Long-acting washing-resistant antibacterial deodorizing textile and preparation method therefor

Abstract

The present invention relates to a preparation method for a long-acting washing-resistant antibacterial deodorizing textile. The preparation method comprises: reacting inorganic photocatalyst particles with a silane coupling agent containing a carbon-carbon double bond so as to modify the surface of a photocatalyst with a carbon-carbon double bond, and then initiating graft polymerization by means of electron beam irradiation, wherein active free radicals are generated on the textile to initiate the graft polymerization of a quaternary ammonium salt monomer containing a carbon-carbon double bond functional group and the photocatalyst particles modified with a carbon-carbon double bond functional group, such that polyquaternium and the photocatalyst particles are firmly fixed to the textile via a covalent bond, and the textile is endowed with the antibacterial deodorizing function. The present invention further relates to a textile obtained according to the preparation method. In the present invention, by means of initiating a grafting polymerization reaction via electron beams, the quaternary ammonium salt monomer and the photocatalyst particles are bonded to the textile via a covalent bond at a normal temperature, and the antibacterial deodorizing group of the prepared textile is firmly bonded with the textile, such that the textile is not prone to falling off during the use process, has a lasting antibacterial deodorizing function, and is safe for both the human body and the environment.

Description

Long-lasting washing-resistant, antibacterial and deodorizing textile and preparation method thereof Technical Field

[0001] The present invention relates to textiles, and more particularly to long-lasting, wash-resistant, antibacterial and deodorizing textiles and a preparation method thereof. Background Art

[0002] Textiles are essential to human life. With economic development and improved living standards, people's expectations for textiles have evolved beyond simply providing coverage, warmth, and aesthetics. They now desire textiles with additional functionality, such as waterproofing, breathability, UV protection, and antibacterial and deodorizing properties.

[0003] Antimicrobial and deodorizing textiles are a type of functional textile that improves people's quality of life. Their antimicrobial properties can kill and inhibit the growth of various bacteria and other microorganisms on textiles, preventing the proliferation and spread of harmful microorganisms into the human body through contact, thus helping to protect the user's health. Furthermore, antimicrobial textiles inhibit the decomposition of human secretions by microorganisms, thereby preventing the production of odor-causing small molecules. Deodorizing textiles not only eliminate odor-causing small molecules produced by microorganisms, but also remove odor-causing small molecules emitted by the body through adsorption or decomposition, enhancing comfort for both the wearer and those around them.

[0004] After years of development, textiles with simple antibacterial functions have already developed some mature processes and a considerable market size. Antimicrobial agents commonly used in textiles can be divided into two categories: inorganic and organic. Inorganic antimicrobial agents include nanometal particles (such as nanosilver, nanocopper, etc., among which nanosilver has been banned in some countries due to its toxicity to the human body), nanoinorganic substances (such as nanozinc oxide, etc.), and metal salts (copper and silver salts such as copper sulfate, etc., and organic antimicrobial agents such as chitosan, guanidine antimicrobial agents, and quaternary ammonium salt antimicrobial agents). The commonly used method for preparing antimicrobial textiles in industry is to use a finishing method, in which the antimicrobial agent dispersion is subjected to high-temperature padding to adhere the antimicrobial agent to the surface of the textile. Sometimes, in order to increase adhesion, a small amount of adhesive is added to the dispersion to stick the antimicrobial agent to the textile.

[0005] Some of the odor emitted by the human body comes from ammonia, isovaleric acid, acetic acid, and other odors released by bacteria growing on the skin. Warm, humid environments (such as after exercise) are particularly prone to bacterial proliferation, making odor more likely. Antimicrobial textiles can kill or inhibit bacterial growth on the skin, thus helping to eliminate this source of odor. Other odors, such as "old age odor," primarily originate from nonenal produced by the body's own metabolism. Diabetic ketoacidosis, advanced kidney disease, and impaired liver function can also contribute to odor. Besides human odor, smoking and hot pot can also cause odor to adhere to clothing, causing discomfort to those around them. Conventional antimicrobial textiles are ineffective in eliminating these odors; they require the addition of functional substances with adsorption or decomposition properties to effectively eliminate them.

[0006] Photocatalysts are a general term for semiconductor materials with photocatalytic properties. The earliest discovered photocatalyst material was nano-TiO2, which can be excited by ultraviolet light to produce strong oxidizing properties, killing bacteria and decomposing organic matter such as formaldehyde. Therefore, it has promising application prospects in the field of antibacterial and deodorization. With technological advancements, more photocatalytic materials with photocatalytic oxidation functions have been synthesized, and the excitation light source is no longer limited to ultraviolet light; it can also produce photocatalytic effects under visible light.

[0007] Due to the bactericidal and photocatalytic decomposition effects of photocatalyst materials on small-molecule organic matter, there has been much research on their application in antibacterial and deodorizing textiles. Currently, the main way to use photocatalysts to prepare antibacterial and deodorizing textiles is to use an adhesive to bond inorganic photocatalyst particles to the surface of the textiles in a post-finishing manner. The drawback of this method is that a considerable portion of the surface of the photocatalyst particles is covered by the adhesive and cannot function, resulting in waste. In addition, the bonding strength between the inorganic photocatalyst particles and the textiles is not high. After friction and washing, the photocatalyst particles are very easy to fall off, so their antibacterial and deodorizing functions are not long-lasting. The detached photocatalyst particles enter the environment or the human body, which may cause adverse effects. Another disadvantage of using photocatalysts for antibacterial and deodorizing is that the photocatalytic reaction takes a long time, and the antibacterial and deodorizing effect is not immediate.

