TW200912084A - Radiation manufacturing method for fabrication of nano compound antibacterial textile - Google Patents

Abstract

The present invention discloses a novel preparation method of nano compound textile with silver-containing metal series having highly antibacterial function. The method is mainly to modify the silver inorganic antiseptic by high-energy γ-ray radiation for crosslinking or grafting it on Nylon or PET (Polyethylene Terephthalates) fiber material, thereby producing the textiles having highly antibacterial function. Its action mechanism is using the nano-silver chemical compound as the functional assistant for the silver particles to generate reduction and to adhere onto Nylon or PET (Polyethylene Terephthalates) fiber material firmly by the irradiation/modification technology of Co-60. Since the silver inorganic antiseptic will act on the enzyme in the bacteria actively, or destroy the cell wall of bacteria, etc., such mechanisms can achieve good antibacterial effect. It is not required initiators or other additives in this radiation modification process, so the manufacturing process is rather simple and effective. Experimental test results prove that it has good antibacterial effect, and quite has the value of market development and applications in daily-life textiles or medical textiles.

Description

200912084 IX. Description of the invention: [Technical field of the invention] The present invention is a process for the preparation of a nano-metal composite anti-g functional fiber fabric. On the surface of a Nylon or PET fiber material, the ray is treated by a high-energy plant to make the ant Containing ^ (4) weaving (four) from «Na, through the real [previous technology] At present, the anti-fabric of the textile 4 is basically an additive of Gu Nai silver particles as an antibacterial function, since it can be added to _ The mother liquid towel is then reduced to anti-Yiwei. However, due to the small particle size and large surface activity, it is often susceptible to process = high temperature affects human ray-shaped wire mirrors. Therefore, it is necessary to add Xu Xi dispersant to disperse the naphtha; Adding only 'also increases the difficulty of the process. Therefore, it is necessary to develop a new technology to simplify the process, and in the textile back-end process, the cap nano-inorganic anti-g powder is firmly attached to the textile fiber. Since I960, _radiation technology can effectively polymerize two different high-polymers by grafting and cross-linking ((10)sslinking) [Hughes' 1973]. After the surface of the substance is irradiated by radiation, the excited state of the object can be excited, and the free radicals and the peroxides can be added to the high scores of the peroxides. Touch grafting technology, only need to benefit from the bribery of the polymer fiber, the _ polymer can be reduced, and the process has a great potential for the textile industry. At present, acrylic acid, N-isopropylacrylamide or chitosan is grafted onto non-woven fabrics by radiation irradiation [Lin Haoci, 2〇〇3] to improve Hydrophilic, functional and anti-g. However, the reaction is more complicated, except that the acrylic acid, isopropyl propylamine, etc. are first formed on the fiber by Cq_6q irradiation, and the polycarboside can be grafted thereon by (10) irradiation. Therefore, the present invention further simplifies the process of synthesizing the antibacterial textile by the radiation irradiation technique, and the fiber cloth is a commonly used Nyl〇n or pet fiber. According to the principle of antibacterial agents, antibacterial materials can be divided into two major categories: organic and inorganic antibacterial powders. In the last century, people developed a variety of organic anti- _, can record rapid machinery (four) to destroy the human body of the fine 200912084 bacteria [axwell and Critchlow, 1997; Subbalakshmi and Sitaram, 1998] 1 sex, although the organic antibacterial agent has a strong antibacterial The biggest drawback of the effect is that the bacteria are also from. In addition, the organic antibacterial agent of Wang Jile, chemical stability is not fresh, not spurt shot grafting technology too half two / too, and the text attaches importance. In addition, 'inorganic antibacterial agents can be classified into photocatalyst types: Actuarial:: bacterial mechanism silver-based antibacterial agents. The photocatalyst type bactericide is a bacterium 12 defibrating fiber. In contrast, silver-based antibacterial agents are mechanisms such as the main wood or the bad cell wall to achieve antibacterial effects. In summary, the silver ruthenium anti-as a starting reactant for antibacterial textiles. -Mm 3: Development, there are various techniques to reduce the particle size of the powder to two characteristics of the intrinsic material. The addition of nano particles can be used to make the silver antibacterial agent. ====== , 姊 姊 姊 姊 织品 。. 〃 接合 同 同 同 同 同 同 同 同 同 同 同 同 同 同 同 同 同 同 同 同 刀 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 However, due to the particle size of the nanoparticles: Dai Da == step, the formation of aggregates in the antibacterial material of the human fiber is not easy to be affected by the high temperature in the process, and the process will be in the middle of the textile process. Inorganic resistance "To simplify the invention, the purpose of the invention is to discuss the celestial green voyage; __ dimension. Zile deposition or binding to PET or Nylon surface two help ^ = 畐 改 改 使 使 使 使 银 银 银 银 银 银 银icP (inductive coupling ^ ^ ^ ^ This product has been deleted (scanning and anti-test analysis, money analysis analysis and analysis of financial and subtractive line optical spectrum analysis) 200912084 [Embodiment] This invention uses the radiation irradiation technology system -60 r-ray (or electron beam) irradiation of the fiber material, the preparation method can be divided into two methods of post-irradiation and pre-irradiation treatment, the main steps of the experiment are as follows: 1, the post-irradiation (mutual irradiation) procedure (a) Nylon-6 or PET woven material is cut into a substrate of 20cm×20cm or more; (b) Nylon-6 or PET woven material is impregnated in silver-doped cerium oxide (Ag/Si〇2) or silver nitrate solution for more than 2 hours; (c) Remove the cloth through the roller of the press machine at a pressure greater than 2. Okg / αη2 Excess silver nitrate solution is discharged; (4) Nylon-6 or PET woven material is placed in plastic, such as PE, and sealed in a light pocket. 〜 2. Pre-irradiation procedure (a) will be Nylon -6 or PET woven material is cut into a substrate of 20cmX20cm or more; (6) Nylon-6 or PET woven material is placed in a plastic, such as PE, after sealing the pocket, followed by irradiation; ° (c) Nylon-6 or PET The fabric is impregnated with Ag/Si〇2 or silver nitrate solution, and the infiltration time is adjusted according to the experimental conditions. Then, the post-irradiation procedure is taken out, and after being sucked, it is placed in an oven for rapid drying. 'Example 1 uses the same Two kinds of fiber woven fabrics of size 20X20cm2), and then immersing such Nyl〇n or ρΕΤ woven materials in a suspension containing more than 2. Owt% Ag/Si〇2 antibacterial powder for about 2 hours or more, after pressing machine The excess suspension is discharged, and the antibacterial powder is combined with the fiber woven fabric by irradiation with a dose of less than 1 〇〇kGy, and then the cloth is washed and dried to obtain an antibacterial fabric. First figure (a) and first Figure (b) shows the nano-antibacterial powder after irradiation On the SEM photographs on Nyl〇n or ρΕτ, we observed that there are many nano-antibacterial powders attached to the surface of the fibers. These powders may be powders that are only adsorbed on the surface of the fibers by van der Waals after drying. Or a powder that has been knotted with fibers (such as covalent bonds, integration, etc.) 200912084 - It is generally believed that the cleaning action can remove the antibacterial powder adsorbed on the surface of the fiber by van der Waals after drying. The silver fiber is stirred in the container for a long time, and the surface of the fiber is repeatedly tapped and collided by the magnet, and the nano-antibacterial powder left on the surface of the silver fiber should be combined with the fiber. The second picture shows the anti-® gambling after cleaning, _ knowing that the anti-age body left on the fibril surface is greatly reduced.

