阅读说明：本技术 一种夜光储能长效光动力抗菌型面料及其制备方法 (Noctilucent energy-storage long-acting photodynamic antibacterial fabric and preparation method thereof ) 是由 王清清 张嘉雯 张欣欣 刘兴谱 魏取福 于 2021-08-09 设计创作，主要内容包括：本发明公开了一种夜光储能长效光动力抗菌型面料,该功能面料表面先后涂覆夜光涂层及光敏剂涂层得到。夜光粉作为蓄太阳能的材料,通过刮涂的方式将其涂覆于织物上,吸收和储存日光中的紫外光和可见光,切断光源后将储存的能量以荧光的形式释放出来,发出的荧光被光敏剂吸收,在光照下增强抗菌效果,在暗室有氧环境中持续产生活性氧物质,达到协同增效抗菌的目的。非织造布的上下层通过图案压花结合,有良好透气性和吸湿性。本发明由于基材为普通的非织造物,因而可以将其应用在人们日常的用品上,特别是户外用品中如帐篷等,实现暗室抗菌效果,同时由于色彩的可更换可以实现户外用品的醒目性。(The invention discloses a noctilucent energy-storage long-acting photodynamic antibacterial fabric, which is obtained by coating a noctilucent coating and a photosensitizer coating on the surface of a functional fabric in sequence. The noctilucent powder is used as a solar energy storage material, is coated on a fabric in a blade coating mode, absorbs and stores ultraviolet light and visible light in sunlight, releases the stored energy in a fluorescent form after a light source is cut off, and the emitted fluorescent light is absorbed by a photosensitizer, so that the antibacterial effect is enhanced under the illumination, active oxygen substances are continuously generated in an aerobic environment in a dark room, and the purposes of synergy and antibiosis are achieved. The upper and lower layers of the non-woven fabric are combined through pattern embossing, and the non-woven fabric has good air permeability and moisture absorption. The invention can be applied to daily articles of people, particularly outdoor articles such as tents and the like, because the base material is a common non-woven fabric, the invention realizes the antibacterial effect of a darkroom, and can realize the eye-catching performance of the outdoor articles because of the color replacement.)

1. A noctilucent energy-storage long-acting photodynamic antibacterial fabric is characterized by comprising a woven cotton cloth or non-woven cloth substrate, wherein the surface of the substrate is coated with a noctilucent powder/photosensitizer coating to form a noctilucent antibacterial substrate, the noctilucent powder is rare earth strontium aluminate noctilucent powder, and the photosensitizer is rose bengal photosensitizer;

the woven cotton cloth base material is a fabric which is formed by weaving cotton threads by using natural cotton fibers as raw materials through a weaving technology; the non-woven fabric base material takes polypropylene as a raw material, fibers formed by high-temperature melt spinning are stretched, refined and sprayed under the clamping and drawing of high-speed hot air flow, and a reticular structure fiber aggregate is formed by utilizing self-adhesion of waste heat.

2. A luminous energy-storing long-acting photodynamic anti-bacterial fabric as claimed in claim 1, wherein the diameters of the microporous structure of the woven cotton cloth substrate and the fibers of the non-woven cloth substrate are 2-5 μm, and the fibers are arranged disorderly and have a three-dimensional microporous structure.

3. A preparation method of a noctilucent energy-storing long-acting photodynamic antibacterial fabric according to any one of claims 1-2, which comprises weaving a woven cotton cloth or non-woven cloth substrate, blending a noctilucent powder/photosensitizer coating and forming a sandwich structure, and comprises the following steps:

(1) weaving of woven cotton cloth or non-woven cloth substrate: manufacturing cotton cloth or non-woven cloth by a weaving/melt-blowing method;

(2) and (3) blending the noctilucent powder/photosensitizer coating:

