Medical adhesive composition and medical adhesive patch

Abstract

The present invention discloses a medical adhesive composition and a medical adhesive patch. The medical adhesive composition includes an acrylate copolymer and a block copolymer. The acrylate copolymer is polymerized from an alkyl acrylate, a hydroxyl-containing acrylate, a carboxyl-containing acrylate, and a nitrogen-containing heterocyclic monomer. The alkyl acrylate includes an alkyl acrylate having 4 to 12 alkyl carbon atoms and / or an alkyl methacrylate having 4 to 12 alkyl carbon atoms. The block copolymer is polymerized from caprolactone and an alcohol. The medical adhesive composition has excellent sweat resistance and is not easily detached from the skin. Furthermore, after prolonged contact with the skin, the adhesive strength does not increase significantly due to temperature increases, thereby avoiding significant pain and skin damage when the adhesive patch is separated from the skin.

Description

Technical Field

[0001] The invention belongs to the technical field of medical pressure-sensitive adhesives, and particularly relates to a medical adhesive composition and a medical adhesive patch. Background Art

[0002] Pressure-sensitive adhesives (PSA) are adhesives that only require an applied force to bond to an adherend. They are easy to use and offer excellent stability, making them widely used in healthcare. Currently, medical PSA is used in a wide range of applications, including wound treatment, bonding biomedical devices, transdermal drug delivery patches, medical labels, and medical tapes.

[0003] Sweat-resistant medical pressure-sensitive adhesives won't fall off due to perspiration, as sweat can be expelled through the adhesive layer. Over time, the peel strength of the adhesive increases significantly. Conventional rubber-based, silicone-based, and hot-melt-based medical pressure-sensitive adhesives are not sweat-resistant. Some medical pressure-sensitive adhesives, silicone-based, and hot-melt-based pressure-sensitive adhesives incorporate low-boiling-point foaming agents to create numerous microbubbles within the adhesive, helping to expel moisture from the skin or by creating specific patterns within the adhesive to facilitate moisture expulsion. However, the release strength of the adhesive can be significantly reduced in areas covered by the adhesive due to moisture, leading to peeling due to perspiration. Some acrylic pressure-sensitive adhesives offer some sweat resistance, but this resistance is insufficient and can also fall off when the skin sweats profusely. Acrylic-based sweat-resistant medical pressure-sensitive adhesives achieve sweat resistance by incorporating hydrophilic and / or water-absorbent materials. These materials are generally highly polar. Because human body temperature is approximately 37°C, 12°C higher than the normal temperature of 25°C, prolonged contact with the skin increases the interaction between the polar components of the adhesive layer and the skin, causing noticeable pain when removing the medical patch. Furthermore, after prolonged contact with the skin, the increased temperature can increase the bonding strength between the adhesive layer and the skin to two or three times or more than the initial bonding strength of the first half-hour. Therefore, using external force to separate the pressure-sensitive adhesive from the skin can be quite painful and can even cause problems such as hair plucking and skin damage.

[0004] Therefore, it is of great significance to develop medical adhesives that are sweat-resistant and have minimal increase in adhesion after long-term contact with the skin. Summary of the Invention

[0005] The present invention aims to at least partially address one of the technical problems in the related art. To this end, one object of the present invention is to provide a medical adhesive composition and a medical adhesive patch. The medical adhesive composition exhibits excellent perspiration resistance, is not easily detached from the skin, and, after prolonged contact with the skin, does not significantly increase its adhesive strength due to elevated temperatures, thereby avoiding significant pain and skin damage caused by separation of the patch from the skin.

[0006] In one aspect, the present invention provides a medical adhesive composition. According to an embodiment of the present invention, the medical adhesive composition includes an acrylate copolymer and a block copolymer. The acrylate copolymer is polymerized from an alkyl acrylate, a hydroxyl-containing acrylate, a carboxyl-containing acrylate, and a nitrogen-containing heterocyclic monomer. The alkyl acrylate includes an alkyl acrylate having an alkyl carbon number of 4 to 12 and / or an alkyl methacrylate having an alkyl carbon number of 4 to 12. The block copolymer is polymerized from caprolactone and an alcohol.

