Preparation method of PP / PE fluorescent non-woven fabric
Patent Information
- Application Number
- CN202611413930.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-09-11
- Publication Date
- 2026-11-03
AI Technical Summary
传统无纺布材料在荧光染料的固色率和荧光效果方面存在局限性，导致发光强度较弱、荧光量子产率低且稳定性差，限制其在高端应用领域的发展。
PP/PE nonwoven fabric was modified by graft polymerization of glycidyl methacrylate (GMA) to introduce active sites on the surface of the nonwoven fabric, thereby enhancing its adsorption performance for Disperse Red 277 dye. The graft polymerization reaction was initiated by ultraviolet light to prepare PP/PE fluorescent nonwoven fabric with excellent fluorescence effect.
It improves the fluorescence fixation rate and stability of nonwoven fabrics, avoids dye aggregation, and achieves uniform fluorescence effect and good color fastness, making it suitable for traffic police uniforms, night-worker uniforms, and signage.
Smart Images
Figure CN123027734A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of functional nonwoven materials technology, specifically to a method for preparing PP / PE fluorescent nonwoven fabric. Background Technology
[0002] With increasing societal demands for safety and visibility, the application of fluorescent materials in various fields such as traffic safety, nighttime operations, and emergency signage is gaining growing attention. The high visibility and warning effect of fluorescent materials are of great significance in the field of safety protection. Nonwoven fabrics, as a widely used textile material, are an ideal choice for fluorescent material carriers due to their unique structure and properties. Polyethylene / polypropylene nonwoven fabric (PE / PP NWF) is a commercially available fiber product with a simple manufacturing process and excellent flexibility, breathability, thermal stability, mechanical properties, and chemical stability.
[0003] However, traditional nonwoven materials have certain limitations in terms of the fixation rate and fluorescence effect of fluorescent dyes, which restricts their development in high-end applications. The preparation process of traditional fluorescent fibers is mainly a physical process, such as melt spinning, solution spinning, electrospinning, and surface coating. The fluorescent agent and the polymer substrate are combined only through physical interaction. This directly leads to defects such as weak luminescence intensity, low fluorescence quantum yield, poor fluorescence stability, and easy fluorescence quenching in the prepared fibers.
[0004] To address these issues, researchers have attempted to improve the fluorescence properties of nonwoven fabrics through chemical modification. Glycidyl methacrylate (GMA), a commonly used grafting monomer, contains epoxy groups and highly reactive acrylate double bonds in its molecular structure, enabling it to be grafted onto polyolefins and improve material properties. Current research reports indicate that GMA has been grafted onto the surface of polypropylene nonwoven fabrics using ultraviolet irradiation. However, further development is needed to combine GMA grafting modification technology with fluorescent dyeing to prepare PP / PE fluorescent nonwoven fabrics with excellent fluorescence effects. Summary of the Invention
[0005] To address the technical problems of low fixation rate, poor fluorescence effect, and unsatisfactory fluorescence stability in existing fluorescent dyeing techniques for nonwoven fabrics, this invention provides a method for preparing PP / PE fluorescent nonwoven fabric. This method involves graft polymerization modification of PP / PE nonwoven fabric with GMA, introducing active sites on the nonwoven fabric surface to enhance its adsorption performance for Disperse Red 277 dye. This results in more uniform Disperse Red 277 adsorption, reducing the likelihood of agglomeration and fluorescence quenching, thereby obtaining a PP / PE fluorescent nonwoven fabric with excellent fluorescence effect and good color fastness.
[0006] A method for preparing PP / PE fluorescent nonwoven fabric includes the following steps: (1) Preparation of GMA emulsion: Deionized water, glycidyl methacrylate (GMA) and Tween 80 are mixed and magnetically stirred for 4-10 hours until completely emulsified and milky white to obtain GMA emulsion; (2) Pretreatment of PP / PE nonwoven fabric: PP / PE nonwoven fabric is placed in deionized water for ultrasonic cleaning, then soaked in anhydrous ethanol for 20-40 minutes, rinsed with deionized water 2-4 times, and finally dried at 40-60℃ for later use. (3) Grafting modification: Take the pretreated PP / PE nonwoven fabric and place it in the GMA emulsion prepared in step (1). Puff nitrogen gas for 10-20 min to remove oxygen. Use a mercury lamp to irradiate at room temperature for 2-4 h to carry out the grafting polymerization reaction. After taking out the sample, wash it with anhydrous ethanol and water 2-4 times, and then place it in a Soxhlet extractor and reflux it with acetone for 4-10 h to obtain GMA-g-PP / PE nonwoven fabric. (4) Fluorescent dyeing: The GMA-g-PP / PE nonwoven fabric prepared in step (3) is placed in a Disperse Red 277 dyeing solution with a dye mass fraction of 0.5%~5% and a dyeing bath ratio of 1:15~1:25. It is dyed in a water bath at 60~100℃ for 1~3h. After dyeing, it is rinsed with deionized water and dried in a vacuum drying oven at 40~60℃ for 4~6h to obtain PP / PE fluorescent nonwoven fabric.
