CN116005443B - A method for manufacturing comfortable antibacterial protective clothing fabric and the prepared fabric - Google Patents
A method for manufacturing comfortable antibacterial protective clothing fabric and the prepared fabric Download PDFInfo
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Abstract
本发明提供了一种舒适性抗菌防护服面料的制造方法及制得的面料，由聚乳酸弹性纤维和高凉感高强高模聚乙烯纤维混织后，经电子束辐照接枝改性后得到成品舒适性抗菌防护服面料。使用不同特性粘度的PLA原料经双组份熔融纺丝和加弹后的聚乳酸弹性纤维，和高凉感高强高模聚乙烯纤维混织，再将织物经带有阳离子功能基团的电子束辐照接枝改性制备。该方法解决现有防护服面料生产工艺中，功能性（如抗菌性、耐磨性等）与穿着舒适性难以同时实现的问题。并且使用本发明制得的舒适性抗菌防护服面料，在兼具持久抗菌性和柔软手感的同时，耐磨性和接触凉感较高。利用电子束辐照接枝改性技术，解决了常规抗菌洗涤后效果差以及常规辐照接枝需要引入引发剂等可能有毒物质的问题。
The present invention provides a method for manufacturing a comfortable antibacterial protective clothing fabric and the prepared fabric. The finished comfortable antibacterial protective clothing fabric is obtained by blending polylactic acid elastic fiber and high-cooling high-strength high-modulus polyethylene fiber, and then subjecting to electron beam irradiation grafting modification. PLA raw materials with different characteristic viscosities are used to blend polylactic acid elastic fiber after two-component melt spinning and stretching, and high-cooling high-strength high-modulus polyethylene fiber, and then the fabric is prepared by electron beam irradiation grafting modification with cationic functional groups. The method solves the problem that functionality (such as antibacterial property, wear resistance, etc.) and wearing comfort are difficult to achieve at the same time in the existing protective clothing fabric production process. And the comfortable antibacterial protective clothing fabric prepared by the present invention has both long-lasting antibacterial property and soft hand feel, and has high wear resistance and cool contact feeling. The electron beam irradiation grafting modification technology solves the problem that the conventional antibacterial effect is poor after washing and the conventional irradiation grafting needs to introduce initiators and other potentially toxic substances.
Description
Technical Field
The invention belongs to the field of protective clothing fabrics, and particularly relates to a manufacturing method of a comfortable antibacterial protective clothing fabric and the manufactured fabric.
Background
The protective clothing is used for defending the injury of external factors such as physics, chemistry, biology and the like, protects the working clothing of human body, meets the wearing requirements of high strength, high wear resistance and the like, and is often different due to different protective purposes and protective principles. Categories include decontamination protective clothing, industrial protective clothing, medical protective clothing, military protective clothing, and protective clothing for special people. In recent years, with the repetition of epidemic situations, the use requirements of medical staff on protective clothing are gradually improved, and higher requirements on antibacterial property, wear resistance and use comfort are put forward.
The conventional method for improving the antibacterial property is a process of internally arranging metal ion fabric, post-treating surface coating and the like. Simple metal ions are added, precipitation is easy, the antibacterial effect is poor in durability, and the wearing comfort of the fabric is affected by the post-treatment surface coating process.
Chinese patent CN115214204A discloses an antibacterial medical protective clothing fabric and a preparation method thereof, and an antibacterial protective clothing is obtained by utilizing an antibacterial coating process.
Chinese patent CN216723211U discloses a breathable anti-infection protective garment, which improves antibacterial effect by using a nano silver ion coating and antibacterial fiber composite form, and the method improves overall antibacterial effect but affects wearing comfort.
With the development of technology, in recent years, there is a method of modifying fibers by irradiation grafting, which enhances the functionality of the fibers. Chinese patent CN103952908a discloses an antiviral and antibacterial fiber, its preparation method and application. The method uses a monomer with a cationic functional group, and uses ultraviolet irradiation or gamma ray irradiation technology to modify the fiber surface, and the obtained product has better functions, but the modification process is complex, and an initiator and the like are required to be added for irradiation.
With the popular trend of the bio-based concept, polylactic acid fibers are paid more attention to, are natural and slightly acidic, have a certain antibacterial effect, and can be applied to the antibacterial textile industry by enhancing the antibacterial property of the polylactic acid fibers.
Chinese patent CN1891870A discloses a production method of antibacterial polylactic acid fibers, wherein the antibacterial polylactic acid fibers are obtained by using a silver ion antibacterial master batch adding mode, the spinning property is poor when the polylactic acid fibers are manufactured by the method, silver ions of the obtained antibacterial fibers are easy to separate out, the antibacterial property is not durable, and the comfort of the manufactured textile is poor.
