Low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster and preparation method thereof

Abstract

The application discloses a low-sensitization hot-melt pressure-sensitive adhesive suitable for Chinese herbal medicine plaster and a preparation method thereof. The low-sensitization hot-melt pressure-sensitive adhesive comprises the following components in parts by weight: 20-40 parts of a main polymer, 10-25 parts of rubber oil, 40-60 parts of resin and 3-5 parts of an additive. The prepared product has good initial adhesion, moderate stiffness, low production cost, high stability, good biocompatibility, low irritation to human skin and low allergy.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hot melt pressure sensitive adhesive, in particular to a low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster and a preparation method thereof. BACKGROUND

[0002] Under the development strategy of "Healthy China", the health industry has ushered in an unprecedented development opportunity. However, the fast-paced social life has led to a large number of people in a sub-healthy state, so people are paying more and more attention to "health preservation"; the medical and health care market demand is broad, the industry has a good future, and the medical and health care industry is also popular among the public and consumer groups.

[0003] Health preservation by plastering plaster is one of the ways adopted by the general public, and the part of the plaster cold compress patch that really has a therapeutic effect on the human body is the gel layer. The general gel layer removes heat through the water content in the high molecular gel and the cooling ingredients, which can achieve local cooling. The drug ingredients combine with the hydrogel, and through hydration, the drug ingredients can quickly penetrate the skin fat layer, penetrate into the subcutaneous tissue, and directly reach the lesion site, acting on the affected area to achieve cold compress pain relief and slow-release drug delivery. In the selection of gel carriers, common high molecular gels, natural rubbers, etc. are used, and the common gel layer carriers in the plaster have problems such as aging, cannot be placed for a long time, cannot be heated, and are prone to leakage. Natural rubber has good performance in terms of adhesion and application, but there are still uncertainties in terms of allergies.

[0004] Patent CN102559111B discloses a styrene-based hot melt pressure sensitive adhesive and a preparation method, which introduces a polar group into the styrene-based thermoplastic elastomer molecule, adds a polarity regulator, changes the lipophilic characteristics of the traditional styrene-based thermoplastic elastomer hot melt pressure sensitive adhesive matrix, and introduces a styrene-butadiene-styrene block copolymer resin to adjust the adhesion performance of the system, to meet the release channel requirements of different drugs. However, it can cause skin irritation and allergic reactions during use. Therefore, it is necessary to prepare a low-sensitization hot melt pressure sensitive adhesive for the human body. SUMMARY

[0005] The present application provides a low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, which comprises the following components by weight: 20-40 parts of main polymer, 10-25 parts of rubber oil, 40-60 parts of resin, and 3-5 parts of auxiliary agent.

[0006] As a preferred technical solution, the main polymer is at least one of polystyrene-polybutadiene-polystyrene block copolymer (SBS), polystyrene-polyisoprene-polystyrene block copolymer (SIS), polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), and hydrogenated polystyrene-polyisoprene-polystyrene block copolymer (SEPS).

[0007] Preferably, the main polymer is a combination of polystyrene-polyisoprene-polystyrene block copolymer (SIS) and polystyrene-polybutadiene-polystyrene block copolymer (SBS).

[0008] Preferably, the weight ratio of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) to the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 2-4:6-8.

[0009] Preferably, the weight ratio of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) to the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 3:7.

[0010] Preferably, the di-block content of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) is 15wt%-18wt%, and the styrene content is 15wt%.

[0011] Preferably, the S / B ratio of the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 30-34:66-70.

[0012] Preferably, the S / B ratio of the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 32:68.

[0013] In the present application, the inventors initially select SBS block copolymer as the main polymer in the system, because it has high styrene content, strong cohesion and large inclusion, and is suitable for the addition of various Chinese herbal medicine additives. However, it is found in the later test and application experiment that the glue with high cohesion generally has high stiffness, and the effect is not good when applied to human skin. Through the research of the inventors, it is accidentally found that when the main polymer is a compound of polystyrene-polyisoprene-polystyrene block copolymer (SIS) and polystyrene-polybutadiene-polystyrene block copolymer (SBS), especially when the weight ratio of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) to the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 2-4:6-8, the change of the content of the double block makes the initial adhesion of the glue increase, has a good first bonding effect and the peeling force also increases accordingly, and the effect that cannot be achieved by SBS is improved, especially when SBS is used as the main polymer, the problem of poor effect when applied to human skin is solved.

