Antibacterial medical hydrocolloid pressure-sensitive adhesive tape and preparation process thereof

Abstract

The invention discloses an antibacterial medical hydrocolloid pressure-sensitive adhesive tape and a preparation process thereof, and belongs to the technical field of adhesives, quaternary ammonium salt chitosan microspheres with an antibacterial effect and iodine elementary substances are loaded through charge transfer to form a composite antibacterial agent, and the composite antibacterial agent is used as a filler of the antibacterial medical hydrocolloid pressure-sensitive adhesive tape and can be used for preparing the antibacterial medical hydrocolloid pressure-sensitive adhesive tape. The long-acting antibacterial requirement of the pressure-sensitive adhesive tape can be met. The antibacterial medical hydrocolloid pressure-sensitive adhesive tape prepared by the invention has very high tensile strength and tear resistance, and the quaternary ammonium salt chitosan microsphere structure can disperse stress, so that the antibacterial medical hydrocolloid pressure-sensitive adhesive tape is not easy to damage and strong in cohesion in the use and activity processes, is integrally stripped when being uncovered, and does not break or leave sticky residual adhesive; the adhesive tape can be firmly adhered to dry skin, can bear a certain degree of body activity, is smooth in stripping during replacement due to high water absorption and softness, has small trauma to skin and new tissues, and is particularly suitable for sensitive skin and long-term application.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adhesives, and particularly relates to an antibacterial medical water glue pressure-sensitive adhesive tape and a preparation process thereof. BACKGROUND

[0002] Pressure-sensitive adhesive is a viscoelastic body, which can be bonded to most dry surfaces and some wet surfaces only with light pressure, and the adhesive is not easy to remain on the surface to be bonded when being torn off. Because the pressure-sensitive adhesive has the advantages of convenient use, good stability, simple preparation and the like, it has been widely applied in the medical and health fields such as surgical dressing, skin wound treatment, bonding biomedical devices, transdermal drug release patches, medical labels and adhesive tapes.

[0003] The acrylate polymer has a large number of hydrophilic groups such as carboxyl, hydroxyl and amide groups densely distributed on the molecular chain, which endows the polymer with high water absorption, and is a main material for synthesizing medical pressure-sensitive adhesive. Meanwhile, the acrylate pressure-sensitive adhesive has two advantages: no additional components are needed for preparation, and the prepared product can be directly used without separation and purification, thus having great cost advantage and avoiding potential safety problems; and different properties of the pressure-sensitive adhesive can be obtained by adjusting the content and type of acrylate monomers, thus having advantages in product diversity and flexibility.

[0004] Because the pressure-sensitive adhesive is often used for covering protection of skin wounds, it is necessary to endow the adhesive with antibacterial property, which can prevent wound infection and is beneficial to wound healing. Iodine is a common medical bactericide, which is usually prepared into iodine alcohol or iodophor solution. Iodophor particles are dissolved in solvent-type acrylate pressure-sensitive adhesive to prepare iodine-containing pressure-sensitive adhesive, and iodophor surgical drape has been prepared. However, because the solubility of iodophor in the pressure-sensitive adhesive solution is very limited, the iodine loading amount is not high; and there is no chemical / coordination bond or other interaction between iodophor and pressure-sensitive adhesive, so that iodophor is quickly released after being pasted on the skin, and cannot play a role in slow release of iodine, thereby failing to meet the requirement of long-acting antibacterial property.

[0005] Chinese patent application with publication number CN115181208A discloses a medical pressure-sensitive adhesive with iodine slow-release effect, a pressure-sensitive adhesive tape and a preparation method thereof. In the scheme, N-vinyl pyrrolidone or polyethylene glycol diacrylate is used as an iodine loading compound to load iodine element, so as to achieve the effect of long-acting antibacterial property. However, the antibacterial effect of iodine in the scheme is single, and the physical adsorption and weak interaction cannot meet the requirement of long-acting antibacterial property of the medical pressure-sensitive adhesive tape. SUMMARY

[0006] The application aims to provide an antibacterial medical hydrocolloid pressure-sensitive adhesive tape and a preparation process thereof, wherein quaternary ammonium salt chitosan microspheres with antibacterial effect are loaded between the quaternary ammonium salt chitosan microspheres and iodine through charge transfer to form a composite antibacterial agent, which is used as a filler of the antibacterial medical hydrocolloid pressure-sensitive adhesive tape, and the antibacterial medical hydrocolloid pressure-sensitive adhesive tape can meet the long-acting antibacterial requirement of the pressure-sensitive adhesive tape.

