CN114016287A - Preparation method of antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric - Google Patents
Preparation method of antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric Download PDFInfo
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- CN114016287A CN114016287A CN202111373946.9A CN202111373946A CN114016287A CN 114016287 A CN114016287 A CN 114016287A CN 202111373946 A CN202111373946 A CN 202111373946A CN 114016287 A CN114016287 A CN 114016287A
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- 239000004744 fabric Substances 0.000 title claims abstract description 297
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 105
- 210000000085 cashmere Anatomy 0.000 title claims abstract description 77
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 83
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- 108010029541 Laccase Proteins 0.000 claims abstract description 46
- 230000003449 preventive effect Effects 0.000 claims abstract description 46
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
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- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 8
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- 239000000243 solution Substances 0.000 claims description 60
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- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims description 16
- 238000000352 supercritical drying Methods 0.000 claims description 13
- 239000007974 sodium acetate buffer Substances 0.000 claims description 12
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
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- 244000269722 Thea sinensis Species 0.000 claims description 8
- 235000012754 curcumin Nutrition 0.000 claims description 8
- 229940109262 curcumin Drugs 0.000 claims description 8
- 239000004148 curcumin Substances 0.000 claims description 8
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
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- 235000013824 polyphenols Nutrition 0.000 claims description 8
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- 238000003381 deacetylation reaction Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 230000008595 infiltration Effects 0.000 claims description 7
- 238000001764 infiltration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
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- BLUAFEHZUWYNDE-NNWCWBAJSA-N artemisinin Chemical compound C([C@](OO1)(C)O2)C[C@H]3[C@H](C)CC[C@@H]4[C@@]31[C@@H]2OC(=O)[C@@H]4C BLUAFEHZUWYNDE-NNWCWBAJSA-N 0.000 claims description 2
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- 239000011425 bamboo Substances 0.000 claims description 2
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- 108090000790 Enzymes Proteins 0.000 abstract description 2
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- 239000003112 inhibitor Substances 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- 230000035699 permeability Effects 0.000 description 27
- 230000000694 effects Effects 0.000 description 11
- 239000004753 textile Substances 0.000 description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 241000222122 Candida albicans Species 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 6
- 241000191967 Staphylococcus aureus Species 0.000 description 6
- 229940095731 candida albicans Drugs 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
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- 239000003795 chemical substances by application Substances 0.000 description 4
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- 102000004169 proteins and genes Human genes 0.000 description 4
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- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 3
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- 238000005054 agglomeration Methods 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
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- 150000004753 Schiff bases Chemical class 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 125000000468 ketone group Chemical group 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
- D06M13/175—Unsaturated ethers, e.g. vinylethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a preparation method of an antibacterial mildew-proof cashmere/cellulose fiber blended knitted fabric, which is characterized in that the laccase/TEMPO system is used for catalyzing the blended knitted fabric to generate aldehyde groups at the C6 position of a cellulose fiber glucose ring and serine in cashmere respectively, so that in-situ grafting of nano carboxyl chitosan on the blended knitted fabric is realized, and the loading capacity and the binding fastness of a natural mildew inhibitor on the blended knitted fabric are increased; the method comprises the following steps: (1) the method comprises the following steps of (1) catalyzing and oxidizing blended knitted fabrics by a laccase/TEMPO system, (2) carrying out in-situ grafting reaction on nano carboxyl chitosan, (3) finishing by a natural mildew preventive, and (4) carrying out aftertreatment on the modified blended knitted fabrics; compared with the antibacterial and mildewproof finishing of the cashmere blended fabric by the traditional chemical crosslinking method, the enzyme catalysis reaction is mild, the grafting efficiency of the nano carboxyl chitosan is high, the process is green and environment-friendly, the antibacterial and mildewproof functions of the blended fabric are lasting, the fabric is comfortable to wear, the additional value is high, and the broad market prospect is realized.
Description
Technical Field
The invention belongs to the technical field of fiber material modification, and particularly relates to a preparation method of an antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric.
