WO2024131999A2 - Long-acting washing-resistant antibacterial deodorizing textile and preparation method therefor - Google Patents

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

The invention relates to textiles, and more particularly to a long-lasting washing-resistant, antibacterial and deodorizing textile and a preparation method thereof.

Background technique

Textiles are a necessity in human life. With economic development and the improvement of people's living standards, people's requirements for textiles are no longer just to cover the body, keep warm and look beautiful, but they hope that textiles have more functions, such as waterproof and breathable, UV protection, antibacterial and deodorizing.

Antibacterial and deodorizing textiles are a type of functional textiles that improve people's quality of life. Their antibacterial function can kill and inhibit the growth of various bacteria and other microorganisms on textiles, prevent the growth of harmful bacteria and other microorganisms and enter the human body through contact, which helps to protect the health of users; at the same time, antibacterial functional textiles can inhibit microorganisms from decomposing human secretions and thus prevent the generation of odorous small molecules. In addition to eliminating odorous small molecules produced by microorganisms, deodorizing functional textiles can also remove odorous small molecules emitted by the body through adsorption or decomposition, increasing the comfort of oneself and the people around.

After years of development, textiles with simple antibacterial functions have some mature processes and a considerable market size. Antibacterial agents commonly used in textiles can be divided into two categories: inorganic and organic. Inorganic antibacterial agents include nanometal particles (such as nanosilver, nanocopper, etc., among which nanosilver has been banned by 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., organic antibacterial agents chitosan, guanidine antibacterial agents, quaternary ammonium salt antibacterial agents, etc.). The commonly used method for preparing antibacterial textiles in industry is to use post-finishing method, which is to pass the antibacterial agent dispersion through high temperature impregnation to make the antibacterial agent adhere to the surface of the textile. Sometimes, in order to increase the adhesion, a small amount of adhesive is added to the dispersion to stick the antibacterial agent to the textile.

The odor emitted by the human body is partly due to the ammonia, isovaleric acid, acetic acid and other odors released during the bacterial growth on the skin surface. In a warm and humid environment (such as after exercise), the bacteria multiply in large numbers, so odor is more likely to occur. Antibacterial textiles can kill or inhibit the growth of bacteria on the skin surface, thus eliminating the odor from this source. The other part of the odor, such as the smell of old people, is mainly derived from the nonenal produced by the body's own metabolism. In addition, diabetic patients with diabetic ketoacidosis Acidosis, late-stage kidney disease, and impaired liver function can also produce odors. In addition to the odors produced by the human body, smoking, eating hot pot, etc. can also cause odors to adhere to clothes, making people around them uncomfortable. Ordinary antibacterial functional textiles cannot eliminate odors from this source, and corresponding functional substances with adsorption or decomposition functions need to be added to achieve deodorization.

Photocatalyst materials are a general term for semiconductor materials with photocatalytic functions. The earliest discovered photocatalyst material is nano-TiO ₂ , which can be excited under ultraviolet light to produce strong oxidizing properties, kill bacteria, and decompose organic matter such as formaldehyde. Therefore, it has good application prospects in the field of antibacterial and deodorizing. With the development of technology, more photocatalyst materials with photocatalytic oxidation functions have been synthesized, and the excitation light source is no longer limited to ultraviolet light, and photocatalysis can also be produced under visible light.

Due to the bactericidal and photocatalytic decomposition effects of photocatalyst materials on small molecular organic matter, there have been many studies on its application in antibacterial and deodorizing textiles. At present, 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 textiles in a post-finishing manner. The disadvantage of this method is that a considerable part 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. Therefore, its antibacterial and deodorizing function is not long-lasting, and 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.

