CN114182522A - Antibacterial, antiviral and mildewproof finishing liquid and application thereof, antibacterial, antiviral and mildewproof cellulose fiber and preparation method and application thereof - Google Patents

Antibacterial, antiviral and mildewproof finishing liquid and application thereof, antibacterial, antiviral and mildewproof cellulose fiber and preparation method and application thereof Download PDF

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CN114182522A
CN114182522A CN202010973663.7A CN202010973663A CN114182522A CN 114182522 A CN114182522 A CN 114182522A CN 202010973663 A CN202010973663 A CN 202010973663A CN 114182522 A CN114182522 A CN 114182522A
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antibacterial
antiviral
mildewproof
cellulose fiber
finishing liquid
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CN114182522B (en
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赵健
李昌垒
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Qingdao Nihimi Biotechnology Co ltd
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Qingdao Nihimi Biotechnology Co ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06Inorganic compounds or elements
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08Organic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08Organic compounds
    • D06M10/10Macromolecular compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention belongs to the technical field of antibacterial, antiviral and mildewproof finishing liquid, and particularly relates to antibacterial, antiviral and mildewproof finishing liquid and application thereof, and antibacterial, antiviral and mildewproof cellulose fiber and a preparation method and application thereof. The antibacterial, antiviral and mildewproof finishing liquid provided by the invention comprises an antibacterial, antiviral and mildewproof agent, a penetrating agent and water; the antibacterial, antiviral and mildewproof agent comprises organic zinc; the concentration of the antibacterial and antiviral mildew preventive in the antibacterial and antiviral mildew preventive finishing liquid is 30-100 g/L; the concentration of the penetrant in the finishing liquid of the antibacterial, antiviral and mildewproof agent is 2-10 g/L. The antibacterial, antiviral and mildewproof finishing liquid provided by the invention can better enable the antibacterial, antiviral and mildewproof agent to penetrate into the cellulose fiber, and the content of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof cellulose fiber is increased, so that the durability of the antibacterial, antiviral and mildewproof performance of the antibacterial, antiviral and mildewproof finishing liquid is improved.

Description

Antibacterial, antiviral and mildewproof finishing liquid and application thereof, antibacterial, antiviral and mildewproof cellulose fiber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of antibacterial, antiviral and mildewproof finishing liquid, and particularly relates to antibacterial, antiviral and mildewproof finishing liquid and application thereof, and antibacterial, antiviral and mildewproof cellulose fiber and a preparation method and application thereof.
Background
The cellulose fiber has the advantages of air permeability, skin friendliness, wearing comfort, good moisture absorption and the like, and is widely applied to the clothing and household industries, particularly as underwear, socks or bed sheets. But provides a suitable growth environment for the growth of bacteria, viruses and molds due to the high hygroscopicity of cellulose fibers and human metabolites and sloughs attached to the surface of cellulose fibers. These bacteria and viruses pose a threat to human health; meanwhile, the existence of the mould can cause the phenomena of mildew, odor emission, color change, coloring and the like of the fabric. It becomes particularly important to impart antimicrobial, antiviral and mold-resistant functionality to cellulosic fiber fabrics.
The antibacterial, antiviral and antifungal fiber is prepared by applying antibacterial agent, antifungal agent, etc. onto the surface and/or inside of fiber to release functional substance for antibacterial, antiviral and antifungal effects. Zinc is one of the essential trace elements for human life, and is called "flower of life" or "source of intelligence". Zinc has important functions on growth and development, immunologic function, material metabolism, reproductive function and the like, zinc element can accelerate the division and growth of epidermal cells, accelerate the formation of new granulation tissue of wounds and shorten the healing time of the wounds, and meanwhile zinc also has the functions of protecting skin health, resisting bacteria and viruses and preventing mildew, so that the susceptibility to infection is reduced, and the zinc has the important function of stabilizing cell membranes or organism membranes. Therefore, the zinc material is used as the antibacterial mildew preventive, and the fibers are ensured to have antibacterial, antiviral and mildew-proof properties without harming human bodies.
Chinese patent application No. 201810795002.2 discloses a preparation method of an environment-friendly antibacterial cellulose fiber, and the antibacterial agent in the patent is nano zinc oxide. The nano powder is difficult to disperse, so that the zinc oxide is not beneficial to uniformly dispersing in the cellulose fiber, and meanwhile, the patent does not protect the antibacterial agent, so that the antibacterial agent in the cellulose fiber is easy to run off, and the durability of the antibacterial performance of the cellulose fiber is influenced.
Chinese patent application No. 201811330617.4 discloses a method for preparing a durable antibacterial cellulose fiber. The patent adopts inorganic micromolecular antibacterial agents comprising zinc chloride, zinc sulfate, zinc hydroxide and zinc carbonate, and the antibacterial agent in the patent contains insoluble zinc hydroxide and zinc carbonate and is not easy to permeate into fibers in the subsequent application process to influence the antibacterial property. Most importantly, the antibacterial agent in the patent is small molecule and is easy to run off, and the problem of functional persistence is to be examined.
Disclosure of Invention
In order to solve the technical problems, the invention provides the antibacterial, antiviral and mildewproof finishing liquid which can enable the antibacterial, antiviral and mildewproof agent to better penetrate into cellulose fibers, and improve the content of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof cellulose fibers, so that the durability of the antibacterial, antiviral and mildewproof performance of the antibacterial, antiviral and mildewproof finishing liquid is improved.
