An automotive interior lining material with bactericidal and deodorizing functions and its preparation method

Abstract

The present invention provides a material for automobile interior lining with bactericidal and odor-removing functions and a preparation method thereof. The material for automobile interior lining comprises a surface layer, a functional layer and a bottom layer which are arranged in sequence, and the functional layer is obtained by surface treatment of a fabric with a MOF-lysozyme material. The silver-based ZIF formed by silver ions and dimethylimidazole not only retains the characteristics of large specific surface area, adjustable pore size and high crystallinity of traditional MOF materials, but also endows the silver-based ZIF with certain antibacterial effects due to silver ions, enhancing the antibacterial properties of the functional layer; due to the characteristics of large specific surface area and large pore size of the silver-based ZIF, more lysozyme can be covalently grafted, and it still has excellent broad-spectrum antibacterial performance; the silver-based ZIF material and lysozyme synergistically enhance the bactericidal ability of the functional layer, playing a role in long-term bactericidal, good bacteriostatic effect and odor elimination, further improving the air quality in the vehicle and providing a healthier and fresher riding environment for passengers.

Description

Technical Field

[0001] The invention belongs to the technical field of automobile interior decoration, and particularly relates to a material for automobile lining with the functions of sterilization and deodorization and a preparation method thereof. Background Art

[0002] With the rapid development of economy and the continuous improvement of people's living standards, the automobile industry has ushered in an unprecedented era of prosperity. People's requirements for automobiles are no longer limited to the quality, function and appearance of the whole vehicle, but have expanded to the comfort and health of the interior environment.

[0003] As the largest decorative surface in the car, the car ceiling interior panel is usually made of a variety of materials such as fabric, fiberglass felt, foam material and non-woven fabric. Traditional non-woven fabric decorative layers are widely used because of their soft texture and easy processing, but at the same time, the material itself is easy to accumulate dust and moisture, providing ideal growth conditions for bacteria and viruses. Especially in an environment with high humidity or moderate temperature, the reproduction rate of bacteria will be further accelerated, making the hygiene problem in the car increasingly serious. Therefore, how to improve the in-car environment, kill or inhibit bacteria, viruses and other microorganisms in a timely and effective manner, and improve the air quality in the car has become a key issue that needs to be solved urgently.

[0004] In response to this situation, the industry has gradually explored and promoted the use of automotive ceiling interior panel materials with sterile functions. This type of sterile material is generally formed by adding antibacterial agents to traditional non-woven fabrics, fabrics or composite materials, or using nanotechnology to treat the surface of the material with antibacterial coatings, thereby forming a protective layer on the surface of the material that can effectively inhibit bacterial growth. Common antibacterial technologies include silver ion antibacterial, zinc oxide and titanium dioxide nano-coatings and other bioactive substances. These technologies can enable interior panels to maintain antibacterial effects for a long time and reduce the reproduction of bacteria and viruses. At the same time, these sterile materials can also effectively inhibit the odor caused by bacterial decomposition of organic matter, thereby further improving the air quality in the car and providing passengers with a healthier and fresher riding environment.

[0005] However, although the application of sterile materials in automotive interiors has obvious advantages, there are also some problems and challenges in the actual promotion process. First of all, due to the addition of antibacterial agents or the application of nano-coatings, the physical properties and durability of the materials will be affected to a certain extent. For example, some antibacterial agents may gradually lose their effectiveness during long-term use, resulting in a decline in antibacterial performance; while some nano-coatings may peel or age under repeated friction, ultraviolet irradiation or temperature changes, thus reducing the overall antibacterial effect of the interior panel. Secondly, the production cost of sterile materials is relatively high, and some high-end technologies have not yet achieved large-scale low-cost applications, which makes automobile manufacturers need to make a trade-off between performance and cost when choosing materials. In addition, some antibacterial additives may have certain safety hazards when in long-term contact with the human body or in high-temperature environments, and their migration and toxicity issues also need to be taken seriously. Finally, with the increasingly strict environmental protection regulations, the environmental performance and sustainability of some traditional antibacterial agents have been questioned, which has prompted the industry to continuously seek new green and environmentally friendly antibacterial materials during the R & D process.