Methods for improving the comfort of polylactic acid fibers are mostly made into elastic yarns or parallel elastic fibers. Chinese patent CN109853084a discloses a polylactic acid/polyester elastomer composite elastic fiber and a preparation method thereof, which uses the form of a parallel fiber made of polylactic acid and polyester elastomer to improve the elasticity so as to improve the comfort. In order to improve the compatibility of polylactic acid and polyester elastomer, a high proportion of compatilizer is added during spinning, so that the spinning property and the product performance are reduced.
Disclosure of Invention
The invention aims to provide a manufacturing method of a comfortable antibacterial protective clothing fabric and the manufactured fabric, and the technical scheme of the invention is as follows:
A comfortable antibacterial protective clothing fabric is prepared by mixing polylactic acid elastic fibers and high-cool high-strength high-modulus polyethylene fibers, and performing electron beam irradiation grafting modification. Comprises the following steps:
(1) Preparing polylactic acid elastic fibers;
(2) Antibacterial modified polylactic acid elastic fiber and high-cool-feeling high-strength high-modulus polyethylene fiber are mixed and woven;
(3) The fabric is modified by electron beam irradiation grafting with cationic functional groups.
According to the manufacturing method of the comfortable antibacterial protective clothing fabric, the polylactic acid elastic fiber is prepared by using polylactic acid raw materials with different intrinsic viscosities, wherein the raw material 1 is polylactic acid with the intrinsic viscosity of 1.2-1.7 dl/g, the raw material 2 is polylactic acid with the intrinsic viscosity of 0.6-1.1 dl/g, and the POY fiber is obtained through spinning by a two-component melt spinning machine, and the antibacterial modified polylactic acid elastic fiber is obtained after low-temperature texturing.
In the manufacturing method of the comfortable antibacterial protective clothing fabric, the contact cool feeling Qmax of the high cool feeling high strength high modulus polyethylene fiber is more than 0.4W/cm 2, the fiber breaking strength is more than 10cN/dtex, the elastic modulus is more than 400cN/dtex, the elongation at break is less than 6%, and the fiber intrinsic viscosity is 1.5-10 dl.
In the manufacturing method of the comfortable antibacterial protective clothing fabric, the mixing ratio of the antibacterial modified polylactic acid elastic fiber to the high-cool-feeling high-strength high-modulus polyethylene fiber is 3:7-7:3.
In the manufacturing method of the comfortable antibacterial protective clothing fabric, the electron beam irradiation grafting modification method with the cationic functional groups comprises the steps of performing hydrophilic pretreatment on the mixed fabric of the antibacterial modified polylactic acid elastic fiber and the high-cool-feeling high-strength high-modulus polyethylene fiber, padding the mixed fabric in a solution containing cationic functional group monomers, wherein the liquid carrying amount is 20% -100%, repeating padding operation for 2-3 times, and performing electron beam irradiation on the padded fabric under the process of 30-80 kGy. After irradiation, the ungrafted monomer is removed with an organic solvent.
In the manufacturing method of the comfortable antibacterial protective clothing fabric, the hydrophilic pretreatment agent is a mixed solution of lipase and nonionic surfactant. The monomer with a cationic functional group is preferably a vinyl cationic monomer.
The comfortable antibacterial protective clothing fabric prepared by the manufacturing method.
The invention solves the problem that the functionality (such as antibacterial property, wear resistance and the like) and wearing comfort are difficult to realize simultaneously in the existing protective clothing fabric production process. The comfortable antibacterial protective clothing fabric prepared by the method has lasting antibacterial property and soft hand feeling, and meanwhile, has high wear resistance and contact cooling feeling. The electron beam irradiation grafting modification technology is utilized to solve the problems that the effect is poor after the conventional antibacterial washing and the initiator and other possibly toxic substances need to be introduced in the conventional irradiation grafting.
Drawings
FIG. 1 is a data diagram of an embodiment of the present invention.
FIG. 2 is a data chart of a comparative example of the present invention.