Quaternary ammonium salts are a general term for positively charged organic substances containing tetravalent nitrogen atoms. Quaternary ammonium salts are often used as antimicrobial agents such as bactericides, and have long been widely used in the fields of water purification, antibacterial fabrics, etc. The positive charge carried by quaternary ammonium salts can attract each other with the negative charge of the cell membrane or lipid layer of microorganisms such as bacteria, thereby capturing bacteria and other microorganisms, and using lipophilic alkyl chains to destroy the cell membrane or envelope, thereby achieving the effect of killing microorganisms. The bactericidal principle of quaternary ammonium salts is the physical effect of charge attraction and lipophilic membrane breaking, so it is safe and effective with few side effects. In particular, polymerized quaternary ammonium salts are highly stable, heat-resistant, and not easy to decompose, making them a commonly used type of disinfectant. At the same time, quaternary ammonium salt disinfectants also have a certain deodorizing effect. They can inhibit bacterial reproduction, thereby eradicating the odor caused by bacterial reproduction from the source; at the same time, quaternary ammonium salts can also adsorb acidic odorous small molecules such as acetic acid and isovaleric acid through charge interaction, and can also play a certain adsorption role on ammonia by combining with the lone pair of electrons on ammonia molecules. Combining quaternary ammonium salts with textiles can have a good broad-spectrum antibacterial effect and can also deodorize some odor sources. The valence bonds are bonded to textiles, making it difficult for quaternary ammonium salts to fall off, and the broad-spectrum antibacterial and partial deodorizing functions are more lasting.

In summary, quaternary ammonium salts and photocatalysts each have their own advantages and certain defects 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.

Summary of the invention

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

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

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 active free radicals generated on the textiles are irradiated with electron beams to initiate free radical addition polymerization of carbon-carbon double bond functional groups, thereby connecting 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 through a carbon-carbon double bond-containing silane coupling agent, modifies the carbon-carbon double bonds on the surface, and then grafts them together with a quaternary ammonium salt antibacterial agent containing carbon-carbon double bonds onto the textiles, thereby preparing antibacterial and deodorizing textiles with long-lasting functions.

In particular, the energy of electron beams 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 the bombardment of electron beams, active macromolecular free radicals can be generated on the surface of almost all types of organic polymer materials (therefore, the present invention is applicable to all types of textile fabrics), and then used to Active macromolecular free radicals initiate the addition polymerization of monomers containing carbon-carbon double bonds, and the antibacterial and deodorizing groups can be firmly bound to the macromolecules of the fiber through covalent bonds. This electron beam processing process can be operated at room temperature, and the energy conversion efficiency is much higher than that of the reaction initiated by heating. At the same time, since the photocatalyst particles are modified by silane coupling agents, a particle will contain multiple carbon-carbon double bonds. Therefore, the modified photocatalyst particles themselves are multifunctional monomers and can have a greater probability of participating in graft polymerization. Therefore, the reaction efficiency of the electron beam grafting process of the present invention is extremely high, and can even be increased to 100%, with almost no waste emissions, and is environmentally friendly.

Preferably, the preparation method of the long-lasting washing-resistant antibacterial deodorizing textile comprises preparing a quaternary ammonium salt monomer containing a carbon-carbon double bond and a photocatalyst particle containing a carbon-carbon double bond into an aqueous phase, an oil phase or an emulsion-like dispersion, immersing the textile in the dispersion and then performing pressure rolling, irradiating with an electron accelerator in a nitrogen or vacuum atmosphere, and then washing and drying to obtain a long-lasting washing-resistant antibacterial 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 particle containing a carbon-carbon double bond is between 0.01% and 10%.

Preferably, the inorganic photocatalyst particles are at least one of the group consisting of _TiO2 , ZnO, _WO3 , _{Fe2O3 , SnO2} , _SrTiO3 , _SiO2 particles. In a preferred embodiment, the inorganic photocatalyst particles are _TiO2 , ZnO, _Fe2O3 , _SnO2 , or a mixture _of two or more thereof.

Preferably, the carbon-carbon double bond-containing silane coupling agent is at least one of the group consisting of vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(β-methoxyethoxy)silane, vinyl tri-tert-butyloxysilane, vinyl tri-tert-butylperoxysilane, vinyl triacetoxysilane, acryloxyethyl trimethoxysilane, acryloxypropyl trimethoxysilane, methacryloxyethyl trimethoxysilane, and methacryloxypropyl trimethoxysilane. In a preferred embodiment, the carbon-carbon double bond-containing silane coupling agent is one or a mixture of two or more of vinyl trichlorosilane, vinyl trimethoxysilane, acryloxyethyl trimethoxysilane, and methacryloxyethyl trimethoxysilane.

Preferably, the reaction of the inorganic photocatalyst particles with the silane coupling agent containing carbon-carbon double bonds is to immerse the inorganic photocatalyst particles in a water or ethanol solution of the silane coupling agent containing carbon-carbon double bonds to react and obtain photocatalyst particles modified with carbon-carbon double bonds.

