CN117624656A - Preparation method and application of antibacterial and antiviral color master batch - Google Patents
Preparation method and application of antibacterial and antiviral color master batch Download PDFInfo
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- CN117624656A CN117624656A CN202210955032.1A CN202210955032A CN117624656A CN 117624656 A CN117624656 A CN 117624656A CN 202210955032 A CN202210955032 A CN 202210955032A CN 117624656 A CN117624656 A CN 117624656A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 100
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 99
- 239000004595 color masterbatch Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 31
- 239000003086 colorant Substances 0.000 claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 9
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000049 pigment Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 14
- 229910001431 copper ion Inorganic materials 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003242 anti bacterial agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 238000007142 ring opening reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 8
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002074 melt spinning Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010345 tape casting Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 claims description 5
- 241000588724 Escherichia coli Species 0.000 claims description 4
- 241000191967 Staphylococcus aureus Species 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 241000222122 Candida albicans Species 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 claims description 2
- 229940095731 candida albicans Drugs 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 208000037797 influenza A Diseases 0.000 claims 2
- 239000004599 antimicrobial Substances 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 241000700605 Viruses Species 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 230000036541 health Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 206010069767 H1N1 influenza Diseases 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000712431 Influenza A virus Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- -1 oxygen free radical Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 201000010740 swine influenza Diseases 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 210000004958 brain cell Anatomy 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
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- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Artificial Filaments (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a preparation method and application of an antibacterial and antiviral color master batch, in particular to a preparation method and application of an antibacterial and antiviral color master batch realized by synergism of nano copper and a colorant. Firstly generating nano elemental copper on the surface of a colorant by an in-situ reduction method, then modifying the colorant carboxylic acid loaded with the nano elemental copper, and introducing polyamide 6 by in-situ polymerization to obtain the antibacterial and antiviral masterbatch. The antibacterial and antiviral color master batch can be melt-spun with polyamide resin according to a certain proportion to obtain antibacterial and antiviral colored fibers. The antibacterial and antiviral color master batch prepared by the invention does not pollute the environment in the use process, and the antibacterial and antiviral colored fiber prepared by the antibacterial and antiviral color master batch has the characteristics of high efficiency in resisting bacteria and viruses and lasting color fixation.
Description
Technical Field
The invention belongs to the field of preparation of polymer functional master batches, relates to a preparation method and application of an antibacterial and antiviral color master batch, and in particular relates to a preparation method and application of an antibacterial and antiviral color master batch realized by nano copper and a colorant.
Background
The health risk caused by pathogenic bacteria brings a next serious test to people who cannot prevent sudden diseases, and arouses the public's health and safety consciousness to the living environment. The harm of the breeding and cross infection of pathogenic bacteria to human health is more difficult to measure. The textile becomes an important transmission medium of pathogenic bacteria, the antibacterial function of the textile is paid more attention, and the development of antibacterial and antiviral functional fibers has important significance.
In recent years, the use of silver-containing antibacterial agents to melt-spin antibacterial fibers in a masterbatch blending manner has been greatly progressed in China, but silver-based antibacterial agents are expensive, are easily degraded by heat, and can damage stem cells, brain cells, liver cells and the like. The use of antimicrobial nanosilver on apparel and other textiles has been limited to publicity abroad. While colorants are generally poorly dispersible in polyamides, the agglomerates formed can affect the spinnability of the post fiber. At present, master batches with antibacterial and antiviral functions and coloring functions are rarely studied.
