A long-lasting antibacterial meltblown nonwoven masterbatch and meltblown nonwoven fabric and preparation method thereof

Abstract

The present invention provides a meltblown nonwoven fabric masterbatch with long-term antibacterial properties, a meltblown nonwoven fabric, and a preparation method thereof, belonging to the technical field of nonwoven fabric preparation. The method comprises the following steps: mixing cordierite, sodium bentonite, and a modified oxide mixture to obtain a mixture; mixing polypropylene with the mixture to obtain a meltblown nonwoven fabric masterbatch with long-term antibacterial properties; and then sequentially subjecting the meltblown nonwoven fabric to heating and melting, extrusion, high-temperature airflow high-speed drawing, and cooling to form a web to obtain a meltblown nonwoven fabric. The meltblown nonwoven fabric obtained by the present invention has excellent antibacterial properties, with an antibacterial rate of more than 99.8% against Staphylococcus aureus, Escherichia coli, and Candida albicans. The meltblown nonwoven fabric obtained by the present invention can maintain a high antibacterial effect after multiple muddy water immersion washing and oil removal washing. The preparation method of the present invention is simple, low-cost, and has good industrial application value.

Description

Technical Field

[0001] The present invention relates to the technical field of non-woven fabric preparation, and in particular to a long-lasting antibacterial melt-blown non-woven fabric masterbatch and a melt-blown non-woven fabric and a preparation method thereof. Background Art

[0002] Nonwoven fabrics, also known as nonwovens, are composed of oriented or random fibers. Antimicrobial nonwovens are widely used in everyday life, particularly in the medical field. Currently, the production of antimicrobial nonwovens primarily involves using known antimicrobial materials as raw materials or performing surface antimicrobial modification on nonwovens.

[0003] From the perspective of R&D difficulty, directly impregnating or coating non-woven fabrics with antibacterial substances is the easiest way to obtain antibacterial non-woven fabrics. For example, Zheng Guiyun et al. in "Research on Herbal Antibacterial Functionalization of Non-woven Fabrics and Its Application" (Zheng Guiyun, Bian Songling, Yang Fanwen et al. Research on Herbal Antibacterial Functionalization of Non-woven Fabrics and Its Application [J]. Guangdong Chemical Industry, 2020, 47(09): 21-24.) used dipping, spraying and dripping methods to add cactus extract to the surface of non-woven fabrics, thereby obtaining non-woven fabrics with antibacterial functions; for example, Zhou Yanan used the dipping coating method to add antibacterial substances chitosan and tea polyphenols to the surface of non-woven fabrics in "Research on the Preparation of Active Packaging Materials by Chitosan / Tea Polyphenols Coated Non-woven Fabrics", and also obtained non-woven fabrics with antibacterial effects. However, the antibacterial effect of non-woven fabrics obtained by this type of technology is usually short-lived, because the antibacterial substances are easy to fall off.

[0004] In addition to direct impregnation or coating of antimicrobial agents, researchers have also studied encapsulating antimicrobial agents and using them to prepare antimicrobial nonwoven fabrics. For example, Lei Min's "Study on Antimicrobial Finishing of Pure Cotton Spunlace Nonwoven Fabrics Based on Microcapsule Technology" uses an inclusion complexation method to prepare microcapsules with β-cyclodextrin as the wall material and forsythia oil as the core material. The microcapsules are then used to finish the nonwoven fabric, ultimately achieving relatively good antibacterial properties. Another example is CN114086323B, which improves antimicrobial properties by using microcapsule electret raw materials. However, due to the high cost of microcapsule preparation, the cost of preparing nonwoven fabrics is also relatively high.