[0007] The medical adhesive composition according to the above embodiment of the present invention includes an acrylate copolymer and a block copolymer. The acrylate copolymer is polymerized by alkyl acrylate, hydroxyl-containing acrylate, carboxyl-containing acrylate and nitrogen-containing heterocyclic monomer. The alkyl acrylate includes alkyl acrylate with 4 to 12 alkyl carbon atoms and / or alkyl methacrylate with 4 to 12 alkyl carbon atoms. The alkyl acrylate monomer with 4 to 12 alkyl carbon atoms provides basic pressure-sensitive properties. The alkyl methacrylate monomer with 4 to 12 alkyl carbon atoms can increase the adhesion of the adhesive to the substrate. The hydroxyl-containing acrylate monomer can enhance the interaction between the adhesive and the skin and enhance the adhesion between the adhesive and the skin. The carboxyl-containing acrylate monomer can enhance the adhesive holding force and prolong the bonding time, so that the adhesive patch is not prone to curling up even when it is attached to the skin for a long time. The nitrogen-containing heterocyclic monomer can enhance the water absorption of the adhesive. , the adhesive can maintain its pressure-sensitive properties after absorbing water, preventing the adhesive from losing its adhesion due to skin sweating. Therefore, the use of the above-mentioned acrylate copolymer can make the adhesive have better adhesion, can interact with the skin for a long time, and have excellent adhesion, so as to have better sweat resistance, and will not cause the adhesion to decrease due to skin sweating, thereby avoiding the phenomenon of the adhesive patch falling off due to skin sweating; the block copolymer is formed by the polymerization of caprolactone and alcohol. On the one hand, caprolactone and alcohol form molecular chains containing ether bonds after polymerization, and the molecular chains containing ether bonds are water-absorbing and hydrophilic, thereby further improving the sweat resistance of the adhesive. On the other hand, the interaction force between caprolactone and skin is small, and the caprolactone block makes the block copolymer have high cohesion and low peeling force, which can prevent the peeling force from increasing and residual glue after the adhesive patch is applied to the skin for a long time; and the acrylate copolymer and the block copolymer have good compatibility, which is conducive to the synergistic effect of the two, further preventing the peeling force from increasing after the adhesive patch is applied to the skin for a long time. Therefore, the medical adhesive composition has excellent sweat resistance and is not easy to fall off from the skin. Moreover, after long-term contact with the skin, the adhesion force will not increase significantly due to temperature increase, thereby avoiding problems such as great pain and skin damage when the adhesive patch is separated from the skin.

[0008] In addition, the medical adhesive composition according to the above embodiment of the present invention may also have the following technical features:

[0009] In some embodiments of the present invention, the mass ratio of the alkyl acrylate, the hydroxyl-containing acrylate, the carboxyl-containing acrylate, and the nitrogen-containing heterocyclic monomer is (50-80):(1-6):(1-6):(4-13). Thus, the medical adhesive composition has excellent sweat resistance.

[0010] In some embodiments of the present invention, the hydroxyl-containing acrylate includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl acrylate.

[0011] In some embodiments of the present invention, the carboxyl-containing acrylate includes at least one of acrylic acid and methacrylic acid.

[0012] In some embodiments of the present invention, the nitrogen-containing heterocyclic monomer includes at least one of N-vinyl pyrrolidone and N-vinyl caprolactam.

[0013] In some embodiments of the present invention, the hydroxyl value of the block copolymer is 5 mgKOH / g-300 mgKOH / g. Thus, the medical adhesive composition has excellent sweat resistance and has little increase in adhesive strength after long-term contact with the skin.

[0014] In some embodiments of the present invention, the molecular weight of the block copolymer is 1000-10000. Thus, the medical adhesive composition has excellent sweat resistance and has little increase in adhesive strength after long-term contact with the skin.

[0015] In some embodiments of the present invention, the alcohol includes at least one of polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer, and polytetramethylene glycol.

[0016] In some embodiments of the present invention, the mass proportion of caprolactone in the block copolymer is 15%-50%. Thus, after the adhesive composition comes into contact with the skin for a long time, the adhesive strength increases slightly.