Disclosure of Invention
The invention aims to provide a preparation method and application of an antibacterial and antiviral color master batch, in particular to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects and stock solution coloring effects through synergistic effect of nano copper and a coloring agent. By loading the nano Cu powder on the uniformly dispersed colorant, the dispersibility of the nano Cu can be improved, the antibacterial and antiviral effects can be improved, and meanwhile, the Cu is loaded on the colorant, so that the nano Cu powder and the colorant can be uniformly dispersed. The nano elemental copper plays an antibacterial and antiviral role by releasing Reactive Oxygen Species (ROS), and does not pollute the environment during antibacterial and antiviral processes. The nano simple substance copper obtained by the method has the size of 2-10nm, the nano simple substance copper with the size has higher catalytic reaction antibacterial and antiviral activity, the nano copper can activate oxygen in water and air to generate ROS (hydroxyl free radicals, superoxide free radicals and hydrogen peroxide), the ROS has strong oxidizing property, the structure and the function of cells can be directly or indirectly damaged, and cell membrane rupture is caused, so that bacteria die. Further, the carboxylic acid modified Cu@ colorant has better compatibility with the polyamide 6, and the carboxylic acid modified Cu@ colorant can be uniformly and stably dispersed in the polyamide 6 in the in-situ polymerization of the polyamide 6 monomer, so that the agglomeration problem of the nano-scale Cu@ colorant is avoided. According to the nano copper disclosed by the invention, the exposed surface defects are more, the carboxyl can be better complexed with the nano copper to maintain the nano copper of the Cu@ colorant in a reduced state all the time, the active oxygen free radical is continuously released to play a role in resisting bacteria and viruses, and the complexed carboxyl can promote the nano copper to generate the active oxygen free radical, so that the antibacterial and antiviral effects are further improved. Therefore, the master batch obtained by the invention has high-efficiency and durable antibacterial and antiviral effects, and can be spun into fibers by different matrixes, thereby meeting the higher requirements of different fields on the antibacterial and antiviral properties of the fibers. The prepared Cu@ colorant is modified by using aliphatic dibasic acid, and carboxyl can be combined with the exposed defect on the surface of nano Cu, so that the stability of the nano Cu structure is facilitated, the antibacterial and antiviral aging is prolonged, the generation of peroxy free radicals is facilitated, and the antibacterial and antiviral effects are enhanced.
According to a first aspect of the present invention, there is provided a method for preparing an antibacterial and antiviral masterbatch, comprising the steps of:
(1) According to the mass parts, 2-5 parts of colorant is dispersed in 50 parts of deionized water by ultrasonic to prepare colorant dispersion liquid, and 0.2-1.0 part of copper salt is dissolved in 50 parts of deionized water to prepare copper ion aqueous solution. The colorant dispersion liquid and the copper ion aqueous solution are mixed in a flask, 50 parts of the reducer aqueous solution is added into the flask dropwise while stirring under heating, condensing and refluxing, and the mixture is stirred for 3 to 24 hours at the temperature of 60 to 90 ℃ to obtain a dark solution. And washing and centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the colorant (Cu@ colorant) with nano elemental copper loaded on the surface. The size of the generated nano elemental copper is 2-10nm;
(2) 3 to 5 parts of aliphatic dibasic acid, 5 to 10 parts of deionized water and 100 to 200 parts of Cu@ coloring agent are added into 100 parts of liquid caprolactam at the temperature of 80 to 90 ℃ and stirred for 0.5 to 5 hours to obtain coloring agent caprolactam slurry of carboxylic acid modified surface-generated nano elemental copper.
(3) Adding 30-40 parts of carboxylic acid modified colorant caprolactam slurry with nano elemental copper generated on the surface, 100 parts of caprolactam and 3-5 parts of deionized water into a polymerization reaction kettle, carrying out ring-opening prepolymerization, carrying out polycondensation, and finally carrying out tape casting, granulating and extraction to obtain the antibacterial and antiviral polyamide 6 color master batch.
In the step (1), the colorant is one or more of carbon black, phthalocyanine pigment, quinacridone pigment, triarylmethane pigment, benzimidazolone pigment, azo pigment, dioxazine, isoindolinone, anthraquinone and perylene;
in the step (1), the condition of ultrasonic dispersion of the colorant means that the time is 20-60 min and the ultrasonic frequency is 30-60 kHz;
in the preparation method of the antibacterial and antiviral color master batch, in the step (1), copper salt refers to one of copper chloride, copper sulfate and copper nitrate;
in the step (1), the aqueous solution of the reducing agent is one of 0.1-0.5 mol/L of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride;
in the step (2), the aliphatic dibasic acid refers to one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid;
in the step (3), the reaction condition of ring-opening pre-polymerization is that the temperature is 200-260 ℃, the pressure is 0.1-1.0 MPa, and the time is 2-5 h;
in the step (3), the reaction condition of polycondensation is that the temperature is 240-260 ℃, the pressure is-0.02-0.10 MPa, and the time is 2-5 h.