The invention provides an antibacterial, antiviral and mildewproof finishing liquid, which comprises an antibacterial, antiviral and mildewproof agent, a penetrating agent and water;
the antibacterial, antiviral and mildewproof agent comprises organic zinc;
the concentration of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof finishing liquid is 30-100 g/L;
the concentration of the penetrant in the antibacterial, antiviral and mildewproof finishing liquid is 2-10 g/L.
Preferably, the organic zinc comprises one or more of zinc gluconate, zinc citrate, zinc lactate and zinc amino acid;
the penetrant comprises one or more of fatty alcohol-polyoxyethylene ether, sodium di-sec-octyl maleate sulfonate, isooctyl alcohol polyoxyethylene ether phosphate sodium and alkali-resistant penetrant AEP.
The invention also provides application of the antibacterial, antiviral and mildewproof finishing liquid in the technical scheme in preparation of antibacterial, antiviral and mildewproof cellulose fibers.
The invention also provides a preparation method of the antibacterial, antiviral and mildewproof cellulose fiber, which comprises the following steps:
activating the cellulose fibers to obtain activated cellulose fibers;
soaking the activated cellulose fiber in an antibacterial, antiviral and mildewproof finishing liquid to perform antibacterial, antiviral and mildewproof finishing to obtain a primary antibacterial, antiviral and mildewproof cellulose fiber;
sequentially irradiating and microwave drying the primary antibacterial antiviral mildew-proof cellulose fiber to obtain the antibacterial antiviral mildew-proof cellulose fiber;
the antibacterial, antiviral and mildewproof finishing liquid is the antibacterial, antiviral and mildewproof finishing liquid in the technical scheme.
Preferably, the activation treatment is carried out in an aqueous solution of ethylenediamine;
the mass percentage of ethylenediamine in the ethylenediamine aqueous solution is 50-70%, and the mass ratio of the cellulose fibers to the ethylenediamine aqueous solution is 1: 5-10;
the activation treatment is carried out under the condition of first ultrasound, and the ultrasonic frequency of the first ultrasound is 2 x 105~2×109Hz, the temperature is 20-50 ℃, and the time is 3-6 h.
Preferably, the mass ratio of the activated cellulose fibers to the antibacterial, antiviral and mildewproof finishing liquid is 1: 10-20;
the antibacterial, antiviral and mildewproof finishing is carried out under the condition of second ultrasound, and the ultrasonic frequency of the second ultrasound is 2 multiplied by 105~2×109Hz, the temperature is 40-70 ℃, and the time is 60-180 min.
Preferably, the irradiation is electron beam irradiation;
the electron beam irradiation intensity is 35-80 kGy, and the time is 60-150 s.
The invention also provides the antibacterial, antiviral and mildewproof cellulose fiber prepared by the preparation method of the technical scheme, which comprises cellulose fiber and organic zinc; the cellulose fiber is grafted and crosslinked with organic zinc.
Preferably, the mass ratio of the zinc element in the organic zinc to the cellulose fiber is 725-1986 mg:1 kg.
The invention also provides application of the antibacterial, antiviral and mildewproof cellulose fiber in the technical scheme in textiles.
The antibacterial, antiviral and mildewproof finishing liquid provided by the invention comprises an antibacterial, antiviral and mildewproof agent, a penetrating agent and water; the antibacterial, antiviral and mildewproof agent comprises organic zinc; the concentration of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof finishing liquid is 30-100 g/L; the concentration of the penetrant in the antibacterial, antiviral and mildewproof finishing liquid is 2-10 g/L. The antibacterial, antiviral and mildewproof finishing liquid provided by the invention can better enable the antibacterial, antiviral and mildewproof agent to penetrate into the cellulose fiber, and the content of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof cellulose fiber is increased, so that the durability of the antibacterial, antiviral and mildewproof performance of the antibacterial, antiviral and mildewproof finishing liquid is improved.
The invention also provides a preparation method of the antibacterial, antiviral and mildewproof cellulose fiber, which comprises the following steps: activating the cellulose fibers to obtain activated cellulose fibers; soaking the activated cellulose fiber in an antibacterial, antiviral and mildewproof finishing liquid to perform antibacterial, antiviral and mildewproof finishing to obtain a primary antibacterial, antiviral and mildewproof cellulose fiber; sequentially irradiating and microwave drying the primary antibacterial antiviral mildew-proof cellulose fiber to obtain the antibacterial antiviral mildew-proof cellulose fiber; the antibacterial, antiviral and mildewproof finishing liquid is the antibacterial, antiviral and mildewproof finishing liquid in the technical scheme. The invention reduces the crystallinity and regularity of the surface of the cellulose fiber through activation treatment, improves the loading capacity of the antibacterial, antiviral and mildewproof agent in the cellulose fiber, and further improves the durability of the antibacterial, antiviral and mildewproof function of the antibacterial, antiviral and mildewproof cellulose fiber; meanwhile, organic zinc and cellulose fibers are subjected to graft crosslinking through irradiation, so that the stability of the antibacterial, antiviral and mildewproof agent in the cellulose fibers is improved, and the durability of the antibacterial, antiviral and mildewproof functions of the antibacterial, antiviral and mildewproof cellulose fibers is further improved.