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

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 5min to 72h.

Preferably, the quaternary ammonium salt monomer containing a carbon-carbon double bond functional group is at least one of the group consisting of acryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium bromide, methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium bromide, dimethyldiallyl ammonium chloride, dimethyldiallyl ammonium bromide, (3-acrylamidopropyl) trimethyl ammonium chloride, and (3-acrylamidopropyl) trimethyl ammonium bromide. In a preferred embodiment, the quaternary ammonium salt monomer containing a carbon-carbon double bond is acryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium bromide, methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium bromide, and dimethyldiallyl ammonium chloride, or a mixture of two or more thereof.

Preferably, the textile, the photocatalyst particles modified with carbon-carbon double bonds and the quaternary ammonium salt monomer containing carbon-carbon double bond functional groups are irradiated with an electron beam of an electron accelerator to initiate graft polymerization. The present invention introduces the advantages of normal temperature operation, low energy consumption, less pollution and firm combination of functional groups and polymer bodies of the graft polymerization on the surface of polymer materials initiated by electron accelerator radiation into the preparation process of antibacterial and deodorizing textiles, providing a new path for preparing textiles with long-lasting antibacterial and deodorizing properties.

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. Free radicals can be generated on the surface of textiles when the energy is less than 100keV, 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 exceeding 10MeV has stronger penetration ability, it is greater than the threshold value for generating induced radioactivity (that is, it will cause the irradiated sample to generate radioactivity), and cannot be used in conventional industrial processing. Therefore, the protection range of the electron beam energy of the present invention is between 100keV and 10MeV, and the preferred energy range is more suitable for textiles of common thickness.

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.

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

The long-lasting washing-resistant antibacterial and deodorizing textile according to the present invention is obtained according to the above-mentioned preparation method.

Preferably, the long-lasting washing-resistant antibacterial and deodorizing textile is a woven fabric, a knitted fabric, a nonwoven fabric, or a yarn. Preferably, the textile is a chemical fiber such as cotton, linen, silk, wool, or a blend of these materials. In a preferred embodiment, the textile is a cotton, silk, wool, linen, bamboo fiber, Tencel, mo At least one of dal, acetate, polyester, nylon, acrylic, spandex, polyethylene, and polypropylene. It should be understood that the mixing ratio of the textiles can be almost any according to needs, 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, so it is suitable for blended textiles.

Preferably, the grafting rate of photocatalyst particles on textiles is between 0.01% and 10%, and the grafting rate of quaternary ammonium salt monomers on textiles 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 quaternary ammonium salt monomers on textiles is between 1% and 50%, and the total grafting rate of photocatalyst particles on textiles 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 (producing more free radicals at 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).

According to the preparation method of the long-lasting washing-resistant antibacterial and deodorizing textiles of the present invention, the quaternary ammonium salt monomer and the photocatalyst particles are covalently bonded to the textiles by means of an electron beam-induced graft polymerization reaction, and the operation process can be carried out at room temperature and can be connected with the current textile finishing process line. Compared with the current conventional industrial preparation method of antibacterial and deodorizing textiles, the antibacterial and deodorizing textiles prepared by the present invention have the antibacterial and deodorizing groups firmly bonded to the textiles, are not easy to fall off during use, have long-lasting antibacterial and deodorizing functions, and are safe for the human body and the environment.

Detailed ways

Basic conception of the present invention is to combine quaternary ammonium salt and photocatalyst, be used on textiles together, make its function complement, play synergistic effect, quaternary ammonium salt can bring into play its rapid broad-spectrum bactericidal effect and suppress the effect of stink produced by bacterial reproduction and adsorption of a small part of ammonia, photocatalyst brings into play the effect of eliminating the stink produced by the odor source that quaternary ammonium salt cannot act on, thereby make textiles have good lasting broad-spectrum antibacterial deodorizing function.Yet, only simply transplanting existing conventional technology combines quaternary ammonium salt and photocatalyst on textiles simultaneously, can not play synergistic effect, on the contrary both can hinder each other.Because existing conventional technology is that photocatalyst is adhered on textiles with adhesive, and relies on the bonding of adhesive, not only the defect that photocatalyst easily comes off, function is not lasting still exists, adhesive can also cover the quaternary ammonium salt molecule of considerable part, hinders it from contacting with bacteria, reduces the antibacterial function of quaternary ammonium salt.