[0005] In addition, researchers have also investigated the preparation of modified masterbatches by mixing antibacterial substances with masterbatch bases to obtain non-woven fabrics with antibacterial properties. For example, CN108864561B blends graphene materials and natural flavonoids to prepare masterbatches, and improves the antibacterial properties of non-woven fabrics through the synergistic effect of nanographene and natural flavonoids in antibacterial properties. However, this method easily causes the antibacterial substances to reduce their antibacterial activity due to changes in the antibacterial environment, and it is necessary to find a combination of antibacterial substances that can produce synergistic effects and a specific combination method. Similarly, CN114685894B also combines nano-zinc oxide and chitosan with antibacterial properties and uses a special mixing method to achieve improved antibacterial performance, while other mixing methods cannot improve antibacterial properties.

[0006] In addition, people have also studied the surface modification of non-woven fabrics to obtain antibacterial properties. For example, Yang Ran et al. in "Surface Functionalization of Polypropylene Non-woven Fabrics and Their Antibacterial Properties" (Yang Ran, Wang Jiabao, Zhang Jing et al. Surface Functionalization of Polypropylene Non-woven Fabrics and Their Antibacterial Properties [J]. Paper and Papermaking, 2020, 39(02): 19-24.) used a surface modification method to construct a polymer brush and introduced vancomycin through azlactone, so that the resulting non-woven fabric has high antibacterial properties. However, this type of technology is limited by the complexity and control difficulty of the surface modification method, and is usually difficult to apply to large-scale production in the industry. In summary, in the existing technology, antibacterial non-woven fabrics can be obtained by different methods, but each method has corresponding disadvantages.

[0007] In general, the direct addition of known antimicrobial agents or indirect doping through methods such as microencapsulation suffers from short antimicrobial duration and high costs. Surface modification methods also suffer from difficult production process control and high costs. Furthermore, organic antimicrobial agents typically exert their antimicrobial effects through close contact with bacterial surfaces or penetration into the interior of bacteria. This makes it difficult to achieve effective and long-lasting antimicrobial effects when added to nonwoven fabrics through microencapsulation or direct doping in masterbatch materials.

[0008] Therefore, it is very important to prepare a non-woven fabric based on inorganic materials with high antibacterial efficiency, long-lasting antibacterial effect and low cost. Summary of the Invention

[0009] The purpose of the present invention is to provide a meltblown nonwoven masterbatch and a meltblown nonwoven fabric with long-lasting antibacterial effect and a preparation method thereof, so as to solve the technical problems in the prior art of short antibacterial time, poor antibacterial effect, difficult production process control and high cost.

[0010] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0011] The present invention provides a long-lasting antibacterial meltblown nonwoven fabric masterbatch, comprising the following raw materials:

[0012] Cordierite, sodium bentonite, modified oxide mixture, and polypropylene;

[0013] The mass ratio of the cordierite, sodium bentonite and modified oxide mixture is 1:1:5-8;

[0014] The mass ratio of the total mass of the cordierite, sodium bentonite and modified oxide mixture to the mass ratio of the polypropylene is 5-8:75-80.

[0015] Furthermore, the preparation method of the modified oxide mixture includes: immersing the oxide mixture in the supernatant of a Bacillus subtilis culture solution and then centrifuging to obtain the modified oxide mixture;

[0016] The oxide mixture consists of nano zirconium oxide, nano calcium oxide and nano zinc oxide in a mass ratio of 2-5:1-3:1-3.

[0017] Furthermore, the immersion treatment temperature is 25-35°C and the time is 1.5-2.5h;

[0018] The centrifugal speed is 400-600 rpm;

[0019] The particle size of the modified oxide mixture is 200-300 nm.

[0020] The present invention provides a method for preparing a long-lasting antibacterial melt-blown non-woven fabric masterbatch, comprising the following steps:

[0021] (1) mixing cordierite, sodium bentonite and a modified oxide mixture to obtain a mixture;

[0022] (2) The polypropylene and the mixture are mixed to obtain a melt-blown non-woven fabric masterbatch with long-lasting antibacterial effect.

[0023] Furthermore, in step (1) and step (2), the mixing speed is independently 400 to 600 rpm.

