CN102115977A - Method for manufacturing anti-bacterial cloth through vacuum ion anchoring technology - Google Patents
Method for manufacturing anti-bacterial cloth through vacuum ion anchoring technology Download PDFInfo
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- CN102115977A CN102115977A CN 201110072018 CN201110072018A CN102115977A CN 102115977 A CN102115977 A CN 102115977A CN 201110072018 CN201110072018 CN 201110072018 CN 201110072018 A CN201110072018 A CN 201110072018A CN 102115977 A CN102115977 A CN 102115977A
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Abstract
The invention provides a method for manufacturing anti-bacterial cloth through the vacuum ion anchoring technology. The method comprises the following steps: the surface of cloth material is pre-treated; a container where a titanium target, a silver target and a germanium target are mounted is filled with inert gas; the pressure in the container is reduced to a vacuum degree of 10-1torr to 10-5torr through vacuum equipment; oxygen gas is led into the container; the pressure in the container is controlled to be 1mtorr to 10mtorr, and the temperature is controlled to be 20 DEG C to 250 DEG C; direct current is led into the titanium target, the silver target and the germanium target at a preset power, so as to produce plasma discharge; the cloth material passes through the titanium target, the silver target and the germanium target at a constant speed in a furled manner, and three metal ions are anchored inside and on the edge of fiber; the maximum deposition rates of the titanium target, the silver target and the germanium target range from 100nm/min to 1,000nm/min; and the cloth material is trimmed, edged, packaged in a vacuum manner, and sent to a radiation exposure center, so as to remove bacteria and bacterial colonies again.
Description
Technical field
The present invention relates to a kind of vacuum ionic grappling technology and make the method for anti-bacteria cloth.
Background technology
Microorganism is ubiquitous at occurring in nature, and is inseparable with the human lives.In the daily life, textiles be these microorganisms well autoeciously.Common microorganism mainly comprises Escherichia coli and staphylococcus aureus etc. on the textiles.Escherichia coli cause acute diarrhea easily; Staphylococcus aureus is a modal pathogen in the humanization pyogenic infection.For human beings'health, people suppress the growth and breedings of pathogenic bacteria by various means, reach the purpose of antibacterial bacteriostatic.Human body is carrying a large amount of microorganisms under normal condition, even can not eliminate these bacteriums through repeatedly washing, situation is just even more serious in particular surroundings, as certain hospital the bed clothes in ward are detected discovery, cotton-wadded quilt and cotton pad contain a large amount of bacteriums, especially SARS virus in 2003 is promptly propagated from south to north and is endangered in China, make our heightened awareness nontoxic to exploitation, have the importance of the antibacterial fabric of good gas defence antibacterial functions.
Exploitation the earliest and also the antibacterial textile moldproof, anti-odour processing method that always continues into the present be the method for back arrangement.The reason that this method is generally adopted is because of easy to process to a great extent, and alternative antiseptic wide range.Textiles is regardless of being Collator Mode acquisition antibiotic effect after raw fiber or yarn or fabric even ready-made clothes all can pass through.Textile manufactures can very optionally select different antiseptic production to have the product of different antibacterial characteristics according to the needs of user or final use, but this method also exists a fatal weakness, and that is exactly that organic products has certain toxicity to human body.
The security of antibacterial fabric is embodied in it when playing the antibacterial and protective effect, and human body is not had toxic and side effect, does not destroy the normal micropopulation of human body.Producing and using the purpose of antibacterial fabric is not eliminating bacteria, but suppresses the too much breeding of bacterium.Generally speaking, the activity of antiseptic is wide more, and senior species are comprised that human toxicity is just big more.Use the chemicals treatment textiles to it is also noted that the side effect of medicament when reaching antibiotic purpose to human body.
All microbial action agent can both be killed the organic matter that lives, as bacterium, saccharomycete.These activating agents have various toxicity to mammal.Therefore the safety to the producers and consumers will have effective guarantee.Although can utilize inhibitor to reduce to minimum to operating personnel's toxicity, for traditional antimicrobial product, it is difficult and expensive eliminating these noxious materials.