(2.1) preliminary treatment of the coating: cutting cotton cloth or non-woven fabric into square cloth of 20 cm × 15 cm, wherein 20 cm is warp yarn direction, 15 cm is weft yarn direction, and the thickness of the fabric is 0.16 m; the content of the noctilucent powder is 75 percent; adding 15 g of noctilucent powder and 5 g of transparent nylon mucilage into a beaker, adding 4 mL of deionized water by using a liquid transfer gun, and stirring by using a glass rod until the mixture is uniformly observed by naked eyes;

(2.2) coating the mixture treated in the step (2.1) on a woven cotton cloth or non-woven cloth base material by screen printing, and drying in an oven at 130 ℃ for 3 min;

(2.3) adding 6 g of PVA-SbQ into a beaker, measuring 60 mL of deionized water by using a measuring cylinder, stirring by using a glass rod until the PVA-SbQ is fully dissolved in the water, weighing 0.06 g of rose bengal, adding the rose bengal into the solution, uniformly stirring, standing and precipitating for 5 min, adding the rose bengal solution uniformly dispersed on the upper layer into a container, soaking the woven cotton cloth or non-woven fabric base material treated in the step (2.2) for 10 min, taking out, attaching one surface without the noctilucent coating to aluminum foil paper, putting the aluminum foil paper into a 60 ℃ oven, drying until the surface of the noctilucent powder coating is dried, taking out, and drying the whole fabric;

(2.4) illuminating the fabric base material coated with the coating with an ultraviolet lamp for 2 hours to crosslink and reinforce the coating and the fabric, so as to obtain a treated noctilucent antibacterial base material;

(3) forming a sandwich structure: and (3) sewing the woven cotton cloth or non-woven cloth substrate obtained in the step (2) and the other woven cotton cloth or non-woven cloth substrate which is not treated by a knurling process by using a needle and thread pattern mode to enable the two substrates to be sewn together, wherein one side containing the noctilucent layer is arranged between the two substrates to form a sandwich structure.

Technical Field

The invention belongs to the field of noctilucent antibacterial fabrics, and particularly relates to a noctilucent energy-storage long-acting photodynamic antibacterial fabric and a preparation method thereof.

Background

It is well known that microorganisms, particularly bacteria and molds, are highly liable to propagate on various fabrics, and among them, various outdoor articles are often used in the field, and are very liable to propagate bacteria, and the infection of microorganisms may cause various adverse effects such as malodor, mold, deterioration, etc., in addition to diseases to the human body. With the further improvement of living standard and health consciousness of people, more and more young people and families choose to do activities in the field when playing on a trip. People have a sharp increase in the demand for various outdoor sports products, and the production of outdoor articles such as tents with antibacterial function is one of effective ways to protect people from or reduce bacterial damage while pursuing the beauty and comfort of the products, so that tents with antibacterial function are more and more favored by people, and have great development potential and application market.

In the market, a method of directly coating and reinforcing and finishing an antibacterial agent on the surface of a fabric is often adopted, so that the fabric has an antibacterial effect, the antibacterial agent is various, and the antibacterial material is usually metal ions, antibiotics and the like. However, metal ions have certain toxic and side effects on human bodies, bacteria can easily generate drug resistance when a large amount of antibiotics are used, and photodynamic antibiosis can well solve the problems. However, a necessary condition of the photosensitive antibacterial agent is light irradiation, and after the light source is cut off, the photosensitive agent cannot generate Reactive Oxygen Species (ROS), so that the antibacterial performance of the light-driven antibacterial material is poor, the material cannot play a role in a dark room, and the application scene is limited.

Disclosure of Invention

The technical problem is as follows: aiming at the defects of the prior art, the invention provides a noctilucent energy-storage long-acting photodynamic antibacterial fabric and a preparation method thereof, and solves the technical problems that microorganisms are easy to breed on the surface of the fabric and the common fabric loaded with a photosensitive antibacterial agent is difficult to generate an antibacterial effect in a dark room environment.

The technical scheme is as follows:

the invention provides a noctilucent energy-storage long-acting photodynamic antibacterial fabric which is characterized by comprising woven cotton cloth or non-woven cloth base material, wherein a noctilucent powder/photosensitizer coating is coated on the surface of the base material to form a noctilucent antibacterial base material, the noctilucent powder is rare earth strontium aluminate noctilucent powder, and the photosensitizer is rose bengal photosensitizer.