[0024] The present invention provides a method for preparing a melt-blown non-woven fabric with long-lasting antibacterial properties. The melt-blown non-woven fabric masterbatch is sequentially subjected to heating, melting, extrusion, and air flow drawing to obtain spun fibers; the spun fibers are cooled into a web to obtain the melt-blown non-woven fabric with long-lasting antibacterial properties.

[0025] Furthermore, the heating and melting temperature is 220-250° C., and the time is 0.3-1 h;

[0026] The extrusion temperature is 230-260° C., and the extrusion time is 0.3-1 h.

[0027] Furthermore, the temperature of the air flow drawing is 200-300° C. and the pressure is 0.3-0.5 MPa;

[0028] The temperature of the cold air used to cool the web is 20-22°C.

[0029] The present invention also provides a method for preparing a long-lasting antibacterial melt-blown non-woven fabric and the long-lasting antibacterial melt-blown non-woven fabric is prepared.

[0030] Beneficial effects of the present invention:

[0031] The present invention uses the supernatant of a Bacillus subtilis culture fluid to modify the oxide mixture, eliminating the need for toxic organic reagents or complex control steps required by conventional modification methods. The resulting nonwoven fabric exhibits an inhibitory effect against Staphylococcus aureus, Escherichia coli, and Candida albicans, with an inhibition rate exceeding 99.8%. Furthermore, the resulting nonwoven fabric maintains its high antibacterial effect even after 1,000 washes in muddy water and 200 washes to remove oil stains. The preparation method of the present invention is simple, low-cost, and has excellent industrial application value. DETAILED DESCRIPTION

[0032] The present invention provides a long-lasting antibacterial meltblown nonwoven fabric masterbatch, comprising the following raw materials:

[0033] Cordierite, sodium bentonite, modified oxide mixture, and polypropylene;

[0034] The mass ratio of the cordierite, sodium bentonite and modified oxide mixture is 1:1:5-8, preferably 1:1:5.5-7.5, and more preferably 1:1:6-7;

[0035] The mass ratio of the total mass of the cordierite, sodium bentonite and modified oxide mixture to polypropylene is 5-8:75-80, preferably 5.5-7.5:76-79, and more preferably 6-7:77-78.

[0036] In the present invention, the preparation method of the modified oxide mixture comprises: immersing the oxide mixture in the supernatant of a Bacillus subtilis culture solution and then centrifuging to obtain the modified oxide mixture;

[0037] The oxide mixture consists of nano zirconium oxide, nano calcium oxide and nano zinc oxide in a mass ratio of 2-5:1-3:1-3, preferably 2.5-4.5:1.5-2.5:1.5-2.5, and more preferably 3-4:2:2.

[0038] In the present invention, the immersion treatment temperature is 25 to 35° C., preferably 27 to 32° C., more preferably 30° C.; the time is 1.5 to 2.5 hours, preferably 1.7 to 2.2 hours, more preferably 2 hours;

[0039] The centrifugal speed is 400-600 rpm, preferably 420-580 rpm, more preferably 450-550 rpm;

[0040] The particle size of the modified oxide mixture is 200 to 300 nm, preferably 220 to 280 nm, and more preferably 240 to 260 nm.

[0041] In the present invention, the oxide mixture is modified using the supernatant of the Bacillus subtilis culture solution, which has a significant impact on the antibacterial properties of the resulting non-woven fabric. This is because the fermentation metabolites of the culture solution supernatant have an adhesive effect on various oxides, allowing different oxides to be better mixed; at the same time, the components in the metabolites change the properties of the oxide surface.

[0042] The present invention provides a method for preparing a long-lasting antibacterial melt-blown non-woven fabric masterbatch, comprising the following steps:

[0043] (1) mixing cordierite, sodium bentonite and a modified oxide mixture to obtain a mixture;

[0044] (2) The polypropylene and the mixture are mixed to obtain a melt-blown non-woven fabric masterbatch with long-lasting antibacterial effect.

