Double-layer composite high-breathability low-sensitivity adhesive tape and preparation method thereof

Abstract

The invention relates to the technical field of breathable adhesive tapes, in particular to a double-layer composite high-breathability low-sensitivity adhesive tape and a preparation method thereof. The adhesive tape comprises a hydrophobic surface layer material, a high-breathability low-sensitivity composite adhesive and release paper. The high-breathability and low-sensitivity adhesive tape comprises a three-dimensional net-shaped breathable layer and a low-sensitivity adhesive layer. The hydrophobic surface layer material adopts a polyvinylidene fluoride electrostatic spinning nanofiber membrane with high specific surface area and porosity, so that the hydrophobicity and the adhesion with the lower layer material are improved; according to the high-breathability and low-sensitivity adhesive tape, polycaprolactone, a polylactic acid-glycolic acid copolymer and polyurethane are copolymerized to obtain a multifunctional three-dimensional net-shaped breathable layer; the high-breathability and low-sensitivity composite adhesive tape is prepared from dopamine modified polydimethylsiloxane microfibers decorated by oxidized dextran modified vinyl siloxane tip fibers, and the adhesive force and biocompatibility of the adhesive tape and skins with different roughness degrees are enhanced. Meanwhile, the lignosulfonate surfactant is added, so that the reproduction of bacteria and fungi in an adhesive tape attachment area can be inhibited.

Description

Technical Field

[0001] The invention relates to the technical field of double-layer composite adhesive tapes, and in particular to a double-layer composite high-air-permeability low-sensitivity adhesive tape and a preparation method thereof. Background Art

[0002] Double-layer composite tape is composed of two or more layers of layered materials with different functions. Common double-layer composite tapes include PET tape, masking tape, conductive tape, electrical tape, medical tape, etc. Due to its good adhesion and cuttability, it is widely used in production and life.

[0003] Highly breathable hypoallergenic tape is a new type of material widely used in the fields of medical treatment, household, personal care, etc. The high breathability of the tape can effectively reduce moisture accumulation on the skin and avoid allergies and infections. There are many tiny sweat gland pores on the human skin. Sweat seeping from the inside will make the tape lose its effect, so most tapes will lose their stickiness after being on the skin for a period of time. Some special materials, such as medical PU film, can be waterproof and sweat-proof, keeping the wound or application area dry, but PU film has poor breathability and is not wear-resistant.

[0004] The Chinese patent with the authorization number CN 219516816 U discloses a hypoallergenic breathable tape, which uses two layers of breathable gauze to sandwich the dressing and is provided with a tape-fitting tear tab, making it easy to use. However, the tape has poor waterproofness and cannot be cut into any shape. Summary of the invention

[0005] The present invention aims to provide a double-layer composite high-breathable and low-sensitivity adhesive tape and a preparation method thereof. The adhesive tape has good breathability and low sensitivity and also maintains excellent hydrophobicity. The low-sensitivity adhesive layer is added with glucan-modified tip fibers, which can enhance the adhesion and biocompatibility with skin of different degrees of roughness, have good bonding properties on the skin surface, will not damage the skin, and inhibit the growth of bacteria and fungi in the area covered by the tape.

[0006] In order to achieve the above-mentioned purpose, the present invention provides a double-layer composite high-permeability low-sensitivity adhesive tape, which includes a hydrophobic surface material, a high-permeability low-sensitivity adhesive and a release paper; the high-permeability low-sensitivity adhesive includes a three-dimensional mesh breathable layer and a low-sensitivity adhesive layer. The hydrophobic surface material is a polyvinylidene fluoride electrospun nanofiber membrane, the three-dimensional mesh breathable composite microfiber tape is based on polycaprolactone, polylactic acid-glycolic acid copolymer and polyurethane copolymer, and is covered with polydopamine-modified polydimethylsiloxane microfibers decorated with oxidized dextran-modified vinyl siloxane tip materials, and the release paper is silicone oil paper, and the combination is prepared to obtain a double-layer composite high-permeability low-sensitivity adhesive tape; the preparation method of the low-sensitivity adhesive layer includes: Step S1, dissolving dopamine in a non-polar solvent, adding a catalyst, and oxidizing to obtain oxidized dopamine; mixing the oxidized dopamine with a silane coupling agent and a surfactant for reaction, adding an alkaline solution to terminate the reaction, and obtaining dopamine-modified polydimethylsiloxane; coating the dopamine-modified polydimethylsiloxane on a glass plate, and drying to obtain a dopamine-modified polydimethylsiloxane adhesive layer; Step S2, dissolving vinyl siloxane in a solvent, mixing with a glucose solution, adding a photoinitiator, and reacting under UV light to obtain glucose-modified vinyl siloxane; Step S3, under nitrogen protection, apply pressure to make the glucose-modified vinyl siloxane pass through a high-flow rate micron-sized nozzle to obtain a glucose-modified vinyl siloxane tip fiber, disperse the glucose-modified vinyl siloxane tip fiber in a solvent, coat it on the dopamine-modified polydimethylsiloxane adhesive layer, and dry it to obtain a low-sensitivity adhesive layer.