[0014] Preferably, the polystyrene-polyisoprene-polystyrene block copolymer (SIS) is YH-1106 purchased from Balin Petroleum Chemical Industry Co., Ltd.; and the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is YH-188 purchased from Balin Petroleum Chemical Industry Co., Ltd.

[0015] As a preferred technical solution, the rubber oil is at least one of naphthenic oil and white mineral oil.

[0016] Preferably, the rubber oil is naphthenic oil, and the pour point of the naphthenic oil is -30℃ to -15℃.

[0017] In the system of the present application, the rubber oil selected is naphthenic oil, which is prepared by several hydrogenation processes, and the oil is pure and basically free of aromatic hydrocarbon components, which is beneficial to improve the biocompatibility of the product prepared in the system of the present application.

[0018] Preferably, the naphthenic oil is Karamay naphthenic oil 4010 purchased from Maoming Runhua Petroleum Chemical Co., Ltd.

[0019] As a preferred technical solution, the resin is at least one of hydrogenated C5 petroleum resin, hydrogenated C9 petroleum resin, dicyclopentadiene resin, and C5C9 copolymer petroleum resin.

[0020] Preferably, the resin is a compound of hydrogenated C5 petroleum resin and hydrogenated C9 petroleum resin.

[0021] Preferably, the softening point of the hydrogenated C5 petroleum resin is 95℃ to 105℃.

[0022] Preferably, the softening point of the hydrogenated C9 petroleum resin is 95-105℃.

[0023] Preferably, the weight ratio of the hydrogenated C5 petroleum resin to the hydrogenated C9 petroleum resin is 8-9:1-2.

[0024] Preferably, the weight ratio of the hydrogenated C5 petroleum resin to the hydrogenated C9 petroleum resin is 8.5:1.5.

[0025] In the system of the application, the inventors find that when the hydrogenated C5 petroleum resin and the hydrogenated C9 petroleum resin are used in combination, the adhesion of the prepared product is increased, especially when the weight ratio of the hydrogenated C5 petroleum resin to the hydrogenated C9 petroleum resin is 8-9:1-2, the compatibility with the mixed main polymer of SIS and SBS in the system is high, and the biocompatibility is good, which is beneficial to reduce the production cost and improve the stability.

[0026] Preferably, the hydrogenated C5 petroleum resin is H5-1001 purchased from Henghe Material Technology Co., Ltd., and the hydrogenated C9 petroleum resin is HA100 purchased from Henghe Material Technology Co., Ltd.

[0027] As a preferred technical solution, the auxiliary agent is at least one of an anti-ultraviolet agent, an anti-yellowing agent, and an antioxidant.

[0028] Preferably, the auxiliary agent is an antioxidant, and the antioxidant is at least one of antioxidant 1010, antioxidant DLTP, and antioxidant 168.

[0029] Preferably, the antioxidant is a combination of antioxidant 1010 and antioxidant DLTP, and the weight ratio of antioxidant 1010 to antioxidant DLTP is 1:0.2-0.3.

[0030] Preferably, the weight ratio of antioxidant 1010 to antioxidant DLTP is 1:0.25.

[0031] Another aspect of the application discloses a preparation method of a low-sensitization hot melt pressure-sensitive adhesive suitable for Chinese herbal plaster, which comprises the following steps: weighing each raw material according to the required weight parts, first pouring rubber oil into a stirring tank and heating to 95-105℃, then adding an equal amount of main polymer for oiling and heating stirring, the temperature is raised to 130-140℃, when the main polymer is stirred to be viscous and filamentous, the remaining main polymer is added for sufficient stirring; after sufficient stirring, the resin and the auxiliary agent are added in equal amounts in 2-4 times and vacuum stirring for 30 min, and finally the adhesive is discharged under pressure to obtain the adhesive.

[0032] Preferably, the method comprises the following steps: weighing each raw material according to the required weight parts, pouring the rubber oil into a stirring tank and heating to 100 DEG C, then adding the same weight part of the main polymer as the rubber oil to heat and stir, the temperature is raised to 135 DEG C, when the main polymer is stirred to viscous silk, the remaining main polymer is added to stir; after stirring, the resin and the additive are added in three times and vacuum stirring for 30 minutes, the amount of resin and additive added each time is one third of the total amount, and finally the rubber is extruded by pressure to obtain the product.

[0033] The order and the amount of each component added in the preparation process are controlled, especially the main polymer is added with the same amount of rubber oil, then the remaining main polymer is added after heating, and finally the resin and the additive are added in batches, so that each component is slowly fused during preparation, the dispersion is good, the uniformity is high, the comprehensive performance of the prepared product is less affected, the product has the characteristics of good adhesion and high biocompatibility, the product has low irritation to human skin and is not easy to cause allergy.