[0045] In the present invention, in step (1) and step (2), the mixing speed is independently 400 to 600 rpm, preferably 420 to 580 rpm, and more preferably 450 to 550 rpm.

[0046] The present invention provides a method for preparing a melt-blown non-woven fabric with long-lasting antibacterial properties. The melt-blown non-woven fabric masterbatch is sequentially subjected to heating, melting, extrusion, and air flow drawing to obtain spun fibers; the spun fibers are cooled into a web to obtain the melt-blown non-woven fabric with long-lasting antibacterial properties.

[0047] In the present invention, the heating and melting temperature is 220-250°C, preferably 225-245°C, more preferably 230-240°C; the time is 0.3-1h, preferably 0.4-0.8h, more preferably 0.5h;

[0048] The extrusion temperature is 230-260° C., preferably 235-255° C., more preferably 240-250° C.; the extrusion time is 0.3-1 h, preferably 0.4-0.8 h, more preferably 0.5 h.

[0049] In the present invention, the temperature of the air flow drawing is 200-300°C, preferably 220-280°C, more preferably 240-260°C; the pressure is 0.3-0.5 MPa, preferably 0.35-0.45 MPa, more preferably 0.4 MPa;

[0050] The temperature of the cold air used to cool the web is 20-22°C, preferably 20.5-21.5°C, and more preferably 21°C.

[0051] The present invention also provides a method for preparing a long-lasting antibacterial melt-blown non-woven fabric and the long-lasting antibacterial melt-blown non-woven fabric is prepared.

[0052] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0053] The cordierite (powder, 400 nm), sodium bentonite (powder, 400 nm), nano zirconium oxide (powder, 250 nm), nano calcium oxide (powder, 250 nm), and nano zinc oxide (powder, 250 nm) used in the present invention are all commercially available products.

[0054] Bacillus subtilis is a commercially available product.

[0055] Example 1

[0056] Bacillus subtilis was placed in LB medium, cultured at 37°C for 12 hours until the plateau phase, and then centrifuged at 500 rpm to obtain the Bacillus subtilis culture supernatant;

[0057] An oxide mixture was obtained by mixing nano-zirconium oxide, nano-calcium oxide, and nano-zinc oxide in a weight ratio of 3:2:2, and then immersed in the supernatant of a Bacillus subtilis culture solution at 30°C for 2 hours, centrifuged at 500 rpm, filtered, and ball-milled to obtain a modified oxide mixture with a particle size of 200 nm;

[0058] A mixture of cordierite, sodium bentonite and modified oxide in a weight ratio of 1:1:6 was mixed in a dry powder mixer at a speed of 500 rpm for 15 minutes to obtain a mixture; polypropylene in a weight ratio of 78:6 and the mixture were mixed in a dry powder mixer at a speed of 500 rpm for 0.5 hours to obtain a melt-blown non-woven fabric masterbatch with long-term antibacterial effect. The melt-blown non-woven fabric masterbatch with long-term antibacterial effect was placed in a screw extruder, heated and melted at 240°C for 0.5 hours, and then extruded through a spinneret at 245°C for 0.5 hours. The fibers were drawn by airflow at 250°C and 0.4 MPa to form primary fibers with a diameter of 0.5 to 5 μm. The primary fibers were cooled by cold air at 20°C to form a web with a gram weight of 150 to 180 g / m 2Long-lasting antibacterial meltblown non-woven fabric.

[0059] Example 2

[0060] Bacillus subtilis was placed in LB medium, cultured at 37°C for 12 hours until the plateau phase, and then centrifuged at 500 rpm to obtain the Bacillus subtilis culture supernatant;

[0061] An oxide mixture was prepared by mixing nano-zirconium oxide, nano-calcium oxide, and nano-zinc oxide in a weight ratio of 5:1:1, and then immersed in the supernatant of a Bacillus subtilis culture solution at 30°C for 2 hours, centrifuged at 500 rpm, filtered, and ball-milled to obtain a modified oxide mixture with a particle size of 250 nm.

