CN116575187B - Preparation and application of formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton - Google Patents

Preparation and application of formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton Download PDF

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CN116575187B
CN116575187B CN202310534271.4A CN202310534271A CN116575187B CN 116575187 B CN116575187 B CN 116575187B CN 202310534271 A CN202310534271 A CN 202310534271A CN 116575187 B CN116575187 B CN 116575187B
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fiber
proof
mildew
deodorizing
antiviral
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CN116575187A (en
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罗彩霞
罗琳威
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Hunan Kangbaoyuan Technology Industrial Co ltd
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Hunan Kangbaoyuan Technology Industrial Co ltd
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
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    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
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    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
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    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
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  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

The invention belongs to the technical field of functional fiber materials, and discloses preparation and application of aldehyde-removing, deodorizing, antibacterial, mildew-proof and antiviral multifunctional fiber cotton. The preparation method comprises the following steps: adding the Chinese medicine antiviral extract into a mixed spinning solution containing chitosan and polyvinyl alcohol for spinning to obtain Chinese medicine antiviral chitosan fibers; mixing and granulating the specific surface modified functional particles with a fiber base material to obtain functional master batches, and mixing and spinning the functional master batches with the fiber base material to obtain the formaldehyde-removing deodorizing antibacterial mildew-proof fiber; the obtained traditional Chinese medicine antiviral chitosan fiber and the formaldehyde-removing deodorizing antibacterial mildew-proof fiber are subjected to composite molding to obtain the formaldehyde-removing deodorizing antibacterial mildew-proof multifunctional fiber cotton. The fiber cotton can effectively combine the antiviral function and the formaldehyde-removing, deodorizing, antibacterial and mildew-proof function of traditional Chinese medicines, and has remarkably improved mechanical strength, ageing resistance and softness. Has good application prospect.

Description

Preparation and application of formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton
Technical Field
The invention belongs to the technical field of functional fiber materials, and particularly relates to preparation and application of aldehyde-removing, deodorizing, antibacterial, mildew-proof and antiviral multifunctional fiber cotton.
Background
Currently, with the improvement of textile technology and life quality, single-function fiber fabrics cannot meet the life demands of people. Multifunction is a necessary trend in the development of fiber fabrics. The development of functional fibers is indicative of the progress of modern fiber science, and functional fibers refer to novel fibers having a specific function in addition to the physical and mechanical properties of general fibers. For example, fibers with health care functions, such as aldehyde-removing, deodorizing, antibacterial, antiviral and the like, are attracting attention, and have wider market prospects and more researches.
As disclosed in patent CN 114000285A, a high molecular formaldehyde-removing fiber capable of strongly absorbing and decomposing formaldehyde is provided, which adopts a high molecular formaldehyde-removing layer containing plant extract, photocatalyst and active carbon, so that the high molecular formaldehyde-removing fiber can strongly absorb and decompose formaldehyde from multiple aspects of phytoremediation, photocatalytic remediation and physical remediation. Patent CN 107476046A discloses a preparation method of formaldehyde-removing antibacterial deodorizing functional fiber, which is characterized in that formaldehyde-removing antibacterial deodorizing functional auxiliary agent for spinning and basic polyester fiber are compounded together in the after-finishing process to form the polyester fiber with formaldehyde-removing antibacterial deodorizing function. The method needs to prepare a single strong formaldehyde absorption and decomposition layer or adopts a single formaldehyde removal antibacterial deodorizing functional auxiliary agent for post-treatment, and the preparation process is complex.
It is a viable direction to add materials with aldehyde-deodorizing and antibacterial functions to fibrous materials by blending techniques to achieve the corresponding effects. As disclosed in patent CN 106364124A, a preparation method of an antibacterial formaldehyde-removing composite fiber film is disclosed, an antibacterial spinning solution is prepared by mixing an antibacterial composite dispersion liquid with a fiber polymer a solution, and then an antibacterial nanofiber is prepared by solution electrostatic spinning; fully mixing diatomite/porous carbon with the fiber polymer B, an antioxidant and a plasticizer to obtain the formaldehyde-removing composite fiber. And then the antibacterial nanofiber and the formaldehyde-removing composite fiber are compounded into a film, and the composite fiber film has excellent antibacterial and formaldehyde-removing performances through the synergistic effect of the antibacterial composite and diatomite/porous carbon. Patent CN 114875521A discloses a preparation method of high-efficiency antibacterial and antiviral fiber, which comprises the steps of firstly preparing a fiber in TiO by an in-situ reduction method 2 Generating nano simple substance Cu on the surface, and then generating TiO of nano simple substance Cu on the surface 2 The high-efficiency antibacterial and antiviral polyamide 6 is obtained by introducing polyamide 6 through in-situ polymerization after modification of carboxylic acid, and the antibacterial and antiviral polyamide 6 is taken as a skin layer, and the conventional polyamide 6 is taken as a core layer, so that the antibacterial and antiviral polyamide 6 composite fiber is obtained through composite spinning. However, the addition of inorganic functional materials to the fibrous material by blending processes affects the mechanical strength and flexibility of the fibrous material.