[0007] Preferably, in step S1, the non-polar solvent is any one or more of ethyl acetate, n-hexane, dichloromethane, and toluene.

[0008] Preferably, in step S1, the catalyst is any one or more of a platinum catalyst, a palladium catalyst, a cobalt catalyst, and a nickel catalyst.

[0009] Preferably, in step S1, the oxidation temperature is 70-80° C., and the oxidation time is 3-5 h.

[0010] Preferably, in step S1, the silane coupling agent is any one or more of 3-aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, and vinyltriethoxysilane.

[0011] Preferably, in step S1, the surfactant is any one or more of sodium lignin sulfonate, calcium lignin sulfonate, ammonium lignin sulfonate, and magnesium lignin sulfonate.

[0012] Preferably, in step S1, the alkaline solution is any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, and ammonia water.

[0013] Preferably, in step S1, the reaction temperature is 40-60° C., and the reaction time is 6-8 h.

[0014] Preferably, in step S1, the mass ratio of the polydimethylsiloxane, solvent, catalyst, dopamine, silane coupling agent and surfactant is 1: (4-5): (0.005-0.03): (1-3): (0.5-1): (0.002-0.012).

[0015] Preferably, in step S1, the drying temperature is 40-60° C., and the drying time is 2-3 h.

[0016] Preferably, in step S2, the photoinitiator is any one or more of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether.

[0017] Preferably, in step S2, the mass ratio of the vinyl siloxane, the solvent, the glucose solution and the photoinitiator is 1:(2-3):(3-5):(0.005-0.05).

[0018] Preferably, in step S2, the reaction temperature is 45-65° C. and the reaction time is 5-6 h.

[0019] Preferably, in step S3, the pressure is 5-10 MPa and the gas flow rate is 100-200 L / min.

[0020] Preferably, in step S3, the mass ratio of the glucose-modified vinylsiloxane tip fiber to the solvent is 1:10.

[0021] Preferably, in step S3, the drying temperature is 50-60° C., and the drying time is 10-14 h.

[0022] Preferably, in step S2 and step S3, the solvent is any one or more of methanol, ethanol, cyclohexane, dichloromethane, acetone, and dimethyl sulfoxide.

[0023] Preferably, the preparation method of the three-dimensional mesh breathable layer is: Step S4, adding lactic acid and glycolic acid into a solvent to dissolve, adding an acid solution, and reacting to obtain a polylactic acid-glycolic acid copolymer; Step S5, adding polylactic acid-glycolic acid copolymer and caprolactone into a solvent to dissolve, adding a cross-linking agent and a catalyst, and reacting to obtain caprolactone-polylactic acid-glycolic acid copolymer; Step S6: caprolactone-polylactic acid-glycolic acid copolymer and polyurethane are added into a solvent to dissolve, and a cross-linking agent and a catalyst are added to react to obtain a three-dimensional mesh breathable layer.

[0024] Preferably, the solvent is any one or more of methanol, ethanol, cyclohexane, dichloromethane, acetone, and dimethyl sulfoxide.

[0025] Preferably, in step S4, the acid solution is a Lewis acid, including any one or more of hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, benzoic acid, and p-toluenesulfonic acid.

[0026] Preferably, in step S4, the solvent is any one or more of methanol, ethanol, cyclohexane, dichloromethane, acetone, and dimethyl sulfoxide.

[0027] Preferably, in step S4, the reaction temperature is 100-120° C., and the reaction time is 5-8 h.

[0028] Preferably, in step S4, the mass ratio of the lactic acid, glycolic acid, acid and solvent is 1:(1-2):(0.046-0.095):(4-5).

[0029] Preferably, in step S5, the reaction temperature is 100-120° C., and the reaction time is 10-12 h.

[0030] Preferably, in step S5, the mass ratio of the caprolactone, the polylactic acid-glycolic acid copolymer, the crosslinking agent, the catalyst and the solvent is 1: (1-3): (0.01-0.2): (0.01-0.1): (4-5).

[0031] Preferably, in step S6, the reaction temperature is 120-140° C., and the reaction time is 14-16 h.

[0032] Preferably, in step S6, the mass ratio of the caprolactone-polylactic acid-glycolic acid copolymer, polyurethane, crosslinking agent, catalyst and solvent is 1: (1-3): (0.01-0.1): (0.01-0.2): (4-5).

[0033] Preferably, in step S5 and step S6, the catalyst is any one or more of a platinum catalyst, a palladium catalyst, a cobalt catalyst, and a nickel catalyst.