[0017] In some embodiments of the present invention, at least one of a tackifying resin and an isocyanate crosslinking agent is further included. The tackifying resin includes a first tackifying resin and a second tackifying resin. The first tackifying resin has a glass transition temperature not higher than 0° C., and the second tackifying resin has a glass transition temperature higher than 0° C. This helps to adjust the initial tack and peel strength of the adhesive composition without generating adhesive residue.

[0018] In some embodiments of the present invention, the first tackifying resin is at least one of modified rosin resin, terpene resin, terpene resin derivative, petroleum resin and petroleum resin derivative.

[0019] In some embodiments of the present invention, the second tackifying resin includes at least one of modified rosin resin, modified terpene and modified C5 petroleum resin.

[0020] In some embodiments of the present invention, the isocyanate cross-linking agent includes at least one of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, and m-xylylene diisocyanate.

[0021] In some embodiments of the present invention, the acrylate copolymer accounts for 50 to 80 parts by weight, the block copolymer accounts for 10 to 30 parts by weight, the tackifying resin accounts for 2 to 15 parts by weight, and the isocyanate crosslinking agent accounts for 0.1 to 5 parts by weight. As a result, the medical adhesive composition has excellent perspiration resistance and exhibits minimal increase in adhesive strength after prolonged contact with the skin.

[0022] In some embodiments of the present invention, the medical adhesive composition further comprises at least one of a solvent and an auxiliary agent. Thus, the medical adhesive composition has excellent sweat resistance and has little increase in adhesive strength after long-term contact with the skin.

[0023] In some embodiments of the present invention, the additives include at least one of a leveling agent, a stabilizer, a defoamer, a filler, a compatibilizing agent, a catalyst, a catalyst promoter, a surfactant, a diluent, a plasticizer, a crosslinking inhibitor, an antioxidant, and an anti-aging agent.

[0024] In another aspect, the present invention provides a medical adhesive patch. According to an embodiment of the present invention, the medical patch comprises a substrate, a pressure-sensitive adhesive layer, and a release layer laminated in sequence, wherein the pressure-sensitive adhesive layer is prepared using the aforementioned medical adhesive composition. As a result, the medical patch exhibits excellent perspiration resistance, high initial tack, low peel force increase after long-term application, and no adhesive residue after removal, significantly reducing pain and skin damage during patch removal.

[0025] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0026] The embodiments of the present invention are described in detail below, which are intended to explain the present invention but are not to be construed as limiting the present invention.

[0027] In one aspect, the present invention provides a medical adhesive composition. According to an embodiment of the present invention, the medical adhesive composition includes an acrylate copolymer and a block copolymer. The acrylate copolymer is polymerized from an alkyl acrylate, a hydroxyl-containing acrylate, a carboxyl-containing acrylate, and a nitrogen-containing heterocyclic monomer. The alkyl acrylate includes an alkyl acrylate having an alkyl carbon number of 4 to 12 and / or an alkyl methacrylate having an alkyl carbon number of 4 to 12. The block copolymer is polymerized from caprolactone and an alcohol.