[0006] Generally speaking, with the continuous improvement of people's requirements for the health of the in-vehicle environment, as an emerging technology, sterile interior materials have broad application prospects in automotive roofs and other interior components. Summary of the Invention

[0007] Object of the Invention: The object of the present invention is to provide a material for automotive inner lining with bactericidal and deodorizing functions and its preparation method. The material for automotive inner lining has strong bactericidal ability, can achieve long-term bactericidal effect, has good antibacterial effect and can eliminate odors.

[0008] Technical Solution of the Present Invention:

[0009] In the first aspect, the present invention provides a material for automotive inner lining with bactericidal and deodorizing functions, including a surface layer, a functional layer and a bottom layer arranged in sequence. The functional layer is obtained by surface treatment of a fabric with MOF-lysozyme material.

[0010] In some embodiments, the fabric can be selected from one or more combinations of non-woven fabric, non-woven paper or cotton fiber.

[0011] In some embodiments, the preparation method of the MOF-lysozyme material includes the following steps:

[0012] S1: Take silver nitrate hexahydrate and dimethylimidazole and dissolve them in a solvent, heat for reaction, after the reaction ends, cool to room temperature, separate out the crystals, wash the crystals and then dry to obtain silver-based ZIF material;

[0013] S2: Take the above silver-based ZIF material and disperse it by ultrasonic wave with a sterile solvent, add 3-aminopropyltriethoxysilane to the dispersion liquid, stir and react at room temperature, after the reaction ends, wash and dry and reserve for use;

[0014] S3: The product prepared in S2 is dispersed in a phosphate buffer solution, glutaraldehyde is added to react at room temperature, centrifuged and washed after the reaction, added to a lysozyme solution, gently shaken to react, the product is separated by centrifugation, washed and dried at low temperature to obtain a MOF-lysozyme material.

[0015] In some embodiments, the molar ratio of silver nitrate hexahydrate to dimethylimidazole is 1: 5-10. The molar ratio of metal ions to ligands will affect the crystal morphology and properties of the silver-based ZIF material, and accordingly affect the content of covalently grafted lysozyme, which is directly related to the final antibacterial effect.

[0016] In some embodiments, the heating reaction of S1 is carried out at a temperature of 40-60° C. and a reaction time of 12-24 h.

[0017] In some embodiments, the added mass ratio of the silver-based ZIF material to 3-aminopropyltriethoxysilane is 1:0.01-0.05; so that 3-aminopropyltriethoxysilane forms an amino coating layer on the surface of ZIF.

[0018] In some embodiments, the added mass of glutaraldehyde accounts for 2-4% of the added mass of 3-aminopropyltriethoxysilane, so that it reacts with the surface amine groups to generate terminal active aldehyde groups.

[0019] In some embodiments, the lysozyme solution is a PBS buffer containing lysozyme, the pH of the PBS buffer is 7.4, and the content of lysozyme is 1-10 mg / mL.

[0020] In some embodiments, the specific steps of the surface treatment include:

[0021] The fabric is first washed with water to remove dust, then immersed in an ethanol solution for ultrasonic treatment to remove surface stains, and the pretreated fabric is obtained after being taken out; the MOF-lysozyme material is then applied to the fabric by dipping or spraying.

[0022] In some embodiments, the immersion method can be performed by the following steps: placing the pretreated fabric in a PBS buffer of a MOF-lysozyme material and reacting at room temperature for 1-2 hours; then washing the fabric with deionized water and drying at 40° C., which is recorded as one finishing step.

[0023] In some embodiments, the spraying method may adopt the following steps: using a spray gun to evenly spray the PBS buffer of the MOF-lysozyme material on the surface of the fabric, and drying at 40°C.

[0024] In some embodiments, the finishing is performed 1 - 4 times; in each finishing step, the mass of the MOF-lysozyme material applied to the fabric per square centimeter is 0.25 - 5 g.

[0025] In a second aspect, the present invention provides a method for preparing the material for automotive interior lining with bactericidal and odor-removing properties, specifically including the following steps:

[0026] Arrange the surface layer, functional layer, and bottom layer in sequence from top to bottom, evenly coat a waterborne polyurethane adhesive between each layer, and perform pressure curing in an environment of 20 - 40°C for a curing time of 12 - 24 h to obtain the material for automotive interior lining with bactericidal and odor-removing properties.