[0034] The application has the following beneficial effects: 1) by selecting specific SIS and SBS copolymer for use, the initial adhesion of the product is improved, and the problem of large stiffness of the product when SBS is used alone is improved; 2) by selecting hydrogenated C5 petroleum resin and a small amount of hydrogenated C9 petroleum resin for use, the production cost is reduced, the stability is improved, and the product has the characteristics of good biocompatibility; 3) by selecting a specific processing method to prepare the product, the fusion and dispersion of each component are good, the uniformity is high, the comprehensive performance of the prepared product is less affected, the product has the characteristics of good adhesion and high biocompatibility, the product has low irritation to human skin and is not easy to cause allergy. DETAILED DESCRIPTION

[0035] Example 1

[0036] The example 1 of the application discloses a low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, which comprises the following components in weight parts: 30 parts of main polymer, 18 parts of rubber oil, 50 parts of resin, and 4 parts of additive.

[0037] The main polymer is a compound of polystyrene-polyisoprene-polystyrene block copolymer (SIS) and polystyrene-polybutadiene-polystyrene block copolymer (SBS).

[0038] The weight ratio of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) to the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 3:7.

[0039] The diblock content of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) is 16.7wt%, and the styrene content is 15wt%.

[0040] The S / B ratio of the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 32:68.

[0041] The polystyrene-polyisoprene-polystyrene block copolymer (SIS) is YH-1106 purchased from Balin Petroleum Chemical Industry Co., Ltd.; the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is YH-188 purchased from Balin Petroleum Chemical Industry Co., Ltd.

[0042] The rubber oil is naphthenic oil, and the pour point of the naphthenic oil is -24℃.

[0043] The naphthenic oil is Karamay naphthenic oil 4010 purchased from Maoming Runhua Petroleum Chemical Co., Ltd.

[0044] The resin is a complex of hydrogenated C5 petroleum resin and hydrogenated C9 petroleum resin.

[0045] The softening point of the hydrogenated C5 petroleum resin is 95-105℃.

[0046] The softening point of the hydrogenated C9 petroleum resin is 95-105℃.

[0047] The weight ratio of the hydrogenated C5 petroleum resin to the hydrogenated C9 petroleum resin is 8.5:1.5.

[0048] The hydrogenated C5 petroleum resin is H5-1001 with a softening point of 100℃, purchased from Henghe Material Technology Co., Ltd.; the hydrogenated C9 petroleum resin is HA100 with a softening point of 100℃, purchased from Henghe Material Technology Co., Ltd.

[0049] The auxiliary agent is an antioxidant, which is a complex of antioxidant 1010 and antioxidant DLTP, and the weight ratio of antioxidant 1010 to antioxidant DLTP is 1:0.25.

[0050] The antioxidant 1010 is purchased from Dongguan Huayun Plastic Raw Material Co., Ltd.; the antioxidant DLTP is purchased from Jiangsu Aofu Biological Technology Co., Ltd.

[0051] The other aspect of the embodiment discloses a preparation method of a low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, comprising the following steps: weighing each raw material according to the required weight parts, first, pouring rubber oil into a stirring tank and heating to 100℃, then adding the same weight part of the main polymer as the rubber oil to heat and stir, the temperature is raised to 135℃, when the main polymer is stirred to be viscous and filamentous, the remaining main polymer is added for sufficient stirring; after sufficient stirring, the resin and the additive are added in three times and vacuum stirring for 30min, the amount of resin and additive added each time is one third of the total amount of each, and finally the adhesive is extruded under pressure to obtain the low-sensitization hot melt pressure sensitive adhesive.

[0052] Embodiment 2

[0053] The embodiment 2 of the present application discloses a low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, comprising the following components in weight parts: 20 parts of main polymer, 10 parts of rubber oil, 40 parts of resin and 3 parts of additive.

[0054] The specific implementation is the same as that in embodiment 1, except that the weight ratio of polystyrene-polyisoprene-polystyrene block copolymer (SIS) to polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 2:8.

[0055] The weight ratio of the hydrogenated C5 petroleum resin to the hydrogenated C9 petroleum resin is 8:2.

[0056] Embodiment 3

[0057] The embodiment 3 of the present application discloses a low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, comprising the following components in weight parts: 40 parts of main polymer, 25 parts of rubber oil, 60 parts of resin and 5 parts of additive.

