Yarn with itching relieving and antibacterial functions and preparation method thereof

Abstract

The invention discloses a yarn with itching relieving and antibacterial functions and a preparation method thereof. According to the yarn with the itching relieving and antibacterial functions, polyester fibers serve as base material fibers, alum with the antibacterial and itching relieving functions serves as an additive, itching relieving functionalized in-situ polyester chips added with itching relieving composition slurry are added, the raw materials are the same as the raw materials of the base material, and the interfacial compatibility of the yarn can be enhanced; the antibacterial and antipruritic effects can be achieved together with the alum; in order to ensure the antibacterial property of the yarn, a novel antibacterial microcapsule prepared from nano antibacterial filler is used as an antibacterial agent. The yarn prepared by the invention has obvious antibacterial and itching-relieving effects, and the technical scheme of the invention can solve the problem that in the prior art, direct sensory experience of pruritus or scratchiness is brought to a human body in the use process of chemical fiber base material fibers.

Description

Technical Field

[0001] The invention relates to the technical field of functional yarn preparation, and in particular to a method for preparing yarn with antipruritic and antibacterial functions. Background Art

[0002] With the development of science and technology, various functional fabrics are rapidly entering people's daily lives, but each functional fiber has only a specific function, and a single fiber cannot meet multiple functional requirements at the same time. Through clever combination of multiple functional fibers, the respective characteristics of the fibers can be maximized, and at the same time, some functional finishing can be performed to meet people's various needs. In daily life, we often encounter the problem of unexplained itching of the skin, especially in the dry weather in the north, the face is prone to dryness, chemical fiber clothes are prone to static electricity, and the surface will absorb a large number of pathogens, itching particles, etc. The skin surface lacks nutrients such as amino acids and vitamins, and has poor antibacterial and moisturizing abilities.

[0003] The patent document with the patent number CN 106835316A discloses a cellulose fiber with antipruritic effect and a preparation method thereof, specifically, adding ingredients such as Moringa extract and peach gum with antipruritic effect to the fiber preparation. The prepared cellulose fiber has an antipruritic effect, and has a significant therapeutic effect on skin diseases such as dermatitis, eczema, folliculitis, and athlete's foot caused by various reasons, and the fiber has good physical indicators; the fiber is woven into fabrics and made into diapers, which has a good antipruritic effect of preventing redness and swelling of the buttocks of infants; the non-woven fabric made of the fiber is made into insoles, which has the effect of preventing and treating athlete's foot.

[0004] The document with patent number CN 112342634B discloses a method for preparing antibacterial nano-cellulose fibers, which mainly includes the preparation of menthol composite zinc oxide microcapsules and mixed spinning. Specifically, menthol liquid paraffin solution and chitosan acid solution are mixed by operation A, and then the pH is adjusted to 5.5-6.5 to obtain a mixed solution I, the mixed solution I is mixed with nano zinc oxide to obtain a mixed solution II by operation B, glutaraldehyde is added to the mixed solution II for cross-linking, and filtration is performed to obtain the obtained solution; mixed spinning is to mix the menthol composite zinc oxide microcapsules and spinning viscose stock solution evenly, and then carry out acid bath spinning, and the antibacterial nano-cellulose fibers are prepared by post-spinning treatment. The technical solution of the present invention can solve the problems in the prior art that nano zinc oxide in antibacterial cellulose fibers have poor blending performance and water resistance, and cannot provide a direct sensory experience of antibacterial fibers to the human body.

[0005] However, most technologies use hygroscopic or natural fibers as base fibers, and then further modify them to have antibacterial and antipruritic functions. In view of this, we disclose a yarn with antipruritic and antibacterial functions and a preparation method thereof. Summary of the invention

[0006] In view of the deficiencies in the prior art, the present invention aims to provide a yarn with antipruritic and antibacterial functions and a preparation method thereof, which uses polyester fiber as a base fiber, adds alum as an antipruritic and antibacterial element, then adds antipruritic functional in-situ polyester slices modified with antipruritic effects, and finally uses antibacterial capsules as reinforcing fillers to enhance the comprehensive performance of the system, so that the yarn has the characteristics of antipruritic and antibacterial and high comprehensive performance.

[0007] To achieve the above object, the present invention proposes the following technical solutions:

[0008] A yarn with antipruritic and antibacterial functions, comprising the following raw material components by weight:

[0009] Polyester chips 100 pieces;

[0010] 25-30 pieces of antipruritic functionalized in-situ polyester slices;

[0011] 15-25 parts of alum;

[0012] 8-13 parts of antibacterial agent;

[0013] Compatibilizer 0.5-3.5 parts.

[0014] Preferably, the polyester chips of the present invention are purchased from Shanghai Hehongcheng Plastic Technology Co., Ltd. PET polyester chips, with a brand name of CZ-302.

[0015] Furthermore, the antipruritic functionalized in-situ polyester chips include, by weight, 100 parts of terephthalic acid, 15-20 parts of ethylene glycol, 0.1-0.5 parts of catalyst, 35-55 parts of antipruritic composition slurry and 4-7 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester.

[0016] Furthermore, the catalyst is antimony trioxide or antimony glycolate.

[0017] Furthermore, the antibacterial agent is a novel antibacterial microcapsule, and the novel antibacterial microcapsule includes nano antibacterial filler.