[0034] Preferably, in step S5 and step S6, the cross-linking agent is any one or more of ethylene oxide, bis(2-aminoethyl) ether, and bis(2-aminoethyl)ethylenediamine.

[0035] Preferably, the preparation method of the hydrophobic surface material is: Step S7, heating and melting polyvinylidene fluoride, dissolving it with a polar solvent, adding a metal salt solution, stirring evenly, and preparing it into nanofibers by electrostatic spinning technology to obtain a hydrophobic surface material.

[0036] Preferably, in step S7, the heating and melting temperature is 160-170° C.; and the stirring time is 30-60 min.

[0037] Preferably, in step S7, the polar solvent is any one or more of water, glycerol, polyethylene glycol, ethanol, and methanol.

[0038] Preferably, in step S7, the metal salt solution is any one or more of sodium chloride, lithium chloride, calcium chloride, and calcium carbonate.

[0039] Preferably, in step S7, the mass ratio of the polyvinylidene fluoride, the polar solvent and the metal salt is 1:(4-5):(0.001-0.005).

[0040] Preferably, in step S7, the electrospinning parameters are voltage 20-30 kV, temperature 40-45° C., humidity 20-25%, and spinning time 6-8 h.

[0041] The present invention also provides a method for preparing a double-layer composite high-air-permeability low-sensitivity adhesive tape, comprising: The hydrophobic surface material is covered on one side of the three-dimensional mesh breathable layer, and the other side of the three-dimensional mesh breathable layer is bonded to the low-sensitive adhesive layer to obtain a highly breathable low-sensitive composite adhesive, and the other side of the highly breathable low-sensitive composite adhesive is covered with release paper to obtain a double-layer composite highly breathable low-sensitive adhesive tape.

[0042] Preferably, the thickness of the hydrophobic surface material is 20-50 μm.

[0043] Preferably, the thickness of the three-dimensional mesh breathable layer is 10-20 μm.

[0044] Preferably, the thickness of the low-sensitivity adhesive layer is 40-50 μm.

[0045] Preferably, the release paper is silicone oil paper.

[0046] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The present invention uses polyvinylidene fluoride electrospun nanofibers as the surface material. Polyvinylidene fluoride electrospun nanofibers have good hydrophobicity, stability and mechanical properties, which enables the hydrophobic layer to provide both hydrophobicity and certain mechanical strength.

[0047] (2) In order to achieve high air permeability and low sensitivity of the tape, the present invention uses a polymer with a stable three-dimensional network structure obtained by copolymerizing polycaprolactone and polylactic acid-glycolic acid polymer with polyurethane as a breathable support material. Polylactic acid and glycolic acid contain functional groups such as hydroxyl and carboxyl groups, which can be directly connected by covalent bonds to form a straight-chain polymer. Polycaprolactone is an aliphatic polyester. The polymer obtained after the polymerization of its monomers is a semi-crystalline polymer. The CC bonds and CO bonds in the molecular chain can rotate freely. Therefore, it can form a unique three-dimensional network structure with a large specific surface area with polylactic acid-glycolic acid polymer and polyurethane, better connect the adhesive layer and the surface material, prevent the generation and accumulation of bubbles between the adhesive layer and the surface material, help the air and liquid to be discharged, and can effectively disperse stress and enhance the thermal stability of polyurethane.

[0048] (3) In order to achieve good adhesion and low sensitivity of the tape, the present invention uses dopamine-modified polydimethylsiloxane as an adhesive, supplemented by glucose-modified vinylsiloxane tip fibers. Polydimethylsiloxane is a common adhesive with strong processability and stability. Dopamine can improve its hydrophilicity, thereby improving its compatibility in biomedical applications; the tip fiber technology can give the tape bionic adsorption properties. Vinylsiloxane is non-toxic and non-irritating, and will not cause rejection reactions in human tissues. It is prepared into vinylsiloxane tip fibers, which can enhance the adhesion of skin to skin, and the fibers provide good mechanical strength and elasticity, ensuring that the tape is not easy to tear or fall off during wearing; glucose modification can improve the compatibility of the fiber with the skin, reduce adverse reactions, and make the material safer for long-term contact with the skin. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 Schematic diagram of the preparation process of a double-layer composite high-breathable and low-sensitivity tape.

[0050] Figure 2 Schematic diagram of the structure of a double-layer composite high-breathable and low-sensitivity tape.

[0051] Figure 3 The following is a comparison chart of the adhesive force of the double-layer composite high-breathable low-sensitivity adhesive tape prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

[0052] Figure 4 It is a comparison chart of the moisture permeability of the double-layer composite high-breathable low-sensitivity adhesive tape prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

[0053] Figure 5 This is a comparison chart of the air permeability of the double-layer composite high-air permeability low-sensitivity tape prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

[0054] Figure 6 The following is a comparison chart of the peeling strength of the double-layer composite high-breathable low-sensitivity adhesive tapes prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

[0055] Figure 7 This is a comparison chart of the allergenicity test between the blank group and the control group (ordinary medical tape).

