A polyamide fiber with antibacterial and odor-removing composite functions and its preparation method and application

Abstract

The present invention relates to the technical field of modified chemical fibers, in particular to polyamide ester fibers with antibacterial and odor-removing composite functions, as well as a preparation method and application thereof. The invention adopts a polyamide ester polymer as a matrix, and fully mixes metal oxide-loaded chitosan nano-microspheres with polyamide ester powder. The polyamide ester masterbatch containing the metal oxide-loaded chitosan nano-microspheres is prepared by twin-screw granulation. The prepared polyamide ester masterbatch is mixed with slices of the matrix, and then melt-spinning is performed to prepare the polyamide ester fiber. The antibacterial component of the polyamide ester fiber has good stability, good antibacterial function, and can eliminate odors generated by bacterial decomposition of organic matter without affecting the spinnability of the fiber. The polyamide ester fiber can be used in the fields of home textile filling, clothing, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of modified chemical fibers, in particular to polyamide ester fibers with antibacterial and odor-removing composite functions, and a preparation method and application thereof. Background Art

[0002] Antimicrobial fiber is a fiber that has the ability to kill or inhibit the growth of microorganisms by adding antimicrobial ingredients. It plays a role in protecting people's health and improving their quality of life. Antimicrobial ingredients commonly added to antimicrobial fibers are inorganic and organic. Inorganic antimicrobial ingredients include nano-copper, nano-silver, and zinc oxide, while organic antimicrobial ingredients include quaternary ammonium salts, quaternary phosphate salts, biguanides, halamines, flavonoids, and polyphenols. While there are many types of antimicrobial fibers, the harmful effects of some antimicrobial agents on the human body remain unclear.

[0003] Chitin is a natural biopolymer and a rare, positively charged alkaline polysaccharide found in nature. It is widely found in the shells of arthropods such as shrimp and crabs, and in the shells and cartilage of shellfish and mollusks. Chitosan is produced by removing the N-acetyl groups from chitin by heating it under alkaline conditions. It is typically blended with other fibers. Most studies believe that chitosan's antibacterial properties primarily stem from the positively charged amino groups on its molecular chain. Bacterial cells typically have a negative charge. These positively charged groups bind to bacterial proteins, modifying them and causing them to flocculate and aggregate, thereby inhibiting their reproductive capacity. Therefore, textile materials made from chitosan fibers, either pure or blended with other fibers, possess excellent antibacterial properties. Silver ions have an oxidizing effect and are commonly used in daily life for disinfection and sterilization. The positively charged silver ions react with the negatively charged sulfhydryl groups in bacterial proteases, rapidly deactivating the proteases due to the loss of the sulfhydryl groups, preventing the bacteria from dividing and reproducing, thus killing them.

[0004] CN104762810A discloses a method for preparing a copper ion antibacterial and anti-ultraviolet finishing agent, which is characterized by exploring the determination of the reagent dosage based on the ratio of basic copper ammonia and salt copper ammonia in the antibacterial agent, which is reflected in the ratio of copper sulfate and sodium hydroxide added in the preparation. This is because basic copper ammonia is easy to open the fiber reaction zone, and salt copper ammonia is easy to provide copper ammonia chelated ions for complexation reaction. The introduction of copper ammonia ions is easy to make the fabric better exert its antibacterial properties. The copper ion finishing agent with the optimal ratio obtained above is used to complex and finish chitosan and cotton blended fabrics, and the parameter conditions of the complexation process are explored to control the complexation of copper ions, thereby solving the current situation that the spinnability of chitosan fiber is poor and the antibacterial property is easily interfered with. However, it is obtained by impregnation treatment, and there are disadvantages such as unstable antibacterial effect and short antibacterial time.

