Antibacterial polylactic acid natural black dye color master batch, preparation method and application thereof
By extracting and boric acid-hybridizing natural black dye from waste animal hair, and combining it with dispersants and antibacterial agents, antibacterial polylactic acid masterbatch was prepared. This solved the problems of decreased mechanical properties and poor color fastness of polylactic acid black masterbatch, and enabled the preparation of environmentally friendly, antibacterial, and UV-resistant fibers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHANGZHOU UNIV
- Filing Date
- 2023-09-26
- Publication Date
- 2026-07-21
Smart Images
Figure BDA0004469675640000021 
Figure BDA0004469675640000101 
Figure BDA0004469675640000102
Abstract
Description
Technical Field
[0001] This invention belongs to the field of textile technology, specifically relating to an antibacterial polylactic acid natural black dye masterbatch, its preparation method, and its application. Background Technology
[0002] Color masterbatch is an aggregate obtained by uniformly loading an extraordinary amount of dye into a resin. It is also called pigment concentrate and consists of three parts: dye, carrier and additives. Color masterbatch has the advantages of uniform color dispersion, excellent quality, no dye dust and excellent operating environment, which is conducive to civilized production.
[0003] Polylactic acid (PLA) is a novel bio-based and renewable biodegradable material that can rapidly cycle in nature. Masterbatches prepared from PLA can be degraded by microorganisms and ultraviolet light during use, exhibiting outstanding environmental friendliness.
[0004] Chinese patent CN102040814A discloses a black masterbatch for polylactic acid-based biodegradable plastics. The preparation method involves two heat treatments of the masterbatch, which reduces the mechanical properties of the masterbatch product. Furthermore, the particle size of the pigment carbon black is not specified; it only states that the black masterbatch is used in plastics, and it is unclear whether it has spinnability. Chinese patent CN113637189A discloses a method for preparing polylactic acid plant dye masterbatch. The dispersant used is sodium lignosulfonate, which is a brownish-red powder and has a certain influence on the color of the masterbatch product. Chinese patent CN115418741A discloses a method for preparing and applying antibacterial polyester plant dye masterbatch. Except for plant indigo, which is a disperse dye, the dyes used are all water-soluble dyes. Masterbatch prepared using these dyes exhibits poor color fastness after washing.
[0005] Natural animal dyes contain various beneficial components, such as proteins, amino acids, and steroids, which have health benefits for humans. Using natural animal dyes results in vibrant colors and good colorfastness, while avoiding the environmental and health hazards associated with chemical dyes. Currently, commonly used black dyes are all chemical dyes or carbon black. A few studies report the extraction of melanin from human hair for hair dyeing, but there are no research reports on the extraction of natural black dyes from animal hair for the preparation of polylactic acid masterbatches. Summary of the Invention
[0006] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.
[0007] In view of the problems existing in the above and / or prior art, the present invention is proposed.
[0008] One objective of this invention is to provide an antibacterial polylactic acid natural black dye masterbatch, comprising the following components by weight percentage:
[0009]
[0010] The black dye is extracted from waste animal hair and then subjected to boric acid hybridization treatment.
[0011] This invention uses PLA resin as a carrier. After being disposed of, PLA resin can be completely degraded by microorganisms in nature and eventually converted into CO2 and water, without damaging the environment and in line with the requirements of green and sustainable development.
[0012] In a preferred embodiment of the present invention, the method for preparing the black dye is as follows:
[0013] (1) Wash and dry the waste animal hair fibers, add them to a 1-butyl-3-methylimidazolium acetate (BMImAc) solution (98% by mass) at a mass ratio of 1:10, and stir at 120°C for 2 hours; filter and centrifuge the stirred solution, and centrifuge the filter residue with ethanol repeatedly until the supernatant is colorless to obtain black dye; finally, concentrate and dry the black dye, and grind it to a particle size of less than 1 μm;
[0014] (2) After the black dye from step (1) is mixed evenly with boric acid, it is placed in a polytetrafluoroethylene reaction vessel and reacted at 170°C for 36 hours. The mass ratio of the unhybridized black dye to boric acid is 3:2.
[0015] The type and amount of dispersant are important influencing factors in the preparation process of color masterbatch. In a preferred embodiment of this invention, the dispersant is one or more of polyethylene wax (AC-6A) and ethylene-acrylic acid copolymer (AC-540A); preferably, the dispersant is AC-540A. More preferably, the amount of dispersant AC-540A is 2%.
[0016] In a preferred embodiment of the present invention, the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a ratio of 2:1.