[0007] The application can be achieved by the following technical scheme.

[0008] An antibacterial medical hydrocolloid pressure-sensitive adhesive tape comprises the following components in parts by mass:

[0009] 15-20 parts of acrylic acid, 15-20 parts of acrylamide, 0.05-0.1 part of N,N-methylene bisacrylamide, 10-20 parts of water-based acrylic ester emulsion, 8-10 parts of glycerol, 30-40 parts of water, 0.5-2 parts of carbomer, 0.5-2 parts of the composite antibacterial agent, 0.1-0.2 part of ammonium persulfate and 0.2-0.4 part of sodium bisulfite.

[0010] Further, the preparation steps of the composite antibacterial agent are as follows:

[0011] Step one: a W / O emulsion crosslinking method is adopted, a mixed solution of chitosan powder and glacial acetic acid solution is used as the water phase, liquid paraffin and Span-80 are used as the oil phase, a W / O emulsion is formed, and then crosslinking is carried out under glutaraldehyde to obtain chitosan microspheres.

[0012] Step two: the amino group at the C2 position of chitosan is positioned and grafted with 2-amino-isonicotinic acid by a carbodiimide coupling method to obtain modified chitosan microspheres; the epoxy group of 2,3-epoxypropyltrimethylammonium chloride is subjected to ring-opening reaction with the primary hydroxyl group at the C6 position of chitosan to prepare quaternary ammonium salt chitosan microspheres.

[0013] Step three: a semi-wet grinding method is adopted, the quaternary ammonium salt chitosan microspheres and acetic acid are ground to a semi-dry state, and then the quaternary ammonium salt chitosan microspheres are ground with iodine, methanol and potassium iodide solution under an infrared lamp to obtain the composite antibacterial agent.

[0014] Step four: acrylic acid, acrylamide, N,N-methylene bisacrylamide, water-based acrylic ester emulsion, glycerol, water, carbomer and the composite antibacterial agent are stirred and mixed, ammonium persulfate and sodium bisulfite are then added, and stirring and mixing are continued, then the mixture is coated on a PVC substrate to form a film, a PET release film is covered, and baking is carried out at 60-70 DEG C to obtain the antibacterial medical hydrocolloid pressure-sensitive adhesive tape.

[0015] Further, the preparation steps of the chitosan microspheres are as follows:

[0016] The chitosan powder and the 3-4% mass fraction of the ice acetic acid solution are added into a reaction kettle, stirred at 20-25℃ and 500-600r / min for 12-14h to obtain a mixed solution; the liquid paraffin and Span-80 as an emulsifier are stirred and mixed, homogenized at 10000-12000r / min for 3-4min to form a uniform oil phase solution, then the mixed solution is added dropwise into the oil phase solution, stirred at 20-25℃ and 500-600r / min for 3-4h to form a stable W / O emulsion, then glutaraldehyde is added, heated to 40-45℃, crosslinking reaction is carried out for 4-6h, naturally cooled to room temperature, centrifuged at 8000-9000r / min for 5-8min, filtered, the precipitate is washed with anhydrous ethanol, petroleum ether and deionized water for 2-4 times respectively, vacuum dried at 40-42℃ for 24-26h to obtain the chitosan microspheres.

[0017] Further, the use amount ratio of the chitosan powder and the ice acetic acid solution is 20-22g:800-820mL.

[0018] Further, the use amount ratio of the liquid paraffin, Span-80, the mixed solution and glutaraldehyde is 900-980mL:4-6g:80-82mL:12-14g.

[0019] Further, the specific preparation steps of the modified chitosan microspheres are as follows:

[0020] The 16-18% mass fraction of the N-hydroxysuccinimide solution, the 30-32% mass fraction of the 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution and the 14-16% mass fraction of the 2-aminoisonicotinic acid are added into a reaction kettle, stirred at 20-25℃ and 500-600r / min for 1-2h, then the chitosan microspheres are added, continue to stir for 24-26h, purified by dialysis with deionized water, the molecular weight cut-off is 8-14kDa, freeze-dried at-20℃ for 1-2h to obtain the modified chitosan microspheres.

[0021] Further, the use amount ratio of the N-hydroxysuccinimide solution, the 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution, the 2-aminoisonicotinic acid and the chitosan microspheres is 50-60mL:50-60mL:100-120mL:12-14g.

