High-moisture-permeability functional medical pressure-sensitive adhesive and preparation method thereof

Abstract

The invention discloses a preparation method of a high-moisture-permeability functional medical pressure-sensitive adhesive, which comprises the following steps: 1) polymerizing tetradecyl methacrylate and an acrylate monomer to prepare an acrylate polymer; 2) compounding the polymer prepared in the step 1) with high-molecular polyether ester according to the following weight ratio to obtain the high-moisture-permeability functional medical pressure-sensitive adhesive: 100 parts of acrylate polymer, 30-50 parts of high-molecular polyether ester and 0.1-1.5 parts of dispersing agent; the invention discloses a medical pressure-sensitive adhesive, which has the advantages of high vapor permeability, good viscosity, very good hydrophilicity, low cost, high viscosity, less residual adhesive, low skin irritation and the like, and can reduce the problems of wetting, eruption and the like caused by air tightness.

Description

Technical Field

[0001] The present invention relates to the technical field of pressure-sensitive adhesives and their applications, and specifically to a highly moisture-permeable functional medical pressure-sensitive adhesive and a preparation method thereof. Background Art

[0002] Pressure-sensitive adhesive products are used in a variety of applications that need to be adhered to the skin, such as medical tapes, wound or surgical dressings. A wound dressing is a product for dressing a wound, which is a material used to cover sores, wounds or other damages. Since medical dressings are attached to the surface of the wound, medical dressings need to have sufficiently high air permeability, water resistance and adhesiveness. In the current market, traditional surgical tape products mainly use rubber pressure-sensitive adhesive systems, which have poor moisture permeability and biocompatibility, and their adhesiveness and sweat resistance cannot meet the standards of imported products, greatly restricting the development of the domestic high-end medical surgical tape industry. How to ensure high moisture permeability of the pressure-sensitive adhesive while having good sweat resistance and adhesive strength has become a difficult problem to be solved in the current high-end surgical tape field. Summary of the Invention

[0003] The purpose of the present invention is to provide a highly moisture-permeable medical pressure-sensitive adhesive and a preparation method thereof to solve the problems raised in the above background art.

[0004] To achieve the above purpose, the present invention provides the following technical solutions: The present invention provides a preparation method of a highly moisture-permeable medical pressure-sensitive adhesive, which includes the following steps by weight: S1. Tetradecyl methacrylate and acrylate monomers are polymerized to obtain an acrylate polymer. S2. 100 parts of the acrylate polymer prepared in step S1, 30-50 parts of a high molecular polyether ester, and 0.1-1.5 parts of a dispersant are compounded to obtain a highly moisture-permeable medical pressure-sensitive adhesive.

[0005] Further, in step S1, it specifically includes the following steps: Weigh 2-10 parts of tetradecyl methacrylate, 2-15 parts of 2-hydroxyethyl acrylate, 10-20 parts of a hard acrylate monomer, 5-25 parts of a medium-soft acrylate monomer, and 40-60 parts of a soft acrylate monomer, dissolve them in a solvent, add an initiator for polymerization to obtain an acrylate polymer.

[0006] Furthermore, the Tg of the above-mentioned rigid acrylate monomer is ≥30, the Tg of the medium-soft acrylate monomer is 29 to -24, and the Tg of the soft acrylate monomer is < -24; preferably, the rigid acrylate monomer includes methyl methacrylate, butyl methacrylate, and acrylic acid, the medium-soft acrylate monomer includes methyl acrylate, ethyl acrylate, vinyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and glycidyl methacrylate, and the soft acrylate monomer includes butyl acrylate, isooctyl acrylate, and octyl acrylate.

[0007] Furthermore, the dosage of the initiator is 2 to 5% of the total mass of tetradecyl methacrylate and acrylate monomers.

[0008] Furthermore, the dosage of the solvent is 60 to 70% of the total mass of tetradecyl methacrylate and acrylate monomers.

[0009] Furthermore, the polymerization temperature is 80 - 92 °C and the polymerization time is 8 h.

[0010] Furthermore, the initiator is one or more of azobisisobutyronitrile, benzoyl peroxide, and tert-butyl peroxybenzoate; the solvent is one or more of ethyl acetate, butyl acetate, and methyl isobutyl ketone.

