Hot melt adhesive, preparation method thereof and application of hot melt adhesive in medical protection products

Abstract

The invention discloses a hot melt adhesive, a preparation method thereof and an application of the hot melt adhesive in a medical protection product. The hot melt adhesive comprises the following components in percentage by mass: 10-25% of a thermoplastic polymer; 10%-40% of maleic anhydride grafted modified rosin resin; 20%-50% of tackifying resin; 10%-30% of naphthenic oil; and 0.1%-1% of an antioxidant. The preparation method of the hot melt adhesive comprises the following steps: mixing the thermoplastic polymer, the maleic anhydride grafted modified rosin resin, the tackifying resin, the naphthenic oil and the antioxidant, heating and stirring until the materials are completely molten, and vacuumizing to remove bubbles. The hot melt adhesive has the advantages of being high in bonding strength, good in flexibility, excellent in waterproof performance, good in anti-seepage effect, suitable for high-humidity and high-temperature environments, safe, environmentally friendly and the like and is suitable for medical protection products, and the preparation method of the hot melt adhesive is simple, convenient, efficient, low in production cost and suitable for large-scale industrial production and application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesives, in particular to a hot melt adhesive, a preparation method thereof and application thereof to medical protective products. BACKGROUND

[0002] With the occasional occurrence of public health events (such as plague, avian influenza, monkeypox, etc.) in countries around the world, the demand for medical protective products (such as protective masks, protective glasses, protective clothing, surgical drapes, etc.) has increased dramatically, and medical personnel have increasingly strict requirements for the performance of medical protective products, such as protection, comfort and air permeability. Medical protective products often need to use adhesives for firm adhesion of protective layers to ensure the overall protection effect of medical protective products. However, traditional solvent-based adhesives cannot meet the requirements of medical protective products in terms of environmental protection and health due to the high content of volatile organic compounds (VOC), and their application has been greatly limited.

[0003] Hot melt adhesive is a kind of adhesive that can be melted into liquid state after heating and can realize rapid bonding (physical combination of materials, not dependent on chemical reaction), which usually has excellent properties such as high bonding strength, no toxic and harmful solvents, no VOC emissions, etc., and has become an ideal choice in the field of medical protective products. However, although the existing hot melt adhesive can provide basic bonding function, its wet bonding performance and hydrostatic pressure resistance performance still have obvious deficiencies (cannot effectively resist the invasion of external liquid, which will seriously affect the overall protection effect of medical protective products), and cannot fully meet the performance requirements of medical protective products in special environments (such as high humidity and high temperature environments).

[0004] Therefore, it is of great significance to develop a hot melt adhesive with high bonding strength, excellent waterproof performance, good water permeation resistance and suitable for use in high humidity and high temperature environments. SUMMARY

[0005] The purpose of the present application is to provide a hot melt adhesive, a preparation method thereof and application thereof to medical protective products.

[0006] The technical solution adopted by the present application is as follows: A hot melt adhesive comprising the following components by mass percentage: Thermoplastic polymer: 10% to 25%; Maleic anhydride grafted modified rosin resin: 10% to 40%; Tackifying resin: 20% to 50%; Naphthenic oil: 10% to 30%; Antioxidant: 0.1% to 1%.

[0007] Preferably, the thermoplastic polymer is at least one of styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer (MAH-g-SEBS), ethylene-vinyl acetate copolymer (EVA).

[0008] Further preferably, the thermoplastic polymer is compounded from styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer (SIS) at a mass ratio of 1:0.8-1.2. Compounding SBS and SIS at a reasonable ratio can significantly improve the bonding strength and flexibility of the hot melt adhesive, enabling it to quickly adhere to the surface of the substrate and form a stable bonding layer, thereby effectively improving the instant protection effect of the medical protective product.

[0009] Preferably, the maleic anhydride grafted rosin resin is made by a preparation method comprising the following steps: a) mixing rosin resin, epoxide compound and nucleophile to perform an epoxide ring-opening reaction to obtain a hydroxyl-containing rosin-epoxide intermediate; b) mixing the hydroxyl-containing rosin-epoxide intermediate and maleic anhydride to perform an esterification reaction to obtain a maleic anhydride grafted rosin resin.