[0022] Further, the specific preparation steps of the quaternary ammonium salt chitosan microspheres are as follows:

[0023] Modified chitosan microspheres and a 0.5-0.7% NaOH solution were added to a reaction vessel and stirred for 20-30 minutes at 70-80℃ and 500-600 r / min. Then, 2,3-epoxypropyltrimethylammonium chloride was added and stirring was continued for 4-6 hours. The mixture was precipitated with anhydrous ethanol and filtered. The precipitate was washed 2-4 times with a 75-80% ethanol solution and then extracted with anhydrous ethanol using a Soxhlet extractor for 24-26 hours to remove unreacted solvent. The remaining precipitate was then vacuum dried at 60-70℃ for 1-2 hours to obtain quaternary ammonium salt chitosan microspheres.

[0024] Furthermore, the ratio of modified chitosan microspheres, NaOH solution, and 2,3-epoxypropyltrimethylammonium chloride is 8-9 g: 320-350 mL: 32-36 g.

[0025] Furthermore, the specific preparation steps of the compound antibacterial agent are as follows:

[0026] Quaternary ammonium salt chitosan microspheres and acetic acid with a mass fraction of 1-2% were placed in a mortar and ground until semi-dry. Then, iodine, methanol and potassium iodide solution with a mass fraction of 40-50% were added. The mixture was ground for 1-2 hours under vertical irradiation with an infrared lamp with a power of 300-400W and an irradiation distance of 12-15cm. The product was washed 2-4 times with deionized water, anhydrous ethanol with a mass fraction of 50-55%, and anhydrous ethanol, respectively. The product was then vacuum dried at 60-70℃ for 1-2 hours to obtain a composite antibacterial agent.

[0027] Furthermore, the ratio of quaternary ammonium salt chitosan microspheres, acetic acid, iodine, methanol, and potassium iodide solution is 5-6g: 5-10mL: 1-1.5g: 8-10mL: 4-5mL.

[0028] The beneficial effects of this invention are:

[0029] 1. The antibacterial medical hydrocolloid pressure-sensitive tape prepared by the present invention utilizes quaternary ammonium salt chitosan microspheres with antibacterial effect to load iodine through charge transfer pairs to form a composite antibacterial agent, which serves as a filler for the antibacterial medical hydrocolloid pressure-sensitive tape and can meet the long-term antibacterial requirements of pressure-sensitive tape.

[0030] 2. The quaternary ammonium salt chitosan microspheres of the present invention are formed by self-assembly of microspheres through a W / O type emulsion crosslinking method, and then grafted to modify the amino group at the C2 position and the primary hydroxyl group at the C6 position respectively. The antibacterial activity of chitosan derivatives formed by chemically modifying the amino group at the C-2 position or the primary hydroxyl group at the C-6 position of chitosan by traditional modification methods is still low. The present invention modifies both the amino group at the C-2 position and the primary hydroxyl group at the C-6 position of chitosan at the same time, thereby increasing the positive charge intensity on the surface. With the large specific surface area of ​​the microspheres, the charge transfer effect on iodine is enhanced, the loading strength of iodine is improved, and quaternary ammonium salt chitosan microspheres with high antibacterial activity are obtained.

[0031] 3. The antibacterial medical hydrocolloid pressure-sensitive tape prepared in this invention is a superabsorbent polymer formed by the emulsion polymerization of acrylic acid, acrylamide, N,N-methylenebisacrylamide, and aqueous acrylate. It possesses superior absorption and water-locking capabilities, rapidly absorbing wound exudate and locking it within a cross-linked network to form a soft gel. The quaternary ammonium salt chitosan microspheres, as a polycationic complex, can combine with the polyanionic polymer carrageenan, achieving a static effect between the polycationic and polyanionic polymers.

[0032] Electrical interactions promote gel formation, which not only creates an ideal moist healing environment for wounds but also effectively prevents exudate from seeping into the surrounding healthy skin, thus avoiding maceration.