Background
With the improvement of living standard and the enhancement of health and environmental protection consciousness of people, the textile garment puts more demands on the functions of environmental protection and health care while paying attention to the beauty and comfort of the textile garment. Chitosan is used as an organic antibacterial agent commonly used for textiles, and is widely used in the field of textile clothing due to wide sources, reproducibility, biocompatibility, no toxicity, no stimulation, high and durable antibacterial ability, wide antibacterial spectrum, safety and sanitation, chitosan is difficultly dissolved in water and only in an acidic solution due to strong hydrogen bond combination between chitosan molecules, and an acid solution is volatile, strong in corrosivity and pollutes the environment, so that the application of chitosan is greatly limited, the problem that the common chitosan only has antibacterial property under an acidic condition needs to be solved, and the utilization rate and the application range of the chitosan are improved;
meanwhile, protein fibers and cellulose fibers are the most widely used natural high molecular polymers, have reproducibility and are common raw materials for textiles; chitosan, protein fiber and cellulose fiber are lack of effective chemical bond combination, so that functional groups such as aldehyde group, carboxyl group, ketone group and the like are introduced by the common periodate oxidation reaction in the prior art, and conditions can be provided for further modification of the fiber, but the periodate oxidation reaction is easy to cause halogen environmental pollution, high energy consumption, fabric fiber strength damage and other defects; therefore, a system capable of catalyzing and oxidizing protein fibers and cellulose fibers is needed, so that the fibers and chitosan can be subjected to in-situ grafting reaction, the grafting amount and the bonding fastness of chitosan on the fibers are improved, the loading amount and the bonding fastness of a natural mildew inhibitor on fiber fabrics are increased, and the mildew resistance of the fiber fabrics is enhanced.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of an antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric to solve the problems in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the preparation method of the antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric is provided, the laccase/2, 2,6, 6-tetramethyl piperidine-nitrogen-oxide system, namely a laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric, active aldehyde groups are generated at the C6 position of a cellulose fiber glucose ring and serine in cashmere respectively, and in-situ grafting of the nano carboxyl chitosan on the blended knitted fabric is realized; the preparation method of the blended knitted fabric with antibacterial and mildewproof functions comprises the following specific steps:
(1) the laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric: immersing the cashmere/cellulose fiber blended knitted fabric into 20-40 g/L NaHCO3 solution, heating and maintaining the temperature at 75-85 ℃, and stirring for 10-20 min; taking out the cashmere/cellulose fiber blended knitted fabric, and washing with water until the surface pH value is neutral; soaking the cashmere/cellulose fiber blended knitted fabric into an acetic acid solution with the mass concentration of 0.9-1.1%, soaking for 15-20 min, washing with water, and drying to obtain a pretreated blended knitted fabric; preparing an acetic acid-sodium acetate buffer solution with the pH value of 4.2-4.8, adding TEMPO to enable the concentration of the TEMPO to be 5-20 g/L, then adding the pretreated blended knitted fabric for infiltration, adding laccase to enable the concentration of the laccase to be 100-250U/mL, and stirring and reacting for 2-4 hours at the temperature of 25-40 ℃; taking out the fabric, washing the fabric with absolute ethyl alcohol, removing residual laccase and TEMPO, drying the fabric in an oven, and putting the fabric into a dryer to obtain an active blended knitted fabric;
(2) in-situ grafting reaction of the nano carboxyl chitosan: adding the active blended knitted fabric obtained in the step (1) into a nano carboxyl chitosan solution with the mass concentration of 0.1-0.2%, dropwise adding 0.1mol/L HCl solution to control the pH value to be 4-4.5, and stirring and reacting at the temperature of 30-45 ℃ for 0.5-2.5 h; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 70-90%; placing the fabric in a supercritical drying instrument, drying for 30-45 min at 10-35 ℃, washing and airing to obtain a nano carboxyl chitosan grafted blended knitted fabric; the working pressure of the supercritical drying instrument is 5-12 MPa, and the medium flow is 100-1000 ml/min;
(3) finishing a natural mildew preventive: adding the nano carboxyl chitosan grafted blended knitted fabric prepared in the step (2) into a mildew preventive finishing liquid with the mass concentration of 1-3%, dropwise adding an acetic acid solution with the mass concentration of 1% to control the pH value to be 4.4-4.8, carrying out oscillation reaction at 40-60 ℃ for 2-4 h, and taking out the nano carboxyl chitosan grafted blended knitted fabric after mildew preventive finishing after the reaction is finished;
(4) post-treatment of the modified blended knitted fabric: and (3) soaking the nanometer carboxyl chitosan grafted and blended knitted fabric subjected to mildew-proof finishing in the step (3) in deionized water for 2-3 h, fully washing with water to remove the unbound mildew preventive, and drying in a vacuum oven at 40 ℃ for 3-5 h to obtain the antibacterial and mildew-proof cashmere/cellulose fiber blended knitted fabric.
Preferably, the bath ratio of the blended knitted fabric to the laccase/TEMPO reaction liquid in the step (1) is set to be 1: 40-60 (w/v).
Preferably, in the step (2), the deacetylation degree of the nano carboxyl chitosan is more than or equal to 92.8%, the content of carboxyl at the C6 position is 42.70-56.43%, the particle size range is 85-228 nm, the particle size dispersion index is 0.108-0.314, and the Zeta potential is 30.59-42.86 mV.
Preferably, the natural mildew preventive in the step (3) is composed of curcumin and one of cassia oil, thujoram oil, artemisinine and tea polyphenol according to the mass ratio of 7: 3-9: 1.
Preferably, the cellulose fibers in the cashmere/cellulose fiber blended knitted fabric are cotton fibers, bamboo pulp fibers, viscose fibers, Tencel fibers and Modal fibers.
Advantageous effects
1. According to the invention, the cashmere/cellulose fiber blended knitted fabric is firstly added into NaHCO3 solution for treatment, and then soaked in acetic acid solution for pretreatment, cellulose fibers and cashmere fibers in the blended knitted fabric are swollen by alkali and acid solution, so that the hydrogen bond effect among fiber molecules is weakened, laccase/TEMPO reagent is favorably permeated into reaction sites in the fibers for catalytic oxidation, the reaction time is shortened, the number of active aldehyde groups in the blended knitted fabric is increased, and the grafting amount of nano carboxyl chitosan on the blended knitted fabric is increased.
2. According to the invention, a laccase/TEMPO system is adopted to catalyze and oxidize the C6 site of the glucose ring of the cellulose fiber in the blended knitted fabric and the serine in the cashmere to form an active aldehyde group, the enzyme treatment condition is mild, the catalytic oxidation reaction of the blended knitted fabric is carried out under the conditions of low temperature and near neutrality, the method has the advantages of low energy consumption, green and environment-friendly treatment process, small fiber oxidative degradation, high oxidation efficiency and good uniformity, and the defects of halogen environment pollution, high energy consumption, fabric fiber strength damage and the like caused by periodate oxidation reaction are avoided.