[0018] Furthermore, the preparation process of the novel antibacterial microcapsule includes nano antibacterial filler, surface coupling treatment, and microcapsule preparation, as follows:

[0019] Step 1: Preparation of nano antibacterial filler

[0020] 3-(trihydroxysilylpropyl)dimethyloctadecylammonium chloride and potassium iodide were added to a three-necked flask in a molar ratio of 1:(1.2-1.3) with magnetic stirring, and an inert gas was introduced to react for 1-2 hours. After the reaction, vacuum filtration and alcohol washing were performed to obtain 3-(trihydroxysilylpropyl)dimethyloctadecylammonium iodide;

[0021] Using the above device, weigh 3-(trihydroxysilylpropyl)dimethyloctadecylammonium iodide and nano-zinc oxide in a molar ratio of 1:(1.1 - 1.3) proportionally, add anhydrous ethanol to submerge the materials and conduct magnetic stirring for 0.5 h; then slowly add anhydrous ethanol with a volume twice that of the original amount, react for 4 h after the addition is completed, and after completion, conduct vacuum filtration and ethanol washing to obtain nano-antibacterial filler.

[0022] Step 2. Surface coupling treatment

[0023] Prepare an aqueous solution of silane coupling agent with a mass fraction of 15 wt%, denoted as premixed substance A; at the same time, prepare an ethanol solution of nano-antibacterial filler with a mass fraction of 20 wt%, denoted as premixed substance B; then add premixed substance A and premixed substance B with a mass ratio of 1:(45 - 53) into a three-necked flask; stir evenly for 0.3 - 1.0 h, then install a condensing reflux device, after 2 - 3 h, the reaction is completed, conduct vacuum filtration and ethanol washing, and then dry in a vacuum drying oven at 60 °C to obtain surface-coupled nano-antibacterial filler.

[0024] Step 3. Preparation of novel antibacterial microcapsules

[0025] Taking the laboratory formula as an example, add dried N,N-dihydroxyethyl-p-methylaniline to triethylene glycol dimethacrylate solvent to prepare a solution with a mass fraction of 1.5 - 4.5 wt%; at the same time, prepare an aqueous dispersion of nano-zinc oxide with a mass fraction of 0.5 - 2.5 wt%, mix the two, and after mixing and stirring evenly at a stirring speed of 425 - 550 rpm, let it stand to obtain a premixed solution;

[0026] Place the round-bottom flask in an ice-water bath, add 100 mL of an aqueous solution of graphene oxide with a mass fraction of 1 - 15 wt% to the round-bottom flask, add 15 mL of an aqueous solution of ethylene maleic anhydride copolymer with a mass fraction of 3.5 - 8.5 wt%, stir, keep the stirring speed between 425 - 550 rpm, and then sequentially add 0.3 - 0.5 mol of urea, 0.09 - 0.15 mol of ammonium chloride, and 0.01 - 0.03 mol of resorcinol to adjust the solution pH to 3.6 - 4.2, and then add the above-mentioned premixed solution after standing. Then add 0.10 - 0.15 mol of formaldehyde, and then add nano-antibacterial filler treated with a surface coupling agent with a mass percentage of 8 - 12% of the formaldehyde mass, raise the water bath temperature to 60 °C at a rate of 2 - 5 °C / min, and the product after the reaction is filtered and washed with distilled water and dried at room temperature to obtain the antibacterial agent of the present invention.

[0027] Further, the compatibilizer is one of styrene / MAH random copolymer, styrene / acrylonitrile / MAH terpolymer, butyl acrylate, or maleic anhydride.

[0028] Further, a method for preparing the yarn with antipruritic and antibacterial functions is characterized by comprising the following steps:

[0029] S1. Pretreatment and preparation of materials

[0030] Dry the polyester chips and the novel antibacterial microcapsules; simultaneously prepare the antipruritic composition slurry and the antibacterial slurry.

[0031] S2. Preparation of antipruritic functionalized in-situ polyester chips

[0032] By weight, mix 100 parts of terephthalic acid, 15 - 20 parts of ethylene glycol, and 0.1 - 0.5 part of catalyst evenly, add them to an esterification and polycondensation reaction kettle, carry out esterification at 220 - 230°C for 0.6 - 1.5 h; then, at this temperature, uniformly add 35 - 55 parts of the antipruritic composition slurry and 4 - 7 parts of N,N - dihydroxyethyl - 3 - aminopropionate methyl ester, and both are added within 1 h; thereafter, use vacuum distillation to remove the excess ethylene glycol; after removing the excess ethylene glycol, raise the temperature of the reaction system to 255 - 260°C, and react under vacuum conditions for 2 - 3 h, and the discharged material is granulated through a cooling water tank to obtain the antipruritic functionalized in-situ polyester chips.

[0033] S3. Mixing of materials

[0034] High-speed stir and mix the polyester chips, the antipruritic functionalized in-situ polyester chips, alum, the novel antibacterial microcapsules, and the compatibilizer material for 5 - 10 min, raise the temperature to 80 - 120°C, then keep the temperature at this condition for 0.5 - 1 h, and then stir and mix at the same stirring rate for 5 - 10 min to obtain a premix, wherein the high-speed stirring rate is 900 - 1200 rpm.