[0017] As a preferred embodiment of the present invention, the antibacterial agent includes one or more of a titanium dioxide silver-loaded composite antibacterial agent or a zirconium phosphate silver-loaded antibacterial agent; preferably, a titanium dioxide silver-loaded composite antibacterial agent.
[0018] The second objective of this invention is to provide a method for preparing the above-mentioned antibacterial polylactic acid natural black dye masterbatch: PLA resin, dispersant, antioxidant, silver-loaded antibacterial agent and black dye are added to a high-speed mixer in proportion and mixed together. The mixture is then melt-extruded through a twin-screw extruder, water-cooled and air-dried, and then sheared into granules to obtain the antibacterial polylactic acid natural black dye masterbatch.
[0019] As a preferred embodiment of the present invention, the temperatures of each zone of the twin-screw extruder are respectively set as follows: Zone 1 155℃~165℃, Zone 2 160℃~170℃, Zone 3 170℃~180℃, Zone 4 170℃~180℃, Zone 5 175℃~185℃, Zone 6 170℃~180℃, Zone 7 165℃~175℃, Zone 8 165℃~175℃, Zone 9 160℃~170℃, and the die head 160℃~170℃.
[0020] A third objective of this invention is to provide the application of the above-mentioned antibacterial polylactic acid natural black dye masterbatch; more specifically, to use the masterbatch in the preparation of fibers.
[0021] Fiber preparation method: Masterbatch and polylactic acid resin are added to a melt spinning machine, and the spun fibers are air-cooled and cured. These fibers are then bundled and drawn to obtain DTY fibers with a specification of 93D / 36F. The amount of antibacterial polylactic acid natural black dye masterbatch added is 3–7 wt%.
[0022] The beneficial effects of this invention are:
[0023] (1) The dye selected in this invention is black dye extracted from waste wool, which can make better use of waste wool. Using this black dye to prepare fibers can avoid the harm caused by chemical dyes to the environment and human body, and has certain advantages such as antibacterial properties, better color fastness, and resistance to ultraviolet rays.
[0024] (2) This invention improves the stability of black dye by hybridizing natural dyes and combining black dyes and inorganic boric acid at the nanoscale through boric acid melting method, so that it can stably pass through granulation and spinning processes.
[0025] (3) In the process of preparing black masterbatch, the present invention adds an antibacterial agent so that it works synergistically with black dye to exert antibacterial effect. Attached image description:
[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:
[0027] Figure 1 Thermogravimetric analysis (TGA) diagrams of hybrid dyes prepared from black dye and boric acid at different weight ratios are shown.
[0028] Figure 2 This is a photograph of the black polylactic acid masterbatch prepared in Example 2 of the present invention.
[0029] Figure 3 This is a photograph of the fibers in Embodiment 3 of the present invention. Detailed Implementation
[0030] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.
[0031] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.
[0032] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.
[0033] Unless otherwise specified, all raw materials used in this invention are commercially available.
[0034] In this invention, the antibacterial properties of fibers are quantitatively tested in accordance with GB / T20944.2-2007 Evaluation of antibacterial properties of textiles - Part 3: Oscillation method.
[0035] The tensile strength and elongation at break of the fiber were tested in accordance with GB / T14344-2008 Test Method for Tensile Properties of Chemical Fiber Filaments.
[0036] Example 1
[0037] The specific method for preparing black dye is as follows:
[0038] (1) Wash the black wool fibers clean, take 2g of black wool and immerse it in 20g of 1-butyl-3-methylimidazolium acetate (BMIMAc) solution (purity 98%), stir at 120℃ for 2 hours; filter and centrifuge the stirred solution, and centrifuge the filter residue with ethanol repeatedly until the supernatant is colorless to obtain black dye; finally, dry the black dye and grind it to a particle size of less than 1μm to obtain unhybridized black dye.
[0039] (2) The black dye from step (1) and boric acid are mixed evenly at a mass ratio of 3:2 and then placed in a polytetrafluoroethylene reaction vessel and melted at 170°C for 36 hours to obtain the hybrid black dye-D3P2.
[0040] Repeat step (1) to obtain sufficient unhybridized black dye. Mix the unhybridized black dye with boric acid at mass ratios of 1:1, 1:2, 2:1, and 2:3 respectively, and then place them in a polytetrafluoroethylene reaction vessel for melting reaction at 170°C to obtain hybridized black dyes -D1P1, D1P2, D2P1, and D2P3 respectively.
[0041] Figure 1 These are thermogravimetric analysis (TGA) graphs of hybrid dyes prepared from black dye and boric acid at different weight ratios. Figure 1 It can be seen that the heat resistance is optimal when the ratio of dye to boric acid is 3:2.
