CN101597860A - A kind of solvay-type anti-bacterial fibre, fabric and preparation method thereof - Google Patents
A kind of solvay-type anti-bacterial fibre, fabric and preparation method thereof Download PDFInfo
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Abstract
A kind of solvay-type anti-bacterial fibre, fabric and preparation method thereof especially relate to the irradiation grafting coordinating group of fiber and fabric face and cover and carry antibacterial components Ag
+, Cu
2+, Zn
2+And solvay-type anti-bacterial fibre of composition, fabric and preparation method thereof, improved the animal migration of antibacterial components in the fiber surface liquid film, have good sterilization, fungistatic effect, be suitable for the modification of various types of organic polymer fibers and fabric and the preparation of corresponding broad spectrum activity anti-bacterial fibre and fabric, fiber, hygroscopicity of fabric, gas permeability and mechanical property are not had a negative impact, preparation technology is simple, is convenient to realize industrialization and reduces production costs.
Description
Technical field
Disclosed in this invention is a kind of solvay-type anti-bacterial fibre, fabric and preparation method thereof, especially relate to the surface modification grafting coordinating group of fiber and fabric and cover the solvay-type anti-bacterial fibre that carries antibacterial components, fabric and preparation method thereof, belong to new function material technology category.
Background technology
Because the fast development of nanosecond science and technology, nanoparticle has obtained wide application in fields such as magnetic material, photoelectric material, aerospace material, catalysis, sensing, ceramic toughening, functional materials.With metals such as Nano Silver, nano-titanium oxide, nano zine oxide, nano cupric oxide and oxide is the nano particle of representative, excellent broad spectrum activity sterilization, anti-microbial property are arranged, make an addition among coating, fiber and the resin, preparation possesses sterilization, antibacterial medical material, garment material, household electrical appliances and domestic ceramics or the like, has formed very big market.
Nano particle with metals such as Nano Silver, nano-titanium oxide, nano zine oxide, nano cupric oxide and oxide, anti-bacterial fibre, fabric with the fiber composite preparation, than the anti-bacterial fibre that adopts organic anti-bacterial components such as quaternary ammonium salt, shitosan, have better broad spectrum activity sterilization, bacteriostasis property, attract people to carry out a large amount of research and development, expedite the emergence of a lot of patents and product, be applied to medical antibacterial cloth, antibiotic fabric and antibiotic filter material field.
Wherein, activated carbon fiber is owing to have good chemical stability, and very big specific area is easy to make the Filters that is suitable for the different shape that different occasions use, as active carbon fiber felt, activated carbon fiber cloth etc., be a kind of desirable absorption, filtering material; For the activated carbon fiber that covers carrying nano silver and nano-metal-oxide, possess sterilization, antibacterial usefulness, especially in concerning the product of health of human body, mouth mask, breathing mask, air conditioner filter etc. obtain wide application.
But people have ignored the potential harm that nano material might produce in the excellent specific property of paying close attention to nano material, and perhaps this harm need long time just can show.In american cancer EASD in 2007 annual meeting, the scholar Pacheco of Massachusetts, United States university points out, thereby nano particle can cause damage to bring out cancer to DNA, should be prudent when people select nm cosmetic.
Though each state is all in the input that strengthens nanotechnology research, mainly concentrate on nano material, nanostructured is improved material property, but so far people still to nano particle in environment effect and and the people between interaction and influence know little about it.Up to now, have only only a few research to relate to nano particle to the influence of health and safety and to the harm of environment.In academic conference, also there are some experts to propose warning with regard to the toxicity problem that nano particle may exist.
The researcher of Univ. of Massachusetts thinks that on the one hand, nano particle is very little, to such an extent as to can permeates cell membranes and barrier; On the other hand, nano particle is enough big again, to such an extent as to the normal growth cycle that can interference cell.According to Britain " New Scientist " magazine, 25 factors such as nano material, transgenic crop, artificial virus and bio-robot are the serious threat earth environment in future, wherein the pollution that causes of nano material and the problem of health threat made number one.Therefore, in the nano-antibacterial component that is not having enough evidence proof to be adopted---before the nano particle of metal such as Nano Silver, nano-titanium oxide, nano zine oxide, nano cupric oxide and oxide does not constitute a threat to human health and environmentAL safety, to being applied to prepare anti-bacterial fibre, the fabric of composite nanoparticle that medical antibacterial cloth, antibiotic fabric, mouth mask, breathing mask, air conditioner filter etc. concern the product of health of human body, should take certain conservative theory.
With regard to the sterilization of metallic compounds such as silver, copper, zinc, oxide, bacteriostasis mechanism, all be to pass through Ag
+, Cu
2+, Cu
+, Zn
2+Deng metal ion, with zymoprotein, DNA, RNA effect, cause its inactivation, thus the growth of kill bacteria and inhibition bacterium.