[0008] Quaternary ammonium salts are a general term for positively charged organic compounds containing tetravalent nitrogen atoms. Quaternary ammonium salts are commonly used as antimicrobial agents, including disinfectants, and have long been widely used in water purification and antibacterial fabrics. The positive charge of quaternary ammonium salts attracts the negative charge of the cell membranes or lipid envelopes of bacteria and other microorganisms, thereby capturing them. The lipophilic alkyl chains disrupt the cell membranes or envelopes, thereby killing the microorganisms. The bactericidal mechanism of quaternary ammonium salts is the physical interaction of charge attraction and lipophilic membrane disruption, making them safe, effective, and with minimal side effects. Polymeric quaternary ammonium salts are particularly stable, heat-resistant, and resistant to decomposition, making them a commonly used disinfectant. Quaternary ammonium salt disinfectants also have a certain deodorizing effect, inhibiting bacterial growth and thus eliminating odors caused by bacterial growth at the source. Quaternary ammonium salts can also adsorb small, odor-causing acidic molecules such as acetic acid and isovaleric acid through charge interactions. They also have a certain adsorption effect on ammonia gas by binding to the lone pair electrons on ammonia molecules. Incorporating quaternary ammonium salts into textiles can provide a broad-spectrum antimicrobial effect and deodorize certain odor sources. This is especially true if graft copolymerization or other methods are used to securely bind quaternary ammonium salts to textiles through strong covalent bonds, making them less likely to fall off and providing a longer-lasting broad-spectrum antimicrobial and partial deodorization effect.

[0009] In summary, quaternary ammonium salts and photocatalysts each have their own advantages and disadvantages in terms of antibacterial and deodorizing effects. Quaternary ammonium salts can achieve long-lasting broad-spectrum antibacterial and certain deodorizing functions, but their deodorizing functions are limited to some odor sources; photocatalysts can play a broad-spectrum deodorizing role, but the existing technology makes it difficult to firmly bond photocatalysts to textiles to make them work for a long time, and it takes a long time for photocatalysts to play their antibacterial and deodorizing effects under photocatalysis.

[0010] Summary of the Invention

[0011] In order to solve the problem that the antibacterial and deodorizing functions of the antibacterial and deodorizing textiles in the prior art are not long-lasting, the present invention provides a long-lasting, wash-resistant antibacterial and deodorizing textile and a preparation method thereof.

[0012] According to the present invention, the preparation method of the long-lasting washing-resistant antibacterial and deodorizing textile comprises providing textiles, inorganic photocatalyst particles, a silane coupling agent containing a carbon-carbon double bond, and a quaternary ammonium salt monomer containing a carbon-carbon double bond functional group, reacting the inorganic photocatalyst particles with the silane coupling agent containing a carbon-carbon double bond to modify the surface of the photocatalyst with a carbon-carbon double bond, initiating graft polymerization by electron beam irradiation, generating active free radicals on the textile, initiating graft polymerization of the quaternary ammonium salt monomer containing a carbon-carbon double bond functional group and the photocatalyst particles modified with the carbon-carbon double bond functional group, thereby firmly fixing the polyquaternary ammonium salt and the photocatalyst particles to the textile through covalent bonds, and imparting the antibacterial and deodorizing function to the textile.

[0013] The basic principle of the present invention is different from the conventional post-finishing process of preparing functional textiles by physically adsorbing or bonding functional groups to textiles through post-finishing. The basic principle of the present invention is to use electron beam irradiation to cause the active free radicals generated on the textiles to trigger the free radical addition polymerization reaction of carbon-carbon double bond functional groups, thereby connecting the antibacterial and deodorizing groups containing carbon-carbon double bond functional groups to the textiles through covalent bonds. Since the covalent bond is very strong, the antibacterial and deodorizing functional groups are not easy to fall off on the textiles, and the antibacterial and deodorizing functions are long-lasting. Since conventional photocatalyst materials are inorganic particles, the surface does not contain carbon-carbon double bonds and cannot participate in graft polymerization reactions. Therefore, the present invention first performs surface treatment on the photocatalyst particles with a carbon-carbon double bond-containing silane coupling agent, modifies the carbon-carbon double bonds on the surface, and then grafts them onto the textiles together with a quaternary ammonium salt antibacterial agent containing carbon-carbon double bonds, thereby preparing antibacterial and deodorizing textiles with long-lasting functions.

[0014] In particular, electron beam energy is 5 to 6 orders of magnitude higher than the bond energy of covalent bonds such as carbon-carbon bonds and carbon-hydrogen bonds. Therefore, through electron beam bombardment, active macromolecular free radicals can be generated on the surface of almost all types of organic polymer materials (thus, the present invention is applicable to all types of textile fabrics). The active macromolecular free radicals are then used to initiate the addition polymerization of monomers containing carbon-carbon double bonds, which can firmly bind the antibacterial and deodorizing groups to the fiber macromolecules through covalent bonds. This electron beam processing process can be operated at room temperature, and the energy conversion efficiency is far higher than that of reactions initiated by heating. At the same time, because the photocatalyst particles are modified with silane coupling agents, each particle will contain multiple carbon-carbon double bonds. Therefore, the modified photocatalyst particles themselves are multifunctional monomers, which can have a greater probability of participating in graft polymerization. Therefore, the electron beam grafting process of the present invention has an extremely high reaction efficiency, which can even be increased to 100%, and almost no waste emissions are generated, which is environmentally friendly.

[0015] Preferably, the method for preparing the long-lasting, wash-resistant, antibacterial and deodorizing textile comprises preparing a quaternary ammonium salt monomer containing a carbon-carbon double bond and photocatalyst particles containing a carbon-carbon double bond into an aqueous, oily or emulsion-like dispersion, immersing the textile in the dispersion and then performing pressure rolling, irradiating the textile with an electron accelerator in a nitrogen or vacuum atmosphere, and then washing and drying the textile to obtain the long-lasting, wash-resistant, antibacterial and deodorizing textile. In a preferred embodiment, the mass concentration of the quaternary ammonium salt monomer containing a carbon-carbon double bond in the dispersion is 0.5% to 50%, and the mass concentration of the photocatalyst particles containing a carbon-carbon double bond is between 0.01% and 10%.