[0033] 4. The antibacterial medical hydrocolloid pressure-sensitive tape prepared by this invention has high tensile strength and tear resistance. The quaternary ammonium salt chitosan microsphere structure can disperse stress, making it less prone to damage during use and activities. It has strong cohesion and can be peeled off as a whole without breaking or leaving sticky residue. It adheres firmly to dry skin and can withstand a certain degree of physical activity. At the same time, due to its high water absorption and softness, it is easy to peel off when changing, causing little trauma to the skin and new tissue, and is especially suitable for sensitive skin and long-term application. Detailed Implementation

[0034] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0035] Example 1: A preparation process for an antibacterial medical hydrocolloid pressure-sensitive tape, comprising the following steps:

[0036] S1: 20g of chitosan powder and 800mL of 3% glacial acetic acid solution were added to a reaction vessel and stirred at 20℃ and 500r / min for 12h to obtain a mixed solution. 900mL of liquid paraffin and 4g of Span-80 as an emulsifier were stirred and mixed, and homogenized at 10000r / min for 3min to form a uniform oil phase solution. Then, 80mL of the mixed solution was added dropwise to the oil phase solution and stirred at 20℃ and 500r / min for 3h to form a stable W / O type emulsion. Then, 12g of glutaraldehyde was added, heated to 40℃, and crosslinked for 4h. After naturally cooling to room temperature, the mixture was centrifuged at 8000r / min for 5min, filtered, and the precipitate was washed twice with anhydrous ethanol, petroleum ether, and deionized water, respectively. The precipitate was then vacuum dried at 40℃ for 24h to obtain chitosan microspheres.

[0037] S2: 50 mL of 16% N-hydroxysuccinimide solution, 50 mL of 30% 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution, and 100 mL of 14% 2-aminoisonicotinic acid solution were added to a reaction vessel and stirred at 20℃ and 500 r / min for 1 h. Then, 12 g of chitosan microspheres were added and stirred for another 24 h. The mixture was purified by dialysis with deionized water, with a molecular weight cutoff of 8 kDa. The mixture was then freeze-dried at -20℃ for 1 h to obtain modified chitosan microspheres.

[0038] The antibacterial effect of traditional chitosan relies on the relatively weak positive charge center of the main chain, so its antibacterial function is limited. After modifying the C2 amino group with 2-aminoisonicotinic acid, the pyridine heterocycle contained in 2-aminoisonicotinic acid is lipophilic, which significantly improves the antibacterial effect of chitosan. In addition, the pyridine heterocycle contains a lone pair of electrons, which, together with the two amino groups it carries, can increase the positive charge strength of chitosan.

[0039] S3: Add 8g of modified chitosan microspheres and 320mL of 0.5% NaOH solution to the reactor and stir for 20min at 70℃ and 500r / min. Then add 32g of 2,3-epoxypropyltrimethylammonium chloride and continue stirring for 4h. Precipitate with anhydrous ethanol, filter, wash the precipitate twice with 75% ethanol solution, and then extract with anhydrous ethanol for 24h to remove unreacted solvent. Place the remaining precipitate in a vacuum dryer at 60℃ for 1h to obtain quaternary ammonium salt chitosan microspheres.

[0040] By grafting quaternary ammonium salt groups at the C-6 position, a large number of amino cations at the C2 position are retained, significantly enhancing the positive charge. This allows the bacteria to carry a positive charge under acidic conditions, forming polycations that act on the bacterial surface. Through strong and rapid electrostatic interactions with the negatively charged phospholipid membrane of the bacterial cell membrane, the bacteria hinder nutrient absorption, leading to weakened cell metabolism and inhibiting bacterial growth and reproduction until eventual apoptosis.

[0041] S4: Place 5g of quaternary ammonium salt chitosan microspheres and 5mL of 1% acetic acid in a mortar and grind until semi-dry. Then add 1g of iodine, 8mL of methanol and 4mL of 40% potassium iodide solution. Grind for 1h under vertical irradiation with a 300W infrared lamp at a distance of 12cm. Wash the product twice with deionized water, 50% anhydrous ethanol and anhydrous ethanol, respectively. Dry under vacuum at 60℃ for 1h to obtain the composite antibacterial agent.

[0042] S5: Mix 15g acrylic acid, 15g acrylamide, 0.05g N,N-methylenebisacrylamide, 10g waterborne acrylic emulsion, 8g glycerin, 30g water, 0.5g carbomer, and 0.5g composite antibacterial agent. Then add 0.1g ammonium persulfate and 0.2g sodium bisulfite, continue mixing, coat the mixture onto a PVC substrate, cover with a PET release film, and bake at 60℃ to obtain antibacterial medical hydrocolloid pressure-sensitive tape.

