Irradiation cross-linked antibacterial pressure-sensitive adhesive as well as preparation method and application thereof
By introducing crosslinking sensitizers into antibacterial pressure-sensitive adhesives and using irradiation crosslinking technology to form a dense crosslinking network, the problem of insufficient performance of traditional antibacterial pressure-sensitive adhesives is solved, and efficient antibacterial protection and physical performance maintenance are achieved. , meet medical sterility requirements.
Patent Information
- Application Number
- CN202411697301.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-26
- Publication Date
- 2025-01-07
AI Technical Summary
Traditional antibacterial pressure-sensitive adhesives have problems with insufficient antibacterial effect and physical performance in long-term use, especially when the medical field has increased the requirements for sterile operation, the prior art is difficult to provide long-lasting antibacterial protection and good physical performance solutions. plan.
An antibacterial pressure-sensitive adhesive with irradiated crosslinking consists of 80% to 99.5% acrylate polymer, 0.5% to 20% antibacterial agent and 0.5% to 3% crosslinking sensitizer by gamma ray or electrons Beam irradiation performs cross-linking to form a dense cross-linking network to improve cohesion and mechanical properties.
The cohesive and mechanical properties of pressure-sensitive adhesives are significantly improved, such as shear strength and peel strength, ensuring that the product can maintain physical properties after sterilization, meet the sterile requirements of medical supplies, and provide long-lasting antibacterial protection.
Abstract
Description
Technical Field
[0001] The present disclosure relates to the technical field of acrylic pressure-sensitive adhesives, and in particular to a radiation-crosslinked antibacterial pressure-sensitive adhesive and a preparation method and application thereof. Background Art
[0002] With the development of medical technology and the improvement of requirements for aseptic operation, antibacterial surgical films are increasingly used in clinical practice. Such films not only need to provide an effective physical barrier during surgery to prevent external microorganisms from invading the wound, but also need to have good antibacterial properties to further reduce the risk of infection. Traditional antibacterial agents, such as iodine and its complexes, although they have strong bactericidal ability, are limited in their use in certain application scenarios due to their volatilization and strong corrosiveness.
[0003] Traditional pressure-sensitive adhesives have deficiencies in maintaining antibacterial effects and physical properties during long-term use. Therefore, it is particularly important to develop a new type of antibacterial pressure-sensitive adhesive that can provide long-lasting antibacterial protection while maintaining good physical properties. Summary of the invention
[0004] The purpose of the present invention is to provide an irradiation-crosslinked antibacterial pressure-sensitive adhesive and a preparation method and application thereof, so as to solve the technical problems existing in the prior art.
[0005] The term "composition", "formulation" or "mixture" refers to a physical blend of different components, which is obtained by simply mixing the different components by physical means.
[0006] The term "(meth)acryl" refers to one or a mixture of "methacryl" and "acryl". For example, (meth)acrylic acid refers to one or a mixture of methacrylic acid and acrylic acid, methyl (meth)acrylate refers to one or a mixture of methyl methacrylate and methyl acrylate, and (meth)acrylamide refers to one or a mixture of methacrylamide and acrylamide.
[0007] In order to achieve the above object, according to the first aspect of the present disclosure, there is provided a radiation cross-linked antibacterial pressure-sensitive adhesive composition, characterized in that its raw material components include 80 wt % to 99.5 wt % of an acrylate polymer, 0.5 wt % to 20 wt % of an antibacterial agent, and 0.5 wt % to 3 wt % of a cross-linking sensitizer; The monomers constituting the acrylic ester polymer include soft monomers, functional monomers and hard monomers. The soft monomers are monomers with a homopolymer glass transition temperature of less than 0°C, including (meth)acrylates having an alkyl group with a carbon number of 2 to 18 carbon atoms. The hard monomers are monomers with a homopolymer glass transition temperature of more than 0°C, including methyl (meth)acrylate, ethyl methacrylate, isobornyl methacrylate and isobutyl methacrylate. The cross-linking sensitizer includes a multifunctional carbon-carbon unsaturated bond compound, and the multifunctional carbon-carbon unsaturated bond compound includes but is not limited to triallyl isocyanurate, trimethallyl isocyanurate, triallyl cyanurate, trimethallyl cyanurate and trimethylolpropane trimethacrylate.
