Ultraviolet-resistant bacteriostatic and deodorant polyamide cool master batch, and preparation method and application thereof

Abstract

This invention provides an anti-UV, antibacterial, and deodorizing polyamide cooling masterbatch, its preparation method, and its application, belonging to the field of polyamide fiber masterbatch technology. The anti-UV, antibacterial, and deodorizing polyamide cooling masterbatch of this invention is made from the following raw materials in parts by weight: 20-70 parts polyamide resin, 10-35 parts modified titanium dioxide micropowder, 10-35 parts modified cooling functional agent, 1-5 parts modified inorganic / organic compound antibacterial and deodorizing agent, 1-2 parts plasticizer, 0.2-1 part antioxidant, and 0.5-1 part stabilizer. This invention modifies the titanium dioxide micropowder, cooling functional agent, and inorganic / organic compound antibacterial and deodorizing agent, improving the interfacial compatibility and dispersibility between TiO2 micropowder, cooling functional agent, and inorganic / organic compound antibacterial and deodorizing agent and polyamide resin. It integrates the three functions of UV protection, contact cooling, and long-lasting antibacterial properties into a single masterbatch through interfacial bonding technology, solving the problems of easy peeling and poor durability of traditional surface coatings.

Description

Technical Field

[0001] This invention relates to the field of polyamide fiber masterbatch technology, and in particular to an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch, its preparation method, and its application. Background Technology

[0002] With the improvement of living standards, people have placed higher demands on the functionality and comfort of fiber fabrics such as outdoor sportswear and medical textiles, especially during the hot summer months when the need for clothing that is cool, comfortable, UV-protective, antibacterial, and odor-resistant is increasing. Polyamide fibers, with their advantages of high elasticity, high abrasion resistance, lightweight, and durability, have been widely used in sportswear, sports socks, yoga wear, mountaineering clothing, windbreakers, and casual wear. However, traditional polyamide fibers have a dense structure, making it difficult for sweat to evaporate, which can lead to a stuffy feeling when worn in summer. They are also susceptible to UV damage, causing fading and aging. Furthermore, skin contact can easily breed bacteria, causing allergic reactions such as redness and itching, significantly limiting their application in clothing and medical textiles and failing to meet people's needs. Therefore, modifying polyamide fibers to improve their UV resistance, antibacterial and odor-resistant properties, as well as their cooling and comfort, is of great significance in meeting the functionality and comfort requirements of fiber fabrics such as outdoor sportswear and medical textiles.

[0003] In recent years, polyamide fiber modification has typically involved surface modification or coating with functional additives, which has improved the functionality of polyamide fibers to some extent. However, this surface coating treatment suffers from poor durability in terms of UV resistance, antibacterial and deodorizing properties, as well as cooling comfort. Furthermore, the coating is prone to peeling off under prolonged exposure to high temperatures, light, and friction, failing to meet the needs of sportswear, medical textiles, and other fiber fabrics. In addition, patents CN106222776B, CN104562277A, and CN104153035A disclose a method for preparing cooling fibers, but their cooling sensation is uneven and their UV resistance and antibacterial properties are not addressed. Therefore, researching a UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatch and its preparation method, and applying it to textiles to improve UV resistance, antibacterial and deodorizing properties, as well as cooling performance, is of great significance. Summary of the Invention

[0004] The purpose of this invention is to provide an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch, its preparation method, and its application, so as to solve the problem that the existing technology of modifying or coating the surface of polyamide fibers with functional additives cannot meet the needs of textile applications.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch, comprising the following raw materials in parts by weight: 20-70 parts of polyamide resin, 10-35 parts of modified titanium dioxide micro powder, 10-35 parts of modified cooling functional agent, 1-5 parts of modified inorganic / organic compound antibacterial and deodorizing agent, 1-2 parts of plasticizer, 0.2-1 part of antioxidant, and 0.5-1 part of stabilizer.

[0006] Preferably, the modified titanium dioxide micro powder is prepared by mixing titanium dioxide micro powder, surface modifier and lubricant and then ball milling to obtain modified titanium dioxide micro powder.

[0007] Preferably, the mass ratio of the titanium dioxide micro powder, surface modifier compound and lubricant is 100:1~2.5:0.5~2; the particle size of the titanium dioxide micro powder is 400~6000 mesh; the ball milling treatment temperature is 60~110℃, the rotation speed is 180~300rpm, and the time is 6~15min.