[0016] Preferably, the inorganic photocatalyst particles are at least one of the group consisting of TiO2, ZnO, WO3, Fe2O3, SnO2, SrTiO3, and SiO2 particles. In a preferred embodiment, the inorganic photocatalyst particles are one or a mixture of two or more of TiO2, ZnO, Fe2O3, and SnO2.

[0017] Preferably, the silane coupling agent containing a carbon-carbon double bond is at least one member selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, vinyltri-tert-butyloxysilane, vinyltri-tert-butylperoxysilane, vinyltriacetoxysilane, acryloyloxyethyltrimethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloyloxyethyltrimethoxysilane, and methacryloyloxypropyltrimethoxysilane. In a preferred embodiment, the silane coupling agent containing a carbon-carbon double bond is one or a mixture of two or more members selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane, acryloyloxyethyltrimethoxysilane, and methacryloyloxyethyltrimethoxysilane.

[0018] Preferably, the reaction of the inorganic photocatalyst particles with the silane coupling agent containing carbon-carbon double bonds is carried out by immersing the inorganic photocatalyst particles in a water or ethanol solution of the silane coupling agent containing carbon-carbon double bonds to obtain photocatalyst particles modified with carbon-carbon double bonds.

[0019] Preferably, the concentration of the water or ethanol solution of the carbon-carbon double bond-containing silane coupling agent is 0.1% to 50%.

[0020] Preferably, the reaction temperature of the inorganic photocatalyst particles immersed in the water or ethanol solution containing the carbon-carbon double bond silane coupling agent is -10°C to 50°C, and the reaction time is 5 minutes to 72 hours.

[0021] Preferably, the quaternary ammonium salt monomer containing a carbon-carbon double bond functional group is at least one member selected from the group consisting of acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium bromide, methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium bromide, dimethyldiallylammonium chloride, dimethyldiallylammonium bromide, (3-acrylamidopropyl)trimethylammonium chloride, and (3-acrylamidopropyl)trimethylammonium bromide. In a preferred embodiment, the quaternary ammonium salt monomer containing a carbon-carbon double bond is one or a mixture of two or more members selected from the group consisting of acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium bromide, methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium bromide, and dimethyldiallylammonium chloride.

[0022] Preferably, the textile, photocatalyst particles modified with carbon-carbon double bonds, and a quaternary ammonium salt monomer containing carbon-carbon double bond functional groups are irradiated with an electron beam from an electron accelerator to initiate graft polymerization. This invention incorporates the advantages of electron accelerator radiation-induced graft polymerization on the surface of polymer materials—room temperature operation, low energy consumption, minimal pollution, and strong bonding of functional groups to the polymer itself—into the production process of antibacterial and deodorizing textiles, providing a new approach for producing textiles with long-lasting antibacterial and deodorizing properties.

[0023] Preferably, the energy of the electron beam is between 100keV and 10MeV. In a preferred embodiment, the energy of the electron beam is between 500keV and 3MeV. It should be understood that the penetration depth of the electron beam is related to the energy, and the higher the energy, the deeper the penetration. Less than 100keV can also produce free radicals on the surface of the textile, but the penetration ability is insufficient, and the reaction usually occurs in the shallow surface layer. Bacteria can still multiply in the deep layer of the textile and cannot be killed. Although the energy exceeds 10MeV, the penetration ability is stronger, but it is greater than the threshold for generating induced radioactivity (that is, it will cause the irradiated sample to also generate radioactivity), and it cannot be used in conventional industrial processing. Therefore, the protection range of the present invention for electron beam energy is between 100keV and 10MeV, and the preferred energy range is more suitable for textiles of common thickness.

[0024] Preferably, the current intensity of the electron beam is between 5 mA and 2 A. In a preferred embodiment, the current intensity of the electron beam is between 50 mA and 500 mA.

[0025] Preferably, the absorbed dose is between 1 kGy and 300 kGy. In a preferred embodiment, the absorbed dose is between 5 and 60 kGy.

[0026] The long-lasting, wash-resistant, antibacterial and deodorizing textile according to the present invention is obtained according to the above-mentioned preparation method.

[0027] Preferably, the long-lasting, wash-resistant, antibacterial, and deodorizing textile is a woven fabric, a knitted fabric, a nonwoven fabric, or a yarn. Preferably, the textile is a variety of chemical fibers such as cotton, linen, silk, and wool, or blends of these materials. In a preferred embodiment, the textile is at least one of cotton, silk, wool, linen, bamboo fiber, Tencel, Modal, acetate, polyester, nylon, acrylic, spandex, polyethylene, and polypropylene. It should be understood that the blending ratio of the textiles can be almost any desired. This is because the energy of the electron beam is much higher than the covalent bond energy in the polymer structure, so it can induce free radicals on almost all polymers, making it suitable for blended textiles.

[0028] Preferably, the grafting rate of the photocatalyst particles on the textile is between 0.01% and 10%, and the grafting rate of the quaternary ammonium salt monomer on the textile is between 0.1% and 200%. Wherein, the calculation formula of the grafting rate is: (textile weight after reaction - textile weight before reaction) / textile weight before reaction * 100%. In a preferred embodiment, the grafting rate of the quaternary ammonium salt monomer on the textile is between 1% and 50%, and the total grafting rate of the photocatalyst particles on the textile is between 0.05% and 3%. It should be understood that the grafting rate is affected by many factors such as whether the substrate is easy to absorb water (the liquid carrying rate is high or low), whether the substrate is sensitive to radiation (more free radicals are generated under the same dose), the compatibility of the substrate and the monomer, the type of monomer, the concentration of the monomer, etc., and is relatively complicated. Because the radiation grafting technology of the present invention is applicable to various textile fabrics).