3. According to the invention, the laccase/TEMPO system is used for catalyzing and oxidizing reaction to generate active aldehyde groups at the C6 position of a glucose ring of cellulose fibers in blended knitted fabrics and in serine in cashmere, and the active aldehyde groups can directly form Schiff base C = N and acetal chemical bonds with amino and hydroxyl in nano carboxyl chitosan respectively; and meanwhile, carboxyl in the nano carboxyl chitosan can also form a C-N amide chemical bond with amino on cashmere fiber in the blended knitted fabric, and carboxyl at the C6 position of the nano carboxyl chitosan can freely rotate in spatial conformation, has small steric hindrance and is more easily in contact reaction with the amino of the cashmere fiber. Therefore, under the condition of not using a chemical cross-linking agent, the blended knitted fabric catalyzed and oxidized by the laccase/TEMPO system can generate multi-site in-situ grafting reaction with the nano carboxyl chitosan, the grafting amount and the bonding fastness of the nano carboxyl chitosan on the blended knitted fabric are improved, the loading amount and the bonding fastness of a natural mildew preventive on the blended knitted fabric are increased, more mildew preventive finishing agents are combined, and the mildew preventive performance of the blended knitted fabric is obviously enhanced.
4. The nano carboxyl chitosan does not use organic solvent and aldehyde cross-linking agent, is green, environment-friendly, safe and sanitary, small in particle size, uniform in distribution, strong in stability, high in biological activity and good in water solubility, contains carboxyl and amino in nano carboxyl chitosan molecules, is an amphoteric polyelectrolyte, is similar to human skin protein structure, and has the characteristics of excellent biocompatibility, skin-friendly property, antibacterial property and the like; meanwhile, the amino in the nano carboxyl chitosan pyranose ring can be protonated by the carboxyl to carry positive charge (-NH3+), so that the antibacterial effect is high and lasting, the limitation that the common chitosan only has antibacterial property under an acidic condition is solved, and the utilization rate and the application range of the chitosan are improved.
5. The invention uses the supercritical fluid drying technology to dry the blended knitted fabric grafted by the nano carboxyl chitosan, the grafted knitted fabric is dried under the conditions of critical temperature and critical pressure of a drying medium, when the drying medium is in a supercritical state, a substance exists in a supercritical fluid form with gas-liquid properties, a gas-liquid interface of the drying medium disappears at the moment, and the surface tension is zero, so that the shrinkage and the fragmentation of a nano material in the drying process can be avoided, the original structure and state of nano particles are kept, and the blended knitted fabric is prevented from poor in hand feeling, poor in antibacterial and mildew-proof effects and reduced in air permeability caused by the agglomeration of the nano carboxyl chitosan particles on the surface of the blended knitted fabric; the supercritical fluid drying has the characteristics of good thermal stability, large amount of dried samples, small sample damage and the like, and can be applied in a large scale.
6. According to the invention, the nano carboxyl chitosan is used as a finishing agent, so that the modified cashmere/cellulose fiber blended knitted fabric has multiple functions of crease resistance, bacteriostasis, reactivity and the like, and the physical and mechanical properties of the blended knitted fabric are improved, so that the serviceability and the grade of the blended knitted fabric are improved; the number of adsorbable sites on component fiber molecular chains in the nano carboxyl chitosan in-situ grafted blended knitted fabric is increased, and the multiple combined natural mildew preventive is green and safe, has spectrum antibacterial property, is compatible with human bodies, has more active ingredients, and can generate firm combination effect with the modified blended knitted fabric through the synergistic effect of multiple sites, thereby solving the problems of poor functional durability, environmental pollution and the like in the after-finishing of the blended knitted fabric.
Detailed Description
The present invention will be further described with reference to the following embodiments, but is not limited thereto.
Example 1
(1) The laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric: the cashmere/cellulose fiber blended knitted fabric is selected from cashmere/cotton fiber blended knitted fabric, which is called blended knitted fabric for short, the blended knitted fabric is immersed into 30g/L NaHCO3 solution, and the mixture is heated, maintained at 80 ℃ and stirred for 15 min; taking out the blended knitted fabric, and washing the blended knitted fabric until the surface pH value is neutral; then soaking the blended knitted fabric into an acetic acid solution with the mass concentration of 1% for 15min, washing with water and drying in the air to obtain a pretreated blended knitted fabric; preparing acetic acid-sodium acetate buffer solution with the pH value of 4.6, adding TEMPO to enable the concentration of the acetic acid-sodium acetate buffer solution to be 10g/L, then adding pretreated blended knitted fabric for infiltration, adding laccase to enable the concentration of the laccase to be 100U/mL, setting the bath ratio of the blended knitted fabric to laccase/TEMPO reaction solution to be 1:50(w/v), and stirring and reacting for 3 hours at the temperature of 30 ℃; taking out the fabric, washing the fabric with absolute ethyl alcohol, removing residual laccase and TEMPO, drying the fabric in an oven, and putting the fabric into a dryer to obtain an active blended knitted fabric;
(2) in-situ grafting reaction of the nano carboxyl chitosan: adding the active blended knitted fabric obtained in the step (1) into a nano carboxyl chitosan solution with the mass concentration of 0.2%, wherein the deacetylation degree of the nano carboxyl chitosan is 93.5%, the carboxyl content at the C6 site is 53.66%, the particle size range is 100-120 nm, the particle size dispersion index is 0.218, and the Zeta potential is 41.69 mV; dropwise adding 0.1mol/L HCl solution to control the pH value to be 4, and stirring and reacting for 2 hours at 40 ℃; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 85%; placing the fabric in a supercritical drying instrument, drying for 40min at 25 ℃, washing and airing to obtain a nano carboxyl chitosan grafted blended knitted fabric; the working pressure of the supercritical drying instrument is 8MPa, and the medium flow is 500 ml/min;