The woven cotton cloth base material is a fabric which is formed by weaving cotton threads by using natural cotton fibers as raw materials through a weaving technology; the non-woven fabric base material takes polypropylene as a raw material, fibers formed by high-temperature melt spinning are stretched, refined and sprayed under the clamping and drawing of high-speed hot air flow, and a reticular structure fiber aggregate is formed by utilizing self-adhesion of waste heat.

Wherein the diameter of the micropore structure of the woven cotton cloth base material and the fiber diameter of the non-woven cloth base material are 2-5 mu m, the arrangement is disordered, and the three-dimensional micropore structure is formed.

The invention also provides a preparation method of the noctilucent energy-storage long-acting photodynamic antibacterial fabric, which comprises the steps of weaving woven cotton cloth or non-woven cloth base material, blending noctilucent powder/photosensitizer coating and forming an interlayer structure, and the preparation method comprises the following specific steps:

(1) weaving of woven cotton cloth or non-woven cloth substrate: manufacturing cotton cloth or non-woven cloth by a weaving/melt-blowing method;

(2) and (3) blending the noctilucent powder/photosensitizer coating:

(2.1) preliminary treatment of the coating: cutting cotton cloth or non-woven fabric into square cloth of 20 cm × 15 cm, wherein 20 cm is warp yarn direction, 15 cm is weft yarn direction, and the thickness of the fabric is 0.16 m; the content of the noctilucent powder is 75 percent; adding 15 g of noctilucent powder and 5 g of transparent nylon mucilage into a beaker, adding 4 mL of deionized water by using a liquid transfer gun, and stirring by using a glass rod until the mixture is uniformly observed by naked eyes;

(2.2) coating the mixture treated in the step (2.1) on a woven cotton cloth or non-woven cloth base material by screen printing, and drying in an oven at 130 ℃ for 3 min;

(2.3) adding 6 g of PVA-SbQ into a beaker, measuring 60 mL of deionized water by using a measuring cylinder, stirring by using a glass rod until the PVA-SbQ is fully dissolved in the water, weighing 0.06 g of rose bengal, adding the rose bengal into the solution, uniformly stirring, standing and precipitating for 5 min, adding the rose bengal solution uniformly dispersed on the upper layer into a container, soaking the woven cotton cloth or non-woven fabric base material treated in the step (2.2) for 10 min, taking out, attaching one surface without the noctilucent coating to aluminum foil paper, putting the aluminum foil paper into a 60 ℃ oven, drying until the surface of the noctilucent powder coating is dried, taking out, and drying the whole fabric;

(2.4) illuminating the fabric base material coated with the coating with an ultraviolet lamp for 2 hours to crosslink and reinforce the coating and the fabric, so as to obtain a treated noctilucent antibacterial base material;

(3) forming a sandwich structure: and (3) sewing the woven cotton cloth or non-woven cloth substrate obtained in the step (2) and the other woven cotton cloth or non-woven cloth substrate which is not treated by a knurling process by using a needle and thread pattern mode to enable the two substrates to be sewn together, wherein one side containing the noctilucent layer is arranged between the two substrates to form a sandwich structure.

Has the advantages that:

(1) the fabric of the invention takes woven cotton cloth or non-woven cloth as a main production raw material, and has the characteristics of soft hand feeling and high comfort. But the fabric has high hygroscopicity, the microporous structure provides a large number of attachment points for bacteria, the bacteria are favorable for propagation, and the situation can be effectively improved after the bacteria are loaded;

(2) the invention utilizes noctilucent powder as a material for storing light energy, coats the material on a fabric substrate in a screen printing mode, absorbs ultraviolet light and visible light under the illumination condition, stores the light energy, releases the light energy in the form of fluorescence in the dark, and can absorb the emitted fluorescence by a photosensitizer, thereby playing an antibacterial role in an aerobic environment in a dark room and achieving the purpose of all-weather antibiosis;

(3) due to the existence of the photosensitizer, the noctilucent energy-storage long-acting photodynamic antibacterial fabric has a good killing effect on staphylococcus aureus under the conditions of illumination and dark room.