[0029] According to the present invention, a method for preparing long-lasting, wash-resistant, antibacterial and deodorizing textiles utilizes electron beam-induced graft polymerization to covalently bond quaternary ammonium salt monomers and photocatalyst particles to the textile. This process can be performed at room temperature and is compatible with existing textile finishing lines. Compared to conventional industrial methods for preparing antibacterial and deodorizing textiles, the antibacterial and deodorizing textiles prepared in this invention exhibit strong bonds between the antibacterial and deodorizing groups, which are not easily detached during use, resulting in long-lasting antibacterial and deodorizing properties and safety for both the human body and the environment. DETAILED DESCRIPTION

[0030] Basic conception of the present invention is that quaternary ammonium salt and photocatalyst are combined, be used on the textiles jointly, make its function complementation, play synergy, quaternary ammonium salt can bring into play its rapid broad-spectrum sterilization effect and suppress the effect of the stink that is produced by bacterial reproduction and the absorption small part ammonia, photocatalyst is played the effect of the stink that eliminates the quaternary ammonium salt and can't act on the textiles, thereby make textiles have good lasting broad-spectrum antibacterial deodorizing function.Yet, only simply transplant existing conventional technology quaternary ammonium salt and photocatalyst are attached to the textiles simultaneously, can not play synergy, and both can hinder each other on the contrary.Because existing conventional technology is that photocatalyst is stuck on the textiles with adhesive, and relies on the bonding of adhesive, not only photocatalyst comes off easily, the defect that function is not lasting still exists, adhesive also can cover the quaternary ammonium salt molecule of considerable part, hinders it to contact with bacteria, has reduced the antibacterial function of quaternary ammonium salt.

[0031] The present invention solves the problem that conventional technologies cannot achieve synergistic effects between quaternary ammonium salts and photocatalysts. The quaternary ammonium salts and photocatalysts are both firmly covalently bonded to textiles, thereby exerting a synergistic effect between the two and preparing textiles with long-lasting broad-spectrum antibacterial and deodorizing properties. Specifically, the surface chemical structure of the photocatalyst is modified to allow the photocatalyst to be bonded with carbon-carbon double bond functional groups capable of participating in free radical addition polymerization. Graft copolymerization of the photocatalyst and the quaternary ammonium salt monomer on the textile is then initiated by ionizing radiation.

[0032] The photocatalyst particles chemically modified with carbon-carbon double bonds contain multiple carbon-carbon double bonds. That is, the modified photocatalyst particles themselves become a large cross-linking agent. When grafted and copolymerized with quaternary ammonium salt monomers on textiles, high-molecular graft chains formed by the polymerization of the photocatalyst and the quaternary ammonium salt monomers form a network structure, which is similar to sewing buttons (photocatalyst particles) on textiles with silk threads (quaternary ammonium salt graft chains). The bond is firm and will not fall off during use, and the antibacterial and deodorizing functions are long-lasting.

[0033] The present invention eliminates the need for the addition of adhesives, preventing the quaternary ammonium salt monomers and photocatalyst particles from being covered and unable to function, allowing the advantages of both to be fully utilized, resulting in a synergistic antibacterial and deodorizing effect. Therefore, this method can impart long-lasting, wash-resistant, broad-spectrum antibacterial and deodorizing properties to textiles. Applicable textiles include woven fabrics, knitted fabrics, and yarns, exhibiting excellent wash resistance and a pleasant hand feel, making them suitable for the production of products such as T-shirts, shirts, underwear, sportswear, home wear, socks, and insoles. Electron beam-initiated graft polymerization is typically performed at room temperature, resulting in energy conservation, environmental protection, and low cost.

[0034] The preferred embodiments of the present invention are given below and described in detail. Experimental methods without specific conditions in the examples are carried out according to conventional methods and conditions, or according to the product specifications.

[0035] Example 1

[0036] Nano-TiO2 particles were immersed in an ethanol solution of vinyltrichlorosilane (50% by mass in the solution) at -10°C for 72 hours, then filtered and dried to obtain nano-TiO2 particles with surface-modified carbon-carbon double bonds. The nano-TiO2 particles containing carbon-carbon double bonds and acryloyloxyethyltrimethylammonium chloride were sonicated in water to obtain a dispersion, wherein the mass percentage of the nano-TiO2 particles in the dispersion was 0.01%, and the mass percentage of the acryloyloxyethyltrimethylammonium chloride in the dispersion was 50%.

[0037] The grafted cotton yarn and knitted fabric were washed in cold water and then dried. The total grafting rate of the photocatalyst particles and quaternary ammonium salt monomer on the cotton yarn and knitted fabric was measured by weighing. The grafting rate of the photocatalyst particles was calculated by measuring the Ti content after microwave digestion. The grafting rate of the quaternary ammonium salt monomer was calculated by subtracting the grafting rate of the photocatalyst particles from the total grafting rate. The grafting rate of the quaternary ammonium salt monomer on the textile was 50.0%, and the grafting rate of the photocatalyst particles on the textile was 0.01%.

[0038] The antibacterial performance of the above-mentioned cotton yarn bundles and knitted fabric samples were tested with reference to the AATCC 100-2012 standard of the American Association of Textile Chemists and Colorists. The above-mentioned cotton yarn bundles and knitted fabric samples were accelerated washed for 20 cycles (equivalent to 100 home washings) with reference to the accelerated washing method of the AATCC 61-2003 standard, and then the antibacterial performance of the washed samples was tested with reference to the AATCC 100-2012 standard. The deodorization performance of the above-mentioned cotton yarn bundles and knitted fabric samples was tested with reference to the JEC 301-2013 standard of the Japan Functional Textile Evaluation Association.

[0039] The antibacterial and deodorizing properties are shown in Example 1.