Patent CN 114775095A discloses a preparation method of an antibacterial mildew-proof formaldehyde-eliminating deodorizing multifunctional soft chip, which comprises the steps of mixing porous antibacterial particles prepared by a specific method with inorganic formaldehyde-eliminating deodorizing powder and a fiber base material, and spinning in a solution to obtain nascent fibers; carrying out steam heat treatment at 160-190 ℃ on the nascent fiber, and carrying out vacuum drying to obtain a porous fiber; finally, weaving, forming and softening finishing are carried out to obtain the antibacterial, mildew-proof, aldehyde-removing and deodorizing multifunctional soft chip. The method solves the defect that the conventional fiber added with the inorganic functional material is poor in softness, fluffiness and air permeability. However, no solution has been proposed for further improving the strength and the aging resistance of the fiber.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the primary aim of the invention is to provide a preparation method of aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton. The method comprises the steps of adding a fiber spinning solution of a traditional Chinese medicine antiviral extracting solution, and spinning through a solution to obtain traditional Chinese medicine antiviral fibers; the formaldehyde-removing deodorizing antibacterial mildew-proof fiber is obtained by adopting inorganic functional materials modified by hydrocarbon groups and polysiloxane surfaces to carry out blending spinning; and then the traditional Chinese medicine antiviral fiber and the formaldehyde-removing deodorizing antibacterial mildew-proof fiber are compounded and molded to obtain the formaldehyde-removing deodorizing antibacterial mildew-proof multifunctional fiber cotton.
The invention also aims to provide aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton prepared by the method.
The invention further aims to provide the application of the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton in the industries of home, home textiles, clothing, toys, outdoor products, mother and infant products, bedding, automobile products and textiles.
The invention aims at realizing the following technical scheme:
a preparation method of aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton comprises the following preparation steps:
(1) The preparation of the traditional Chinese medicine antiviral chitosan fiber comprises the following steps: adding the Chinese medicine antiviral extract into a mixed spinning solution containing chitosan and polyvinyl alcohol (PVA), and obtaining Chinese medicine antiviral chitosan fibers through wet spinning;
(2) Preparing aldehyde-removing deodorizing antibacterial mildew-proof fiber: adding alpha-olefin, a vinyl silane coupling agent and hydrogen-containing silicone oil into an organic solvent, then adding a chloroplatinic acid catalyst, stirring and mixing uniformly, and heating to 60-120 ℃ under the protection of nitrogen for reaction to obtain a modified polysiloxane solution containing coupling groups and hydrocarbon groups; then adding an inorganic formaldehyde-removing deodorizing powder material and an inorganic antibacterial mildew-proof powder material, uniformly stirring and mixing, dripping water for coupling reaction, and vacuum drying to remove a solvent to obtain surface modified functional particles; mixing and granulating the surface modified functional particles and a fiber base material to obtain functional master batches, and mixing and spinning the functional master batches and the fiber base material to obtain the formaldehyde-removing, deodorizing, antibacterial and mildew-proof fiber;
(3) The traditional Chinese medicine antiviral chitosan fiber obtained in the step (1) and the formaldehyde-removing, deodorizing, antibacterial and mildew-proof fiber obtained in the step (2) are subjected to batching, opening, carding, lapping, glue spraying, shaping, ironing, winding and packaging to obtain the formaldehyde-removing, deodorizing, antibacterial, mildew-proof and antiviral multifunctional fiber cotton.
Further, the antiviral extract of the traditional Chinese medicine in the step (1) comprises an extract of at least one of radix isatidis, sarcandra glabra, mint, radix bupleuri, honeysuckle, wild chrysanthemum, dandelion, cordate houttuynia, wormwood, liquorice, cyrtomium rhizome and agastache rugosus.