U.S. Pat 5,985,301 have announced employing year silver-colored magnetic breeze as antiseptic, compound with cellulose fibre, prepare the anti-bacterial fibre cellulose fiber, and are applied to the medical antibacterial cloth products, as bandage, gauze etc.; A kind of antibacterial viscose fiber and production method thereof that Chinese patent 200410060290 is similarly announced adopt zeolite with carrying silver to form antibacterial viscose fiber as antiseptic and the spinning of cellulose sulfonate solution blending; And a kind of antibiotic multifunctional fibre material of being announced of Chinese patent 200610026052 and preparation method thereof, with nano titanium oxide (photocatalysis), zinc oxide, cupric oxide, tin oxide as the inorganic antibacterial powder, and polypropylene (80-85%, wt%) make the antibiotic multifunction master batch, prepare anti-bacterial fibre with resin alloy, spinning; The anti-bacterial fibre of these methods preparation, most of antibacterial components is covered by fibrous inside, the effect that is not fully exerted of its active ingredient; Similarly defective also is present in U.S. Pat 6,815, and in 379 a kind of this part of anti-bacteria cloth patented technologies of being announced, what this patent adopted is to contain Ag
2The glass micro mist of O makes an addition in textile fabric or the nonwoven fabric, and preparation can be as the anti-bacteria cloth of medical material, this product in use, except majority contains Ag
2The glass micro mist of O is coated on outside the fibrous inside, even fiber surface is because absorption steam forms liquid film, because the carrier that is exposed to the glass material of fiber surface and mineral material is to Ag
+Crystallized ability very strong, on micro-scale, limited the release and the migration of silver ion, thereby reduced its bactericidal potency; Also similar phenomenon will occur in a kind of complex antimicrobials that Chinese patent 200510010995 is released, and be prepared into Powdered antiseptic with silver complex and silicon sol solution composite drying, the release of its silver ion and migration also are subjected to serious restriction.
U.S. Pat 6,413,405 have announced that deposition AgI prepares antibacterial fibre of activated carbon on activated carbon fiber, AgI is easy to light and decomposes and thermal decomposition, and too little (Ksp=8.3 * 10 of solubility of itself
-17), limited Ag
+Release, the antibiotic stability when using for a long time to its bactericidal effect with as filter material all will have a negative impact.
Fiber has natural plants, animal fiber and artificial synthetic fiber, according to different functional requirements, can carry out modification, blending, various types of fibers are at aspects such as water imbibition, gas permeability, mechanical property, roughness, feel, stainabilitys, because of material capability, the different significant differences that exist with the blending component of method of modifying.Except chitin fiber had certain bacteriostasis, fiber itself did not generally possess antibiotic, the bacteriostasis property of broad spectrum activity, must cover year antibiotic accordingly, an antibacterial component and just can make fiber, fabric possess antibiotic, bacteriostasis property on fiber.Consider that nano material exists uncertain to the The Long-term Effect of health, and metal ions such as silver, copper, zinc have good broad spectrum activity sterilization, bacteriostasis property, metal ions such as silver, copper, zinc are covered on dissimilar fibers effectively to be carried, and when fiber top layer absorption steam forms liquid film, having transfer ability preferably in liquid film, is the key problem in technology of high performance antibiotic, bacteriostatic fiber of preparation and fabric.
Formerly apply for a patent 03147863 a kind of antibacterial fibre of activated carbon of being announced, be a kind of soluble-salt solution that contains silver ion, copper ion and zinc ion on directly activated carbon fiber being soaked or sprays at least, cover a kind of solubility or the slightly soluble salt that is loaded onto rare silver ion, copper ion and zinc ion by absorption, chemical reaction on activated carbon fiber, oven dry is made then; Ignored and had a large amount of hydroxyls in the activated carbon fiber, easily made Ag
+, Cu
2+Simple substance Ag and copper are separated out in reduction, simple substance Ag and copper to the inhibition ability of bacterium and animal migration in liquid film than ionic condition relative a little less than, cause sterilization, antibacterial active principle Ag
+, Cu
2+Concentration pass in time and will greatly descend; For directly with Ag
+, Cu
2+Cover as antibacterial components and to be stated from the prepared anti-bacterial fibre of natural plant fibre, animal fiber, chitin fiber and this series products of anti-bacteria cloth,, will cause Ag owing to have a large amount of hydroxyls and aldehyde carbonyl in this fibrid, fabric with this fibrid preparation
+, Cu
2+Reduction causes in use causing fiber, fabric flavescence phenomenon; In like manner, also there is similar phenomenon in the application of silver-series antibacterial agent in plastics, coating.A kind of silver-containing antibacterial material that Chinese patent 200410069799 is announced and preparation method thereof and application, by chitin and/or its derivative is matrix, adhering to Ag-containing compound on it forms, realized on chitin and derivative thereof, evenly being coated with or adsorption and oxidation silver or silver peroxide, be applied to all kinds of antibiotic material in medical use and comprise antibiotic woven cloth, nonwoven fabric, felt and fibrous material; Owing to have a large amount of hydroxyls in the chitin fiber, unavoidably can produce the reduction of silver oxide or silver peroxide.In like manner, a kind of fiber that Chinese patent 200610042866 is announced and the bactericidal property treatment technique of fibre, after taking directly fiber or fibre fully flooded with liquor argenti nitratis ophthalmicus, taking out centrifuge dripping or the mode of drying prepares, obviously, this processing mode blending fabric that is not suitable for natural plant fibre, animal fiber and chitin fiber and comprises these fibers.
In addition, the water imbibition of different fibers and hydrophobicity difference are very big, cover for different fibers and carry an antibacterial components, if directly with metallic slurry or metal salt solution dipping, are difficult to control as the carrying capacity of covering of the metallic of antibacterial components; Especially for the bigger fiber of hydrophobicity, in dry run, be difficult to avoid solution to shrink and cause liquid phase component to concentrate relatively, cause that serious uneven phenomenon appears in the distribution of antibacterial components because of evaporation.