[0027] In some embodiments, the coating method can be one or more of knife coating, spraying, or roll coating, and can be specifically selected according to the type and thickness of the fabric.

[0028] Beneficial effects:

[0029] 1. The silver-based ZIF formed by silver ions and 2-methylimidazole not only retains the characteristics of large specific surface area, adjustable pore size, and high crystallinity of traditional MOF materials, but also has a certain antibacterial effect due to silver ions, enhancing the antibacterial properties of the functional layer.

[0030] 2. Due to the characteristics of large specific surface area and large pore size of the silver-based ZIF, more lysozyme can be covalently grafted, and it still has excellent broad-spectrum antibacterial performance.

[0031] 3. The silver-based ZIF material and lysozyme synergistically enhance the bactericidal ability of the functional layer, playing a role in long-term bactericidal, good bacteriostatic effect, and odor elimination, further improving the air quality in the vehicle and providing a healthier and fresher riding environment for passengers. Specific embodiments

[0032] The following will describe the present invention in combination with specific implementation examples. It should be noted that the following examples are examples of the present invention, only for explaining the present invention, and not for limiting the present invention. Other combinations and various improvements within the concept of the present invention can be made without departing from the main idea or scope of the present invention.

[0033] Unless otherwise specified, the chemical reagents used in the present invention are all ordinary commercially available analytical pure.

[0034] The lysozyme solution used in the examples is a PBS (pH 7.4) solution with a lysozyme concentration of 1 mg / mL.

[0035] The waterborne polyurethane adhesive used in the examples is purchased from Anhui Zhongen Chemical Co., Ltd., with the product number PU1179.

[0036] The PET used in the examples was purchased from DuPont, USA, with the grade RE5264.

[0037] The PP used in the examples was purchased from Wanhua Chemical, with the grade EP548R.

[0038] Preparation example of MOF-lysozyme material 1

[0039] S1: Take 0.1 mol of silver nitrate hexahydrate and 1 mol of dimethylimidazole and dissolve them separately in 100 mL of methanol solvent. Stir evenly to obtain a dimethylimidazole solution and a silver nitrate hexahydrate solution respectively; slowly drip the dimethylimidazole solution into the silver nitrate hexahydrate solution, heat at 40 °C for 20 h, cool to room temperature after the reaction, centrifuge the reaction solution at 5000 rpm for 10 min to collect the crystals, wash the crystals and dry them to obtain the silver-based ZIF material;

[0040] S2: Weigh 50 mg of the above silver-based ZIF material and disperse it by ultrasound for 10 minutes with 50 ml of a sterile solvent (a mixed solution of sterile ethanol / water with a volume ratio of 1:2). Then add 0.5 mg of 3-aminopropyltriethoxysilane to the dispersion, stir and react at room temperature for 2 h. After the reaction, wash and dry for later use;

[0041] S3: Take 10 mg of the product prepared in S2 and disperse it in 10 ml of phosphate buffer (PBS, pH 7.4). Add 0.02 mg of glutaraldehyde and react at room temperature for 2 h. After the reaction, centrifuge and wash, add it to 20 ml of lysozyme solution, gently oscillate and react for 6 h, separate the product by centrifugation, wash and dry at low temperature to obtain MOF-lysozyme material 1.

[0042] Preparation example of MOF-lysozyme material 2

[0043] Basically the same as the preparation example of MOF-lysozyme material 1, the difference is that the added molar amounts of silver nitrate hexahydrate and dimethylimidazole are 0.1 mol and 0.5 mol respectively, and MOF-lysozyme material 2 is prepared.

[0044] Preparation example of MOF-lysozyme material 3

[0045] Basically the same as the preparation example of MOF-lysozyme material 1, the difference is that the added molar amounts of silver nitrate hexahydrate and dimethylimidazole are 0.1 mol and 1.5 mol respectively, and MOF-lysozyme material 3 is prepared.

