Composite material non-woven fabric and preparation method thereof

Abstract

The invention relates to the technical field of non-woven fabric materials, in particular to a composite non-woven fabric and a preparation method thereof.The composite non-woven fabric is characterized in that cotton fiber non-woven fabric serves as a matrix, a composite bacteriostatic agent is grafted to the matrix, and the composite bacteriostatic agent comprises a quaternary ammonium salt component, a photosensitive antibacterial component and m-toluene isocyanate; according to the composite material non-woven fabric and the preparation method thereof, the composite material non-woven fabric has good antibacterial performance, the long-acting antibacterial performance is still kept after water washing, and the durability is high; in addition, the quaternary ammonium salt component and the benzophenone derivative in the non-woven fabric can cooperate with each other, bacterial wreckage accumulation is avoided under illumination, and more excellent antibacterial performance is obtained. 4-methacrylamide benzophenone has a more stable grafting structure, m-toluene isocyanate can form a group with an antibacterial effect, although the single antibacterial property of m-toluene isocyanate is general, the m-toluene isocyanate also has a long-term effect, and on the whole, the composite bacteriostatic agent is mutually matched, so that good antibacterial performance can be kept in a darkroom and a light environment.

Description

Technical Field

[0001] The invention relates to the technical field of non-woven fabric materials, and in particular to a composite material non-woven fabric and a preparation method thereof. Background Art

[0002] Composite non-woven fabric is a new functional material with a wide range of applications. It has the effects of water absorption, thermal insulation, and filtration. It can be used in vegetable preservation, filter bags, sunshade cloth, mulch cloth, protective equipment and other fields.

[0003] Functional antibacterial non-woven fabrics will be used in many of the above-mentioned fields to avoid or reduce the growth and spread of bacteria. However, the functionality of the current antibacterial non-woven fabrics is mostly achieved by physical impregnation or spraying of antibacterial agents followed by drying, and their long-term effectiveness is poor. The existing patent with publication number CN111379161A provides a method for preparing a silver ion antibacterial non-woven fabric, comprising the following steps: preparing an antibacterial finishing agent, performing a post-finishing treatment on the non-woven fabric with the antibacterial finishing agent, and then drying at 115-125°C; the antibacterial finishing agent is an aqueous solution containing 0.1%-15% silver ion antibacterial agent.

[0004] In summary, the anti-silver ion antibacterial agent can be physically attached to the non-woven fabric through the physical impregnation method, so that the non-woven fabric has an antibacterial effect; however, the non-woven fabric physically loaded with the antibacterial agent has poor durability. After several washings, the antibacterial agent will continue to peel off, which will lead to a significant decrease in subsequent antibacterial ability, which is not conducive to the application of the non-woven fabric; in summary, consider designing a non-woven fabric with excellent antibacterial properties. In view of this, we propose a composite material non-woven fabric and a preparation method thereof. Summary of the invention

[0005] The purpose of the present invention is to solve the deficiencies mentioned in the above background technology and provide a composite material non-woven fabric and a preparation method thereof.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A composite material non-woven fabric, with cotton fiber non-woven fabric as a matrix, and a composite antibacterial agent grafted onto the matrix;

[0008] The composite antibacterial agent comprises a quaternary ammonium salt component, a photosensitive antibacterial component and meta-toluene isocyanate.

[0009] Preferably, the mass fractions of the composite antibacterial agent and the cotton fiber nonwoven fabric are specifically:

[0010]

[0011] Preferably, the quaternary ammonium salt component is one of methacryloyloxyethyl dimethylbenzyl ammonium chloride and methacryloyloxyethyl trimethylammonium chloride.

[0012] Preferably, the photosensitive antibacterial component is 4-methylacrylamide benzophenone.