[0010] Preferably, the molar ratio of the rosin resin, epoxide compound, and maleic anhydride is 1:0.4-0.6:0.5-1.0.

[0011] Preferably, the molar ratio of the rosin resin and nucleophile is 1:0.01-0.02.

[0012] Preferably, in step a), the epoxide compound is at least one of bisphenol A type epoxy resin, phenolic epoxy resin, and ethylene glycol diglycidyl ether.

[0013] Preferably, in step a), the nucleophile is at least one of tetrabutylammonium bromide, triphenylphosphine, tetramethyl ethylenediamine, and triethylamine.

[0014] Preferably, in step a), the epoxide ring-opening reaction is performed at a temperature of 105-120°C for 1-2.5h.

[0015] Preferably, in step a), the epoxide ring-opening reaction is performed in a protective atmosphere.

[0016] Further preferably, in step a), the epoxide ring-opening reaction is performed in a nitrogen atmosphere.

[0017] Preferably, the esterification reaction in step b) is carried out at a temperature of 105-120°C, and the reaction time is 1-2.5h.

[0018] Preferably, the esterification reaction in step b) is carried out in a protective atmosphere.

[0019] Further preferably, the esterification reaction in step b) is carried out in a nitrogen atmosphere.

[0020] Preferably, the tackifying resin is at least one of petroleum resin, terpene resin, and rosin resin.

[0021] Preferably, the antioxidant is at least one of hindered phenol antioxidant, phosphite antioxidant, and thioester antioxidant.

[0022] A preparation method of the hot melt adhesive as described above comprises the following steps: mixing a thermoplastic polymer, a maleic anhydride grafted modified rosin resin, a tackifying resin, a naphthenic oil, and an antioxidant, heating and stirring until the materials are completely melted, and then vacuuming to remove bubbles to obtain the hot melt adhesive.

[0023] Preferably, the heating and stirring is carried out at a temperature of 160-180°C.

[0024] The hot melt adhesive as described above is applied in the preparation of medical protective products.

[0025] Preferably, the medical protective product is one of protective masks, protective glasses, protective clothing, and surgical drapes.

[0026] The hot melt adhesive of the present application has the advantages of high bonding strength, good flexibility, excellent waterproof performance, good water permeation resistance, suitability for use in high-humidity and high-temperature environments, safety and environmental protection, and the like, and is suitable for use in medical protective products. The preparation method is simple and efficient, the production cost is low, and the hot melt adhesive is suitable for large-scale industrial production and application.

[0027] Specifically: 1) The hot melt adhesive of the present application contains maleic anhydride grafted modified rosin resin, which can significantly improve the wet bonding performance and hydrostatic pressure resistance of the hot melt adhesive. 2) The hot melt adhesive of the present application contains naphthenic oil, which can improve the softness and ductility of the hot melt adhesive, ensure the comfort of the medical protective product during use, and reduce the possibility of skin discomfort or allergy. 3) The hot melt adhesive of the present invention has the advantages of high bonding strength, good flexibility, excellent waterproof performance, good water resistance, suitable for high humidity and high temperature environments, and safety and environmental protection. It can maintain a long-lasting bonding effect in high humidity and high temperature environments and can ensure that the hot melt adhesive still has reliable sealing performance under harsh use conditions. It is suitable for medical protective products such as protective masks, protective glasses, protective clothing, and surgical drapes. 4) The preparation method of the hot melt adhesive of the present invention is simple and efficient, the raw materials are readily available, and the production cost is low, making it suitable for large-scale industrial production and application. Attached Figure Description

[0028] Figure 1 The image shows the infrared spectrum of the rosin resin and the maleic anhydride grafted modified rosin resin in Example 1. Detailed Implementation

[0029] The present invention will be further explained and described below with reference to specific embodiments.