[0028] The inventors have discovered that the medical adhesive composition comprises an acrylate copolymer and a block copolymer. The acrylate copolymer is polymerized by alkyl acrylate, hydroxyl-containing acrylate, carboxyl-containing acrylate and nitrogen-containing heterocyclic monomer. The alkyl acrylate comprises alkyl acrylate with 4 to 12 alkyl carbon atoms and / or alkyl methacrylate with 4 to 12 alkyl carbon atoms. The alkyl acrylate monomer with 4 to 12 alkyl carbon atoms provides basic pressure-sensitive properties. The alkyl methacrylate monomer with 4 to 12 alkyl carbon atoms can increase the adhesion of the adhesive to the substrate. The hydroxyl-containing acrylate monomer can enhance the interaction between the adhesive and the skin and enhance the adhesion between the adhesive and the skin. The carboxyl-containing acrylate monomer can enhance the adhesive's holding power and prolong the bonding time, so that the adhesive patch is not prone to curling up even when it is attached to the skin for a long time. The nitrogen-containing heterocyclic monomer can enhance the water absorption of the adhesive. The adhesive retains its pressure-sensitive properties after absorbing water, preventing the adhesive's adhesion from decreasing due to skin sweating. Therefore, the use of the above-mentioned acrylate copolymer can make the adhesive have better adhesion, can interact with the skin for a long time, and have excellent adhesion, thereby having better sweat resistance, and will not cause the adhesion to decrease due to skin sweating, thereby avoiding the phenomenon of the adhesive patch detaching due to skin sweating; the block copolymer is formed by the polymerization of polycaprolactone and alcohol. On the one hand, after the polymerization of caprolactone and alcohol, a molecular chain containing ether bonds is formed, and the molecular chain containing ether bonds is water-absorbing and hydrophilic, thereby further improving the sweat resistance of the adhesive; on the other hand, the interaction force between caprolactone and skin is small, and the caprolactone block makes the block copolymer have high cohesion and low peeling force, which can prevent the adhesive patch from increasing peeling force and residual adhesive after being applied to the skin for a long time; and the acrylate copolymer and the block copolymer have good compatibility, which is conducive to the synergistic effect of the two, further preventing the adhesive patch from increasing peeling force after being applied to the skin for a long time. Therefore, the medical adhesive composition has excellent sweat resistance and is not easy to fall off from the skin. Moreover, after long-term contact with the skin, the adhesion force will not increase significantly due to temperature increase, thereby avoiding problems such as great pain and skin damage when the adhesive patch is separated from the skin.

[0029] It should be noted that hydroxyl-containing acrylates, carboxyl-containing acrylates, nitrogen-containing heterocyclic monomers and alcohols are conventional materials in the field, and those skilled in the art can select them according to actual conditions. For example, hydroxyl-containing acrylates include at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate; carboxyl-containing acrylates include at least one of acrylic acid and methacrylic acid; nitrogen-containing heterocyclic monomers include at least one of N-vinyl pyrrolidone and N-vinyl caprolactam; and alcohols include at least one of polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer and polytetramethylene glycol.

[0030] According to an embodiment of the present invention, the mass ratio of alkyl acrylate, hydroxyl-containing acrylate, carboxyl-containing acrylate and nitrogen-containing heterocyclic monomer is (50-80):(1-6):(1-6):(4-13). The inventors found that alkyl acrylates have relatively high pressure sensitivity, can effectively adhere to the skin, have relatively high cohesion, prevent the adhesive from producing residual adhesive during use, and have a certain sweat resistance. The pressure-sensitive adhesive remains pressure-sensitive after the skin sweats. If the alkyl acrylate content is too low, the initial adhesion of the adhesive will be reduced, which is not conducive to effective adhesion. If the alkyl acrylate content is too high, residual adhesive will be caused. If the hydroxyl-containing acrylate content is too low, it will be not conducive to the interaction between the adhesive and the skin and the improvement of the adhesion to the skin. If the hydroxyl-containing acrylate content is too high, it will cause difficulties in the process and it will not be easy to produce stably. If the carboxyl-containing acrylate content is too high, the pressure sensitivity will be lost. If the content is too low, the cohesion will be insufficient, which may cause residual adhesive. If the content of nitrogen-containing heterocyclic monomers is too high, the polymer structure will be uneven and the stability of the adhesive will be reduced. If the content is too low, the sweat resistance will be affected. Therefore, the present application adopts an acrylate copolymer with a mass ratio of (50-80):(1-6):(1-6):(4-13) of alkyl acrylate, hydroxyl-containing acrylate, carboxyl-containing acrylate and nitrogen-containing heterocyclic monomer, which can make the medical adhesive composition have excellent sweat resistance and no residual glue.

[0031] According to an embodiment of the present invention, the hydroxyl value of the block copolymer is 5mgKOH / g-300mgKOH / g. The inventors have discovered that if the hydroxyl value of the block copolymer is too high, the polarity of the block copolymer and the polyacrylate will differ significantly, hindering their compatibility. If the hydroxyl value of the block copolymer is too low, it will be difficult to crosslink with the polyacrylate when using an isocyanate curing agent, resulting in the risk of adhesive residue. As a result, the medical adhesive composition has excellent perspiration resistance and minimal increase in adhesion after prolonged contact with skin.