[0042] Example 2
[0043] (1) Wash the black wool fibers clean, immerse the black wool in a 1-butyl-3-methylimidazolium acetate (BMIMAc) solution (purity 98%) (solid-liquid mass ratio 1:10), and stir at 120℃ for 2 hours; filter and centrifuge the stirred solution, and centrifuge the filter residue repeatedly with ethanol until the supernatant is colorless to obtain the black dye; finally, dry the black dye and grind it to a particle size of less than 1μm to obtain the unhybridized black dye; mix the unhybridized black dye with boric acid at a mass ratio of 3:2 and place it in a polytetrafluoroethylene reaction vessel to melt and react at 170℃ for 36 hours to obtain the hybridized black dye;
[0044] (2) 77.7 wt% PLA resin, 2 wt% AC-540 dispersant, 0.3 wt% antioxidant, 10% titanium dioxide silver-loaded composite antibacterial agent and 10 wt% hybrid black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0045] (3) Mix the color masterbatch and PLA resin at a mass ratio of 3:97, add them to a melt spinning machine, and air-cool and solidify the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0046] Example 3
[0047] (1) The preparation of the hybrid black dye is the same as in Example 2;
[0048] (2) 77.7 wt% PLA resin, 2 wt% AC-540 dispersant, 0.3 wt% antioxidant, 10% titanium dioxide silver-loaded composite antibacterial agent and 10 wt% hybrid black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0049] (3) Mix the color masterbatch and PLA resin at a mass ratio of 5:95, add them to the melt spinning machine, and air-cool and solidify the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0050] Example 4
[0051] (1) The preparation of the hybrid black dye is the same as in Example 2;
[0052] (2) 77.7 wt% PLA resin, 2 wt% AC-540 dispersant, 0.3 wt% antioxidant, 10% titanium dioxide silver-loaded composite antibacterial agent and 10 wt% hybrid black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0053] (3) Mix the color masterbatch and PLA resin at a mass ratio of 7:93, add them to a melt spinning machine, and air-cool and solidify the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0054] Example 5
[0055] (1) The preparation of the hybrid black dye is the same as in Example 2;
[0056] (2) 77.7 wt% PLA resin, 2 wt% AC-540 dispersant, 0.3 wt% antioxidant, 10% zirconium phosphate silver-loaded antibacterial agent and 10 wt% hybrid black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0057] (3) Mix the color masterbatch and PLA resin at a mass ratio of 5:95, add them to the melt spinning machine, and air-cool and solidify the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0058] Example 6
[0059] (1) The preparation of the hybrid black dye is the same as in Example 2;
[0060] (2) 77.7 wt% PLA resin, 2 wt% AC-6A dispersant, 0.3 wt% antioxidant, 10% titanium dioxide silver-loaded composite antibacterial agent and 10 wt% pre-hybridized black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0061] (3) Mix the color masterbatch and PLA resin at a mass ratio of 5:95, add them to the melt spinning machine, and air-cool and solidify the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0062] Example 7
[0063] (1) The preparation of the hybrid black dye is the same as in Example 2;
[0064] (2) 78.7 wt% PLA resin, 1 wt% AC-540 dispersant, 0.3 wt% antioxidant, 10% titanium dioxide silver-loaded composite antibacterial agent and 10 wt% hybrid black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0065] (3) Mix the color masterbatch and PLA resin at a mass ratio of 5:95, add them to the melt spinning machine, and air-cool and solidify the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0066] Example 8
[0067] (1) The preparation of the hybrid black dye is the same as in Example 2;
[0068] (2) 76.7 wt% PLA resin, 3 wt% AC-540 dispersant, 0.3 wt% antioxidant, 10% titanium dioxide silver-loaded composite antibacterial agent and 10 wt% hybrid black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0069] (3) Mix the color masterbatch and PLA resin at a mass ratio of 5:95, add them to the melt spinning machine, and air-cool and solidify the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0070] Comparative Example 1
[0071] (1) Preparation of unhybridized black dye is the same as in Example 2: Wash the black wool fibers clean, immerse the black wool in a 1-butyl-3-methylimidazolium acetate (BMIMAc) solution (purity 98%) (solid-liquid mass ratio 1:10), and stir at 120°C for 2 hours; filter and centrifuge the stirred solution, and repeatedly centrifuge the filter residue with ethanol until the supernatant is colorless to obtain the black dye; finally, dry the black dye and grind it to a particle size of less than 1 μm to obtain the unhybridized black dye;
[0072] (2) 77.7 wt% PLA resin, 2 wt% AC-540 dispersant, 0.3 wt% antioxidant, 10% titanium dioxide silver-loaded composite antibacterial agent and 10 wt% unhybridized black dye were placed in a high-speed mixer and stirred at 1500 rpm for 10 min. After mixing evenly, the mixture was fed into a twin-screw extruder. The temperatures of each zone were set as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 175℃, Zone 7 170℃, Zone 8 170℃, Zone 9 165℃, and the die head 165℃. After melt extrusion, the mixture was water-cooled, air-dried and cut into granules to obtain antibacterial polylactic acid natural dye masterbatch.