Further, in the mixed spinning solution in the step (1), the mass concentration of chitosan is 2% -10%, the mass concentration of PVA is 1% -5%, and the added mass concentration of the traditional Chinese medicine antiviral extract is 1% -5%.
Further, the alpha-olefin in the step (2) is a long chain alpha-olefin having 6 to 18 carbon atoms. Too short an olefin molecular chain may cause a decrease in dispersibility of the modified functional particles in the fiber base material, thereby decreasing the modifying effect.
Further, the vinyl silane coupling agent in the step (2) refers to vinyl trimethoxy silane or vinyl triethoxy silane.
Further, the molar ratio of the alpha-olefin to the vinyl silane coupling agent in the step (2) is 0.8-2:1. The mole ratio of the alpha-olefin to the vinyl silane coupling agent has obvious influence on the performance of the fiber material, wherein the introduction of the alpha-olefin molecular chain is mainly used for enhancing the compatibility of polysiloxane and the fiber material, so that the modification effect of the polysiloxane and the dispersion effect and the binding force of modified functional particles in the fiber material are enhanced; the main purpose of the vinyl silane coupling agent molecular chain is to introduce a coupling group, form chemical bond coupling with the surfaces of inorganic aldehyde-removing deodorizing powder materials and inorganic antibacterial mildew-proof powder materials through coupling reaction, obviously improve the binding force with the inorganic powder materials, form a layer of flexible polysiloxane film on the surfaces of the inorganic powder materials, and obviously improve the dispersion effect of the inorganic powder materials in fiber materials through the improvement of alpha-olefin compatibility.
Further, the hydrogen-containing silicone oil in the step (2) is a hydrogen-containing silicone oil having a viscosity of 20 to 100 mPas at 25℃and a hydrogen content (m/m) of 0.2 to 1.5%.
Further, the total molar quantity of the alpha-olefin and the vinyl silane coupling agent added in the step (2) is 0.8 to 1.2 times of the molar quantity of hydrogen contained in the hydrogen-containing silicone oil.
Further, the organic solvent in the step (2) is one or more solvents selected from ethanol, propanol, isopropanol, butanol, petroleum ether and n-hexane.
Further, the inorganic aldehyde-removing deodorizing powder material in the step (2) comprises at least one of titanium dioxide powder, anion powder, bamboo charcoal powder, active carbon powder, photocatalyst, far infrared ceramic powder and diatomite powder with the particle size of 1.5-5 mu m; the inorganic antibacterial mildew-proof powder material comprises at least one of silver oxide powder, zinc oxide powder, copper oxide powder, graphene powder, aluminum oxide powder, sodium oxide powder, magnesium oxide powder, calcium oxide powder, manganese oxide powder, iron oxide powder and ceramic powder containing silver, copper or zinc ions, wherein the particle size of the silver oxide powder, the zinc oxide powder, the copper oxide powder, the graphene powder, the aluminum oxide powder, the sodium oxide powder, the magnesium oxide powder, the calcium oxide powder, the manganese oxide powder and the iron oxide powder are 1.5-5 mu m.
Further, the adding total amount of the inorganic aldehyde-removing deodorizing powder material and the inorganic antibacterial mildew-proof powder material in the step (2) is 1-5 times of the mass of the hydrogen-containing silicone oil.
Further, the fiber substrate in step (2) includes at least one of polyester fiber, polypropylene fiber, polyethylene fiber, polylactic acid fiber, polyaramid fiber, polyamide fiber, polyacrylonitrile fiber, polyurethane fiber, and cellulose fiber.
Further, in the step (2), the mass ratio of the modified functional particles in the functional master batch to the fiber base material is 6-45:55-94; the mass ratio of the functional master batch to the fiber base material through mixed spinning is 2-30:70-98.
Further, the mixing granulation in the step (2) refers to mixing extrusion granulation through an extruder; the mixed spinning refers to melt blending spinning by an extruder.
The formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton is prepared by the method.
The formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton is applied to household, home textile, clothing, toys, outdoor products, infant and mother products, bedding, automobile products and textile industries.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts chitosan and PVA mixed fiber as the carrier of the antiviral component of the traditional Chinese medicine, and has the advantages of high antiviral activity and lasting antiviral activity.
