Hypoallergenic pressure-sensitive adhesive for medical dressing and preparation method thereof

Abstract

The invention discloses a low-sensitivity pressure-sensitive adhesive for medical dressings and a preparation method thereof, and the pressure-sensitive adhesive is used for medical tapes. The pressure-sensitive adhesive is mainly prepared from the following raw materials in parts by weight: 1 to 10 parts of acrylic homopolymer, 5 to 30 parts of ethyl acrylate, 5 to 30 parts of butyl acrylate, 0.1 to 0.5 parts of azobisisobutyronitrile, 1 to 5 parts of 2-hydroxypropyl acrylate, 1 to 5 parts of 2-hydroxyethyl methacrylate and 40 to 60 parts of ethyl acetate. The pressure-sensitive adhesive prepared by the present invention can achieve long-term skin adhesion with a low glue coating amount, and has good liquid absorption capacity, high air permeability, low acid value, and little skin irritation.

Description

Technical Field

[0001] The invention belongs to the technical field of medical pressure-sensitive adhesives, and in particular relates to a low-allergenic pressure-sensitive adhesive for medical dressings and a preparation method thereof. Background Art

[0002] The skin is the largest organ in the human body and plays an important role as a barrier between the body and the outside world. It protects the body from physical, mechanical, chemical and pathogenic microorganisms; prevents the loss of water, electrolytes and various nutrients in the body; perceives various sensations, causes corresponding nerve reflexes, and keeps people away from harmful stimuli; the stratum corneum, hair follicles, sebaceous glands and sweat ducts in it have absorption functions and can also secrete sweat, sebum, etc.; the skin is also an important part of the body temperature regulation system; at the same time, it is also an immune and psychological organ.

[0003] The main reasons for allergies when medical dressings come into contact with intact skin are:

[0004] 1. Medical dressings (such as medical tapes) have poor air permeability, and the evaporation of water from skin pores is blocked, which reduces the air permeability of the dressings;

[0005] 2. The dressing does not absorb liquid very well, so the water remains on the surface of the skin;

[0006] 3. The acid value of pressure-sensitive adhesive is high and it is irritating to the skin.

[0007] As the requirements for the performance of pressure-sensitive adhesives for medical dressings are getting higher and higher, medical pressure-sensitive adhesives must not only meet the requirements of adhesive properties, but also meet the requirements of biological properties and moisture permeability. For example, pressure-sensitive adhesives attached to the skin must be non-irritating and non-toxic to the skin. Therefore, it is urgent to develop a hypoallergenic pressure-sensitive adhesive for medical dressings that has strong skin-friendliness, high efficiency, breathability, and hypoallergenicity. Summary of the invention

[0008] Purpose of the invention: The purpose of the present invention is to provide a low-allergenic pressure-sensitive adhesive for medical dressings and a preparation method thereof in view of the deficiencies of the prior art. The pressure-sensitive adhesive prepared by the present invention can achieve long-term skin adhesion with a low coating amount, and has good liquid absorption capacity, high air permeability, low acid value, and little skin irritation.

[0009] Technical solution: The purpose of the present invention is achieved through the following technical solution:

[0010] The present invention provides a low-allergenic pressure-sensitive adhesive for medical dressings, wherein the pressure-sensitive adhesive is mainly prepared from the following raw materials in parts by weight:

[0011] 1-10 parts of acrylic copolymer, 5-30 parts of ethyl acrylate, 5-30 parts of butyl acrylate, 0.1-0.5 parts of azobisisobutyronitrile, 1-5 parts of 2-hydroxypropyl acrylate, 1-5 parts of 2-hydroxyethyl methacrylate and 40-60 parts of ethyl acetate.

[0012] The invention adopts acrylic copolymer to prepare a pressure-sensitive adhesive for medical dressings. The copolymer can increase skin comfort, reduce skin irritation and reduce allergies.