The invention also provides an antibacterial, antiviral and mildewproof cellulose fiber, which comprises cellulose fiber and organic zinc; the cellulose fiber is grafted and crosslinked with organic zinc. According to the invention, the organic zinc is used as the antibacterial, antiviral and mildewproof agent, and the organic zinc and the cellulose fiber are grafted and crosslinked, so that the stability of the organic zinc on the surface of the cellulose fiber is improved, and the durability of the antibacterial, antiviral and mildewproof properties of the antibacterial, antiviral and mildewproof cellulose fiber is improved. The antibacterial, antiviral and mildewproof cellulose fiber provided by the invention has good antibacterial, antiviral and mildewproof performances, and the results of the embodiment show that the antibacterial activity value of the antibacterial, antiviral and mildewproof cellulose fiber provided by the invention is 2.3-3.9, the bactericidal activity value is 0.2-0.9, the antiviral activity value on influenza A virus is 3.0-4.1, the antiviral activity value on influenza B virus is 2.8-3.9, and the mildewproof grade can reach more than 1 grade.
Detailed Description
The invention provides an antibacterial, antiviral and mildewproof finishing liquid, which comprises an antibacterial, antiviral and mildewproof agent, a penetrating agent and water;
the antibacterial, antiviral and mildewproof agent comprises organic zinc;
the concentration of the antibacterial and antiviral mildew preventive in the antibacterial and antiviral mildew preventive finishing liquid is 30-100 g/L;
the concentration of the penetrant in the finishing liquid of the antibacterial, antiviral and mildewproof agent is 2-10 g/L.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the antibacterial, antiviral, and antifungal agent includes organic zinc; the organic zinc preferably comprises one or more of zinc gluconate, zinc citrate, zinc lactate and zinc amino acid; when the organic zinc comprises more than two specific substances, the proportion of the specific substances is not particularly limited, and any proportion can be adopted. In the invention, the concentration of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof finishing liquid is 30-100 g/L, and preferably 55-83 g/L. The antibacterial, antiviral and mildewproof performance of the organic zinc antibacterial, antiviral and mildewproof agent provided by the invention does not depend on the illumination condition, and the organic zinc antibacterial, antiviral and mildewproof agent can play a role in resisting bacteria, viruses and mildews under the condition of no light.
In the present invention, the antibacterial, antiviral, and antifungal agent includes a penetrant; the penetrating agent preferably comprises one or more of fatty alcohol-polyoxyethylene ether (JFC), di-sec-octyl maleate sodium sulfonate (rapid penetrating agent T), isooctanol polyoxyethylene ether sodium phosphate (alkali-resistant penetrating agent OEP-70) and alkali-resistant penetrating agent AEP; when the penetrating agent is more than two of the specific substances, the proportion of the specific substances is not particularly limited, and any proportion can be adopted. In the embodiment of the invention, the penetrant is specifically fatty alcohol-polyoxyethylene ether (JFC), sodium di-sec-octyl maleate sulfonate (rapid penetrant T), sodium isooctanol polyoxyethylene ether phosphate (alkali-resistant penetrant OEP-70), or alkali-resistant penetrant AEP. In the invention, the concentration of the penetrant in the antibacterial, antiviral and mildewproof finishing liquid is 2-10 g/L, and preferably 4.9-7.5 g/L.
In the invention, the penetrant improves the permeability of the organic zinc, increases the content of the organic zinc in the antibacterial, antiviral and mildewproof cellulose fiber, and improves the durability of the antibacterial, antiviral and mildewproof performance.
In the present invention, the water is preferably deionized water.
In the invention, the antibacterial, antiviral and mildewproof finishing liquid is preferably prepared according to the following steps:
and mixing the antibacterial, antiviral and mildewproof agent, the penetrating agent and water to obtain the antibacterial, antiviral and mildewproof finishing liquid.
The mixing mode is not particularly limited as long as the uniform mixing can be achieved, and in the embodiment of the invention, the mixing is performed under the condition of stirring, the rotating speed of the stirring is preferably 500-1500 r/min, more preferably 755-950 r/min, and the time is preferably 10-30 min, more preferably 18-20 min.
The invention also provides application of the antibacterial, antiviral and mildewproof finishing liquid in the technical scheme in preparation of antibacterial, antiviral and mildewproof cellulose fibers.
The invention also provides a preparation method of the antibacterial, antiviral and mildewproof cellulose fiber, which comprises the following steps:
activating the cellulose fibers to obtain activated cellulose fibers;
soaking the activated cellulose fiber in an antibacterial, antiviral and mildewproof finishing liquid to perform antibacterial, antiviral and mildewproof finishing to obtain a primary antibacterial, antiviral and mildewproof cellulose fiber;
sequentially irradiating and microwave drying the primary antibacterial antiviral mildew-proof cellulose fiber to obtain the antibacterial antiviral mildew-proof cellulose fiber;
the antibacterial, antiviral and mildewproof finishing liquid is the antibacterial, antiviral and mildewproof finishing liquid in the technical scheme.
The invention carries out activation treatment on cellulose fiber to obtain the activated cellulose fiber. In the present invention, the cellulose fibers preferably comprise one or more of cotton fibers, viscose fibers, modal fibers and lyocell fibers; when the cellulose fiber comprises more than two specific fibers, the proportion of the fibers is not particularly limited, and any proportion can be adopted. In an embodiment of the invention, the cellulose fibres are in particular cotton fibres, viscose fibres, modal fibres or lyocell fibres.