It is difficult to judge whether or not the silver component is contained in the XRD (X-ray diffractometer) pattern of the antibacterial fiber material. The reason may be that the silver content on the fiber is too low, so we use XPS photoelectron spectra to judge whether the fiber contains silver. ingredient. The third and fourth graphs are Nyl〇n or pE1^々Xps* spectrograms containing nano-Ag/Si〇2~ and Ag/Si〇zP (porous) antibacterial powders, respectively. From the third and fourth®, the 纟(iv) characteristic peak appears near 368eV in Binding Energy, which makes it possible to conclude that the antibacterial fiber fabric we have synthesized contains silver. "In addition, in order to understand || after the irradiation of silver containing i, we paste the silver in the antibacterial powder attached to the fabric dissolved (since silver easily reacts with nitric acid to form silver nitrate), and then use ICP (inductive coupling The slurry is fixed in the silver content of the antibacterial fiber. Table 1 shows the powder and silver content of the Nylon or PET fiber before and after the dose modification of c〇_6〇 irradiated less than 1〇〇k. Cleaning: The silver content is as high as 1 on X. But the silver content after cleaning is good, only after cleaning. The nano-antibacterial powder of P is left on the surface of the fiber. By means of the table, we also found pET fiber. The silver content is lower than that of Nylon fiber. After testing, the Ag/Si〇2 powder after cleaning and the Ag〇2 powder in Ag/Si〇2p remain on the surface of Nyl〇n fiber respectively, 15 and 16wt%. The powder on the surface of pET fiber is lower than that of Ag/Si〇2 powder and Ag/SiOzP containing 5 wt% and 4 wt0/〇, respectively; however, the silver content of these two antibacterial powders is very high. Less, thus making the silver content of Nyl〇n or pET fiber woven material quite low. Table 1 Nylon before and after irradiation of T-60 (less than l〇〇kGy dose) Magic 〇2 powder and a silver content of the material contained in the PET fiber