(2) The invention carries out surface modification on the inorganic aldehyde-removing deodorizing powder material and the inorganic antibacterial mildew-proof powder material by using a silane coupling agent, polysiloxane and hydrocarbon groups, wherein the silane coupling agent enhances the binding force with the inorganic materials through coupling reaction, and obviously enhances the surface modification effect; the polysiloxane can obviously enhance the flexibility and ageing resistance of the fiber material; the long-chain alkane can obviously enhance the compatibility of the surface modified functional particles and the fiber base material, thereby obviously improving the mixing and dispersing effects of the functional particles and polysiloxane in the fiber base material, fully playing the modifying effect of the polysiloxane and reducing the adverse effect of the inorganic powder material on the strength of the fiber material.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton comprises the following preparation steps:
(1) The preparation of the traditional Chinese medicine antiviral chitosan fiber comprises the following steps: adding 3% wt of Chinese medicinal antiviral extractive solution (water decoction of radix Isatidis, bupleuri radix, flos Lonicerae, flos Chrysanthemi Indici, folium Artemisiae Argyi, and herba Agastaches) into mixed spinning solution containing 5% wt of chitosan and 2.5% wt of polyvinyl alcohol (PVA), and wet spinning to obtain Chinese medicinal antiviral chitosan fiber.
(2) Adding 0.18mol of 1-decene, 0.12mol of vinyl trimethoxy silane and 30g of hydrogen-containing silicone oil with the viscosity of 60 mPa.s at 25 ℃ and the hydrogen content of 0.92% into 200ml of mixed solvent of ethanol and cyclohexane, adding 100ppm of chloroplatinic acid catalyst, stirring and mixing uniformly, and heating to 90 ℃ under the protection of nitrogen for reacting for 4 hours to obtain a modified polysiloxane solution containing coupling groups and alkane groups; then adding 20g of titanium dioxide powder with the particle size of 1.5-5 mu m, 20g of bamboo charcoal powder with the particle size of 1.5-5 mu m and 20g of silver oxide powder with the particle size of 1.5-5 mu m, stirring and mixing uniformly, dripping a proper amount of water for coupling reaction for 2 hours, and vacuum drying to remove the solvent, thereby obtaining the surface modified functional particles. And mixing the surface modified functional particles with a polyester fiber substrate according to the weight ratio of 30:70 by an extruder, extruding and granulating to obtain functional master batches, and melting, blending and spinning the functional master batches and the fiber substrate according to the weight ratio of 15:85 by the extruder to obtain the formaldehyde-removing, deodorizing, antibacterial and mildew-proof polyester fiber.
(3) The traditional Chinese medicine antiviral chitosan fiber obtained in the step (1) and the formaldehyde-removing deodorizing antibacterial mildew-proof polyester fiber obtained in the step (2) are subjected to batching (coarse and fine fibers are prepared according to the product requirement, or hot melt cotton or other functional fibers are further added), opening (fiber impurity and other impurities are automatically and finely opened according to the required quantity of a carding machine), carding (the opened fiber is finely carded into a net for the next working procedure), lapping (lapping according to the product gram weight requirement or other requirements, N layers can be paved), glue spraying (adhesive spraying or functional auxiliary agent adding, functional upgrading is carried out), shaping (drying and shaping) and ironing (ironing the surface, reducing the cotton-running rate), winding (cutting is carried out according to the customer requirement), and packaging (common packaging or vacuum packaging) to obtain the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton.
This practice isThe result of the antiviral performance test (the test virus is coronavirus Hcov-229E) of the traditional Chinese medicine antiviral chitosan fiber obtained in the embodiment shows that the antiviral activity rate is 99%. The obtained formaldehyde-removing deodorizing antibacterial mildew-proof polyester fiber has formaldehyde-removing deodorizing performance test (GB/T33610.2-2017, test gas is formaldehyde and ammonia), antibacterial performance test (GB/T20944.3-2008, test bacterium is escherichia coli) and mildew-proof performance test (GB/T24346-2009, blood culture method, diameter of 3.8cm circular sample, high-pressure steam sterilization, test bacterium: aspergillus niger ATCC 16404 th generation, penicillium funiculosum ATCC 10509 th generation, chaetomium globosum ATCC 6205 th generation, trichoderma viride ATCC 28020 th generation, bacterial liquid concentration: 1.6X10:4) 6 Individual/ml, test temperature: 28 ℃, humidity: 90%, period: 28 days) shows that the formaldehyde removal rate is 90%, the deodorization rate is 72%, the antibacterial rate is 98%, the mildew-proof grade is 0, the fungus mildew coverage area is 0, and no obvious mildew grows under a magnifying glass. The results of the mechanical strength test (ISO 5079-1995) showed a breaking strength of 7.5cN/dtex and an elongation at break of 57%. Anti-aging test (AATCC 186-2009, UV-A fluorescent lamp, irradiation intensity 0.77W/m) 2 The result of the irradiation time of 720 hours and the relative humidity of 65.+ -. 2%) showed an intensity retention of 94.7% and an elongation retention of 96.5%. The results of the softness test (refer to ZB W04003-87, method for testing fabric stiffness by inclined cantilever method; the smaller the stiffness, the better the softness of the fabric) showed a stiffness of 1.54cm. The mechanical strength performance test breaking strength of the pure polyester fiber substrate is 5.3cN/dtex, and the breaking elongation is 34%; the aging resistance test strength retention is 73.6% and the elongation retention is 70.6%; the softness test stiffness was 2.04cm.