[0013] A method for preparing a composite material non-woven fabric, the specific steps of the preparation method are:

[0014] Step 1: Preparation of photosensitive antibacterial components, synthesis of photosensitive antibacterial component 4-methacrylamide benzophenone for later use;

[0015] Step 2: non-woven fabric treatment, immersing the cotton fiber non-woven fabric in acetone for 2-4 hours, ultrasonic cleaning at 20-60kHz for 10-30 minutes, rinsing with deionized water and drying at 80-100°C;

[0016] Step 3: Prepare the grafting solution and take 6×10 -3 mol / L ammonium cerium nitrate was dissolved in 50 ml of deionized water;

[0017] Step 4: Mixing: weigh the photosensitive antibacterial component, the quaternary ammonium salt component, and m-toluene isocyanate according to their mass fractions and dissolve them in anhydrous ethanol, and then mix them into the grafting solution of step 3;

[0018] Step 5: Grafting treatment, stirring at 50-70°C and 180-300 r / min for 6-8h, then washing with ethanol and filtering three times, washing with deionized water three times and filtering, and drying at 70-80°C to constant weight.

[0019] Preferably, in step 3, nitric acid is added dropwise during the process of preparing the grafting solution to adjust the pH value to 3-5.

[0020] Preferably, the specific steps for preparing the photosensitive antibacterial component are:

[0021] Step 1: Add 6.6 g of 4-aminobenzophenone and 6 ml of triethylamine to a reaction vessel and dissolve in 30 ml of N,N-dimethylformamide;

[0022] Step 2: Weigh 6 ml of methacryloyl chloride and dissolve it in 10 ml of N,N-dimethylformamide, and add it dropwise into the reaction container;

[0023] Step 3: After stirring at room temperature for 10-12 hours, pour in cooling water to room temperature, stir evenly and filter to obtain a filter cake;

[0024] Step 4: washing three times with a 5 wt % sodium carbonate aqueous solution, then washing multiple times with deionized water, and drying at 50-60° C. to obtain 4-methylacrylamide benzophenone.

[0025] Preferably, the rate of dripping into the reaction container in step 2 is controlled to be complete within 25-30 minutes.

[0026] Preferably, a nitrogen protective atmosphere is provided in the reaction container during the preparation of the photosensitive antibacterial component.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The composite material non-woven fabric and the preparation method thereof have good antibacterial properties, and can still maintain long-lasting antibacterial properties after washing with water, and have strong durability; in addition, the quaternary ammonium salt component and the benzophenone derivative in the non-woven fabric can cooperate with each other to avoid the accumulation of bacterial debris under light, thereby obtaining more excellent antibacterial properties; 4-methylacrylamide benzophenone has a more stable grafting structure, and meta-toluene isocyanate can form a group with antibacterial effect, and although its single antibacterial property is general, it also has long-lasting properties; on the whole, the composite antibacterial agents cooperate with each other to maintain good antibacterial properties in both dark rooms and light environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0030] Figure 1 It is the synthetic chemical formula of 4-methacrylamide benzophenone of the present invention. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. In the absence of conflict, the embodiments in this application and the features in the embodiments can be combined with each other. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work belong to the scope of protection of the present invention.

[0032] See also Figure 1 The present invention describes the above technical solution in detail through the following embodiments:

[0033] Example 1

[0034] A composite material non-woven fabric, with cotton fiber non-woven fabric as a matrix, and a composite antibacterial agent grafted onto the matrix;

[0035] The composite antibacterial agent comprises a quaternary ammonium salt component, a photosensitive antibacterial component and meta-toluene isocyanate.

[0036] The specific mass fractions of the composite antibacterial agent and the cotton fiber non-woven fabric are:

[0037]

[0038] The quaternary ammonium salt component can be one of methacryloyloxyethyl dimethyl benzyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride with a specification of 99% sold by Chengdu Runze Local Chemical Co., Ltd. In this embodiment, the quaternary ammonium salt component uses methacryloyloxyethyl dimethyl benzyl ammonium chloride.

[0039] Specifically, the cotton fiber nonwoven fabric of this embodiment was purchased from Yangzhou Aotelong Nonwoven Fabric Co., Ltd. and sold at 80g / cm 2 Specification products; 4-aminobenzophenone was purchased from Sigam-Aldrich, Co. with analytical grade specifications; triethylamine, N,N-dimethylformamide, nitric acid, acetone, anhydrous ethanol and ammonium cerium nitrate were all purchased from Chengdu Kelon Chemical Reagent Factory with analytical grade specifications; methacryloyl chloride was purchased from Shanghai Ciyu Chemical Technology Co., Ltd. with analytical grade specifications; m-toluene isocyanate was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd. with analytical grade specifications.