[0008] Optionally, the cross-linking sensitizer is triallyl isocyanurate.
[0009] Optionally, the soft monomer (meth)acrylate includes but is not limited to 2-ethylhexyl acrylate, isooctyl acrylate, butyl acrylate, hexyl acrylate, nonyl acrylate, decyl acrylate, isobornyl acrylate, dodecyl acrylate and a mixture of one or more of the isomers of these monomers.
[0010] Optionally, the soft monomer is selected from one or more of 2-ethylhexyl acrylate, isooctyl acrylate and butyl acrylate.
[0011] Optionally, the functional monomer includes but is not limited to alkoxy (meth)acrylate, ethoxyethoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and acrylamide.
[0012] Optionally, the antibacterial agent is selected from one or more of elemental iodine, iodine complexes, iodide, iodine-containing compounds, chlorhexidine gluconate, polyhexamethylene biguanide hydrochloride and polyquaternary ammonium salts.
[0013] According to a second aspect of the present disclosure, a method for preparing the above-mentioned radiation-crosslinked antibacterial pressure-sensitive adhesive is provided, and the preparation method comprises the following steps: S1, adding 1-3 g of antibacterial agent to 4-10 g of ethanol, stirring evenly to prepare a mixed solution 1; S2, adding the prepared mixed solution into 10-30g of acrylate polymer adhesive, and then adding 0.05-0.3g of triallyl isocyanurate to prepare an antibacterial pressure-sensitive adhesive.
[0014] According to a third aspect of the present disclosure, a use of a radiation-crosslinked antibacterial pressure-sensitive adhesive is provided.
[0015] An antibacterial surgical towel comprises the above-mentioned radiation cross-linked antibacterial pressure-sensitive adhesive.
[0016] A method for preparing an antibacterial surgical towel comprises the following steps: (1) uniformly coating the antibacterial pressure-sensitive adhesive on one side of the release layer and drying at 80-150° C. for 5-15 minutes to obtain a coating layer; (2) pasting a vapor permeable membrane layer onto one side of the antibacterial pressure-sensitive adhesive in the coating layer to obtain a composite membrane layer; (3) The prepared composite film layer is sterilized by γ-ray or electron beam irradiation, with an irradiation dose of 25-50 kGy.
[0017] Optionally, in S3, the coating layer has a grammage of 30-60 gsm.
[0018] Optionally, the vapor permeable membrane layer is a polyether polyurethane membrane layer, and the water vapor permeability of the polyether polyurethane membrane layer is greater than 800 g / (m²·24hr).
[0019] Compared with the prior art, the present invention has the following beneficial effects: The antibacterial pressure-sensitive adhesive provided by the present invention introduces a cross-linking sensitizer (such as triallyl isocyanurate) during the preparation process. Triallyl isocyanurate is a highly efficient cross-linking agent that can effectively react with double bonds in acrylic polymers to form a cross-linked network. This cross-linked structure can significantly improve the cohesion and mechanical properties of the pressure-sensitive adhesive, such as shear strength and peel strength.
[0020] In addition, γ-ray irradiation can provide sufficient energy to promote the cross-linking reaction between triallyl isocyanurate and the double bonds in acrylic polymers, forming a denser and more stable cross-linked network. In other words, γ-ray irradiation can not only promote the cross-linking reaction, but also maintain the performance of the pressure-sensitive adhesive while effectively sterilizing, so as to ensure that the product is sterile and can still maintain its physical properties after sterilization, meeting the sterility requirements of medical supplies.
[0021] Other features and advantages of the present disclosure will be described in detail in the following detailed description. DETAILED DESCRIPTION
[0022] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0023] The present disclosure provides a radiation cross-linked antibacterial pressure-sensitive adhesive, the raw material components of which include 80 wt % to 99.5 wt % of an acrylate polymer, 0.5 wt % to 20 wt % of an antibacterial agent, and 0.5 wt % to 3 wt % of a cross-linking sensitizer; The monomers constituting the acrylic ester polymer include soft monomers, functional monomers and hard monomers. The soft monomers are monomers with a homopolymer glass transition temperature of less than 0°C, including (meth)acrylates having an alkyl group with a carbon number of 2 to 18 carbon atoms. The hard monomers are monomers with a homopolymer glass transition temperature of more than 0°C, including methyl (meth)acrylate, ethyl methacrylate, isobornyl methacrylate and isobutyl methacrylate. The crosslinking sensitizer includes a multifunctional carbon-carbon unsaturated bond compound, and the multifunctional carbon-carbon unsaturated bond compound includes but is not limited to triallyl isocyanurate (TAIC), trimethallyl isocyanurate, triallyl cyanurate, trimethallyl cyanurate and trimethylolpropane trimethacrylate.