The second aspect of the invention provides application of the nano copper antibacterial and antiviral color master batch, which adopts the following technical scheme:
and drying the prepared antibacterial and antiviral color master batch and polyamide resin for a period of time at 90-120 ℃, then blending the antibacterial and antiviral color master batch and the polyamide resin according to a certain proportion, and adding the mixture into a melt spinning machine for spinning after the mixture is uniformly mixed to obtain the antibacterial and antiviral colored fiber.
The application of the antibacterial and antiviral color master batch comprises that the polyamide resin is one of polyamide 6 and polyamide 66;
the antibacterial and antiviral masterbatch is applied, wherein the ratio of the antibacterial and antiviral masterbatch to the polyamide resin is 10-20% of the antibacterial and antiviral masterbatch;
according to the application of the antibacterial and antiviral masterbatch, the breaking strength of spun fibers is 2.8-4.0 cN/dtex, the breaking elongation is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach more than 99%, the antiviral effect on H1N1 influenza A virus can reach more than 99%, the antibacterial rate on escherichia coli and staphylococcus aureus can still reach more than 97% after the fibers are washed for 50 times, the antiviral effect on H1N1 influenza A virus can reach more than 97%, and the antibacterial and antiviral masterbatch has good water-washing resistance and high-efficiency antibacterial and antiviral performance.
By adopting the technical scheme of the invention, the invention can obtain the following beneficial effects:
1. the nano Cu is adopted as a main antibacterial antiviral agent, so that no ions overflow and no harm to the environment can be caused.
2. The colorant loaded nano Cu antibacterial agent has good dispersibility and compatibility in polyamide, and has small influence on the spinning performance and the fiber mechanical property of the polyamide.
3. The nano copper in the antibacterial and antiviral color master batch is always in a reduced state, and plays an antibacterial and antiviral role by continuously releasing active oxygen free radicals, so that the antibacterial and antiviral master batch has high-efficiency and durable antibacterial and antiviral effects.
4. The antibacterial and antiviral color master batch disclosed by the invention has the characteristics of health and environmental friendliness, and the problem of colorant precipitation and pollution to water resources are avoided in the application process.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Embodiment 1, a preparation method and application of a high-efficiency antibacterial and antiviral masterbatch, comprising the following specific steps:
(1) According to the mass parts, adding 2.5 parts of phthalocyanine pigment into 50 parts of deionized water, and performing ultrasonic treatment in an ultrasonic machine with the frequency of 60kHz for 20 minutes to prepare the phthalocyanine pigment dispersion liquid. An aqueous copper ion solution was prepared by dissolving 0.3 part of copper sulfate in 50 parts of deionized water. The phthalocyanine pigment dispersion was mixed with a copper ion aqueous solution in a flask, and then subjected to condensation reflux at 80℃and 50 parts of a 0.1mol/L aqueous solution of citric acid were added dropwise to the flask with stirring, and the mixture was stirred at 60℃for 3 hours to obtain a dark solution. And washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the Cu@ phthalocyanine pigment antibacterial agent.
(2) 3.5 parts of suberic acid, 100 parts of Cu@ phthalocyanine pigment and 4 parts of deionized water are added to 100 parts of liquid caprolactam at 80 ℃ and stirred for 0.5h to obtain a carboxylic acid modified Cu@ phthalocyanine pigment caprolactam slurry.
(3) Adding 32 parts of carboxylic acid modified Cu@ phthalocyanine pigment caprolactam slurry, 100 parts of caprolactam and 3 parts of deionized water into a polymerization reaction kettle, firstly carrying out ring-opening prepolymerization at 200 ℃ and 0.1Mpa for 2 hours, then carrying out polycondensation at 240 ℃ and-0.02 Mpa for 2 hours, and finally carrying out tape casting, granulating and extraction to obtain the high-efficiency antibacterial and antiviral color master batch.
(4) And drying the prepared Cu@ phthalocyanine pigment antibacterial and antiviral master batch and polyamide 6 at 110 ℃ for 24 hours, adding the Cu@ phthalocyanine pigment antibacterial and antiviral master batch into the polyamide 6 according to the proportion of 10%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral blue fiber.