[0032] According to an embodiment of the present invention, the molecular weight of the block copolymer is 1,000-10,000. The inventors have discovered that if the molecular weight of the block copolymer is too high, the viscosity is too high, which causes processing inconvenience; if the molecular weight of the block copolymer is too low, the polycaprolactone segments are too short, making it difficult to demonstrate the cohesive reinforcement effect of the adhesive matrix and the role of stabilizing the peel force. As a result, the medical adhesive composition has excellent sweat resistance and a minimal increase in adhesion after prolonged contact with skin.

[0033] According to an embodiment of the present invention, the mass proportion of caprolactone in the block copolymer is 15%-50%. The inventors found that polycaprolactone has good compatibility with acrylate copolymers, but alcohol has low compatibility with acrylate copolymers. Therefore, if the mass proportion of caprolactone in the block copolymer is too small, the compatibility of the block copolymer and the acrylate copolymer will be low, affecting the synergistic effect of the two. If the mass proportion of caprolactone in the block copolymer is too large, the effect of reducing the peeling force increase after the adhesive patch is pasted for a long time is not obvious. Therefore, the present application adopts a block copolymer with a mass proportion of caprolactone of 15%-50%, which can make the adhesive composition have a smaller increase in adhesion after prolonged contact with the skin.

[0034] According to an embodiment of the present invention, the medical adhesive composition further includes at least one of a tackifying resin and an isocyanate cross-linking agent, the tackifying resin includes a first tackifying resin and a second tackifying resin, the first tackifying resin softening point is not higher than 0°C, and the second tackifying resin softening point is higher than 0°C. The inventors have found that the first tackifying resin can increase the initial tack of the adhesive, which helps to facilitate application on the skin, and the second tackifying resin helps to improve the peeling force of the adhesive. The first tackifying resin and the second tackifying resin work together to adjust the balance between the initial tack and the holding force of the adhesive, so that the initial tack of the adhesive is high, easy to apply, and the holding force is high, so that it can be applied for a long time without falling off, and the cohesion is high to prevent residual glue. Thus, the medical adhesive composition of the present application includes a tackifying resin, which helps to adjust the initial tack and peeling force of the adhesive composition, is not easy to fall off, and avoids the generation of residual glue. It should be noted that the tackifying resin and the isocyanate cross-linking agent are conventional materials in the field, and those skilled in the art can select them according to actual conditions. For example, the first tackifying resin includes at least one of modified rosin resin, terpene resin, terpene resin derivative, petroleum resin and petroleum resin derivative; the second tackifying resin includes at least one of modified rosin resin, modified terpene and modified C5 petroleum resin; the isocyanate cross-linking agent includes at least one of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate and m-phenylenediisocyanate.

[0035] According to an embodiment of the present invention, the acrylate copolymer accounts for 50 to 80 parts by weight, the block copolymer accounts for 10 to 30 parts by weight, the tackifying resin accounts for 2 to 15 parts by weight, and the isocyanate cross-linking agent accounts for 0.1 to 5 parts by weight. The inventors found that if the acrylate copolymer accounts for less than 50 parts by weight, it cannot provide sufficient pressure sensitivity and sweat resistance. If the acrylate copolymer accounts for more than 80 parts by weight, the peeling force will increase significantly after long-term application. If the block copolymer accounts for less than 10 parts by weight, the peeling force will increase significantly after long-term application. If the block copolymer accounts for more than 30 parts by weight, the peeling force will decrease and a small amount of residual glue will be produced. Therefore, the present application adopts an adhesive composition with each formula within the above-mentioned mass proportion range, which has excellent sweat resistance and a small increase in adhesion after long-term contact with the skin. Furthermore, the medical adhesive composition also includes at least one of a solvent and an auxiliary agent. It should be noted that the solvents and additives are conventional materials in the field, and those skilled in the art can select them according to actual conditions. For example, the additives include at least one of a leveling agent, a stabilizer, a defoaming agent, a filler, a compatibilizing agent, a catalyst, a catalyst promoter, a surfactant, a diluent, a plasticizer, a crosslinking inhibitor, an antioxidant and an anti-aging agent. The solvents include common solvents such as ethyl acetate, butyl acetate, butanone, acetone, DMF, DMAc, benzene, and toluene. One or more of them can be selected.