[0011] Furthermore, the molecular weight of the high molecular polyether ester is 5000 - 10000.

[0012] Furthermore, the dispersant is used to adjust the viscosity of the present invention, and any dispersant that can adjust the viscosity can be used in the present invention.

[0013] The present invention also provides a highly moisture-permeable medical pressure-sensitive adhesive prepared by the preparation method as described above.

[0014] Furthermore, the solid content of the highly moisture-permeable medical pressure-sensitive adhesive is 49 - 51%, the viscosity is controlled at 4000 - 8000 mPa·s, and the water vapor transmission rate > 2200 (g / day·m 2 )

[0015] During specific use, adding isocyanate resin (L-75) to crosslink and cure the highly moisture-permeable medical pressure-sensitive adhesive of the present invention can form an IPN structure of acrylic resin, high molecular polyether ester, and isocyanate resin. The dosage of the isocyanate resin is 5 - 12% of the total amount of tetradecyl methacrylate and acrylate monomers.

[0016] Compared with the prior art, the beneficial effects of the present invention are: The functional monomer of the present invention mainly consists of tetradecyl methacrylate, enabling the copolymerized acrylic resin to have good conformability with human skin, achieving the effects of no warping, easy removal, and painlessness, solving the technical problems in the current industry. By querying the literature, there is currently no report on the modification of acrylic resin with tetradecyl methacrylate and its application in high moisture permeability pressure-sensitive adhesives. Moreover, by forming an IPN structure polymer with a high molecular weight polyether ester, it has good moisture permeability performance, low skin irritation, and other advantages, and can reduce problems such as wetting and rash caused by airtightness. Detailed implementation mode

[0017] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] In the following embodiments, the involved Dispersant: BYK Chemical, the chemical composition of BYK-101 dispersant is long-chain polyamine amide; High molecular weight polyether ester: Shanghai Yuyu New Material Technology Co., Ltd., high molecular weight polyether ester, model 174.

[0019] Preparation method of high moisture permeability medical pressure-sensitive adhesive, including the following steps: S1 Polymerize tetradecyl methacrylate and acrylate monomers under the following conditions to obtain an acrylate polymer: A. The weight ratio of copolymer monomers: 2-10 parts of tetradecyl methacrylate, 2-15 parts of hydroxyethyl acrylate, 10-20 parts of hard acrylate monomer, 5-25 parts of medium-soft acrylate monomer, and 40-60 parts of soft acrylate monomer are dissolved in a solvent, and an initiator is added for polymerization to obtain an acrylate polymer; the Tg of the above hard acrylate monomer is ≥30, the Tg of the medium-soft acrylate monomer is 29--24, and the Tg of the soft acrylate monomer is <-24; B. The dosage of the initiator is 2-5% of the total mass of tetradecyl methacrylate and acrylate monomers; C. Polymerize by nitrogen protection solvent method in an intermittent dropping manner, and the dosage of the solvent is 60-70% of the total mass of tetradecyl methacrylate and acrylate monomers; D. Control the polymerization temperature at 80-92°C, and the polymerization time is 8h; S2 Compound the polymer obtained in step 1) with polyurethane resin according to the following weight ratio: 100 parts of acrylate polymer, 30-50 parts of polyurethane resin, and 0.1-1.5 parts of dispersant; compound to obtain a high moisture permeability medical pressure-sensitive adhesive.

[0020] The main technical indicators of the high moisture permeability functional medical pressure-sensitive adhesive described in the present invention are shown in Table 1: Table 1 Appearance: Light yellow transparent liquid Standard Solid content: 50±1% GB / T 2793-1995 Viscosity (25°C): 6000±2000 mpa.s GB / T 2794-2022 180° peel strength >8 N / 25mm GB / T 2792-1998 Water vapor permeability (moisture permeability) (g / day.m2) >2200 YY / T 0471.2-2004 Adhesiveness It can adhere to the skin for 24 hours without warping and leave no residue when peeled off. Biocompatibility test No allergy or abnormality GB / T 16886.10 Example 1

