Automobile lining material with sterilization and peculiar smell removal functions and preparation method thereof

Abstract

The invention provides an automobile lining material with sterilization and peculiar smell removal functions and a preparation method of the automobile lining material. The material for the automobile lining comprises a surface layer, a functional layer and a bottom layer which are sequentially arranged, wherein the functional layer is obtained by performing surface treatment on a fabric through an MOF-lysozyme material. Silver-based ZIF is formed by silver ions and dimethylimidazole, the characteristics of large specific surface area, adjustable aperture and high crystallinity of a traditional MOF material are reserved, and the silver-based ZIF has a certain antibacterial effect due to the silver ions, so that the antibacterial characteristic of a functional layer is enhanced; as the silver-based ZIF has the characteristics of large specific surface area and large aperture, more lysozyme can be covalently grafted, and the silver-based ZIF still has excellent broad-spectrum antibacterial performance; the silver-based ZIF material and the lysozyme synergistically enhance the bactericidal ability of the functional layer, so that the effects of long-acting sterilization, good antibacterial effect and peculiar smell elimination are achieved, the air quality in a vehicle is further improved, and a healthier and fresher riding environment is provided 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, the addition of antimicrobial agents or the application of nano-coatings will affect the physical properties and durability of the materials to a certain extent. For example, some antimicrobial agents may gradually fail in long-term use, resulting in the attenuation of antimicrobial performance; and some nano-coatings may peel off or age under repeated friction, ultraviolet radiation or temperature changes, thereby reducing the overall antimicrobial effect of the interior panels. Secondly, the production cost of sterile materials is relatively high, and some high-end technologies have not yet been applied on a large scale at low cost, which requires automakers to make a trade-off between performance and cost when selecting materials. In addition, some antimicrobial additives may have certain safety hazards in long-term contact with the human body or in high-temperature environments, and their migration and toxicity issues also need to be given enough attention. Finally, environmental regulations are becoming increasingly stringent, and the environmental performance and sustainability of some traditional antimicrobial agents are questioned, which has prompted the industry to continuously seek new green and environmentally friendly antimicrobial materials during the research and development process.

[0006] In general, as people's requirements for the health of the in-car environment continue to increase, sterile interior materials, as an emerging technology, have broad application prospects in car ceilings and other interior parts. Summary of the invention

[0007] Purpose of the invention: The purpose of the present invention is to provide a car lining material with sterilization and deodorization function and a preparation method thereof. The car lining material has strong sterilization ability, long-term sterilization, good antibacterial effect and the function of eliminating odor.

[0008] The technical solution of the present invention: In a first aspect, the present invention provides a car lining material with sterilization and deodorization properties, comprising a surface layer, a functional layer and a bottom layer arranged in sequence, wherein the functional layer is obtained by surface treating the fabric with a MOF-lysozyme material.

[0009] In some embodiments, the fabric may be selected from one or more combinations of non-woven fabric, non-woven paper or cotton fiber.

[0010] In some embodiments, the method for preparing 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; S2: taking the silver-based ZIF material and dispersing it ultrasonically with a sterile solvent, adding 3-aminopropyltriethoxysilane to the dispersion, stirring and reacting at room temperature, and washing and drying after the reaction is completed for later use; 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.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] In some embodiments, 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.

[0017] 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.

[0018] 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.

[0019] In some embodiments, the finishing times are 1-4 times; in each finishing step, the weight of MOF-lysozyme material finished on each square centimeter of fabric is 0.25-5 g.

[0020] In a second aspect, the present invention provides a method for preparing the automobile lining material having the function of sterilization and deodorization, which specifically comprises the following steps: 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.

[0021] In some embodiments, the coating method may be one or more of blade coating, spray coating or roller coating, which may be selected according to the type and thickness of the fabric.

[0022] Beneficial effects: 1. 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 because of the silver ions, the silver-based ZIF has a certain antibacterial effect and enhances the antibacterial properties of the functional layer.

[0023] 2. Due to the large specific surface area and large pore size of silver-based ZIF, more lysozyme can be covalently grafted and still have excellent broad-spectrum antibacterial properties.

[0024] 3. Silver-based ZIF materials and lysozyme synergistically enhance the bactericidal ability of the functional layer, playing a role in long-term bactericidal, good antibacterial effect, and eliminating odor, further improving the air quality in the car and providing passengers with a healthier and fresher riding environment. DETAILED DESCRIPTION

[0025] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0026] Unless otherwise specified, the chemical reagents used in the present invention are all commercially available analytically pure.

