WO2023016142A1 - 一种夜光储能长效光动力抗菌型面料及其制备方法 - Google Patents

一种夜光储能长效光动力抗菌型面料及其制备方法 Download PDF

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WO2023016142A1
WO2023016142A1 PCT/CN2022/103821 CN2022103821W WO2023016142A1 WO 2023016142 A1 WO2023016142 A1 WO 2023016142A1 CN 2022103821 W CN2022103821 W CN 2022103821W WO 2023016142 A1 WO2023016142 A1 WO 2023016142A1
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woven
fabric
luminous
coating
substrate
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French (fr)
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王清清
张嘉雯
张欣欣
刘兴谱
魏取福
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Jiangnan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/06—Embossing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/06—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/008—Sewing, stitching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/422—Luminescent, fluorescent, phosphorescent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the invention belongs to the field of luminous antibacterial fabrics, in particular to a luminous energy storage long-acting photodynamic antibacterial fabric and a preparation method thereof.
  • microorganisms especially bacteria and molds
  • various outdoor products are often used in the wild, and it is very easy to breed bacteria.
  • the infection of microorganisms can also cause diseases such as stench, Mildew, deterioration and many other adverse consequences.
  • people's living standards and hygiene awareness With the further improvement of people's living standards and hygiene awareness, more and more young people and families choose to carry out activities in the wild when traveling.
  • People's demand for various outdoor sports products has surged. While pursuing the beauty and comfort of the products, they have put forward higher requirements for their health care functions.
  • the production of outdoor products such as tents with antibacterial functions is to protect people from or reduce them.
  • tents with antibacterial function are more and more popular, and have huge development potential and application market.
  • the method of directly coating and reinforcing the surface of the fabric with antibacterial agents is often used in the market to make the fabric have an antibacterial effect, and there are many kinds of antibacterial agents.
  • Antibacterial materials are usually metal ions, antibiotics, etc.
  • metal ions have certain toxic and side effects on the human body, and the extensive use of antibiotics can easily lead to drug resistance of bacteria, and photodynamic antibacterial can solve the above problems well. It is efficient and fast, can be used locally, and is not easy to produce drug resistance, etc.
  • a necessary condition for photosensitive antibacterial agents is light. When the light source is cut off, the photosensitizer cannot produce reactive oxygen species (ROS), which makes the antibacterial performance of light-driven antibacterial materials worse, making it unable to function in darkrooms, and the application scenarios are limited. .
  • ROS reactive oxygen species
  • the present invention provides a luminous energy storage long-lasting photodynamic antibacterial fabric and its preparation method, which solves the problem of easy breeding and reproduction of microorganisms on the surface of the fabric fabric, and the common problem of fabrics loaded with photosensitive antibacterial agents in darkrooms. Difficult to produce technical problems of antimicrobial effect in the environment.
  • the invention provides a luminous energy storage long-lasting photodynamic antibacterial fabric, which is characterized in that it includes a woven cotton or non-woven fabric substrate, and the substrate is coated with luminous powder/photosensitizer to form luminous
  • the antibacterial substrate, the luminous powder is rare earth strontium aluminate luminous powder, and the photosensitizer is rose bengal photosensitizer.
  • the woven cotton base material is made of natural cotton fiber, and the cotton thread is woven through weaving technology;
  • the non-woven fabric base material is polypropylene, and the fiber formed by high-temperature melt spinning is used as the raw material. Under the clamping and traction of high-speed hot air flow, it is stretched, thinned and sprayed, and self-adhesive with residual heat to form a network structure fiber aggregate.
  • the microporous structure of the woven cotton base material and the fiber diameter of the non-woven fabric base material are 2-5 ⁇ m and the arrangement is disorderly and disorderly, having a three-dimensional microporous structure.
  • the present invention also provides a method for preparing a luminous energy storage long-lasting photodynamic antibacterial fabric, which includes weaving woven cotton or non-woven fabric substrates, preparing luminous powder/photosensitizer coatings, and forming interlayer structures. Proceed as follows:
  • step (2.2) Scrape-coat the mixture treated in step (2.1) onto a woven cotton or non-woven fabric substrate by screen printing, and put it in an oven at 130°C for 3 minutes to dry;
  • step (3) Formation of sandwich structure: the woven cotton cloth or non-woven fabric base material obtained in step (2), and another layer of woven cotton cloth or non-woven fabric base material without any treatment through the embossing process with a needlework pattern
  • the method is to sew the two substrates together, and the side containing the luminous layer is in the middle of the two substrates to form a sandwich structure.