Example 2, a preparation method and application of a high-efficiency antibacterial and antiviral masterbatch, specifically comprises the following steps:
(1) According to the mass parts, 4.5 parts of quinacridone pigment is added into 50 parts of deionized water, and the mixture is subjected to ultrasonic treatment in an ultrasonic machine with the frequency of 30kHz for 60 minutes to prepare a quinacridone pigment dispersion liquid. 0.6 part of copper nitrate was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. The quinacridone pigment dispersion was mixed with an aqueous copper ion solution in a flask, and then subjected to condensation reflux at 70℃to obtain a dark solution, 50 parts of a 0.4mol/L aqueous citric acid solution was added dropwise to the flask with stirring, and the mixture was stirred at 90℃for 5 hours. And washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the Cu@ quinacridone pigment antibacterial agent.
(2) 4 parts of suberic acid, 100 parts of Cu@ quinacridone pigment and 10 parts of deionized water are added to 100 parts of liquid caprolactam at 90 ℃ and stirred for 5 hours to obtain a carboxylic acid modified Cu@ quinacridone pigment caprolactam slurry.
(3) 30 parts of carboxylic acid modified Cu@ quinacridone pigment caprolactam slurry, 100 parts of caprolactam and 3 parts of deionized water are added into a polymerization reaction kettle, ring-opening pre-polymerization is carried out at 260 ℃ for 5 hours under 1.0Mpa, polycondensation is carried out at 260 ℃ and-0.07 Mpa for 5 hours, and finally, the high-efficiency antibacterial and antiviral master batch is obtained through tape casting, granulating and extraction.
(4) And drying the prepared Cu@ quinacridone pigment antibacterial and antiviral color master batch and polyamide 6 at 110 ℃ for 36 hours, adding the Cu@ quinacridone pigment antibacterial and antiviral color master batch into the polyamide 6 according to the proportion of 15%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral red fiber.
Example 3, a preparation method and application of a high-efficiency antibacterial and antiviral masterbatch, specifically comprises the following steps:
(1) According to parts by mass, 4 parts of dioxazine pigment is added into 50 parts of deionized water, and the mixture is subjected to ultrasonic treatment in an ultrasonic machine with the frequency of 40kHz for 40 minutes to prepare a dioxazine pigment dispersion. An aqueous copper ion solution was prepared by dissolving 0.7 part of copper chloride in 50 parts of deionized water. The dioxazine pigment dispersion was mixed with an aqueous copper ion solution in a flask, and then subjected to condensation reflux at 80℃to obtain a dark solution, 50 parts of a 0.3mol/L aqueous citric acid solution was added dropwise to the flask with stirring, and the mixture was stirred at 90℃for 10 hours. And washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the Cu@ dioxazine pigment antibacterial agent.
(2) 4 parts of dodecanedioic acid, 100 parts of Cu@ dioxazine pigment and 8 parts of deionized water are added to 100 parts of liquid caprolactam at 80℃and stirred for 2 hours to obtain a carboxylic acid modified Cu@ dioxazine pigment caprolactam slurry.
(3) 35 parts of carboxylic acid modified Cu@ dioxazine pigment caprolactam slurry, 100 parts of caprolactam and 3 parts of deionized water are added into a polymerization reaction kettle, ring-opening pre-polymerization is carried out for 4 hours at 230 ℃ and 0.6Mpa, polycondensation is carried out for 4 hours at 250 ℃ and-0.06 Mpa, and finally, the high-efficiency antibacterial and antiviral masterbatch is obtained through casting, granulating and extracting.
(4) And (3) drying the prepared Cu@ dioxazine pigment antibacterial and antiviral color master batch and polyamide 6 for 30 hours at 110 ℃, adding the Cu@ dioxazine pigment antibacterial and antiviral color master batch into the polyamide 6 according to the proportion of 20%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral red-purple fiber.
Example 4, a preparation method and application of a high-efficiency antibacterial and antiviral masterbatch, specifically comprises the following steps:
(1) According to the mass parts, 5 parts of phthalocyanine pigment is added into 50 parts of deionized water, and ultrasonic is carried out for 50 minutes in an ultrasonic machine with the frequency of 30kHz, so that the phthalocyanine pigment dispersion liquid is prepared. An aqueous copper ion solution was prepared by dissolving 0.9 part of copper sulfate in 50 parts of deionized water. The phthalocyanine pigment dispersion was mixed with a copper ion aqueous solution in a flask, and then subjected to condensation reflux at 80℃and 50 parts of a 0.5mol/L aqueous solution of citric acid was added dropwise to the flask with stirring, and the mixture was stirred at 80℃for 6 hours to obtain a dark solution. And washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the Cu@ phthalocyanine pigment antibacterial agent.