For clothing, the bedding of often washing, washing promptly loses antibacterial effect through several times.Though it is crosslinked that the used for textiles that has has the antiseptic and the fiber of active group, still greatly differ from each other from lasting or permanent antibiotic requirement.In addition, processing often causes many cotton knots to bulk fibre, makes the postorder difficult processing to carry out.However, because natural fabric is difficult to obtain antibacterial effect by the mode of fibre modification, so up to the present, the still later Collator Mode of antibacterial treatment of the textiles made from natural fabric is main.
Along with chemical fibre develop and in the fiber consumer field, occupy gradually leading position rapidly, the blending product of various purifying fibres or chemical fibre and natural fabric has become the leading role of all kinds of textiless.Because the easier chemical modification of chemical fibre, thereby people turn to the macromolecular structure modification of fiber and the method for blending and modifying and produce the persistence anti-bacterial fibre, wherein based on blending method.The early stage antiseptic that is used for the chemical fibre co-blended spinning generally is the compound of metal ion, wherein has many antiseptics to contain heavy metal ion.In recent years, enhancing along with people's environmental consciousness, heavy metal ion causes people's attention gradually to the eco-toxicity problem of human body, good anti-bacterial effect but the bigger antiseptic that contains heavy metal ion of toxicity are eliminated gradually, the substitute is some harmless metal oxides, salt or load with active metallic ion on the inorganic non-metallic compound, as contain Ag zeolite, Zn, Cu compound and TiO2 etc. as the main antiseptic of synthetic fiber blending and modifying.This class antiseptic has broad-spectrum antimicrobial effect, and is harmless, and Heat stability is good, but also discovers, now the antibacterial fabric of the co-blended spinning that exists on the market have that persistence is poor, prompt effect difference and the wide inadequately defective of antimicrobial spectrum.Main cause is that selected antiseptic is too single; The defective tightness that combines of antiseptic and textile fiber uses and washs easily and the fiber disengaging through long-term, loses antibacterial effect.
Making a general survey of the achievement in research of existing antibacterial fabric, mainly is with methods such as absorption, spray and blending, with antiseptic attached to fabric face.Can play certain antibacterial action so at short notice, but along with the passing of service time, antibacterial effect descends significantly.Simultaneously, because the antiseptic kind of using is more single, antibacterial effect is also not ideal enough.
Summary of the invention
The purpose of this invention is to provide a kind of vacuum ionic grappling technology and make the method for anti-bacteria cloth, it is achieved through the following technical solutions.
Vacuum ionic grappling technology is promptly under a kind of relatively stable vacuum state, the cathode titanium target, produce glow discharge between silver target and germanium target and anode, the interpolar gas molecule is ionized and produces charged particles, wherein cation is subjected to the negative potential accelerated motion of negative electrode and clashes into the titanium target, silver target and germanium target, the motion of particle high speeds such as its atom is flown out, this atom that flies out then grappling is embedded in textile fiber inside and forms electric conductor closely, excite and see through, dissociate, ionization ... molecule Deng the reaction generation, atom, the excited state material, electronics, negative ions, free radical, UV light (ultraviolet light), visible light ... Deng material, the state that these materials mix is referred to as electricity slurry Plasma.Under ultra-high vacuum state, with titanium, silver, germanium three metal ion species firmly grappling be embedded on the textile fiber, the antibacterial effect of these three kinds of metals has been contained the viral kind that causes infection clinically easily substantially.
T i-titanium makes the organic matter decomposition and has antibiotic, antivirus action based on light-catalyzed reaction.In the water and air system, under sunlight especially ultraviolet irradiation, serial reaction takes place in the hole (h+) that produces electronegative electronics (e one) and positively charged that is activated, and forms hole-electron pair.The H of these hole-electron pairs and its surface absorption
2O or OH
-And O
2Effect generates hydroxyl radical free radical OH and superoxide anion free radical O
2 -Newly-generated free radical has very strong chemism, particularly elemental oxygen can react (oxidation) with most organic matters, thereby can decompose effectively and destroy airborne multiple toxic gas, but when running into bacterium the cell membrane of directtissima bacterium, cell membrane or intracellular constituent.In addition, these active oxygens also cause the fracture of the phosphodiester bond between the base in the DNA chain, destroy the dna double helical structure, thus the dna replication dna of destroy microorganisms cell and the metabolism of disorderly cell.