[0024] It will be appreciated that the glass transition temperature (Tg) can be measured by a variety of techniques including, for example, differential scanning calorimetry (DSC) or by calculation using the Fox equation.
[0025] Preferably, the crosslinking sensitizer is triallyl isocyanurate (TAIC).
[0026] Optionally, the soft monomer (meth)acrylate includes, but is not limited to, 2-ethylhexyl acrylate, isooctyl acrylate, butyl acrylate, hexyl acrylate, nonyl acrylate, decyl acrylate, isobornyl acrylate, dodecyl acrylate, and a mixture of one or more of the isomers of these monomers.
[0027] It is to be understood that a mixture refers to a physical blend of the different components, ie obtained by simply mixing the different components in a physical manner.
[0028] Preferably, the soft monomer is selected from one or more of 2-ethylhexyl acrylate, isooctyl acrylate and butyl acrylate.
[0029] Optionally, the functional monomer includes, but is not limited to, alkoxy (meth)acrylate, ethoxyethoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and acrylamide.
[0030] Optionally, the antibacterial agent is selected from one or more of elemental iodine, iodine complexes, iodide, iodine-containing compounds, chlorhexidine gluconate, polyhexamethylene biguanide hydrochloride and polyquaternary ammonium salts.
[0031] A method for preparing a radiation-crosslinked antibacterial pressure-sensitive adhesive, the method comprising the following steps: S1, adding 1-3 g of antibacterial agent to 4-10 g of ethanol, stirring evenly to prepare a mixed solution 1; S2, adding the prepared mixed solution into 10-30 g of acrylate polymer adhesive, and then adding 0.05-0.3 g of triallyl isocyanurate to prepare an antibacterial pressure-sensitive adhesive.
[0032] An antibacterial surgical towel comprises the above-mentioned radiation cross-linked antibacterial pressure-sensitive adhesive.
[0033] A method for preparing an antibacterial surgical towel comprises the following steps: (1) uniformly coating the antibacterial pressure-sensitive adhesive on one side of the release layer and drying at 80-150° C. for 5-15 minutes to obtain a coating layer; (2) pasting the vapor permeable film layer onto one side of the antibacterial pressure-sensitive adhesive in the coating layer to obtain a composite film layer; (3) The prepared composite film layer is sterilized by γ-ray or electron beam irradiation, with an irradiation dose of 25-50 kGy.
[0034] Optionally, in step (1), the coating layer has a grammage of 30-60 gsm.
[0035] Optionally, the vapor permeable membrane layer is a polyether polyurethane membrane layer, and the water vapor permeability of the polyether polyurethane membrane layer is greater than 800 g / (m²·24hr).
[0036] Example 1: Preparation of radiation cross-linked antibacterial pressure-sensitive adhesive and antibacterial surgical towel A radiation cross-linked antibacterial pressure-sensitive adhesive, whose raw material components include 18g of acrylate polymer with a solid content of 45%, 2g of antibacterial agent and 0.08g of cross-linking sensitizer (triallyl isocyanurate).
[0037] A method for preparing a radiation-crosslinked antibacterial pressure-sensitive adhesive, the method comprising the following steps: S1, adding 2 g of povidone iodine powder to 6 g of ethanol, stirring evenly to prepare a mixed solution 1; S2, adding the prepared mixed solution to 18g of a solvent-based acrylic pressure-sensitive adhesive having a solid content of 45%, and then adding 0.08g of triallyl isocyanurate, and mixing well to prepare an antibacterial pressure-sensitive adhesive (a cross-linkable iodine-containing adhesive).