[0036] Another aspect of the present invention provides a medical patch. According to an embodiment of the present invention, the medical patch includes a substrate, a pressure-sensitive adhesive layer and a release layer stacked in sequence, wherein the pressure-sensitive adhesive layer is made of the above-mentioned medical adhesive composition. As a result, the medical patch has good sweat resistance, high initial adhesion, low peeling force increase after long-term application, no residual adhesive after removal, and can significantly reduce the pain and skin damage problems caused by removing the patch. The substrate and the release layer are conventional materials in this field, and those skilled in the art can select them according to actual conditions. For example, the substrate includes polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, or polycarbonate-based polymers. It should be noted that the features and advantages described above for the medical adhesive composition are also applicable to the medical patch and will not be repeated here.

[0037] The present invention is described below with reference to specific examples. It should be noted that these examples are merely illustrative and do not limit the present invention in any way.

[0038] (1) Preparation of acrylic acid ester copolymer M

[0039] A four-necked flask equipped with a stirrer, reflux condenser, thermometer, constant pressure dropping funnel, and nitrogen inlet tube was purged with nitrogen until all air in the system was replaced by nitrogen. A mixed solution of 60 g of ethyl acetate, 22 g of isooctyl acrylate, and 0.1 g of benzoyl peroxide was added, and nitrogen was introduced to remove oxygen from the mixture. The temperature was raised to 80°C and maintained for 0.5 hours. A mixed solution of 9 g of N-vinyl pyrrolidone, 4 g of vinyl acetate, 3 g of acrylic acid, 2 g of hydroxyethyl acrylate, 10 g of butyl methacrylate, 25 g of isooctyl acrylate, and 0.3 g of benzoyl peroxide was slowly added dropwise over 3 hours and maintained for 6 hours to obtain an acrylate polymer. The mass ratio of the alkyl acrylate, hydroxyl-containing acrylate, carboxyl-containing acrylate, and nitrogen-containing heterocyclic monomer in the acrylate polymer prepared above was 57:2:3:9.

[0040] (2) Preparation of Acrylate Copolymer N

[0041] The main differences between the preparation method of acrylate copolymer N and the preparation method of acrylate copolymer M are: no N-vinyl pyrrolidone is added, and 25 g of isooctyl acrylate in the dropwise addition is replaced by 45 g.

[0042] (3) Preparation of Block Copolymer A1

[0043] 6.73 g of polyethylene glycol (1500 molecular weight) was added to a Schlenk reaction tube, heated under vacuum to remove water, and then cooled naturally. 1.5 g of caprolactone and stannous octoate were added, followed by 1.77 g of polyethylene glycol (500 molecular weight). After each addition, the tube was vacuumed and filled with nitrogen. The reaction was carried out at 120°C under magnetic stirring for 24 hours to obtain a polyethylene glycol-polycaprolactone-polyethylene glycol triblock copolymer. The weight proportion of caprolactone in block copolymer A1 was 15%. Block copolymer A1 had a hydroxyl value of 94.7 mgKOH / g and a molecular weight of 1246.

[0044] (4) Preparation of block copolymer A2

[0045] The main differences in the preparation of block copolymer A2 compared to block copolymer A1 are: 4.5 g of polyethylene glycol 1000 was used instead of 6.73 g of polyethylene glycol 1500, 2 g of polyethylene glycol 500 was used instead of 1.77 g, and 3.5 g of caprolactone was used, with the weight percentage of caprolactone in block copolymer A2 being 35%. Block copolymer A2 had a hydroxyl value of 100 mgKOH / g and a molecular weight of 1176.