[0056] Figure 8 The comparison chart of the allergenicity test of the double-layer composite high-breathable low-sensitivity adhesive tape prepared in Examples 1 to 3 is shown.

[0057] Fig. 9 A comparison chart of the allergenicity test of a double-layer composite high-breathable low-sensitivity tape prepared for comparative examples 1 to 3.

[0058] The meaning of the accompanying symbols: 1. Hydrophobic surface material, 2. Highly breathable and low-sensitivity composite glue, 3. Three-dimensional mesh breathable layer, 4. Low-sensitivity glue layer, 5. Release paper. DETAILED DESCRIPTION

[0059] The following embodiments are only used to more clearly illustrate the technical solutions of the present invention, and are not intended to limit the protection scope of the present invention.

[0060] The main compounds used in the examples and comparative examples are all commercially available products without any further purification.

[0061] Example 1

[0062] like Figure 1 As shown, a double-layer composite high-permeability low-sensitivity adhesive tape, the preparation method of which includes: Step S1, accurately weigh 5 g of dopamine, dissolve it in 25 g of n-hexane, add 0.025 g of platinum catalyst, oxidize it at 70°C for 5 h, add 5 g of polydimethylsiloxane, 2.5 g of 3-aminopropyltriethoxysilane, and 0.01 g of sodium lignin sulfonate, react at 40°C for 8 h, add 2 mL of sodium hydroxide solution to terminate the reaction, centrifuge to obtain dopamine-modified polydimethylsiloxane, coat it on a glass plate, and dry it at 40°C for 3 h to obtain a dopamine-modified polydimethylsiloxane adhesive layer.

[0063] Step S2, accurately weigh 5 g of vinyl siloxane and dissolve it in 25 g of n-hexane, filter out undissolved substances and impurities, add 15 g of glucose solution, mix well, add 0.025 g of benzoin dimethyl ether, react at 45° C. for 6 h, and obtain glucose-modified vinyl siloxane.

[0064] Step S3, under nitrogen protection, with a gas flow rate of 100 L / min, apply a pressure of 5 MPa to make the glucose-modified vinyl siloxane pass through the micron-sized nozzle at a high flow rate, disconnect the applied stress after 30 minutes, irradiate with UV light for 15 minutes and wait for the fiber to cool and solidify; 5 g of vinyl siloxane tip fiber is dispersed in 50 g of anhydrous ethanol, ultrasonically treated for 30 minutes, evenly coated on the dopamine-modified polydimethylsiloxane adhesive layer, and dried at 50°C for 14 hours to obtain a low-sensitivity adhesive layer 4.

[0065] Step S4, accurately weigh 5 g of lactic acid and 5 g of glycolic acid, dissolve them in 25 g of anhydrous ethanol, add 0.23 g of hydrochloric acid, and react at 100° C. for 8 h to obtain a polylactic acid-glycolic acid copolymer.

[0066] Step S5, accurately weigh 5 g of caprolactone and 5 g of polylactic acid-glycolic acid copolymer, mix them, dissolve them in 25 g of anhydrous ethanol, add 0.05 g of platinum catalyst and 0.05 g of ethylene oxide, react at 100° C. for 12 h to obtain polycaprolactone-polylactic acid-glycolic acid copolymer.

[0067] Step S6, accurately weigh 5 g of caprolactone-polylactic acid-glycolic acid copolymer and 5 g of polyurethane, mix them, dissolve them in 25 g of methanol, add 0.05 g of ethylene oxide and 0.05 g of platinum catalyst in sequence, react at 120°C for 16 h, and obtain a three-dimensional mesh breathable layer 3, such as Figure 4 shown.

[0068] Step S7, accurately weigh 5 g of polyvinylidene fluoride, heat to melt at 160°C, dissolve in 20 g of glycerol, add 0.005 g of sodium chloride, stir at room temperature for 30 min, spin for 8 h at 20 kV, 40°C, and 20% humidity to obtain a hydrophobic surface material 1.

[0069] Step S8: sterilize the above-mentioned prepared materials. Figure 2 As shown, the hydrophobic surface material 1 covers one side of the three-dimensional mesh breathable layer 3, and the other side of the three-dimensional mesh breathable layer 3 is bonded with the low-sensitive adhesive layer 4 to obtain a highly breathable low-sensitive composite adhesive 2, and the other side of the highly breathable low-sensitive composite adhesive 2 is covered with a release paper 5 to obtain a double-layer composite highly breathable low-sensitive adhesive tape.