According to the invention, the cellulose fiber is preferably pretreated before being subjected to the activation treatment, and the pretreatment preferably comprises impurity removal, third ultrasonic treatment and first dehydration which are sequentially carried out. In the present invention, the impurity removal can remove impurities and fiber bundles in the cellulose fibers. The invention has no special limitation on the mode of impurity removal, and can be realized by adopting a conventional mode in the field. In the embodiment of the invention, the opening and picking combination machine is specifically adopted for removing impurities. In the invention, the third ultrasonic treatment is preferably carried out in a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is preferably 30-90 g/L, and more preferably 45-73 g/L. In the invention, the mass ratio of the cellulose fiber after impurity removal to the sodium hydroxide solution is preferably 1: 5-15, and more preferably 1: 8-12. In the present invention, the ultrasonic frequency of the third ultrasonic is preferably 2 × 105~2×109Hz, more preferably 2X 106~2×108Hz; the temperature of the third ultrasonic is preferably 20-50 ℃, and more preferably 35-41 ℃; the time of the third ultrasonic is preferably 25-60 min, and more preferably 36-49 min. In the invention, the first dewatering is preferably carried out under the condition of first centrifugation, and the rotating speed of the first centrifugation is preferably 700-2000 r/min, and more preferably 1225-1675 r/min. In the present invention, the moisture content of the cellulose fiber after the first dehydration is preferably 60 to 90%, more preferably 72 to 81%. In the present invention, the time for the first centrifugation is not particularly limited as long as the cellulose fibers after the first centrifugation can have the desired moisture content.
According to the invention, the cellulose fiber is pretreated, impurities in the cellulose fiber are removed, grease adsorbed on the surface of the cellulose fiber is stripped, the cleanliness of the cellulose fiber is improved, and the subsequent processes are facilitated.
In the invention, the activation treatment is preferably performed in an ethylenediamine aqueous solution, and the mass percentage of ethylenediamine in the ethylenediamine aqueous solution is preferably 50-70%, and more preferably 56-63%.
In the present invention, the mass ratio of the cellulose fibers to the ethylenediamine aqueous solution is preferably 1:5 to 10, and more preferably 1:6 to 8. In the present invention, the activation treatment is preferably performed under the condition of first ultrasound, and the ultrasonic frequency of the first ultrasound is preferably 2 × 105~2×109Hz, more preferably 2X 106~2×108Hz; the temperature of the activation treatment is preferably 20-50 ℃, and more preferably 31-44 ℃; the time is preferably 3.0 to 6.0 hours, and more preferably 4.5 to 5.1 hours.
In the invention, the ethylenediamine aqueous solution can make the cellulose fiber generate microcrystalline internal swelling to generate strong decrystallization, reduce the crystallinity and regularity of the surface of the cellulose fiber, improve the accessibility of organic zinc, facilitate the diffusion of the organic zinc in the cellulose fiber, and improve the content of the effective antibacterial, antiviral and mildewproof ingredients in the antibacterial, antiviral and mildewproof cellulose fiber, thereby improving the durability of the antibacterial, antiviral and mildewproof performance of the antibacterial, antiviral and mildewproof cellulose fiber. Meanwhile, the ethylenediamine aqueous solution in the invention can not reduce the polymerization degree of the activated cellulose fiber, namely, the mechanical property of the activated cellulose fiber can not be influenced.
After the activation treatment, the present invention preferably subjects the obtained activated product to a second dehydration to obtain activated cellulose fibers. In the invention, the second dewatering is preferably carried out under the condition of second centrifugation, and the rotation speed of the second centrifugation is preferably 700-2000 r/min, and more preferably 1150-1680 r/min. In the present invention, the moisture content of the cellulose fiber after the second dehydration is preferably 60 to 90%, more preferably 69 to 78%. In the present invention, the time for the second centrifugation is not particularly limited as long as the cellulose fibers after the second centrifugation can have a desired moisture content.
After the activated cellulose fiber is obtained, the activated cellulose fiber is soaked in the antibacterial, antiviral and mildewproof finishing liquid for antibacterial, antiviral and mildewproof finishing to obtain the primary antibacterial, antiviral and mildewproof cellulose fiber. In the invention, the antibacterial, antiviral and mildewproof finishing liquid is the antibacterial, antiviral and mildewproof finishing liquid in the technical scheme; the mass ratio of the activated cellulose fibers to the antibacterial, antiviral and mildewproof finishing liquid is preferably 1: 10-20, and more preferably 1: 13-16. In the invention, the antibacterial, antiviral and mildewproof finishing is preferably carried out under the condition of second ultrasound, and the ultrasonic frequency of the second ultrasound is preferably 2 x 105~2×109Hz, more preferably 2X 107~2×108Hz; the temperature of the second ultrasonic is preferably 40-70 ℃, and more preferably 55-61 ℃; the second ultrasonic treatment time is preferably 60-180 min, and more preferably 105-151 min.