[0040] The 4-methacrylamide benzophenone used as the photosensitive antibacterial component in this application is homemade, as shown in the attached Figure 1 The structure shown in the figure can form a saturated carbon chain graft structure with the non-woven fabric fiber after grafting, and has better stability; the preparation steps are specifically as follows: first, according to the mass ratio, 66g of 4-aminobenzophenone and 60ml of triethylamine are dissolved in 300ml of N,N-dimethylformamide in a reactor, and the reactor is evacuated and nitrogen is injected to provide a protective atmosphere to normal pressure; then 60ml of methacryloyl chloride is weighed and dissolved in 100ml of N,N-dimethylformamide, and the mixture is added dropwise to the reaction container, and the addition process is controlled to be complete within 30min, and the mixture is stirred at room temperature for 12h. An ice bath is applied during the process, and after the reaction is completed, sufficient cooling water is poured into the reactor to cool the solution inside the reactor to room temperature, and the filter cake is obtained by suction filtration after uniform stirring; the mixture is washed three times with a 5wt% sodium carbonate aqueous solution, and then washed three times with deionized water, and dried at 50°C to obtain 4-methacrylamidebenzophenone.

[0041] The preparation method of the composite material non-woven fabric of this embodiment has the following specific steps: first, the non-woven fabric is treated by immersing the cotton fiber non-woven fabric in acetone for 4 hours, ultrasonically cleaning it at 30kHz for 30 minutes, rinsing it with deionized water and drying it at 100°C; then, 6×10 -3 The grafting solution was prepared by dissolving nitric acid in 50 ml of deionized water to form a grafting solution. It should be noted that nitric acid was added dropwise in the present application to adjust the pH value to 5. The main purpose of adjusting the pH in this process is to provide an acidic environment to make the ammonium cerium nitrate more stable, which is conducive to more effective grafting and activation of cellulose. Finally, the materials were mixed, and the photosensitive antibacterial component, the quaternary ammonium salt component, and m-toluene isocyanate were weighed and dissolved in anhydrous ethanol, mixed into the grafting solution, stirred at 60 ° C and 240 r / min for 6 hours, and then washed with ethanol and filtered three times, washed with deionized water three times and filtered, and dried at 70 ° C to constant weight to obtain a composite non-woven fabric with antibacterial properties.

[0042] It should be explained that the composite antibacterial agent in this embodiment can be stably and permanently connected to the cotton fiber non-woven fabric through grafting, and its structural stability is more reliable and durable than physical dipping or spraying, which is conducive to obtaining more long-term functionality.

[0043] Specifically, it should be noted that the quaternary ammonium salt component in the present application adopts methacryloyloxyethyl dimethylbenzyl ammonium chloride, and its antibacterial effect comes from electrostatic contact killing. However, electrostatic effect can cause microorganisms to adsorb, which will lead to continuous adsorption and accumulation of bacterial debris and reduce the long-term antibacterial ability of the quaternary ammonium salt component.

[0044] In the present application, 4-methacrylamide benzophenone is a benzophenone derivative, which is a photoactive antibacterial agent. Its mechanism of action is that it will produce active oxides under light conditions and then kill bacteria. The active oxides produced can oxidatively degrade bacterial organic matter to avoid the accumulation of bacterial debris and affect the antibacterial effect of the quaternary ammonium salt component. That is, it cooperates with the quaternary ammonium salt component to achieve self-cleaning of bacterial debris under light, avoiding the problem of decreased antibacterial ability of the quaternary ammonium salt component.

[0045] In addition, compounds containing amino groups generally exhibit good antibacterial activity, and m-toluene isocyanate can chemically graft with the hydroxyl groups on cotton non-woven fibers to form stably grafted amino groups on the cellulose molecules, which in turn impart long-lasting antibacterial ability to the non-woven fabric.

[0046] Example 2

[0047] The difference between this embodiment and embodiment 1 is that in this embodiment, nitric acid is added dropwise to adjust the pH value to 3, and other conditions are the same.

[0048] Example 3

[0049] The difference between this embodiment and embodiment 1 is that in this embodiment, nitric acid is added dropwise to adjust the pH value to 6, and other conditions are the same.

[0050] Example 4

[0051] The difference between this embodiment and embodiment 1 is that the amount of 4-methacrylamide benzophenone in this embodiment is 6 parts, and other conditions are the same.