[0035] S4. Extrusion granulation

[0036] The premix is melt - blended and extruded through a twin - screw extruder, and then drawn, granulated, and dried to prepare the antipruritic and antibacterial functional masterbatch.

[0037] S5. Spinning treatment

[0038] Place the dried antipruritic and antibacterial functional masterbatch in a vacuum drum for post - treatment. First, raise the temperature at a speed of 1 - 2°C / min to 130 - 135°C for pre - crystallization for 2.5 - 3 h; then raise the temperature at a speed of 10 - 15°C / min to 165 - 170°C and keep the temperature for 4 - 5 h; then put the post - treated antipruritic and antibacterial functional masterbatch into a spinning machine for spinning treatment, the spinning temperature is 310 - 315°C, and the spinning speed is 2500 - 3000 m / min to obtain the antipruritic and antibacterial functional yarn.

[0039] Further, by weight, the antipruritic composition slurry described in step S1 includes 1-2 parts of silicone oil, 3-6 parts of a mixture of alginic acid components, 6-8 parts of camellia oil, 10-15 parts of graphene oxide powder, 5-8 parts of a compound dispersant, and 100-200 parts of ethylene glycol.

[0040] Further, the vacuum condition described in step S2 means that the pressure inside the reaction kettle is below 100 Pa.

[0041] Compared with the prior art, the technical solution of the present invention has obtained the following beneficial effects:

[0042] The present invention discloses a yarn with antipruritic and antibacterial functions, which uses polyester fiber as the base fiber, alum with antibacterial and antipruritic properties as an additive, and an antipruritic functionalized in-situ polyester chip added with an antipruritic composition slurry. Being the same as the base material raw material, it can enhance its interfacial compatibility and can play a synergistic antibacterial and antipruritic role with alum; in order to ensure the antibacterial property of the yarn, a new type of antibacterial microcapsule prepared with a nano antibacterial filler is also used as an antibacterial agent. The yarn prepared by the present invention has obvious antibacterial and antipruritic effects, and through the technical solution of the present invention, it is possible to solve the direct sensory experience of itching or tingling brought to the human body during the use of chemical fiber base fibers in the prior art.

[0043] It should be understood that all combinations of the foregoing concepts and additional concepts described in more detail below can be regarded as part of the disclosure of the subject matter of the present invention as long as such concepts do not contradict each other.

[0044] The foregoing and other aspects, embodiments, and features of the teachings of the present invention can be more fully understood from the following description. Other additional aspects of the present invention, such as the features and / or beneficial effects of exemplary embodiments, will be apparent from the following description, or will be learned through the practice of specific embodiments according to the teachings of the present invention. Detailed Embodiments

[0045] In order to enable those skilled in the art to better understand the technical solution of the present invention, the preferred implementation schemes of the present invention are described below in conjunction with specific embodiments, but it should not be construed as a limitation of this patent.

[0046] The test methods or testing methods described in the following examples / comparative examples are all conventional methods unless otherwise specified; the reagents and materials are all obtained from conventional commercial channels or prepared by conventional methods unless otherwise specified.

[0047] In the present invention, in order to achieve the antibacterial and antipruritic functions of the yarn, alum is added as one of the additives. Alum, also known as potassium alum dodecahydrate, with the chemical formula KAl(SO4)2·12H2O, is an inorganic substance, specifically a double salt of potassium sulfate and aluminum sulfate containing crystal water, soluble in water and insoluble in ethanol. Generally, traditional Chinese medicine believes that alum has a sour, astringent, cold taste and has antibacterial effects, and is commonly used in purifying water quality in daily life. At present, there is no research on the preparation of alum in fiber yarns. The alum in the present invention enables the yarn to have the effects of inhibiting metabolism, antipruritic and antibacterial.

[0048] Further, the preparation of the antipruritic functionalized in-situ polyester chips includes the preparation of the antipruritic composition slurry and the preparation of the in-situ polymerization polyester chips, which are specifically as follows:

[0049] (1) Preparation of the antipruritic composition slurry

[0050] By weight, 1-2 parts of silicone oil, 3-6 parts of the alginic acid component mixture, 6-8 parts of camellia oil, 10-15 parts of graphene oxide powder, and 5-8 parts of the compound dispersant are added to 100-200 parts of ethylene glycol, stirred evenly at high speed, and the undispersed particles are removed by centrifugation to obtain the antipruritic composition slurry.

[0051] Among them, the silicone oil is a water-oil dispersant; the compound dispersant includes fatty alcohol polyoxyethylene ether silane and polyvinylpyrrolidone, specifically mixed in a molar ratio of (1.1-1.5):1; the graphene oxide powder is specifically obtained by subjecting the graphite oxide prepared by the Hummers method to ultrasonic treatment to obtain graphene oxide, then drying the graphene oxide solution with a solid content exceeding 4.5 wt% to obtain graphene oxide flakes, using a crusher to crush to obtain crushed materials, and finally grinding the crushed materials into a powder with a particle size of 1.1-1.5 μm using a planetary ball mill. The graphene oxide powder is premixed with the ethylene glycol solution first, and when adding other materials, the friction and collision between the materials can be utilized to reduce the possibility of powder agglomeration. Moreover, graphene oxide has a large specific surface area and rich functional groups in the solution, and can be used as a water-oil affinity agent to ensure the stability and uniformity of the antipruritic composition slurry.