[0027] The lysozyme solution used in the examples was a PBS (pH 7.4) solution with a lysozyme concentration of 1 mg / mL.

[0028] The water-based polyurethane adhesive used in the examples was purchased from Anhui Zhongen Chemical Co., Ltd., with the brand name PU1179.

[0029] The PET used in the examples was purchased from DuPont, USA, with the brand number RE5264.

[0030] The PP used in the examples was purchased from Wanhua Chemical, with the brand name EP548R.

[0031] Preparation Example of MOF-lysozyme Material 1 S1: Take 0.1 mol of silver nitrate hexahydrate and 1 mol of dimethylimidazole and dissolve them in 100 mL of methanol solvent respectively, stir them evenly to obtain dimethylimidazole solution and silver nitrate hexahydrate solution respectively; slowly add the dimethylimidazole solution dropwise to the silver nitrate hexahydrate solution, heat at 40°C to react for 20 hours, cool to room temperature after the reaction is completed, centrifuge the reaction solution at 5000 rpm for 10 minutes to collect crystals, wash the crystals and dry them to obtain the silver-based ZIF material; S2: Weigh 50 mg of the above silver-based ZIF material and use 50 ml of sterile solvent (sterile ethanol / water mixed solution with a volume ratio of 1:2) for ultrasonic dispersion for 10 minutes, then add 0.5 mg of 3-aminopropyltriethoxysilane to the dispersion, stir and react at room temperature for 2 hours, wash and dry after the reaction is completed, and then set aside; S3: Take 10 mg of the product prepared by 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 hours, centrifuge and wash after the reaction, add it to 20 ml of lysozyme solution, gently shake and react for 6 hours, separate the product by centrifugation, wash and dry at low temperature to obtain MOF-lysozyme material 1.

[0032] Preparation Example of MOF-lysozyme Material 2 The preparation example of MOF-lysozyme material 2 is basically the same as that of MOF-lysozyme material 1, except that the molar amounts of silver nitrate hexahydrate and dimethylimidazole added are 0.1 mol and 0.5 mol, respectively.

[0033] Preparation Example of MOF-lysozyme Material 3 The preparation example is basically the same as that of MOF-lysozyme material 1, except that the molar amounts of silver nitrate hexahydrate and dimethylimidazole added are 0.1 mol and 1.5 mol, respectively, to prepare MOF-lysozyme material 3.

[0034] Preparation Example of MOF-lysozyme Material 4 S1: Take 0.1 mol of silver nitrate hexahydrate and 1 mol of dimethylimidazole and dissolve them in 100 mL of methanol solvent respectively, stir them evenly to obtain dimethylimidazole solution and silver nitrate hexahydrate solution respectively; slowly add the dimethylimidazole solution dropwise to the silver nitrate hexahydrate solution, heat at 40°C to react for 20 hours, cool to room temperature after the reaction is completed, centrifuge the reaction solution at 5000 rpm for 10 minutes to collect crystals, wash the crystals and dry them to obtain the silver-based ZIF material; S2: Take 10 mg of the silver-based ZIF material prepared by S1 and add it to 20 ml of lysozyme solution. Gently shake the reaction for 6 hours. Separate the product by centrifugation, wash and dry at low temperature to obtain MOF-lysozyme material 4.

[0035] Preparation example of silver-based ZIF materials Take 0.1 mol of silver nitrate hexahydrate and 1 mol of dimethylimidazole and dissolve them in 100 mL of methanol solvent respectively, stir evenly to obtain dimethylimidazole solution and silver nitrate hexahydrate solution respectively; slowly add the dimethylimidazole solution dropwise to the silver nitrate hexahydrate solution, heat to 40°C to react for 20 hours, cool to room temperature after the reaction, centrifuge the reaction solution at 5000 rpm for 10 minutes to collect crystals, wash the crystals and dry them to obtain the silver-based ZIF material.

[0036] The MOF-lysozyme material 1, MOF-lysozyme material 2, MOF-lysozyme material 3, MOF-lysozyme material 4, silver-based ZIF material and lysozyme were used to surface treat the non-woven fabric respectively, and the treatment steps were as follows: The fabric was first washed with water to remove dust, then immersed in an ethanol solution for ultrasonic treatment for 30 minutes to remove surface stains, and then taken out and dried to obtain the pretreated fabric; the pretreated fabric was cut into 2cm×2cm square pieces, and placed in 200ml PBS buffer containing 10g MOF-lysozyme material 1, MOF-lysozyme material 2, MOF-lysozyme material 3, MOF-lysozyme material 4, silver-based ZIF material and lysozyme, and soaked at room temperature for 2h; the fabric was then washed with deionized water and dried at 40℃, which was recorded as one finishing; the finishing of the fabric was repeated 4 times to complete the finishing, and functional layers 1-6 were obtained in turn.