(3) finishing a natural mildew preventive: adding the nano carboxyl chitosan grafted blended knitted fabric prepared in the step (2) into mildew preventive finishing liquid with the mass concentration of 2%, wherein the natural mildew preventive is composed of curcumin and tea polyphenol according to the mass ratio of 7:3, dropwise adding acetic acid solution with the mass concentration of 1%, controlling the pH value to be 4.5, carrying out oscillation reaction at 50 ℃ for 3 hours, and taking out the nano carboxyl chitosan grafted blended knitted fabric after mildew preventive finishing after the reaction is finished;
(4) post-treatment of the modified blended knitted fabric: soaking the nanometer carboxyl chitosan grafted and blended knitted fabric subjected to mildew-proof finishing in the step (3) in deionized water for 3 hours, fully washing with water to remove the unbound mildew preventive, and drying in a vacuum oven at 40 ℃ for 5 hours to obtain the antibacterial and mildew-proof cashmere/cotton fiber blended knitted fabric;
(5) the air permeability effect of the finished product antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is detected, the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is subjected to air permeability performance test according to the standard GB/T5453-1997 determination of textile fabric air permeability, and the air permeability R is 1.75 m/s;
(6) the antibacterial effect of the finished product antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is detected, the antibacterial performance of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is tested according to the American AATCC Test Method100-1999 quantitative Test Method and the industry standard of FZ/T73023-2006 antibacterial knitted fabric, the antibacterial rate of staphylococcus aureus is 99.5%, the antibacterial rate of escherichia coli is 84.9%, the antibacterial rate of candida albicans is 79.5%, and the antibacterial rate of the finished product after being washed by water is respectively tested 10 times, 20 times and 50 times, and the Test results are shown in the following table 2 comparison table of the antibacterial performance detection results of examples and a comparison group.
Example 2
(1) The laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric: the cashmere/cellulose fiber blended knitted fabric is selected from cashmere/cotton fiber blended knitted fabric, which is called blended knitted fabric for short, the blended knitted fabric is immersed into 30g/L NaHCO3 solution, and the mixture is heated, maintained at 80 ℃ and stirred for 15 min; taking out the blended knitted fabric, and washing the blended knitted fabric until the surface pH value is neutral; then soaking the blended knitted fabric into an acetic acid solution with the mass concentration of 1% for 15min, washing with water and drying in the air to obtain a pretreated blended knitted fabric; preparing acetic acid-sodium acetate buffer solution with the pH value of 4.6, adding TEMPO to enable the concentration of the acetic acid-sodium acetate buffer solution to be 10g/L, then adding pretreated blended knitted fabric for infiltration, adding laccase to enable the concentration of the laccase to be 250U/mL, setting the bath ratio of the blended knitted fabric to laccase/TEMPO reaction solution to be 1:50(w/v), and stirring and reacting for 3 hours at the temperature of 30 ℃; taking out the fabric, washing the fabric with absolute ethyl alcohol, removing residual laccase and TEMPO, drying the fabric in an oven, and putting the fabric into a dryer to obtain an active blended knitted fabric;
(2) in-situ grafting reaction of the nano carboxyl chitosan: adding the active blended knitted fabric obtained in the step (1) into a nano carboxyl chitosan solution with the mass concentration of 0.2%, wherein the deacetylation degree of the nano carboxyl chitosan is 93.5%, the carboxyl content at the C6 site is 53.66%, the particle size range is 100-120 nm, the particle size dispersion index is 0.218, and the Zeta potential is 41.69 mV; dropwise adding 0.1mol/L HCl solution to control the pH value to be 4, and stirring and reacting for 2 hours at 40 ℃; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 85%; placing the fabric in a supercritical drying instrument, drying for 40min at 25 ℃, washing and airing to obtain a nano carboxyl chitosan grafted blended knitted fabric; the working pressure of the supercritical drying instrument is 8MPa, and the medium flow is 500 ml/min;
(3) finishing a natural mildew preventive: adding the nano carboxyl chitosan grafted blended knitted fabric prepared in the step (2) into mildew preventive finishing liquid with the mass concentration of 2%, wherein the natural mildew preventive is composed of curcumin and tea polyphenol according to the mass ratio of 7:3, dropwise adding acetic acid solution with the mass concentration of 1%, controlling the pH value to be 4.5, carrying out oscillation reaction at 50 ℃ for 3 hours, and taking out the nano carboxyl chitosan grafted blended knitted fabric after mildew preventive finishing after the reaction is finished;
(4) post-treatment of the modified blended knitted fabric: soaking the nanometer carboxyl chitosan grafted and blended knitted fabric subjected to mildew-proof finishing in the step (3) in deionized water for 3 hours, fully washing with water to remove the unbound mildew preventive, and drying in a vacuum oven at 40 ℃ for 5 hours to obtain the antibacterial and mildew-proof cashmere/cotton fiber blended knitted fabric;
(5) the air permeability effect of the finished product antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is detected, the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is subjected to air permeability performance test according to the standard GB/T5453-1997 determination of textile fabric air permeability, and the air permeability R is 1.62 m/s;
(6) the antibacterial effect of the finished product antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is detected, the antibacterial performance of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is tested according to the American AATCC Test Method100-1999 quantitative Test Method and the industry standard of FZ/T73023-2006 antibacterial knitted fabric, the antibacterial rate of staphylococcus aureus is 99.6%, the antibacterial rate of escherichia coli is 87.8%, the antibacterial rate of candida albicans is 75.6%, and the antibacterial rate of the finished product after being washed by water is respectively tested 10 times, 20 times and 50 times, and the Test results are shown in the comparison table of the antibacterial performance detection results of the embodiment and the comparison group in the following table 2.