[0052] Furthermore, the alginate component mixture is composed of alginic acid and sodium alginate, and the mass ratio of the two is alginic acid:sodium alginate = (1 - 2):(6 - 10). The use of the mixed components is, on the one hand, to utilize the water solubility of the sodium salt, and on the other hand, to utilize the formation of a network by alginic acid molecules on the surface of the nanoparticles, which helps to reduce the possibility of nanoparticle aggregation. Moreover, the combined slurry prepared from alginic acid and sodium alginate has a moisturizing effect when coated on the skin surface, retains skin moisture, and helps to solve the itching caused by dry climate. In this process, since alginic acid is slightly soluble in hot water, alginic acid is first heated and dissolved, then sodium alginate solution is slowly added, and then camellia oil and the ethylene glycol solution of graphene oxide powder that has been mixed evenly are dropped in, and stirred at high speed to obtain the anti-itching composition slurry.

[0053] Regarding the anti-itching composition slurry, the use of camellia oil, on the one hand, is due to its own properties, which can keep the skin in a moist state and solve the itching caused by dry climate; on the other hand, there are many organic compounds in camellia oil, and their chemical bonds are mainly covalent bonds. The quaternary ammonium salt bactericidal component in the novel antibacterial microcapsule can obtain a more stable antibacterial effect through the covalent bonds in camellia oil.

[0054] (2) Preparation of anti-itching functionalized in-situ polyester chips

[0055] By weight, 100 parts of terephthalic acid, 15 - 20 parts of ethylene glycol, and 0.1 - 0.5 part of catalyst are mixed evenly, added to an esterification and polycondensation reaction kettle, and esterified at 220 - 230 °C for 0.6 - 1.5 h; then at this temperature, 35 - 55 parts of the anti-itching composition slurry and 4 - 7 parts of N,N-di(hydroxyethyl)-3-aminopropionic acid methyl ester are added uniformly, and both are added within 1 h; thereafter, the excess ethylene glycol is removed by vacuum distillation; after removing the excess ethylene glycol, the temperature of the reaction system is raised to 255 - 260 °C, and the reaction is carried out under vacuum conditions for 2 - 3 h, and the product is granulated through a cooling water tank to obtain the anti-itching functionalized in-situ polyester chips.

[0056] For polyester fiber yarns, the direct addition of a large amount of slurry can make the skin have excellent affinity and enhance the anti-itching effect. On the other hand, it has excellent antibacterial properties and can kill bacteria and relieve itching. However, excessive addition is likely to cause agglomerates of slurry additives, reduce the stability of polyester fibers, and also easily reduce other properties such as the mechanics of polyester fiber yarns. Therefore, we will try appropriate addition amounts of the anti-itching composition slurry, spray it in the form of atomization into the reaction kettle for mixing, granulate the product through a cooling water tank to obtain the anti-itching functionalized in-situ polyester chips, and then carry out processes such as blending, granulation, and spinning with the base material in the form of in-situ polyester chips with anti-itching slurry.

[0057] Further, the antibacterial agent is a novel antibacterial microcapsule. The preparation process of the novel antibacterial microcapsule includes nano antibacterial filler, surface coupling treatment, and microcapsule preparation. The preparation method is as follows:

[0058] Step 1: Preparation of nano antibacterial filler

[0059] To prevent the oxidation and deterioration of potassium iodide during the reaction, an operation of using excessive potassium iodide and an inert gas atmosphere for the reaction is adopted. Specifically, nitrogen is introduced at room temperature, and 3-(trimethoxysilylpropyl)dimethylstearylammonium chloride and potassium iodide are added to a three-necked flask in a molar ratio of 1:1.2 and magnetically stirred for 1-2 h. After the reaction, vacuum filtration is carried out, and the product is washed with absolute ethanol to obtain 3-(trimethoxysilylpropyl)dimethylstearylammonium iodide.

[0060] Using the above-mentioned device, 3-(trimethoxysilylpropyl)dimethylstearylammonium iodide and nano zinc oxide with a molar ratio of 1:1.1 are weighed according to the ratio and placed in a three-necked flask for magnetic stirring. Absolute ethanol is added to submerge the materials, and stirring is continued for 0.5 h. Then, absolute ethanol with a volume twice that of the original is slowly added dropwise. After the addition is completed, the reaction is carried out for 4 h. After the reaction, vacuum filtration is carried out, and the product is washed with absolute ethanol to obtain the nano antibacterial filler. The use of nano zinc oxide is to enhance the mechanical resistance of the capsule wall, enhance the overall mechanical properties of the microcapsule antibacterial agent, and nano zinc oxide also has a certain antibacterial effect.