[0005] Polyamide fiber is a new type of synthetic fiber. It is spun from polyamide polymer formed by copolymerization of terephthalic acid, ethylene glycol, and caprolactam blocks. It has the characteristics of moderate strength and soft feel, and is well used in home textile filling, workwear and other fields. However, the current domestic polyamide fiber product structure is relatively simple, and there is a lack of functional polyamide fiber products such as antibacterial products, which cannot meet market demand well. Summary of the Invention

[0006] In response to the shortcomings of the above-mentioned existing technologies, a polyamide polyester fiber with antibacterial and odor-removing composite functions and a preparation method thereof are provided. The antibacterial component thereof has good stability, good antibacterial function, and can eliminate the odor produced by bacterial decomposition of organic matter without affecting the spinnability of the fiber. It can be used in home textile filling, clothing and other fields.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is a polyamide ester fiber with antibacterial and odor-removing composite functions, which is based on a polyamide ester polymer. Chitosan nanoparticles loaded with metal oxides are fully mixed with polyamide ester powder, and polyamide ester masterbatch containing chitosan nanoparticles loaded with metal oxides is prepared by twin-screw granulation. The prepared polyamide ester masterbatch is mixed with slices of the matrix and then prepared by melt spinning.

[0008] The above-mentioned polyamide fiber with antibacterial and odor-removing composite functions, the polyamide polymer matrix refers to a polymer formed by copolymerization of terephthalic acid, ethylene glycol, and caprolactam blocks, wherein the caprolactam content is 8.0% to 30%, the intrinsic viscosity is 0.60 to 0.85, and the melting point is 210 to 245°C.

[0009] The polyamide ester fiber with antibacterial and odor-removing composite functions, the chitosan nano-microspheres loaded with metal oxides are zinc oxide-chitosan composite materials, and the particle size thereof is 20 to 300 nm.

[0010] The polyamide ester fiber with the composite function of antibacterial and deodorizing has a fiber fineness of 0.6 to 10.0 dtex.

[0011] The polyamide ester fiber with antibacterial and odor-removing composite functions has a moisture regain of 1.0%, an antibacterial rate of more than 99% against coccus aureus and Escherichia coli, and an antibacterial rate of more than 90% against Candida albicans, and a breaking strength of more than 2.2 cN / dtex.

[0012] The polyamide ester fiber with the composite function of antibacterial and deodorizing has a polyamide ester powder with a diameter of 10 to 50 μm.

[0013] The method for preparing the polyamide ester fiber having the composite function of antibacterial and deodorizing comprises the following steps:

[0014] (1) Fully mixing the metal oxide-loaded chitosan nanoparticles, a dispersant, and polyamide ester powder, wherein the metal oxide-loaded chitosan nanoparticles are 10 to 40 parts, the dispersant is 3 to 10 parts, and the polyamide ester powder is 50 to 80 parts;

[0015] (2) melt-granulating the polyamide ester powder containing metal oxide-loaded chitosan nanoparticles using a twin-screw extruder to obtain a polyamide ester masterbatch containing zinc oxide-loaded chitosan nanoparticles;

[0016] (3) Adding the prepared polyamide polyester masterbatch containing loaded metal oxide chitosan nanoparticles to polyamide polyester chips in a certain proportion, and then performing melt spinning to obtain polyamide polyester fibers with antibacterial and odor-removing composite functions, wherein the addition amount of the polyamide polyester masterbatch containing loaded metal oxide chitosan nanoparticles is 5% to 20%.

[0017] In the above-mentioned method for preparing polyamide ester fiber with antibacterial and odor-removing composite functions, in step (2), the content of chitosan nanospheres in the polyamide ester masterbatch is 10% to 30%, and the content of zinc oxide is 10% to 25%.

[0018] In the above-mentioned method for preparing polyamide ester fiber with antibacterial and odor-removing composite functions, in step (1), the dispersant is a mixture of carboxyl-modified wax and vinyl bisstearamide, with a mass ratio of 1:2.

[0019] The application of polyamide polyester fiber with antibacterial and odor-removing composite functions is used in home textile filling and clothing fields.