There are 3 kinds of antibiotic mechanism in Ag silver type inorganic antiseptic: the antibiotic mechanism of (1) Ag+ stripping: the Ag+ that promptly slowly releases is attracted by the microorganism that the surface has negative electrical charge, thus the electrolytic equilibrium of destroy microorganisms. make its cell membrane impaired and dead; (2) contact antibiotic mechanism: bacterium relies on Coulomb attraction firmly to be adsorbed on the electronegative cell membrane with after Ag+ contacts. and further the penetration cell wall enters bacterium inside. with sulfenyl reaction wherein. destroy the activity of cell synzyme. make cell forfeiture division growth ability and death; (3) photocatalysis antibacterial mechanism: .Ag+ can play the effect of catalytic active center under the illumination of certain wavelength is penetrated, thereby makes the hydroxide ion, water and the oxygen that are adsorbed on the antiseptic surface become hydroxyl, the contour active group of active oxygen. and these active groups can act on Bacteria destroyed bacterium tissue. suppress its growth and breeding.
The Ge organic germanium compounds is a kind of compound that can regulate immunization in the host that autoimmune function changes, energy inducement interferon, activation NK cell and macrophage.As human oral You Machine Germanium 2250mg.As human oral organic germanium 2250mg, all Hou Xue Germanium Zhong deterrent Ke Da peak values.But interferon peaking in the blood germanium after the week.Dan Even Continued reduces to previous level, Said Ming Over amount Fu Yong No effect with Drug one Ge month, The.But continuous use one month is then reduced to previous level, illustrates that excessive use does not have effect.Make Try Examination with mouse, Elixirs amount As 300mg/kg, 20 Xiao Time Hou Gan Interference Su Da be to physiology Yi Righteousness level, the highest Concentrated degree 320 Single position/ml of 24 Xiao Time Ke Da.Test with mouse, dosage is 300mg/kg, and interferon reaches the physiological significance level after 20 hours, can reach maximum concentration 320 units/ml in 24 hours.Try Examination like someone the Chong Complex Class, the Elixirs amount is identical, and 25～30 Xiao Time can arrive 167.1～367.5 Single position/ml.Someone repeats similar test, and dosage is identical, and 25～30 hours can arrive 167.1～367.5 units/ml.48 Xiao Time Hous descend.Descend after 48 hours.Can be increased by Zeng Strong Machine Body De Fang Royal ability, deterrent by the Yu deterrent, immune Neng Li The adds Strong.Because interferon can strengthen the defence capability of body, interferon increases, and immunocompetence is then strengthened.It has Reported Guide to take NK Fine cytoactive increase among the Machine Germanium 24 Xiao Time, Pi Dirty, and lumbar injection 48 Xiao Time, the huge Fine of the biting Bao of abdominal cavity Inner Chu Now Fine cellular toxicity show that a bit the raising Shi You Machine Germanium Neng of immunocompetence prevents and control the reason of Ge Seed disease of Treatment.Also have report to take organic germanium 24 hours, the NK cytoactive increases in the spleen, and cytotoxic macrophage appears in lumbar injection 48 hours in the abdominal cavity, and these show that the raising of immunocompetence is the reason that organic germanium could prevent and treat various diseases.
Three kinds of metallic element synergies can effectively solve the prompt effect of antimicrobial product and the problem of durability.Simultaneously, add the germanium metal, can effectively prevent the problem of silver ion chance air oxidation blackening.