Nylon before washing After washing ^―___Ag wt°/〇 Si〇2 wt°/〇

Ag/Si〇2 1.09 wt% 0.57 wt°/〇 15 wt°/〇

Ag/Si〇2P 2-21 wt% 0.31 wt% 16 wt% 200912084

PET 0.19 wt% 5 wt% 〇. 〇8 wt% 4 rt0/〇

Ag/Si〇2 1.22 wt%

Ag/SiOaP_0. 22 wt% Example 2 The irradiation method is to paste the direct Wei Luzi on the surface of the fiber. First, the Nylon or PET fiber material (U_cm2) is immersed in the Gu silver solution for about 2 hours, and then pressed. The suction machine discharges the excess _ acid silver solution, and then performs light irradiation (the irradiation amount is <chi) (8). The fifth and sixth figures are respectively impregnated with silver - or the SEM irradiation of the pET fiber woven material after light irradiation The SEM photograph. The ugly (4) picture shows the foot of Nyl〇n fiber before washing. The surface of the ruthenium is scattered with many tiny particles. Although there are a few large aggregates, the particle distribution is quite uniform. After riding through the radiation, the silver particles deposited on the surface of the fiber should be reduced by the silver particles and the sediments of the Jewish silver. The anger particles should be subdivided into the wires that are adsorbed on the surface of the fiber by Van der Waals force. Silk?, and after washing, the surface of the fiber should be bonded to the fiber or silver particles. The fifth picture) is the SEM picture after cleaning. The particle distribution is sparse than the ugly (4) image, showing most of the The silver particles are taken first, And leaving the silver particles or fiber bonded occurrence of chelated. The sixth (a) is a SEM photograph of the silver fiber impregnated pet fiber after irradiation. According to the SEM image, the deposition of PET on the surface of the fiber before washing is a lot of dendritic and granular deposits, but the dendritic deposits after washing can be washed away, leaving many tiny granular silver. The particles are on the surface of the PET fiber as shown in Figure 6(b). In addition, we used XPS (X-ray photoelectron spectra) to determine whether silver is contained in the fiber. Figures 7 and 8 show the antibacterial powders containing nano Ag and AgN〇3, respectively.

Xps analysis of Nylon or PET antibacterial fiber materials. From the seventh and eighth figures, the characteristic peak of Agw appears near the binding energy (BindingEnergy) of 368 eV, which can be concluded that the antibacterial fiber woven material we have developed contains silver. Table 2 shows the content of silver particles grafted onto the surface of the fiber before and after cleaning by ICP measurement of pure water after light irradiation. After injecting pet and Nylon fibers containing 0.25 M or more of silver nitrate solution, the content of silver ions was π. 57 wt% and 15·33 wt%, and the silver ion content after washing with water was measured by ICP before washing with water. Will be greatly reduced, respectively, to 〇8 %% and 2 also 200912084 wt%