[0008] Preferably, the modified cooling functional agent is prepared by mixing the cooling functional agent, surface modifier compound and lubricant and then ball milling them to obtain the modified cooling functional agent.

[0009] Preferably, the mass ratio of the cooling functional agent, the surface-modifying compound agent, and the lubricant is 100:2~5:1~3; the cooling functional agent includes one or more of jade powder, alumina, magnesium oxide, aluminum nitride, and boron nitride; the ball milling treatment is performed at a temperature of 80~120℃, a rotation speed of 300~800rpm, and a time of 6~13min.

[0010] Preferably, the surface-modifying compound includes one or more of aminosilane coupling agents, titanates, and aluminates; the lubricant includes one or more of N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, polyamide wax, and zinc stearate.

[0011] Preferably, the modified inorganic / organic compound antibacterial and deodorizing agent is prepared by mixing and heating the inorganic / organic compound antibacterial and deodorizing agent with a surface modifier to obtain the modified inorganic / organic compound antibacterial and deodorizing agent.

[0012] Preferably, the compound antibacterial and deodorizing agent includes two or more of nano-silver, silver oxide, zinc oxide, calcium phosphate, titanium dioxide, and polyhexamethylene biguanide; the surface modifier includes one or more of silane coupling agent, titanate, aluminate, zinc stearate, and polyamide wax; the mass ratio of the inorganic / organic compound antibacterial and deodorizing agent to the surface modifier is 100:1.0~2.5; the mixing and heating temperature is 60~100℃, the rotation speed is 300~800rpm, and the time is 6~15min.

[0013] The present invention also provides a method for preparing the above-mentioned anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch, comprising the following steps: mixing the above raw materials according to the weight parts and then extruding and granulating to obtain the anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0014] The present invention also provides the application of the above-described anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch in clothing textiles and medical textiles.

[0015] The beneficial effects of this invention are: This invention modifies titanium dioxide micropowder, cooling functional agents, and inorganic / organic compound antibacterial and deodorizing agents through surface functionalization and in-situ plasticization using high-speed shear ball milling. This forms a chemical bond bridge between the inorganic powder, coupling agent, and polyamide resin, creating a stable interfacial bond. This improves the interfacial compatibility between TiO2 micropowder, cooling functional agents, and the inorganic / organic compound antibacterial and deodorizing agents and the polyamide resin, effectively improving the dispersibility of the inorganic / organic compound antibacterial and deodorizing agents, TiO2 micropowder, and cooling functional agents in the polyamide resin. Consequently, it enhances the deodorizing, antibacterial, cooling, and UV-resistant properties of the polyamide cooling masterbatch, effectively solving the problems of stuffiness, poor UV resistance, and poor antibacterial and deodorizing performance in polyamide products.

[0016] The spun products of this invention, which incorporate anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch, are widely used in outdoor sportswear, medical textiles, and other fields. They greatly improve the deodorizing, antibacterial, cooling, and UV-resistant properties of the fiber products used in clothing and medical textiles, resulting in immeasurable economic and social benefits. Detailed Implementation

[0017] This invention provides an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch, comprising the following raw materials in parts by weight: 20-70 parts of polyamide resin, 10-35 parts of modified titanium dioxide micro powder, 10-35 parts of modified cooling functional agent, 1-5 parts of modified inorganic / organic compound antibacterial and deodorizing agent, 1-2 parts of plasticizer, 0.2-1 part of antioxidant, and 0.5-1 part of stabilizer.

[0018] In this invention, the polyamide resin is preferably 30-60 parts by weight, more preferably 35-55 parts, and even more preferably 40-50 parts by weight; the modified titanium dioxide micro powder is preferably 15-30 parts by weight, more preferably 17-27 parts, and even more preferably 22-25 parts by weight; the modified cooling functional agent is preferably 15-30 parts by weight, more preferably 17-27 parts, and even more preferably 22-25 parts by weight; and the modified inorganic / organic compound antibacterial and deodorizing agent is preferably 2-4 parts by weight, and even more preferably 3 parts by weight.

[0019] In this invention, the plasticizer is preferably 1.2 to 1.8 parts by weight, more preferably 1.5 parts by weight; the antioxidant is preferably 0.3 to 0.9 parts by weight, more preferably 0.5 to 0.8 parts by weight; and the stabilizer is preferably 0.6 to 1 part by weight, more preferably 0.8 to 1 part by weight.

