Antibacterial, mildew-proof and waterproof multifunctional filter material and preparation method thereof

Abstract

The invention belongs to the technical field of filter materials, and particularly relates to an antibacterial, mildewproof and waterproof multifunctional filter material and a preparation method thereof.The preparation method comprises the following steps that S1, porous nano-zinc oxide is added into water containing a dispersing agent to be evenly dispersed, then organic silicon polyurethane is added, a reflux reaction is conducted, and a solution containing organic silicon polyurethane modified porous nano-zinc oxide is obtained; and S2, putting the solution obtained in the step S1 into a dipping tank, and carrying out an after-finishing process on the non-woven fabric to obtain the antibacterial, mildew-proof and waterproof multifunctional filter material. Compared with the prior art, the antibacterial, mildew-proof and waterproof multifunctional filter material prepared by the invention not only has excellent antibacterial and mildew-proof functions, but also has a very good waterproof function.

Description

Technical Field

[0001] The present invention relates to the technical field of filter materials, and particularly relates to an antibacterial, mildew-proof and waterproof multifunctional filter material and a preparation method thereof. Background Art

[0002] With the improvement of people's living standards, the degree of automation of household cleaning products is also getting higher and higher. Generally, the filters supporting cleaning products need to have three functions. One is to seal the entire device to improve the vacuum degree of the whole machine, so as to make the force of sucking dust or sewage greater; the second is to intercept the sucked dust or water from entering the electrical components to prevent damage to the device; the third is that the filter material used preferably has antibacterial and mildew-proof functions, which can better improve the user experience. To achieve the above functions, but without making the resistance too large to avoid high noise, so when selecting materials for the filter, a washable, low-resistance antibacterial, mildew-proof and waterproof filter material needs to be used.

[0003] Generally, filter materials such as meltblown use electrostatic methods to capture dust. Once washed and used for a long time, the static electricity will decay, thus weakening the function of adsorbing dust. And highly efficient filter materials that intercept physically, such as glass fiber filter materials and polytetrafluoroethylene filter materials, have too high resistance, which will make the noise of the device too large, thus affecting the user experience.

[0004] Antibacterial, mildew-proof and waterproof filter materials are generally achieved through post-treatment of the filter materials. Considering the performance conflicts of several functional agents, a multi-step post-treatment is selected to achieve multiple functions. For example, in "A Composite Functional Finishing Technology for an Antibacterial Waterproof, Oil-proof and Stain-proof Fabric" in the 12th issue (total 214th issue) of 2014 in "Shandong Textile Economy", a method of separately finishing waterproofing and antibacterial is mentioned to achieve excellent waterproof and antibacterial functions. This method will increase costs such as labor and electric energy on the one hand, and on the other hand, it will also weaken the functions finished previously by the functions post-treated. Summary of the Invention

[0005] The purpose of the present invention is to provide an antibacterial, mildew-proof and waterproof multifunctional filter material and a preparation method thereof to overcome at least one of the defects existing in the above-mentioned prior art.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] One of the purposes of the present invention lies in a preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material, including the following steps:

[0008] S1. Add porous nano-zinc oxide into water containing a dispersant, disperse evenly, then add organosilicon polyurethane, and carry out a reflux reaction to obtain a solution containing porous nano-zinc oxide modified by organosilicon polyurethane;

[0009] S2. Place the solution obtained in S1 in an impregnation tank. After the non-woven fabric undergoes a finishing process, an antibacterial, mildew-proof, and waterproof multifunctional filter material is obtained.

[0010] Furthermore, the preparation method of the porous nano-zinc oxide is as follows:

[0011] Dissolve zinc nitrate hexahydrate in a mixed solution of water and ethanol, add urea while stirring, and carry out a hydrothermal reaction to obtain a hydrothermal reaction product; then calcine the hydrothermal reaction product to obtain porous nano-zinc oxide.

[0012] Furthermore, the mass ratio of zinc nitrate hexahydrate, water, ethanol, and urea is (1 - 3):(0.5 - 1.5):(30 - 35):(15 - 20), preferably 2:1:33:17.

[0013] Furthermore, the hydrothermal reaction temperature is 150 - 200 °C, and the time is 10 - 25 h.

[0014] Furthermore, the calcination temperature is 400 - 450 °C, and the calcination time is 2 - 6 h.

[0015] Furthermore, the mass ratio of the dispersant, porous nano-zinc oxide, and water is 1:1:(90 - 110), preferably 1:1:100.

[0016] Furthermore, the mass ratio of the porous nano-zinc oxide and organosilicon polyurethane is (9 - 11):1.