[0046] (5) Preparation of block copolymer A3

[0047] The main differences in the preparation of block copolymer A3 compared to block copolymer A1 are: 6.73 g of polyethylene glycol 1500 was replaced with 4.3 g of polyethylene glycol 1000, 1.77 g of polyethylene glycol 500 was replaced with 0.7 g of polyethylene glycol 800, and the amount of caprolactone used was 5.0 g, with the weight percentage of caprolactone in block copolymer A3 being 50%. Block copolymer A3 had a hydroxyl value of 61 mgKOH / g and a molecular weight of 1932.

[0048] (6) Commercially available Changxing 5120 was used instead of the block copolymer. Changxing 5120 is composed of ethylene glycol adipate, containing ethylene glycol acetal, without caprolactone and long-chain ethylene glycol, with a hydroxyl value of 53-59 mgKOH / g and a molecular weight of 2000.

[0049] Example 1

[0050] Weigh the acrylic ester copolymer M prepared in step (1) and the block copolymer A2 prepared in step (4), add the first tackifying resin and the second tackifying resin, an isocyanate crosslinking agent, and 20 g of toluene, mix thoroughly, and obtain a coating liquid. Apply the coating liquid on release paper, dry at 60°C for 5 min, remove the solvent, cover with elastic fabric using a laminating machine, the elastic fabric having an elongation of 160% in the coating direction, and place in an oven at 40°C for aging for 5 days to obtain a medical adhesive patch. The material ratios for preparing the medical adhesive patch are shown in Table 1.

[0051] Example 2

[0052] The main difference between Example 2 and Example 1 is that the ratios of the materials used to prepare the medical adhesive patch are different, as shown in Table 1.

[0053] Example 3

[0054] The main difference between Example 3 and Example 1 is that the ratios of the materials used to prepare the medical adhesive patch are different, as shown in Table 1.

[0055] Example 4

[0056] The main difference between Example 4 and Example 1 is that the acrylic ester copolymer M prepared in step (1) and the block copolymer A3 prepared in step (5) are weighed, and the material ratios for preparing the medical adhesive patch are shown in Table 1.

[0057] Example 5

[0058] The main difference between Example 5 and Example 1 is that the acrylic ester copolymer M prepared in step (1) and the block copolymer A1 prepared in step (3) are weighed, and the material ratios for preparing the medical adhesive patch are shown in Table 1.

[0059] Comparative Example 1

[0060] The acrylic copolymer M prepared in step (1) was weighed, and a second tackifying resin, an isocyanate crosslinking agent, and 20 g of toluene were added and mixed thoroughly to obtain a coating solution. The coating solution was applied to release paper and dried at 60°C for 5 min. The solvent was removed and covered with elastic fabric using a laminating machine. The elastic fabric had an elongation of 160% in the coating direction. The medical adhesive patch was cured in an oven at 40°C for 5 days to obtain the medical adhesive patch. The material ratios for preparing the medical adhesive patch are shown in Table 1.

[0061] Comparative Example 2

[0062] The main difference between Comparative Example 2 and Comparative Example 1 is that the acrylic ester copolymer N and Huafeng PE-1000 prepared in step (2) are weighed, and the material ratios for preparing the medical adhesive patch are shown in Table 1.

[0063] Comparative Example 3

[0064] The main difference between Comparative Example 3 and Comparative Example 1 is that the acrylate copolymer N prepared in step (2) and the block copolymer A3 prepared in step (5) are weighed, and the material ratios for preparing the medical adhesive patch are shown in Table 1.

[0065] The first tackifying resin used in Examples 1-5 and Comparative Examples 1-3 was DRT-Pinova Dercolyte LTG terpene resin with a glass transition temperature of -20°C; the second tackifying resin was DRT-Pinova Foral 85, a modified rosin resin with a glass transition temperature of 80-88°C; and the isocyanate crosslinking agent was Asahi Kasei AE700-100.

[0066] The performance of the medical adhesive patches of Examples 1-5 and Comparative Examples 1-3 was measured, and the specific test method is as follows:

[0067] Peel strength: Tested according to the standard GB / T2792-2014 Adhesive Tape Peel Strength Test Method 1, Adhesive Tape and Stainless Steel 180° Peel Strength Test Method.