[0020] In this invention, the plasticizer includes one or more of epoxidized soybean oil, acetylated tributyl citrate, trioctyl citrate, cashew phenol, and castor oil derivatives.

[0021] In this invention, the antioxidant includes one or more of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (1098), polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol) ester, and a composite antioxidant (HC6607).

[0022] In this invention, the stabilizer includes one or more of the following: high molecular weight hindered amine stabilizers (HALS), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, and halogen-free and copper-free long-lasting heat stabilizers (Themstab SH2621, Themstab SH150).

[0023] In this invention, the modified titanium dioxide micro powder is prepared by mixing titanium dioxide micro powder, surface modifier and lubricant and then ball milling to obtain modified titanium dioxide micro powder.

[0024] In this invention, the mass ratio of the titanium dioxide micro powder, surface modifier compound, and lubricant is 100:1~2.5:0.5~2, preferably 100:1.4~2.2:0.8~1.6, and more preferably 100:1.6~2.0:1.2~1.4; the particle size of the titanium dioxide micro powder is 400~6000 mesh, preferably 1000~5000 mesh, and more preferably 2500~4000 mesh; the ball milling temperature is 60~110℃, specifically 70℃, 80℃, 90℃, or 100℃, the rotation speed is 180~300 rpm, specifically 200 rpm, 240 rpm, 260 rpm, 250 rpm, 280 rpm, or 300 rpm, and the time is 6~15 min, preferably 8 min, 9 min, 10 min, 12 min, or 14 min.

[0025] In this invention, the modified cooling functional agent is prepared by mixing the cooling functional agent, the surface modifying compound agent and the lubricant and then ball milling them to obtain the modified cooling functional agent.

[0026] In this invention, the mass ratio of the cooling functional agent, the surface-modifying compound agent, and the lubricant is 100:2~5:1~3, preferably 100:3~4:1.5~2.5, and more preferably 100:4:2; the cooling functional agent includes one or more of jade powder, alumina, magnesium oxide, aluminum nitride, and boron nitride; the ball milling temperature is 80~120℃, specifically 90℃, 95℃, 100℃, 105℃, or 110℃, the rotation speed is 300~800rpm, specifically 400rpm, 500rpm, 600rpm, or 700rpm, and the time is 6~13min, specifically 7min, 8min, 9min, 10min, 11min, or 12min.

[0027] In this invention, the particle size of the cooling functional agent is preferably 400-6000 mesh, more preferably 1500-4500 mesh, and even more preferably 2500-4000 mesh.

[0028] In this invention, the surface-modifying compound agent includes one or more of aminosilane coupling agents, titanates, and aluminates; the lubricant includes one or more of N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, polyamide wax, and zinc stearate.

[0029] In this invention, the aminosilane coupling agent in the surface-modifying compound provides an active group that reacts with the terminal amino group of the polyamide, while the titanate / aluminate binds to the surface of the inorganic powder through chelation, forming a chemical bridge of "inorganic powder-coupling agent-polyamide resin", which fundamentally improves the interfacial compatibility.

[0030] In this invention, the aminosilane coupling agent comprises one or more of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (KH792), γ-aminopropyltriethoxysilane (KH550), and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (KH602); the titanate is bis(dioctylpyrophosphate)oxyacetic acid titanate; and the aluminate is aluminate stearate.

[0031] In this invention, the modified inorganic / organic compound antibacterial and deodorizing agent is prepared by mixing and heating an inorganic / organic compound antibacterial and deodorizing agent with a surface modifier to obtain the modified inorganic / organic compound antibacterial and deodorizing agent.

[0032] In this invention, the inorganic / organic compound antibacterial and deodorizing agent comprises two or more of nano-silver, silver oxide, zinc oxide, calcium phosphate, titanium dioxide, and polyhexamethylene biguanide, preferably nano-silver and polyhexamethylene biguanide, wherein the mass ratio of nano-silver and polyhexamethylene biguanide is preferably 1~3:1~3, specifically 1:3, 1:1, or 3:1; the surface modifier comprises one or more of silane coupling agent, titanate, aluminate, zinc stearate, and polyamide wax; the mass ratio of the inorganic / organic compound antibacterial and deodorizing agent and the surface modifier is specified. The ratio is 100:1.0~2.5, preferably 100:1.5~2.0; the temperature of the mixed heating is 60~100℃, specifically 70℃, 75℃, 80℃, 85℃, 90℃, 95℃; the rotation speed is 300~800rpm, specifically 400rpm, 500rpm, 600rpm, 700rpm; the time is 6~15min, specifically 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min.