Example 3
(1) The laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric: the cashmere/cellulose fiber blended knitted fabric is selected from cashmere/cotton fiber blended knitted fabric, which is called blended knitted fabric for short, the blended knitted fabric is immersed into 30g/L NaHCO3 solution, and the mixture is heated, maintained at 80 ℃ and stirred for 15 min; taking out the blended knitted fabric, and washing the blended knitted fabric until the surface pH value is neutral; then soaking the blended knitted fabric into an acetic acid solution with the mass concentration of 1% for 15min, washing with water and drying in the air to obtain a pretreated blended knitted fabric; preparing acetic acid-sodium acetate buffer solution with the pH value of 4.6, adding TEMPO to enable the concentration of the buffer solution to be 20g/L, then adding pretreated blended knitted fabric for infiltration, adding laccase to enable the concentration of the laccase to be 250U/mL, setting the bath ratio of the blended knitted fabric to laccase/TEMPO reaction solution to be 1:50(w/v), and stirring and reacting for 3 hours at the temperature of 30 ℃; taking out the fabric, washing the fabric with absolute ethyl alcohol, removing residual laccase and TEMPO, drying the fabric in an oven, and putting the fabric into a dryer to obtain an active blended knitted fabric;
(2) in-situ grafting reaction of the nano carboxyl chitosan: adding the active blended knitted fabric obtained in the step (1) into a nano carboxyl chitosan solution with the mass concentration of 0.2%, wherein the deacetylation degree of the nano carboxyl chitosan is 93.5%, the carboxyl content at the C6 site is 53.66%, the particle size range is 100-120 nm, the particle size dispersion index is 0.218, and the Zeta potential is 41.69 mV; dropwise adding 0.1mol/L HCl solution to control the pH value to be 4, and stirring and reacting for 2 hours at 40 ℃; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 85%; placing the fabric in a supercritical drying instrument, drying for 40min at 25 ℃, washing and airing to obtain a nano carboxyl chitosan grafted blended knitted fabric; the working pressure of the supercritical drying instrument is 8MPa, and the medium flow is 500 ml/min;
(3) finishing a natural mildew preventive: adding the nano carboxyl chitosan grafted blended knitted fabric prepared in the step (2) into mildew preventive finishing liquid with the mass concentration of 2%, wherein the natural mildew preventive is composed of curcumin and tea polyphenol according to the mass ratio of 7:3, dropwise adding acetic acid solution with the mass concentration of 1%, controlling the pH value to be 4.5, carrying out oscillation reaction at 50 ℃ for 3 hours, and taking out the nano carboxyl chitosan grafted blended knitted fabric after mildew preventive finishing after the reaction is finished;
(4) post-treatment of the modified blended knitted fabric: soaking the nanometer carboxyl chitosan grafted and blended knitted fabric subjected to mildew-proof finishing in the step (3) in deionized water for 3 hours, fully washing with water to remove the unbound mildew preventive, and drying in a vacuum oven at 40 ℃ for 5 hours to obtain the antibacterial and mildew-proof cashmere/cotton fiber blended knitted fabric;
(5) the air permeability effect of the finished product antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is detected, the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is subjected to air permeability performance test according to the standard GB/T5453-1997 determination of textile fabric air permeability, and the air permeability R is 1.73 m/s;
(6) the antibacterial effect of the finished product antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is detected, the antibacterial performance of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is tested according to the American AATCC Test Method100-1999 quantitative Test Method and the industry standard of FZ/T73023-2006 antibacterial knitted fabric, the antibacterial rate of staphylococcus aureus is 99.7%, the antibacterial rate of escherichia coli is 82.9%, the antibacterial rate of candida albicans is 78.5%, and the antibacterial rate of the finished product after being washed by water is respectively tested 10 times, 20 times and 50 times, and the Test results are shown in the following table 2 comparison table of the antibacterial performance detection results of examples and a comparison group.