[0068] Long-term peel strength: According to the standard GB / T2792-2014 Adhesive Tape Peel Strength Test Method 1, prepare specimens. Place the specimens in a 37°C oven for 24 hours, keep warm, and cool naturally. Then test the peel strength according to the GB / T2792-2014 test method.

[0069] Residual adhesive test: Prepare specimens according to the long-term peel strength test method, stretch them at 180° and a speed of 100mm / min, and observe the residual adhesive on the test board after stretching.

[0070] Initial tack: tested according to standard GB / T4852-2002 test method for initial tack of pressure-sensitive adhesive tapes.

[0071] Adhesion: Tested according to the standard GB / T4851-2014 test method for adhesive tape adhesion.

[0072] The performance test results of the medical adhesive tapes of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1.

[0073] Table 1

[0074]

[0075] As can be seen from the test results in Table 1, the medical adhesive patch provided by the present invention has a peel force of 1.2-2N / 15mm, a long-term peel force of 1.8-2.7N / 15mm, no residual adhesive in the residual adhesive test, an initial adhesive force of 10-16#, and a lasting adhesive force of more than 15 minutes. The initial adhesive force is high and easy to adhere; the peel force is low, and the peel force is still low after long-term adhesion, which does not cause pain when removing; the lasting adhesive force is high, it is not easy to warp or curl, and it will not fall off during use, there is no residual adhesive, and it will not contaminate the skin surface.

[0076] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0077] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A medical adhesive composition, characterized in that: The invention comprises 50 to 80 parts by weight of an acrylate copolymer, 10 to 30 parts by weight of a block copolymer, 2 to 15 parts by weight of a tackifying resin, and 0.1 to 5 parts by weight of an isocyanate crosslinking agent, wherein the acrylate copolymer is polymerized by an alkyl acrylate, a hydroxyl-containing acrylate, a carboxyl-containing acrylate, and a nitrogen-containing heterocyclic monomer, wherein the alkyl acrylate comprises an alkyl acrylate having an alkyl carbon atom number of 4 to 12 and an alkyl methacrylate having an alkyl carbon atom number of 4 to 12, and the block copolymer is polymerized by caprolactone and an alcohol; the mass ratio of the alkyl acrylate, the hydroxyl-containing acrylate, the carboxyl-containing acrylate, and the nitrogen-containing heterocyclic monomer is (50 to 80):(1 to 6):(1 to 6):(4 to 13); The hydroxyl-containing acrylate includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate; The hydroxyl value of the block copolymer is 5 mgKOH / g-300 mgKOH / g; The molecular weight of the block copolymer is 1000-10000; The alcohol comprises at least one of polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer and polytetramethylene glycol; The mass proportion of caprolactone in the block copolymer is 15%-50%; The tackifying resin includes a first tackifying resin and a second tackifying resin, wherein the first tackifying resin is a terpene resin with a glass transition temperature of -20°C, and the second tackifying resin is a modified rosin resin with a glass transition temperature of 80-88°C; The carboxyl-containing acrylate comprises at least one of acrylic acid and methacrylic acid; The nitrogen-containing heterocyclic monomer includes at least one of N-vinyl pyrrolidone and N-vinyl caprolactam.

2. The medical adhesive composition according to claim 1, wherein the isocyanate crosslinking agent comprises at least one of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate and m-xylylene diisocyanate.

3. The medical adhesive composition according to claim 1, wherein The invention further comprises at least one of a solvent and an auxiliary agent.

4. The medical adhesive composition according to claim 3, characterized in that The auxiliary agent includes at least one of a leveling agent, a stabilizer, a defoaming agent, a filler, a compatibilizing auxiliary agent, a catalyst, a catalyst accelerator, a surfactant, a diluent, a plasticizer, a crosslinking inhibitor, an antioxidant and an anti-aging agent.

5. A medical adhesive patch, characterized in that: The invention comprises a substrate, a pressure-sensitive adhesive layer and a release layer stacked in sequence, wherein the pressure-sensitive adhesive layer is prepared by adopting the medical adhesive composition according to any one of claims 1 to 4.

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