[0030] Example 1: A maleic anhydride-grafted modified rosin resin is prepared by the following method: a) Under nitrogen protection, 0.2 mol of rosin resin (Guangdong Kemao Forestry Chemical Co., Ltd.) and 0.1 mol of bisphenol A epoxy resin were mixed, stirred and heated to 115°C to melt the material, and then 2.9 mmol of triphenylphosphine was added. The mixture was then stirred at 115°C for 2 hours to obtain a hydroxyl-containing rosin-epoxy intermediate. b) Under nitrogen protection, 0.1 mol of maleic anhydride was added to the hydroxyl-containing rosin-epoxy intermediate, and then stirred at 115°C for 2 h to obtain maleic anhydride grafted modified rosin resin.

[0031] Performance testing: The infrared spectra of rosin resin and maleic anhydride grafted modified rosin resin in this embodiment are as follows: Figure 1 As shown.

[0032] Depend on Figure 1 It can be seen that: maleic anhydride grafted modified rosin resin at 1780cm -1 The presence of a characteristic absorption peak for the carbonyl stretching vibration of maleic anhydride indicates the successful synthesis of maleic anhydride-grafted modified rosin resin.

[0033] A hot melt adhesive comprising the following components by weight percentage: SIS (Model LH-1516, Zibo Luhua Hongjin New Material Group Co., Ltd.): 10%; SBS (model Globalprene 3546, Huizhou Li Changrong Rubber Co., Ltd.): 10%; Maleic anhydride grafted modified rosin resin (prepared in this example): 30%; Hydrogenated petroleum resin (model HD1100, Zibo Luohua Hongjin New Material Group Co., Ltd.): 15%; Rosin resin (model SYLVALTE RE100L, KRATON): 13.5%; Naphthenic oil (model KN4010, PetroChina Karamay Petrochemical Co., Ltd.): 21%; Antioxidant (model Rianox 412S, Tianjin Lianlong New Material Co., Ltd.): 0.5%.

[0034] The preparation method of the hot melt adhesive is as follows: SIS, SBS, maleic anhydride grafted modified rosin resin, hydrogenated petroleum resin, rosin resin, naphthenic oil and antioxidant are mixed, and then stirred and heated to 170℃ to melt the materials. Then continuously stir and vacuum to a vacuum degree of-0.8MPa or less, and vacuum to no bubbles to obtain the hot melt adhesive.

[0035] Example 2: A maleic anhydride grafted modified rosin resin, the preparation method of which is as follows: a) Under nitrogen protection, 0.2mol of rosin resin (Guangdong Kemao Linchan Chemical Co., Ltd.) and 0.1mol of bisphenol A type epoxy resin are mixed, and then stirred and heated to 115℃ to melt the materials. Then 2.9mmol of triphenylphosphine is added, and then constant temperature stirring at 115℃ for 2h to obtain a rosin-epoxy intermediate containing hydroxyl groups; b) Under nitrogen protection, 0.2mol of maleic anhydride is added to the rosin-epoxy intermediate containing hydroxyl groups, and then constant temperature stirring at 115℃ for 2h to obtain the maleic anhydride grafted modified rosin resin.

[0036] Tested (infrared test), the infrared spectrum of the maleic anhydride grafted modified rosin resin in this example is similar to that of the maleic anhydride grafted modified rosin resin in Example 1, and the carbonyl stretching vibration characteristic absorption peak of maleic anhydride also appears at 1780cm -1 , indicating that the maleic anhydride grafted modified rosin resin is successfully synthesized.

[0037] A hot melt adhesive, except that the maleic anhydride grafted modified rosin resin prepared in this example is used, and the rest is exactly the same as the hot melt adhesive of Example 1 (the preparation process of the hot melt adhesive is also exactly the same).

[0038] Example 3: A hot melt adhesive, except that the weight of "rosin resin (model SYLVALTE RE100L, KRATON) " and the like is replaced with "hydrogenated petroleum resin (model HD1100, Zibo Luohua Hongjin New Material Group Co., Ltd.)", and the rest is exactly the same as the hot melt adhesive of Example 2 (the preparation process of the hot melt adhesive is also exactly the same).