[0021] Weigh 41 g of butyl acrylate, 12.7 g of ethyl acrylate, 1.9 g of methyl acrylate, 5 g of 2-hydroxyethyl acrylate, 3 g of tetradecyl methacrylate, 2 g of azobisisobutyronitrile (initiator), and 70 g of ethyl acetate. Add the above substances to the reaction kettle in batches by the nitrogen protection solvent method for polymerization. Start stirring and quickly heat up to reflux at 80 - 92 °C. Reflux for 1.5 hours, then add the initiator solution once every hour and complete the addition in 5 hours. Keep the reflux state and keep warm for 2 hours. Add 30 g of high molecular polyether ester 174, cool to 30 °C, add 1 g of dispersant BYK-101, stir for 1 h, filter and discharge. The solid content is 50%, the viscosity is 5000 cps / 25 °C, the 180° peel strength is 9 N / 25 mm, the water vapor permeability (moisture permeability) is 2300 g / day·m2, there is no residual glue in the adhesion test, and there is no allergy in the biocompatibility test. Example 2

[0022] Weigh 42 g of octyl acrylate, 6.8 g of ethyl acrylate, 9 g of tetradecyl methacrylate, 4 g of 2-hydroxyethyl acrylate, 3.2 g of azobisisobutyronitrile (initiator), 65 g of a mixed solvent of ethyl acetate and methyl isobutyl ketone, 50 g of high molecular polyether ester 174, and 1.2 g of dispersant BYK-101. The polymerization reaction is carried out according to Example 1. The solid content is 51%, the viscosity is 6000 cps / 25 °C, the 180° peel strength is 9.5 N / 25 mm, and the water vapor permeability (moisture permeability) is 2350 g / day·m2. There is no residual glue in the adhesion test, and there is no allergy in the biocompatibility test. Example 3

[0023] Weigh 50 g of butyl acrylate, 5 g of methyl methacrylate, 5 g of 2-hydroxyethyl acrylate, 2.76 g of glycidyl methacrylate, 5 g of tetradecyl methacrylate, 3 g of azobisisobutyronitrile (initiator), 55 g of ethyl acetate, and 15 g of butyl acetate. Add the above substances dropwise into the reaction kettle in batches by the nitrogen protection solvent method for polymerization. Start stirring and quickly heat up to reflux at 80 - 92 °C. After the reflux state is stable, start dropping the initiator solution and monomers, and complete it in 4 hours. Keep the reflux state and keep warm for 4 hours. Add 40 g of high molecular polyether ester 174. Cool to about 30 °C, add 1.1 g of dispersant BYK-101, stir for 1 h, filter and discharge. The solid content is 50%, the viscosity is 6500 cps / 25 °C, the 180° peel strength is 10 N / 25 mm, and the water vapor permeability (moisture permeability) is 2450 g / day·m2. There is no residual glue in the adhesion test, and there is no allergy in the biocompatibility test. Comparative Example 1

[0024] Weigh 41 g of butyl acrylate, 12.7 g of ethyl acrylate, 1.9 g of methyl acrylate, 5 g of 2-hydroxyethyl acrylate, 1 g of tetradecyl methacrylate, 2 g of azobisisobutyronitrile (initiator), and 70 g of ethyl acetate. Add the above substances dropwise into the reaction kettle in batches by the nitrogen protection solvent method for polymerization. Start stirring and quickly heat up to reflux at 80 - 92 °C. Reflux for 1.5 hours, then drop the initiator solution once an hour and complete it in 5 hours. Keep the reflux state and keep warm for 2 hours. Add 10 g of high molecular polyether ester 174. Cool to 30 °C, add 1 g of dispersant BYK-101, stir for 1 h, filter and discharge. The solid content is 50%, the viscosity is 3000 cps / 25 °C, the 180° peel strength is 7 N / 25 mm, and the water vapor permeability (moisture permeability) is 1500 g / day·m2. There is residual glue in the adhesion test, and there is no allergy in the biocompatibility test. Comparative Example 2