The present invention solves the problem that conventional technology cannot make the quaternary ammonium salt and the photocatalyst fuse and work synergistically with each other. The problem is to make both quaternary ammonium salt and photocatalyst bond to textiles with strong covalent bonds, give full play to the synergistic effect of the two, and prepare textiles with long-lasting and broad-spectrum antibacterial and deodorizing effects, that is: by modifying the surface chemical structure of the photocatalyst, it is combined with carbon-carbon double bond functional groups that can participate in free radical addition polymerization, and then with quaternary ammonium salt monomers containing carbon-carbon double bonds through ionizing radiation to induce the graft copolymerization of photocatalyst and quaternary ammonium salt monomers on textiles.

The photocatalyst particles chemically modified with carbon-carbon double bonds of the present invention contain multiple carbon-carbon double bonds on one particle, that is, the photocatalyst particles themselves become a large cross-linking agent after modification, and are grafted and copolymerized with quaternary ammonium salt monomers on textiles. The polymer 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 combination is firm and will not fall off during use, and the antibacterial and deodorizing functions are long-lasting.

The present invention does not need to add adhesives, etc., and will not cause the surface of quaternary ammonium salt monomers and photocatalyst particles to be covered and unable to function, so that the advantages of both can be exerted and synergistically produce antibacterial and deodorizing effects. Therefore, the method can give textiles long-lasting and wash-resistant broad-spectrum antibacterial and deodorizing functions. Applicable textiles include woven fabrics, knitted fabrics, yarns, etc., which have excellent washing resistance and good hand feel, and are suitable for the production of T-shirts, shirts, underwear, sportswear, home clothes, socks, insoles and other products. Electron beam-induced graft polymerization is usually carried out at room temperature, which is energy-saving and environmentally friendly, and has low cost.

The preferred embodiments of the present invention are given below and described in detail. The experimental methods without specific conditions in the embodiments are selected according to conventional methods and conditions, or according to the product instructions.

Example 1

At -10°C, nano _-TiO2 particles were immersed in an ethanol solution of vinyl trichlorosilane (the mass percentage of vinyl trichlorosilane in the solution was 50%) 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 acryloyloxyethyl trimethyl ammonium chloride were ultrasonically treated 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 acryloyloxyethyl trimethyl ammonium chloride in the dispersion was 50%.

The grafted cotton yarn bundle and knitted fabric were washed with cold water and then dried. The total grafting rate of photocatalyst particles and quaternary ammonium salt monomers on the cotton yarn bundle and knitted fabric was measured by weighing method. The grafting rate of photocatalyst particles was calculated by measuring the Ti element content after microwave digestion. The grafting rate of quaternary ammonium salt monomers was obtained by subtracting the grafting rate of photocatalyst particles from the total grafting rate. After testing, the grafting rate of quaternary ammonium salt monomers on textiles The rate is 50.0%, and the grafting rate of photocatalyst particles on textiles is 0.01%.

The antibacterial properties of the above-mentioned cotton yarn bundles and knitted fabric samples were tested with reference to the American Association of Textile Chemists and Dyers AATCC 100-2012 standard, and the accelerated washing method of the above-mentioned cotton yarn bundles and knitted fabric samples was used for 20 cycles of accelerated washing (equivalent to 100 home washings) according to the AATCC 61-2003 standard. Then, the antibacterial properties of the washed samples were tested with reference to the AATCC 100-2012 standard, and the deodorizing performance was tested with reference to the Japan Functional Textiles Evaluation Association JEC 301-2013 standard.

The test results of antibacterial performance and deodorizing performance are shown in Example 1.

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.

Example 2

At 50°C, ZnO particles were immersed in an aqueous solution of vinyl trimethoxysilane (the mass percentage of vinyl trimethoxysilane in the solution was 0.1%) for 5 minutes, then filtered and dried to obtain nano ZnO particles with surface modified carbon-carbon double bonds. The above nano ZnO particles containing carbon-carbon double bonds and methacryloyloxyethyl trimethyl ammonium chloride were ultrasonically treated in ethanol to obtain a dispersion, the mass percentage of the nano ZnO particles in the dispersion was 10%, and the percentage of methacryloyloxyethyl trimethyl ammonium chloride in the dispersion was 30%.