[0039] Example 4: A hot melt adhesive consisting of the following mass percentage of components: SIS (model LH-1516, Zibo Luohua Hongjin New Material Group Co., Ltd.): 10%; SBS (model Globalprene3546, Huizhou Lichangrong Rubber Co., Ltd.): 10%; Maleic anhydride grafted modified rosin resin (same as Example 2): 10%; Hydrogenated petroleum resin (model HD1100, Zibo Luohua Hongjin New Material Group Co., Ltd.): 15%; Rosin resin (model SYLVALTE RE100L, KRATON): 33.5%; Naphthenic oil (model KN4010, PetroChina Karamay Petrochemical Co., Ltd.): 21%; Antioxidant (model Rianox 412S, Tianjin Lianlon New Material Co., Ltd.): 0.5%.

[0040] The preparation process of the hot melt adhesive of this example is the same as Example 1.

[0041] Example 5: A hot melt adhesive, except that the weight of "rosin resin (model SYLVALTE RE100L, KRATON) " and the like is replaced with "non-hydrogenated C5 petroleum resin (model SUNIONOREZ-M90, Guangdong Luzhonghua New Material Co., Ltd.)", and the rest is exactly the same as the hot melt adhesive of Example 2 (the preparation process of the hot melt adhesive is also exactly the same).

[0042] Comparative Example 1: A hot melt adhesive (without maleic anhydride grafted modified rosin resin and rosin resin), consisting of the following mass percentage of components: SIS (model LH-1516, Zibo Luohua Hongjin New Material Group Co., Ltd.): 10%; SBS (model Globalprene3546, Huizhou Lichangrong Rubber Co., Ltd.): 10%; Hydrogenated petroleum resin (model HD1100, Zibo Luohua Hongjin New Material Group Co., Ltd.): 58.5%; Naphthenic oil (model KN4010, Karamay Petrochemical Co., Ltd.): 21%; Antioxidant (model Rianox 412S, Tianjin Li'anlong New Material Co., Ltd.): 0.5%.

[0043] The preparation method of the hot melt adhesive is as follows: SIS, SBS, hydrogenated petroleum resin, naphthenic oil and antioxidant are mixed, and then heated to 170℃ for melting, and then continuously stirred and vacuumed to a vacuum degree of-0.8 MPa or less, until no bubbles are generated, to obtain the hot melt adhesive.

[0044] Comparative Example 2: A hot melt adhesive (containing no maleic anhydride grafted modified rosin resin) is composed of the following components in mass percentage: SIS (model LH-1516, Zibo Luohua Hongjin New Material Group Co., Ltd.): 10%; SBS (model Globalprene3546, Huizhou Lichangrong Rubber Co., Ltd.): 10%; Hydrogenated petroleum resin (model HD1100, Zibo Luohua Hongjin New Material Group Co., Ltd.): 45%; Rosin resin (model SYLVALTE RE100L, Kraton): 13.5%; Naphthenic oil (model KN4010, Karamay Petrochemical Co., Ltd.): 21%; Antioxidant (model Rianox 412S, Tianjin Li'anlong New Material Co., Ltd.): 0.5%.

[0045] The preparation method of the hot melt adhesive is as follows: SIS, SBS, hydrogenated petroleum resin, rosin resin, naphthenic oil and antioxidant are mixed, and then heated to 170℃ for melting, and then continuously stirred and vacuumed to a vacuum degree of-0.8 MPa or less, until no bubbles are generated, to obtain the hot melt adhesive.

[0046] Comparative Example 3: A hot melt adhesive (containing no maleic anhydride grafted modified rosin resin and hydrogenated petroleum resin) is completely the same as the hot melt adhesive of Comparative Example 1 (and the preparation process is also completely the same) except that the “hydrogenated petroleum resin (model HD1100, Zibo Luohua Hongjin New Material Group Co., Ltd.)” is replaced by “rosin resin (model SYLVALTE RE100L, Kraton)” in weight.

[0047] Comparative Example 4: A hot melt adhesive (not containing maleic anhydride grafted modified rosin resin and SIS) is completely same as the hot melt adhesive of Comparative Example 1 (the preparation process of the hot melt adhesive is also completely same) except that "SIS (model LH-1516, Zibo Luohua Hongjin New Material Group Co., Ltd.)" is replaced by "SBS (model Globalprene 3546, Huizhou Lichangrong Rubber Co., Ltd.)" in the same weight.