[0007] Preferably, in step (1), the volume ratio of deionized water and glycidyl methacrylate is 20mL:0.2mL to 20mL:2mL, and the ratio of deionized water and Tween 80 is 20mL:0.1g to 20mL:0.3g.
[0008] Preferably, the mass-to-volume ratio of the PP / PE nonwoven fabric to the GMA emulsion in step (3) is 0.2g:20mL to 0.5g:50mL.
[0009] Preferably, in step (4), the mass fraction of the dye in the Disperse Red 277 dyeing solution is 2%, the dyeing bath ratio is 1:20, the dyeing temperature is 70~80℃, and the dyeing time is 1~2h.
[0010] 1. This invention uses GMA to graft polymerize and modify PP / PE nonwoven fabric. The graft polymerization reaction is initiated by ultraviolet light, and active sites such as epoxy groups are introduced on the surface of the nonwoven fabric, which significantly enhances the adsorption performance and fixation rate of the nonwoven fabric for Disperse Red 277 dye.
[0011] 2. This invention uses GMA grafting modification to uniformly disperse Disperse Red 277 dye on the surface of nonwoven fabric, avoiding fluorescence quenching caused by dye aggregation. The resulting fluorescent nonwoven fabric is pink under natural light and orange-red under ultraviolet light, with a maximum fluorescence emission wavelength of 590nm. The fluorescence effect is uniform and stable.
[0012] 3. The PP / PE fluorescent nonwoven fabric prepared by this invention has good air permeability and luminescence stability, and can be widely used in traffic police uniforms, night-worker uniforms, and signage.
[0013] 4. This invention uses a mercury lamp room temperature irradiation grafting method, which has mild reaction conditions, does not require high temperature and high pressure, has a simple production process, low production cost, and is suitable for industrial production. Attached Figure Description
[0014] Figure 1 Scanning electron microscope (SEM) images of various samples obtained in the embodiments of the present invention; Among them, (a) is a SEM image of PP / PE nonwoven fabric; (b) is a SEM image of GMA-g-PP / PE nonwoven fabric; (c) is a SEM image of GMA-g-PP / PE fluorescent nonwoven fabric dyed with Disperse Red 277; and (d) is a SEM image of PP / PE nonwoven fabric dyed with Disperse Red 277 (without GMA grafting).
[0015] Figure 2 The following are the Fourier Transform Infrared (FTIR) spectra of various samples prepared in the embodiments of the present invention and Disperse Red 277. Among them, (a) is the infrared spectrum of GMA; (b) is the infrared spectrum of Disperse Red 277; (c) is the infrared spectrum of PP / PE nonwoven fabric; (d) is the infrared spectrum of GMA-g-PP / PE nonwoven fabric; (e) is the infrared spectrum of GMA-g-PP / PE fluorescent nonwoven fabric dyed with Disperse Red 277; and (f) is the infrared spectrum of PP / PE nonwoven fabric dyed with Disperse Red 277 (without GMA grafting).
[0016] Figure 3 Fluorescence spectrum of GMA-g-PP / PE fluorescent nonwoven fabric stained with Disperse Red 277. Detailed Implementation
[0017] The specific embodiments of the present invention will be further described in detail below with reference to examples. These examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Example 1
[0018] (1) Preparation of GMA emulsion: Weigh 20 mL of deionized water, 1 mL of glycidyl methacrylate (GMA) and 0.2 g of Tween 80 into a 50 mL beaker and stir magnetically for 8 h until it turns completely milky white, thus obtaining GMA emulsion.
[0019] (2) Pretreatment of PP / PE nonwoven fabric: The PP / PE nonwoven fabric is placed in deionized water for ultrasonic cleaning, then soaked in anhydrous ethanol for 30 minutes, rinsed with deionized water 3 times, and finally dried at 50°C for later use.
[0020] (3) Grafting modification: Take 0.2g of washed PP / PE nonwoven fabric and add 20mL of GMA emulsion. Puff nitrogen gas for 15min to remove oxygen. Use a mercury lamp to irradiate at room temperature for 3h to carry out grafting polymerization reaction. Take out the sample, wash it three times with anhydrous ethanol and water, and then place the sample in a Soxhlet extractor and wash it with acetone for 8h to obtain GMA-g-PP / PE nonwoven fabric.