The silk yarn bundle and woven fabric were cut into appropriate sizes, immersed in the above dispersion, rolled once with a rolling wheel at a pressure of 0.5 kg, and then placed in an electron accelerator for processing in a nitrogen atmosphere. The parameters of the electron accelerator were electron beam energy of 10 MeV, electron beam current of 5 mA, and an absorbed dose of 60 kGy.

The grafted silk yarn bundle and woven fabric were washed with cold water and then dried. The total grafting rate of photocatalyst and quaternary ammonium salt monomer on the textile was measured by weighing method. The grafting rate of photocatalyst particles was calculated by measuring the Zn element content after microwave digestion. The grafting rate of quaternary ammonium salt monomer was obtained by subtracting the grafting rate of photocatalyst particles from the total grafting rate. After testing and calculation, the grafting rate of photocatalyst particles on the above silk yarn bundle and woven fabric was 10%, and the grafting rate of quaternary ammonium salt monomer was 25.5%.

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

The test results of antibacterial performance and deodorizing performance are shown in Example 2.

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.

Example 3

At ₂₅ °C, _Fe2O3 particles were immersed in a mixed aqueous solution of acryloyloxyethyl trimethoxysilane and methacryloyloxyethyl trimethoxysilane (the mass percentages of acryloyloxyethyl trimethoxysilane and methacryloyloxyethyl trimethoxysilane in the aqueous solution were 1% and 4%, respectively) 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, acryloyloxyethyl _trimethyl ammonium bromide and Tween-85 were ultrasonically treated in dimethyl sulfoxide to obtain an emulsion dispersion, wherein the _mass percentage of _{nano Fe2O3} particles in the dispersion was 0.4%, the mass percentage of acryloyloxyethyl trimethyl ammonium bromide in the dispersion was 0.5%, and the mass percentage of Tween-85 in the dispersion was 0.05%.

The polyester and spandex blended knitted fabric (polyester and spandex ratio is 95:5) was cut into appropriate size, immersed in the above dispersion, rolled once with a rolling mill at a pressure of 0.2 kg, and then placed in an electron accelerator for processing in a nitrogen atmosphere. The parameters of the electron accelerator are electron beam energy 3MeV, electron beam current intensity 10mA. The absorbed dose is 300kGy.

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 polyester and spandex blended knitted fabric was 0.05%, and 0.1%.

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

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, acryloyloxyethyl trimethylammonium bromide, Sinopharm Chemical Reagent Co., Ltd.

Example 4

At 5°C, a mixture of nano-TiO ₂ and SnO ₂ particles (the mass percentage of nano-TiO ₂ and SnO ₂ particles is 100:1) is immersed in an aqueous solution of methacryloxypropyl trimethoxysilane (the mass percentage of methacryloxypropyl trimethoxysilane in the solution is 20%) for 30 minutes, then filtered and dried to obtain nano-Fe ₂ O ₃ particles with surface modified carbon-carbon double bonds. The nano-TiO ₂ and SnO ₂ particles containing carbon-carbon double bonds and methacryloxypropyl trimethylammonium chloride are ultrasonically treated in water to obtain a dispersion. The total mass percentage of nano-TiO ₂ and SnO ₂ particles in the dispersion is 3%, and the mass percentage of methacryloxypropyl trimethoxysilane is 20%. The percentage of acryloyltrimethoxysilane in the dispersion is 38%.

The hemp, wool and polypropylene blended woven fabric (the ratio of hemp, wool and polypropylene is 88:10:2) is cut into appropriate sizes, immersed in the above dispersion, rolled once with a rolling wheel at a pressure of 1 kg, and then placed in an electron accelerator for processing in a vacuum atmosphere. The parameters of the electron accelerator are electron beam energy 2MeV, electron beam current intensity 50mA, and the absorbed dose is 5kGy.

The grafted hemp, wool and polypropylene blended woven fabric was washed with cold water and then dried. 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% by weighing method and element content analysis method.