[0013] The copolymer is prepared from the following raw materials in parts by weight:

[0014] 1-10 parts of methacryloxypropyltriethoxysilane, 1-20 parts of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 5-10 parts of methacrylic acid, 5-20 parts of butyl acrylate, 40-60 parts of ethyl acetate, 0.05-0.1 parts of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 0.05-0.1 parts of cuprous chloride, and 0.05-0.5 parts of 1,2-bis(bromoisobutyryloxy)ethane.

[0015] Preferably, the 1,2-bis(bromoisobutyryloxy)ethane is prepared by stirring α-bromoisobutyryl bromide and ethylene glycol at 30-40° C. for 5 hours.

[0016] Furthermore, the weight ratio of α-bromoisobutyryl bromide to ethylene glycol is (50-60):(40-50).

[0017] The present invention also provides a method for preparing the hypoallergenic pressure-sensitive adhesive for medical dressings, comprising the following steps:

[0018] (1) Under nitrogen, methacryloxypropyltriethoxysilane, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, methacrylic acid, butyl acrylate, ethyl acetate, 1,1,4,7,10,10-hexamethyltriethylenetetramine, cuprous chloride, and 1,2-bis(bromoisobutyryloxy)ethane were reacted at 60° C. for 4 hours to obtain a copolymer;

[0019] The weight ratio of the methacryloxypropyltriethoxysilane, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, methacrylic acid, butyl acrylate, ethyl acetate, 1,1,4,7,10,10-hexamethyltriethylenetetramine, cuprous chloride, and 1,2-bis(bromoisobutyryloxy)ethane is (1-10):(1-20):(5-10):(5-20):(40-60):(0.05-0.1):(0.05-0.1):(0.05-0.5);

[0020] (2) reacting acrylic acid copolymer, ethyl acrylate, azobisisobutyronitrile, butyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and ethyl acetate at 60-80° C. for 3-4 hours to obtain a pressure-sensitive adhesive;

[0021] The weight ratio of the copolymer, ethyl acrylate, azobisisobutyronitrile, butyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and ethyl acetate is (1-10):(5-30):(0.1-0.5):(5-30):(1-5):(1-5):(40-60).

[0022] The present invention also provides application of the hypoallergenic pressure-sensitive adhesive for medical dressings in the preparation of medical supplies.

[0023] Preferably, the medical product is a medical tape.

[0024] The medical adhesive tape provided by the invention is prepared by coating the pressure-sensitive adhesive on a PET release film, drying at 100° C. for 2 minutes, and laminating the film on a non-woven fabric at a pressure of 5 kg.

[0025] Beneficial effects:

[0026] The pressure-sensitive adhesive provided by the present invention can achieve long-term skin adhesion with a low glue coating amount; has good liquid absorption capacity; high air permeability; low acid value, and little skin irritation, meets the product requirements of medical tapes, and can be used in medical tapes to reduce the glue coating weight and increase the air permeability, thereby effectively reducing skin allergy. DETAILED DESCRIPTION

[0027] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0028] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0029] The experimental methods in the following examples are conventional methods unless otherwise specified. The experimental materials used in the following examples are commercially available products unless otherwise specified. Example 1

[0030] The hypoallergenic pressure-sensitive adhesive for medical dressing of this embodiment is prepared by a method comprising the following steps:

[0031] (1) Synthesis of initiator 1,2-bis(bromoisobutyryloxy)ethane:

[0032] Take 2 g of α-bromoisobutyryl bromide, pour it dropwise into a 25 ml three-necked flask filled with 1.5 g of ethylene glycol (5 ml), stir at room temperature for 5 h, and then purify it through a chromatography column using n-hexane as the eluent to obtain the final product.

[0033] (2) Preparation of low-sensitivity pressure-sensitive adhesive:

[0034] Take 5 grams of methacryloxypropyltriethoxysilane, 5 grams of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 10 grams of methacrylic acid, 20 grams of butyl acrylate, 59.68 grams of ethyl acetate, 0.07 grams of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 0.05 grams of cuprous chloride, and 0.2 grams of 1,2-bis(bromoisobutyryloxy)ethane, and react at 60°C for 4 hours under nitrogen to obtain a copolymer.