[0021] (4) Fluorescent dyeing: The GMA-g-PP / PE nonwoven fabric prepared in step (3) was placed in a Disperse Red 277 dyeing solution with a dye mass fraction of 2% and a dyeing bath ratio of 1:20, and dyed in a water bath at 60℃ for 1 hour. After dyeing, the fluorescently dyed modified nonwoven fabric was rinsed with deionized water and dried in a vacuum drying oven at 50℃ for 5 hours to obtain PP / PE fluorescent nonwoven fabric. Example 2
[0022] (1) Preparation of GMA emulsion: Weigh 25 mL of deionized water, 1.25 mL of glycidyl methacrylate (GMA) and 0.25 g of Tween 80 into a 50 mL beaker and stir magnetically for 8 h until it turns completely milky white, thus obtaining GMA emulsion.
[0023] (2) Pretreatment of PP / PE nonwoven fabric: Same as step (2) in Example 1.
[0024] (3) Grafting modification: Take 0.25g of washed PP / PE nonwoven fabric and add 25mL of GMA emulsion. Puff nitrogen gas for 15min to remove oxygen. Use a mercury lamp to irradiate at room temperature for 2h to carry out grafting polymerization reaction. Take out the sample, wash it three times with anhydrous ethanol and water, and then place the sample in a Soxhlet extractor and wash it with acetone for 8h to obtain GMA-g-PP / PE nonwoven fabric.
[0025] (4) Fluorescent dyeing: The GMA-g-PP / PE nonwoven fabric prepared in step (3) was placed in a Disperse Red 277 dyeing solution with a dye mass fraction of 2% and a dyeing bath ratio of 1:20, and dyed in a water bath at 70℃ for 2 hours. After dyeing, the fluorescently dyed modified nonwoven fabric was rinsed with deionized water and dried in a vacuum drying oven at 50℃ for 5 hours to obtain PP / PE fluorescent nonwoven fabric. Example 3
[0026] (1) Preparation of GMA emulsion: Weigh 50 mL of deionized water, 2.5 mL of glycidyl methacrylate (GMA) and 0.5 g of Tween 80 into a 100 mL beaker and stir magnetically for 8 h until it turns completely milky white, thus obtaining GMA emulsion.
[0027] (2) Pretreatment of PP / PE nonwoven fabric: Same as step (2) in Example 1.
[0028] (3) Grafting modification: Take 0.5g of washed PP / PE nonwoven fabric and add 50mL of GMA emulsion. Puff nitrogen gas for 15min to remove oxygen. Use a mercury lamp to irradiate at room temperature for 3h to carry out grafting polymerization reaction. Take out the sample, wash it three times with anhydrous ethanol and water, and then place the sample in a Soxhlet extractor and wash it with acetone for 8h to obtain GMA-g-PP / PE nonwoven fabric.
[0029] (4) Fluorescent dyeing: The GMA-g-PP / PE nonwoven fabric prepared in step (3) was placed in a Disperse Red 277 dyeing solution with a dye mass fraction of 2% and a dyeing bath ratio of 1:20, and dyed in a water bath at 80℃ for 1 hour. After dyeing, the fluorescently dyed modified nonwoven fabric was rinsed with deionized water and dried in a vacuum drying oven at 50℃ for 5 hours to obtain PP / PE fluorescent nonwoven fabric.
[0030] The following performance tests were performed on the PP / PE fluorescent nonwoven fabrics prepared in Examples 1 to 3 and the samples prepared in the comparative examples.
[0031] The morphology of the samples was characterized using scanning electron microscopy (SEM). The results showed that the surface of the ungrafted PP / PE nonwoven fabric fibers was smooth; after GMA grafting modification, the filaments of the PP / PE nonwoven fabric were thicker, and GMA homopolymers appeared on the surface of the material. The homopolymers were relatively rounded and had no obvious edges. The filaments of the GMA-g-PP / PE fluorescent nonwoven fabric stained with Disperse Red 277 were further thickened, and Disperse Red 277 was uniformly dispersed on its surface without agglomeration. However, after dyeing, the PP / PE nonwoven fabric without GMA grafting showed aggregated particles of Disperse Red 277 on its surface. These particles had distinct edges and were attached to the surface of the PP / PE nonwoven fabric. Due to the agglomeration, the fluorescence was quenched, and no fluorescence was produced under ultraviolet light.
[0032] The samples were characterized using Fourier transform infrared spectroscopy (FTIR). The results showed that the GMA-grafted PP / PE nonwoven fabric exhibited a strong absorption peak of the carbonyl stretching vibration of GMA near 1725 cm⁻¹, proving that GMA was successfully grafted onto the PP / PE nonwoven fabric.