[0033] The present invention also provides a method for preparing the above-mentioned anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch, comprising the following steps: mixing the above raw materials according to the weight parts and then extruding and granulating to obtain the anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0034] In this invention, the extrusion granulation temperature is 210~280℃, preferably 220~260℃, more preferably 230~250℃, and even more preferably 240℃; the current is 120~160A, preferably 125~155A, more preferably 130~150A, and even more preferably 140A; the pressure is ≤10MPa, preferably 4~9MPa, more preferably 5~8MPa, and even more preferably 6~7MPa.

[0035] The present invention also provides the application of the above-described anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch in clothing textiles and medical textiles.

[0036] In this invention, the clothing textiles include outdoor sportswear, mountaineering clothing, hiking clothing, and cycling clothing; the medical textiles are used to prepare protective clothing, surgical gowns, medical bed sheets, etc.

[0037] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0038] Example 1

[0039] 1 kg of TiO2 micro powder with a particle size of 2500~4000 mesh was dried at 105℃ for 2 hours for later use. The dried TiO2 micro powder was then added to a ball mill with bis(dioctylpyrophosphoryloxyacetate)titanate, aminosilane coupling agent KH602 and N,N'-ethylenebisstearamide in a mass ratio of 25:0.2:0.2:0.3. The mixture was ball-milled at 250 rpm and 100℃ for 10 min to obtain modified TiO2 micro powder.

[0040] 1 kg of jade powder with a particle size of 2500~4000 mesh was dried at 105℃ for 2 hours for later use. The dried jade powder, aminosilane coupling agent KH792, aluminate stearate and polyamide wax were added to a high-speed mixer at a mass ratio of 25:0.5:0.5:0.4. The mixture was stirred at 500 rpm and 105℃ for 10 minutes to obtain modified cooling functional agent jade powder micron powder.

[0041] 0.2 kg of an inorganic / organic compound antibacterial and deodorizing agent (composed of nano-silver and polyhexamethylene biguanide in a mass ratio of 3:1) and 0.003 kg of zinc stearate were added to a temperature-controlled high-speed mixer and reacted at a stirring rate of 500 rpm and a temperature of 85°C for 11 min to obtain a modified inorganic / organic compound antibacterial and deodorizing agent.

[0042] By weight, 50 parts of polyamide resin, 22 parts of modified TiO2 micro powder, 22 parts of modified cooling functional agent jade powder micro powder, 3 parts of modified inorganic / organic compound antibacterial and deodorizing agent, 1.5 parts of cashew phenol, 0.5 parts of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and 1.0 part of halogen-free and copper-free long-lasting heat stabilizer (Themstab SH2621) were added to a high-speed mixer and stirred at 600 rpm for 15 minutes. The uniformly mixed material was then added to a twin-screw extruder and extruded and granulated under the conditions of temperature 240℃, current 140A and pressure 7MPa to obtain UV-resistant antibacterial and deodorizing polyamide cooling masterbatch.

[0043] Example 2

[0044] The difference from Example 1 is that the mass ratio of nano-silver to polyhexamethylene biguanide is 1:1, and all other conditions are the same, to obtain an anti-UV, antibacterial, and deodorizing polyamide cooling masterbatch.

[0045] Example 3

[0046] The difference from Example 1 is that the mass ratio of nano-silver to polyhexamethylene biguanide is 1:3, and all other conditions are the same, to obtain an anti-UV, antibacterial, and deodorizing polyamide cooling masterbatch.

[0047] Example 4

[0048] The difference from Example 1 is that the polyamide resin is 45 parts and the modified TiO2 micro powder is 27 parts, while all other conditions are the same, to obtain an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch.

[0049] Example 5

[0050] The difference from Example 2 is that the polyamide resin is 45 parts and the modified TiO2 micro powder is 27 parts, while all other conditions are the same, to obtain an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch.

[0051] Example 6

[0052] The difference from Example 3 is that the polyamide resin is 45 parts and the modified TiO2 micro powder is 27 parts, while all other conditions are the same, to obtain an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch.