[0025] Weigh 42 g of octyl acrylate, 6.8 g of ethyl acrylate, 9 g of tetradecyl methacrylate, 4 g of 2-hydroxyethyl acrylate, 3.2 g of azobisisobutyronitrile (initiator), 65 g of a mixed solvent of ethyl acetate and methyl isobutyl ketone, 5 g of high molecular polyether ester 174, and 1.2 g of dispersant BYK-101. Carry out the polymerization reaction according to Example 1. The solid content is 51%, the viscosity is 4000 cps / 25 °C, the 180° peel strength is 5 N / 25 mm, and the water vapor permeability (moisture permeability) is 1350 g / day·m2. There is no residual glue in the adhesion test, and there is no allergy in the biocompatibility test. Comparative Example 3

[0026] Weigh 50 g of butyl acrylate, 5 g of methyl methacrylate, 5 g of 2-hydroxyethyl acrylate, 2.76 g of glycidyl methacrylate, 3 g of azobisisobutyronitrile (initiator), 55 g of ethyl acetate, and 15 g of butyl acetate. Add the above substances dropwise into the reaction kettle in batches by the nitrogen protection solvent method for polymerization. Start stirring and quickly heat up to reflux at 80 - 92 °C. After the reflux state is stable, start dropping the initiator solution and monomers, and complete it in 4 hours. Keep the reflux state and keep warm for 4 hours. Cool to about 30 °C and add 1.1 g of dispersant BYK-101 and stir for 1 h. Filter and discharge. The solid content is 50%, the viscosity is 3500 cps / 25 °C, the 180° peel strength is 5 N / 25 mm, and the water vapor permeability (moisture permeability) is 850 g / day·m2. There is residual glue in the adhesion test, and there is no allergy in the biocompatibility test.

[0027] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device.

[0028] It should be noted that the above content only illustrates the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. For those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and retouches can still be made, and these improvements and retouches all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a highly moisture-permeable medical pressure-sensitive adhesive, characterized in that: By weight, the method comprises the following steps: S1, tetradecyl methacrylate and acrylate monomers are polymerized to obtain acrylate polymer; S2. Compounding 100 parts of the acrylate polymer prepared in step S1, 30-50 parts of high molecular weight polyether ester, and 0.1-1.5 parts of a dispersant to obtain a highly moisture-permeable medical pressure-sensitive adhesive.

2. The method for preparing a highly moisture-permeable medical pressure-sensitive adhesive according to claim 1, characterized in that: In parts by weight, in step S1, The method comprises the following steps: weighing 2-10 parts of tetradecyl methacrylate, 2-15 parts of hydroxyethyl acrylate, 10-20 parts of hard acrylate monomer, 5-25 parts of medium-soft acrylate monomer and 40-60 parts of soft acrylate monomer, dissolving them in a solvent, adding an initiator for polymerization, and obtaining an acrylate polymer.

3. The method for preparing a highly moisture-permeable medical pressure-sensitive adhesive according to claim 2, characterized in that: The amount of the initiator used is 2-5% of the total mass of tetradecyl methacrylate and acrylate monomers.

4. The method for preparing a highly moisture-permeable medical pressure-sensitive adhesive according to claim 2, characterized in that: The amount of the solvent used is 60-70% of the total mass of tetradecyl methacrylate and the acrylate monomer.

5. The method for preparing a highly moisture-permeable medical pressure-sensitive adhesive according to claim 2, characterized in that: The polymerization temperature is 80-92°C and the polymerization time is 8h.

6. The method for preparing a highly moisture-permeable medical pressure-sensitive adhesive according to claim 2, characterized in that: The initiator is one or more of azobisisobutyronitrile, benzoyl peroxide, and tert-butyl benzoyl peroxide; the solvent is one or more of ethyl acetate, butyl acetate, and methyl isobutyl ketone.

7. The method for preparing a highly moisture-permeable medical pressure-sensitive adhesive according to claim 1, characterized in that: The molecular weight of the high molecular weight polyether ester is 5000-10000.

8. A highly moisture-permeable medical pressure-sensitive adhesive prepared by the preparation method according to any one of claims 1 to 7.

9. A highly moisture permeable medical pressure-sensitive adhesive according to claim 8, characterized in that: The high moisture permeability medical pressure-sensitive adhesive has a solid content of 49-51%, a viscosity controlled at 4000-8000 mpa / s, and a water vapor permeability of >2200 g / day.m 2 .