[0035] Weigh 5 g of copolymer, 20 g of ethyl acrylate, 0.3 g of azobisisobutyronitrile, 20 g of butyl acrylate, 5 g of 2-hydroxypropyl acrylate, 5 g of 2-hydroxyethyl methacrylate, and 44.7 g of ethyl acetate and react at 75° C. for 4 h to obtain a pressure-sensitive adhesive. Example 2

[0036] The hypoallergenic pressure-sensitive adhesive for medical dressing of this embodiment is prepared by a method comprising the following steps:

[0037] (1) Synthesis of initiator 1,2-bis(bromoisobutyryloxy)ethane:

[0038] Take 2 g of α-bromoisobutyryl bromide, pour it dropwise into a 25 ml three-necked flask filled with 1.5 g of ethylene glycol (5 ml), stir at room temperature for 5 h, and then purify it through a chromatography column using n-hexane as the eluent to obtain the final product.

[0039] (2) Preparation of low-sensitivity pressure-sensitive adhesive:

[0040] Take 3 grams of methacryloxypropyltriethoxysilane, 4 grams of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 10 grams of methacrylic acid, 23 grams of butyl acrylate, 59.68 grams of ethyl acetate, 0.07 grams of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 0.05 grams of cuprous chloride, and 0.2 grams of 1,2-bis(bromoisobutyryloxy)ethane, and react at 60°C for 4 hours under nitrogen to obtain a copolymer.

[0041] 4 g of copolymer, 20 g of ethyl acrylate, 0.4 g of azobisisobutyronitrile, 20 g of butyl acrylate, 4 g of 2-hydroxypropyl acrylate, 4 g of 2-hydroxyethyl methacrylate, and 47.6 g of ethyl acetate were reacted at 75° C. for 4 h to obtain a pressure-sensitive adhesive. Example 3

[0042] The hypoallergenic pressure-sensitive adhesive for medical dressing of this embodiment is prepared by a method comprising the following steps:

[0043] (1) Synthesis of initiator 1,2-bis(bromoisobutyryloxy)ethane:

[0044] Take 2 g of α-bromoisobutyryl bromide, pour it dropwise into a 25 ml three-necked flask filled with 1.5 g of ethylene glycol (5 ml), stir at room temperature for 5 h, and then purify it through a chromatography column using n-hexane as the eluent to obtain the final product.

[0045] (2) Preparation of low-sensitivity pressure-sensitive adhesive:

[0046] Take 3 grams of methacryloxypropyltriethoxysilane, 3 grams of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 8 grams of methacrylic acid, 26 grams of butyl acrylate, 59.65 grams of ethyl acetate, 0.05 grams of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 0.05 grams of cuprous chloride, and 0.25 grams of 1,2-bis(bromoisobutyryloxy)ethane, and react at 60°C for 4 hours under nitrogen to obtain a copolymer.

[0047] 7 g of copolymer, 20 g of ethyl acrylate, 0.4 g of azobisisobutyronitrile, 20 g of butyl acrylate, 3 g of 2-hydroxypropyl acrylate, 5 g of 2-hydroxyethyl methacrylate, and 44.6 g of ethyl acetate were reacted at 75° C. for 4 h to obtain a pressure-sensitive adhesive. Example 4

[0048] The hypoallergenic pressure-sensitive adhesive for medical dressing of this embodiment is prepared by a method comprising the following steps:

[0049] (1) Synthesis of initiator 1,2-bis(bromoisobutyryloxy)ethane:

[0050] Take 2 g of α-bromoisobutyryl bromide, pour it dropwise into a 25 ml three-necked flask filled with 1.5 g of ethylene glycol (5 ml), stir at room temperature for 5 h, and then purify it through a chromatography column using n-hexane as the eluent to obtain the final product.