[0053] Example 7

[0054] The difference from Example 1 is that the polyamide resin is 55 parts and the modified TiO2 micro powder is 17 parts, while all other conditions are the same, to obtain an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch.

[0055] Example 8

[0056] The difference from Example 2 is that the polyamide resin is 55 parts and the modified TiO2 micro powder is 17 parts, while all other conditions are the same, to obtain an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch.

[0057] Example 9

[0058] The difference from Example 3 is that the polyamide resin is 55 parts and the modified TiO2 micro powder is 17 parts, while all other conditions are the same, to obtain an anti-ultraviolet, antibacterial, and deodorizing polyamide cooling masterbatch.

[0059] Example 10

[0060] The difference from Example 1 is that the modified TiO2 micro powder is 17 parts and the modified cooling functional agent jade powder micro powder is 27 parts, while all other conditions are the same, to obtain an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0061] Example 11

[0062] The difference from Example 2 is that the modified TiO2 micro powder is 17 parts and the modified cooling functional agent jade powder micro powder is 27 parts, while other conditions are the same, to obtain an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0063] Example 12

[0064] The difference from Example 3 is that the modified TiO2 micro powder is 17 parts and the modified cooling functional agent jade powder micro powder is 27 parts, while other conditions are the same, to obtain an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0065] Example 13

[0066] The difference from Example 1 is that the modified TiO2 micro powder is 27 parts and the modified cooling functional agent jade powder micro powder is 17 parts, while all other conditions are the same, to prepare an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0067] Example 14

[0068] The difference from Example 2 is that the modified TiO2 micro powder is 27 parts, the modified cooling functional agent jade powder micro powder is 17 parts, and all other conditions are the same, to obtain an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0069] Example 15

[0070] The difference from Example 3 is that the modified TiO2 micro powder is 27 parts, the modified cooling functional agent jade powder micro powder is 17 parts, and all other conditions are the same, to obtain an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0071] Example 16

[0072] The difference from Example 1 is that, in the preparation of the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatch, the amount of cashew phenol was 1.6 parts, the amount of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine was 0.6 parts, and the amount of halogen-free and copper-free long-lasting heat stabilizer (Themstab SH2621) was 0.8 parts, while all other conditions were the same, and the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatch was obtained.

[0073] Example 17

[0074] The only difference from Example 2 is that, in the preparation of the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatch, 1.6 parts of cashew phenol, 0.6 parts of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, and 0.8 parts of halogen-free and copper-free long-lasting heat stabilizer (Themstab SH2621) were used, while all other conditions were the same, and the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatch was obtained.

[0075] Example 18

[0076] The only difference from Example 3 is that, in the preparation of the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatch, 1.6 parts of cashew phenol, 0.6 parts of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, and 0.8 parts of halogen-free and copper-free long-lasting heat stabilizer (Themstab SH2621) were used, while all other conditions were the same, and the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatch was obtained.

[0077] Comparative Example 1

[0078] The only difference from Example 1 is that unmodified TiO2 micro powder was directly added, while all other conditions were the same, to obtain an anti-UV, antibacterial, and deodorizing polyamide cooling masterbatch.

[0079] Comparative Example 2

[0080] The only difference from Example 1 is that an unmodified cooling functional agent was directly added, while all other conditions were the same, to obtain an anti-UV, antibacterial, and deodorizing polyamide cooling masterbatch.

[0081] Comparative Example 3

[0082] The only difference from Example 1 is that an unmodified organic / inorganic compound antibacterial and deodorizing agent was directly added, while all other conditions were the same, to obtain an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch.

[0083] Comparative Example 4

[0084] The only difference from Example 1 is that the preparation process of the modified inorganic / organic compound antibacterial and deodorizing agent is different. Specifically, 0.2 kg of the inorganic / organic compound antibacterial and deodorizing agent (composed of nano-silver and polyhexamethylene biguanide in a mass ratio of 3:1) and 0.0015 kg of zinc stearate are added to a temperature-controlled high-speed mixer and reacted at a stirring rate of 500 rpm and a temperature of 85°C for 11 min to obtain the modified inorganic / organic compound antibacterial and deodorizing agent. All other conditions are the same, and the UV-resistant antibacterial and deodorizing polyamide cooling masterbatch is obtained.