[0020] The present invention discloses a polyamide fiber with antibacterial and odor-removing composite functions, as well as a preparation method and application thereof. The present invention utilizes zinc oxide-loaded chitosan nanospheres to develop polyamide fibers with antibacterial and odor-removing composite functions. The chitosan and zinc oxide used are non-toxic to the human body. Zinc oxide is a safe and non-toxic inorganic substance with certain antibacterial properties, making it suitable for use in baby powder and external medications. Furthermore, the addition of zinc oxide-loaded chitosan nanospheres effectively ensures uniform dispersion of the antibacterial component. This solves the problem of dispersing the chitosan nanospheres in polyamide fibers, and the antibacterial material is directly kneaded into the matrix material, preventing it from easily falling off. The fiber exhibits excellent stability and long-term bacterial resistance and killing effects. The chitosan functional masterbatch is then mixed with polyamide chips and melt-spun to produce a modified polyamide fiber. The polyamide fiber exhibits excellent antibacterial properties and can eliminate odors produced by bacterial decomposition of organic matter. It has a breaking strength of at least 2.2 cN / dtex and a fiber fineness of 0.6 to 10.0 dtex. It can be used in home textile filling and clothing fields, especially as bedding filling, and will not produce odor after long-term use.

[0021] The content of chitosan nano-microspheres in the polyamide polyester masterbatch is 10% to 30%, and the content of zinc oxide is 10% to 25%. Based on this component content, the uniformity of the dispersion of the antibacterial component can be ensured, while the production efficiency is improved and the production cost is reduced.

[0022] The particle size of the metal oxide-loaded chitosan nanospheres is 20 to 300 nm, preferably 50 to 100 nm, which avoids the decrease of spinnability and ensures the fiber quality.

[0023] The spun polyamide polyester fiber has a moisture regain of 1.0%, which can reduce static electricity and improve comfort.

[0024] The addition amount of polyamide masterbatch is 5% to 20%. Although the antibacterial properties will be improved when the addition amount of polyamide masterbatch exceeds the upper limit of this range, the spinnability will decrease at the same time. If the addition amount is below the lower limit of this range, the functionality will be affected, and the antibacterial function will decrease. That is, based on the addition amount of 5% to 20% of polyamide masterbatch, the antibacterial rate against coccus aureus and Escherichia coli can reach more than 99%, and the antibacterial rate against Candida albicans can reach more than 90%, without affecting the spinnability of the fiber. DETAILED DESCRIPTION

[0025] The present invention is described in detail below with reference to specific embodiments.

[0026] A polyamide fiber with antibacterial and odor-removing composite functions is prepared by using a polyamide polymer as a matrix, fully mixing metal oxide-loaded chitosan nanoparticles with polyamide powder, and preparing a polyamide masterbatch containing metal oxide-loaded chitosan nanoparticles through twin-screw granulation. The prepared polyamide masterbatch is mixed with slices of the matrix, and then melt-spinning is performed to prepare the fiber.

[0027] Example 1

[0028] The method for preparing the polyamide ester fiber having the composite function of antibacterial and deodorizing comprises the following steps:

[0029] (1) Fully mix the metal oxide-loaded chitosan nanoparticles, dispersant, and polyamide ester powder, wherein the metal oxide-loaded chitosan nanoparticles are 10 parts, the dispersant is 3 parts, and the polyamide ester powder is 50 parts;

[0030] (2) melt-granulating the polyamide ester powder containing metal oxide-loaded chitosan nanoparticles using a twin-screw extruder to obtain a polyamide ester masterbatch containing zinc oxide-loaded chitosan nanoparticles;

[0031] (3) Adding the prepared polyamide polyester masterbatch containing loaded metal oxide chitosan nanoparticles to polyamide polyester chips in a certain proportion, and then melt spinning is performed to obtain polyamide polyester fibers with antibacterial and odor-removing composite functions, wherein the addition amount of the polyamide polyester masterbatch containing loaded metal oxide chitosan nanoparticles is 5%.

[0032] In the step (2), the content of chitosan nano-microspheres in the polyamide ester masterbatch is 10%, and the content of zinc oxide is 10%.

[0033] In the step (1), the dispersant is a mixture of carboxyl-modified wax and vinyl bisstearamide, with a mass ratio of 1:2.

[0034] The polyamide ester polymer matrix is ​​a polymer formed by block copolymerization of terephthalic acid, ethylene glycol and caprolactam, wherein the caprolactam content is 8.0%, the intrinsic viscosity is 0.60 and the melting point is 210.

[0035] The metal oxide-loaded chitosan nanospheres are zinc oxide-chitosan composite materials with a particle size of 20 nm. The diameter of the polyamide ester powder is 10 μm.