  • the fabric of the present invention is mainly produced from woven cotton or non-woven fabric base material, which has the characteristics of soft hand feeling and high comfort.
  • the hygroscopicity of the fabric is high, and the microporous structure provides a large number of attachment points for bacteria, which is conducive to bacterial reproduction. This situation can be effectively improved after loading;
  • the present invention uses luminous powder as a material for storing light energy, and coats it on the fabric substrate by screen printing, absorbs ultraviolet light and visible light under light conditions, and stores light energy, and emits fluorescent light in the dark.
  • the emitted fluorescence can be absorbed by the photosensitizer, so it can also play an antibacterial effect in the aerobic environment of the darkroom, and achieve the purpose of antibacterial around the clock;
  • the luminous energy storage long-acting photodynamic antibacterial fabric of the present invention has a good killing effect on Staphylococcus aureus under the conditions of light and dark room.
  • Fig. 1 is the laser confocal scanning microscope figure of surface microstructure figure and section of the present invention
  • Fig. 2 is the fluorescence emission and excitation spectrum of the rare earth strontium aluminate luminous powder SAOED of the present invention and the ultraviolet-visible light absorption spectrum of Bengal rose red RB;
  • Fig. 3 is that the present invention uses KI as a substrate to detect the singlet oxygen detection figure of Rose Bengal RB;
  • Fig. 4 is the effect diagram of the anti-staphylococcus aureus performance of the light-dark cycle photodynamic material of the present invention
  • Fig. 5 is a graph showing the antibacterial properties of the present invention against Staphylococcus aureus under cyclic light-dark conditions (white irradiation and gray dark period irradiation).
  • the sample in this experiment is rare earth strontium aluminate luminous powder/Bengal rose red loaded woven cotton fabric, which is divided into three steps: the first step is to cut the plain weave cotton fabric with a specification of 80s 151 ⁇ 152 threads/inch into 20cm ⁇ 15cm (20cm is the warp direction, 15cm is the weft direction) size square cloth, the fabric thickness is 0.16m. After adding 15g of luminous powder and 5g of transparent nylon glue into the beaker, add 4mL of deionized water with a pipette gun, and stir with a glass rod until it is evenly observed with the naked eye.
  • the treated mixture is scraped-coated on a woven cotton or non-woven fabric substrate by screen printing, and dried in an oven at 130° C. for 3 minutes.
  • the third step is to add 6g of PVA-SbQ to the beaker and measure 60mL of deionized water (10% w/v PVA-SbQ/deionized water) with a measuring cylinder, stir with a glass rod until the PVA-SbQ is fully dissolved in water, and weigh Take 0.06g Rose Bengal (1%w/w Rose Bengal/PVA-SbQ) and add it to the solution, stir evenly, let it settle for 5min, take all the evenly dispersed Rose Bengal solution in the upper layer and add it to the container, and put the treated Soak the woven cotton cloth or non-woven fabric base material for 10 minutes, take it out, put the non-luminous coating side close to the aluminum foil paper, put it in a 60°C oven and dry until the luminous powder coating surface is dry, take it out and turn it over, and then bake it until the whole fabric Remove after drying. Finally, the coated fabric substrate was irradiated with ultraviolet light for 2 hours to make the coating and the fabric cross-linked and strengthened, and finally
  • Fig. 1 is the laser confocal scanning electron microscope picture of the surface microstructure figure of the base material of the present invention and the section, wherein a is the scanning electron microscope picture of the surface topography of cotton yarn, b is the scanning electron microscope picture of the microcosmic topography of the base material surface, and c is the cross section Scanning electron micrograph of microscopic morphology; d is the laser confocal scanning microscope image of the cross-section of the luminous antibacterial fabric.
  • Fig. 2 is the fluorescence emission and excitation spectrum of the rare earth strontium aluminate luminous powder SAOED of the present invention and the ultraviolet-visible light absorption spectrum of Bengal Rose Red RB; for the rare earth strontium aluminate luminous powder SAOED, it has a typical excitation peak at about 368nm , the excitation spectrum covers ultraviolet light and visible light, which means that sunlight can excite luminous powder to store solar energy; about 512nm is the maximum emission wavelength of the photoluminescence spectrum of rare earth strontium aluminate luminous powder SAOED (excitation wavelength is 368nm); Bengal rose The ultraviolet-visible spectrum of red RB has a strong peak at around 540nm; the RB absorption spectrum overlaps with the SAOED emission spectrum in a large range, which provides a strong basis for the feasibility of luminous powder to supply energy to Bengal rose red.