[0061] Step 2: Surface coupling treatment of the nano antibacterial filler

[0062] The silane coupling agent is dropped into deionized water and stirred with a magnetic stirrer to obtain a premixed substance A with a mass fraction of 15 wt%. At the same time, a 20 wt% ethanol solution of nano antibacterial filler is prepared and stirred evenly to obtain a premixed substance B. Then, premixed substance A and premixed substance B with a mass ratio of 1:50 are added to a three-necked flask and stirred evenly for 0.5 h. Then, glacial acetic acid is added to the three-necked flask to adjust the pH to 3.3, and stirring is continued for 0.5 h. Then, a condensing reflux device is installed. After 2 h, the reaction is completed, vacuum filtration is carried out, and the product is washed with absolute ethanol. Then, it is dried in a vacuum drying oven at 60 °C to obtain the surface-coupled nano antibacterial filler. In the present invention, the coupling agent used is KH560.

[0063] The reason for directly blending the alcohol solution of the nano antibacterial filler with the aqueous solution of the silane coupling agent is that directly dropping the nano antibacterial filler into the aqueous solution of the silane coupling agent will cause flocculation and agglomeration phenomena. Therefore, two systems of premixed substance A and premixed substance B are blended, and glacial acetic acid is used to adjust the pH. In this way, not only the surface treatment of the coupling agent can be carried out, but also the possibility of material agglomeration is reduced. Moreover, the nano antibacterial filler treated with the coupling agent is a surface-treated activated filler, which makes the filler easier to be uniformly dispersed in the system; second, because in the preparation process of the nano antibacterial filler, the raw materials used contain hydroxyl silicon groups, and similar structures not only have similar solubility, which is beneficial to the mixing between materials; third, it can form stable hydrogen bonds with the raw material groups to ensure the stability of the system and is beneficial to further use and expansion; moreover, the amphiphilicity of graphene oxide can be utilized to provide binding sites for the wall material coating of graphene oxide sheets in the next step.

[0064] Step 3: Preparation of the novel antibacterial microcapsule

[0065] Taking the laboratory formula as an example, the dried N,N - dihydroxyethyl - p - toluidine is added to the triethylene glycol dimethacrylate solvent to prepare a 2wt% solution; at the same time, a 1wt% aqueous dispersion of nano zinc oxide is prepared, and the two are mixed. After mixing and stirring evenly at a stirring speed of 450 rpm, the mixture is left standing to obtain a premixed solution.

[0066] Prepare a round - bottom flask and place it in an ice - water bath. Add 100 mL of an aqueous solution of graphene oxide with a mass fraction of 6.5wt% to the round - bottom flask, and add 15 mL of an aqueous solution of 5.0wt% ethylene maleic anhydride copolymer as an emulsifier. Keep the stirring speed between 450 rpm, and then successively add 0.4 mol of urea, 0.11 mol of ammonium chloride, and 0.01 mol of resorcinol to adjust the pH of the solution to 4.0, and then drop the above - mentioned premixed solution after standing. Then add 0.125 mol of formaldehyde, and then add the surface - coupled nano antibacterial filler with 10% of the mass percentage of formaldehyde. Raise the water - bath temperature to 60 °C at a rate of 2 °C / min and react for 4 h. The product after the reaction is repeatedly filtered and washed with distilled water, and then dried at room temperature for 24 h to obtain the antibacterial agent of the present invention.

[0067] Uniformly dispersed nano-zinc oxide and graphene oxide can form a conductive channel network structure in the whole system with graphene oxide as the network and zinc oxide as the conductive points to strengthen, which can avoid the generation of static electricity and solve the itching caused by dryness. Generally, the aqueous solution of the copolymer of N,N-dihydroxyethyl-p-toluidine and maleic anhydride ethylene of the present invention can complete the reaction with equal mass. However, in order to add nano-zinc oxide, the form of excessive N,N-dihydroxyethyl-p-toluidine will be adopted. By using the steric hindrance of the macromolecule and the polarity of the two hydroxyethyl groups in this molecule, the aggregation of nano-zinc oxide is prevented during mixing. Then, the added aqueous solution of graphene oxide serves as the aqueous solution environment for microcapsule preparation on the one hand; on the other hand, it is conducive to the landing and coating of nano-zinc oxide at the low-potential positions of the surface wrinkles of graphene oxide, and has a synergistic effect with the antibacterial filler to enhance the mechanical strength, and further reduces the possibility of nano-zinc oxide aggregation.

[0068] Performance Test

[0069] Mechanical Property Test

[0070] Referring to GB / T14337-2008 "Test Method for Tensile Properties of Chemical Fiber Staple Fibers", the yarns are cut into the same test length, and a single-filament strength tester for electronic yarns (LLY-06E) purchased from China Laizhou Electronic Instrument Co., Ltd. is used to evaluate the mechanical properties of the sample yarns, with the breaking strength (unit: cN / dtex) as the evaluation standard.

[0071] Itching Relief Performance

[0072] The yarns of Examples 1-3 and Comparative Examples 1-8 of the present invention are woven into fabrics, and the same equipment, a knitting machine, is used to knit them into sleeves of the same size, numbered in sequence and pasted on the sleeves. Randomly select 100 volunteers, wear the sleeves on the same arm and record the feelings. The feeling levels will be divided into five levels of itching feelings: no itching feeling (5 points), a little itching feeling (4 points), general feeling (3 points), frequent itching feeling (1 point), and obvious itching feeling (0 point), and the forms will be collected and recorded. Taking the feeling level corresponding to a score ≥ 3 points as the evaluation criterion for having itching relief performance, and calculate the itching relief ratio of each sample.