[0038] A method for preparing an antibacterial surgical towel comprises the following steps: (1) The antibacterial pressure-sensitive adhesive was evenly coated on a release surface layer of 60 g of white glassine release paper and dried at 120° C. for 10 min to obtain a coating layer, wherein the coating layer had a weight of 47 gsm; (2) pasting a 25 μm thick polyether polyurethane film layer on one side of the antibacterial pressure-sensitive adhesive in the coating layer to obtain a composite film layer; (3) The prepared composite film layer is sterilized by γ-ray irradiation with an irradiation dose of 45 kGy.
[0039] Comparative Example 1 Compared with Example 1, the difference of Comparative Example 1 is that after the prepared mixed solution is added to 18 g of acrylate with a solid content of 45%, 0.08 g of triallyl isocyanurate (TAIC) is not added to prepare the antibacterial pressure-sensitive adhesive.
[0040] The antibacterial pressure-sensitive adhesives obtained in Example 1 and Comparative Example 1 were subjected to relevant performance tests, and the test results are shown in Table 1.
[0041] The test items and conditions are as follows: 1) Shear strength performance test: FINAT No. 8 shear resistance test method is used.
[0042] 2) Other performance tests: conducted using YY-0852. The results are as follows: Table 1 Test results Example 1 Comparative Example 1 Stickiness No slip No slip Shear strength (hr) >5 1 Peel strength (N / inch) 20 15 Water barrier No water seepage No water seepage Water vapor transmission rate (g / (m²·24hr)) 850 800 From the test results of Example 1 and Comparative Example 1, it can be seen that the specific analysis is as follows: Stickiness: The stickiness of Example 1 and Comparative Example 1 both showed "no slip", indicating that the two performed similarly in this respect and were able to remain well on the surface without moving.
[0043] Shear strength (hr): The shear strength of Example 1 is greater than 5 hr, while that of Comparative Example 1 is only 1 hr. This indicates that the antibacterial pressure-sensitive adhesive of Example 1 has better cohesion and shear resistance, and can resist shear stress for a longer period of time without failure. In other words, the addition of the cross-linking sensitizer TAIC can obviously improve the cohesion of the pressure-sensitive adhesive.
[0044] Peel strength (N / inch): The peel strength of Example 1 is 20 N / inch, while that of Comparative Example 1 is 15 N / inch. The peel strength can reflect the adhesion between the polymer adhesive and the patient's skin, and a higher peel strength means a stronger adhesion. In other words, the higher peel strength of Example 1 can indicate that it has better bonding performance.
[0045] Water barrier property: The water barrier property of Example 1 and Comparative Example 1 both showed “no water penetration”, indicating that both can effectively prevent water penetration and maintain good waterproof performance.
[0046] Water vapor permeability: The water vapor permeability of Example 1 is comparable to that of Comparative Example 1, ensuring the moisture permeability of the antibacterial surgical membrane and the comfort of adhering to the skin.
[0047] From the above test results, it can be seen that Example 1 (adding the cross-linking sensitizer TAIC) is significantly better than Comparative Example 1 (no cross-linking sensitizer TAIC) in shear strength and peel strength. This shows that the addition of TAIC can significantly improve the cohesion and adhesion of the pressure-sensitive adhesive, making the pressure-sensitive adhesive more reliable and durable in practical applications. That is, the performance of the antibacterial pressure-sensitive adhesive prepared in Example 1 of the present disclosure is significantly better than that of the antibacterial pressure-sensitive adhesive prepared in Comparative Example 1, especially in shear strength and peel strength.
[0048] In addition, the addition of triallyl isocyanurate (TAIC) in combination with irradiation treatment (such as gamma rays) can achieve better cross-linking effects while sterilizing.
[0049] Specifically, regarding crosslinking efficiency, triallyl isocyanurate (TAIC) is a highly efficient crosslinking agent that can accelerate the crosslinking reaction with double bonds in acrylic polymers, making the crosslinking process faster and more thorough, forming a crosslinked network. This crosslinked structure can significantly improve the cohesion and mechanical properties of the pressure-sensitive adhesive, such as shear strength and peel strength.
[0050] Regarding the sterilization effect, gamma ray irradiation can provide sufficient energy to promote the cross-linking reaction between TAIC and the double bonds in the acrylic polymer to form a more compact and stable cross-linked network. In other words, gamma ray irradiation can not only promote the cross-linking reaction, but also maintain the performance of the pressure-sensitive adhesive under the condition of effective sterilization, so as to ensure that the product is sterile and can still maintain its physical properties after sterilization, meeting the sterility requirements of medical supplies.