  • Fig. 3 is a singlet oxygen detection diagram of the present invention using KI as a substrate to detect Rose Bengal.
  • Sample 2 is the substrate containing only rare earth strontium aluminate luminous powder SAOED, which is the control group
  • sample 3 is the substrate containing both rare earth strontium aluminate luminous powder SAOED and Bengal rose red RB
  • sample 4 is only containing Bengal rose red RB base material.
  • Rose Bengal produces singlet oxygen under light, which can oxidize KI, so that I - is oxidized to I 3- , and an absorption peak appears around 352nm, and its absorbance increases with I 3
  • concentration of - increased and gradually increased, and a 20-min light-dark fatigue cycle light radiation experiment was carried out on the relevant samples (lighting for 5 minutes, dark room for 15 minutes), as shown in the figure, sample 2 had no photooxidative effect.
  • the singlet oxygen of samples 3 and 4 is mainly produced during the light period, while sample 4 does not produce 1 O 2 in the dark, and sample 3 can still produce a small amount of 1 O 2 in the dark (in the dark room, the absorbance of sample 3 at 365nm
  • the curve shows an upward trend), which is a good proof that light is one of the necessary factors for the occurrence of antibacterial photodynamic inactivation: when the light source is cut off, the antibacterial photodynamic inactivation mechanism is suspended.
  • Sample 4 in the dark room emits afterglow from luminous powder as a light source, which can continue the occurrence of antibacterial photodynamic inactivation. When the light source irradiated the sample again, the ROS production increased significantly without a significant decrease in activity.
  • sample 3 showed stronger photooxidative activity than sample 4, which is mainly reflected in the absorbance of sample 3 at 365nm is about 2.36 times that of sample 4, indicating that under the energy of luminous powder, the photodynamic material