Drawings

FIG. 1 is a scanning confocal laser scanning microscope showing a surface microstructure and a cross section of the present invention;

FIG. 2 is a graph showing the fluorescence emission and excitation spectra of the rare earth strontium aluminate luminescent powder SAOED of the present invention and the ultraviolet-visible light absorption spectrum of rose bengal RB;

FIG. 3 is a singlet oxygen detection diagram of the invention for detection of rose bengal RB using KI as substrate;

FIG. 4 is a graph showing the effect of the light-dark cycle photodynamic material of the present invention on the resistance to Staphylococcus aureus;

FIG. 5 is a graph of the antimicrobial performance of the present invention against Staphylococcus aureus under cyclic light-dark conditions (white and gray dark-phase illumination).

Detailed Description

The embodiments of the present invention will be described in further detail with reference to the accompanying drawings. This embodiment is directed to only some embodiments, not all embodiments, of the invention.

The experimental sample is rare earth strontium aluminate noctilucent powder/rose bengal loaded woven cotton cloth, and the method comprises the following three steps: in the first step, a plain-weave cotton fabric having a gauge of 80 s 151 × 152 pieces/inch was cut into a square cloth having a size of 20 cm × 15 cm (20 cm is the warp direction and 15 cm is the weft direction), and the fabric had a thickness of 0.16 m. After 15 g of noctilucent powder and 5 g of transparent nylon mucilage are added into the beaker, 4 mL of deionized water is added by a liquid transfer gun, and the mixture is stirred by a glass rod until the mixture is uniformly observed by naked eyes.

And secondly, coating the treated mixture on a woven cotton cloth or non-woven cloth substrate by utilizing screen printing, and drying in an oven at 130 ℃ for 3 min.

And thirdly, adding 6 g of PVA-SbQ into a beaker, measuring 60 mL of deionized water (10% w/v of PVA-SbQ/deionized water) by using a measuring cylinder, stirring by using a glass rod until the PVA-SbQ is fully dissolved in the water, adding 0.06 g of rose bengal (1% w/w rose bengal/PVA-SbQ) into the solution, uniformly stirring, standing and precipitating for 5 min, adding all the uniformly dispersed rose bengal solution on the upper layer into a container, soaking the treated woven cotton cloth or non-woven cloth base material for 10 min, taking out, attaching one surface without the noctilucent coating to the aluminum foil paper, putting into a 60 ℃ oven, drying until the surface of the noctilucent powder coating is dried, taking out and turning, and drying the whole fabric and taking out. And finally, irradiating the fabric base material coated with the coating with an ultraviolet lamp for 2 hours to crosslink and reinforce the coating and the fabric, and finally obtaining the photodynamic antibacterial fabric with luminous powder as the background.

FIG. 1 is a surface microstructure diagram and a cross-sectional confocal scanning laser microscope diagram of a base material according to the present invention, wherein a is a scanning electron microscope diagram of a surface morphology of cotton yarn, b is a scanning electron microscope diagram of a surface microstructure of a base material, and c is a scanning electron microscope diagram of a cross-sectional microstructure; d is a cross-section laser confocal scanning microscope picture of the noctilucent antibacterial fabric.

FIG. 2 is a graph showing the fluorescence emission and excitation spectra of the rare earth strontium aluminate luminescent powder SAOED of the present invention and the ultraviolet-visible light absorption spectrum of rose bengal RB; for the rare earth strontium aluminate luminous powder SAOED, a typical excitation peak is formed at about 368 nm, and an excitation spectrum covers ultraviolet light and visible light, which means that sunlight can excite the luminous powder to store solar energy; the maximum emission wavelength (excitation wavelength is 368 nm) of the photoluminescence spectrum of the rare earth strontium aluminate luminous powder SAOED is about 512 nm; the UV-visible spectrum of rose bengal RB has a strong peak around 540 nm; the overlapping range of the RB absorption spectrum and the SAOED emission spectrum is large, and powerful basis is provided for feasibility of energy supply of the noctilucent powder to rose bengal.