Specifically, vacuum ionic grappling technology of the present invention is made the method for anti-bacteria cloth, may further comprise the steps:
1) preliminary treatment is carried out on the cloth surface, said preliminary treatment is to clean with organic solvent and deionized water successively under the ultrasonic wave condition, scavenging period respectively is 5～15 minutes, at last under vacuum condition in 15～85 ℃ of dryings 0.5～3 hour, said organic solvent is the mixed liquor of acetone and ethanol; Said preliminary treatment also can be selected to use electrophoresis to remove the cloth pollutant.
2) in the container that titanium target, silver-colored target and germanium target are installed, charge into inert gas, utilize vacuum equipment to make container inner pressure drop to vacuum 10
-1～10
-5Torr, aerating oxygen gas, the control container inner pressure is that 1～10 mtorr, temperature are 20～250 ℃, preferred 100～200 ℃, direct current is fed titanium target, silver-colored target and germanium target with predetermined electric power, produce the discharge of electricity slurry;
Said inert gas is argon gas or nitrogen, said galvanic voltage: 300～800V, preferred 300～500V, current density: 4～60mA/cm, power density: 1～40W/cm;
In order to improve ultrahigh vacuum deep layer ion grappling efficient, setting is parallel to the magnetic field on titanium target, silver-colored target and surface, germanium target target source to said vesse, the motion of initiating electron can be limited in the zone of adjacent cathodes, thereby strengthen the ionization efficient of gas atom, said magnetic field intensity is about: 50～300G; Catch electronics by externally-applied magnetic field, prolong and fettered the electronic motion path, improved ionization level, increased textiles deep layer ion grappling speed;
3) cloth is at the uniform velocity passed through titanium target, silver-colored target and germanium target to furl mode, make three metal ion species be anchored on fibrous inside and outer rim; The maximum deposition rate of titanium target, silver-colored target and germanium target is 100nm/min～1000nm/min;
The target source of titanium target, silver-colored target and germanium target is divided into balanced type and unbalanced, and the source grappling of balanced type target is inlayed evenly, and the source grappling of unbalanced target is inlayed with basal body binding force strong.Balance target source is used for hollow textile class textiles, non-equilibriumly is used for solid chemical fibre textile.Negative electrode distributes different according to magnetic field configuration, be divided into equilibrium state and non-equilibrium negative electrode.The magnetic flux of equilibrium state negative electrode internal-external magnetic steel about equally, bipolar magnetic line of force closure is in target surface, well with electronics/plasma confinement at the titanium target, near the target surface of silver target and germanium target, increase collision probability, improved ionization efficient, thereby just can build-up of luminance under lower operating air pressure and voltage and keep glow discharge, make the titanium target, the silver target is relative with the utilization rate of germanium target higher, but because electronics moves main closure in target surface along the magnetic line of force, the textiles suffered ion bom bardment in zone is less, promptly allow negative electrode outer magnetic pole magnetic flux greater than internal magnetic pole, the bipolar magnetic line of force is not exclusively closed at target surface, the part magnetic line of force can extend to the textiles zone along the edge of target, thereby portions of electronics can expand to textiles along the magnetic line of force, increase the plasma density and the gas ionization rate of textiles. no matter balance/unbalance, if magnet is static, its magnetic signature decision titanium target, the target utilization of silver target and germanium target is less than 30%.
Bombarded high-velocity particles motion easily with metal alloy, this is because the source target (negative electrode) of titanium target, silver-colored target and germanium target, plasma and can be formed the loop by textiles.Metallic target is used in the ultrahigh vacuum deep layer ion grappling that we adopt exactly, adds argon gas and reacting gas such as nitrogen or oxygen, because energy transforms, generates nitride or oxide with reacting gas chemical combination when metal targets hits textiles.
The ion grappling is stable to be carried out in order to make, preferably the target source is cooled off, because in ion grappling process, produce a large amount of heats, if do not have cooling or cooling deficiency, this heat will make the target source temperature of titanium target, silver-colored target and germanium target raise, even dissolve the target source, therefore adopt recirculated water cooling mode cooled target source.
4) cut cloth, car limit, vacuum packaging;
5) cloth is delivered to radiation irradiation center, degerming and bacterium colony once more.