  • the production of 1 O 2 is greatly increased, that is, the luminous powder has a synergistic effect on the production of 1 O 2 of Rose Bengal.
  • Fig. 5 is a graph showing the antibacterial properties of the present invention against Staphylococcus aureus under cyclic light-dark conditions (white irradiation and gray dark period irradiation). It can be seen from the figure that the photosensitizer can destroy the structure of Staphylococcus aureus. After adding luminous powder, the structure of Staphylococcus aureus is destroyed more thoroughly. The above all prove that the rare earth strontium aluminate luminous powder and Bengal rose red have a synergistic effect antibacterial effect.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

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。

Description

一种夜光储能长效光动力抗菌型面料及其制备方法 技术领域
本发明属于夜光抗菌型面料领域，具体涉及一种夜光储能长效光动力抗菌型面料及其制备方法。
背景技术
众所周知，微生物特别是细菌和霉菌极易在各种织物上繁殖，其中各种户外用品常用于野外，非常容易滋生细菌，而微生物的侵染除对人体造成疾病以外，还可酿成如恶臭、发霉、变质等多种不良后果。随着人们生活水平和卫生意识进一步的提高，越来越多的年轻人和家庭出行游玩时，选择野外进行活动。人们对各种户外运动产品的需求激增，在追求产品的美观、舒适的同时，对其卫生保健功能提出了更高的要求，生产具有抗菌功能的帐篷等户外用品是使人们免受或少受细菌侵害的有效途径之一，因此具有抗菌功能的帐篷越来越受到人们的青睐，具有巨大的开发潜力和应用市场。
市场上常常采用以抗菌剂直接涂层、加固整理到织物表面的方法，使织物具有抗菌效果，而抗菌剂的种类繁多，抗菌材料通常为金属离子，抗生素等。但金属离子对人体有一定的毒副作用，而抗生素的大量使用易使细菌产生耐药性，而光动力抗菌可以很好地解决上述问题，有着高效快速，可局部使用，不易产生耐药性等的优点。但光敏抗菌剂的一个必要条件就是光照，当光源切断后光敏剂无法产生活性氧物质(ROS)，使光驱动抗菌材料的抗菌性能变差，使其在暗室中无法发挥作用，应用场景受限。
发明内容
技术问题：针对现有技术不足，本发明提供了一种夜光储能长效光动力抗菌型面料及其制备方法，解决了织物面料表面易滋生繁殖微生物，以及普通负载光敏抗菌剂的面料在暗室环境中难以产生抗菌作用的技术问题。
技术方案：
本发明提供了一种夜光储能长效光动力抗菌型面料，其特征在于，包括机织棉布或非织造布基材，所述基材在表面敷有夜光粉/光敏剂涂层后形成夜光抗菌基材，所述夜光粉为稀土铝酸锶夜光粉，所述光敏剂为孟加拉玫瑰红光敏剂。
所述的机织棉布基材是以天然棉纤维为原料，将棉线通过机织技术织造形成的面料；所述非织造布基材是以聚丙烯为原料，通过高温熔融纺丝形成的纤维在高速热气流的夹持牵引下被拉伸细化并喷射，利用余热自粘接形成网状结构纤维集合体。
其中，所述机织棉布基材的微孔结构和非织造布基材纤维直径为2-5μm且排列杂乱无序，具有三维多微孔结构。
本发明还提供了一种夜光储能长效光动力抗菌型面料的制备方法，包括机织棉布或非织造布基材的织造、夜光粉/光敏剂涂层的调配以及夹层结构的形成，具体步骤如下：
(1)机织棉布或非织造布基材的织造：采用机织/熔喷法制造棉布或非织造布；
(2)夜光粉/光敏剂涂层的调配：
(2.1)涂层的初步处理：将棉布或非织造布裁成20cm×15cm大小的方形布，20cm为经纱方向，15cm为纬纱方向，该织物厚度为0.16m；夜光粉含量为75％；烧杯中加入15g夜光粉、5g透明尼龙胶浆后，用移液枪加入4mL去离子水，用玻璃棒搅拌至肉眼观察均匀；