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

The sources of the raw materials used in this example are as follows: hemp, wool and polypropylene blended woven fabric, Zhejiang Shengtai Group; nano-TiO ₂ , nano-SnO ₂ , methacryloxypropyl trimethoxysilane, methacryloxypropyl trimethylammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

Example 5

At 40°C, _SrTiO3 particles were immersed in a mixed aqueous solution of vinyl tri(β-methoxyethoxy)silane and vinyl tri-tert-butoxysilane (the mass percentages of vinyl tri(β-methoxyethoxy)silane and vinyl tri-tert-butoxysilane in the aqueous solution were 20% and 10%, respectively) for 48 hours, 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, methacryloyloxyethyl trimethyl ammonium bromide, and dimethyl diallyl ammonium chloride were ultrasonically treated in water to obtain a dispersion, wherein the mass percentage of nano _SrTiO3 particles in the dispersion was 5%, the mass percentage of methacryloyloxyethyl trimethyl ammonium bromide in the dispersion was 15%, and the mass percentage of dimethyl diallyl ammonium chloride in the dispersion was 35%.

The cotton, modal, and ethylene blended woven fabric (the ratio of cotton, modal, and ethylene is 80:15:5) is cut into appropriate sizes, immersed in the above dispersion, rolled once with a rolling wheel at a pressure of 0.2 kg, and then placed in a nitrogen atmosphere under an electron accelerator for processing. The parameters of the electron accelerator are electron beam energy 500keV, electron beam current intensity 500mA, and the absorbed dose is 30kGy.

The grafted cotton, modal and polyethylene blended woven fabric was washed with cold water and then dried. The grafting rate of 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 total grafting rate of quaternary ammonium salt monomers on the cotton, modal and polyethylene blended woven fabric was 4.5%, and 50.0%.

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

The sources of the raw materials used in this embodiment are as follows: cotton, modal, and vinyl blended woven fabrics, Zhejiang Jiang Shengtai Group; Nano-SrTiO ₃ particles, vinyl tri(β-methoxyethoxy)silane, vinyl tri-tert-butoxysilane, methacryloxyethyl trimethoxysilane, methacryloxyethyl trimethylammonium bromide, dimethyldiallylammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

Example 6

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, in which the total mass percentage of nano _WO3 and _SiO2 particles in the dispersion is 0.5%, the 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%.

The nylon and acetate blended woven fabric (the ratio of nylon to acetate is 60:40) was cut into appropriate sizes, immersed in the above dispersion, rolled once with a rolling mill at a pressure of 2 kg, and then placed in an electron accelerator for processing in a nitrogen atmosphere. The parameters of the electron accelerator were electron beam energy 500keV, electron beam current intensity 100mA, and the absorbed dose was 80kGy.

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 1%.

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

The sources of the raw materials used in this example are as follows: nylon and acetate blended woven fabric, Zhejiang Shengtai Group; nano WO ₃ , nano SiO ₂ , vinyl tri-tert-butyl peroxysilane, vinyl triacetoxysilane, acryloxyethyl trimethoxysilane, (3-acrylamidopropyl) trimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium bromide, Sinopharm Chemical Reagent Co., Ltd.

Example 7

At 20°C, nano _-TiO2 was immersed in an aqueous solution of methacryloxypropyltrimethoxysilane (the mass percentage of methacryloxypropyltrimethoxysilane 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. Nano _-TiO2 particles with carbon double bonds, methacryloyloxyethyltrimethylammonium bromide, dimethyldiallyl ammonium chloride, and dimethyldiallyl ammonium bromide are ultrasonically treated in water to obtain a dispersion, in which the mass percentage of the nano- _TiO2 particles in the dispersion is 0.1%, and the mass percentages of methacryloyloxyethyltrimethylammonium bromide, dimethyldiallyl ammonium chloride, and dimethyldiallyl ammonium bromide in the dispersion are 0.1%, 1%, and 10%, respectively.

The bamboo fiber and Tencel blended knitted fabric (the ratio of bamboo fiber to Tencel is 80:20) is cut into appropriate sizes, immersed in the above dispersion, rolled once with a rolling wheel at a pressure of 2 kg, and then placed in an electron accelerator for processing in a nitrogen atmosphere. The parameters of the electron accelerator are electron beam energy of 100 keV and electron beam current of 20 mA. The absorbed dose is 40 kGy.

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 of the quaternary ammonium salt monomer was 10.0%.