[0017] Furthermore, the temperature of the reflux reaction is 100 - 110 °C, and the time is 15 - 25 h.

[0018] Furthermore, the dispersant is cetyltrimethylammonium bromide.

[0019] The second object of the present invention is an antibacterial, mildew-proof, and waterproof multifunctional filter material, which is prepared by using the preparation method described in any one of the above.

[0020] Compared with the prior art, the organosilicon polyurethane polymer in the present invention has good film-forming properties, and the long-chain alkyl group has the property of low surface energy, which can achieve a good waterproof effect. At the same time, the organosilicon polyurethane structure contains certain polar groups and silicon-oxygen bonds, which can ensure good adhesion ability with fibers. Therefore, while having good water-repellent performance, it also has certain washability. In addition, the silicon-oxygen bond in the organosilicon can be combined with the hydroxyl groups on the surface of nano-zinc oxide through hydrolysis, thereby forming porous nano-zinc oxide modified by organosilicon polyurethane polymer. Thus, the composite agent not only has the antibacterial and mildew-proof functions of nano-zinc oxide but also has the waterproof function of organosilicon polyurethane. Moreover, the addition of porous nano-zinc oxide will cause more unevenness on the fiber surface, which is more conducive to the waterproof function of the material. Description of the Drawings

[0021] Figure 1 It is the post-treatment process diagram in Examples 1 and 2 and Comparative Examples 1 and 2;

[0022] Figure 2 It is the physical diagram of the filter materials prepared in Examples 1 and 2 and Comparative Examples 1 and 2;

[0023] As shown in the figure: 1 - drying tunnel; 2 - dipping tank; 3 - antibacterial, mildew-proof and waterproof filter material out of the drying tunnel. Detailed Embodiments

[0024] The present invention will be described in detail below with reference to the drawings and specific embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.

[0025] The specifications of the non-woven fabrics selected in Examples 1 - 2 and Comparative Examples 1 - 3 are as follows: the material is polyester, the gram weight is 70 g / m 2 , and the thickness is 0.36 mm.

[0026] Example 1

[0027] (1) Preparation of porous nano-zinc oxide: Zinc nitrate hexahydrate was added to the mixed solution of water and ethanol. After fully stirring and dissolving, urea was added, and stirring was continued for 30 minutes. The mass ratio of the added zinc nitrate hexahydrate, urea, water, and ethanol was 2:1:33:17. After stirring and reacting for 2 h, the solution was transferred to a hydrothermal autoclave with a polytetrafluoroethylene inner liner, and hydrothermal reaction was carried out at 180 °C for 18 h. The product was filtered, washed thoroughly, dried at 80 °C for 12 h, and then transferred to a muffle furnace and calcined at 450 °C for 4 h to obtain porous nano-zinc oxide.

[0028] (2) Preparation of organosilicon polyurethane: Bis(2-hydroxypropyl) polysiloxane with a molecular weight of 3000 - 5000, polycarbonate diol with a molecular weight of 1000 - 2000, and isophorone diisocyanate were weighed according to a mass ratio of 50:50:1 and added to a reactor filled with tetrahydrofuran. Under stirring and at 60 - 80 °C, cooling and reflux were carried out for 2 - 3 h to react to form an organosilicon polyurethane prepolymer solution; then 2,3,5,6-tetrafluoroterephthalic alcohol, dibutyltin dilaurate, and 1,4-butanediol were added; the mass of 2,3,5,6-tetrafluoroterephthalic alcohol was 0.004 times that of bis(2-hydroxypropyl) polysiloxane, and the mass ratio of 2,3,5,6-tetrafluoroterephthalic alcohol, dibutyltin dilaurate, and 1,4-butanediol was 2:1:3; under stirring and at 60 - 80 °C, cooling and reflux were continued for 3 h to obtain a solution containing organosilicon polyurethane.

[0029] (3) Add cetyltrimethylammonium bromide as a dispersant into water, stir for 20 minutes to dissolve, and then add the porous nano-zinc oxide obtained from the above reaction. The mass ratio of the dispersant, porous nano-zinc oxide to water is 1:1:100. After stirring evenly, add a solution containing organosilicon polyurethane. Control the mass ratio of porous nano-zinc oxide to organosilicon polyurethane to be 100:10; reflux and react at 105 °C for 20 h. After the reaction is completed, set aside.

[0030] Pour the above solution into the impregnation tank 2, and then the non-woven fabric undergoes a finishing process to obtain an antibacterial, mildew-proof and filter-proof material. The prepared filter material is shown in Figure 2 , and the specific parameters are shown in Table 1.