[0036] Example 2

[0037] The same parts as those in Example 1 will not be described in detail. The difference between the present embodiment and Example 1 is that the method for preparing the polyamide ester fiber with antibacterial and odor-removing composite functions comprises the following steps:

[0038] (1) Fully mix the metal oxide-loaded chitosan nanoparticles, dispersant, and polyamide ester powder, wherein the metal oxide-loaded chitosan nanoparticles are 25 parts, the dispersant is 7 parts, and the polyamide ester powder is 65 parts;

[0039] (2) melt-granulating the polyamide ester powder containing metal oxide-loaded chitosan nanoparticles using a twin-screw extruder to obtain a polyamide ester masterbatch containing zinc oxide-loaded chitosan nanoparticles;

[0040] (3) The prepared polyamide polyester masterbatch containing metal oxide-loaded chitosan nanoparticles is added to polyamide polyester chips in a certain proportion, and then melt-spinning is performed to obtain polyamide polyester fibers with antibacterial and odor-removing composite functions, wherein the addition amount of the polyamide polyester masterbatch containing metal oxide-loaded chitosan nanoparticles is 10%.

[0041] In the step (2), the content of chitosan nano-microspheres in the polyamide ester masterbatch is 20%, and the content of zinc oxide is 20%.

[0042] The polyamide ester polymer matrix is ​​a polymer formed by block copolymerization of terephthalic acid, ethylene glycol and caprolactam, wherein the caprolactam content is 18%, the intrinsic viscosity is 0.7 and the melting point is 225°C.

[0043] The metal oxide-loaded chitosan nanoparticles are zinc oxide-chitosan composite materials with a particle size of 100 nm.

[0044] The diameter of the polyamide polyester powder is 30 μm.

[0045] Example 3

[0046] The same parts as those in Example 1 will not be described in detail. The difference between the present embodiment and Example 1 is that the method for preparing the polyamide ester fiber with antibacterial and odor-removing composite functions comprises the following steps:

[0047] (1) Fully mix the metal oxide-loaded chitosan nanoparticles, dispersant, and polyamide ester powder, wherein the metal oxide-loaded chitosan nanoparticles are 40 parts, the dispersant is 10 parts, and the polyamide ester powder is 80 parts;

[0048] (2) melt-granulating the polyamide ester powder containing metal oxide-loaded chitosan nanoparticles using a twin-screw extruder to obtain a polyamide ester masterbatch containing zinc oxide-loaded chitosan nanoparticles;

[0049] (3) The prepared polyamide polyester masterbatch containing metal oxide-loaded chitosan nanoparticles is added to polyamide polyester chips in a certain proportion, and then melt-spinning is performed to obtain polyamide polyester fibers with antibacterial and odor-removing composite functions, wherein the addition amount of the polyamide polyester masterbatch containing metal oxide-loaded chitosan nanoparticles is 20%.

[0050] In the step (2), the content of chitosan nano-microspheres in the polyamide ester masterbatch is 30%, and the content of zinc oxide is 25%.

[0051] In the step (1), the dispersant is a mixture of carboxyl-modified wax and vinyl bisstearamide.

[0052] The polyamide ester polymer matrix is ​​a polymer formed by block copolymerization of terephthalic acid, ethylene glycol and caprolactam, wherein the caprolactam content is 30%, the intrinsic viscosity is 0.85 and the melting point is 245°C.

[0053] The metal oxide-loaded chitosan nanoparticles are zinc oxide-chitosan composite materials with a particle size of 300 nm.

[0054] The diameter of the polyamide polyester powder is 50 μm.