After the antibacterial, antiviral and mildewproof finishing, the obtained finishing product is preferably subjected to third dehydration to obtain the primary antibacterial, antiviral and mildewproof cellulose fiber. In the invention, the third dehydration is preferably high-pressure dehydration, and the pressure of the high-pressure dehydration is preferably 50-80 MPa, and more preferably 61-72 MPa. In the present invention, the moisture content of the cellulose fiber after the high-pressure dewatering is preferably 60 to 95%, more preferably 70 to 86%, and still more preferably 78%. The device for high-pressure dehydration is not particularly limited, and the device can be a conventional device in the field, and in the embodiment of the invention, a high-pressure padder is particularly adopted for high-pressure dehydration. The time for high-pressure dehydration is not particularly limited in the present invention, as long as the above-mentioned water content can be achieved.
After the primary antibacterial antiviral mildew-proof cellulose fiber is obtained, the invention sequentially performs irradiation and microwave drying on the primary antibacterial antiviral mildew-proof cellulose fiber to obtain the antibacterial antiviral mildew-proof cellulose fiber. The invention also preferably comprises wet opening and pre-drying in sequence before irradiation. The wet opening is not particularly limited in the present invention, and a process well known in the art may be used. In the invention, the pre-drying temperature is preferably 80-120 ℃, more preferably 96-108 ℃, and the time is preferably 40-60 min, more preferably 25-45 min. In the present invention, the moisture content of the cellulose fiber after the pre-drying is preferably 7.2 to 10%, and more preferably 7.6 to 8.8%.
In the invention, the irradiation is preferably electron beam irradiation, and the intensity of the electron beam irradiation is preferably 35-80 kGy, and more preferably 56-63 kGy; the time of the electron beam irradiation is preferably 60-150 s, and more preferably 96-125 s.
In the invention, the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof finishing liquid and the cellulose fiber are subjected to graft crosslinking under the irradiation condition, so that the stability of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof cellulose fiber is improved, and the durability of the antibacterial, antiviral and mildewproof is further improved.
In the present invention, it is preferable that the irradiation is further followed by oil spraying, and the oil for oil spraying is preferably a softener, and the softener preferably comprises one or more of spindle oil, sorbitan palmitate (Span40) and silicone softener. In the present invention, the silicone softener preferably comprises Magnasoft68 available from Momentive or RRJ-214 available from tungada chemical engineering ltd, guangzhou. When the softening agent comprises more than two specific substances, the ratio of the substances is not particularly limited, and any ratio can be adopted. In the invention, the oil agent is preferably diluted before the oil agent is sprayed, and the concentration of the oil agent in the solution obtained after dilution is preferably 4.0-9.0 g/L, and more preferably 5.5-7.3 g/L. In the invention, the diluted oil is preferably uniformly sprayed on the surface of the cellulose fiber, and in the invention, the content (oil content) of the oil in the antibacterial, antiviral and mildewproof cellulose fiber is preferably 0.23-0.45%, and more preferably 0.32-0.38%. The invention preferably continuously stirs the cellulose fiber when the oil agent is sprayed to ensure that the oil agent is uniformly sprayed on the surface of the cellulose fiber, so that the prepared antibacterial, antiviral and mildewproof cellulose fiber has smooth and soft hand feeling.
In the invention, the frequency of the microwave for microwave drying is preferably 915-2450 MHz, and more preferably 1560-1950 MHz. In the invention, the microwave drying time is preferably 20-40 min, and more preferably 29-36 min. In the present invention, the moisture content of the cellulose fiber after microwave drying is preferably 9.0% or less, more preferably 7.0 to 8.2%, and further preferably 7.8%.
In the invention, the microwave for microwave drying has stronger penetrating power and is easy to penetrate through the crystalline region of the cellulose fiber, so that the structure of the crystalline region of the cellulose fiber is damaged, thereby being beneficial to the diffusion of the antibacterial, antiviral and mildewproof agent in the cellulose fiber, leading the antibacterial, antiviral and mildewproof agent to be capable of penetrating into the antibacterial, antiviral and mildewproof cellulose fiber, reducing the loss of the antibacterial, antiviral and mildewproof agent and improving the durability of the antibacterial, antiviral and mildewproof performance of the antibacterial, antiviral and mildewproof cellulose fiber.
In the invention, the microwave drying process preferably further comprises dry opening cotton, and the dry opening cotton is not particularly limited in the invention and can be prepared by adopting conventional technical means in the field.
After the antibacterial, antiviral and mildewproof cellulose fiber is obtained, the antibacterial, antiviral and mildewproof cellulose fiber is preferably packaged for later use.
The invention also provides the antibacterial, antiviral and mildewproof cellulose fiber prepared by the preparation method of the technical scheme, which comprises cellulose fiber and organic zinc; the cellulose fiber is grafted and crosslinked with organic zinc.
In the invention, the mass ratio of the zinc element in the organic zinc to the cellulose fiber is preferably 725-1986 mg:1kg, and more preferably 1355-1760 mg:1 kg.
In the invention, the cellulose fiber and the organic zinc are grafted and crosslinked, so that the stability of the organic zinc in the antibacterial, antiviral and mildewproof cellulose fiber is improved, and the antibacterial, antiviral and mildewproof cellulose fiber has lasting antibacterial, antiviral and mildewproof properties.
The invention also provides application of the antibacterial, antiviral and mildewproof cellulose fiber prepared by the technical scheme or the preparation method in the technical scheme in textiles.