[0085] Comparative Example 5

[0086] The only difference from Example 1 is that the preparation process of the modified inorganic / organic compound antibacterial and deodorizing agent is different. Specifically, 0.2 kg of the inorganic / organic compound antibacterial and deodorizing agent (composed of nano-silver and polyhexamethylene biguanide in a mass ratio of 3:1) and 0.0045 kg of zinc stearate are added to a temperature-controlled high-speed mixer and reacted at a stirring rate of 500 rpm and a temperature of 85°C for 11 min to obtain the modified inorganic / organic compound antibacterial and deodorizing agent. All other conditions are the same, and an anti-ultraviolet antibacterial and deodorizing polyamide cooling masterbatch is obtained.

[0087] Comparative Example 6

[0088] The only difference from Example 1 is the preparation process of the modified TiO2 micro powder. Specifically, 1 kg of TiO2 micro powder with a particle size of 2500~4000 mesh is dried at 105℃ for 2 hours for later use. The dried TiO2 micro powder is added to a ball mill with bis(dioctylpyrophosphoryloxy)oxyacetate titanate, aminosilane coupling agent KH602 and N,N'-ethylenebisstearamide in a mass ratio of 25:0.15:0.15:0.2. The mixture is ball-milled at 250 rpm and 100℃ for 10 min to obtain modified TiO2 micro powder. All other conditions are the same to obtain an anti-ultraviolet, antibacterial and deodorizing polyamide cooling masterbatch.

[0089] Comparative Example 7

[0090] The only difference from Example 1 is the preparation process of the modified TiO2 micro powder. Specifically, 1 kg of TiO2 micro powder with a particle size of 2500~4000 mesh is dried at 105℃ for 2 hours for later use. The dried TiO2 micro powder is added to a ball mill with bis(dioctylpyrophosphoryloxyacetate)titanate, aminosilane coupling agent KH602 and N,N'-ethylenebisstearamide in a mass ratio of 25:0.25:0.25:0.4. The mixture is ball-milled at 250 rpm and 100℃ for 10 min to obtain modified TiO2 micro powder. All other conditions are the same to obtain an anti-UV antibacterial and deodorizing polyamide cooling masterbatch.

[0091] Take 40 parts each of the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatches prepared in Examples 1-18 and Comparative Examples 1-7, and mix them evenly with 60 parts of polyamide. Then, process the mixture using a twin-screw extruder, a melt spinning machine, and a spinning drawing device to prepare a 100 g / m² masterbatch. 2 The single-layer plain weave fabric was tested for performance. Antibacterial properties, deodorizing properties, ultraviolet protection factor (UPF), tensile strength, and cooling properties were tested according to national standards GB / T20944.3-2008, GB / T33610.1-2017, GB / T18830-2009, GB / T3923-1997, and GB / T 35263-2017. The test results are shown in Table 1 below.

[0092] Table 1 Performance Test Results

[0093] As shown in Table 1, the test results in Comparative Examples 1-3 indicate that the unmodified TiO2 micropowder, unmodified jade powder micropowder, and unmodified inorganic / organic compound antibacterial and deodorizing agents did not have ideal effects on improving the UV-resistant, antibacterial, deodorizing, and cooling properties of polyamide fiber fabrics. However, adding modified TiO2 micropowder, modified jade powder micropowder, and modified inorganic / organic compound antibacterial and deodorizing agents (nano silver and polyhexamethylene biguanide) to polyamide not only improved the UV-resistant and antibacterial properties of the polyamide fiber fabric but also effectively enhanced its deodorizing and cooling effects, while significantly reducing the cost of the polyamide fiber fabric. This is because the modified TiO2 micro powder, modified jade powder micro powder, and modified inorganic / organic compound antibacterial and deodorizing agent (nano silver and polyhexamethylene biguanide) can be uniformly dispersed in polyamide fibers, which greatly improves the dispersibility of TiO2 micro powder, jade powder micro powder, and inorganic / organic compound antibacterial and deodorizing agent (nano silver and polyhexamethylene biguanide) in polyamide fibers and forms a stable interfacial bonding force.