[0052] Example 5

[0053] The difference between this embodiment and embodiment 1 is that the amount of 4-methacrylamide benzophenone in this embodiment is 10 parts, and other conditions are the same.

[0054] Example 6

[0055] The difference between this embodiment and embodiment 1 is that the same mass fraction of benzophenone tetracarboxylic dianhydride, which is also a benzophenone derivative and has photosensitivity, is used in this embodiment, and other conditions are the same.

[0056] Comparative Example 1

[0057] The difference between this comparative example and Example 1 is that this comparative example is a blank control group, and the cotton fiber non-woven fabric without the composite antibacterial agent grafted thereto is directly used, and other conditions are the same.

[0058] Comparative Example 2

[0059] The difference between this comparative example and Example 1 is that in this comparative example, sodium hydroxide is added dropwise to adjust the pH value to 8, and other conditions are the same.

[0060] Comparative Example 3

[0061] The difference between this comparative example and Example 1 is that 6 parts of 4-methacrylamide benzophenone are not added in this comparative example, and other conditions are the same.

[0062] Comparative Example 4

[0063] The difference between this comparative example and Example 1 is that no quaternary ammonium salt component is added in this comparative example, and other conditions are the same.

[0064] Comparative Example 5

[0065] The difference between this comparative example and Example 1 is that the comparative example does not add quaternary ammonium salt components and meta-toluene isocyanate, and other conditions are the same.

[0066] Comparative Example 6

[0067] The difference between this comparative example and Example 1 is that 4-methacrylamide benzophenone and quaternary ammonium salt components are not added in this comparative example, and other conditions are the same.

[0068] Antibacterial performance test

[0069] Samples were prepared according to Examples 1-6 and Comparative Examples 1-7, washed 200 times, and the antibacterial properties of the nonwoven fabrics of each sample were tested with reference to AATCC100-2012 "Evaluation Method for Antibacterial Textiles";

[0070] First, a piece of non-woven fabric with a side length of 2.5 cm was placed on a flat dish, and 25 μl of bacterial solution was dropped on the surface. The dish was then cultured for 10 min in a light (xenon lamp with a wavelength of 600 nm filter) and dark room environment. Then, the original bacterial solution and the bacterial solution on the sample were diluted in a centrifuge tube in a gradient of 10 6 times, making a 10-fold dilution series;

[0071] Take 10 μl of solution from each centrifuge tube of the dilution series and inject it into a plate containing agar medium. Place it in a constant temperature incubator at 37°C and culture it for 24 hours. Finally, measure the number of colonies, calculate the antibacterial rate (%), and evaluate the antibacterial effect:

[0072] Inhibition rate = (number of colonies in the original sample - number of colonies remaining after antibacterial treatment) / number of colonies in the original sample × 100%;

[0073] The bacterial solution used two groups of bacteria, with a concentration of 1.36×10 6 CFU / sample of Staphylococcus aureus and a concentration of 1.79×10 6 CFU / sample of Escherichia coli;

[0074] See Table 1 and Table 2 for specific data:

[0075] Table 1:

[0076]

[0077] Table 2:

[0078]

[0079] From the data in Table 1 and Table 2, we can see that:

[0080] The smaller the pH value within the scope of this application, the more stable the antibacterial performance is, with a slight improvement. Considering that excessive acidity is not conducive to the mechanical strength of non-woven fabrics, a strong acid pH value is not used. However, when the pH is 6 and the data of Comparative Example 2 in an alkaline environment show obvious attenuation of antibacterial performance, the pH value will affect the antibacterial performance of the product.

[0081] The data of Example 5 tend to be consistent with the data of Example 1. From the perspective of actual production cost, high-dose formulations are not considered; however, the antibacterial properties of Example 4 and Example 1 are attenuated under light conditions, but the antibacterial properties in the darkroom environment are also maintained well; combined with Comparative Example 3, it can be seen that 4-methylacrylamide dibenzophenone can further improve the antibacterial properties under light conditions.