[0046] Preparation example of MOF-lysozyme material 4

[0047] S1: Dissolve 0.1 mol of silver nitrate hexahydrate and 1 mol of dimethylimidazole in 100 mL of methanol solvent respectively, and stir evenly to obtain a dimethylimidazole solution and a silver nitrate hexahydrate solution respectively; slowly drip the dimethylimidazole solution into the silver nitrate hexahydrate solution, heat at 40 °C for 20 h, cool to room temperature after the reaction, centrifuge the reaction solution at 5000 rpm for 10 min to collect the crystals, wash the crystals and dry them to obtain the silver-based ZIF material;

[0048] S2: Take 10 mg of the silver-based ZIF material prepared in S1 and add it to 20 ml of lysozyme solution, gently oscillate and react for 6 h, separate the product by centrifugation, wash and dry it at low temperature to obtain the MOF-lysozyme material 4.

[0049] Preparation example of silver-based ZIF material

[0050] Dissolve 0.1 mol of silver nitrate hexahydrate and 1 mol of dimethylimidazole in 100 mL of methanol solvent respectively, and stir evenly to obtain a dimethylimidazole solution and a silver nitrate hexahydrate solution respectively; slowly drip the dimethylimidazole solution into the silver nitrate hexahydrate solution, heat at 40 °C for 20 h, cool to room temperature after the reaction, centrifuge the reaction solution at 5000 rpm for 10 min to collect the crystals, wash the crystals and dry them to obtain the silver-based ZIF material.

[0051] Perform surface treatment on non-woven fabrics with the above-mentioned MOF-lysozyme material 1, MOF-lysozyme material 2, MOF-lysozyme material 3, MOF-lysozyme material 4, silver-based ZIF material and lysozyme respectively. The treatment steps are as follows:

[0052] First, wash the fabric with water to remove dust, then immerse it in an ethanol solution and ultrasonically treat it for 30 min to remove surface stains, take it out and dry it in the air to obtain the pretreated fabric; cut the pretreated fabric into 2 cm × 2 cm squares, and place them in 200 ml of PBS buffer containing 10 g of MOF-lysozyme material 1, MOF-lysozyme material 2, MOF-lysozyme material 3, MOF-lysozyme material 4, silver-based ZIF material and lysozyme respectively, soak at room temperature for 2 h; then wash the fabric with deionized water and dry it at low temperature of 40 °C. The above is recorded as 1 time of finishing; repeat the finishing of the fabric 4 times to complete the finishing, and obtain the functional layers 1-6 in turn.

[0053] Examples and comparative examples

[0054] Arrange the surface layer, functional layer and bottom layer from top to bottom in sequence, evenly coat a water-based polyurethane adhesive between each layer, and carry out pressure curing in an environment of 40 °C. The curing time is 24 h to obtain the materials for automotive interior lining respectively. The specific materials are shown in Table 1.

[0055] Table 1

[0056]

[0057] Performance test:

[0058] 1. The antibacterial performance was tested according to the standard of QB / T 2591 2003 "Test Methods for Antibacterial Properties and Antibacterial Effects of Antibacterial Plastics". The test strains were Escherichia coli (ATCC25922) and Staphylococcus aureus (ATCC6528).

[0059] 2. The test samples were placed in a beaker containing 1000 mL of distilled water, and then the beaker was placed in a water bath at 40 °C and continuously stirred with a blender. The water was changed every 12 h. The antibacterial efficiency against Escherichia coli and Staphylococcus aureus after the samples were soaked for 240 h and 720 h was measured, and the antibacterial efficiency retention rate at 720 h was calculated.

[0060] The obtained results are shown in Table 2.

[0061] Table 2

[0062]

[0063] It can be seen from the above examples and comparative examples that the material for automotive interior lining provided by the present invention has excellent antibacterial effect and antibacterial stability, with a high initial antibacterial efficiency of up to 99.9%. Moreover, after being treated in a water bath and stirred for 720 h, the antibacterial efficiency retention rate reaches more than 96 - 97%. This shows that the material for automotive interior lining provided by the present invention can effectively improve the antibacterial efficiency and antibacterial stability by preparing the silver-based MOF-lysozyme material, and can be used to improve the antibacterial effect of automotive interior lining materials, making the materials have high and lasting antibacterial performance.