[0062] A mixture of cordierite, sodium bentonite and modified oxide in a weight ratio of 1:1:5 was mixed in a dry powder mixer at a speed of 500 rpm for 15 minutes to obtain a mixture; polypropylene in a weight ratio of 80:5 and the mixture were mixed in a dry powder mixer at a speed of 500 rpm for 0.5 hours to obtain a melt-blown non-woven fabric masterbatch with long-term antibacterial effect. The melt-blown non-woven fabric masterbatch with long-term antibacterial effect was placed in a screw extruder, heated and melted at 240°C for 0.8 hours, and then extruded through a spinneret at 245°C for 0.3 hours. It was then air-drawn at 250°C and 0.4 MPa to form primary fibers with a diameter of 0.5 to 5 μm. The primary fibers were cooled by cold air at 20°C to form a web with a gram weight of 150 to 180 g / m 2 Long-lasting antibacterial meltblown non-woven fabric.

[0063] Example 3

[0064] Bacillus subtilis was placed in LB medium, cultured at 37°C for 12 hours until the plateau phase, and then centrifuged at 500 rpm to obtain the Bacillus subtilis culture supernatant;

[0065] An oxide mixture was prepared by mixing nano-zirconium oxide, nano-calcium oxide, and nano-zinc oxide in a weight ratio of 3:2:2, and then immersed in the supernatant of a Bacillus subtilis culture solution at 30°C for 2 hours, centrifuged at 500 rpm, filtered, and ball-milled to obtain a modified oxide mixture with a particle size of 250 nm.

[0066] A mixture of cordierite, sodium bentonite and modified oxide in a weight ratio of 1:1:8 was mixed in a dry powder mixer at a speed of 500 rpm for 15 minutes to obtain a mixture; polypropylene in a weight ratio of 75:8 and the mixture were then mixed in a dry powder mixer at a speed of 500 rpm for 0.5 hours to obtain a melt-blown non-woven fabric masterbatch with long-term antibacterial effect. The melt-blown non-woven fabric masterbatch with long-term antibacterial effect was placed in a screw extruder, heated and melted at 240°C for 0.4 hours, and then extruded through a spinneret at 245°C for 1 hour. The fibers were drawn by airflow at 250°C and 0.4 MPa to form primary fibers with a diameter of 0.5 to 5 μm. The primary fibers were cooled by cold air at 20°C to form a web with a gram weight of 150 to 180 g / m 2 Long-lasting antibacterial meltblown non-woven fabric.

[0067] Comparative Example 1

[0068] Comparative Example 1 is compared with Example 1, with other conditions remaining unchanged, except that the modified oxide mixture is replaced by the oxide mixture.

[0069] Comparative Example 2

[0070] Comparative Example 2 is compared with Example 1, with other conditions remaining unchanged, except that nano-calcium oxide is not added to the oxide mixture.

[0071] Comparative Example 3

[0072] Comparative Example 3 is compared with Example 1, with other conditions remaining unchanged, except that nano-zirconium oxide is replaced by nano-magnesium oxide.

[0073] Comparative Example 4

[0074] Comparative Example 4 is compared with Example 1, with other conditions remaining unchanged, except that sodium bentonite is not added.

[0075] The long-acting antibacterial melt-blown non-woven fabrics prepared in Examples 1 to 3 and Comparative Examples 1 to 4 with a size of 300 mm × 300 mm were tested for antibacterial properties using GB / T20944.3-2008. The test results are shown in Tables 1 to 3, where Table 1 shows the antibacterial rate of Staphylococcus aureus; Table 2 shows the antibacterial rate of Escherichia coli; and Table 3 shows the antibacterial rate of Candida albicans.

[0076] The muddy water immersion washing treatment method is: the non-woven fabric is immersed in a 10% by mass mud and sand aqueous solution for 5 minutes (each time), referring to the "household double-tub washing machine washing method" in GB / T20944.3-2008. The non-woven fabric is not immersed in pollutants and is only immersed in clean water.