Carry antibacterial components for fiber surface is covered effectively, need carry out modification or add crosslinked grappling component fiber surface, to improve the crystallized ability of fiber surface to antibacterial components.The fiber that Chinese patent 200480034895 is announced with the antiseptic processing, proposed to adopt the performed polymer of formaldehyde, dihydroxymethyl or dihydroxy ethyl urea, melamine to modify fiber surface as self-crosslinking resin, on the non-cellulosic fibres such as polyester, polyamide, polyurethane and cellulose acetate of regain≤5%, cover and carry the quaternary ammonium salt antiseptic, with preparation anti-bacterial fibre and fabric as the composition that suppresses growth of microorganism; This fiber surface is carried out the modification scheme, be unwell to the bigger polypropylene fibre of inertia, natural plant fibre and chitin fiber that water imbibition is stronger.The fiber that comprises bactericidal composition that Chinese patent 200610101336 is announced, by containing coordinating group, crosslinkable Coordination Polymers, the nano particle bactericidal composition component of copper, silver, gold, tin, zinc and combination thereof covered be loaded on fiber, the fabric, reach antibiotic, fungistatic effect; A kind of preparing nanometer antibiosis fabric that Chinese patent 200610122059 is announced, with high molecular polymer as dispersant and auxiliary adhesive, with metal ion as antimicrobial factors, with nitrogen azole organic matter as the anchoring agent of metal ion on fabric fibre, combine with coordinate bond with metal ion, on fiber, form nano particle, make fabric produce good antibacterial and deodouring function; Can above scheme for dissimilar fibers, all differ greatly with the effective crosslinked and formed crosslinking degree of crosslinkable coordination polymerization deposits yields; If the crosslinkable Coordination Polymers negligible amounts that adds, then on the microcosmic, there is the skewness phenomenon in antibacterial components at fiber and fabric; If the bigger or crosslinkable Coordination Polymers molecular weight of addition is bigger, all have a strong impact on the gas permeability of fabric; And for the processing of the more weak fiber of crosslinked ability, fabric, in fiber, the fabric washing process after crosslinking Treatment, a large amount of uncrosslinked coordination performed polymers will be influenced the loading capability that covers of antibacterial components by wash-out.
In sum, well behaved broad spectrum activity anti-bacterial fibre and fabric and corresponding preparation method must possess following feature:
(1), the technology that adopted can satisfy the bigger fiber of all kinds, performance difference and the surface modification of fabric, covers the needs that carry the broad spectrum activity antibacterial components to satisfy dissimilar fibers and fabric;
(2), through surface modification with cover an anti-bacterial fibre and a fabric that carries the antibacterial components preparation, can not have a negative impact to fiber and hygroscopicity of fabric, gas permeability and mechanical property;
(3), adopt Ag
+, Cu
2+, Cu
+, Zn
2+And composition is as the broad spectrum activity antibacterial components, preferably be uniformly distributed in the fabric and the fiber surface of institute's modification with the ionic state of easy release, guarantee the effective rate of utilization of antibacterial components and good animal migration, guaranteeing good sterilization, antibacterial ability, cover the antibacterial components that carries and do not form nano particle or ultrafine dust;
(4), reducibility group such as aldehyde radical, the hydroxyl etc. of fiber surface, in fiber and loomage surface modification process, reduce as far as possible, to avoid Ag
+, Cu
2+, Cu
+Be reduced etc. antibiotic active principle and reduce antibacterial ability;
(5), preparation technology is simple, be convenient to realize industrialization and reduce production costs.
For achieving the above object, the spy finishes the present invention.
Summary of the invention
Purpose of the present invention, provide a kind of surface graft modification by fiber and fabric make its contain coordinating group, with antibacterial components (Ag
+, Cu
2+, Cu
+, Zn
2+And composition) forms complex compound and be evenly distributed on fiber and the solvay-type anti-bacterial fibre of fabric face and fabric and corresponding preparation method, be suitable for the modification of various types of fibers and fabric and cover a year antibacterial components Ag
+, Cu
2+, Cu
+, Zn
2+And composition, to guarantee good sterilization, fungistatic effect.
Technical conceive of the present invention is:
Fiber, fabric face are evenly sprayed or flood the aqueous solution, alcoholic solution or the C of the unsaturated monomer that contains coordinating group
4～C
10Saturated alkane solution, centrifugal or extruding is removed excessive solution and reclaim to be used; Use high-energy ray, preferably then
60Co gamma-ray irradiation fiber, fabric, the unsaturated monomer that contains coordinating group is grafted on fiber surface in fiber surface generation radical reaction, makes fiber surface modification, forms the solvay-type fiber and the fabric that are rich in coordinating group.
With solvay-type fiber, the fabric after the surface modification, spray or dipping with soluble silver salt, mantoquita, zinc salt and composition solution thereof, excessive solution is removed in centrifugal or extruding, and its solution reclaims and uses, with fiber, fabric drying, make solvay-type anti-bacterial fibre, fabric then.
The described coordinating group R that contains
xUnsaturated monomer be a kind of of unsaturated carboxylic acid and derivative (I), unsaturated amides and derivative (II) thereof, the pyrrolidones that contains the unsaturated alkyl chain and derivative (III), the pyridine that contains the unsaturated alkyl chain and derivative thereof (IV, V) at least, they have following structure:
Wherein:
R
1Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl, C
6H
5, and contain N, O, the heteroatomic unsaturated heterocycle of S or heteroaromatic;
R
2Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl;
R
3Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl, C
6H
5
R
4, R
5Be selected from H, CH respectively
3, CH
2CH
3, CH (CH
3)
2, CH
2CH
2CH
3, C
6H
5
N is 0～20 positive integer;
They provide the coordinating group R that contains N, O coordination atom
x, be selected from (VI)～(X).