[0073] Spinnability

[0074] Observe and record the spinnability during the yarn preparation process.

[0075] Antibacterial Performance

[0076] The yarns are woven into fabrics by the same process and then cut into test fabrics of the same area. According to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", the antibacterial properties of the PET composite antibacterial fibers against Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 25922) and Candida albicans (ATCC 10231) are tested, and the antibacterial activity of the yarns is expressed as the inhibition rate (%).

[0077] To compare the antibacterial stability of the functional yarns, we will use the same antibacterial property test method. The yarns of different examples and comparative examples are woven into fabrics by the same process and then cut into test fabrics of the same area. After 20 machine washes, the antibacterial properties of the test samples are tested. To save the test cost, the antibacterial property after washing is referenced by the inhibition rate against Escherichia coli.

[0078] Example 1

[0079] A yarn with antipruritic and antibacterial functions, by weight, comprises the following raw material components:

[0080] 100 parts of polyester chips;

[0081] 27 parts of antipruritic functionalized in-situ polyester chips;

[0082] 20 parts of alum;

[0083] 10 parts of antibacterial agent;

[0084] 2.0 parts of compatibilizer.

[0085] Furthermore, the antibacterial agent is a novel antibacterial microcapsule, the novel antibacterial microcapsule comprises a nano antibacterial filler, and the nano antibacterial filler is a surface-coupled nano antibacterial filler. Its preparation method is as follows:

[0086] Step 1. Preparation of nano antibacterial filler

[0087] In order to prevent the oxidation and deterioration of potassium iodide during the reaction, an operation of taking excessive potassium iodide and reacting in an inert gas atmosphere is adopted. Specifically, nitrogen is introduced at room temperature, 3-(trihydroxysilylpropyl) dimethyloctadecylammonium chloride and potassium iodide are added to a three-necked flask in a molar ratio of 1:1.2 and stirred magnetically for 1-2 h. After completion, vacuum filtration is carried out and washed with absolute ethanol to obtain 3-(trihydroxysilylpropyl) dimethyloctadecylammonium iodide.

[0088] Using the above device, weigh out 3-(trihydroxysilylpropyl) dimethyloctadecylammonium iodide and nano-zinc oxide in a molar ratio of 1:1.1 proportionally, place them in a three-necked flask and stir magnetically. Add anhydrous ethanol to submerge the materials, and continue stirring for 0.5 h. Then slowly add twice the volume of anhydrous ethanol dropwise. After the addition is complete, react for 4 h. After completion, perform vacuum filtration and wash with anhydrous ethanol to obtain nano-antibacterial filler. The use of nano-zinc oxide is, firstly, to enhance the mechanical resistance of the capsule wall; secondly, to enhance the overall mechanical properties of the microcapsule antibacterial agent; thirdly, nano-zinc oxide also has a certain antibacterial effect.

[0089] Step 2. Surface coupling treatment of the nano-antibacterial filler

[0090] Drop the silane coupling agent into deionized water and stir with a magnetic stirrer to obtain premixed substance A with a mass fraction of 15 wt%. At the same time, prepare a 20 wt% ethanol solution of nano-antibacterial filler, and stir evenly to obtain premixed substance B. Then add premixed substance A and premixed substance B with a mass ratio of 1:50 into a three-necked flask, stir evenly for 0.5 h, then add glacial acetic acid to the three-necked flask to adjust the pH to 3.3, and continue stirring for 0.5 h. Then install a condensing reflux device. After 2 h, after the reaction is completed, perform vacuum filtration, wash with anhydrous ethanol, and then dry in a 60 °C vacuum drying oven to obtain the surface-coupled nano-antibacterial filler. In the present invention, the coupling agent used is KH560.

[0091] The direct blending of the nano-antibacterial filler alcohol solution with the aqueous solution of the silane coupling agent is because direct dropping of the nano-antibacterial filler into the aqueous solution of the silane coupling agent will cause flocculation and agglomeration phenomena. Therefore, the two systems of premixed substance A and premixed substance B are blended, and the pH is adjusted with glacial acetic acid. In this way, not only the surface treatment of the coupling agent can be carried out, but also the possibility of material agglomeration is reduced. Moreover, the nano-antibacterial filler treated with the coupling agent, firstly, activates the surface of the filler, making the filler easier to disperse evenly in the system; secondly, because in the preparation process of the nano-antibacterial filler, the raw materials used contain hydroxy-silyl groups, similar structures not only have similar solubility, which is beneficial to the mixing of materials; thirdly, it can form stable hydrogen bonds with the raw material groups to ensure the stability of the system and is beneficial to further use and expansion; moreover, the amphiphilicity of graphene oxide can be utilized to provide binding sites for the wall material coating of graphene oxide sheets in the next step.

[0092] Step 3. Preparation of novel antibacterial microcapsules

[0093] Taking the laboratory formula as an example, the dried N,N-dihydroxyethyl-p-methylaniline is added to the triethylene glycol dimethacrylate solvent to prepare a 2wt% solution; at the same time, a 1wt% aqueous dispersion of nano zinc oxide is prepared, the two are mixed, and the mixture is stirred evenly at a stirring speed of 450 rpm and then allowed to stand to obtain a premixed solution.