[0070] Example 2

[0071] like Figure 1 As shown, a double-layer composite high-permeability low-sensitivity adhesive tape, the preparation method of which includes: Step S1, accurately weigh 10 g of dopamine, dissolve it in 50 g of n-hexane, add 0.075 g of platinum catalyst, oxidize it at 75°C for 4 h, add 5 g of polydimethylsiloxane, 3.8 g of 3-aminopropyltriethoxysilane, and 0.04 g of sodium lignin sulfonate, react at 50°C for 7 h, add 2 mL of sodium hydroxide solution to terminate the reaction, and obtain dopamine-modified polydimethylsiloxane, which is coated on a glass plate and dried at 50°C for 2 h to obtain a dopamine-modified polydimethylsiloxane adhesive layer.

[0072] Step S2, accurately weigh 5 g of vinyl siloxane and dissolve it in 25 g of n-hexane, filter out undissolved substances and impurities, add 20 g of glucose solution, mix well, add 0.025 g of benzoin dimethyl ether, react at 55° C. for 6 h, and obtain glucose-modified vinyl siloxane.

[0073] Step S3, under nitrogen protection, with a gas flow rate of 150 L / min, apply a pressure of 7.5 MPa to make the glucose-modified vinyl siloxane pass through the micron-sized nozzle at a high flow rate, disconnect the applied stress after 30 minutes, irradiate with UV light for 15 minutes and wait for the fiber to cool and solidify; 5 g of vinyl siloxane tip fiber is dispersed in 50 g of anhydrous ethanol, ultrasonically treated for 30 minutes, evenly coated on the dopamine-modified polydimethylsiloxane adhesive layer, and dried at 55°C for 12 hours to obtain a low-sensitivity adhesive layer 4.

[0074] Step S4, accurately weigh 5 g of lactic acid and 7.5 g of glycolic acid, dissolve them in 25 g of anhydrous ethanol, add 0.41 g of hydrochloric acid, and react at 110° C. for 7 h to obtain a polylactic acid-glycolic acid copolymer.

[0075] Step S5, accurately weigh 10 g of caprolactone and 5 g of polylactic acid-glycolic acid copolymer, mix them, dissolve them in 25 g of anhydrous ethanol, add 0.1 g of platinum catalyst and 0.25 g of ethylene oxide, react at 110° C. for 11 h to obtain polycaprolactone-polylactic acid-glycolic acid copolymer.

[0076] Step S6, accurately weigh 5 g of caprolactone-polylactic acid-glycolic acid copolymer and 10 g of polyurethane, mix them, dissolve them in 25 g of methanol, add 0.25 g of ethylene oxide and 0.1 g of platinum catalyst in sequence, react at 130°C for 15 h, and obtain a three-dimensional mesh breathable layer 3.

[0077] Step S7, accurately weigh 5 g of polyvinylidene fluoride, heat to melt at 165°C, dissolve in 18 mL of glycerol, add 0.01 g of sodium chloride, stir at room temperature for 40 min, and spin for 7 h at a voltage of 25 kV, a temperature of 45°C, and a humidity of 25% to obtain a hydrophobic surface material 1.

[0078] Step S8: sterilize the above-mentioned prepared materials. Figure 2 As shown, the hydrophobic surface material 1 covers one side of the three-dimensional mesh breathable layer 3, and the other side of the three-dimensional mesh breathable layer 3 is bonded with the low-sensitive adhesive layer 4 to obtain a highly breathable low-sensitive composite adhesive 2, and the other side of the highly breathable low-sensitive composite adhesive 2 is covered with a release paper 5 to obtain a double-layer composite highly breathable low-sensitive adhesive tape.

[0079] Example 3

[0080] like Figure 1 As shown, a double-layer composite high-permeability low-sensitivity adhesive tape, the preparation method of which includes: Step S1, accurately weigh 10 g of dopamine, dissolve it in 50 g of n-hexane, add 0.15 g of platinum catalyst, oxidize it at 80°C for 3 h, add 5 g of polydimethylsiloxane, 5 g of 3-aminopropyltriethoxysilane, and 0.06 g of sodium lignin sulfonate, react at 60°C for 6 h, add 2 mL of sodium hydroxide solution to terminate the reaction, and obtain dopamine-modified polydimethylsiloxane, which is coated on a glass plate and dried at 60°C for 2 h to obtain a dopamine-modified polydimethylsiloxane adhesive layer.

[0081] Step S2, accurately weigh 5 g of vinyl siloxane and dissolve it in 25 g of n-hexane, filter out undissolved substances and impurities, add 25 g of glucose solution, mix well, add 0.25 g of benzoin dimethyl ether, react at 65° C. for 5 h, and obtain glucose-modified vinyl siloxane.