The results show that the fiber material has good aldehyde removal, deodorization, antibacterial, mildew prevention and antiviral functions. And has remarkably improved mechanical strength, ageing resistance and flexibility.
Example 2
The preparation method of the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton comprises the following preparation steps:
(1) The preparation of the traditional Chinese medicine antiviral chitosan fiber comprises the following steps: adding 2% wt of Chinese medicinal antiviral extractive solution (water decoction of radix Isatidis, bupleuri radix, flos Lonicerae, flos Chrysanthemi Indici, folium Artemisiae Argyi, and herba Agastaches) into mixed spinning solution containing 6% wt of chitosan and 3% wt of polyvinyl alcohol (PVA), and wet spinning to obtain Chinese medicinal antiviral chitosan fiber.
(2) Adding 0.15mol of 1-dodecene, 0.15mol of vinyl triethoxysilane and 30g of hydrogen-containing silicone oil with the viscosity of 60 mPa.s at 25 ℃ and the hydrogen content of 0.92% into 200ml of mixed solvent of ethanol and cyclohexane, adding 100ppm of chloroplatinic acid catalyst, stirring and mixing uniformly, and heating to 90 ℃ under the protection of nitrogen for reacting for 4 hours to obtain a modified polysiloxane solution containing coupling groups and alkane groups; then adding 20g of titanium dioxide powder with the particle size of 1.5-5 mu m, 20g of bamboo charcoal powder with the particle size of 1.5-5 mu m and 20g of zinc oxide powder with the particle size of 1.5-5 mu m, stirring and mixing uniformly, dripping a proper amount of water for coupling reaction for 2 hours, and vacuum drying to remove the solvent, thereby obtaining the surface modified functional particles. And mixing the surface modified functional particles with a polyamide fiber base material according to the weight ratio of 30:70 by an extruder, extruding and granulating to obtain functional master batches, and melting, blending and spinning the functional master batches and the fiber base material according to the weight ratio of 15:85 by the extruder to obtain the formaldehyde-removing, deodorizing, antibacterial and mildew-proof polyamide fiber.
(3) The traditional Chinese medicine antiviral chitosan fiber obtained in the step (1) and the formaldehyde-removing deodorizing antibacterial mildew-proof polyamide fiber obtained in the step (2) are subjected to batching (coarse and fine fibers are prepared according to the product requirement, or hot melt cotton or other functional fibers are further added), opening (automatic fine opening of the fiber according to the required quantity of a carding machine to remove fiber impurities and other impurities), carding (fine carding of the opened fiber into a net for the next working procedure), lapping (lapping according to the product gram weight requirement or other requirements, N layers can be paved), glue spraying (adhesive spraying or functional auxiliary agent adding, functional upgrading), shaping (drying and shaping), ironing (ironing the surface, reducing the cotton-running rate), winding (cutting according to the customer requirement, winding length), and packaging (common packaging or vacuum packaging), so as to obtain the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton.
The antiviral property test result of the traditional Chinese medicine antiviral chitosan fiber obtained in the embodiment shows that the antiviral activity rate is 99%. The formaldehyde-removing deodorizing antibacterial mildew-proof polyamide fiber has the formaldehyde-removing rate of 91%, the deodorizing rate of 74%, the antibacterial rate of 97%, the mildew-proof level of 0, the fungus-proof coverage area of 0, and no obvious mildew under a magnifying glass. The mechanical strength performance test result shows that the breaking strength is 5.8cN/dtex and the breaking elongation is 52%. The aging resistance test result showed that the strength retention was 93.1% and the elongation retention was 96.2%. The softness test results showed a stiffness of 1.40cm. The mechanical strength performance test breaking strength of the pure polyamide fiber base material is 4.6cN/dtex, and the breaking elongation is 39%; the aging resistance test strength retention is 82.6%, and the elongation retention is 76.9%; the softness test stiffness was 1.95cm.