[0040] The sources of the raw materials used in this example are as follows: cotton yarn bundles and knitted fabrics, Shanghai Textile Science Research Institute; nano-TiO2 particles, vinyl trichlorosilane, and acryloyloxyethyl trimethylammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

[0041] Example 2

[0042] ZnO particles were immersed in an aqueous solution of vinyltrimethoxysilane (0.1% by mass in the solution) at 50°C for 5 minutes, then filtered and dried to obtain surface-modified carbon-carbon double-bond nano-ZnO particles. The carbon-carbon double-bond nano-ZnO particles and methacryloyloxyethyltrimethylammonium chloride were sonicated in ethanol to obtain a dispersion containing 10% by mass of the nano-ZnO particles and 30% by mass of the methacryloyloxyethyltrimethylammonium chloride.

[0043] Silk yarn bundles and woven fabrics were cut into appropriate sizes, immersed in the above dispersion, and then rolled once with a padder at a pressure of 0.5 kg. The fabrics were then processed in a nitrogen atmosphere under an electron accelerator with parameters of 10 MeV electron beam energy and 5 mA electron beam current. The absorbed dose was 60 kGy.

[0044] The grafted silk yarn and woven fabric were washed in cold water and then dried. The total grafting rate of the photocatalyst and quaternary ammonium salt monomers on the textiles was measured by weighing. The grafting rate of the photocatalyst particles was calculated by measuring the Zn content after microwave digestion. The grafting rate of the quaternary ammonium salt monomer was calculated by subtracting the grafting rate of the photocatalyst particles from the total grafting rate. Testing and calculation showed that the grafting rate of the photocatalyst particles on the silk yarn and woven fabric was 10%, and the grafting rate of the quaternary ammonium salt monomer was 25.5%.

[0045] The antibacterial performance of the silk yarn bundles and woven fabric samples was tested with reference to the AATCC 100-2012 standard of the American Association of Textile Chemists and Colorists, and the deodorizing performance of the silk yarn bundles and woven fabric samples was tested with reference to the JEC 301-2013 standard of the Japan Functional Textile Evaluation Association.

[0046] The antibacterial and deodorizing properties are shown in Example 2.

[0047] The sources of the raw materials used in this example are as follows: silk yarn bundles and woven fabrics, Zhejiang Shengtai Group; nano ZnO particles, vinyl trimethoxysilane, and methacryloyloxyethyl trimethylammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

[0048] Example 3

[0049] Fe2O3 particles were immersed in a mixed aqueous solution of acryloyloxyethyltrimethoxysilane and methacryloyloxyethyltrimethoxysilane (the mass percentages of acryloyloxyethyltrimethoxysilane and methacryloyloxyethyltrimethoxysilane in the aqueous solution were 1% and 4%, respectively) at 25°C for 30 minutes, then filtered and dried to obtain nano-Fe2O3 particles with surface modified carbon-carbon double bonds. The nano-Fe2O3 particles containing carbon-carbon double bonds, acryloyloxyethyltrimethylammonium bromide, and Tween-85 were sonicated in dimethyl sulfoxide to obtain an emulsion dispersion. The mass percentage of the nano-Fe2O3 particles in the dispersion was 0.4%, the mass percentage of acryloyloxyethyltrimethylammonium bromide in the dispersion was 0.5%, and the mass percentage of Tween-85 in the dispersion was 0.05%.

[0050] A polyester and spandex blended knitted fabric (polyester:spandex ratio of 95:5) was cut to an appropriate size, immersed in the above dispersion, and then rolled once with a roller at a pressure of 0.2 kg. The fabric was then processed in a nitrogen atmosphere under an electron accelerator with an electron beam energy of 3 MeV and a current of 10 mA. The absorbed dose was 300 kGy.

[0051] The grafted polyester and spandex blended knitted fabric was washed with cold water and then dried. The grafting rate of the photocatalyst particles on the polyester and spandex blended knitted fabric was calculated by weighing method and element content analysis method, and the grafting rate of the quaternary ammonium salt monomer on the above-mentioned polyester and spandex blended knitted fabric was 0.05%, and the grafting rate was 0.1%.

[0052] Through the above steps, an antibacterial and deodorizing polyester and spandex blended knitted fabric is prepared.

[0053] The sources of the raw materials used in this example are as follows: polyester and spandex blended knitted fabric, Zhejiang Shengtai Group; nano ZnO particles, acryloyloxyethyl trimethoxysilane, methacryloyloxyethyl trimethoxysilane, and acryloyloxyethyl trimethylammonium bromide, Sinopharm Chemical Reagent Co., Ltd.

[0054] Example 4

[0055] A mixture of nano-TiO2 and SnO2 particles (the mass percentage of the nano-TiO2 and SnO2 particles is 100:1) is immersed in an aqueous solution of methacryloxypropyltrimethoxysilane (the mass percentage of methacryloxypropyltrimethoxysilane in the solution is 20%) at 5°C for 30 minutes, then filtered and dried to obtain nano-Fe2O3 particles with surface modified carbon-carbon double bonds. The nano-TiO2 and SnO2 particles containing carbon-carbon double bonds and methacryloxypropyltrimethylammonium chloride are ultrasonically treated in water to obtain a dispersion. The total mass percentage of the nano-TiO2 and SnO2 particles in the dispersion is 3%, and the mass percentage of methacryloxypropyltrimethoxysilane in the dispersion is 38%.

[0056] A blend of linen, wool, and polypropylene (the ratio of linen, wool, and polypropylene was 88:10:2) was cut to a suitable size, immersed in the above dispersion, and then rolled using a roller with a pressure of 1 kg. The fabric was then processed in a vacuum atmosphere using an electron accelerator with an electron beam energy of 2 MeV and a current of 50 mA. The absorbed dose was 5 kGy.

[0057] The grafted hemp, wool and polypropylene blended woven fabric was washed with cold water and then dried. The grafted fabric was tested and calculated using the weighing method and element content analysis method. The results showed that the grafting rate of photocatalyst particles on the hemp, wool and polypropylene blended woven fabric was 3%, and the grafting rate of quaternary ammonium salt monomer was 200%.