[0094] Prepare a round-bottom flask, place it in an ice-water bath, add 100 mL of a 6.5 wt% graphene oxide aqueous solution to the round-bottom flask, and add 15 mL of a 5.0 wt% ethylene maleic anhydride copolymer aqueous solution as an emulsifier. Keep the stirring speed between 450 rpm, and then add 0.4 mol urea, 0.11 mol ammonium chloride and 0.01 mol resorcinol to adjust the pH of the solution to 4.0, and then drop the above-mentioned premixed solution after standing. Then add 0.125 mol of formaldehyde, and then add a surface-coupled nano antibacterial filler with a 10% mass percentage of formaldehyde, raise the water bath temperature to 60 ° C at a rate of 2 ° C / min, react for 4 hours, and the product after the reaction is completed is repeatedly filtered and washed with distilled water, and then dried at room temperature for 24 hours to obtain the antibacterial agent of the present invention.

[0095] Furthermore, the antipruritic functionalized in-situ polyester chips include, by weight, 100 parts of terephthalic acid, 17 parts of ethylene glycol, 0.25 parts of catalyst, 45 parts of antipruritic composition slurry and 5 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester. The antipruritic composition slurry includes, by weight, 1 part of silicone oil, 5 parts of alginate component mixture, 7 parts of camellia oil, 12 parts of graphene oxide powder, and 7 parts of compound dispersant added to 150 parts of ethylene glycol.

[0096] Example 2

[0097] Different from the above-mentioned embodiment 1, a yarn with antipruritic and antibacterial functions comprises the following raw material components by weight:

[0098] Polyester chips 100 pieces;

[0099] 25 pieces of antipruritic functionalized in-situ polyester slices;

[0100] 15 parts of alum;

[0101] 8 parts of antimicrobial agent;

[0102] 0.5 parts of compatibilizer.

[0103] For other steps, refer to Example 1.

[0104] Example 3

[0105] Different from the above-mentioned embodiment 1, a yarn with antipruritic and antibacterial functions comprises the following raw material components by weight:

[0106] 100 parts of polyester chips;

[0107] 30 parts of itch-relieving functional in-situ polyester chips;

[0108] 25 parts of alum;

[0109] 13 parts of antibacterial agent;

[0110] 3.5 parts of compatibilizer.

[0111] For other steps, refer to Example 1.

[0112] Comparative Example 1

[0113] The difference from Example 1 is only that alum is missing here to prove the role of alum here, and other steps are the same as those in Example 1.

[0114] Comparative Example 2

[0115] The difference from Example 1 is only that in the itch-relieving functional in-situ polyester chips, camellia oil is not added to the itch-relieving composition slurry, and other steps refer to Example 1.

[0116] Comparative Example 3

[0117] The difference from Example 1 is only that in the itch-relieving functional in-situ polyester chips, graphene oxide powder is not added to the itch-relieving composition slurry, and other steps refer to Example 1.

[0118] Comparative Example 4

[0119] The difference from Example 1 is only that the itch-relieving functional in-situ polyester chips are missing here to prove the role of the itch-relieving functional in-situ polyester chips here, and other steps are the same as those in Example 1.

[0120] Comparative Example 5

[0121] Different from Example 1, in the preparation process of the novel antibacterial microcapsule, there is no nano-zinc oxide component in the nano-antibacterial filler in Step 1, and other steps refer to Example 1.

[0122] Comparative Example 6

[0123] Different from Example 1, in the preparation process of the novel antibacterial microcapsule, there is no step of surface coupling treatment of the nano-antibacterial filler in Step 2, and other steps refer to Example 1.

[0124] Comparative Example 7

[0125] Different from Example 1, the antibacterial agent includes two steps: nano-antibacterial filler and surface coupling treatment, and other steps refer to Example 1.

[0126] Comparative Example 8

[0127] The difference from Example 1 is only that the novel antibacterial microcapsule as the antibacterial agent is missing here to prove the role of the antibacterial agent here, and other steps are the same as those in Example 1.

[0128] Samples of the yarns of Examples 1-3 and Comparative Examples 1-8 were taken, and then sample preparation and characterization were carried out in accordance with relevant performance test standards. See Table 1 for the relevant test comparisons.

[0129] Table 1 Comparison of Relevant Test Characterizations

[0130] It can be seen from the comparison in the above table that the yarn prepared by the present invention has the characteristics of antibacterial and antipruritic, good mechanical properties, and no floating filaments and no broken ends during the spinning process, and has good spinnability.

[0131] For antibacterial properties, among Comparative Examples 5 to 8, the incomplete structure of the antibacterial agent has a greater impact on antibacterial properties, and due to the surface treatment of coupling, it also affects the mechanical properties of the yarn. However, the absence of alum has a greater impact on the overall antibacterial properties. In addition, from the analysis of the antibacterial results of Comparative Example 3 and Comparative Example 1, although there is an antipruritic composition slurry containing nano-silver antibacterial powder in the functionalized in-situ polyester chip for antipruritic, due to the relatively low overall usage amount, the impact on antibacterial properties is not as obvious as the antibacterial effect of alum. It should be noted that alum and the antipruritic composition slurry have a greater impact on the overall antipruritic determination of the yarn. Alum inhibits metabolism and can relieve itching and antibacterial; the mixture of alginic acid components in the composition slurry helps to solve the itching problem caused by dry climate. Moreover, according to the change of the washing antibacterial rate in Comparative Example 2 and Comparative Example 5, the combination of camellia oil and antibacterial microcapsules has the effect of enhancing antibacterial stability. The quaternary ammonium salt bactericidal component in the novel antibacterial microcapsule can obtain a more stable antibacterial effect through the covalent bond in camellia oil, and it can be considered to further verify the actual use experience in the medical and health field for further promotion and use.