The characteristics of the antibiotic cloth of the present invention:
(1) high security, without any side effects.
(2) no stripping property does not enter human body, adopts the absorption system anti-bacteria and anti-virus, and preferable durability is arranged.
(3) broad spectrum antibacterial, the kind difference of metal ion has good inhibition effect to various bacteria and virus.
(4) do not develop immunity to drugs.
(5) good heat resistance, heated scrub repeatedly.
Generally speaking, from physical property, the slow stripping of antibiotic cloth antibacterial material of common dissolution type, reach antibacterial action, this antiseptic cost is lower, antibacterial effect is fine, but bacterium in the fabric and the bacterium on the skin can be killed without exception, can destroy the microecological balance of skin surface microorganism, and antibacterials are also easily invaded application on human skin and blood vessel from the fine hair hole of human body, continuously long-time use might reduce body immunity and produce drug resistance, so no matter still consider that from durability this antiseptic is not optimal selection from security.The textile cloth that the present invention adopts ultrahigh vacuum deep layer ion grappling technology to produce, security can be rated as first-class, only kill the bacterium on the skin that bacterium in the fabric and fabric fibre can touch, suppress harmful bacterium breeding, thereby can not destroy the microecological balance of skin surface microorganism, have security and durability.
The specific embodiment
Below in conjunction with embodiment the present invention is explained detailedly.
Embodiment 1
1) preliminary treatment is carried out on the cloth surface, cleaned with organic solvent and deionized water successively under the ultrasonic wave condition, scavenging period respectively is 10 minutes, at last under vacuum condition in 25 ℃ of dryings 1 hour, said organic solvent is the mixed liquor of acetone and ethanol;
2) in the container that titanium target, silver-colored target and germanium target are installed, charge into argon gas, utilize vacuum equipment to make container inner pressure drop to vacuum 10
-2Torr, aerating oxygen, the pressure in the control container is that 2 mtorr, temperature are 50 ℃, and direct current is fed titanium target, silver-colored target and germanium target, produces the discharge of electricity slurry, said galvanic voltage: 300V, current density: 6mA/cm, power density: 5W/cm;
3) cloth is at the uniform velocity passed through titanium target, silver-colored target and germanium target to furl mode, make three metal ion species be anchored at fibrous inside and outer rim; The maximum deposition rate of titanium target, silver-colored target and germanium target is 100nm/min;
4) cut cloth, car limit, vacuum packaging;
5) cloth is delivered to radiation irradiation center, degerming and bacterium colony once more.
Embodiment 2
The repetition embodiment 1 just preliminary treatment of cloth uses the electrophoresis mode to remove the cloth surface contaminant; Container inner pressure drops to vacuum 10
-3Torr, aerating oxygen, the control container inner pressure is that 4 mtorr, temperature are 80 ℃, said galvanic voltage: 500V, current density: 10mA/cm, power density: 10W/cm, the magnetic field that is parallel to titanium target, silver-colored target and surface, germanium target target source is set in container in addition, and magnetic field intensity is 50G; The maximum deposition rate of titanium target, silver-colored target and germanium target is 200nm/min
Embodiment 3
Repeat embodiment 1 magnetic field that is parallel to titanium target, silver-colored target and surface, germanium target target source just is set in container, container inner pressure drops to vacuum 10
-5Torr, aerating oxygen, the control container inner pressure is that 10 mtorr, temperature are 250 ℃, said galvanic voltage: 800V, current density: 60mA/cm, power density: 40W/cm, magnetic field intensity is 280G; The maximum deposition rate of titanium target, silver-colored target and germanium target is 1000nm/min.
Embodiment 4
Repeating embodiment 3 is that container inner pressure drops to vacuum 10
-1Torr, the pressure behind the aerating oxygen in the control container is that 8 mtorr, temperature are 200 ℃, said galvanic voltage: 700V, current density: 50mA/cm, power density: 35W/cm, magnetic field intensity is 250G; The maximum deposition rate of titanium target, silver-colored target and germanium target is 800nm/min.