The antibacterial, antiviral and mildewproof cellulose fiber provided by the invention is processed into textiles, and has lasting antibacterial, antiviral and mildewproof properties; the textile preferably comprises clothing, ornaments, bedding and the like.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
The embodiment of the invention has no limitation on the grade of the dosage of each raw material, and the raw materials can be prepared by adopting any weight grade as long as the raw materials are mixed according to a specific ratio.
Example 1
Removing impurities from cotton fiber with a combined opening and picking machine, soaking the cotton fiber in sodium hydroxide solution with concentration of 90g/L and temperature of 50 deg.C, and treating with ultrasonic wave at frequency of 2 × 105Carrying out ultrasonic treatment for 60min under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 700r/min to obtain pretreated cotton fibers with the water content of 90%; wherein the mass ratio of the cotton fiber after impurity removal to the sodium hydroxide solution is 1: 5;
soaking the pretreated cotton fiber in an ethylenediamine aqueous solution with the mass percentage of 50% and the temperature of 20 ℃, and performing ultrasonic treatment at the frequency of 2 multiplied by 105Carrying out activation treatment for 6 hours under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 2000r/min to obtain activated cotton fibers with the water content of 60%; wherein the mass ratio of the pretreated cotton fibers to the ethylene diamine aqueous solution is 1: 10;
stirring zinc gluconate, JFC and deionized water at the rotating speed of 1500r/min for 10min to obtain an antibacterial and antiviral finishing liquid with the concentration of 30g/L, JFC and the concentration of 2 g/L;
soaking the activated cotton fiber in an antibacterial, antiviral and mildewproof finishing liquid at the temperature of 40 ℃ under the ultrasonic frequency of 2 multiplied by 105Carrying out 180min antibacterial antiviral mildew-proof finishing under the condition of Hz, and then carrying out high-pressure (50MPa) dehydration in a high-pressure padder to obtain primary antibacterial antiviral mildew-proof cellulose fibers with the water content of 95%; wherein the mass ratio of the activated cotton fiber to the antibacterial, antiviral and mildewproof finishing liquid is1:20;
The primary antibacterial, antiviral and mildewproof cellulose fiber is subjected to wet opening, pre-drying (the temperature is 80 ℃, the time is 60min, the water content of the fiber is 10%), electron beam irradiation (the irradiation intensity is 35kGy, the time is 150s), oil agent spraying (the oil agent is a diluted solution of Magnasoft68 of 4 g/LMmentive company, the cellulose fiber is stirred while being sprayed), microwave drying (the microwave frequency is 915MHz, the time is 40min, the water content of the fiber is 9%), dry opening, the oil content is 0.23%, and finally packaging is carried out to obtain the antibacterial, antiviral and mildewproof cotton fiber.
Example 2
Removing impurities from cotton fiber with a combined opening and picking machine, soaking the viscose fiber in sodium hydroxide solution with concentration of 73g/L and temperature of 41 deg.C, and treating with ultrasonic wave at frequency of 2 × 106Carrying out ultrasonic treatment for 49min under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 1225r/min to obtain the pretreated viscose fiber with the water content of 81 percent; wherein the mass ratio of the viscose fiber after impurity removal to the sodium hydroxide solution is 1: 8;
soaking the pretreated viscose fiber in an ethylenediamine aqueous solution with the mass percentage of 56% and the temperature of 31 ℃, and performing ultrasonic treatment at the frequency of 2 multiplied by 107Carrying out activation treatment for 5.1h under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 1680r/min to obtain activated viscose fibers with the water content of 69%; wherein the mass ratio of the pretreated viscose fibers to the ethylene diamine aqueous solution is 1: 8;
stirring zinc citrate, a rapid penetrant T and deionized water at a rotating speed of 950r/min for 18min to obtain an antibacterial and antiviral finishing liquid with the concentration of the zinc citrate of 55g/L and the concentration of the rapid penetrant T of 4.9 g/L;
soaking the activated viscose fiber in 55 deg.C antibacterial antiviral antimildew finishing liquid at ultrasonic frequency of 2 × 107Performing 151min antibacterial antiviral mildew-proof finishing under the condition of Hz, and then performing high-pressure (61MPa) dehydration in a high-pressure padder to obtain primary antibacterial antiviral mildew-proof cellulose fibers with the water content of 86%; wherein the mass ratio of the activated viscose fiber to the antibacterial, antiviral and mildewproof finishing liquid is 1: 16;
the primary antibacterial, antiviral and mildewproof cellulose fiber is subjected to wet opening, pre-drying (the temperature is 96 ℃, the time is 52min, the water content of the fiber is 8.8%), electron beam irradiation (the irradiation intensity is 56kGy, the time is 125s), oil agent spraying (oil agent is a diluted solution of 5.5g/L sorbitol palmitate (Span40), the cellulose fiber is stirred while spraying), microwave drying (the microwave frequency is 1560MHz, the time is 36min, the water content of the fiber is 8.2%), dry opening is carried out, the oil content is 0.32%, and finally packaging is carried out to obtain the antibacterial, antiviral and mildewproof viscose fiber.