[0077] The oil stain immersion washing method is: the non-woven fabric is immersed in a 5% by mass edible oil aqueous solution (the edible oil is commercially available peanut oil) for 5 minutes (each time), and then washed using the "household double-tub washing machine washing method" in GB / T20944.3-2008.

[0078] Table 1 Antibacterial rate of Staphylococcus aureus

[0079]

[0080]

[0081] Table 2 Antibacterial rate of Escherichia coli

[0082]

[0083] Table 3 Test the antibacterial rate of Candida albicans

[0084]

[0085]

[0086] As can be seen from the above examples, the present invention provides a meltblown nonwoven fabric masterbatch with long-lasting antibacterial properties, a meltblown nonwoven fabric, and a method for preparing the same, comprising the following steps: mixing cordierite, sodium bentonite, and a modified oxide mixture to obtain a mixture; mixing polypropylene with the mixture to obtain a meltblown nonwoven fabric masterbatch with long-lasting antibacterial properties; and then sequentially performing heating and melting, extrusion, high-temperature airflow high-speed drawing, and cooling to form a web to obtain a meltblown nonwoven fabric. The resulting meltblown nonwoven fabric has excellent antibacterial properties. After 1000 washes with muddy water and 200 washes to remove oil stains, the antibacterial rates against Staphylococcus aureus, Escherichia coli, and Candida albicans all reached over 94%.

[0087] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A long-lasting antibacterial meltblown nonwoven masterbatch, characterized in that: Including the following ingredients: Cordierite, sodium bentonite, modified oxide mixture, and polypropylene; The mass ratio of the cordierite, sodium bentonite and modified oxide mixture is 1:1:5-8; The mass ratio of the total mass of the cordierite, sodium bentonite and modified oxide mixture to the mass ratio of the polypropylene is 5-8:75-80; The preparation method of the modified oxide mixture comprises: immersing the oxide mixture in a supernatant of a Bacillus subtilis culture solution and then centrifuging to obtain the modified oxide mixture; The oxide mixture consists of nano zirconium oxide, nano calcium oxide and nano zinc oxide in a mass ratio of 2-5:1-3:1-3.

2. The meltblown nonwoven masterbatch according to claim 1, characterized in that The immersion temperature is 25-35°C and the time is 1.5-2.5h; The centrifugal speed is 400-600 rpm; The particle size of the modified oxide mixture is 200-300 nm.

3. The method for preparing the long-lasting antibacterial meltblown nonwoven masterbatch according to claim 1 or 2, characterized in that: The following steps are involved: (1) mixing cordierite, sodium bentonite and a modified oxide mixture to obtain a mixture; (2) The polypropylene and the mixture are mixed to obtain a melt-blown non-woven fabric masterbatch with long-lasting antibacterial effect.

4. The preparation method according to claim 3, characterized in that In step (1) and step (2), the mixing speed is independently 400-600 rpm.

5. A method for preparing a long-lasting antibacterial meltblown nonwoven fabric, characterized in that: The meltblown nonwoven fabric masterbatch according to claim 1 or 2 is sequentially subjected to heating, melting, extrusion, and air flow drawing to obtain nascent fibers; the nascent fibers are cooled into a web to obtain a long-lasting antibacterial meltblown nonwoven fabric.

6. The preparation method according to claim 5, characterized in that The heating and melting temperature is 220-250°C and the time is 0.3-1h; The extrusion temperature is 230-260° C., and the extrusion time is 0.3-1 h.

7. The preparation method according to claim 5 or 6, characterized in that: The temperature of the air flow drawing is 200-300°C and the pressure is 0.3-0.5MPa; The temperature of the cold air used to cool the web is 20-22°C.

8. The long-lasting antibacterial meltblown nonwoven fabric prepared by the preparation method according to any one of claims 5 to 7.

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