[0058] Through the above steps, the antibacterial and deodorizing hemp, wool and polypropylene blended woven fabric is prepared.

[0059] The sources of the raw materials used in this example are as follows: hemp, wool and polypropylene blended woven fabric, Zhejiang Shengtai Group; nano-TiO2, nano-SnO2, methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethylammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

[0060] Example 5

[0061] At 40° C., SrTiO3 particles were immersed in a mixed aqueous solution of vinyltri(β-methoxyethoxy)silane and vinyltri-tert-butoxysilane (the mass percentages of vinyltri(β-methoxyethoxy)silane and vinyltri-tert-butoxysilane in the aqueous solution were 20% and 10%, respectively), and then filtered and dried to obtain nano-SrTiO3 particles with surface modified carbon-carbon double bonds. The above-mentioned nano-SrTiO3 particles containing carbon-carbon double bonds, methacryloyloxyethyltrimethylammonium bromide, and dimethyldiallyl ammonium chloride were sonicated in water to obtain a dispersion. The mass percentage of the nano-SrTiO3 particles in the dispersion was 5%, the mass percentage of methacryloyloxyethyltrimethylammonium bromide in the dispersion was 15%, and the mass percentage of dimethyldiallyl ammonium chloride in the dispersion was 35%.

[0062] A cotton, modal, and polyethylene blended woven fabric (cotton, modal, and polyethylene in a ratio of 80:15:5) was cut to a suitable size, immersed in the above dispersion, and then rolled once with a padder at a pressure of 0.2 kg. The fabric was then processed in a nitrogen atmosphere under an electron accelerator with an electron beam energy of 500 keV and a current of 500 mA. The absorbed dose was 30 kGy.

[0063] The grafted cotton, modal, and polyethylene blended woven fabric was washed with cold water and then dried. The grafting rate of the photocatalyst particles on the cotton, modal, and polyethylene blended woven fabric was tested and calculated by weighing method and element content analysis method, and the result was that the grafting rate of the photocatalyst particles on the above-mentioned cotton, modal, and polyethylene blended woven fabric was 4.5%, and the total grafting rate of the quaternary ammonium salt monomer was 50.0%.

[0064] Through the above steps, the antibacterial and deodorizing cotton, modal and polyethylene blended woven fabric is prepared.

[0065] The sources of the raw materials used in this example are as follows: cotton, modal, and polyethylene blended woven fabrics, Zhejiang Shengtai Group; nano-SrTiO3 particles, vinyl tris(β-methoxyethoxy) silane, vinyl tri-tert-butoxysilane, methacryloxyethyl trimethoxysilane, methacryloxyethyl trimethylammonium bromide, and dimethyl diallyl ammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

[0066] Example 6

[0067] At 15°C, a mixture of nano-WO3 and SiO2 particles (the mass ratio of nano-WO3 and SiO2 particles is 1:100) is immersed in a mixed ethanol solution of vinyl tri-tert-butyl peroxide silane, vinyl triacetoxy silane, and acryloxyethyl trimethoxy silane (the mass percentages of vinyl tri-tert-butyl peroxide silane, vinyl triacetoxy silane, and acryloxyethyl trimethoxy silane in the aqueous solution are 1%, 5%, and 20%, respectively) for 24 hours, and then filtered and dried to obtain nano-WO3 and SiO2 particles with surface modified carbon-carbon double bonds. The above-mentioned nano-SrTiO3 particles containing carbon-carbon double bonds, (3-acrylamidopropyl)trimethylammonium chloride, and (3-acrylamidopropyl)trimethylammonium bromide are ultrasonically treated in water to obtain a dispersion, wherein the total mass percentage of nano-WO3 and SiO2 particles in the dispersion is 0.5%, the mass percentage of (3-acrylamidopropyl)trimethylammonium chloride in the dispersion is 0.5%, and the mass percentage of (3-acrylamidopropyl)trimethylammonium bromide in the dispersion is 5%.

[0068] Nylon and acetate blended woven fabric (nylon:acetate ratio 60:40) was cut to appropriate size, immersed in the above dispersion, and rolled once with a padder at a pressure of 2 kg. The fabric was then processed in a nitrogen atmosphere under an electron accelerator with an electron beam energy of 500 keV and a current of 100 mA. The absorbed dose was 80 kGy.

[0069] The grafted nylon and acetate blended woven fabric was washed with cold water and then dried. The grafting rate of the photocatalyst particles on the nylon and acetate blended woven fabric was tested and calculated by weighing method and element content analysis method, and the grafting rate of the quaternary ammonium salt monomer on the nylon and acetate blended woven fabric was 0.5%, and the grafting rate of the quaternary ammonium salt monomer was 1%.

[0070] Through the above steps, the antibacterial and deodorizing nylon and acetate blended woven fabric is prepared.

[0071] The sources of the raw materials used in this example are as follows: nylon and acetate blended woven fabric, Zhejiang Shengtai Group; nano-WO3, nano-SiO2, vinyl tri-tert-butyl peroxysilane, vinyl triacetoxysilane, acryloyloxyethyl trimethoxysilane, (3-acrylamidopropyl)trimethylammonium chloride, and (3-acrylamidopropyl)trimethylammonium bromide, Sinopharm Chemical Reagent Co., Ltd.

[0072] Example 7

[0073] At 20° C., nano-TiO2 was immersed in an aqueous solution of methacryloyloxypropyltrimethoxysilane (the mass percentage of methacryloyloxypropyltrimethoxysilane in the aqueous solution was 20%) for 48 hours, then filtered and dried to obtain nano-TiO2 particles with surface modified carbon-carbon double bonds. The above-mentioned nano-TiO2 particles containing carbon-carbon double bonds, methacryloyloxyethyltrimethylammonium bromide, dimethyldiallyl ammonium chloride, and dimethyldiallyl ammonium bromide were sonicated in water to obtain a dispersion, wherein the mass percentage of the nano-TiO2 particles in the dispersion was 0.1%, and the mass percentages of methacryloyloxyethyltrimethylammonium bromide, dimethyldiallyl ammonium chloride, and dimethyldiallyl ammonium bromide in the dispersion were 0.1%, 1%, and 10%, respectively.