(2.2)将经步骤(2.1)处理后的混合物利用丝网印刷刮涂至机织棉布或非织造布基材上，放入130℃烘箱3min烘干；
(2.3)烧杯中加入6g PVA-SbQ后用量筒量取60mL去离子水，用玻璃棒搅拌至PVA-SbQ在水中充分溶解后，称取0.06g孟加拉玫瑰红加入溶液中，搅拌均匀，静置沉淀5min，取上层均匀分散的孟加拉玫瑰红溶液全部加至容器中，将经步骤(2.2)处理后的机织棉布或非织造布基材浸泡10min后取出，无夜光涂层的一面贴近铝箔纸，放入60℃烘箱中烘至夜光粉涂层面干燥后取出翻面，再烘至整块织物干燥后取出；
(2.4)将敷有涂层的织物基材用紫外光灯光照2h使涂层与织物交联加固，得到处理好的夜光抗菌基材；
(3)夹层结构的形成：将步骤(2)得到的机织棉布或非织造布基材，与另外一层未经任何处理的机织棉布或非织造布基材通过压花工艺用针线图案方式将两片基材缝合在一起，含夜光层的一面在两片基材中间，形成夹层结构。
有益效果：
(1)本发明织物由机织棉布或非织造布基材为主要生产原料，其具有柔软手感好、舒适性高的特点。但织物的吸湿性高、微孔结构给细菌提供大量附着点有利于细菌繁殖，负载后可有效改善这一情况；
(2)本发明利用夜光粉作为储光能的材料，通过丝网印刷的方式涂覆于织物基材上，在光照条件下吸收紫外光和可见光，并将光能储存，在黑暗中以荧光的形式释放出来，发出的荧光可被光敏剂吸收，从而在暗室有氧环境中也能起到抗菌作用，达到全天候抗菌的目的；
(3)本发明的夜光储能长效光动力抗菌型面料由于光敏剂的存在，在光照和暗室的情况下，对金黄色葡萄球菌均具有良好的灭杀效果。
附图说明
图1为本发明的表面微观结构图及截面的激光共聚焦扫描显微镜图；
图2为本发明稀土铝酸锶夜光粉SAOED的荧光发射和激发光谱以及孟加拉玫瑰红RB的紫外-可见光吸收光谱图；
图3为本发明以KI为底物检测孟加拉玫瑰红RB的单线态氧检测图；
图4为本发明光-暗周期循环光动力材料抗金黄色葡萄球菌的性能效果图；
图5为本发明在循环光照-黑暗条件下(白色照射和灰色暗期照射)对金黄色葡萄球菌的抗菌性能图。
具体实施方式
以下将结合本发明的附图，对本发明的实施例作进一步清楚、详细的描述。本实施例所涉及的仅仅是本发明一部分实施例，而不是全部的实施例。
本实验样品为稀土铝酸锶夜光粉/孟加拉玫瑰红负载机织棉布，共分为三个步骤：第一步将规格为80s 151×152根/吋的平纹机织棉织物裁成20cm×15cm(20cm为经纱方向，15cm为纬纱方向)大小的方形布，该织物厚度为0.16m。烧杯中加入15g夜光粉、5g透明尼龙胶浆后，用移液枪加入4mL去离子水，用玻璃棒搅拌至肉眼观察均匀。
第二步将经处理后的混合物利用丝网印刷刮涂至机织棉布或非织造布基材上，放入130℃烘箱3min烘干。
第三步在烧杯中加入6g PVA-SbQ后用量筒量取60mL去离子水(10％w/v PVA-SbQ/去离子水)，用玻璃棒搅拌至PVA-SbQ在水中充分溶解后，称取0.06g孟加拉玫瑰红(1％w/w孟加拉玫瑰红/PVA-SbQ)加入溶液中，搅拌均匀，静置沉淀5min，取上层均匀分散的孟加拉玫瑰红溶液全部加至容器中，将处理后的机织棉布或非织造布基材浸泡10min后取出，无夜光涂层的一面贴近铝箔纸，放入60℃烘箱中烘至夜光粉涂层面干燥后取出翻面，再烘至整块织物干燥后取出。最后将敷有涂层的织物基材用紫外光灯光照2h使涂层与织物交联加固，最终制得以发光夜光粉为背景的光动力抗菌织物。
图1为本发明的基材的表面微观结构图及截面的激光共聚焦扫描显微镜图，其中a为棉纱线表面形貌扫描电镜图，b为基材表面微观形貌扫描电镜图，c为截面微观形貌扫描电镜图；d为夜光抗菌面料的截面激光共聚焦扫描显微镜图。
图2为本发明稀土铝酸锶夜光粉SAOED的荧光发射和激发光谱以及孟加拉玫瑰红RB的紫外-可见光吸收光谱图；对于稀土铝酸锶夜光粉SAOED，其在368nm左右有一个典型的激发峰，激发光谱覆盖紫外光和可见光，意味着太阳光即可以激发夜光粉储存太阳能； 在512nm左右是稀土铝酸锶夜光粉SAOED的光致发光光谱的最大发射波长(激发波长为368nm)；孟加拉玫瑰红RB的紫外可见光谱在540nm左右处有一个强峰；RB吸收光谱与SAOED发射光谱重叠范围较大，为夜光粉向孟加拉玫瑰红供能可行性提供了有力依据。