The results show that the fiber material has good aldehyde removal, deodorization, antibacterial, mildew prevention and antiviral functions. And has remarkably improved mechanical strength, ageing resistance and flexibility.
Example 3
The preparation method of the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton comprises the following preparation steps:
(1) The preparation of the traditional Chinese medicine antiviral chitosan fiber comprises the following steps: adding 4% wt of Chinese medicinal antiviral extractive solution (water decoction of radix Isatidis, bupleuri radix, flos Lonicerae, flos Chrysanthemi Indici, folium Artemisiae Argyi, and herba Agastaches) into mixed spinning solution containing 4% wt of chitosan and 2% wt of polyvinyl alcohol (PVA), and wet spinning to obtain Chinese medicinal antiviral chitosan fiber.
(2) Adding 0.15mol of 1-octene, 0.15mol of vinyl trimethoxysilane and 25g of hydrogen-containing silicone oil with the viscosity of 50 mPa.s at 25 ℃ and the hydrogen content of 1.05% into 200ml of mixed solvent of ethanol and cyclohexane, adding 100ppm of chloroplatinic acid catalyst, stirring and mixing uniformly, and heating to 80 ℃ under the protection of nitrogen for reacting for 6 hours to obtain a modified polysiloxane solution containing coupling groups and alkane groups; then adding 20g of titanium dioxide powder with the particle size of 1.5-5 mu m, 20g of bamboo charcoal powder with the particle size of 1.5-5 mu m and 20g of copper oxide powder with the particle size of 1.5-5 mu m, stirring and mixing uniformly, dripping a proper amount of water for coupling reaction for 2 hours, and vacuum drying to remove the solvent, thereby obtaining the surface modified functional particles. And mixing the surface modified functional particles with a polylactic acid fiber base material according to the weight ratio of 20:80 by an extruder, extruding and granulating to obtain functional master batches, and melting, blending and spinning the functional master batches and the fiber base material according to the weight ratio of 30:70 by the extruder to obtain the formaldehyde-removing, deodorizing, antibacterial and mildew-proof polylactic acid fiber.
(3) The traditional Chinese medicine antiviral chitosan fiber obtained in the step (1) and the formaldehyde-removing deodorizing antibacterial mildew-proof polylactic acid fiber obtained in the step (2) are subjected to batching (coarse and fine fibers are prepared according to the product requirement, or hot melt cotton or other functional fibers are further added), opening (automatic fine opening of the fiber according to the required quantity of a carding machine to remove fiber impurities and other impurities), carding (fine carding of the opened fiber into a net for the next working procedure), lapping (lapping according to the product gram weight requirement or other requirements, N layers can be paved), glue spraying (adhesive spraying or functional auxiliary agent adding, functional upgrading), shaping (drying and shaping), ironing (ironing the surface, reducing the cotton-running rate), winding (cutting according to the customer requirement, winding length), and packaging (common packaging or vacuum packaging), so as to obtain the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton.
The antiviral property test result of the traditional Chinese medicine antiviral chitosan fiber obtained in the embodiment shows that the antiviral activity rate is 99%. The formaldehyde removal performance test and the antibacterial and mildew-proof performance test result of the obtained formaldehyde removal, odor removal, antibacterial and mildew-proof polylactic acid fiber show that the formaldehyde removal rate is 92%, the odor removal rate is 70%, the antibacterial rate is 96%, the mildew-proof grade is 0, the fungus mildew coverage area is 0, and no obvious mildew grows under a magnifying glass. The mechanical strength performance test result shows that the breaking strength is 6.9cN/dtex and the breaking elongation is 40%. The aging resistance test result showed that the strength retention was 91.3% and the elongation retention was 95.0%. The softness test results showed a stiffness of 1.23cm. The mechanical strength performance test breaking strength of the pure polylactic acid fiber base material is 5.5cN/dtex, and the breaking elongation is 26%; the aging resistance test strength retention is 76.4% and the elongation retention is 76.9%; the softness test stiffness was 1.82cm.
The results show that the fiber material has good aldehyde removal, deodorization, antibacterial, mildew prevention and antiviral functions. And has remarkably improved mechanical strength, ageing resistance and flexibility.