[0064] Specifically, by comparing Comparative Example 1 with the example, it can be seen that the silver-based ZIF material prepared in Comparative Example 1 has a smaller surface area, and the number of covalently grafted lysozyme is reduced, resulting in a decrease in the initial antibacterial efficiency value. In the preparation process of the MOF-lysozyme material 4 in Comparative Example 2, without surface treatment with 3-aminopropyltriethoxysilane and glutaraldehyde, the grafted lysozyme cannot be well fixed on the surface of the silver-based ZIF material. Although the initial antibacterial efficiency can reach 99%, after multiple oscillation washings, the antibacterial efficiency of the material decays to about 77%, showing poor antibacterial stability.

[0065] It can be seen from the comparison between Comparative Examples 3-4 and the Examples that the functional layers prepared from the fabrics treated with the silver-based ZIF material or lysozyme alone have inferior antibacterial effects and antibacterial stabilities compared with the products obtained in the Examples. Therefore, the silver-based ZIF material and lysozyme can synergistically enhance the bactericidal ability of the functional layer, achieving a long-lasting bactericidal effect, good antibacterial effect, and odor elimination, further improving the air quality in the vehicle and providing a healthier and fresher riding environment for passengers.

[0066] Ordinary technicians in the art will realize that the examples here are to help readers understand the principles of the present invention, and it should be understood that the protection scope of the present invention is not limited to such specific statements and examples. Ordinary technicians in the art can make various other specific deformations and combinations that do not depart from the essence of the present invention based on these technical revelations disclosed in the present invention, and these deformations and combinations are still within the protection scope of the present invention.

Claims

1. An automotive interior lining material with bactericidal and odor-removing functions, comprising a surface layer, a functional layer, and a bottom layer arranged in sequence, characterized in that, The functional layer is obtained by treating the surface of the fabric with MOF-lysozyme material; The preparation method of the MOF-lysozyme material comprises the following steps: S1: dissolving silver nitrate hexahydrate and dimethylimidazole in a solvent, heating to react, cooling to room temperature after the reaction, separating crystals, washing the crystals and drying them to obtain a silver-based ZIF material; the molar ratio of the silver nitrate hexahydrate and dimethylimidazole is 1:5-10; S2: taking the silver-based ZIF material and dispersing it ultrasonically with a sterile solvent, adding 3-aminopropyltriethoxysilane to the dispersion, stirring the dispersion at room temperature, and washing and drying the dispersion after the reaction is completed for later use; the mass ratio of the silver-based ZIF material to 3-aminopropyltriethoxysilane is 1:0.01-0.05; S3: The product prepared in S2 is dispersed in a phosphate buffer solution, glutaraldehyde is added to react at room temperature, centrifuged and washed after the reaction, added to a lysozyme solution, gently shaken for reaction, the product is separated by centrifugation, washed and dried at low temperature to obtain a MOF-lysozyme material; the added mass of the glutaraldehyde accounts for 2-4% of the added mass of 3-aminopropyltriethoxysilane.

2. The material for automotive inner lining according to claim 1, characterized in that, The fabric is selected from one or more combinations of non-woven fabric, non-woven paper or cotton fiber.

3. The material for automotive interior lining according to claim 1, characterized in that, The heating reaction described in S1, wherein the heating temperature is 40-60°C and the reaction time is 12-24h.

4. The material for automotive interior lining according to claim 1, characterized in that, The lysozyme solution is a PBS buffer solution containing lysozyme, the pH of the buffer solution is 7.4, and the content of lysozyme is 1-10 mg / mL.

5. The material for automobile inner lining according to claim 1, characterized in that, The specific steps of the surface treatment include: The fabric is first washed with water to remove dust, then immersed in an ethanol solution for ultrasonic treatment to remove surface stains, and the pretreated fabric is obtained after being taken out; the MOF-lysozyme material is then applied to the fabric by dipping or spraying.

6. The material for automobile inner lining according to claim 5, characterized in that, The finishing is performed 1-4 times; in each finishing step, the mass of the MOF-lysozyme material finished on each square centimeter of the fabric is 0.25-5 g.

7. The preparation method of the material for automobile inner lining according to any one of claims 1-6, characterized in that, The following steps are involved: The surface layer, the functional layer and the bottom layer are arranged in sequence from top to bottom, the water-based polyurethane adhesive is evenly coated between the layers, and pressure curing is performed at an environment of 20-40°C for 12-24 hours to obtain a car lining material with sterilization and deodorization properties.

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