[0082] Step S3, under nitrogen protection, with a gas flow rate of 120 L / min, apply a pressure of 10 MPa to make the glucose-modified vinyl siloxane pass through the micron-sized nozzle at a high flow rate, disconnect the applied stress after 30 minutes, irradiate with UV light for 15 minutes and wait for the fiber to cool and solidify; 5 g of vinyl siloxane tip fiber is dispersed in 50 g of anhydrous ethanol, ultrasonically treated for 30 minutes, evenly coated on the dopamine-modified polydimethylsiloxane adhesive layer, and dried at 60°C for 10 hours to obtain a low-sensitivity adhesive layer 4.

[0083] Step S4, accurately weigh 5 g of lactic acid and 10 g of glycolic acid, dissolve them in 25 g of anhydrous ethanol, add 0.48 g of hydrochloric acid, and react at 120° C. for 5 h to obtain a polylactic acid-glycolic acid copolymer.

[0084] Step S5, accurately weigh 15 g of caprolactone and 5 g of polylactic acid-glycolic acid copolymer, mix them, dissolve them in 25 g of anhydrous ethanol, add 0.2 g of platinum catalyst and 0.5 g of ethylene oxide, react at 120° C. for 10 h to obtain polycaprolactone-polylactic acid-glycolic acid copolymer.

[0085] Step S6, accurately weigh 5 g of caprolactone-polylactic acid-glycolic acid copolymer and 15 g of polyurethane, mix them, dissolve them in 25 g of methanol, add 0.5 g of ethylene oxide and 0.2 g of platinum catalyst in sequence, react at 140°C for 14 h, and obtain a three-dimensional mesh breathable layer 3.

[0086] Step S7, accurately weigh 5 g of polyvinylidene fluoride, heat to melt at 170°C, dissolve in 20 mL of glycerol, add 0.01 g of sodium chloride, stir at room temperature for 60 min, spin for 6 h at 30 kV, 45°C, and 25% humidity to obtain a hydrophobic surface material 1.

[0087] Step S8: sterilize the above-mentioned prepared materials. Figure 2 As shown, the hydrophobic surface material 1 covers one side of the three-dimensional mesh breathable layer 3, and the other side of the three-dimensional mesh breathable layer 3 is bonded with the low-sensitive adhesive layer 4 to obtain a highly breathable low-sensitive composite adhesive 2, and the other side of the highly breathable low-sensitive composite adhesive 2 is covered with a release paper 5 to obtain a double-layer composite highly breathable low-sensitive adhesive tape.

[0088] Comparative Example 1 A double-layer composite high-breathable low-sensitivity adhesive tape, the preparation method of which is different from that of Example 2 in that polylactic acid-glycolic acid copolymer is not added in step (6).

[0089] Comparative Example 2 A double-layer composite high-breathable low-sensitivity adhesive tape, the preparation method of which is different from that of Example 2 in that no oxidized glucose-modified vinyl silicone tip fiber is added in step (3).

[0090] Comparative Example 3 A double-layer composite high-breathable low-sensitivity adhesive tape, the preparation method of which is different from that of Example 2 in that dopamine is not added in step (1).

[0091] Performance test: The double-layer composite tapes prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were tested for moisture permeability (GB / T26253-2010), air permeability (YY / T 0148-2006), peel strength test (YY / T 0148-2006), adhesion retention and hypoallergenicity.

[0092] Adhesion test: Rinse the test area of ​​the subject with saline. Select the joints of the elbows and knees, and apply glycerin to the test area after moistening the skin. Cut the tape into rectangles of the same size and shape (7 cm × 10 cm), cover the test area, start counting, observe whether the tape curls up, and record the time when the tape curls up. Perform at least 3 parallel experiments for each group of tapes and take the average value.

[0093] Hypoallergenicity test: The back skin of female nude mice weighing 18-22 g was rinsed with saline, and the tape was cut into rectangles of the same size and shape (2 cm × 3 cm) and covered on the back area of ​​the mice. The control group was ordinary medical tape, and the blank group was not pasted with tape. There were 5 mice in each group, and at least 3 parallel experiments were performed for each tape. The mice were killed on the seventh day to observe whether there were adverse reactions such as allergies or pigmentation on the back skin. The skin of the experimental area on the back was removed for HE staining to observe whether the skin had lesions.

[0094] according to Figure 3As shown, the adhesive tapes prepared in Examples 1 to 3 have stronger adhesive strength on joints, non-joints, dry skin and wet skin than the comparative examples. Comparative Example 2 does not add oxidized glucose-modified vinyl siloxane tip fibers, and the adhesive tape does not form crosslinks with the skin surface, and the adhesiveness is gradually weakened over time. Comparative Example 3 does not add dopamine, and the compatibility of the adhesive tape with the skin is weak, and the adhesive tape's adhesive strength is greatly reduced.