Detailed Description
The preparation method of the comfortable antibacterial protective clothing fabric comprises the steps of using polylactic acid raw materials with different intrinsic viscosities, wherein raw material 1 is polylactic acid with the intrinsic viscosity of 1.2-1.7 dl/g, raw material 2 is polylactic acid with the intrinsic viscosity of 0.6-1.1 dl/g, spinning by a bicomponent melt spinning machine to obtain POY fibers, and obtaining the polylactic acid elastic fibers after low-temperature texturing. Polylactic acid fibers with different intrinsic viscosities are used, so that the melt spinning double components have sufficient melt viscosity difference, the stress difference during spinning is improved, and the elasticity of the elastic fibers is improved. When the intrinsic viscosity of the raw material 1 is less than 1.2dl/g, the difference in two-component viscosity is too small and the fiber elasticity is low, and when the intrinsic viscosity of the raw material 1 is more than 1.7dl/g, the melt flowability is poor and the spinning property and the dispersibility of the antibacterial master batch are poor. When the intrinsic viscosity of the raw material 2 is lower than 0.6dl/g, the polylactic acid viscosity is too small, the spinning forming effect is poor, the fiber strength is low, and when the intrinsic viscosity of the raw material 2 is higher than 1.1dl/g, the two-component viscosity difference is too small, and the fiber elasticity is low. The lactic acid elastic fiber with higher elasticity can be obtained by preparing POY fiber at first and then adding the elastic fiber at low temperature. If the POY is not added with the bullet again, the melt direct spinning FDY or the two-step stretching mode is used, the elasticity of the fiber is weaker, and the comfort and the hand feeling are not satisfied. When the high-temperature texturing is adopted, the polylactic acid fiber textured yarn is poor in molding, stiff yarn is easy to occur, and the elasticity is low. Preferably, the texturing temperature is 90-120 ℃.
The high-cool feeling high-strength high-modulus polyethylene fiber has the contact cool feeling Qmax of more than 0.4W/cm < 2 >, and realizes higher contact cool feeling by utilizing the high heat conduction characteristic. If the contact cooling feeling is less than 0.4W/cm2, the characteristic of high cooling feeling cannot be realized. The breaking strength of the fiber is more than 10cN/dtex, the elastic modulus is more than 400cN/dtex, the breaking elongation is less than 6%, the characteristics of high strength and high modulus are met, and the characteristics of tensile strength, high performance and the like are realized. The high strength cannot be realized if the breaking strength is less than 10cN/dtex, the high modulus cannot be realized if the elastic modulus is less than 400cN/dtex, and the high strength and high modulus cannot be realized if the breaking elongation is more than 6%, so that the high crystal orientation is difficult to obtain. The characteristic of high wear resistance is achieved through the characteristic of high strength and high modulus. The intrinsic viscosity of the fiber is 1.5-10 dl/g so as to maintain the melt spinning processability and high strength and high modulus characteristics of the polyethylene fiber. Melting and conveying a high molecular weight polyethylene raw material with the intrinsic viscosity of 3.5-10 dl/g and the weight average molecular weight and number average molecular weight ratio (Mw/Mn) of 5-10 through a low-shear high-conveying screw extruder, then entering a spinning component with a combined spinneret plate, extruding into filaments by using the combined spinneret plate capable of releasing the macromolecular orientation and the melt elastic potential energy of a polyethylene melt to obtain a primary fiber, and carrying out multistage stretching and heat setting on the primary fiber to obtain the finished product of the high-cool-feeling high-strength high-modulus polyethylene fiber.
The mixed weaving ratio of the polylactic acid elastic fiber to the high-cool-feeling high-strength high-modulus polyethylene fiber is 3:7-7:3. Within this ratio, comfort and wear resistance, and cooling sensation can be better. When the blending proportion is lower than 3:7, the elasticity and the comfort are poor, and when the blending proportion is higher than 7:3, the wear resistance and the cool feeling are poor.
In the manufacturing method of the comfortable antibacterial protective clothing fabric, the electron beam irradiation grafting modification method with the cationic functional groups comprises the steps of performing hydrophilic pretreatment on the mixed fabric of the antibacterial modified polylactic acid elastic fiber and the high-cool-feeling high-strength high-modulus polyethylene fiber, padding the mixed fabric in a solution containing cationic functional group monomers, wherein the liquid carrying amount is 20% -100%, and performing electron beam irradiation on the padded fabric under the process of 30-80 kGy. Repeating the padding and irradiation operations for 2-3 times, and removing the ungrafted monomer by using an organic solvent after irradiation. Polylactic acid and polyethylene fiber are relatively poor in hydrophilicity, and the mixed solution containing lipase nonionic surfactant is used for hydrophilic pretreatment, so that the hydrophilicity of the fabric is improved, and the subsequent padding processing is facilitated. The lipase treatment can generate polar groups on the surface of the matrix, so that the hydrophilicity of the matrix is improved. Meanwhile, the lipase hydrolysis only acts on the surface of the matrix, and the physical and mechanical properties of the matrix are not greatly influenced. The simple lipase has longer surface modification time, and the lipase treatment time can be effectively reduced after the surfactant is added. The invention grafts monomer with cation functional group on blended fabric by covalent bond, and generates electrostatic adsorption action with the microorganism, after adsorption, the lipophilic part contained in grafted monomer can be inserted into envelope to destroy the envelope, thus realizing the aim of eliminating microorganism. Thereby achieving the antibacterial effect. When the liquid carrying amount is less than 20%, a good grafting effect is difficult to obtain, and when the liquid carrying amount is more than 100%, the phenomenon of poor uniformity of grafting reaction is easy to occur. And repeating the padding operation for 2-3 times, and then irradiating by using an electron beam, so that the grafting rate is 10-30%, and a better antibacterial effect is achieved. Under the condition of the grafting rate, the antibacterial performance and the lasting antibacterial performance are good. In the manufacturing method of the comfortable antibacterial protective clothing fabric, the monomer with the cationic functional group is preferably a vinyl cationic monomer.