[0058] The specific implementation is the same as that in embodiment 1, except that the weight ratio of polystyrene-polyisoprene-polystyrene block copolymer (SIS) to polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 4:6.

[0059] The weight ratio of the hydrogenated C5 petroleum resin to the hydrogenated C9 petroleum resin is 9:1.

[0060] Comparative Example 1

[0061] The comparative example 1 of the present application discloses a low-sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, and the specific implementation is the same as that in embodiment 1, except that the polystyrene-polyisoprene-polystyrene block copolymer (SIS) in the main polymer is replaced by an equal amount of polystyrene-polybutadiene-polystyrene block copolymer (SBS).

[0062] Comparative Example 2

[0063] The present application comparative example 2 discloses a low sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, the specific implementation is the same as example 1, the difference is that the weight ratio of polystyrene-polyisoprene-polystyrene block copolymer (SIS) and polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 1:1.

[0064] Comparative example 3

[0065] The present application comparative example 3 discloses a low sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, the specific implementation is the same as example 1, the difference is that the weight ratio of hydrogenated C5 petroleum resin and hydrogenated C9 petroleum resin is 6:4.

[0066] Comparative example 4

[0067] The present application comparative example 4 discloses a low sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, the specific implementation is the same as example 1, the difference is that the resin is a compound of non-hydrogenated C5 petroleum resin and non-hydrogenated C9 petroleum resin.

[0068] Comparative example 5

[0069] The present application comparative example 5 discloses a low sensitization hot melt pressure sensitive adhesive suitable for Chinese herbal plaster, the specific implementation is the same as example 1, the difference is that in the preparation method, the main polymer, resin and auxiliary agent are not added batch by batch, that is, first pour the rubber oil into the stirring tank and heat to 100℃, then add the main polymer for oiling and heating stirring, after stirring sufficiently, add the resin and auxiliary agent and vacuum stirring for 30min, finally press out the glue.

[0070] Performance test

[0071] 1. Cell compatibility test: according to the detection standards GB / T 16886.5-2017, GB / T 16886.10-2017, GB / T 16886.10-2017, the in vitro cytotoxicity test, skin sensitization test and skin irritation test of example and comparative example are carried out respectively;

[0072] 2. Initial adhesion test: the initial adhesion test of example and comparative example is carried out according to the test standard GB4852.

[0073] The test results are shown in table 1.

[0074] Table 1

[0075]

Claims

1. A low-allergenic hot-melt pressure sensitive adhesive suitable for Chinese herbal plasters, characterized in that, By weight parts, including the following components: main polymer is 30 parts, rubber oil is 18 parts, resin is 50 parts, auxiliary 4 parts;The main polymer is a compound of polystyrene-polyisoprene-polystyrene block copolymer (SIS) and polystyrene-polybutadiene-polystyrene block copolymer (SBS); The weight ratio of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) and the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 3:7; The double block content of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) is 16.7wt%, and the styrene content is 15wt%; The S / B ratio of the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is 32:68; The model of the polystyrene-polyisoprene-polystyrene block copolymer (SIS) is YH-1106;The model of the polystyrene-polybutadiene-polystyrene block copolymer (SBS) is YH-188, The rubber oil is naphthenic oil, and the pour point of the naphthenic oil is-24℃. The model of the naphthenic oil is Karamay naphthenic oil 4010, and the resin is a compound of hydrogenated C5 petroleum resin and hydrogenated C9 petroleum resin; The weight ratio of the hydrogenated C5 petroleum resin and the hydrogenated C9 petroleum resin is 8.5:1.5; The model of the hydrogenated C5 petroleum resin is H5-1001, and the softening point is 100℃;The model of the hydrogenated C9 petroleum resin is HA100, and the softening point is 100℃; The auxiliary is an antioxidant, and the antioxidant is a compound of antioxidant 1010 and antioxidant DLTP, and the weight ratio of antioxidant 1010 to antioxidant DLTP is 1:0.

25.

2. A process for the preparation of a low-allergenic hot-melt pressure sensitive adhesive suitable for Chinese herbal plasters as claimed in claim 1, characterized in that, The steps include: weighing each raw material according to the required weight parts, first pouring the rubber oil into the stirring tank and heating to 95-105℃, then adding an equal amount of main polymer for oiling and heating stirring, the temperature is raised to 130-140℃, when the main polymer is stirred to viscous silk, the remaining main polymer is added for sufficient stirring;After stirring sufficiently, the resin and the auxiliary are added in 2-4 equal parts and vacuum stirring for 30min, and finally the rubber is extruded by pressure to obtain the product.

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