[0074] A bamboo fiber and Tencel blended knitted fabric (bamboo fiber:Tencel ratio of 80:20) was cut into appropriate sizes, immersed in the above dispersion, and rolled once with a roller at a pressure of 2 kg. The fabric was then processed in a nitrogen atmosphere under an electron accelerator with an electron beam energy of 100 keV and a current of 20 mA. The absorbed dose was 40 kGy.

[0075] The grafted bamboo fiber and Tencel blended knitted fabric was washed with cold water and then dried. The grafting rate of the photocatalyst particles on the bamboo fiber and Tencel blended knitted fabric was tested and calculated by weighing method and element content analysis method, and the grafting rate of the quaternary ammonium salt monomer on the bamboo fiber and Tencel blended knitted fabric was 0.1%, and the grafting rate was 10.0%.

[0076] Through the above steps, the antibacterial and deodorizing bamboo fiber and Tencel blended knitted fabric is prepared.

[0077] The sources of the raw materials used in this example are as follows: bamboo fiber and Tencel blended knitted fabric, Zhejiang Shengtai Group; nano-TiO2, methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, acryloyloxyethyltrimethoxysilane, methacryloxyethyltrimethylammonium bromide, dimethyldiallylammonium chloride, and dimethyldiallylammonium bromide, Sinopharm Chemical Reagent Co., Ltd.

[0078] Example 8

[0079] A mixture of nano-WO3, SiO2, and SnO2 particles (the mass percentage of nano-WO3, SiO2, and SnO2 is 100:10:1) is immersed in an aqueous solution of acryloyloxyethyltrimethoxysilane (the mass percentage of acryloyloxyethyltrimethoxysilane in the aqueous solution is 1%) at 40°C for 72 hours, then filtered and dried to obtain a mixture of nano-WO3, SiO2, and SnO2 particles with surface modified carbon-carbon double bonds. The mixture of nano-WO3, SiO2, and SnO2 particles containing carbon-carbon double bonds, acryloyloxyethyltrimethylammonium chloride, and methacryloyloxyethyltrimethylammonium chloride are sonicated in water to obtain a dispersion. The total mass percentage of the nano-WO3, SiO2, and SnO2 particle mixture in the dispersion is 5%, and the mass percentages of acryloyloxyethyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride in the dispersion are 10% and 0.1%, respectively.

[0080] A polyethylene nonwoven fabric (cut into a suitable size) was immersed in the above dispersion, rolled once with a padder at a pressure of 2 kg, and then placed in an electron accelerator in a nitrogen atmosphere for processing. The parameters of the electron accelerator were an electron beam energy of 1.5 MeV and an electron beam current of 15 mA. The absorbed dose was 250 kGy.

[0081] The grafted polyethylene nonwoven fabric was washed with cold water and then dried. The grafting rate of the photocatalyst particles on the cotton, polyester and spandex blended knitted fabric was tested and calculated by weighing method and element content analysis method, and the total grafting rate of the quaternary ammonium salt monomer was 3.0%, and 14.7%.

[0082] Through the above steps, the antibacterial and deodorizing polyethylene nonwoven fabric is prepared.

[0083] The sources of the raw materials used in this example are as follows: polyethylene nonwoven fabric, Zhejiang Shengtai Group; nano WO3, nano SiO2, nano SnO2, acryloyloxyethyl trimethoxysilane, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

[0084] Effect Example 1

[0085] Table 1 Antibacterial performance test results of cotton yarn bundles and knitted fabric samples prepared in Example 1

[0086] The long-lasting, wash-resistant, antibacterial and deodorizing cotton yarn bundle and knitted fabric samples prepared in Example 1 were tested for antibacterial properties according to AATCC 100-2012 standards. The results are shown in Table 1. The bacterial species used in the antibacterial tests were Escherichia coli, a typical Gram-negative bacteria species; Staphylococcus aureus, a typical Gram-positive bacteria species; and Candida albicans, a typical fungal species. As shown in Table 1, the cotton yarn bundle and knitted fabric samples prepared in Example 1 exhibited an antibacterial rate of 99% against all three bacterial species, demonstrating excellent antibacterial properties. Furthermore, after 20 cycles of accelerated washing (equivalent to 100 household washes), the antibacterial rate remained virtually unchanged, exceeding 99%.

[0087] Table 2 Deodorizing performance test results of cotton yarn bundles and knitted fabric samples prepared in Example 1

[0088] The long-lasting, wash-resistant, antibacterial, and deodorizing cotton yarn bundles and knitted fabric samples prepared in Example 1 were tested for deodorization performance with reference to JEC 301-2013. The results are shown in Table 2. The samples prepared in Example 1 demonstrated removal rates for the four major odorants, ammonia, acetic acid, isovaleric acid, and nonenal, exceeding the JEC standard requirement (over 70%). Furthermore, the removal rates remained high even after 10 washes according to the JEC standard.

[0089] The above antibacterial and deodorizing test results indicate that the method of the present invention can firmly combine the antibacterial groups with the textiles, thereby making the antibacterial properties of the textiles very long-lasting.