This should be the content of silver particles produced by silk and fiber. PE silver ion content is lower than Nylon fiber material, this is 4, ° 12 / into 1 ^ 曰 ± ^ 7 &quot; ', the mouth should be PET fiber is a hydrophobic material, after the absorption of water, read low, 峨 峨Maid ride - the child content recorded _n age. Table 2 Contents of silver particles grafted to the surface of the fiber before and after cleaning by light measurement after cleaning. Before cleaning, wt% PET 11.57 — Nylon 15.33 After cleaning — wt% 1.08 2.15 Example 3 except for the above-mentioned post-irradiation and direct In addition to the irradiation method, this procedure also studies the change in the silver content of Nyl〇n or ρΕτ fibers after pre-irradiati treatment (pre-irradiati.!!). The synthetic steps of the antibacterial fiber of the former Zhaoyin modification method are as follows. After the Nyl〇n or PET woven material is first passed through 7 _ ray, at 60kGy, the immersion person contains the positional return 2Q, and then After the steps of suction, drying, washing, etc., silver-containing nano-antibacterial fiber fabric is obtained. ~, Table 3 is the result of the fiber content of the pre-illumination bribe. From this table, it can be seen that the silver content of the pretreated fiber after cleaning is low, and it is not as good as 〇·1 w. There are two reasons for this. First, the Nyi〇n Ge PET fiber is smothered by the hoof, and the self-domain or peroxide produced by the silk series (4) 5 = beans, so that the silver ions in the silver nitrate solution cannot be reliably reduced. Second, the reduction of silver particles requires hydrated electrons. However, the pre-irradiation procedure does not provide a large amount of hydration electrons, so that silver ions in the effective reduction of silver nitrate solution cannot be achieved. Ny Ion and PET fiber materials containing pre-irradiation treatment with silver sample sampling ^ Ag wt% Nyl &gt; 0.25M AgN before cleaning (0.14" PET &gt; 0.25M AgNOs 0.191 after cleaning Ag wt ° / 〇 ~ ToP ο. 006 200912084 It is known from the above experimental results and antibacterial value test that the antibacterial effect of the pre-irradiation treatment method is less than that of the other two methods, and the other two methods have anti-g force, especially the silver-containing system of direct radiation reduction method. Or the antibacterial effect of the PET fiber woven material is very remarkable, and its antibacterial power is as high as 99. 〇% (for Staphylococcus aureus), wherein the antibacterial effect of the silver-containing pET antibacterial fiber is better than that of Nylon. Antibacterial fiber wovens. References 1. Hughes G., Radiation Chemistry, Oxford University Press, London, UK, (1973). 2. Hayashi S., K. Fujiki, N. Tsubokawa, Grafting of hyperbranched polymers onto ultrafine silica -postgraft polymerization of vinyl monomers initiated by pendant initiating groups of polymer chains grafted onto the surface, Reactive &amp; Functional Polymers, 46, (2000) 193-201. 3. Lin Hao, you borrow Study on the hydrophilicity and antibacterial properties of acrylic, isopropyl acrylamide or poly-chitosan-modified polypropylene non-woven fabrics under the 60-ray and UV-light irradiation methods, PhD thesis, Changkang University, (2003). 4. Maxwell A , Critchlow SE: Mode of Action, In Quinolone Antibacterials, Edited by Kuhlmann J., Dalhoff A., Zeiler HJ, Springer Verlag (1997), P.119. 5. Subbalakshmi CN Sitaram: Mechanism of antimicrobaial action of indelicidin, FEMS Microbiol Letts, (1998), P. 91. [Simple description of the diagram] The first figure is an SEM image of (a) Nylon and (b) PET fiber containing Ag/Si〇2 powder after irradiation. The second figure is an SEM image of (a) Nylon and (b) PET fiber containing Ag/Si〇2 powder after irradiation with water. The third figure shows the XPS spectrum of the (A) Ag/Si〇2P and 〇)) Ag/Si〇2 antibacterial powders of Nylon fibers after irradiation. The fourth figure shows the XPS spectrum of the PET fiber containing (a) Ag/Si〇2P and 〇) Ag/Si〇2 antibacterial powder after irradiation. The fifth graph is an SEM image of the Nylon fiber impregnated with silver nitrate solution after irradiation, and (a) is before water washing, and (b) is after water washing. 200912084 - Figure 6 is an SEM image (magnified 2000 times) of irradiated PET fiber impregnated with silver nitrate. Figure (a) is before water washing and Figure (b) is after water washing. The seventh figure shows the XPS spectrum of the Nylon fiber-containing Ag particle antibacterial powder after direct irradiation. The eighth figure shows the XPS spectrum of the antibacterial powder of the Ag-containing particles of PET fibers after direct irradiation. [Main component symbol description] Benefit f t 12

Claims (1)

200912084 X. Patent application scope: 1. A preparation method of silver-containing metal compound nano composite woven material, comprising the steps of: (a) cutting nylon (Nylon-6) or polyester (PET) woven material into 2〇cmX2 (b) The nylon (Nylon-6) or polyester (PET) woven material is immersed in the Ag/Si〇2 or silver nitrate solution for more than 2 hours; (c) the fabric is taken out to be greater than 2. Okg Under the pressure of /cm2, the roller of the press machine is used to discharge the excess silver nitrate solution; and 1 (the magical 1011-6 or PET woven material is placed in the plastic sealing pocket, and then irradiated, in this kind of weaving The antibacterial powder is formed on the material. 2. According to the method of preparing the silver-based metal compound nano-completion gambling according to the patent application method, wherein the antibacterial powder is silver-loaded oxidized stone (Ag/Si〇2) When the solution is used, the irradiation dose is between 5kGy and 100kGy. 3. According to the method of preparing the silver-containing metal compound nano composite material according to the patent application, the antibacterial powder is a solution of silver nitrate (AgN0s). At the time, the radiation dose is between £80kGy and l100kGy. Scope 1 The preparation method of the silver-containing metal compound nano composite woven material, wherein the light irradiation can be irradiated with cobalt-60 7 ray. 5. According to the scope of the patent application, the first silver-containing metal compound nano composite The material of the fabric is prepared, and the light beam irradiation can be irradiated by electron beam radiation. 6. According to the scope of the patent application, the silver-containing metal compound nano-composite weave, the preparation method, wt%, the antibacterial powder system Grafted on nylon (Nylon) or polyester (PET), which can reach 15 and 5 Wt°/e ', respectively, but the silver content is less than 1 wt%. 13 200912084 7. According to the patent application scope The first item contains silver, the preparation method of anti-system, _m nano-composite woven material, _ containing silver-driving compound, after radiation-shooting, Γ=azimuth increase (10) paste. The preparation method of the silver metal compound nano composite woven material, and the antibacterial force value of the composite woven material "material wealth up to 99.".