Carry Ag on fiber and fabric, covering with complexing mode
+, Cu
2+, Cu
+, Zn
2+And composition is during as sterilization, antibacterial components, and complexing atom does not adopt the S atom as far as possible, and coordinating group cannot comprise-SH, in order to avoid to Ag
+, Cu
2+, Cu
+, Zn
2+Component produces very strong combination, causes Ag
+, Cu
2+, Cu
+, Zn
2+Antimicrobial efficiency be suppressed.
Adopt high-energy ray irradiation to produce a large amount of free radicals, shown in (1)～(8), press the radical reaction mode with unsaturated bond, coordinating group in the fiber surface addition grafting of fiber surface and fabric is shown in (9)～(18).R, R ' are the polymer segment of fiber, R
xRepresentative contains the coordinating group of N, O coordination atom.Owing to adopt high-energy ray irradiation, make hydroxyl-OH, aldehyde carbonyl-COH, the methyl-CH of fiber surface
3, methylene-CH
2-, amino-NH
2, group such as amido-NH-form high reaction activity free radical H ,-O,
-CH
2, CH
3,
Unsaturated carbon atom generation free radical addition reaction with the unsaturated monomer that contains coordinating group makes coordinating group on the fibre grafting, thereby realizes the modification of fiber and fabric face.The hydroxyl-OH that is easy to oxidation, aldehyde carbonyl-COH that the fiber surface of string, activated carbon fiber exists, because graft reaction is transformed into the more stable ehter bond and the structure of alkyl ketone, shown in reaction (12), (13), thereby cover a year sterilization, antibacterial components Ag at fiber and fabric
+, Cu
2+, Cu
+, Zn
2+And during composition, can avoid Ag
+, Cu
2+, Cu
+Produce reduction and the phenomenon of reduction sterilization, antibacterial ability.Spandex fibre, chitin fiber, polyurethane, nylon etc. contains-NH-,-NH
2The fiber of group also has the radical reaction of (3), (4), (9), (17) formula to exist; For synthetic fiber such as polyester fiber, polypropylene fiber, vinylon fiber, polyster fibres, will be based on (5), (6), (9), (10), (15), the reaction of (16) formula, wherein the irradiation grafting of polyester fiber also exists (11), (14) radical reaction; Because high-energy ray can make aromatic ring produce free radical, also can make the conjugation phenyl ring of graphite-structure produce defective and open loop, by irradiation dose and the isoparametric control of close rate, can realize that aramid fiber, this class of carbon fiber are difficult to carry out the surface modification of the fiber of surface modification, modification, shown in reaction (7), (9), (18).This shows that this fiber and constitute the technology of the fiber surface radiation modification grafting coordinating group of fabric goes for the modification of all organic polymer fibers and fabric.
Wherein: R, R ' represent the polymer segment of fiber;
R
xRepresentative contains the coordinating group of N, O coordination atom.
Usually, in the irradiation grafting modifying process of fiber, can adopt high-energy ray have electron beam, neutron beam, X ray, ultraviolet ray and
60Co gamma-rays, irradiation are impregnated with fiber, the fabric initiation radical reaction of the unsaturated monomer of coordinating group and carry out graft modification, with
60The Co radiation gamma is handled and is compared, and the operating cost of electron beam, neutron beam, X ray is higher, and ultraviolet energy and penetration capacity and limited are handled for large batch of industrialization, can not meet the demands, to adopt
60The Co gamma-rays is good; For small lot and experimental production, also can adopt electron beam, neutron beam, X ray and ultraviolet ray irradiation.
After the fiber surface grafting coordinating group of fiber and fabric, not only can form complex compound and cover a year Ag
+, Cu
2+, Cu
+, Zn
2+And composition guarantees Ag as antibacterial components
+, Cu
2+, Cu
+, Zn
2+In the moisture film that fiber surface forms, good animal migration and sterilization are arranged, fungistatic effect, but also fiber and fabric hydrophilic have been improved greatly, make electric charge be easy to migration, thereby fiber and fabric are possessed lastingly, good antistatic performance, fiber handled by the specific surface activating agent and fabric makes the antistatic property of its generation effectively lasting more, the loss because surfactant easily is in the suds, and the fiber and the fabric of the modification of process irradiation grafting coordinating group, be the change on the high molecular microstructure of forming fiber, its hydrophilic radical can not disappear with the change of washing and applied environment.
The solution of the unsaturated monomer with coordinating group that is adopted is with water, alcohol, C
4～C
10The combination of saturated alkane, cyclohexane and derivative thereof as solvent, take into account solubility property and environmental requirement to the unsaturated monomer that contains coordinating group, the alcohol that is adopted is C
2～C
6Unit alcohol and composition thereof, alkane is C
4～C
10Saturated alkane or cyclohexane derivant, consider dissolving and destructiveness when using alkane, general C to fiber, fabric
4～C
10Saturated alkane or cyclohexane still be smaller to the solubility property of synthetic fiber, fabric, and in use solvent is reclaimed and recycles.Not under the condition to the dissolving of fiber, fabric, also can consider this kind solvent of ketone and ester at solvent, but general ketone, esters solvent can dissolve a lot of synthetic resin and fiber, and fabric is BLENDED FABRIC mostly, therefore should not adopts.