[0094] In addition, the UV-resistant, antibacterial, and deodorizing polyamide cooling masterbatches prepared in Examples 1-18 and Comparative Examples 4-5 were used to make polyamide fiber fabrics. Performance tests were conducted on the fabrics for comparison. It can be seen that the amount of modified TiO2 micropowder added affects the UV resistance of the polyamide fiber fabric, and different concentrations of surface modifiers also affect the antibacterial and deodorizing effects of the modified inorganic / organic compound antibacterial and deodorizing agent on the polyamide fiber fabric. Specifically, when the mass ratio of TiO2 micropowder to surface modifier (bis(dioctylpyrophosphate)oxyacetate titanate, aminosilane coupling agent KH602, and lubricant in a 1:1 mass ratio) was 100:1.6:1.2, the resulting modified TiO2 micropowder showed the best effect in improving the UV resistance of the polyamide fiber fabric; when the mass ratio of the inorganic / organic compound antibacterial and deodorizing agent to the surface modifier was 100:1.5, the resulting modified inorganic / organic compound antibacterial and deodorizing agent showed the best effect in improving the antibacterial and deodorizing effects of the polyamide fiber fabric.

[0095] This invention combines modified inorganic / organic compound antibacterial and deodorizing agents, jade powder micron powder, and TiO2 micron powder with polyamide resin, effectively improving the dispersibility of the inorganic / organic compound antibacterial and deodorizing agents, jade powder micron powder, and TiO2 micron powder in polyamide resin. This enhances the UV resistance, antibacterial and deodorizing properties, and cooling sensation of polyamide fiber fabrics, making it widely applicable in outdoor sportswear and medical textiles such as mountaineering clothing, hiking clothing, cycling clothing, protective clothing, surgical gowns, and medical bed sheets.

[0096] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch, characterized in that, The raw materials include the following parts by weight: 20-70 parts polyamide resin, 10-35 parts modified titanium dioxide micro powder, 10-35 parts modified cooling functional agent, 1-5 parts modified inorganic / organic compound antibacterial and deodorizing agent, 1-2 parts plasticizer, 0.2-1 part antioxidant, and 0.5-1 part stabilizer.

2. The UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to claim 1, characterized in that, The modified titanium dioxide micro powder is prepared by mixing titanium dioxide micro powder, surface modifier and lubricant and then ball milling to obtain modified titanium dioxide micro powder.

3. The UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to claim 1 or 2, characterized in that, The mass ratio of the titanium dioxide micro powder, surface modifier compound and lubricant is 100:1~2.5:0.5~2; the particle size of the titanium dioxide micro powder is 400~6000 mesh; the ball milling treatment temperature is 60~110℃, the rotation speed is 180~300rpm, and the time is 6~15min.

4. The UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to claim 3, characterized in that, The modified cooling functional agent is prepared by mixing the cooling functional agent, surface modifier compound and lubricant and then ball milling them to obtain the modified cooling functional agent.

5. The UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to claim 4, characterized in that, The mass ratio of the cooling functional agent, surface modifier compound and lubricant is 100:2~5:1~3; the cooling functional agent includes one or more of jade powder, alumina, magnesium oxide, aluminum nitride and boron nitride; the ball milling treatment temperature is 80~120℃, the rotation speed is 300~800rpm, and the time is 6~13min.

6. The UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to claim 2 or 4, characterized in that, The surface-modifying compound includes one or more of aminosilane coupling agents, titanates, and aluminates; the lubricant includes one or more of N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, polyamide wax, and zinc stearate.

7. The UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to claim 1, 2, 4, or 5, characterized in that, The modified inorganic / organic compound antibacterial and deodorizing agent is prepared by mixing and heating the inorganic / organic compound antibacterial and deodorizing agent with a surface modifier to obtain the modified inorganic / organic compound antibacterial and deodorizing agent.

8. The UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to claim 7, characterized in that, The inorganic / organic compound antibacterial and deodorizing agent includes two or more of nano-silver, silver oxide, zinc oxide, calcium phosphate, titanium dioxide, and polyhexamethylene biguanide; the surface modifier includes one or more of silane coupling agent, titanate, aluminate, zinc stearate, and polyamide wax; the mass ratio of the inorganic / organic compound antibacterial and deodorizing agent to the surface modifier is 100:1.0~2.5; the mixing and heating temperature is 60~100℃, the rotation speed is 300~800rpm, and the time is 6~15min.

9. The method for preparing the UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to any one of claims 1 to 8, characterized in that, The process includes the following steps: mixing the above raw materials according to the weight parts and then extruding and granulating them to obtain UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch.

10. The application of the UV-resistant, antibacterial, and odor-resistant polyamide cooling masterbatch according to any one of claims 1 to 8 in clothing textiles and medical textiles.

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