Comparative example 1
(1) The laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric: the cashmere/cellulose fiber blended knitted fabric is selected from cashmere/cotton fiber blended knitted fabric, which is called blended knitted fabric for short, the blended knitted fabric is immersed into 30g/L NaHCO3 solution, and the mixture is heated, maintained at 80 ℃ and stirred for 15 min; taking out the blended knitted fabric, and washing the blended knitted fabric until the surface pH value is neutral; then soaking the blended knitted fabric into an acetic acid solution with the mass concentration of 1% for 15min, washing with water and drying in the air to obtain a pretreated blended knitted fabric; preparing acetic acid-sodium acetate buffer solution with the pH value of 4.6, adding TEMPO to enable the concentration of the acetic acid-sodium acetate buffer solution to be 10g/L, then adding pretreated blended knitted fabric for infiltration, adding laccase to enable the concentration of the laccase to be 100U/mL, setting the bath ratio of the blended knitted fabric to laccase/TEMPO reaction solution to be 1:50(w/v), and stirring and reacting for 3 hours at the temperature of 30 ℃; taking out the fabric, washing the fabric by using absolute ethyl alcohol, removing residual laccase and TEMPO, drying the fabric in an oven, and putting the fabric into a dryer to obtain the active blended knitted fabric in the comparative example 1;
(2) infiltrating and drying the blended knitted fabric: adding the active blended knitted fabric obtained in the step (1) in the comparative example 1 into deionized water; dropwise adding 0.1mol/L HCl solution to control the pH value to be 4, and stirring and reacting for 2 hours at 40 ℃; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 85%; placing the fabric in a supercritical dryer to dry for 40min at 25 ℃, and washing and airing to obtain the intermediate blended knitted fabric of the comparative example 1; the working pressure of the supercritical drying instrument is 8MPa, and the medium flow is 500 ml/min;
(3) finishing a natural mildew preventive: adding the intermediate blended knitted fabric prepared in the step (2) in the comparative example 1 into a mildew preventive finishing liquid with the mass concentration of 2%, wherein the natural mildew preventive consists of curcumin and tea polyphenol in a mass ratio of 7:3, dropwise adding an acetic acid solution with the mass concentration of 1% to control the pH value to be 4.5, carrying out oscillation reaction at 50 ℃ for 3 hours, and taking out the mildew-proof finished intermediate blended knitted fabric of the comparative example 1 after the reaction is finished;
(4) post-treatment of the modified blended knitted fabric: soaking the intermediate blended knitted fabric of the comparative example 1 subjected to mildew-proof finishing in the step (3) in deionized water for 3 hours, fully washing with water to remove the unbound mildew-proof agent, and drying in a vacuum oven at 40 ℃ for 5 hours to obtain the antibacterial and mildew-proof cashmere/cotton fiber blended knitted fabric of the comparative example 1;
(5) the air permeability effect of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 1 is detected, the air permeability of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 1 is tested according to the GB/T5453-1997 determination of textile fabric air permeability, and the air permeability R is 1.76 m/s;
(6) the antibacterial effect of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 1 is detected, the antibacterial performance of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is tested according to the industry standards of American AATCC Test Method100-1999 quantitative Test Method and FZ/T73023-2006 antibacterial knitted fabric, the antibacterial rate of staphylococcus aureus is 65.8%, the antibacterial rate of escherichia coli is 54.8%, the antibacterial rate of candida albicans is 50.6%, and the antibacterial rate of the cashmere/cotton fiber blended knitted fabric after being washed by 10 times, 20 times and 50 times respectively, and the Test results are shown in a comparison table of the antibacterial performance Test results of an embodiment and a comparative group in Table 2 below.
Comparative example 2
(1) Pretreatment of the blended knitted fabric: the cashmere/cellulose fiber blended knitted fabric is selected from cashmere/cotton fiber blended knitted fabric, which is called blended knitted fabric for short, the blended knitted fabric is immersed into 30g/L NaHCO3 solution, and the mixture is heated, maintained at 80 ℃ and stirred for 15 min; taking out the blended knitted fabric, and washing the blended knitted fabric until the surface pH value is neutral; then soaking the blended knitted fabric into an acetic acid solution with the mass concentration of 1% for 15min, washing with water and drying in the air to obtain a pretreated blended knitted fabric; preparing acetic acid-sodium acetate buffer solution with pH of 4.6, and stirring and reacting for 3h at 30 ℃; the fabric was taken out and washed with absolute ethyl alcohol, and after drying in an oven, the fabric was put into a dryer to obtain the intermediate blended knitted fabric of comparative example 2;
(2) in-situ grafting reaction of the nano carboxyl chitosan: adding the intermediate blended knitted fabric obtained in the step (1) in the control example 2 into a nano carboxyl chitosan solution with the mass concentration of 0.1%, wherein the deacetylation degree of the nano carboxyl chitosan is 93.5%, the carboxyl content at the C6 site is 53.66%, the particle size range is 100-120 nm, the particle size dispersion index is 0.218, and the Zeta potential is 35.68 mV; dropwise adding 0.1mol/L HCl solution to control the pH value to be 4, and stirring and reacting for 2 hours at 40 ℃; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 85%; placing the fabric in a supercritical drying instrument, drying for 40min at 25 ℃, washing and airing to obtain the nano carboxyl chitosan grafted blended knitted fabric in the comparative example 2; the working pressure of the supercritical drying instrument is 8MPa, and the medium flow is 500 ml/min;
(3) finishing a natural mildew preventive: adding the nano carboxyl chitosan grafted blended knitted fabric prepared in the comparative example 2 in the step (2) into mildew preventive finishing liquid with the mass concentration of 2%, wherein the natural mildew preventive consists of curcumin and tea polyphenol in a mass ratio of 7:3, dropwise adding acetic acid solution with the mass concentration of 1% to control the pH value to be 4.5, carrying out oscillation reaction at 50 ℃ for 3 hours, and taking out the nano carboxyl chitosan grafted blended knitted fabric prepared in the comparative example 2 after the mildew preventive finishing;
(4) post-treatment of the modified blended knitted fabric: soaking the nanometer carboxyl chitosan grafted and blended knitted fabric of the comparative example 2 subjected to mildew-proof finishing in the step (3) in deionized water for 3 hours, fully washing with water to remove the unbound mildew preventive, and drying in a vacuum oven at 40 ℃ for 5 hours to obtain the antibacterial and mildew-proof cashmere/cotton fiber blended knitted fabric of the comparative example 2;
(5) the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 2 is subjected to air permeability effect detection, the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 2 is subjected to air permeability performance detection according to GB/T5453-1997 determination of textile fabric air permeability, and the air permeability R is 1.23 m/s;
(6) the antibacterial effect of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 2 is detected, the antibacterial performance of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is tested according to the industry standards of American AATCC Test Method100-1999 quantitative Test Method and FZ/T73023-2006 antibacterial knitted fabric, the antibacterial rate of staphylococcus aureus is 42.6%, the antibacterial rate of escherichia coli is 38.9%, the antibacterial rate of candida albicans is 37.6%, and the antibacterial rate of the cashmere/cotton fiber blended knitted fabric after being washed by 10 times, 20 times and 50 times respectively, and the Test results are shown in a comparison table of the antibacterial performance Test results of the example and the comparative group in Table 2 below.