(2) 3 parts of sebacic acid, 150 parts of Cu@ phthalocyanine pigment and 10 parts of deionized water are added into 100 parts of liquid caprolactam at 85 ℃ and stirred for 5 hours to obtain Cu@ phthalocyanine pigment caprolactam slurry modified by carboxylic acid.
(3) Adding 40 parts of carboxylic acid modified Cu@ phthalocyanine pigment caprolactam slurry, 100 parts of caprolactam and 4 parts of deionized water into a polymerization reaction kettle, firstly carrying out ring-opening prepolymerization at 250 ℃ and 0.5Mpa for 4h, then carrying out polycondensation at 240 ℃ and-0.06 Mpa for 3h, and finally carrying out tape casting, granulating and extraction to obtain the high-efficiency antibacterial and antiviral color master batch.
(4) And drying the prepared Cu@ phthalocyanine pigment antibacterial and antiviral master batch and polyamide 6 at 120 ℃ for 24 hours, adding the Cu@ phthalocyanine pigment antibacterial and antiviral master batch into the polyamide 6 according to the proportion of 20%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral blue fiber.
Example 5, a preparation method and application of a high-efficiency antibacterial and antiviral masterbatch, specifically comprises the following steps:
(1) According to the mass parts, 4.5 parts of quinacridone pigment is added into 50 parts of deionized water, and the mixture is subjected to ultrasonic treatment in an ultrasonic machine with the frequency of 50kHz for 30 minutes to prepare a quinacridone pigment dispersion liquid. An aqueous copper ion solution was prepared by dissolving 0.8 part of copper sulfate in 50 parts of deionized water. The quinacridone pigment dispersion was mixed with an aqueous copper ion solution in a flask, and then subjected to condensation reflux at 80℃to obtain a dark solution, 50 parts of an aqueous 0.4mol/L ascorbic acid solution was added dropwise to the flask with stirring, and the mixture was stirred at 70℃for 5 hours. And washing and centrifuging the obtained product by using deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the Cu@ quinacridone pigment antibacterial agent.
(2) 4 parts of adipic acid, 200 parts of Cu@ quinacridone pigment and 8 parts of deionized water are added to 100 parts of liquid caprolactam at 90 ℃ and stirred for 3 hours to obtain a carboxylic acid modified Cu@ quinacridone pigment caprolactam slurry.
(3) Adding 40 parts of carboxylic acid modified Cu@ quinacridone pigment caprolactam slurry, 100 parts of caprolactam and 5 parts of deionized water into a polymerization reaction kettle, firstly carrying out ring opening pre-polymerization for 5 hours at 240 ℃ and 0.8Mpa, then carrying out polycondensation for 2 hours at 250 ℃ and-0.09 Mpa, and finally carrying out tape casting, granulating and extraction to obtain the high-efficiency antibacterial and antiviral color master batch.
(4) And drying the prepared Cu@ quinacridone pigment antibacterial and antiviral color master batch and polyamide 6 at 100 ℃ for 36 hours, adding the Cu@ quinacridone pigment antibacterial and antiviral color master batch into the polyamide 6 according to the proportion of 16%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral red fiber.
The mechanical properties of the high-efficiency antibacterial and antiviral colored fibers prepared in examples 1 to 5 were measured according to GB/T14344-2008 "test method for tensile Property of chemical fiber filaments", wherein the clamping distance was 500mm and the tensile speed was 500mm/min, and the results are shown in Table 1. Evaluation of antimicrobial Properties of textiles according to GB/T20944.2-2008 part 2: the absorption method detects the antibacterial property of the fabrics woven by the antibacterial and antiviral colored fibers of examples 1 to 5; according to ISO18184:2019 measurement of antiviral Activity of textile products the antiviral properties of fabrics woven from the antibacterial and antiviral colored fibers of examples 1 to 5 were examined, and the results are shown in Table 2. The method for weaving the fabric by using the fiber has no special requirement, and the method is realized by adopting a conventional mode in the field.