[0037] Examples and Comparative Examples 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 40°C for 24 hours to obtain automotive lining materials. The specific materials are shown in Table 1.

[0038] Table 1 Performance Test: 1. The antibacterial performance was tested in accordance with QB / T 2591-2003 "Test methods and antibacterial effects of antibacterial plastics". The test bacteria were Escherichia coli (ATCC25922) and Staphylococcus aureus (ATCC6528).

[0039] 2. Place the test sample in a beaker filled with 1000 mL of distilled water, then place the beaker in a 40°C water bath, stir continuously with a stirrer, change the water every 12 hours, measure the antibacterial efficiency of the sample against Escherichia coli and Staphylococcus aureus after immersion for 240 hours and 720 hours, and calculate the antibacterial efficiency retention rate at 720 hours.

[0040] The results are shown in Table 2.

[0041] Table 2 It can be seen from the above embodiments and comparative examples that the automobile lining material provided by the present invention has excellent antibacterial effect and antibacterial stability, and has a high initial antibacterial efficiency of up to 99.9%. Moreover, after being treated in a water bath and stirred for 720 hours, the antibacterial efficiency retention rate reaches more than 96-97%. This shows that the automobile lining material provided by the present invention can effectively improve the antibacterial efficiency and antibacterial stability by preparing a silver-based MOF-lysozyme material, and can be used to improve the antibacterial effect of the automobile lining material, so that the material has efficient and lasting antibacterial properties.

[0042] Specifically, by comparing Comparative Example 1 with the embodiment, it can be seen that the surface area of ​​the silver-based ZIF material prepared in Comparative Example 1 is smaller, the amount of covalently grafted lysozyme is reduced, and the initial antibacterial efficiency value is reduced; during the preparation of MOF-lysozyme material 4 of Comparative Example 2, the surface treatment with 3-aminopropyltriethoxysilane and glutaraldehyde was not performed, and the grafted lysozyme could not be well fixed on the surface of the silver-based ZIF material. Although the initial antibacterial efficiency can reach 99%, after multiple oscillations and washings, the antibacterial efficiency of the material decays to about 77%, and the antibacterial stability is poor.

[0043] It can be seen from the comparison between Comparative Examples 3-4 and the Examples that the functional layer prepared by using only the silver-based ZIF material or the fabric treated with lysozyme has inferior antibacterial effect and antibacterial stability as the product obtained in the Examples. Therefore, the silver-based ZIF material and lysozyme can synergistically enhance the bactericidal ability of the functional layer, play a role in long-term bactericidal, good antibacterial effect, and elimination of odor, further improving the air quality in the car and providing passengers with a healthier and fresher riding environment.

[0044] Those skilled in the art will appreciate that the embodiments herein are intended to help readers understand the principles of the present invention, and should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific variations and combinations that do not deviate from the essence of the present invention based on the technical revelations disclosed by the present invention, and these variations and combinations are still within the protection scope of the present invention.

Claims

1. A car lining material with sterilization and deodorization function, 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; S2: taking the silver-based ZIF material and dispersing it ultrasonically with a sterile solvent, adding 3-aminopropyltriethoxysilane to the dispersion, stirring and reacting at room temperature, and washing and drying after the reaction is completed for later use; 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.

2. The material for automobile 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 automobile lining according to claim 1, characterized in that: The added molar ratio of the silver nitrate hexahydrate to dimethylimidazole is 1:5-10.

4. The automotive lining material 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.

5. The automobile lining material according to claim 1, characterized in that: The added mass ratio of the silver-based ZIF material to 3-aminopropyltriethoxysilane is 1:0.01-0.

05.

6. The automobile lining material according to claim 1, characterized in that: The added mass of the glutaraldehyde accounts for 2-4% of the added mass of 3-aminopropyltriethoxysilane.

7. The automobile lining material according to claim 1, characterized in that: The lysozyme solution is a PBS buffer solution containing lysozyme, wherein the pH of the buffer solution is 7.4 and the content of lysozyme is 1-10 mg / mL.

8. The automobile lining material 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.

9. The automobile lining material according to claim 8, 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.

10. The method for preparing the automobile inner lining material according to any one of claims 1 to 9, 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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