Through the fiber and the fabric face of irradiation grafting coordinating group modification, cover the antibacterial components Ag that carries
+, Cu
2+, Cu
+, Zn
2+And composition, to adopt corresponding soluble-salt solution to spray or flood, centrifugal or extruding is removed excessive solution and is reclaimed and use, and carries effect and production efficiency for guaranteeing to cover, and the concentration of antibacterial components is not less than 1.0mMol/L in the solution; Fiber and fabric drying are got final product, and bake out temperature must be considered can not fiber and the mechanical property of fabric, can adopt hot-air seasoning, even not being small lot batch manufacture or the test occasion that takes much count of to production efficiency, can consider to dry to get final product; The antibacterial components soluble-salt solution that reclaims behind the dipping, its content of effective is replenished corresponding salt and deionization or distilled water after tested, and being mixed with required concentration is reusable edible, and saving cost and realization environmental protection do not have discharging.Antibacterial components Ag wherein
+, Cu
2+, Cu
+, Zn
2+And the soluble-salt of composition can adopt nitrate, sulfate, citric acid, tartrate and composition thereof, Cu
2+, Zn
2+And composition can also adopt hydrochloride, acetate, but hydrochloride can not with Ag
+, Cu
+Soluble-salt composite, in order to avoid produce precipitation.Certainly, Ag
+, Cu
2+, Cu
+, Zn
2+And the soluble-salt of composition, should not adopt the very strong ethylenediamine tetra-acetic acid of complexing power (EDTA), nitrilotriacetic acid (NTA), anti-form-1,2-1,2-diaminocyclohexane tetraacetic acid (CyDTA), diethylenetriamine pentaacetic acid (DTPA), teiethylene tetramine-hexacetic acid (TTHA), 1, the salt of 2-diamino-cyclohexane tetraacethyl (DCTA/CDTA), ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) (EGTA), otherwise its active ingredient will be fixed by strong chelating agent, and sterilization, antibiotic, fungistatic effect are had very big negative effect.
Technical scheme of the present invention is as follows:
A kind of solvay-type anti-bacterial fibre, fabric and preparation method thereof especially relate to the surface grafting coordinating group modification of fiber and fabric and cover the solvay-type anti-bacterial fibre that carries antibacterial components, fabric and preparation method thereof; It is characterized in that: (a) coordinating group in fiber, the grafting of fabric radiation modification is formed solvay-type fiber, fabric; (b) on solvay-type fiber, fabric, cover year antibacterial components and form solvay-type anti-bacterial fibre, fabric; Wherein:
(1), coordinating group in fiber, the grafting of fabric radiation modification is formed solvay-type fiber, fabric: the solution that evenly sprays or flood the unsaturated monomer that contains coordinating group at fiber, fabric face, excessive solution is removed in centrifugal or extruding, use high-energy ray irradiation fiber, fabric then, make have coordinating group unsaturated monomer in fiber surface generation free radical addition reactive grafting at fiber surface, make solvay-type fiber and fabric that coordinating group is rich on the surface;
(2), covering a year antibacterial components formation solvay-type anti-bacterial fibre, fabric on solvay-type fiber, the fabric: with solvay-type fiber, the fabric after the irradiation grafting surface modification, spray or dipping with soluble silver salt, mantoquita, zinc salt and composition solution thereof, excessive solution is removed in centrifugal or extruding, with fiber, fabric drying, make solvay-type anti-bacterial fibre, fabric then.
1, the described unsaturated monomer that contains coordinating group is a kind of of unsaturated carboxylic acid and derivative (I), unsaturated amides and derivative (II) thereof, the pyrrolidones that contains the unsaturated alkyl chain and derivative (III), the pyridine that contains the unsaturated alkyl chain and derivative thereof (IV, V) at least, and they have following structure:
In the formula:
R
1Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl, C
6H
5, and contain N, O, the heteroatomic unsaturated heterocycle of S or heteroaromatic;
R
2Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl;
R
3Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl, C
6H
5
R
4, R
5Be selected from H, CH respectively
3, CH
2CH
3, CH (CH
3)
2, CH
2CH
2CH
3, C
6H
5, R
4, R
5Can be identical, also can be different;
N is 0～20 positive integer.
2, the described solvent that solution adopted that contains the unsaturated monomer of coordinating group is water, C at least
2～C
6Unit alcohol, C
4～C
10Saturated alkane, cyclohexane and derivative thereof a kind of.
3, the high-energy ray that coordinating group forms solvay-type fiber, fabric in the described radiation modification grafting be at least electron beam, neutron beam, X ray, ultraviolet ray and
60Co is gamma-ray a kind of, the preferred employing
60Co gamma-ray irradiation fiber, fabric.
It is 4, described that to cover the antibacterial components that carries on solvay-type fiber, fabric be Ag at least
+, Cu
2+, Cu
+, Zn
2+Soluble-salt a kind of, wherein:
(i), Ag
+Soluble-salt be a kind of of nitrate, sulfate, citric acid, tartrate at least;
(ii), Cu
+Soluble-salt be a kind of of nitrate, sulfate, citric acid, tartrate at least;
(iii), Cu
2+Soluble-salt be a kind of of nitrate, sulfate, hydrochloride, citric acid, tartrate, acetate at least;
(iv), Zn
2+Soluble-salt be a kind of of nitrate, sulfate, hydrochloride, citric acid, tartrate, acetate at least.
5, as (1) is described coordinating group in fiber, the grafting of fabric radiation modification is formed solvay-type fiber, fabric, can be applied to prepare persistence antistatic fibre, fabric.