[0132] During the experimental preparation process, in Comparative Examples 6 to 7, due to the lack of surface coupling treatment, the possibility of stable sedimentation of the wall material was reduced, resulting in defects in the novel antibacterial microcapsules. Its overall structure is more loosely dispersed than the antibacterial agent in Example 1, thereby affecting its overall comprehensive performance. Moreover, there are more floating filaments and broken ends in this comparative example during the spinning process, and the spinnability is poor.

[0133] Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope defined in the claims.

Claims

1. A yarn with antipruritic and antibacterial functions, characterized in that: The composition includes the following raw materials by weight: Polyester chips 100 pieces; 25-30 pieces of antipruritic functionalized in-situ polyester slices; 15-25 parts of alum; 8-13 parts of antibacterial agent; Compatibilizer 0.5-3.5 parts.

2. The yarn with antipruritic and antibacterial functions according to claim 1, characterized in that: The antipruritic functionalized in-situ polyester slice comprises, by weight, 100 parts of terephthalic acid, 15-20 parts of ethylene glycol, 0.1-0.5 parts of a catalyst, 35-55 parts of an antipruritic composition slurry and 4-7 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester.

3. The yarn with antipruritic and antibacterial functions according to claim 2, characterized in that: The catalyst is antimony trioxide or antimony glycolate.

4. The yarn with antipruritic and antibacterial functions according to claim 1, characterized in that: The antibacterial agent is a novel antibacterial microcapsule, and the novel antibacterial microcapsule comprises nano antibacterial filler.

5. The yarn with antipruritic and antibacterial functions according to claim 4, characterized in that: The nano antibacterial filler is a nano antibacterial filler with surface coupling treatment.

6. The yarn with antipruritic and antibacterial functions according to claim 1, characterized in that: The compatibilizer is one of styrene / MAH random copolymer, styrene / acrylonitrile / MAH terpolymer, butyl acrylate or maleic anhydride.

7. A method for preparing the yarn with antipruritic and antibacterial functions as claimed in any one of claims 1 to 6, characterized in that: The following steps are involved: S1. Material pretreatment and preparation The polyester slices and the novel antibacterial microcapsules are dried; and an antipruritic composition slurry is prepared at the same time; S2. Preparation of antipruritic functionalized in-situ polyester slices According to weight parts, 100 parts of terephthalic acid, 15-20 parts of ethylene glycol, and 0.1-0.5 parts of a catalyst are mixed uniformly, added into an esterification polycondensation reaction kettle, and esterified at 220-230° C. for 0.6-1.5 hours; then, at the same temperature, 35-55 parts of an antipruritic composition slurry and 4-7 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester are uniformly added, and both are added within 1 hour; thereafter, excess ethylene glycol is removed by vacuum distillation; after removing excess ethylene glycol, the temperature of the reaction system is increased to 255-260° C., the reaction is carried out under vacuum conditions for 2-3 hours, and the discharged material is granulated through a cooling water tank to obtain antipruritic functionalized in-situ polyester chips; S3. Material mixing The polyester slice, antipruritic functionalized in-situ polyester slice, alum, novel antibacterial microcapsule and compatibilizer are mixed at high speed for 5-10 minutes, the temperature is raised to 80-120°C, and then kept at this temperature for 0.5-1h, and then stirred and mixed at the same stirring speed for 5-10 minutes to obtain a premix, wherein the high-speed stirring speed is 900-1200rpm; S4, extrusion granulation The premix is ​​melt-blended and extruded through a twin-screw extruder, followed by pulling, granulation and drying to prepare an antipruritic and antibacterial functional masterbatch; S5. Post-treatment and spinning The dried antipruritic and antibacterial functional masterbatch is placed in a vacuum drum for post-treatment, firstly heated to 130-135°C at a rate of 1-2°C / min for pre-crystallization for 2.5-3h; then heated to 165-170°C at a rate of 10-15°C / min for preservation for 4-5h; then the post-treated antipruritic and antibacterial functional masterbatch is put into a spinning machine for spinning treatment, the spinning temperature is 310-315°C, and the spinning speed is 2500-3000m / min, to obtain antipruritic and antibacterial functional yarn.

8. The method for preparing the yarn with antipruritic and antibacterial functions according to claim 7, characterized in that: In parts by weight, the antipruritic composition slurry in step S1 includes 1-2 parts of silicone oil, 3-6 parts of alginate component mixture, 6-8 parts of camellia oil, 10-15 parts of graphene oxide powder, 5-8 parts of compound dispersant, and 100-200 parts of ethylene glycol.

9. The method for preparing the yarn with antipruritic and antibacterial functions according to claim 7, characterized in that: The vacuum condition in step S2 means that the pressure in the reactor is below 100 Pa.

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