Comparative example 3
(1) The laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric: the cashmere/cellulose fiber blended knitted fabric is selected from cashmere/cotton fiber blended knitted fabric, which is called blended knitted fabric for short, the blended knitted fabric is immersed into 30g/L NaHCO3 solution, and the mixture is heated, maintained at 80 ℃ and stirred for 15 min; taking out the blended knitted fabric, and washing the blended knitted fabric until the surface pH value is neutral; then soaking the blended knitted fabric into an acetic acid solution with the mass concentration of 1% for 15min, washing with water and drying in the air to obtain a pretreated blended knitted fabric; preparing acetic acid-sodium acetate buffer solution with the pH value of 4.6, adding TEMPO to enable the concentration of the acetic acid-sodium acetate buffer solution to be 10g/L, then adding pretreated blended knitted fabric for infiltration, adding laccase to enable the concentration of the laccase to be 100U/mL, setting the bath ratio of the blended knitted fabric to laccase/TEMPO reaction solution to be 1:50(w/v), and stirring and reacting for 3 hours at the temperature of 30 ℃; taking out the fabric, washing the fabric with absolute ethyl alcohol, removing residual laccase and TEMPO, drying the fabric in an oven, and putting the fabric into a dryer to obtain an active blended knitted fabric;
(2) in-situ grafting reaction of the nano carboxyl chitosan: adding the active blended knitted fabric obtained in the step (1) into a nano carboxyl chitosan solution with the mass concentration of 0.2%, wherein the deacetylation degree of the nano carboxyl chitosan is 93.5%, the carboxyl content at the C6 site is 53.66%, the particle size range is 100-120 nm, the particle size dispersion index is 0.218, and the Zeta potential is 41.69 mV; dropwise adding 0.1mol/L HCl solution to control the pH value to be 4, and stirring and reacting for 2 hours at 40 ℃; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 85%; placing the fabric in a vacuum oven for pre-drying at 40 ℃ for 40min, then heating to 100 ℃ for baking for 3min, and washing and drying in the air to obtain a nano carboxyl chitosan grafted blended knitted fabric;
(3) finishing a natural mildew preventive: adding the nano carboxyl chitosan grafted blended knitted fabric prepared in the step (2) into mildew preventive finishing liquid with the mass concentration of 2%, wherein the natural mildew preventive is composed of curcumin and tea polyphenol according to the mass ratio of 7:3, dropwise adding acetic acid solution with the mass concentration of 1%, controlling the pH value to be 4.5, carrying out oscillation reaction at 50 ℃ for 3 hours, and taking out the nano carboxyl chitosan grafted blended knitted fabric after mildew preventive finishing after the reaction is finished;
(4) post-treatment of the modified blended knitted fabric: soaking the nanometer carboxyl chitosan grafted and blended knitted fabric subjected to mildew-proof finishing in the step (3) in deionized water for 3 hours, fully washing with water to remove the unbound mildew preventive, and drying in a vacuum oven at 40 ℃ for 5 hours to obtain the antibacterial and mildew-proof cashmere/cotton fiber blended knitted fabric of the comparative example 3;
(5) the air permeability effect of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 3 is detected, the air permeability of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 3 is tested according to the GB/T5453-1997 determination of textile fabric air permeability, and the air permeability R is 0.67 m/s;
(6) the antibacterial effect of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric in the comparative example 3 is detected, the antibacterial performance of the antibacterial and mildewproof cashmere/cotton fiber blended knitted fabric is tested according to the industry standards of American AATCC Test Method100-1999 quantitative Test Method and FZ/T73023-2006 antibacterial knitted fabric, the antibacterial rate of staphylococcus aureus is 99.5%, the antibacterial rate of escherichia coli is 84.9%, the antibacterial rate of candida albicans is 79.5%, and the antibacterial rate of the cashmere/cotton fiber blended knitted fabric after being washed by 10 times, 20 times and 50 times respectively, and the Test results are shown in a comparison table of the antibacterial performance Test results of the example and the comparative group in Table 2 below.
TABLE 1 comparison table of main parameter differences between examples and control groups
TABLE 2 comparison table of antibacterial property test results of examples and control groups
As can be seen from the comparison of the data of the above examples and the comparative examples, the blended knitted fabric catalyzed and oxidized by the laccase/TEMPO system and the nano carboxyl chitosan can have a multi-site in-situ grafting reaction without using a chemical cross-linking agent, so that the grafting amount and the binding fastness of the nano carboxyl chitosan on the blended knitted fabric are improved, the loading amount and the binding fastness of a natural mildew preventive on the blended knitted fabric are increased, the combination of a larger amount of mildew preventive finishing agent is facilitated, and the mildew preventive performance of the blended knitted fabric is remarkably enhanced.