图3为本发明以KI为底物检测孟加拉玫瑰红的单线态氧检测图。样品2为只含有稀土铝酸锶夜光粉SAOED的基材，为对照组，样品3为同时含有稀土铝酸锶夜光粉SAOED和孟加拉玫瑰红RB的基材，样品4为只含有孟加拉玫瑰红RB的基材。用KI作为间接检测单线态氧的底物，孟加拉玫瑰红在光照下产生了单线态氧可以氧化KI，使得I -被氧化成I 3-，在352nm左右出现吸收峰，其吸光度随着I 3-的浓度增多而逐渐变大，对相关样品进行20min时长的光-暗疲劳周期循环光辐射实验(光照5min，暗室15min)，如图所示样品2无光氧化效果。样品3和样品4的单线态氧主要在光照期间产生，而样品4在黑暗中不产生 1O 2，样品3在黑暗中仍然可以产生少量 1O 2(暗室中，样品3在365nm处的吸光度曲线呈上升趋势)，这很好的证明了光是发生抗菌光动力灭活的必要因素之一：当光源切断，抗菌光动力灭活机制暂停。样品4在暗室中由夜光粉发出余辉作为光源可以延续抗菌光动力灭活的发生。当光源再次照射样品，ROS产量显著增加，活性没有明显降低。在四个循环周期后样品3表现出比样品4更强的光氧化活性，这主要体现在样品3在365nm处的吸光度是样品4的约2.36倍，表明夜光粉供能下，光动力材料的 1O 2产量大大增加，即夜光粉对于孟加拉玫瑰红产生 1O 2有增效作用。
图4在对光动力材料进行光-暗周期抗菌效果测试时，将细菌溶液与材料提前暗室接触40min，再进行接续的抗菌实验。结果表明，在20min光照后，样品3和样品4的抑菌率分别为93.3858％和96.9767％。比上述实验中未进行暗接触的样品抑菌率分别增加0.72个对数单位和0.98个对数单位，再一次验证了暗接触可以提高光动力失活效率。在进行第一次40min暗室后，发现样品4有细菌繁殖，细菌存活率由3.0232％上升至4％，而样品3在暗室中并无细菌再次增殖现象的发生，这一现象表明对于夜光粉增效的孟加拉玫瑰红材料来说，在光源切断时具有抑制细菌再次繁殖的功能。两个光-暗循环后，样品2(无光敏剂对照组)在光照和暗室中都没有抗菌效果，样品4抑菌率为99.9879％，样品3抑菌率达到99.9965％(增加0.544个对数单位)，这与上述底物氧化和电子顺磁共振波谱结果一致。总而言之，该实验证明夜光粉对光敏剂杀菌效果有协同增效作用。
图5为本发明在循环光照-黑暗条件下(白色照射和灰色暗期照射)对金黄色葡萄球菌的抗菌性能图。由图可见，光敏剂可以破坏金黄色葡萄球菌的结构，加入夜光粉后，金黄色葡萄球菌的结构被破坏的更加彻底，以上均可证明稀土铝酸锶夜光粉和孟加拉玫瑰红具有协 同增效的抗菌效果。

Claims (3)

  1. 一种夜光储能长效光动力抗菌型面料，其特征在于，包括机织棉布或非织造布基材，所述基材在表面敷有夜光粉/光敏剂涂层后形成夜光抗菌基材，所述夜光粉为稀土铝酸锶夜光粉，所述光敏剂为孟加拉玫瑰红光敏剂；
    所述的机织棉布基材是以天然棉纤维为原料，将棉线通过机织技术织造形成的面料；所述非织造布基材是以聚丙烯为原料，通过高温熔融纺丝形成的纤维在高速热气流的夹持牵引下被拉伸细化并喷射，利用余热自粘接形成网状结构纤维集合体。
  2. 根据权利要求1所述的夜光储能长效光动力抗菌型面料，特征在于，所述机织棉布基材的微孔结构和非织造布基材纤维直径为2-5μm且排列杂乱无序，具有三维多微孔结构。
  3. 一种根据权利要求1-2任一所述的夜光储能长效光动力抗菌型面料的制备方法，其特征在于，包括机织棉布或非织造布基材的织造、夜光粉/光敏剂涂层的调配以及夹层结构的形成，步骤如下：
    (1)机织棉布或非织造布基材的织造：采用机织/熔喷法制造棉布或非织造布；
    (2)夜光粉/光敏剂涂层的调配：
    (2.1)涂层的初步处理：将棉布或非织造布裁成20cm×15cm大小的方形布，20cm为经纱方向，15cm为纬纱方向，该织物厚度为0.16m；夜光粉含量为75％；烧杯中加入15g夜光粉、5g透明尼龙胶浆后，用移液枪加入4mL去离子水，用玻璃棒搅拌至肉眼观察均匀；
    (2.2)将经步骤(2.1)处理后的混合物利用丝网印刷刮涂至机织棉布或非织造布基材上，放入130℃烘箱3min烘干；
    (2.3)烧杯中加入6g PVA-SbQ后用量筒量取60mL去离子水，用玻璃棒搅拌至PVA-SbQ在水中充分溶解后，称取0.06g孟加拉玫瑰红加入溶液中，搅拌均匀，静置沉淀5min，取上层均匀分散的孟加拉玫瑰红溶液全部加至容器中，将经步骤(2.2)处理后的机织棉布或非织造布基材浸泡10min后取出，无夜光涂层的一面贴近铝箔纸，放入60℃烘箱中烘至夜光粉涂层面干燥后取出翻面，再烘至整块织物干燥后取出；
    (2.4)将敷有涂层的织物基材用紫外光灯光照2h使涂层与织物交联加固，得到处理好的夜光抗菌基材；
    (3)夹层结构的形成：将步骤(2)得到的机织棉布或非织造布基材，与另外一层未经任何处理的机织棉布或非织造布基材通过压花工艺用针线图案方式将两片基材缝合在一起，含夜光层的一面在两片基材中间，形成夹层结构。
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