[0082] It should be noted that the data of Example 6 in Table 1 are significantly different from those of Example 1. A parallel group of Example 6 was set up separately, and the antibacterial rates of Staphylococcus aureus and Escherichia coli were tested after 200 times without water washing. The antibacterial rates of Staphylococcus aureus and Escherichia coli in the light environment were 99.39% and 99.75%, respectively, and the antibacterial rates of Staphylococcus aureus and Escherichia coli in the dark room environment were 95.57% and 96.98%, respectively. The data are similar to those of Example 1, but the antibacterial performance is not well maintained after water washing. Considering that the saturated carbon chain graft structure formed in Example 1 is stable and resistant to water washing.

[0083] The data of Comparative Example 4 show that the quaternary ammonium salt component has antibacterial properties, and the data of Comparative Example 5 can be used with Comparative Example 3 to further prove that 4-methacrylamide benzophenone can further improve the antibacterial performance under light conditions, but it has almost no antibacterial ability under dark room conditions; and Comparative Example 6 shows that the single meta-toluene isocyanate is not affected by light and has an antibacterial effect, but the effect is not as good as 4-methacrylamide benzophenone under light.

[0084] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A composite nonwoven fabric, characterized in that: A cotton fiber nonwoven fabric is used as a substrate, and a composite antibacterial agent is grafted onto the substrate; The composite antibacterial agent comprises a quaternary ammonium salt component, a photosensitive antibacterial component and meta-toluene isocyanate.

2. The composite nonwoven fabric according to claim 1, characterized in that: The mass fractions of the composite antibacterial agent and the cotton fiber nonwoven fabric are specifically as follows:

3. The composite nonwoven fabric according to claim 2, characterized in that: The quaternary ammonium salt component is one of methacryloyloxyethyl dimethyl benzyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride.

4. The composite nonwoven fabric according to claim 2, characterized in that: The photosensitive antibacterial component is 4-methylacrylamide benzophenone.

5. A method for preparing a composite nonwoven fabric, applicable to the composite nonwoven fabric according to any one of claims 1 to 4, characterized in that: The specific steps of the preparation method are: Step 1: Preparation of photosensitive antibacterial components, synthesis of photosensitive antibacterial component 4-methacrylamide benzophenone for later use; Step 2: non-woven fabric treatment, immersing the cotton fiber non-woven fabric in acetone for 2-4 hours, ultrasonic cleaning at 20-60kHz for 10-30 minutes, rinsing with deionized water and drying at 80-100°C; Step 3: Prepare the grafting solution and take 6×10 -3 mol / L ammonium cerium nitrate was dissolved in 50 ml of deionized water; Step 4: Mixing: weigh the photosensitive antibacterial component, the quaternary ammonium salt component, and m-toluene isocyanate according to their mass fractions and dissolve them in anhydrous ethanol, and then mix them into the grafting solution of step 3; Step 5: Grafting treatment, stirring at 50-70°C and 180-300 r / min for 6-8h, then washing with ethanol and filtering three times, washing with deionized water three times and filtering, and drying at 70-80°C to constant weight.

6. The method for preparing a composite material nonwoven fabric according to claim 5, characterized in that: In step 3, nitric acid is added dropwise during the preparation of the grafting solution to adjust the pH value to 3-5.

7. The method for preparing a composite material nonwoven fabric according to claim 5, characterized in that: The specific steps for preparing the photosensitive antibacterial component are: Step 1: Add 6.6 g of 4-aminobenzophenone and 6 ml of triethylamine to a reaction vessel and dissolve in 30 ml of N,N-dimethylformamide; Step 2: Weigh 6 ml of methacryloyl chloride and dissolve it in 10 ml of N,N-dimethylformamide, and add it dropwise into the reaction container; Step 3: After stirring at room temperature for 10-12 hours, pour in cooling water to room temperature, stir evenly and filter to obtain a filter cake; Step 4: washing three times with a 5 wt % sodium carbonate aqueous solution, then washing multiple times with deionized water, and drying at 50-60° C. to obtain 4-methylacrylamide benzophenone.

8. The method for preparing a composite material nonwoven fabric according to claim 7, characterized in that: The rate of dripping into the reaction container in step 2 is controlled to be complete within 25-30 minutes.

9. The method for preparing a composite material nonwoven fabric according to claim 7, characterized in that: During the preparation of the photosensitive antibacterial component, a nitrogen protective atmosphere is provided in the reaction container.

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