unless otherwise specified.

Claims

1. A method for preparing an antibacterial and antifouling functional adhesive tape, characterized in that: The preparation method is carried out according to the following steps: Step (1), under a nitrogen atmosphere, add butyl acrylate, methyl methacrylate, acrylic acid and deionized water to a reaction bottle equipped with a dropping funnel, stir at a temperature of 80-95° C. and a rotation speed of 800-1000 r / min for 5-15 minutes to obtain a pre-emulsion, first take 1 / 4 of the pre-emulsion and add 1 / 3 of the initiator, stir at 75-85° C. for 20-40 minutes, and then add the remaining 3 / 4 of the pre-emulsion, 2 / 3 of the initiator and the structural formula The alkenyl organosilicon fluorobetaine was added, stirring was continued for 3-8 hours, cooled to room temperature, ammonia water was added, the pH was adjusted to 8-9, and filtered to obtain an antibacterial and antifouling viscous emulsion; Step (2), laying a PET substrate film on a flat and smooth glass plate, fixing both ends, pouring an antibacterial and antifouling viscous emulsion on one end of the film, and slowly pushing it from one end to the other end with a scraper to evenly coat the emulsion on the film, placing it at room temperature for 30-50 minutes, drying it in a constant temperature drying oven, and after cooling, sticking a release paper on the adhesive surface, transferring it with both sides of the PET substrate film by composite roller pressing, and obtaining an antibacterial and antifouling functional adhesive tape after slitting.

2. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 1, characterized in that: The initiator in step (1) is any one of dibenzoyl peroxide, azobisisobutyronitrile or isopropylbenzene hydroperoxide.

3. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 1, characterized in that: In the step (1), butyl acrylate: methyl methacrylate: acrylic acid: dibenzoyl peroxide: alkenyl organosilicon fluorobetaine = 100g: 30-45g: 5-10g: 0.5-0.8g: 3-15g.

4. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 1, characterized in that: The coating thickness in step (2) is 20-40 μm.

5. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 1, characterized in that: The preparation method of alkenyl organosilicon fluorobetaine in step (1) is carried out according to the following steps: Step S1, under a nitrogen atmosphere, add 4-dimethylaminophenol and acetone to a reaction flask, stir evenly, add 1-propylene 1,3-sultone, stir to react, and after the reaction is completed, cool to room temperature, filter, and recrystallize from acetonitrile to obtain alkenyl betaine phenol; Step S2, under a nitrogen atmosphere, add alkenyl betaine type phenol and N, N-dimethylformamide to a reaction flask, stir evenly, add 1H, 1H, 2H, 2H-perfluorooctylmethyldichlorosilane and pyridine, stir to react, after the reaction is completed, cool to room temperature, extract with ethyl acetate and deionized water, concentrate the organic phase, and distill under reduced pressure to obtain alkenyl organosilicon fluorobetaine.

6. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 5, characterized in that: In the step S1, the ratio of 4-dimethylaminophenol to 1-propylene 1,3-sultone is 1 mol:(1.3-1.5) mol.

7. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 5, characterized in that: In step S1, the reaction temperature is 45-60° C. and the reaction time is 24-48 hours.

8. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 5, characterized in that: In the step S2, the ratio of alkenyl betaine phenol, 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and pyridine is 1 mol:(1.05-1.2) mol:(1.3-1.8) mol.

9. The method for preparing the antibacterial and antifouling functional adhesive tape according to claim 5, characterized in that: In step S2, the reaction temperature is 80-100° C. and the reaction time is 5-12 h.

10. An antibacterial and antifouling functional tape, characterized in that: Obtained by the preparation method according to any one of claims 1 to 9.

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