[0095] according to Figure 4 and Figure 5 As shown, the moisture permeability and air permeability of the double-layer composite tapes prepared in Examples 1 to 3 are higher than those prepared in Comparative Examples 1 to 3, and the tape prepared in Example 2 is significantly better than the others. In Comparative Example 1, no polylactic acid-glycolic acid copolymer is added, and only polycaprolactone and polyurethane copolymer are used, which cannot form a three-dimensional network structure, and the polymer molecular chains are tightly cross-linked and lack a pore structure, which limits the passage of moisture and air.

[0096] according to Figure 6 As shown, there is no significant difference in the peel strength of the tapes prepared by Examples 1 to 3 and Comparative Examples 1 to 3, but they are significantly better than ordinary tapes. Lower peel strength helps to reduce the pain and damage when the tape is peeled off from the skin. The composite fiber tape relies on the cross-linking between the fiber and the skin to produce an adhesive effect, which can adapt to skins of different roughness, giving the tape good adhesion while having low peel strength.

[0097] according to Figures 7-9 As shown, the HE staining results of the mouse back skin covered with the tape prepared in Examples 1 to 3 were not significantly different from those of the blank group. The tape did not cause damage to the mouse skin, and no allergic symptoms occurred, proving the low allergenicity of the tape. The HE staining results of Comparative Examples 1 to 3 and the control group showed that there was neutrophil infiltration and lymphocyte infiltration in the skin, the cell nucleus was often irregularly lobed, and the cytoplasm contained fine neutrophil granules and less cytoplasm, indicating that there was inflammation in the epithelial tissue. The experiment proved that the tape prepared in Examples 1 to 3 was low in allergenicity and low in irritation to the mouse skin.

[0098] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A double-layer composite high-breathable low-sensitivity adhesive tape, characterized in that: It comprises a hydrophobic surface material (1), a highly breathable and low-sensitivity composite adhesive (2) and a release paper (5); the highly breathable and low-sensitivity composite adhesive (2) comprises a three-dimensional mesh-shaped breathable layer (3) and a low-sensitivity adhesive layer (4); the hydrophobic surface material (1) is a polyvinylidene fluoride electrospun nanofiber membrane; The release paper (5) is silicone oil paper; The method for preparing the low-sensitivity adhesive layer (4) comprises: Step S1, dissolving dopamine in a non-polar solvent, adding a catalyst, and oxidizing to obtain oxidized dopamine; mixing the oxidized dopamine with a silane coupling agent and a surfactant for reaction, adding an alkaline solution to terminate the reaction, and obtaining dopamine-modified polydimethylsiloxane; coating the dopamine-modified polydimethylsiloxane on a glass plate, and drying to obtain a dopamine-modified polydimethylsiloxane adhesive layer; Step S2, dissolving vinyl siloxane in a solvent, mixing with a glucose solution, adding a photoinitiator, and reacting under UV light to obtain glucose-modified vinyl siloxane; Step S3, under nitrogen protection, applying pressure to make the glucose-modified vinyl siloxane pass through a high-flow rate micron-sized nozzle to obtain a glucose-modified vinyl siloxane tip fiber, dispersing the glucose-modified vinyl siloxane tip fiber in a solvent, coating it on the dopamine-modified polydimethylsiloxane adhesive layer, and drying to obtain a low-sensitivity adhesive layer (4).

2. A double-layer composite high-air-permeability low-sensitivity adhesive tape according to claim 1, characterized in that: In the method for preparing the low-sensitivity adhesive layer (4), in step S1, the non-polar solvent is any one or more of ethyl acetate, n-hexane, dichloromethane, and toluene; the catalyst is any one or more of a platinum catalyst, a palladium catalyst, a cobalt catalyst, and a nickel catalyst; the oxidation temperature is 70-80°C, and the oxidation time is 3-5 h; the silane coupling agent is any one or more of 3-aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, and vinyltriethoxysilane; the surfactant is any one or more of sodium lignin sulfonate, calcium lignin sulfonate, ammonium lignin sulfonate, and magnesium lignin sulfonate; the alkaline solution is any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, and ammonia water; the reaction temperature is 40-60°C, and the reaction time is 6-8 h; the mass ratio of the polydimethylsiloxane, solvent, catalyst, dopamine, silane coupling agent and surfactant is 1: (4-5): (0.005-0.03): (1-3): (0.5-1): (0.002-0.012); the drying temperature is 40-60°C and the drying time is 2-3 h.

3. A double-layer composite high-permeability low-sensitivity adhesive tape according to claim 1, characterized in that: In the method for preparing the low-sensitivity adhesive layer (4), in step S2, the photoinitiator is any one or more of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether; the mass ratio of the vinyl siloxane, the solvent, the glucose solution, and the photoinitiator is 1:(2-3):(3-5):(0.005-0.05); the reaction temperature is 45-65°C, and the reaction time is 5-6 h.