[0043] Example 2: A preparation process for an antibacterial medical hydrocolloid pressure-sensitive tape, comprising the following steps:

[0044] S1: 21g of chitosan powder and 810mL of 3.5% glacial acetic acid solution were added to a reaction vessel and stirred at 22.5℃ and 550r / min for 13h to obtain a mixed solution. 940mL of liquid paraffin and 5g of Span-80 as an emulsifier were stirred and mixed, and homogenized at 11000r / min for 3.5min to form a homogeneous oil phase solution. Then, 81mL of the mixed solution was added dropwise to the oil phase solution and stirred at 22.5℃ and 550r / min for 3.5h to form a stable W / O type emulsion. Then, 13g of glutaraldehyde was added, heated to 42.5℃, and crosslinked for 5h. After naturally cooling to room temperature, the mixture was centrifuged at 8500r / min for 6.5min, filtered, and the precipitate was washed three times each with anhydrous ethanol, petroleum ether, and deionized water. The precipitate was then vacuum dried at 41℃ for 25h to obtain chitosan microspheres.

[0045] S2: 55 mL of 17% N-hydroxysuccinimide solution, 55 mL of 31% 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution, and 110 mL of 15% 2-aminoisonicotinic acid solution were added to a reaction vessel and stirred for 1.5 h at 22.5 °C and 550 r / min. Then, 13 g of chitosan microspheres were added and stirring was continued for 25 h. The mixture was purified by dialysis with deionized water, and the molecular weight cutoff was 11 kDa. The mixture was then freeze-dried at -20 °C for 1.5 h to obtain modified chitosan microspheres.

[0046] S3: Add 8.5g of modified chitosan microspheres and 335mL of 0.6% NaOH solution to the reactor. Stir for 25min at 75℃ and 550r / min. Then add 34g of 2,3-epoxypropyltrimethylammonium chloride and continue stirring for 5h. Precipitate with anhydrous ethanol, filter, wash the precipitate three times with 77.5% ethanol solution, and then extract with anhydrous ethanol for 25h to remove unreacted solvent. Place the remaining precipitate in a vacuum dryer at 65℃ for 1.5h to obtain quaternary ammonium salt chitosan microspheres.

[0047] S4: 5.5g of quaternary ammonium salt chitosan microspheres and 7.5mL of 1.5% acetic acid were placed in a mortar and ground until semi-dry. Then, 1.25g of iodine, 9mL of methanol and 4.5mL of 45% potassium iodide solution were added. The mixture was ground for 1.5h under vertical irradiation with an infrared lamp of 350W at a distance of 13.5cm. The product was washed three times each with deionized water, 52.5% anhydrous ethanol and anhydrous ethanol, and then vacuum dried at 65℃ for 1.5h to obtain the composite antibacterial agent.

[0048] S5: Mix 17.5g acrylic acid, 17.5g acrylamide, 0.075g N,N-methylenebisacrylamide, 15g waterborne acrylic emulsion, 9g glycerin, 35g water, 1.25g carbomer, and 1.25g composite antibacterial agent. Then add 0.15g ammonium persulfate and 0.3g sodium bisulfite. Continue mixing and coating the mixture onto a PVC substrate. Cover with a PET release film and bake at 65°C to obtain an antibacterial medical hydrocolloid pressure-sensitive tape.

[0049] Example 3: A preparation process for an antibacterial medical hydrocolloid pressure-sensitive tape, comprising the following steps:

[0050] S1: 22g of chitosan powder and 820mL of 4% glacial acetic acid solution were added to a reaction vessel and stirred at 25℃ and 600r / min for 14h to obtain a mixed solution. 980mL of liquid paraffin and 6g of Span-80 as an emulsifier were stirred and mixed, and homogenized at 12000r / min for 4min to form a uniform oil phase solution. Then, 82mL of the mixed solution was added dropwise to the oil phase solution and stirred at 25℃ and 600r / min for 4h to form a stable W / O type emulsion. Then, 14g of glutaraldehyde was added, heated to 45℃, and crosslinked for 6h. After naturally cooling to room temperature, the mixture was centrifuged at 9000r / min for 8min, filtered, and the precipitate was washed four times with anhydrous ethanol, petroleum ether, and deionized water, respectively. The precipitate was then vacuum dried at 42℃ for 26h to obtain chitosan microspheres.

[0051] S2: 60 mL of 18% N-hydroxysuccinimide solution, 60 mL of 32% 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution, and 120 mL of 16% 2-aminoisonicotinic acid solution were added to a reaction vessel and stirred at 25℃ and 600 r / min for 2 h. Then, 14 g of chitosan microspheres were added and stirred for another 26 h. The mixture was purified by dialysis with deionized water, with a molecular weight cutoff of 14 kDa. The mixture was then freeze-dried at -20℃ for 2 h to obtain modified chitosan microspheres.