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

The sources of the raw materials used in this example are as follows: bamboo fiber and tencel blended knitted fabric, Zhejiang Shengtai Group; nano-TiO ₂ , methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, acryloyloxyethyl trimethoxysilane, methacryloxyethyl trimethylammonium bromide, dimethyl diallyl ammonium chloride, dimethyl allyl ammonium bromide, Sinopharm Chemical Reagent Co., Ltd.

Example 8

At 40°C, a mixture of nano-WO ₃ , SiO ₂ , SnO ₂ particles (the mass percentage of nano-WO ₃ , SiO ₂ , SnO ₂ is 100:10:1) is immersed in an aqueous solution of acryloyloxyethyl trimethoxysilane (the mass percentage of acryloyloxyethyl trimethoxysilane in the aqueous solution is 1%) for 72 hours, then filtered and dried to obtain a mixture of nano-WO ₃ , SiO ₂ , SnO ₂ particles with surface modified carbon-carbon double bonds. The above-mentioned nano-WO ₃ , SiO ₂ , SnO ₂ particle mixture containing carbon-carbon double bonds, acryloyloxyethyl trimethyl ammonium chloride, and methacryloyloxyethyl trimethyl ammonium chloride are ultrasonically treated in water to obtain a dispersion, the total mass percentage of the nano-WO ₃ , SiO ₂ , SnO ₂ particle mixture in the dispersion is 5%, and the mass percentages of acryloyloxyethyl trimethyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride in the dispersion are 10% and 0.1%, respectively.

The polyethylene nonwoven fabric (cut into a suitable size, immersed in the above dispersion, rolled once with a rolling mill at a pressure of 2 kg, and then placed in an electron accelerator for processing in a nitrogen atmosphere. The parameters of the electron accelerator are electron beam energy 1.5 MeV, electron beam current intensity 15 mA. The absorbed dose is 250kGy.

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%.

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

The sources of the raw materials used in this example are as follows: polyethylene nonwoven fabric, Zhejiang Shengtai Group; nano WO ₃ , nano SiO ₂ , nano SnO ₂ , acryloyloxyethyl trimethoxysilane, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, Sinopharm Chemical Reagent Co., Ltd.

Effect Example 1

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

The long-lasting washing-resistant antibacterial and deodorizing cotton yarn bundle and knitted fabric samples prepared in the above Example 1 were tested for antibacterial performance according to the AATCC 100-2012 standard, and the results are shown in Table 1. The bacterial species selected for the antibacterial test, Escherichia coli, are typical species of Gram-negative bacteria, Staphylococcus aureus are typical species of Gram-positive bacteria, and Candida albicans are typical species of fungi. It can be seen from Table 1 that the cotton yarn bundle and knitted fabric samples prepared in the embodiment have an antibacterial rate of 99% against the three species, and have excellent antibacterial performance. Moreover, after 20 cycles of accelerated washing (equivalent to 100 household washings), the antibacterial rate remains almost unchanged, still above 99%.

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

The deodorizing performance of the long-lasting washing-resistant antibacterial deodorizing cotton yarn bundle and knitted fabric samples prepared in Example 1 was tested with reference to JEC 301-2013, and the results are shown in Table 2. The removal rates of the four main odorants, ammonia, acetic acid, isovaleric acid, and nonenal, prepared in Example 1 were all higher than the requirements of the JEC standard (more than 70%), and after washing 10 times according to the JEC standard, the removal rate of the odorants was still good.

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 durable.

Effect Example 2

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

The long-lasting washing-resistant antibacterial and deodorizing silk yarn bundle and woven fabric samples prepared in the above Example 2 were tested for antibacterial properties according to the AATCC 100-2012 standard, and the results are shown in Table 3. The bacterial species selected for the antibacterial test, Escherichia coli, are typical species of Gram-negative bacteria, Staphylococcus aureus are typical species of Gram-positive bacteria, and Candida albicans are typical species of fungi. It can be seen from Table 3 that the silk yarn bundle and woven fabric samples prepared in Example 2 have an antibacterial rate of 99% against the three species, and have excellent antibacterial properties. Moreover, after 20 cycles of accelerated washing (equivalent to 100 household washings), the antibacterial rate remains almost unchanged, still above 99%.