4. A double-layer composite high-permeability low-sensitivity adhesive tape according to claim 1, characterized in that: In the method for preparing the low-sensitive adhesive layer (4), in step S3, the pressure is 5-10 MPa and the gas flow rate is 100-200 L / min; the mass ratio of the glucose-modified vinylsiloxane tip fiber to the solvent is 1:10; the drying temperature is 50-60°C and the drying time is 10-14 h; in steps S2 and S3, the solvent is any one or more of methanol, ethanol, cyclohexane, dichloromethane, acetone, and dimethyl sulfoxide.

5. A double-layer composite high-air-permeability low-sensitivity adhesive tape according to claim 1, characterized in that: The preparation method of the three-dimensional mesh air-permeable layer (3) is as follows: Step S4, adding lactic acid and glycolic acid into a solvent to dissolve, adding an acid solution, and reacting to obtain a polylactic acid-glycolic acid copolymer; Step S5, adding polylactic acid-glycolic acid copolymer and caprolactone into a solvent to dissolve, adding a cross-linking agent and a catalyst, and reacting to obtain caprolactone-polylactic acid-glycolic acid copolymer; Step S6: caprolactone-polylactic acid-glycolic acid copolymer and polyurethane are added to a solvent and dissolved, and a cross-linking agent and a catalyst are added to react to obtain a three-dimensional mesh breathable layer (3).

6. A double-layer composite high-air-permeability low-sensitivity adhesive tape according to claim 5, characterized in that: The solvent is any one or more of methanol, ethanol, cyclohexane, dichloromethane, acetone, and dimethyl sulfoxide; in step S4, the acid solution is a Lewis acid, including any one or more of hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, benzoic acid, and p-toluenesulfonic acid; the solvent is any one or more of methanol, ethanol, cyclohexane, dichloromethane, acetone, and dimethyl sulfoxide; the reaction temperature is 100-120°C, and the reaction time is 5-8 h; the mass ratio of lactic acid, glycolic acid, acid, and solvent is 1: (1-2): (0.046-0.095): (4-5); in step S5, the reaction temperature is 100-120°C, and the reaction time is 10-12 h; the mass ratio of caprolactone, polylactic acid-glycolic acid copolymer, crosslinking agent, catalyst, and solvent is 1: (1-3): (0.01-0.2): (0.01-0.1): (4-5).

7. A double-layer composite high-air-permeability low-sensitivity adhesive tape according to claim 5, characterized in that: In the step S6, the reaction temperature is 120-140° C., and the reaction time is 14-16 h. The mass ratio of the caprolactone-polylactic acid-glycolic acid copolymer, polyurethane, crosslinking agent, catalyst, and solvent is 1: (1-3): (0.01-0.1): (0.01-0.2): (4-5). In the steps S2 and S3, the catalyst is any one or more of a platinum catalyst, a palladium catalyst, a cobalt catalyst, and a nickel catalyst. The crosslinking agent is any one or more of ethylene oxide, bis(2-aminoethyl) ether, and bis(2-aminoethyl)ethylenediamine.

8. The double-layer composite high-air-permeability low-sensitivity adhesive tape according to claim 1, characterized in that: The preparation method of the hydrophobic surface material (1) is: Step S7, heat and melt the polyvinylidene fluoride, dissolve it with a polar solvent, add a metal salt solution, stir it evenly, and prepare it into nanofibers by electrospinning technology to obtain a hydrophobic surface material (1).

9. A double-layer composite high-air-permeability low-sensitivity adhesive tape according to claim 8, characterized in that: In step S7, the heating melting temperature is 160-170°C; the stirring time is 30-60 min; the polar solvent is any one or more of water, glycerol, polyethylene glycol, ethanol, and methanol; the metal salt solution is any one or more of sodium chloride, lithium chloride, calcium chloride, and calcium carbonate; the mass ratio of polyvinylidene fluoride, polar solvent, and metal salt is 1: (4-5): (0.001-0.005); the electrospinning parameters are voltage 20-30 kV, temperature 40-45°C, humidity 20-25%, and spinning time 6-8 h.

10. The method for preparing a double-layer composite high-air-permeability low-sensitivity adhesive tape according to any one of claims 1 to 9, characterized in that: include: A hydrophobic surface material (1) is covered on one side of a three-dimensional mesh breathable layer (3), and the other side of the three-dimensional mesh breathable layer (3) is bonded to a low-sensitivity adhesive layer (4) to obtain a highly breathable and low-sensitivity composite adhesive (2). The other side of the highly breathable and low-sensitivity composite adhesive (2) is covered with a release paper (5) to obtain a double-layer composite highly breathable and low-sensitivity adhesive tape; the thickness of the hydrophobic surface material (1) is 20-50 μm; the thickness of the three-dimensional mesh breathable layer (3) is 10-20 μm; the thickness of the low-sensitivity adhesive layer (4) is 40-50 μm; and the release paper is silicone oil paper.

Images