TABLE 1 mechanical Properties of high-efficient antibacterial and antiviral colored fibers prepared in examples 1 to 5
TABLE 2 antibacterial and antiviral Properties of the high-efficiency antibacterial and antiviral colored fibers prepared in examples 1 to 5
According to tables 1 and 2, the antibacterial and antiviral colored fiber prepared by taking the high-efficiency antibacterial and antiviral color master batch provided by the invention as a raw material has higher mechanical strength, antibacterial and antiviral performance and good washing resistance, and can be applied to the field with higher requirements on health protection.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of an antibacterial and antiviral masterbatch is characterized by comprising the following steps of: the method comprises the following steps:
(1) According to the mass parts, 2-5 parts of colorant is ultrasonically dispersed in 50 parts of deionized water to prepare colorant dispersion liquid, and 0.2-1.0 part of copper salt is dissolved in 50 parts of deionized water to prepare copper ion aqueous solution; mixing the colorant dispersion liquid and the copper ion aqueous solution in a flask, heating, condensing, refluxing, adding 50 parts of the reducer aqueous solution dropwise into the flask while stirring, and stirring for 3-24 hours at 60-90 ℃ to obtain a dark solution; washing and centrifugally separating the obtained product with deionized water and absolute ethyl alcohol, and finally drying to obtain a coloring antibacterial agent of which the surface is provided with nano elemental copper;
(2) Adding 3-5 parts of aliphatic dibasic acid, 5-10 parts of deionized water and 100-200 parts of colorant of which the surface is provided with nano elemental copper into 100 parts of liquid caprolactam at 80-90 ℃, and stirring for 0.5-5 h to obtain colorant caprolactam slurry of carboxylic acid modified colorant of which the surface is provided with nano elemental copper;
(3) Adding 30-40 parts of carboxylic acid modified colorant caprolactam slurry with nano elemental copper generated on the surface, 100 parts of caprolactam and 3-5 parts of deionized water into a polymerization reaction kettle, carrying out ring-opening prepolymerization, carrying out polycondensation, and finally carrying out tape casting, granulating and extraction to obtain the antibacterial and antiviral polyamide 6 color master batch.
2. The method for preparing an antibacterial and antiviral color master batch according to claim 1, wherein in the step (1), the colorant is one or more of carbon black, phthalocyanine pigment, quinacridone pigment, triarylmethane pigment, benzimidazolone pigment, azo pigment, dioxazine, isoindolinone, anthraquinone and perylene; the condition of ultrasonic dispersion of the colorant means that the time is 20-60 min, and the ultrasonic frequency is 30-60 kHz; the copper salt refers to one of copper chloride, copper sulfate and copper nitrate; the aqueous solution of the reducing agent is one of 0.1-0.5 mol/L of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride.
3. The method for preparing antibacterial and antiviral color master batch according to claim 1, wherein in the step (2), the aliphatic dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid.
4. The method for preparing antibacterial and antiviral master batch according to claim 1, wherein in the step (3), the reaction condition of ring-opening pre-polymerization is that the temperature is 200-260 ℃, the pressure is 0.1-1.0 MPa, and the time is 2-5 h; the reaction condition of polycondensation is that the temperature is 240-260 ℃, the pressure is-0.02-0.10 MPa, and the time is 2-5 h.
5. An application of antibacterial and antiviral color master batch antibacterial and antiviral colored fibers is characterized in that: drying the antibacterial and antiviral color master batch and polyamide resin prepared by the preparation method of any one of claims 1-4 at 90-120 ℃ for a period of time, and then uniformly mixing the antibacterial and antiviral color master batch and the polyamide resin according to a proportion, and adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral colored fiber.
6. The use of an antimicrobial and antiviral color master batch according to claim 5 wherein said polyamide resin is one of polyamide 6 and polyamide 66; the proportion of the antibacterial and antiviral color master batch to the polyamide resin is 10-20% of the antibacterial and antiviral color master batch.
7. The application of the antibacterial and antiviral color master batch according to claim 5, wherein the breaking strength of the antibacterial and antiviral colored fiber is 2.8-4.0 cN/dtex, the elongation at break is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can be over 99%, the antiviral effect on influenza A H1N1 virus can be over 99%, the antibacterial rate on escherichia coli and staphylococcus aureus can still be over 97% after the fiber is washed for 50 times, and the antiviral effect on influenza A H1N1 virus can be over 97%.
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