The fiber of the present invention and the method for producing the same will be specifically described below by way of examples.
The following evaluations were performed in examples and comparative examples:
(1) Intrinsic viscosity
With reference to GB/T10247-2008 standard, the intrinsic viscosity is measured in dl/g using a full-automatic Ubbelohde viscometer IV3400X, produced by Hangzhou Zhuo Xiang.
(2) Fiber breaking strength, elongation at break and fiber elastic modulus
The stress-strain curve was measured using a tension tester "Tensilon" manufactured by the company of Tbook under conditions of a sample length of 20cm and a tensile speed of 100%/min. The load at the time of breaking was read, and the breaking strength was calculated by dividing the load by the initial fineness, and the deformation at the time of breaking was calculated by dividing the deformation by the sample length, and the elongation at break was calculated by multiplying the obtained value by 100 times. The Young's modulus was calculated by using the stress-strain curve and then using the fiber density and fineness. All of these values are obtained by repeating this operation 5 times with the same standard, and the simple average value of the obtained results is obtained, the breaking strength is obtained by rounding the 2 nd bit after the decimal point, and the elongation at break is obtained by rounding the decimal point after the decimal point. The modulus of elasticity of the fiber is calculated from the tangent line giving the maximum gradient near the origin of the stress-deformation curve.
(3) Fiber, fabric contact cool feeling
Referring to GB/T35263-2017 standard, a KES-QM contact cool feeling tester is used to manufacture the fiber into a woven fabric test piece, and the contact cool feeling Qmax is tested in W/cm2.
(1) Antibacterial property of fabric
The antibacterial performance was tested by reference to GB/T20944.3-2008 shaking method.
(2) Wear resistance of fabrics
With reference to GB/T21196-2007 standard, the abrasion resistance rating is tested.
(3) Elasticity of fabric (thickness characterization)
The woven fabric thickness test was performed according to JIS 10962010 standard.
The present invention will be specifically described based on the embodiments.
Example 1
According to the total 10 parts, 5 parts of high-cool-feeling high-strength high-modulus polyethylene fiber is used, the contact cool feeling Qmax of the high-cool-feeling high-modulus polyethylene fiber is 0.51W/cm < 2 >, the fiber breaking strength is 18cN/dtex, the elastic modulus is 700cN/dtex, the elongation at break is 4.8%, the fiber intrinsic viscosity is 5.4dl/g, and 5 parts of PLA/PLA elastic fiber is used, and the two are blended to prepare the fabric. The PLA/PLA elastic fiber is obtained by melt spinning a PLA raw material 1 (high-viscosity PLA) with an intrinsic viscosity of 1.5dl/g and a PLA raw material 2 (low-viscosity PLA) with an intrinsic viscosity of 0.8dl/g at a spinning speed of 2800m/min at 230 ℃ to obtain POY, and texturing the POY at a hot box at 110 ℃.
Repeatedly padding the fabric in a solution with vinyl cation quaternary ammonium salt monomer for 3 times, and irradiating to obtain the finished comfortable antibacterial protective clothing fabric when the electron beam irradiation process (absorption dose) is 40 kGy.
The fabric has good antibacterial performance under the conditions of good cool feeling, wear resistance and elasticity. The results are shown in Table 1.
Example 2
According to the total of 10 parts, 3 parts of high-cool-feeling high-strength high-modulus polyethylene fiber and 7 parts of PLA/PLA elastic fiber are used, and the finished comfortable antibacterial protective clothing fabric is obtained under the process of the example 1.
The fabric has good antibacterial performance under the conditions of good cool feeling, wear resistance and elasticity. The results are shown in Table 1.
Example 3
According to the total of 10 parts, 7 parts of high-cool-feeling high-strength high-modulus polyethylene fiber and 3 parts of PLA/PLA elastic fiber are used, and the finished comfortable antibacterial protective clothing fabric is obtained according to the process of the example 1.