[0031] The described finishing process is as follows: During the drying process, drying can be carried out using a heating drying tunnel 1 under the following process parameters:

[0032] The heating drying tunnel is 8 - 15 meters long,

[0033] Heating zone Ⅰ is 60 - 170 degrees,

[0034] Heating zone Ⅱ is 60 - 170 degrees,

[0035] Heating zone Ⅲ is 80 - 170 degrees,

[0036] Heating zone Ⅳ is 80 - 170 degrees,

[0037] Heating zone Ⅴ is 80 - 170 degrees,

[0038] Heating zone Ⅵ is 100 - 170 degrees, and

[0039] Vehicle speed: 2 - 50 m / min.

[0040] After being treated by the above process, the thickness and resistance of the material will not change, but it has antibacterial, mildew-proof and waterproof properties.

[0041] The antibacterial, mildew-proof and waterproof filter material can be folded by folding and then made into a filter through an injection molding process.

[0042] Example 2

[0043] (1) Prepare porous nano-zinc oxide: Add zinc nitrate hexahydrate into a mixed solution of water and ethanol, stir well to dissolve, then add urea and continue to stir for 30 minutes. The mass ratio of added zinc nitrate hexahydrate, urea, water, and ethanol is 2:1:33:17. After stirring and reacting for 2 h, transfer the solution to a hydrothermal autoclave with a polytetrafluoroethylene liner, carry out hydrothermal reaction at 180 °C for 18 h, filter the product, wash it thoroughly, dry it at 80 °C for 12 hours, and then transfer it to a muffle furnace and calcine it at 450 °C for 4 hours to obtain porous nano-zinc oxide.

[0044] (2) Preparation of a solution containing organosilicon polyurethane: Weigh bis - hydroxypropyl silicone oil with a molecular weight of 3000 - 5000, polycarbonate diol with a molecular weight of 1000 - 2000, and isophorone diisocyanate according to a mass ratio of 50:50:1, and add them to a reactor filled with tetrahydrofuran. Under stirring and at a temperature of 60 - 80 °C, cool and reflux for 2 - 3 h to generate an organosilicon polyurethane prepolymer solution; then add 2,3,5,6 - tetrafluoroterephthalic alcohol, diisobutyltin dilaurate, and 1,4 - butanediol. The mass of 2,3,5,6 - tetrafluoroterephthalic alcohol is 0.004 times that of bis - hydroxypropyl silicone oil, and the mass ratio of 2,3,5,6 - tetrafluoroterephthalic alcohol, diisobutyltin dilaurate, and 1,4 - butanediol is 2:1:3; continue to cool and reflux for 3 h under stirring and at a temperature of 60 - 80 °C to obtain a solution containing organosilicon polyurethane.

[0045] Add the dispersant cetyltrimethylammonium bromide to water, stir for 20 minutes to dissolve, then add the porous nano - zinc oxide obtained from the above reaction. The mass ratio of the dispersant, porous nano - zinc oxide, and water is 1:1:100. After stirring evenly, add the solution containing organosilicon polyurethane. Control the mass ratio of porous nano - zinc oxide and polyurethane to be 100:10; reflux and react at 105 °C for 20 h. After the reaction is completed, set aside for later use.

[0046] Pour the above solution into an impregnation tank, and then the non - woven fabric is processed through a finishing process to obtain an antibacterial, mildew - proof, and waterproof filter material, as shown in Figure 2 , and the specific parameters are shown in Table 1.

[0047] Comparative Example 1

[0048] Add zinc nitrate hexahydrate prepared in Example 1 to a mixed solution of water and ethanol. After stirring and dissolving thoroughly, add urea and continue to stir for 30 minutes. The mass ratio of the added zinc nitrate hexahydrate, urea, water, and ethanol is 2:1:33:17. After stirring and reacting for 2 h, transfer the solution to a hydrothermal reactor lined with polytetrafluoroethylene, and carry out hydrothermal reaction at 180 °C for 18 h. Filter the product, wash it thoroughly, dry it at 80 °C for 12 h, and then transfer it to a muffle furnace and calcine it at 450 °C for 4 h to obtain porous nano - zinc oxide.

[0049] Add the dispersant cetyltrimethylammonium bromide to water, stir for 20 minutes to dissolve, and then add the porous nano - zinc oxide obtained from the above reaction. The mass ratio of porous nano - zinc oxide to water is 1:100, and stir evenly.

[0050] The non - woven fabric in this example is the same as that in Example 1. Pour the above solution into an impregnation tank, and then the non - woven fabric is processed through a finishing process to obtain an antibacterial and mildew - proof filter material. The prepared filter material is shown in Figure 2 , and the specific parameters are shown in Table 1.