Meanwhile, the invention dries the blended knitted fabric grafted by the nano carboxyl chitosan by using a supercritical fluid drying technology, avoids the shrinkage and the fragmentation of the nano material in the drying process, keeps the original structure and state of the nano particles, and prevents the problems of poor hand feeling, poor antibacterial and mildewproof effects and poor air permeability of the blended knitted fabric caused by the agglomeration of the nano carboxyl chitosan particles on the surface of the blended knitted fabric; thereby enhancing the hand feeling, the mould-proof performance and the air permeability of the blended knitted fabric.
While the foregoing description of the disclosed embodiments will so fully enable those skilled in the art to make or use the invention, many modifications of the embodiments will become apparent to those skilled in the art that will be necessary in view of the teachings of the present invention, and it is to be understood that other arrangements may be devised in accordance with the principles of the invention and that the invention is not to be limited to the embodiments illustrated herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A preparation method of an antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric is characterized by comprising the following steps: the blended knitted fabric is catalyzed and oxidized by a laccase/2, 2,6, 6-tetramethyl piperidine-nitrogen-oxide system, namely a laccase/TEMPO system, active aldehyde groups are respectively generated at the C6 position of a glucose ring of cellulose fibers and serine in cashmere, and in-situ grafting of the nano carboxyl chitosan on the blended knitted fabric is realized; the preparation method of the blended knitted fabric with antibacterial and mildewproof functions comprises the following specific steps:
(1) the laccase/TEMPO system is used for catalyzing and oxidizing the blended knitted fabric: immersing cashmere/cellulose fiber blended knitted fabric into 20-40 g/L NaHCO3Heating the solution and stirring for 10-20 min at 75-85 ℃; taking out the cashmere/cellulose fiber blended knitted fabric, and washing with water until the surface pH value is neutral; soaking the cashmere/cellulose fiber blended knitted fabric into an acetic acid solution with the mass concentration of 0.9-1.1%, soaking for 15-20 min, washing with water, and drying to obtain a pretreated blended knitted fabric; preparing an acetic acid-sodium acetate buffer solution with the pH value of 4.2-4.8, adding TEMPO to enable the concentration of the TEMPO to be 5-20 g/L, then adding the pretreated blended knitted fabric for infiltration, adding laccase to enable the concentration of the laccase to be 100-250U/mL, and stirring and reacting for 2-4 hours at the temperature of 25-40 ℃; taking out the fabric, washing the fabric with absolute ethyl alcohol, removing residual laccase and TEMPO, drying the fabric in an oven, and putting the fabric into a dryer to obtain an active blended knitted fabric;
(2) in-situ grafting reaction of the nano carboxyl chitosan: adding the active blended knitted fabric obtained in the step (1) into a nano carboxyl chitosan solution with the mass concentration of 0.1-0.2%, dropwise adding 0.1mol/L HCl solution to control the pH value to be 4-4.5, and stirring and reacting at the temperature of 30-45 ℃ for 0.5-2.5 h; then padding the fabric to remove redundant liquid, so that the liquid carrying rate of the fabric is 70-90%; placing the fabric in a supercritical drying instrument, drying for 30-45 min at 10-35 ℃, washing and airing to obtain a nano carboxyl chitosan grafted blended knitted fabric; the working pressure of the supercritical drying instrument is 5-12 MPa, and the medium flow is 100-1000 ml/min;
(3) finishing a natural mildew preventive: adding the nano carboxyl chitosan grafted blended knitted fabric prepared in the step (2) into a mildew preventive finishing liquid with the mass concentration of 1-3%, dropwise adding an acetic acid solution with the mass concentration of 1% to control the pH value to be 4.4-4.8, carrying out oscillation reaction at 40-60 ℃ for 2-4 h, and taking out the nano carboxyl chitosan grafted blended knitted fabric after mildew preventive finishing after the reaction is finished;
(4) post-treatment of the modified blended knitted fabric: and (3) soaking the nanometer carboxyl chitosan grafted and blended knitted fabric subjected to mildew-proof finishing in the step (3) in deionized water for 2-3 h, fully washing with water to remove the unbound mildew preventive, and drying in a vacuum oven at 40 ℃ for 3-5 h to obtain the antibacterial and mildew-proof cashmere/cellulose fiber blended knitted fabric.
2. The preparation method of the antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric according to claim 1, characterized by comprising the following steps: the bath ratio of the blended knitted fabric to the laccase/TEMPO reaction liquid in the step (1) is set to be 1: 40-60 (w/v).
3. The preparation method of the antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric according to claim 1, characterized by comprising the following steps: in the step (2), the deacetylation degree of the nano carboxyl chitosan is more than or equal to 92.8%, the content of carboxyl at the C6 site is 42.70-56.43%, the particle size range is 85-228 nm, the particle size dispersion index is 0.108-0.314, and the Zeta potential is 30.59-42.86 mV.
4. The preparation method of the antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric according to claim 1, characterized by comprising the following steps: the natural mildew preventive in the step (3) is prepared from curcumin and one of cassia oil, thujoram oil, artemisinin and tea polyphenol in a mass ratio of 7: 3-9: 1.
5. The preparation method of the antibacterial and mildewproof cashmere/cellulose fiber blended knitted fabric according to claim 1, characterized by comprising the following steps: the cellulose fiber in the cashmere/cellulose fiber blended knitted fabric is cotton fiber, bamboo pulp fiber, viscose fiber, Tencel fiber and Modal fiber.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116289179A (en) * | 2023-04-04 | 2023-06-23 | 和也健康科技有限公司 | A kind of preparation method of functional fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116289179A (en) * | 2023-04-04 | 2023-06-23 | 和也健康科技有限公司 | A kind of preparation method of functional fiber |
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Application publication date: 20220208 |