Example 3
Removing impurities from cotton fiber with a combined cotton opening and picking machine, soaking the purified modal fiber in sodium hydroxide solution with concentration of 45g/L and temperature of 35 deg.C, and treating with ultrasonic frequency of 2 × 108Carrying out ultrasonic treatment for 36min under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 1675r/min to obtain pretreated modal fibers with the water content of 72%; wherein the mass ratio of the modal fiber after impurity removal to the sodium hydroxide solution is 1: 12;
soaking the pretreated modal fiber in an ethylenediamine aqueous solution with the mass percentage of 63% and the temperature of 44 ℃, and performing ultrasonic treatment at the ultrasonic frequency of 2 multiplied by 108Carrying out activation treatment for 4.5h under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 1150r/min to obtain activated modal fibers with the water content of 78%; wherein the mass ratio of the pretreated modal fiber to the ethylenediamine aqueous solution is 1: 6;
stirring zinc lactate, an alkali-resistant penetrant OEP-70 and deionized water at the rotating speed of 755r/min for 20min to obtain an antibacterial and antiviral finishing liquid with the zinc lactate concentration of 83g/L and the alkali-resistant penetrant OEP-70 concentration of 7.5 g/L;
soaking the activated modal fiber in an antibacterial, antiviral and mildewproof finishing liquid with the temperature of 61 ℃ and the ultrasonic frequency of 2 multiplied by 108Carrying out 105-min antibacterial antiviral mildew-proof finishing under the condition of Hz, and then carrying out high-pressure (72MPa) dehydration in a high-pressure padder to obtain primary antibacterial antiviral mildew-proof cellulose fibers with the water content of 78%; wherein the mass ratio of the activated modal fiber to the antibacterial, antiviral and mildewproof finishing liquid is 1: 13;
the primary antibacterial, antiviral and mildewproof cellulose fiber is subjected to wet opening, pre-drying (the temperature is 108 ℃, the time is 45min, the water content of the fiber is 7.6%), electron beam irradiation (the irradiation intensity is 63kGy, the time is 96s), oil agent spraying (the oil agent is a diluted solution of 7.3g/L spindle oil, the cellulose fiber is stirred while spraying), microwave drying (the microwave frequency is 1950MHz, the time is 29min, the water content of the fiber is 7.8%), dry opening and the oil content is 0.38%, and finally packaging is carried out to obtain the antibacterial, antiviral and mildewproof modal fiber.
Example 4
Removing impurities from cotton fiber with a combined cotton opening and picking machine, soaking the removed lyocell fiber in sodium hydroxide solution with concentration of 30g/L and temperature of 20 deg.C, and treating with ultrasonic frequency of 2 × 109Carrying out ultrasonic treatment for 25min under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 2000r/min to obtain pretreated lyocell fiber with the water content of 60%; wherein the mass ratio of the lyocell fiber after impurity removal to the sodium hydroxide solution is 1: 15;
soaking the pretreated lyocell fiber in 70 wt% of ethylenediamine aqueous solution at 50 deg.C, and treating with ultrasonic wave at frequency of 2 × 109Carrying out activation treatment for 3 hours under the condition of Hz, and then carrying out centrifugal dehydration at the rotating speed of 700r/min to obtain activated lyocell fibers with the water content of 90%; wherein the mass ratio of the pretreated lyocell fiber to the ethylenediamine aqueous solution is 1: 5;
stirring amino acid zinc, an alkali-resistant penetrant AEP and deionized water at the rotating speed of 500r/min for 30min to obtain an antibacterial and antiviral finishing liquid with the amino acid zinc concentration of 83g/L and the alkali-resistant penetrant AEP concentration of 10 g/L;
soaking the activated lyocell fiber in an antibacterial, antiviral and mildewproof finishing liquid at the temperature of 70 ℃ under the ultrasonic frequency of 2 multiplied by 109Carrying out 60min antibacterial antiviral mildew-proof finishing under the condition of Hz, and then carrying out high-pressure (80MPa) dehydration in a high-pressure padder to obtain primary antibacterial antiviral mildew-proof cellulose fibers with the water content of 70%; wherein the mass ratio of the activated lyocell fiber to the antibacterial, antiviral and mildewproof finishing liquid is 1: 10;
the primary antibacterial, antiviral and mildewproof cellulose fiber is subjected to wet opening, pre-drying (the temperature is 120 ℃, the time is 40min, the water content of the fiber is 7.2%), electron beam irradiation (the irradiation intensity is 80kGy, and the time is 60s), oil agent spraying (9 g/L of a diluted solution of RRJ-214 of Guangzhou Tongda chemical engineering Limited company, the cellulose fiber is stirred while being sprayed), microwave drying (the microwave frequency is 2450MHz, the time is 20min, the water content of the fiber is 7.0%), dry opening is carried out, the oil content is 0.45%, and finally packaging is carried out to obtain the antibacterial, antiviral and mildewproof lyocell fiber.
Test example
According to JISL 1902: 2008 antibacterial effect of textile antibacterial performance test method, the antibacterial activity value and the bactericidal activity value of the antibacterial, antiviral and mildewproof cellulose fiber prepared in examples 1 to 4 are detected, and the results are listed in table 1.
The antiviral activity values of the antibacterial, antiviral and mildewproof cellulose fibers prepared in the examples 1 to 4 on influenza A virus and influenza B virus are detected according to ISO198184:2014 'antiviral test method for textile products', and the results are listed in Table 1.