Effect of the present invention and advantage are as follows:
1, adopt the irradiation grafting coordinating group that fiber, fabric face are carried out modification, preparation solvay-type fiber, fabric, because irradiation produces the free radical of a large amount of high reaction activities, make the unsaturated monomer that contains coordinating group pass through the free radical addition reactive grafting at fiber surface, can satisfy the surface modification of all organic polymer fibers and fabric, cover a year broad spectrum activity antibacterial components with fiber and the fabric that satisfies different needs; Than the surface modification of the crosslinkable Coordination Polymers that contains coordinating group to fiber, fabric, more even, and do not influence gas permeability;
2, through solvay-type fiber, the fabric of irradiating surface modify and graft coordinating group, can improve the hygroscopicity of fiber, make electric charge be easy to migration, can good, lasting antistatic fibre and the fabric of processability;
3, on microcosmic, solvay-type fiber, fabric through irradiating surface modify and graft coordinating group, contain the unsaturated monomer addition of coordinating group by control, the group of institute's grafting does not have a large amount of crosslinked and auto polymerization phenomenons, and gas permeability, the mechanical property of fiber and fabric had no adverse effects;
4, Ag
+, Cu
2+, Cu
+, Zn
2+And composition is the broad spectrum activity antibacterial components, the fabric and the fiber surface that adsorb and be evenly distributed on institute's modification with the ionic state form complexed of easy release, because coordinating group is to the hygroscopic improvement in surface, can guarantee that antibacterial components is just having good animal migration at the moisture film of fiber surface absorption, thereby guarantee the effective rate of utilization and the antibacterial effect of antibacterial components, cover antibacterial components that carries and the coordinating group that is uniformly distributed in fiber surface form and exist with ionic complex salt, do not form nano particle or ultrafine dust;
5, in radiation modification grafting process, reducibility group such as aldehyde radical, the hydroxyl etc. of fiber surface are converted into stable ehter bond and ketone carbonyl structure, have avoided Ag
+, Cu
2+, Cu
+Caused antibacterial ability to reduce phenomenon etc. antibiotic active principle by the reduction of reducibility groups such as aldehyde radical, hydroxyl;
6, the technical scheme that adopts, simple, the environmental protection of technology is convenient to realize industrialization and is reduced production costs.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further described:
The preparation of embodiment 1, antibacterial fibre of activated carbon
(1), activated carbon fiber irradiation grafting coordinating group
With vinyl pyrrolidone and 4-vinylpridine unsaturated monomer as the grafting coordinating group.
Take by weighing that 20 (gross weight 15.8g) are of a size of 80mm * 120mm, average thickness is that 1～1.5mm, specific area are 1000M
2The viscose base activated carbon fiber felt of/g places the 800mL beaker, is the vinyl pyrrolidone and the 4-vinylpridine hybrid ring hexane solution (vinyl pyrrolidone: 4-vinylpridine=1: 1 of 1% (wt%) with 300mL concentration, mass ratio) dipping, fail to be soaked into fully liquid level, active carbon fiber felt is taken out, put into once more after the upset, push 2～3 times, so upset, extruding repetitive operation 5 times guarantee that dipping evenly, takes out, extract solution, adopt
60The grafting of Co gamma-ray irradiation.
Radiation parameter: close rate is 51.10Gy/min, and exposure time is 23min, and actual irradiation dose is 1175Gy.
(2), the activated carbon fiber after vinyl pyrrolidone and the 4-vinylpridine graft modification covers and carries the active carbon fiber felt of antibacterial components after with irradiation grafting and be divided into 4 groups, 5 every group, the m that weighs (g) is C with 150.0mL concentration respectively
0(mol/L) liquor argenti nitratis ophthalmicus, 150.0mL silver nitrate and copper sulphate mixed solution, 150.0mL copper sulphate and zinc acetate mixed solution, 150.0mL copper chloride solution dipping 20min handle, extract solution then, dried 1 hour for 105 ℃, the preparation antibacterial fibre of activated carbon, Treatment Solution concentration and antibacterial effect see table 1 for details.Wherein, measure residual Ag with the solution after the 150.0mL silver nitrate impregnation process with Moire technique
+Concentration C
1(mol/L) and the Ag of calculated activity carbon fiber felt
+Cover carrying capacity Q (wt%); With 10 concentration K that is 5% (wt%)
2Cr
2O
4As indicator, with the AgNO after the impregnation process
3Solution titration 20.00mL 0.0100mol/L NaCl standard liquid, titration to sundown is a terminal point, the AgNO of consumption
3Volume be V mL; Be blank with the 20.00mL deionized water in addition, the blank consumption V of deduction to silver nitrate
0ML can calculate the AgNO after the impregnation process
3The concentration C of solution
1(mol/L):
C
1＝20.00×0.0100/(V-V
0) (19)
Q＝{150×(C
0-C
1)×108×10
-3/m}×100％ (20)
I, bactericidal effect evaluation:
With reference to GB15979-2002 " disposable use amenities sanitary standard " appendix C 4, sample is cut into 20mm * 30mm size, with onesize active carbon fiber felt (handle and cover the active carbon fiber felt former state of carrying antibacterial components) sample in contrast without grafting, inoculation 20min action time, detection is respectively Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538 with bacterium, test sterilization, fungistatic effect.
According to the GB15979-2002 standard code, bacteriostasis rate has bacteriostasis greater than 50% product, and bacteriostasis rate is strong bacteriostasis greater than 90% product.As can be seen from Table 1, the sterilization of prepared antibacterial fibre of activated carbon, fungistatic effect are very remarkable.