[0052] S3: Add 9g of modified chitosan microspheres and 350mL of 0.7% NaOH solution to the reactor and stir for 30min at 80℃ and 600r / min. Then add 36g of 2,3-epoxypropyltrimethylammonium chloride and continue stirring for 6h. Precipitate with anhydrous ethanol, filter, wash the precipitate 4 times with 80% ethanol solution, and then extract with anhydrous ethanol for 26h to remove unreacted solvent. Place the remaining precipitate at 70℃ and vacuum dry for 2h to obtain quaternary ammonium salt chitosan microspheres.

[0053] S4: Place 6g of quaternary ammonium salt chitosan microspheres and 10mL of 2% acetic acid in a mortar and grind until semi-dry. Then add 1.5g of iodine, 10mL of methanol and 5mL of 50% potassium iodide solution. Grind for 2 hours under vertical irradiation with an infrared lamp of 400W at a distance of 15cm. Wash the product four times with deionized water, 55% anhydrous ethanol and anhydrous ethanol, respectively. Dry under vacuum at 70℃ for 2 hours to obtain the composite antibacterial agent.

[0054] S5: Mix 20g acrylic acid, 20g acrylamide, 0.1g N,N-methylenebisacrylamide, 20g waterborne acrylic emulsion, 10g glycerin, 40g water, 2g carbomer and 2g compound antibacterial agent. Then add 0.2g ammonium persulfate and 0.4g sodium bisulfite. Continue mixing and coating the mixture onto a PVC substrate to form a film. Cover with a PET release film and bake at 70°C to obtain antibacterial medical hydrocolloid pressure-sensitive tape.

[0055] Comparative Example 1: Based on Example 3, the chitosan microspheres in step S2 were replaced with chitosan powder in step S1, while the other steps remained unchanged, to prepare an antibacterial medical hydrocolloid pressure-sensitive tape.

[0056] Comparative Example 2: Based on Example 3, the modified chitosan microspheres in step S3 were replaced with the chitosan microspheres prepared in step S1, while the other steps remained unchanged, to prepare an antibacterial medical hydrocolloid pressure-sensitive tape.

[0057] Comparative Example 3: Based on Example 3, the quaternary ammonium salt chitosan microspheres in step S4 were replaced with the modified chitosan microspheres prepared in step S2, while the other steps remained unchanged, to prepare an antibacterial medical hydrocolloid pressure-sensitive tape.

[0058] In the examples and comparative examples:

[0059] 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide was purchased from Sigma-Aldrich, CAS No.: 1892-57-5, molecular weight: 155.24.

[0060] N-hydroxysuccinimide was purchased from Sigma-Aldrich, CAS No.: 6066-82-6, molecular weight: 115.09.

[0061] 2-Aminoisonicotinic acid was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 13362-28-2, molecular weight: 138.13.

[0062] N,N-methylenebisacrylamide was purchased from Sigma-Aldrich, CAS No.: 110-26-9, molecular weight: 154.17.

[0063] The water-based acrylic emulsion was purchased from Guangdong Xidun New Material Technology Co., Ltd., with a viscosity of <1000.

[0064] The carbomer was purchased from Sigma-Aldrich, CAS No.: 138789-85-2.

[0065] The performance of the antibacterial medical hydrocolloid pressure-sensitive tapes prepared in Examples 1-3 and Comparative Examples 1-3 was tested:

[0066] 1. The adhesiveness of the antibacterial medical aqueous colloidal pressure-sensitive tape was tested using a universal testing machine according to GB / T2792-1998. The commercially available 3M iodine surgical film (Ioban2 6640) was used as a control group. No adhesive residue was found when the tape was removed, indicating that the tape has good removability.

[0067] 2. Cut the antibacterial medical hydrocolloid pressure-sensitive tape into small pieces of 30mm×30mm and apply them to the skin surface. After 4 hours, remove the tape every 1 hour. Use sodium thiosulfate titration to determine the residual iodine content in the pressure-sensitive adhesive and calculate the iodine release rate. Stop the experiment and record the time when the release rate is >90%.

[0068] 3. Cut the antibacterial medical hydrocolloid pressure-sensitive tape into round pieces with a diameter of 25 mm. Determine the inhibition zone against Staphylococcus aureus and Escherichia coli according to the standard GB / T20944.1-2007. After incubating the petri dishes in a 37℃ incubator for 24 h, measure the diameter of the inhibition zone.