According to the invention, the mildew-proof effect of the antibacterial, antiviral and mildew-proof cellulose fibers prepared in the embodiments 1 to 4 on aspergillus niger and chaetomium globosum is detected by a culture dish method in GB/T24346-2009 'evaluation of textile mildew-proof performance', and the results are listed in Table 1.
TABLE 1 antibacterial, antiviral and antifungal Properties of antibacterial and antiviral cellulose fibers prepared in examples 1 to 4
Figure BDA0002684988910000131
The data in table 1 show that the antibacterial, antiviral and mildewproof cellulose fiber provided by the invention has higher bacteriostatic activity value and bactericidal activity value, has higher antiviral activity values for influenza a virus and influenza b virus, has mildewproof effect reaching 0 level above level 1, and has better antibacterial, antiviral and mildewproof performance.
The antibacterial and antiviral cellulose fibers prepared in examples 1 to 4 were washed 50 times according to standard FZ/T73023-2006 appendix c4. simplified washing conditions and washing methods in the procedure, and then according to JISL 1902: 2008 and ISO198184:2014, the antibacterial, antiviral and antifungal performances of the antibacterial, antiviral and antifungal cellulose fiber after 50 times of washing are tested, and the results are listed in Table 2.
Table 2 antibacterial, antiviral, and antifungal cellulose fibers prepared in examples 1 to 4 were washed with water 50 times and then subjected to antibacterial and antiviral properties
Figure BDA0002684988910000141
As can be seen from table 2, the antibacterial, antiviral and antifungal cellulose fiber provided by the present invention still has high antibacterial, antiviral and antifungal properties after being washed for 50 times, which proves that the antibacterial, antiviral and antifungal cellulose fiber provided by the present invention has lasting antibacterial, antiviral and antifungal properties.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (10)

1. An antibacterial, antiviral and mildewproof finishing liquid comprises an antibacterial, antiviral and mildewproof agent, a penetrating agent and water; the antibacterial, antiviral and mildewproof agent comprises organic zinc;
the concentration of the antibacterial, antiviral and mildewproof agent in the antibacterial, antiviral and mildewproof finishing liquid is 30-100 g/L;
the concentration of the penetrant in the antibacterial, antiviral and mildewproof finishing liquid is 2-10 g/L.
2. The antibacterial, antiviral, mildewproof finishing liquid according to claim 1, wherein the organic zinc comprises one or more of zinc gluconate, zinc citrate, zinc lactate and zinc amino acid;
the penetrant comprises one or more of fatty alcohol-polyoxyethylene ether, sodium di-sec-octyl maleate sulfonate, isooctyl alcohol polyoxyethylene ether phosphate sodium and alkali-resistant penetrant AEP.
3. Use of the antibacterial, antiviral and antifungal finishing liquid as claimed in claim 1 or 2 for preparing antibacterial, antiviral and antifungal cellulose fibers.
4. A preparation method of antibacterial, antiviral and mildewproof cellulose fiber comprises the following steps:
activating the cellulose fibers to obtain activated cellulose fibers;
soaking the activated cellulose fiber in an antibacterial, antiviral and mildewproof finishing liquid to perform antibacterial, antiviral and mildewproof finishing to obtain a primary antibacterial, antiviral and mildewproof cellulose fiber;
sequentially irradiating and microwave drying the primary antibacterial antiviral mildew-proof cellulose fiber to obtain the antibacterial antiviral mildew-proof cellulose fiber;
the antibacterial, antiviral and mildewproof finishing liquid is the antibacterial, antiviral and mildewproof finishing liquid as claimed in claim 1 or 2.
5. The production method according to claim 4, wherein the activation treatment is carried out in an aqueous solution of ethylenediamine;
the mass percentage of ethylenediamine in the ethylenediamine aqueous solution is 50-70%, and the mass ratio of the cellulose fibers to the ethylenediamine aqueous solution is 1: 5-10;
the activation treatment is carried out under the condition of first ultrasound, and the ultrasonic frequency of the first ultrasound is 2 x 105~2×109Hz, the temperature is 20-50 ℃, and the time is 3-6 h.
6. The preparation method according to claim 4, characterized in that the mass ratio of the activated cellulose fibers to the antibacterial, antiviral and mildewproof finishing liquid is 1: 10-20;
the antibacterial, antiviral and mildewproof finishing is carried out under the condition of second ultrasound, and the ultrasonic frequency of the second ultrasound is 2 multiplied by 105~2×109Hz, the temperature is 40-70 ℃, and the time is 60-180 min.
7. The production method according to claim 4, wherein the irradiation is electron beam irradiation;
the electron beam irradiation intensity is 35-80 kGy, and the time is 60-150 s.
8. The antibacterial, antiviral and mildewproof cellulose fiber prepared by the preparation method of any one of claims 4 to 7 comprises cellulose fiber and organic zinc; the cellulose fiber is grafted and crosslinked with organic zinc.
9. The antibacterial, antiviral and mildewproof cellulose fiber as claimed in claim 8, wherein the mass ratio of the zinc element in the organic zinc to the cellulose fiber is 725-1986 mg:1 kg.
10. Use of the antibacterial, antiviral and antifungal cellulose fiber of claim 8 or 9 in textiles.
CN202010973663.7A 2020-09-16 Antibacterial antiviral mildew-proof finishing liquid and application thereof, antibacterial antiviral mildew-proof cellulose fiber and preparation method and application thereof Active CN114182522B (en)

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