The antibacterial effect of table 1, antibacterial fibre of activated carbon
The reducibility evaluation of ii, antibacterial fibre of activated carbon:
Get 5 without grafting handle be of a size of 80mm * 120mm, average thickness is that 1～1.5mm, specific area are 1000M
2The active carbon fiber felt of/g is weighed, with the AgNO of 150.0mL0.050mol/L
3Liquor argenti nitratis ophthalmicus dipping 20min handles, and extracts solution then, dries 1 hour for 105 ℃; AgNO after the impregnation process
3Solution is measured residual Ag with Moire technique
+The Ag of concentration and calculated activity carbon fiber
+Cover carrying capacity.
In order to determine the reducibility difference of the activated carbon fiber before and after the irradiation grafting modification, will be through the irradiation grafting modification and cover the active carbon fiber felt ACF-Ag that carries silver nitrate and without radiation treatment but covered each 2 in the sample that carries after silver nitrate and the oven dry, m weighs
1, use 300.00mL 0.25mol/L CuSO respectively
4Solution soaking 1 hour changes solution over to the clean beaker of 1000mL then respectively, uses 600mL0.25mol/L CuSO in addition respectively
4Solution divides three washings two groups of carbon fiber felts, respectively the solution under two groups of washings is mixed separately, and constant volume is 1000.00mL respectively.Measure respectively with aas determination and to use Cu
2+The Ag of the ionic state that exchanges
+Concentration C
2(ppm), estimate the reducibility difference through irradiation grafting modification and untreated activated carbon fiber, the result sees table 2 for details.
Available Cu
2+The Ag of exchange
+The shared percentage δ (wt%) that covers year silver-colored total amount can react Ag to a certain extent
+Situation about being reduced because bake out temperature is 105 ℃, if carbon fiber contains a large amount of reducibility groups, will cause a large amount of Ag
+Be restored simple substance silver, can be by Cu
2+Exchange.
δ(wt％)＝{C
2×10
-3/(Q×m
1)}×100％ (21)
As can be seen from Table 2, through the activated carbon fiber of irradiation grafting vinyl pyrrolidone and 4-vinylpridine grafting, the silver nitrate that institute is covered year mainly is with solubility Ag
+The form of ionic complex salt exists, and without the activated carbon fiber of radiation treatment, has very strong reducibility, in dried, and can be with Ag
+Be reduced into simple substance silver, can be by Cu
2+Exchange.
Table 2, cover the commutative Ag of the different activities carbon fiber felt that carries silver nitrate
+Content
| Sample | 5 gross weights (g) | Residual Ag +Concentration C 1(mol/L) | Ag +Cover carrying capacity Q (wt%) | 2 cover year silver nitrate active carbon fiber felt weight (g) | C 2 (ppm) | δ (wt％) |
| ACF-Ag is through irradiation grafting modified activated carbon fiber felt | 4.056 | 0.0420 | 3.2％ | 1.620 | 48 | 92.6 |
| Cover and carry the unmodified active carbon fiber felt of silver nitrate | 3.956 | 0.0472 | 1.1％ | 1.576 | Do not pick | 0 |
The preparation of embodiment 2, antibiotic cotton/third fabric
Table 3, cotton/third fabric composition and structure
| No. | The fabric title | Polypropylene fibre fiber number/d tex | Polypropylene fibre content % | Yam count | Grammes per square metre (the g/cm of fabric unit 2) |
| 1 | Textile woven plain | - | 0 | 40 | 112.7 |
| 2 | Cotton/third woven the plain | 1.11 | 30 | 32 | 124.2 |
| 3 | The pure cotton knitting interlock fabric | - | 0 | 40 | 185.9 |
| 4 | Cotton/third knitting the fleece | 1.3 | 30 | 32 | 269.1 |
| 5 | The woven plain of polypropylene fibre | 1.11 | 95 | 32 | 312.3 |
That thin dawn, super fine denier polypropylene fibre have is soft, lead moist strong advantage, with the cotton fiber blending as lining, be a great development trend in recent years.But the surface modification of polypropylene fiber, common method are difficult to realize that the irradiation grafting coordinating group to polypropylene fibre and BLENDED FABRIC thereof has certain representativeness, and the test material that is adopted sees Table 3.
(1), the cotton/third fabric irradiation grafting coordinating group
With vinyl pyrrolidone and methacrylic acid unsaturated monomer as the grafting coordinating group.
With the fabric sample in the table 3, respectively cut 2 cloth sheets that are of a size of 200mm * 300mm, place the 800mL beaker, with 200mL concentration is the vinyl pyrrolidone of 2% (wt%) and the mixing aqueous isopropanol of methacrylic acid (vinyl pyrrolidone: methacrylic acid=3: 1, mass ratio) dipping evenly, take out, extract solution, adopt
60The grafting of Co gamma-ray irradiation.
Radiation parameter: close rate is 33.08Gy/min, and exposure time is 54min, and actual irradiation dose is 1786Gy.
A slice fabric covers and carries antibacterial components, and another sheet stays the sample of doing the gas permeability test.
(2), vinyl pyrrolidone and and the methacrylic acid graft modification after cotton/third fabric cover and carry an antibacterial components
Respectively getting cotton/third fabric sample behind a slice irradiation grafting, is that 0.010mol/L liquor argenti nitratis ophthalmicus dipping 30min handles with 150.0mL concentration respectively, extracts solution then, and 65 ℃ of vacuum dryings 2 hours prepare antibiotic cotton/third fabric.