[0051] (2) Preparation of low-sensitivity pressure-sensitive adhesive:

[0052] Take 2 grams of methacryloxypropyltriethoxysilane, 8 grams of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 9 grams of methacrylic acid, 33 grams of butyl acrylate, 47.70 grams of ethyl acetate, 0.05 grams of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 0.05 grams of cuprous chloride, and 0.2 grams of 1,2-bis(bromoisobutyryloxy)ethane, and react at 60°C for 4 hours under nitrogen to obtain a copolymer.

[0053] 2 g of copolymer, 15 g of ethyl acrylate, 0.3 g of azobisisobutyronitrile, 25 g of butyl acrylate, 3 g of 2-hydroxypropyl acrylate, 4 g of 2-hydroxyethyl methacrylate, and 50.7 g of ethyl acetate were reacted at 75° C. for 4 h to obtain a pressure-sensitive adhesive.

[0054] Example 5 Skin patch test

[0055] Preparation of medical tape: The pressure-sensitive adhesive prepared in Examples 1-4 and the comparative example was coated on a PET release film at an adhesive amount of 20 g / m2, dried at 100°C for 2 minutes, and laminated on a non-woven fabric at a pressure of 5 kg.

[0056] Peel strength test: YY / T 0148-2006 "General requirements for medical tapes" Appendix B

[0057] Width: 25mm

[0058] Speed: 300mm / min

[0059] Water vapor permeability (g / (m 2 ·24h)) : YY / T 0148-2006 "General Requirements for Medical Tapes" Appendix C

[0060] Drying oven temperature: 37°C

[0061] Opening area: 80mm×10mm

[0062] Equilibration time: 18h

[0063] The performance of the pressure-sensitive adhesive prepared in Examples 1-4 was evaluated by testing the performance of the prepared medical tapes. The results are shown in Table 1:

[0064] Table 1 Skin-fitting test results

[0065]

[0066] As can be seen from Table 1, the medical tape made of the hypoallergenic pressure-sensitive adhesive prepared by the present invention has a coating weight of about 20 grams, which can achieve good peel strength and long-term skin-adhering effect without allergic reactions. The coating weight of the traditional tape is about 40 grams.

[0067] It can also be seen from Table 1 that the medical tape made of the low-allergenic pressure-sensitive adhesive of the present invention did not cause stinging, redness or swelling after being applied to the skin for 24 hours, which indicates that the pressure-sensitive adhesive prepared by the present invention has good liquid absorption capacity and no moisture is accumulated on the skin surface.

[0068] The acid value is the ratio of the acrylic acid content to the methacrylic acid content. As can be seen from the examples of the present invention, the acid value of the present invention is very low and has little irritation to the skin.

[0069] Example 6 In vitro cytotoxicity test

[0070] The safety of the low-sensitivity pressure-sensitive adhesive of the present invention was evaluated by testing the biological response of the medical tape prepared in Example 5 and the physiotherapy muscle patch prepared with ordinary pressure-sensitive adhesive to L-929 cells. Reference standard: Biological evaluation of medical devices Part 5: In vitro cytotoxicity test GB / T 16886.5-2017.

[0071] Physiotherapy muscle patch made of ordinary pressure-sensitive adhesive: 3H2204-924, manufactured by 3H2204-924 Medical Supplies Co., Ltd.

[0072] Negative control: high-density polyethylene, purchased from Jiangsu Haiao Sihui Biological, batch number M02F017

[0073] Positive control: ZDEC, purchased from Tokyo Chemical Industry Co., Ltd., batch number DUDQG-JF

[0074] Blank control: MEM medium containing 10% fetal bovine serum

[0075] L-929 cells: from the American Type Culture Collection CCL1 (NCTC clone 929)

[0076] The test sample extract was cultured with vigorously growing L-929 cells (37°C, 5% CO 2 ) After 24 hours, the cell morphology was observed and the results were detected by MTT method. The detection results are shown in Table 2.