[0069] 4. Cut the antibacterial medical hydrocolloid pressure-sensitive tape into 30mm×30mm pieces and determine the elastic modulus according to the standard GB / T1040-2006.

[0070] The results are shown in Table 1:

[0071] Table 1 Performance Test Results of Antibacterial Medical Aqueous Colloidal Pressure-Sensitive Adhesive Tape

[0072] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Control Dry skin peel strength (gf / cm) 118 123 127 88 103 105 72 Wet skin peel strength (gf / cm) 69 73 77 47 58 66 33 Adhesive residue No No No No No No No Time for >90% dry skin iodine release (h) 38 40 42 11 23 26 6 Time for >90% wet skin iodine release (h) 30 32 35 9 20 22 4 S. aureus zone of inhibition (mm) 34 36 37 17 25 27 24 E. coli zone of inhibition (mm) 32 33 35 15 22 24 18 Elastic modulus (GPa) 1.4 1.5 1.7 0.6 0.9 1.0 1.2

[0073] As shown in Table 1, the peel strength, iodine release time, inhibition zone, and elastic modulus of the antibacterial medical hydrocolloid pressure-sensitive tapes prepared in Examples 1-3 are significantly better than those of the comparative examples, indicating that the antibacterial medical hydrocolloid pressure-sensitive tapes prepared in this invention...

[0074] In Comparative Example 1, chitosan microspheres were replaced with chitosan powder in S1. Chitosan powder has no spherical structure, a small specific surface area, and is prone to agglomeration. It cannot disperse stress in the pressure-sensitive adhesive matrix, resulting in a decrease in the peel strength of dry / wet skin. It is easily damaged and broken during use and cannot withstand the stretching and friction caused by body activities. It does not have the high specific surface area of ​​microspheres and has not been modified in any way. Its interaction with iodine is only weak physical adsorption, resulting in a fast iodine release rate. It cannot achieve the long-lasting antibacterial effect required for wound care and is prone to secondary wound infection.

[0075] Comparative Example 2 replaced the modified chitosan microspheres with unmodified chitosan microspheres. The surface of the unmodified chitosan microspheres contained only natural amino groups and lacked the introduced pyridine ring and additional amino groups. The charge transfer effect on iodine was weak, resulting in a shortened iodine release time and a decrease in antibacterial activity. It could not effectively inhibit common pathogens in wounds. Chitosan microspheres need to form electrostatic interactions with polyanionic polymers through positive charges to promote gel formation and improve water absorption and retention capacity. Due to insufficient positive charge, Comparative Example 2 had a low gel network density.

[0076] Comparative Example 3 replaced the quaternary ammonium salt chitosan microspheres with modified chitosan microspheres. Only the C2 position was modified, lacking the quaternary ammonium salt group at the C6 position. The surface positive charge density was low, the iodine loading strength was insufficient, and the inhibition zone was small. Although it could meet the basic antibacterial requirements, the antibacterial effect was insufficient in long-term application scenarios. The quaternary ammonium salt group is a typical broad-spectrum antibacterial group, which has a strong inhibitory effect on both Gram-positive and Gram-negative bacteria and is not prone to drug resistance. Due to the lack of this group, the antibacterial spectrum is narrower than that of the example, and the inhibitory effect on some drug-resistant Staphylococcus aureus may be poor, thus limiting the clinical application scenarios.

[0077] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape, characterized by, The components include the following by mass fraction: 15-20 parts of acrylic acid, 15-20 parts of acrylamide, 0.05-0.1 parts of N,N-methylene bisacrylamide, 10-20 parts of aqueous acrylate emulsion, 8-10 parts of glycerol, 30-40 parts of water, 0.5-2 parts of carbomer, 0.5-2 parts of composite antibacterial agent, 0.1-0.2 parts of ammonium persulfate, and 0.2-0.4 parts of sodium bisulfite.

2. An antiseptic medical hydrocolloid pressure-sensitive adhesive tape as set forth in claim 1, characterized by The specific preparation steps of the composite antibacterial agent are as follows: The quaternary ammonium salt chitosan microspheres and acetic acid with a mass fraction of 1-2% are placed in a mortar and ground to a semi-dry state, then iodine, methanol and potassium iodide solution with a mass fraction of 40-50% are added, and grinding is carried out under the vertical irradiation of an infrared lamp with a power of 300-400 W for 1-2 h, the irradiation distance is 12-15 cm, and the product is washed with deionized water, anhydrous ethanol with a mass fraction of 50-55% and anhydrous ethanol for 2-4 times respectively, and vacuum dried at 60-70°C for 1-2 h to obtain the composite antibacterial agent.

3. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape according to claim 2, characterized in that, The amount ratio of the quaternary ammonium salt chitosan microspheres, acetic acid, iodine, methanol and potassium iodide solution is 5-6 g:5-10 mL:1-1.5 g:8-10 mL:4-5 mL.

4. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape according to claim 2, wherein The specific preparation steps of the quaternary ammonium salt chitosan microspheres are as follows: The modified chitosan microspheres and NaOH solution with a mass fraction of 0.5-0.7% are added to a reaction kettle, stirred at 70-80°C and 500-600 r / min for 20-30 min, then 2,3-epoxypropyltrimethylammonium chloride is added, and stirring is continued for 4-6 h, then precipitation is carried out with anhydrous ethanol, filtration is carried out, the precipitate is washed with ethanol solution with a mass fraction of 75-80% for 2-4 times, Soxhlet extraction is carried out with anhydrous ethanol as the solvent for 24-26 h, unreacted solvent is removed, and the remaining precipitate is vacuum dried at 60-70°C for 1-2 h to obtain the quaternary ammonium salt chitosan microspheres.

5. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape according to claim 4, characterized in that, The amount ratio of the modified chitosan microspheres, NaOH solution and 2,3-epoxypropyltrimethylammonium chloride is 8-9 g:320-350 mL:32-36 g.

6. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape according to claim 4, wherein The specific preparation steps of the modified chitosan microspheres are as follows: N-hydroxysuccinimide solution with a mass fraction of 16-18%, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution with a mass fraction of 30-32% and 2-amino-isonicotinic acid with a mass fraction of 14-16% are added to a reaction kettle, stirred at 20-25°C and 500-600 r / min for 1-2 h, then chitosan microspheres are added, and stirring is continued for 24-26 h, then dialysis purification is carried out with deionized water, the molecular weight cut-off is 8-14 kDa, and freeze-drying is carried out at -20°C for 1-2 h to obtain the modified chitosan microspheres.

7. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape according to claim 6, characterized in that, The amount ratio of the N-hydroxysuccinimide solution, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution, 2-amino-isonicotinic acid and chitosan microspheres is 50-60 mL:50-60 mL:100-120 mL:12-14 g.

8. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape according to claim 6, wherein The specific preparation steps of the chitosan microspheres are as follows: The chitosan powder and the 3-4% mass fraction of the ice acetic acid solution are added into a reaction kettle, and stirred at 20-25 ℃ and 500-600 r / min for 12-14 h to obtain a mixed solution; the liquid paraffin and Span-80 as an emulsifier are stirred and mixed, and homogenized at 10000-12000 r / min for 3-4 min to form a uniform oil phase solution, then the mixed solution is added dropwise into the oil phase solution, and stirred at 20-25 ℃ and 500-600 r / min for 3-4 h to form a stable W / O emulsion, then glutaraldehyde is added, heated to 40-45 ℃, and crosslinked for 4-6 h, and naturally cooled to room temperature, centrifuged at 8000-9000 r / min for 5-8 min, filtered, and the precipitate is washed with anhydrous ethanol, petroleum ether and deionized water for 2-4 times respectively, and vacuum dried at 40-42 ℃ for 24-26 h to obtain the chitosan microspheres.

9. An antimicrobial medical hydrocolloid pressure-sensitive adhesive tape according to claim 8, characterized in that, The amount ratio of the chitosan powder and the ice acetic acid solution is 20-22 g:800-820 mL; the amount ratio of the liquid paraffin, Span-80, the mixed solution and glutaraldehyde is 900-980 mL:4-6 g:80-82 mL:12-14 g.

10. The process for preparing an antiseptic medical hydrocolloid pressure-sensitive adhesive tape according to claim 1, characterized in that, The method comprises the following steps: The acrylic acid, acrylamide, N,N-methylene bisacrylamide, aqueous acrylate emulsion, glycerol, water, carbomer and composite antibacterial agent are stirred and mixed, then ammonium persulfate and sodium bisulfite are added, and after continuous stirring and mixing, a film is coated on a PVC substrate, and a PET release film is covered, and baking is carried out at 60-70 ℃ to obtain an antibacterial medical water gel pressure-sensitive adhesive tape.