[0055] Example 4

[0056] The same parts as those in Example 1 will not be described in detail. The difference between the present embodiment and Example 1 is that the method for preparing the polyamide ester fiber with antibacterial and odor-removing composite functions comprises the following steps:

[0057] (1) Selecting polyamide ester chips with a caprolactam segment content of 18% and an intrinsic viscosity of 0.69 as the substrate;

[0058] (2) Select zinc oxide-loaded chitosan nanoparticles with an average particle size of 60 nm, and the mass ratio of zinc oxide to chitosan nanoparticles is 1:1;

[0059] (3) 30 parts of zinc oxide-loaded chitosan nanoparticles, 10 parts of a mixture of carboxyl-modified wax and vinyl bisstearamide (mass ratio 1:2), and 60 parts of polyamide ester powder with an average particle size of 40 μm were fully mixed, and then granulated using a twin-screw extruder at 270° C. to obtain polyamide ester masterbatch containing zinc oxide-loaded chitosan nanoparticles;

[0060] (4) 16 parts of polyamide polyester masterbatch loaded with zinc oxide chitosan nanoparticles were added to 84 parts of polyamide polyester chips for melt spinning to obtain polyamide polyester fibers with antibacterial and odor-removing composite functions. The total content of zinc oxide chitosan nanoparticles was 4.8%, and the contents of zinc oxide and chitosan nanoparticles were both 2.4%.

[0061] Example 5

[0062] The polyamide fiber with antibacterial and odor-removing composite functions prepared in the above examples has a moisture regain of 1.0%, an antibacterial rate of greater than 99% against Coccus aureus and Escherichia coli, and an antibacterial rate of greater than 90% against Candida albicans. It also has a breaking strength of greater than 2.2 cN / dtex and a fiber fineness of 0.6 to 10.0 dtex. It can be used in home textile filling and clothing, especially as a bedding filling, and produces no odor over long-term use.

[0063] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by ordinary technicians in this technical field within the essential scope of the present invention should also fall within the scope of protection of the present invention.

Claims

1. A polyamide fiber with antibacterial and odor-removing composite functions, characterized by: The invention adopts polyamide ester polymer as matrix, and fully mixes metal oxide loaded chitosan nano-microspheres with polyamide ester powder, and prepares polyamide ester masterbatch containing metal oxide loaded chitosan nano-microspheres by twin-screw granulation. The prepared polyamide ester masterbatch is mixed with matrix slices, and then prepared by melt spinning. The polyamide ester polymer matrix refers to a polymer formed by block copolymerization of terephthalic acid, ethylene glycol and caprolactam, wherein the caprolactam content is 8.0% to 3.0%. 0%, the intrinsic viscosity is 0.60-0.85, and the melting point is 210-245°C; the chitosan nanospheres loaded with metal oxides are zinc oxide-chitosan composite materials with a particle size of 20-300nm. The spun polyamide ester fiber has a moisture regain of 1.0%, an antibacterial rate against coccus aureus and Escherichia coli greater than 99%, and an antibacterial rate against Candida albicans greater than 90%, and a breaking strength of above 2.2cN / dtex; the fiber fineness is 0.6-10.0dtex.

2. The polyamide fiber with antibacterial and deodorizing composite functions according to claim 1, characterized in that: The diameter of the polyamide polyester powder is 10 to 50 μm.

3. A method for preparing the polyamide ester fiber with antibacterial and odor-removing composite functions according to any one of claims 1 to 2, characterized in that: The following steps are involved: (1) Fully mix the chitosan nanoparticles loaded with metal oxides, a dispersant, and polyamide ester powder, wherein the chitosan nanoparticles loaded with metal oxides are 10 to 40 parts, the dispersant is 3 to 10 parts, and the polyamide ester powder is 50 to 80 parts; the dispersant is a mixture of carboxyl modified wax and vinyl bisstearamide, with a mass ratio of 1:2; (2) The polyamide ester powder containing metal oxide-loaded chitosan nanoparticles is melt-granulated using a twin-screw extruder to obtain a polyamide ester masterbatch containing zinc oxide-loaded chitosan nanoparticles; the content of chitosan nanoparticles in the polyamide ester masterbatch is 10% to 30%, and the content of zinc oxide is 10% to 25%; (3) The prepared polyamide polyester masterbatch containing metal oxide-loaded chitosan nanoparticles is added to polyamide polyester chips in a certain proportion, and then melt-spinning is performed to obtain polyamide polyester fibers with antibacterial and odor-removing composite functions, wherein the addition amount of the polyamide polyester masterbatch containing metal oxide-loaded chitosan nanoparticles is 5% to 20%.

4. An application of the polyamide fiber with antibacterial and odor-removing composite functions according to any one of claims 1-2, characterized in that: Used in home textile filling and clothing fields.