[0077] Table 2 Test results

[0078]

[0079] The results showed that the survival rate of 100% medical tape extract was 91.1%, and the control group results showed that the test results were effective. This indicates that the extract of the medical tape of the present invention has no potential toxic effect on L-929 cells. At the same time, the survival rate of 100% sample extract of the physiotherapy muscle patch prepared by ordinary pressure-sensitive adhesive was 77.2%. This shows that the safety of the low-sensitivity pressure-sensitive adhesive of the present invention is better than that of ordinary pressure-sensitive adhesive.

[0080] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes may be made to it in form and detail without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. A hypoallergenic pressure-sensitive adhesive for medical dressings, characterized in that: The pressure-sensitive adhesive is mainly prepared from the following raw materials in parts by weight: 1-10 parts of acrylic acid copolymer, 5-30 parts of ethyl acrylate, 5-30 parts of butyl acrylate, 0.1-0.5 parts of azobisisobutyronitrile, 1-5 parts of 2-hydroxypropyl acrylate, 1-5 parts of 2-hydroxyethyl methacrylate and 40-60 parts of ethyl acetate; The acrylic acid copolymer is prepared from the following raw materials in parts by weight: 1-10 parts of methacryloxypropyltriethoxysilane, 1-20 parts of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 5-10 parts of methacrylic acid, 5-20 parts of butyl acrylate, 40-60 parts of ethyl acetate, 0.05-0.1 parts of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 0.05-0.1 parts of cuprous chloride, and 0.05-0.5 parts of 1,2-bis(bromoisobutyryloxy)ethane.

2. The hypoallergenic pressure-sensitive adhesive for medical dressing according to claim 1, characterized in that: The 1,2-bis(bromoisobutyryloxy)ethane is prepared by stirring α-bromoisobutyryl bromide and ethylene glycol at 30-40° C. for 5 hours.

3. The hypoallergenic pressure-sensitive adhesive for medical dressing according to claim 2, characterized in that: The weight ratio of the α-bromoisobutyryl bromide to ethylene glycol is (50-60):(40-50).

4. The method for preparing the hypoallergenic pressure-sensitive adhesive for medical dressing according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) Under nitrogen, methacryloxypropyltriethoxysilane, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, methacrylic acid, butyl acrylate, ethyl acetate, 1,1,4,7,10,10-hexamethyltriethylenetetramine, cuprous chloride, and 1,2-bis(bromoisobutyryloxy)ethane were reacted at 60° C. for 4 hours to obtain a copolymer; The weight ratio of the methacryloxypropyltriethoxysilane, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, methacrylic acid, butyl acrylate, ethyl acetate, 1,1,4,7,10,10-hexamethyltriethylenetetramine, cuprous chloride, and 1,2-bis(bromoisobutyryloxy)ethane is (1-10):(1-20):(5-10):(5-20):(40-60):(0.05-0.1):(0.05-0.1):(0.05-0.5); (2) reacting acrylic acid copolymer, ethyl acrylate, azobisisobutyronitrile, butyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and ethyl acetate at 60-80° C. for 3-4 hours to obtain a pressure-sensitive adhesive; The weight ratio of the copolymer, ethyl acrylate, azobisisobutyronitrile, butyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and ethyl acetate is (1-10):(5-30):(0.1-0.5):(5-30):(1-5):(1-5):(40-60).

5. Use of the low-allergenic pressure-sensitive adhesive for medical dressings according to any one of claims 1 to 3 in the preparation of medical supplies.

6. The use according to claim 5, characterized in that: The medical product is a medical tape.

7. A medical tape, characterized in that: The pressure-sensitive adhesive according to any one of claims 1 to 3 is coated on a PET release film, dried at 100° C. for 2 minutes, and laminated on a non-woven fabric under a pressure of 5 kg to obtain the product.

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