Comparative example 1
In this comparative example, compared with example 1, the titanium dioxide powder, the bamboo charcoal powder and the silver oxide powder were not surface-modified with a modified polysiloxane solution containing a coupling group and an alkane group, and the rest were the same.
The formaldehyde removal rate of the formaldehyde removal deodorizing antibacterial mildew-proof polyester fiber obtained by testing the comparative example is 89%, the odor removal rate is 76%, the antibacterial rate is 98%, the mildew-proof grade is 0, the fungus mildew coverage area is 0, and no obvious mildew grows under a magnifying glass; the breaking strength is 4.4cN/dtex, and the breaking elongation is 26%; the strength retention was 77.3% and the elongation retention was 76.9%; the stiffness was 3.75cm.
As can be seen from the comparison result of the comparative example and the example 1, the mechanical strength, the ageing resistance and the softness of the functional fiber material can be remarkably improved by carrying out surface modification on the inorganic functional material by the modified polysiloxane containing the coupling group and the alkane group. And has no obvious adverse effect on the functions of aldehyde removal, deodorization, antibiosis, mildew prevention and the like of the fiber material.
Comparative example 2
In this comparative example, compared to example 1, no 1-decene was added during the preparation of the modified polysiloxane solution, and the remainder were the same.
The formaldehyde-removing deodorizing antibacterial mildew-proof polyester fiber obtained by testing the comparative example has the formaldehyde-removing rate of 83%, the deodorizing rate of 62%, the antibacterial rate of 96%, the mildew-proof grade of 1, the fungus-mould coverage area of less than 10% and the fungus-mould growth of rare; the breaking strength is 5.1cN/dtex, and the breaking elongation is 35%; the strength retention was 82.4% and the elongation retention was 77.1%; the stiffness was 3.07cm.
As can be seen from the comparison of the present comparative example with example 1, the mechanical strength, aging resistance and softness improvement effect of the fiber material were not significant without adding 1-decene, and the aldehyde-removing, deodorizing, antibacterial and mildew-preventing effects were also reduced to some extent. The reason is that the inorganic functional material modified by the simple polysiloxane surface has poor compatibility with the fiber base material, so that the dispersion performance is poor, and the corresponding performance is reduced.
Comparative example 3
In this comparative example, as compared with example 1, no vinyltrimethoxysilane was added during the preparation of the modified polysiloxane solution, and the remainder were the same.
The formaldehyde-removing deodorizing antibacterial mildew-proof polyester fiber obtained by testing the comparative example has the formaldehyde-removing rate of 88%, the deodorizing rate of 74%, the antibacterial rate of 97%, the mildew-proof grade of 0 grade, the fungus mildew coverage area of 0 and no obvious mildew under a magnifying glass; the breaking strength is 5.3cN/dtex, and the breaking elongation is 39%; the strength retention was 83.0% and the elongation retention was 82.1%; the stiffness was 2.93cm.
As can be seen from the comparison of the present comparative example with example 1, the mechanical strength, aging resistance and softness improvement effect of the fiber material were not significant without adding vinyltrimethoxysilane. The reason is that the alkyl modified polysiloxane can not effectively modify the surface of the inorganic functional material, so that the dispersion performance of the inorganic functional material in the fiber base material is poor, and the corresponding performance is reduced. In addition, the comparative example has significantly improved mechanical strength, aging resistance and flexibility compared with the comparative example 1, but the effect of example 1 is not as remarkable, which indicates that the improved effect of the modified polysiloxane can be better exerted by introducing a good combination of the coupling group and the inorganic functional material.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (9)

1. The preparation method of the formaldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton is characterized by comprising the following preparation steps of:
(1) The preparation of the traditional Chinese medicine antiviral chitosan fiber comprises the following steps: adding the traditional Chinese medicine antiviral extract into a mixed spinning solution containing chitosan and polyvinyl alcohol, and obtaining traditional Chinese medicine antiviral chitosan fibers through wet spinning;
(2) Preparing aldehyde-removing deodorizing antibacterial mildew-proof fiber: adding alpha-olefin, a vinyl silane coupling agent and hydrogen-containing silicone oil into an organic solvent, then adding a chloroplatinic acid catalyst, stirring and mixing uniformly, and heating to 60-120 ℃ under the protection of nitrogen for reaction to obtain a modified polysiloxane solution containing coupling groups and hydrocarbon groups; then adding an inorganic formaldehyde-removing deodorizing powder material and an inorganic antibacterial mildew-proof powder material, uniformly stirring and mixing, dripping water for coupling reaction, and vacuum drying to remove a solvent to obtain surface modified functional particles; mixing and granulating the surface modified functional particles and a fiber base material to obtain functional master batches, and mixing and spinning the functional master batches and the fiber base material to obtain the formaldehyde-removing, deodorizing, antibacterial and mildew-proof fiber;
(3) The traditional Chinese medicine antiviral chitosan fiber obtained in the step (1) and the formaldehyde-removing, deodorizing, antibacterial and mildew-proof fiber obtained in the step (2) are subjected to batching, opening, carding, lapping, glue spraying, shaping, ironing, winding and packaging to obtain formaldehyde-removing, deodorizing, antibacterial, mildew-proof and antiviral multifunctional fiber cotton;
the alpha-olefin in the step (2) refers to long-chain alpha-olefin with 6-18 carbon atoms; the vinyl silane coupling agent refers to vinyl trimethoxy silane or vinyl triethoxy silane; the molar ratio of the alpha-olefin to the vinyl silane coupling agent is 0.8-2:1.