[0048] Performance test: The peel strength and hydrohead performance test results of the hot melt adhesives of Examples 1-5 and Comparative Examples 1-4 are shown in the following table: Table 1 Peel strength and hydrohead performance test results of hot melt adhesives

[0049] Note: Peel strength: the hot melt adhesive is coated on the substrate by a coater for bonding and compounding, the coating method is doctor blade coating, the coating amount is 4 gsm, the substrate is blue hydrophilic non-woven fabric and PE film, and then the average value of the peel strength of the compounded material is tested by a tensile tester (the speed of the tensile tester is 300 mm / min, and the sample needs to be soaked in water for 5 min before testing the wet strength performance).

[0050] Hydrohead: the hot melt adhesive is coated on the substrate by a coater for bonding and compounding, the coating method is doctor blade coating, the coating amount is 4 gsm, the substrate is blue hydrophilic non-woven fabric and PE film, and then the hydrohead performance of the compounded material is tested by a hydrohead tester (when testing, the non-woven fabric side faces the water, and the hydrohead pressure increasing speed is 10 cm H2O / min).

[0051] As can be seen from Table 1, the hot melt adhesives of Examples 1-5 for bonding hydrophilic non-woven fabric and PE film can make the compounded material have excellent dry / wet state bonding performance and hydrohead performance (the performance of the hot melt adhesive of Example 2 is the best), and can all meet the reference standard value, while the dry / wet state bonding performance and hydrohead performance of the hot melt adhesives of Comparative Examples 1-4 cannot meet the reference standard value.

[0052] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application should be equivalent replacement methods, and all are included in the protection scope of the present application.

Claims

1. A hot melt adhesive, characterized in that, Comprise the following components by mass percentage: Thermoplastic polymer: 10%~25%; Maleic anhydride grafted modified rosin resin: 10%~40%; Tackifying resin: 20%~50%; Naphthenic oil: 10%~30%; Antioxidant: 0.1%~1%.

2. The hot melt adhesive of claim 1, wherein: The thermoplastic polymer is at least one of styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, maleic anhydride grafted modified styrene-ethylene-butylene-styrene block copolymer, ethylene-vinyl acetate copolymer.

3. The hot melt adhesive of claim 1, wherein: The maleic anhydride grafted modified rosin resin is made by a preparation method comprising the following steps: a) mixing rosin resin, epoxide compound and nucleophile to perform an epoxide ring-opening reaction to obtain a hydroxyl-containing rosin-epoxide intermediate; b) mixing the hydroxyl-containing rosin-epoxide intermediate and maleic anhydride to perform an esterification reaction to obtain the maleic anhydride grafted modified rosin resin.

4. The hot melt adhesive of claim 3, wherein: The molar ratio of the rosin resin, epoxide compound and maleic anhydride is 1:0.4~0.6:0.5~1.

0.

5. Hot-melt adhesive according to claim 3 or 4, characterized in that: The epoxide compound in step a) is at least one of bisphenol A type epoxy resin, phenolic epoxy resin, ethylene glycol diglycidyl ether.

6. Hot-melt adhesive according to claim 3 or 4, characterized in that: The epoxide ring-opening reaction in step a) is performed at a temperature of 105℃~120℃, and the reaction time is 1h~2.5h.

7. The hot melt adhesive of claim 3 or 4, wherein: The esterification reaction in step b) is performed at a temperature of 105℃~120℃, and the reaction time is 1h~2.5h.

8. The hot melt adhesive according to any one of claims 1 to 3, characterized in that: The tackifying resin is at least one of petroleum resin, terpene resin, rosin resin.

9. A method of producing the hot melt adhesive according to any one of claims 1 to 8, characterized by, Comprise the following steps: mixing thermoplastic polymer, maleic anhydride grafted modified rosin resin, tackifying resin, naphthenic oil and antioxidant, then heating and stirring until the material is completely melted, then vacuuming to remove bubbles to obtain hot melt adhesive.

10. Use of the hot melt adhesive according to any one of claims 1~8 in the preparation of medical protective products.

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