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

The deodorizing performance of the long-lasting washing-resistant antibacterial deodorizing silk yarn bundle and woven fabric samples prepared in Example 2 was tested with reference to JEC 301-2013, and the results are shown in Table 4. The removal rates of the four main odorants, ammonia, acetic acid, isovaleric acid, and nonenal, prepared in Example 2 were all higher than those in the JEC standard. Requirements (more than 70%), and after washing 10 times according to JEC standards, the odor removal rate has hardly decreased and still maintains a good level.

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 durable.

Because the products in the field of textiles are directly facing consumers, and consumers have intuitive feelings and corresponding requirements for the color, feel, smell, color fastness and other aspects of textiles. According to the preparation method of the antibacterial and deodorizing textiles of the present invention, the textiles can be endowed with the function of lasting antibacterial and deodorizing without affecting the basic clothing performance of the textiles such as the feel, and has practical application value.

The above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. The above embodiment of the present invention can also be modified in various ways. That is, all simple, equivalent changes and modifications made according to the claims and the description of the present invention fall within the scope of protection of the claims of the present invention. The contents not described in detail in the present invention are all conventional technical contents.

Claims (14)

1. A method for preparing a long-lasting, wash-resistant, antibacterial and deodorizing textile, characterized in that the preparation method comprises providing a textile, an inorganic photocatalyst particle, 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 particle 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, and initiating graft polymerization of the quaternary ammonium salt monomer containing a carbon-carbon double bond functional group and the photocatalyst particle modified with the carbon-carbon double bond functional group by generating active free radicals on the textile, thereby firmly fixing the polyquaternary ammonium salt and the photocatalyst particle to the textile through covalent bonds, thereby giving the textile an antibacterial and deodorizing function.
2. The preparation method according to claim 1, characterized in that the inorganic photocatalyst particles _are at least one of 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 of the group consisting of vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(β-methoxyethoxy)silane, vinyl tri-tert-butyloxysilane, vinyl tri-tert-butyl peroxide silane, vinyl triacetoxysilane, acryloxyethyl trimethoxysilane, acryloxypropyl trimethoxysilane, methacryloyloxyethyl trimethoxysilane and methacryloyloxypropyl trimethoxysilane.
4. The preparation method according to claim 1 is characterized in that the reaction of the inorganic photocatalyst particles and the silane coupling agent containing carbon-carbon double bonds is to immerse the inorganic photocatalyst particles in a water or ethanol solution containing the silane coupling agent containing carbon-carbon double bonds to react and obtain photocatalyst particles modified with carbon-carbon double bonds.
5. The preparation method according to claim 4 is 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 is characterized in that 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 5min to 72h.
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 of the group consisting of acryloyloxyethyl trimethylammonium chloride, acryloyloxyethyl trimethylammonium bromide, methacryloyloxyethyl trimethylammonium chloride, methacryloyloxyethyl trimethylammonium bromide, dimethyldiallylammonium chloride, dimethyldiallylammonium bromide, (3-acrylamidopropyl)trimethylammonium chloride, and (3-acrylamidopropyl)trimethylammonium bromide.
8. The preparation method according to claim 1 is characterized in that the textile, the photocatalyst particles modified with carbon-carbon double bonds and the quaternary ammonium containing carbon-carbon double bond functional groups are induced by using an electron beam of an electron accelerator. The salt monomers are irradiated to initiate graft polymerization.
9. The preparation method according to claim 9 is characterized in that the energy of the electron beam is between 100 keV and 10 MeV.
10. The preparation method according to claim 9 is characterized in that the current intensity of the electron beam is between 5 mA and 2 A.
11. The preparation method according to claim 9, characterized in that the absorbed dose is between 1 kGy and 300 kGy.
12. A long-lasting washing-resistant antibacterial and deodorizing textile, characterized in that the long-lasting washing-resistant antibacterial and deodorizing textile is obtained according to the preparation method described in any one of claims 1-11.
13. The long-lasting washing-resistant antibacterial and deodorizing textile according to claim 12 is characterized in that the long-lasting washing-resistant antibacterial and deodorizing textile is a woven fabric, a knitted fabric, a non-woven fabric, or a yarn.
14. The long-lasting, wash-resistant, antibacterial and deodorizing textile according to claim 12 is characterized in that 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%.