2. The method for preparing aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton according to claim 1, wherein the antiviral extract of the traditional Chinese medicine in the step (1) comprises an extract of at least one of radix isatidis, sarcandra glabra, peppermint, radix bupleuri, honeysuckle, wild chrysanthemum flower, dandelion, houttuynia cordata, wormwood, liquorice, cyrtomium fortunei and wrinkled gianthyssop; in the mixed spinning solution, the mass concentration of chitosan is 2% -10%, the mass concentration of PVA is 1% -5%, and the added mass concentration of the traditional Chinese medicine antiviral extract is 1% -5%.
3. The method for preparing aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton according to claim 1, wherein the hydrogen-containing silicone oil in the step (2) is hydrogen-containing silicone oil with the viscosity of 20-100 mPa.s at 25 ℃ and the hydrogen content of 0.2% -1.5%; the total added molar quantity of the alpha-olefin and the vinyl silane coupling agent is 0.8-1.2 times of the molar quantity of hydrogen contained in the hydrogen-containing silicone oil.
4. The method for preparing aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton according to claim 1, wherein the organic solvent in the step (2) is selected from one or more mixed solvents of ethanol, propanol, isopropanol, butanol, petroleum ether and n-hexane.
5. The method for preparing aldehyde-removing, deodorizing, antibacterial, mildew-proof and antiviral multifunctional fiber cotton according to claim 1, wherein the inorganic aldehyde-removing, deodorizing and deodorizing powder material in the step (2) comprises at least one of titanium dioxide powder, anion powder, bamboo charcoal powder, activated carbon powder, photocatalyst, far infrared ceramic powder and diatomite powder with the particle size of 1.5-5 μm; the inorganic antibacterial mildew-proof powder material comprises at least one of silver oxide powder, zinc oxide powder, copper oxide powder, graphene powder, aluminum oxide powder, sodium oxide powder, magnesium oxide powder, calcium oxide powder, manganese oxide powder, iron oxide powder and ceramic powder containing silver, copper or zinc ions, wherein the particle size of the silver oxide powder, the zinc oxide powder, the copper oxide powder, the graphene powder, the aluminum oxide powder, the sodium oxide powder, the magnesium oxide powder, the calcium oxide powder, the manganese oxide powder and the iron oxide powder are 1.5-5 mu m; the total addition amount of the inorganic formaldehyde-removing deodorizing powder material and the inorganic antibacterial mildew-proof powder material is 1-5 times of the mass of the hydrogen-containing silicone oil.
6. The method for preparing aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton according to claim 1, wherein the fiber base material in the step (2) comprises at least one of polyester fiber, polypropylene fiber, polyethylene fiber, polylactic acid fiber, polyaramid fiber, polyamide fiber and polyurethane fiber.
7. The method for preparing aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton according to claim 1, wherein the mass ratio of modified functional particles in the functional master batch to fiber base materials in the step (2) is 6-45:55-94; the mass ratio of the functional master batch to the fiber base material through mixed spinning is 2-30:70-98; the mixing granulation refers to mixing extrusion granulation through an extruder; the mixed spinning refers to melt blending spinning by an extruder.
8. An aldehyde-removing deodorizing antibacterial mildew-proof antiviral multifunctional fiber cotton, characterized by being prepared by the method of any one of claims 1-7.
9. The use of a multifunctional fiber cotton with aldehyde, odor, bacteria, mold and virus removal functions in home, home textile, clothing, toys and automobile products according to claim 8.
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