(i), antibacterial effect evaluation
Compare with the cotton in the table 3/third fabric former state, with reference to GB15979-2002 " disposable use amenities sanitary standard " appendix C 4, sample is cut into 20mm * 30mm size, inoculation 20min action time, detection is respectively Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538 with bacterium, test sterilization, fungistatic effect the results are shown in table 4.
According to the GB15979-2002 standard code, bacteriostasis rate is strong bacteriostasis greater than 90% product.As can be seen from Table 4, sterilization, the fungistatic effect of prepared antibiotic cotton/third fabric are very remarkable.
(ii), fabric graft modified, cover and carry the evaluation that gas permeability changes after the antibacterial components
With reference to GB5453-85, adopt in the YG461 type fabric and press the Air permenbility instrument to analyze.Sample diameter 70mm, the fabric pressure differential keeps 13mmH
2O.Before the test, fabric is pre-equilibration 24 hours under 20 ℃, the condition of relative humidity 65% earlier, and test result is listed in table 5.As can be seen from Table 5, grafting coordinating group on the irradiation fiber of cotton/third fabric, cover and carry an antibacterial components and make after antibiotic cotton/third fabric, the gas permeability of fabric is not had significant change.
The antibacterial effect of table 4, antibiotic cotton/third fabric
The gas permeability of table 5, graft modification, antibiotic cotton/third fabric
The preparation of embodiment 3, antibiotic spandex elastoplast
The elastomeric polyurethane fiber bandage is made by natural cotton yarn and elastic polyurethane fiber filament, and is fixing solid, comfortable, is fit to medical science, clinic, and health care and sports are used.
Buy commercially available elastomeric polyurethane fiber bandage, specification 10cm * 4.5m, 2 sections bandage prints that are of a size of 10cm * 30cm of clip are with the modification of vinyl pyrrolidone irradiation grafting.
With 200mL concentration be 2.5% (wt%) vinyl pyrrolidone the ethanolic solution dipping evenly, take out, extract solution, adopt
60The grafting of Co gamma-ray irradiation.
Radiation parameter: close rate is 38.88Gy/min, and exposure time is 47min, and actual irradiation dose is 1827Gy.
With the bandage print behind the irradiation, be that 0.010mol/L silver nitrate and 0.030mol/L copper-bath dipping 10min handles with 150.0mL concentration, extract solution then, 70 ℃ of vacuum dryings 2 hours, preparation antibiotic spandex elastoplast.
The antibacterial effect evaluation method is done contrast with reference to embodiment 1,2 with the bandage former state without any processing, and test antibiotic spandex elastoplast all greater than 99%, has strong fungistatic effect to the bacteriostasis rate of Escherichia coli and Staphylococcus aureus.
Should be pointed out that the above specific embodiment can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.Therefore, although this specification and embodiment have been described in detail to the present invention,, it will be appreciated by those skilled in the art that still and can make amendment or be equal to replacement the present invention; And all do not break away from the technical scheme and the improvement thereof of the spirit and scope of the present invention, and it all should be encompassed in the middle of the protection domain of patent of the present invention.
Claims (2)
1, the present invention is a kind of solvay-type anti-bacterial fibre, fabric and preparation method thereof, especially relates to the surface grafting coordinating group of fiber and fabric and covers the solvay-type anti-bacterial fibre that carries antibacterial components, fabric and preparation method thereof, it is characterized in that:
(1), evenly spray, flood the solution of the unsaturated monomer that contains coordinating group at fiber, fabric face, excessive solution is removed in centrifugal or extruding, with high-energy ray irradiation fiber, fabric, the solvay-type fiber and the fabric of preparation surface grafting coordinating group;
(2), with the spray solution of antibacterial components or dipping solvay-type fiber, fabric, excessive solution is removed in centrifugal or extruding, then with fiber, fabric drying, makes solvay-type anti-bacterial fibre, fabric;
Wherein:
A, the described unsaturated monomer that contains coordinating group are a kind of of unsaturated carboxylic acid and derivative (I), unsaturated amides and derivative (II) thereof, the pyrrolidones that contains the unsaturated alkyl chain and derivative (III), the pyridine that contains the unsaturated alkyl chain and derivative thereof (IV, V) at least, and its structure is:
In the formula:
R
1Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl, C
6H
5, and contain N, O, the heteroatomic unsaturated heterocycle of S or heteroaromatic;
R
2Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl;
R
3Be selected from H, CH
3, CH
2CH
3, C
3～C
10Alkyl, C
6H
5
R
4, R
5Be selected from H, CH respectively
3, CH
2CH
3, CH (CH
3)
2, CH
2CH
2CH
3, C
6H
5N is 0～20 positive integer;
B, described high-energy ray be at least electron beam, neutron beam, X ray, ultraviolet ray and
60Co is gamma-ray a kind of, the preferred employing
60The Co gamma-rays;
C, described antibacterial components are Ag at least
+, Cu
2+, Zn
2+Soluble-salt a kind of, comprise:
(i), Ag
+Soluble-salt be a kind of of nitrate, sulfate, citric acid, tartrate at least;
(ii), Cu
2+Soluble-salt be a kind of of nitrate, sulfate, hydrochloride, citric acid, tartrate, acetate at least;
(iii), Zn
2+Soluble-salt be a kind of of nitrate, sulfate, hydrochloride, citric acid, tartrate, acetate at least.
2, a kind of solvay-type anti-bacterial fibre according to claim 1, fabric and preparation method thereof is characterized in that the irradiation grafting coordinating group can be applicable to prepare antistatic fibre and fabric on fiber, the fabric.
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