[0090] Effect Example 2

[0091] Table 3 Antibacterial performance test results of silk yarn bundles and woven fabric samples prepared in Example 2

[0092] The long-lasting, wash-resistant, antibacterial and deodorizing silk yarn and woven fabric samples prepared in Example 2 were tested for antibacterial properties according to AATCC 100-2012 standards. The results are shown in Table 3. The bacterial species used in the antibacterial tests were Escherichia coli, a typical Gram-negative bacteria; Staphylococcus aureus, a typical Gram-positive bacteria; and Candida albicans, a typical fungal species. As shown in Table 3, the silk yarn and woven fabric samples prepared in Example 2 exhibited an antibacterial rate of 99% against all three bacterial species, demonstrating excellent antibacterial properties. Furthermore, after 20 cycles of accelerated washing (equivalent to 100 household washes), the antibacterial rate remained virtually unchanged, exceeding 99%.

[0093] Table 4 Deodorizing performance test results of silk yarn bundles and woven fabric samples prepared in Example 2

[0094] The long-lasting, wash-resistant, antibacterial, and deodorizing silk yarn and woven fabric samples prepared in Example 2 were tested for deodorization performance with reference to JEC 301-2013. The results are shown in Table 4. The samples prepared in Example 2 demonstrated removal rates for four major odorants, including ammonia, acetic acid, isovaleric acid, and nonenal, exceeding the JEC standard (over 70%). Furthermore, after 10 washes according to the JEC standard, the odorant removal rate remained relatively unchanged, maintaining a good level.

[0095] The above antibacterial and deodorizing test results indicate that the method of the present invention can firmly combine the antibacterial groups with the textiles, thereby making the antibacterial properties of the textiles very long-lasting.

[0096] Because textile products directly impact consumers, who have intuitive perceptions and corresponding requirements for textile color, feel, odor, color fastness, and other aspects, the method for preparing antibacterial and deodorizing textiles according to the present invention can impart long-lasting antibacterial and deodorizing properties to textiles without affecting their basic apparel properties, such as feel, and thus possesses practical application value.

[0097] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Various modifications are possible. In other words, any simple, equivalent changes and modifications made in accordance with the claims and description of the present invention are within the scope of protection of the patent claims. Anything not fully described in this invention constitutes conventional technology.

Claims

1. A method for preparing long-lasting, wash-resistant, antibacterial and deodorizing textiles, characterized in that: The preparation method comprises providing textiles, inorganic photocatalyst particles, a silane coupling agent containing a carbon-carbon double bond, and a quaternary ammonium salt monomer containing a carbon-carbon double bond functional group; reacting the inorganic photocatalyst particles with the silane coupling agent containing a carbon-carbon double bond to modify the surface of the photocatalyst with a carbon-carbon double bond; initiating graft polymerization by electron beam irradiation; generating active free radicals on the textile to initiate graft polymerization of the quaternary ammonium salt monomer containing a carbon-carbon double bond functional group and the photocatalyst particles modified with the carbon-carbon double bond functional group, thereby firmly fixing the polyquaternary ammonium salt and the photocatalyst particles to the textile through covalent bonds, thereby giving the textile antibacterial and deodorizing functions.

2. The preparation method according to claim 1, characterized in that The inorganic photocatalyst particles are at least one selected from the group consisting of TiO2, ZnO, WO3, Fe2O3, SnO2, SrTiO3, and SiO2 particles.

3. The preparation method according to claim 1, characterized in that The carbon-carbon double bond-containing silane coupling agent is at least one member selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, vinyltri-tert-butyloxysilane, vinyltri-tert-butylperoxysilane, vinyltriacetoxysilane, acryloyloxyethyltrimethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloyloxyethyltrimethoxysilane, and methacryloyloxypropyltrimethoxysilane.

4. The preparation method according to claim 1, characterized in that The reaction of the inorganic photocatalyst particles with the silane coupling agent containing a carbon-carbon double bond is carried out by immersing the inorganic photocatalyst particles in a water or ethanol solution of the silane coupling agent containing a carbon-carbon double bond to react and obtain photocatalyst particles modified with carbon-carbon double bonds.

5. The preparation method according to claim 4, characterized in that The concentration of the water or ethanol solution containing the carbon-carbon double bond silane coupling agent is 0.1% to 50%.

6. The preparation method according to claim 4, characterized in that The inorganic photocatalyst particles are immersed in a water or ethanol solution containing a carbon-carbon double bond silane coupling agent, and the reaction temperature is -10°C to 50°C, and the reaction time is 5 minutes to 72 hours.

7. The preparation method according to claim 1, characterized in that The quaternary ammonium salt monomer containing a carbon-carbon double bond functional group is at least one member selected from the group consisting of acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium bromide, methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium bromide, dimethyldiallylammonium chloride, dimethyldiallylammonium bromide, (3-acrylamidopropyl)trimethylammonium chloride, and (3-acrylamidopropyl)trimethylammonium bromide.

8. The preparation method according to claim 1, characterized in that The electron beam of an electron accelerator is used to irradiate textiles, photocatalyst particles modified with carbon-carbon double bonds and quaternary ammonium salt monomers containing carbon-carbon double bond functional groups to initiate graft polymerization.

9. The preparation method according to claim 9, characterized in that The energy of the electron beam ranges from 100 keV to 10 MeV.

10. The preparation method according to claim 9, characterized in that The current intensity of the electron beam is between 5mA and 2A.

11. The preparation method according to claim 9, characterized in that The absorbed dose is between 1kGy and 300kGy.

12. A long-lasting, wash-resistant, antibacterial and deodorizing textile, characterized in that: The long-lasting, wash-resistant, antibacterial and deodorizing textile is obtained according to the preparation method described in any one of claims 1 to 11.

13. The long-lasting, wash-resistant, antibacterial and deodorizing textile according to claim 12, characterized in that: The long-lasting, wash-resistant, antibacterial and deodorizing textile is made of woven fabric, knitted fabric, non-woven fabric or yarn.

14. The long-lasting, wash-resistant, antibacterial and deodorizing textile according to claim 12, characterized in that: The grafting rate of the photocatalyst particles on the textiles is between 0.01% and 10%, and the grafting rate of the quaternary ammonium salt monomer on the textiles is between 0.1% and 200%.

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