FIG. 3 is a singlet oxygen detection scheme for the detection of rose bengal according to the invention using KI as substrate. Sample 2 is a substrate containing only rare earth strontium aluminate luminescent powder SAOED, a control, sample 3 is a substrate containing both rare earth strontium aluminate luminescent powder SAOED and rose bengal RB, and sample 4 is a substrate containing only rose bengal RB. KI is used as a substrate for indirectly detecting singlet oxygen, and the generated singlet oxygen of rose bengal under illumination can oxidize KI, so that I^-Is oxidized to form I^3-An absorption peak appears around 352 nm, and the absorbance thereof is dependent on I^3-The concentration of the sample (2) is increased and gradually increased, and a light-dark fatigue cycle light radiation experiment (illumination for 5 min, dark room for 15 min) is carried out on the relevant sample for 20 min, and as shown in the figure, the sample has no light oxidation effect. Singlet oxygen of samples 3 and 4 was mainly generated during light, while sample 4 did not generate in the dark¹O₂Sample 3 can still produce small amounts in the dark¹O₂(the absorbance curve at 365 nm for sample 3 in the dark tends to rise), which is a good demonstration that light is one of the essential factors for the development of antimicrobial photodynamic inactivation: when the light source is switched off, the antibacterial photodynamic inactivation mechanism is suspended. The sample 4 can continue the generation of antibacterial photodynamic inactivation by using afterglow emitted by the noctilucent powder as a light source in a darkroom. When the light source re-irradiates the sample, ROS production is significantly increased without significant reduction in activity. Sample 3 exhibited greater photooxidation activity than sample 4 after four cycles, which is primarily due to the fact that sample 3 had about 2.36 times greater absorbance at 365 nm than sample 4, indicating that the photodynamic material is energized by the luminescent powder¹O₂The yield is greatly increased, namely the noctilucent powder generates rose bengal¹O₂Has synergistic effect.

FIG. 4 shows that when the photodynamic material is subjected to a light-dark cycle antibacterial effect test, the bacterial solution and the material are brought into contact with each other in a dark room for 40 min in advance, and then a subsequent antibacterial experiment is carried out. The results show that after 20 min of illumination, the bacteriostatic rates of sample 3 and sample 4 were 93.3858% and 96.9767%, respectively. Compared with the sample bacteriostasis rate without dark contact in the experiment, the bacteriostasis rate of the sample is respectively increased by 0.72 logarithmic units and 0.98 logarithmic units, and the photodynamic inactivation efficiency can be improved by the dark contact. After the first 40 min dark room, sample 4 was found to have bacterial proliferation, the bacterial survival rate increased from 3.0232% to 4%, while sample 3 did not have bacterial re-proliferation in the dark room, which indicates that the rose bengal material with synergistic effect of noctilucent powder has the function of inhibiting bacterial re-proliferation when the light source is switched off. After two light-dark cycles, sample 2 (control without photosensitizer) had no antimicrobial effect in both the light and dark, with the bacteriostatic rate of 99.9879% for sample 4 and 99.9965% for sample 3 (0.544 log units increase), which is consistent with the above substrate oxidation and electron paramagnetic resonance spectroscopy results. In conclusion, the experiment proves that the luminous powder has synergistic effect on the sterilizing effect of the photosensitizer.

FIG. 5 is a graph of the antimicrobial performance of the present invention against Staphylococcus aureus under cyclic light-dark conditions (white and gray dark-phase illumination). As can be seen from the figure, the photosensitizer can destroy the structure of the staphylococcus aureus, and after the noctilucent powder is added, the structure of the staphylococcus aureus can be destroyed more thoroughly, so that the rare earth strontium aluminate noctilucent powder and rose bengal can be proved to have synergistic antibacterial effect.