[0073] (3) Mix the color masterbatch and PLA resin at a mass ratio of 5:95, add them to the melt spinning machine, and air-cool the sprayed fiber filaments. Bundle and stretch them to obtain DTY fiber with specifications of 93D / 36F.
[0074] Table 1. Factors affecting black masterbatch spinning
[0075]
[0076] As shown in Table 1, the type and amount of dispersant directly affect the uniformity of dye dispersion; the masterbatch prepared using 2-3 wt% dispersant AC-540 has better spinnability.
[0077] Table 2 PLA fiber performance test results
[0078]
[0079] As shown in Table 2, the use of boric acid hybrid dyes and AC-540A dispersant is more suitable for spinning natural black dye PLA masterbatch into yarn, giving it excellent mechanical properties.
[0080] Table 3 Antibacterial Performance Table
[0081]
[0082] As shown in Table 3, the titanium dioxide-loaded silver composite antibacterial agent has the best antibacterial effect compared with the zirconium phosphate-loaded silver antibacterial agent, and it also exhibits a synergistic antibacterial effect with the dye hybridized with boric acid.
[0083] Table 4. Mass change of PLA fiber in soil suspension over 1 month
[0084]
[0085] As shown in Table 4, the masterbatches prepared in the examples all have excellent biodegradability.
Claims
1. An antibacterial polylactic acid natural black dye masterbatch, characterized in that, Includes the following components by weight percentage: Polylactic acid resin 76.7~80% Dispersant 2% Antioxidant 0.1~0.5% Antibacterial agent 5-15% 10% black dye; The dispersant is an ethylene-acrylic acid copolymer; The black dye is extracted from waste black wool and obtained through boric acid hybridization treatment. The preparation method is as follows: (1) Add waste black wool fibers to a 98% (w / w) 1-butyl-3-methylimidazolium acetic acid solution and stir at 120°C for 2 hours; filter and centrifuge the stirred solution, and centrifuge the filter residue repeatedly with ethanol until the supernatant is colorless. Concentrate the filtrate, dry it, and grind it to a particle size of less than 1 μm to obtain the unhybridized black dye; wherein, the mass ratio of waste black wool fibers to 1-butyl-3-methylimidazolium acetic acid solution is 1:10; (2) After mixing the unhybridized black dye from step (1) with boric acid, react at 170°C for 36 hours to obtain the hybridized black dye. The mass ratio of the unhybridized black dye to boric acid is 3:
2.
2. The antibacterial polylactic acid natural black dye masterbatch according to claim 1, characterized in that: The antioxidant includes one or more of antioxidant 1010 and antioxidant 168.
3. The antibacterial polylactic acid natural black dye masterbatch according to claim 1, characterized in that: The antibacterial agent includes one or more of the following: titanium dioxide silver-loaded composite antibacterial agent and zirconium phosphate silver-loaded antibacterial agent.
4. A method for preparing antibacterial polylactic acid natural black dye masterbatch as described in any one of claims 1-3, characterized in that: Polylactic acid resin, dispersant, antioxidant, antibacterial agent and black dye are added to a high-speed mixer in proportion and mixed together. The mixture is then melt-extruded through a twin-screw extruder, water-cooled and air-dried, and then sheared into granules to obtain antibacterial polylactic acid natural dye masterbatch.
5. The method for preparing antibacterial polylactic acid natural black dye masterbatch according to claim 4, characterized in that: The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 155℃~165℃, Zone 2 160℃~170℃, Zone 3 170℃~180℃, Zone 4 170℃~180℃, Zone 5 175℃~185℃, Zone 6 170℃~180℃, Zone 7 165℃~175℃, Zone 8 165℃~175℃, Zone 9 160℃~170℃, and the die head 160℃~170℃.
6. An application of the antibacterial polylactic acid natural black dye masterbatch as described in claim 1, characterized in that: The preparation of fibers using the antibacterial polylactic acid natural black dye masterbatch includes adding the masterbatch and polylactic acid resin into a melt spinning machine, air-cooling and curing the sprayed fiber filaments, and then bundling and stretching them to obtain fibers.
7. The application of the antibacterial polylactic acid natural black dye masterbatch according to claim 6, characterized in that: The amount of the antibacterial polylactic acid natural black dye masterbatch added is 3~7wt%.