[0033] The fluorescence emission spectrum of the dyed nonwoven fabric was tested using a fluorescence spectrometer. The results showed that the maximum emission wavelength of the GMA-g-PP / PE fluorescent nonwoven fabric dyed with Disperse Red 277 was 590 nm, and the maximum excitation wavelength was 467 nm. The dyed nonwoven fabric exhibited a pinkish-red fluorescence under natural light and an orange-red fluorescence under ultraviolet light.
[0034] Under conditions of 2% dye by mass and a dyeing bath ratio of 1:20, dyeing was carried out at temperatures of 60℃, 70℃, 80℃, 90℃, and 100℃ for 1–3 hours, and the fluorescence intensity was tested. The results showed that the fluorescence intensity gradually increased with increasing dyeing temperature, reaching a peak at 80℃. Further increasing the temperature caused dye aggregation on the nonwoven fabric, resulting in fluorescence quenching and a decrease in fluorescence intensity. Therefore, the optimal dyeing temperature is 70–80℃.
[0035] Under dyeing conditions of 80℃ and a dyeing bath ratio of 1:20, dyeing was performed using dye concentrations of 0.5%, 1%, 2%, 3%, 4%, and 5% by mass, and the fluorescence intensity was tested. The results showed that the dyeing effect and fluorescence intensity were optimal when the dye concentration was 2% by mass; excessively high dye concentrations led to dye aggregation on the nonwoven fabric, resulting in a decrease in fluorescence intensity.
[0036] The results showed that the fluorescence intensity gradually increased with prolonged staining time, but excessively long staining time led to dye aggregation, fluorescence quenching, and a decrease in fluorescence intensity. The optimal staining time was 1–2 hours.
[0037] The method for preparing PP / PE fluorescent nonwoven fabric provided by this invention is simple and low in cost. The resulting fluorescent nonwoven fabric has uniform fluorescence effect, stable luminescence, and good air permeability. It can be widely used in safety protection fields such as traffic police uniforms, night-worker clothing, and signage, and has good industrial application prospects and market economic value.
Claims
1. A method for preparing PP / PE fluorescent nonwoven fabric, characterized in that, Includes the following steps: (1) Preparation of GMA emulsion: Deionized water, glycidyl methacrylate and Tween 80 were mixed and stirred until completely emulsified to obtain GMA emulsion; (2) Pretreatment of PP / PE nonwoven fabric: Clean the PP / PE nonwoven fabric, then soak it in anhydrous ethanol, rinse it with deionized water, and dry it for later use. (3) Grafting modification: The PP / PE nonwoven fabric after the pretreatment in step (2) is placed in the GMA emulsion prepared in step (1), nitrogen is introduced to remove oxygen, and the grafting polymerization reaction is carried out by mercury lamp irradiation at room temperature. After the reaction is completed, the sample is taken out, washed, and then placed in a Soxhlet extractor for reflux washing with acetone to obtain GMA-g-PP / PE nonwoven fabric. (4) Fluorescent dyeing: The GMA-g-PP / PE nonwoven fabric prepared in step (3) is placed in the Disperse Red 277 dyeing solution for water bath dyeing. After dyeing, it is rinsed with deionized water and dried to obtain PP / PE fluorescent nonwoven fabric.
2. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The volume ratio of deionized water to glycidyl methacrylate in step (1) is 20mL:0.2mL to 20mL:2mL; the ratio of deionized water to Tween 80 is 20mL:0.1g to 20mL:0.3g.
3. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The stirring time in step (1) is 4 to 10 hours, preferably 8 hours.
4. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The cleaning in step (2) is ultrasonic cleaning, the immersion time in anhydrous ethanol is 20~40min, preferably 30min; the drying temperature is 40~60℃, preferably 50℃.
5. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The mass-volume ratio of PP / PE nonwoven fabric to GMA emulsion in step (3) is 0.2g:10mL~0.2g:50mL.
6. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The nitrogen gas introduction time in step (3) is 10-20 min, preferably 15 min; the mercury lamp room temperature irradiation time is 1-4 h, preferably 2 h; and the acetone reflux cleaning time is 4-10 h, preferably 8 h.
7. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The mass fraction of the dye in the Disperse Red 277 dye solution in step (4) is 0.5% to 5%, preferably 2%.
8. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The dyeing bath ratio in step (4) is 1:15 to 1:25, preferably 1:
20.
9. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The water bath staining temperature in step (4) is 60~100℃, preferably 70~80℃; the staining time is 1~3h.
10. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The drying temperature in step (4) is 40~60℃, preferably 50℃, and the drying time is 4~6h, preferably 5h.
11. The method for preparing PP / PE fluorescent nonwoven fabric according to claim 1, characterized in that, The PP / PE fluorescent nonwoven fabric described in step (4) is pink under natural light and orange-red under ultraviolet light, with a maximum fluorescence emission wavelength of 590nm.