The fabric has good antibacterial performance under the conditions of good cool feeling, wear resistance and elasticity. The results are shown in Table 1.
Examples 4 and 5
According to the PLA/PLA elastic fiber raw material 1 (high viscosity PLA), the intrinsic viscosity was changed to 1.2dl/g (example 4) and 1.7dl/g (example 5), and the other materials were obtained according to the process of example 1 to obtain the comfortable antibacterial protective clothing fabric.
The fabric has good antibacterial performance under the conditions of good cool feeling, wear resistance and elasticity. The results are shown in Table 1.
Examples 6 and 7
According to the PLA/PLA elastic fiber raw material 2 (low viscosity PLA), the intrinsic viscosity was changed to 0.6dl/g (example 6) and 1.1dl/g (example 7), and the other materials were obtained according to the process of example 1 to obtain the comfortable antibacterial protective clothing fabric.
The fabric has good antibacterial performance under the conditions of good cool feeling, wear resistance and elasticity. The results are shown in Table 1.
Example 8
The finished comfort antibacterial protective clothing fabric was obtained according to the procedure of example 1, except that the treatment was carried out according to an electron beam irradiation process (absorbed dose) of 30 kGy.
The fabric has good antibacterial performance under the conditions of good cool feeling, wear resistance and elasticity. The results are shown in Table 1.
Comparative example 1
According to the total of 10 parts, 2 parts of high-cool-feeling high-strength high-modulus polyethylene fiber and 8 parts of PLA/PLA elastic fiber are used, and the finished comfortable antibacterial protective clothing fabric is obtained under the process of the example 1.
The fabric has the test performance, and the fabric is found to be poor in cool feeling and wear resistance under the conditions of good elasticity and antibacterial property, and cannot achieve the protection effect. The results are shown in Table 2.
Comparative example 2
According to the total of 10 parts, 8 parts of high-cool-feeling high-strength high-modulus polyethylene fiber and 2 parts of PLA/PLA elastic fiber are used, and the finished comfortable antibacterial protective clothing fabric is obtained according to the process of the example 1.
The fabric has the advantages of poor elasticity and poor comfort effect under the conditions of good cooling feeling, wear resistance and antibacterial property. The results are shown in Table 2.
Comparative examples 3 and 4
According to the PLA/PLA elastic fiber raw material 1 (high viscosity PLA), the intrinsic viscosity was changed to 1.8dl/g (comparative example 3) and 1.1dl/g (comparative example 4), and the other materials were obtained according to the process of example 1 to obtain the comfortable antibacterial protective clothing fabric.
In comparative example 3, when the PLA/PLA elastic fiber was spun, the high viscosity PLA was poor in fluidity, easy to break, and poor in spinnability, and the finished fiber and fabric could not be obtained.
The fabric obtained in comparative example 4 has poor elasticity and does not achieve comfort effect under the conditions of good cooling feeling, wear resistance and antibacterial property. The results are shown in Table 2.
Comparative examples 5 and 6
According to the PLA/PLA elastic fiber raw material 2 (low viscosity PLA), the intrinsic viscosity was changed to 0.5dl/g (comparative example 5) and 1.2dl/g (comparative example 6), and the other materials were obtained according to the process of example 1 to obtain the comfortable antibacterial protective clothing fabric.
Comparative example 5 low-viscosity PLA could not be molded during the spinning of PLA/PLA elastic fiber, and spinnability was poor, failing to obtain finished fibers and fabrics.
The fabric obtained in comparative example 6 has poor elasticity and cannot achieve the comfort effect under the conditions of good cooling feeling, wear resistance and antibacterial property. The results are shown in Table 2.
Comparative example 7
The finished fabric was obtained according to the procedure of example 1, except that the padding liquid amount was 10%.
The performance of the fabric is tested, and the fabric is found to have poorer antibacterial performance under the conditions of better cool feeling, wear resistance and elasticity. The results are shown in Table 2.
Comparative example 8
The finished fabric was obtained according to the procedure of example 1, except that the electron beam irradiation process (absorbed dose) was 15 kGy.
The performance of the fabric is tested, and the fabric is found to have poorer antibacterial performance under the conditions of better cool feeling, wear resistance and elasticity. The results are shown in Table 2.
Comparative example 9
The blend fabric obtained according to example 1 was obtained as a finished fabric in the form of a 3-pass pad coating using a silver ion coating.
The performance of the fabric is tested, and the fabric is found to have poorer antibacterial performance under the conditions of better cool feeling, wear resistance and elasticity. The results are shown in Table 2.
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