[0051] The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in any form. Although the present invention has been disclosed as above in the form of preferred embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some changes or modifications to equivalent embodiments of equivalent changes using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.
Claims
1. An irradiation cross-linked antibacterial pressure-sensitive adhesive, characterized in that: The raw material components include 80 wt % to 99.5 wt % of an acrylate polymer, 0.5 wt % to 20 wt % of an antibacterial agent, and 0.5 wt % to 3 wt % of a cross-linking sensitizer; The monomers constituting the acrylic ester polymer include soft monomers, functional monomers and hard monomers. The soft monomers are monomers with a homopolymer glass transition temperature of less than 0°C, including (meth)acrylates having an alkyl group with a carbon number of 2 to 18 carbon atoms. The hard monomers are monomers with a homopolymer glass transition temperature of more than 0°C, including methyl (meth)acrylate, ethyl methacrylate, isobornyl methacrylate and isobutyl methacrylate. The cross-linking sensitizer includes a multifunctional carbon-carbon unsaturated bond compound, and the multifunctional carbon-carbon unsaturated bond compound includes triallyl isocyanurate, trimethallyl isocyanurate, triallyl cyanurate, trimethallyl cyanurate and trimethylolpropane trimethacrylate.
2. The antibacterial pressure-sensitive adhesive according to claim 1, characterized in that: The cross-linking sensitizer is triallyl isocyanurate.
3. The antibacterial pressure-sensitive adhesive according to claim 1, characterized in that: The soft monomer (meth)acrylate includes, but is not limited to, 2-ethylhexyl acrylate, isooctyl acrylate, butyl acrylate, hexyl acrylate, nonyl acrylate, decyl acrylate, isobornyl acrylate, dodecyl acrylate, and a mixture of one or more of the isomers of these monomers.
4. The antibacterial pressure-sensitive adhesive according to claim 3, characterized in that: The soft monomer is selected from one or more of 2-ethylhexyl acrylate, isooctyl acrylate and butyl acrylate.
5. The antibacterial pressure-sensitive adhesive according to claim 1, characterized in that: The functional monomers include, but are not limited to, alkoxy (meth)acrylates, ethoxyethoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and acrylamide.
6. The antibacterial pressure-sensitive adhesive according to claim 1, characterized in that: The antibacterial agent is selected from one or more of elemental iodine, iodine complexes, iodide, iodine-containing compounds, chlorhexidine gluconate, polyhexamethylene biguanide hydrochloride and polyquaternary ammonium salts.
7. A method for preparing the radiation cross-linked antibacterial pressure-sensitive adhesive according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: S1, adding 1-3 g of antibacterial agent to 4-10 g of ethanol, stirring evenly to prepare a mixed solution 1; S2, adding the prepared mixed solution into 10-30g of acrylate polymer adhesive, and then adding 0.05-0.3g of triallyl isocyanurate to prepare an antibacterial pressure-sensitive adhesive.
8. An antibacterial surgical towel, characterized in that: The invention relates to an antibacterial pressure-sensitive adhesive comprising the radiation-crosslinked antibacterial pressure-sensitive adhesive according to any one of claims 1 to 6.
9. The method for preparing the antibacterial surgical towel according to claim 8, characterized in that: The following steps are involved: (1) uniformly coating the antibacterial pressure-sensitive adhesive on one side of the release layer and drying at 80-150° C. for 5-15 minutes to obtain a coating layer; (2) pasting a vapor permeable membrane layer onto one side of the antibacterial pressure-sensitive adhesive in the coating layer to obtain a composite membrane layer; (3) The prepared composite film layer is sterilized by γ-ray or electron beam irradiation at a dose of 25-50 kGy.
10. The method for preparing the radiation cross-linked antibacterial pressure-sensitive adhesive according to claim 9, characterized in that: In the step (1), the coating layer has a grammage of 30-60 gsm.
11. The antibacterial surgical towel according to claim 9, characterized in that: The vapor permeable membrane layer is a polyether polyurethane membrane layer, and the water vapor permeability of the polyether polyurethane membrane layer is greater than 800 g / (m²·24hr).