[0051] Comparative Example 2

[0052] The non-woven fabric in this comparative example is the same as that in Example 1. The organosilicon polyurethane prepared in Example 1 was poured into an impregnation tank, and then the non-woven fabric was subjected to a finishing process to obtain a waterproof filter material. The prepared filter material is shown in Figure 2 , and the specific parameters are shown in Table 1.

[0053] Comparative Example 3

[0054] The non-woven fabric in this comparative example is the same as that in Example 1, but it does not undergo finishing. The prepared filter material is shown in Figure 2 , and the specific parameters are shown in Table 1.

[0055] Table 1 Specific parameters of the filter materials prepared in Examples 1-2 and Comparative Examples 1-3

[0056] Serial number Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Remarks Waterproof grade 4-5 3-4 1-2 4-5 1-2 GB / T 4745 Antibacterial property 99％ 99％ 99％ 38％ 25％ Appendix A of GB 21551.2 Mildewproof grade Grade 0 Grade 0 Grade 0 / Grade 3 Grade 4 GB / T 24346

[0057] As can be seen from the above table, the waterproof, antibacterial, and antifungal properties of Examples 1-2 are better than those of Comparative Examples 1-3. This is because the organosilicon polyurethane polymer in the present invention has good film-forming properties and the long-chain alkyl group has the property of low surface energy, which can achieve a good waterproof effect. At the same time, the organosilicon polyurethane structure contains certain polar groups and silicon-oxygen bonds, which can ensure good adhesion to the fiber. Therefore, while having good water-repellent performance, it also has certain wash resistance. In addition, the silicon-oxygen bond in the organosilicon can combine with the hydroxyl groups on the surface of nano-zinc oxide through hydrolysis, thereby forming porous nano-zinc oxide modified by organosilicon polyurethane polymer. Thus, the composite agent not only has the antibacterial and antifungal functions of nano-zinc oxide but also has the waterproof function of organosilicon polyurethane. Moreover, the addition of porous nano-zinc oxide will cause more irregularities on the fiber surface, which is more conducive to the waterproof function of the material.

[0058] The above are only the preferred embodiments of the present invention, and are not limitations to the present invention in other forms. Any person skilled in the art may use the technical content disclosed above to make changes or modifications into equivalent embodiments with equivalent changes. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the technical solution content of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material, characterized in that, It includes the following steps: S1. Add porous nano-zinc oxide into water containing a dispersant, disperse evenly, then add organosilicon polyurethane, and carry out a reflux reaction to obtain a solution containing porous nano-zinc oxide modified by organosilicon polyurethane; S2. Place the solution obtained in S1 in an impregnation tank, and the non-woven fabric undergoes a finishing process to obtain an antibacterial, mildew-proof and waterproof multifunctional filter material.

2. The preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material according to claim 1, characterized in that, The preparation method of the porous nano-zinc oxide is as follows: Dissolve zinc nitrate hexahydrate in a mixed solution of water and ethanol, add urea while stirring, and carry out a hydrothermal reaction to obtain a hydrothermal reaction product; then calcine the hydrothermal reaction product to obtain porous nano-zinc oxide.

3. The preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material according to claim 2, characterized in that, The mass ratio of the zinc nitrate hexahydrate, water, ethanol and urea is (1 - 3):(0.5 - 1.5):(30 - 35):(15 - 20).

4. The preparation method of an antibacterial, mildew-proof and waterproof multi-functional filter material according to claim 2, characterized in that, The hydrothermal reaction temperature is 150 - 200 °C, and the time is 10 - 25 h.

5. The preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material according to claim 2, characterized in that, The calcination temperature is 400 - 450 °C, and the calcination time is 2 - 6 h.

6. The preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material according to claim 1, characterized in that, The mass ratio of the dispersant, porous nano-zinc oxide and water is 1:1:(90 - 110).

7. The preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material according to claim 1, characterized in that, The mass ratio of the porous nano-zinc oxide and organosilicon polyurethane is (9 - 11):

1.

8. The preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material according to claim 1, characterized in that The temperature of the reflux reaction is 100 - 110 °C, and the time is 15 - 25 h.

9. The preparation method of an antibacterial, mildew-proof and waterproof multifunctional filter material according to claim 1, characterized in that, 10. An antibacterial, mildew-proof and waterproof multifunctional filter material, characterized in that, The dispersant is cetyltrimethylammonium bromide. It is prepared by using the preparation method described in any one of claims 1 - 9.

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