Embodiment 5
Repeating embodiment 3 is that container inner pressure drops to vacuum 10
-5Torr, the pressure behind the aerating oxygen in the control container is that 6 mtorr, temperature are 180 ℃, said galvanic voltage: 600V, current density: 40mA/cm, power density: 30W/cm, magnetic field intensity is 200G; The maximum deposition rate of titanium target, silver-colored target and germanium target is 700nm/min.
Embodiment 6
Repeating embodiment 3 is that container inner pressure drops to vacuum 10
-4Torr, the pressure behind the aerating oxygen in the control container is that 5 mtorr, temperature are 150 ℃, said galvanic voltage: 500V, current density: 30mA/cm, power density: 25W/cm, magnetic field intensity is 100G; The maximum deposition rate of titanium target, silver-colored target and germanium target is 500nm/min.
Embodiment 7
Repeating embodiment 3 is that container inner pressure drops to vacuum 10
-3Torr, the pressure behind the aerating oxygen in the control container is that 4 mtorr, temperature are 100 ℃, said galvanic voltage: 500V, current density: 20mA/cm, power density: 20W/cm, magnetic field intensity is 80G; The maximum deposition rate of titanium target, silver-colored target and germanium target is 300nm/min.
Claims (10)
1. a vacuum ionic grappling technology is made the method for anti-bacteria cloth, may further comprise the steps:
1) preliminary treatment is carried out on the cloth surface;
2) in the container that titanium target, silver-colored target and germanium target are installed, charge into inert gas, utilize vacuum equipment to make container inner pressure drop to vacuum 10
-1～10
-5Torr, aerating oxygen, the control container inner pressure is that 1～10 mtorr, temperature are 20～250 ℃, and direct current is fed titanium target, silver-colored target and germanium target with predetermined electric power, produces the discharge of electricity slurry; Said galvanic voltage: 300～800V, current density: 4～60mA/cm, power density: 1～40W/cm;
3) cloth is at the uniform velocity passed through titanium target, silver-colored target and germanium target to furl mode, make three metal ion species be anchored on fibrous inside and outer rim, the maximum deposition rate of titanium target, silver-colored target and germanium target is 100nm/min～1000nm/min;
4) cut cloth, car limit, vacuum packaging;
5) cloth is delivered to radiation irradiation center, degerming and bacterium colony once more.
2. method according to claim 1, wherein said preliminary treatment are to use organic solvent and washed with de-ionized water cloth under the ultrasonic wave condition successively, and scavenging period respectively is 5～15 minutes, at last under vacuum condition in 15～85 ℃ of dryings 0.5～3 hour.
3. method according to claim 1, wherein said preliminary treatment use electrophoresis to remove the cloth pollutant.
4. method according to claim 2, wherein said organic solvent are the mixed liquors of acetone and ethanol.
5. method according to claim 1, wherein said inert gas is argon gas or nitrogen.
6. method according to claim 1 is characterized in that described container setting is parallel to the magnetic field on titanium target, silver-colored target and surface, germanium target target source, and said magnetic field intensity is about 50～300G.
7. method according to claim 1 is characterized in that cooled target source between step 3) and step 4).
8. as method as described in the claim 7, it is characterized in that said cooling adopts the recirculated water cooling mode.
9. method according to claim 1 is characterized in that step 2) in temperature in the container be 100～200 ℃.
10. method according to claim 1 is characterized in that step 2) in galvanic voltage be 300～500V.
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Citations (6)
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| CN1387760A (en) * | 2001-05-30 | 2003-01-01 | 纪祖煌 | Bactericidal nano-silver cloth and its making process and use |
| CN1414168A (en) * | 2001-10-26 | 2003-04-30 | 青岛大学 | Bactericidal and for infrared radiation fabric or fibre and its preparation method |
| CN1888168A (en) * | 2006-07-19 | 2007-01-03 | 万薛平 | Health yarn containing germanium and producing method thereof |
| CN101608246A (en) * | 2009-07-20 | 2009-12-23 | 西安工程大学 | A kind of method for preparing antibacterial silver-plating leather |
| CN101637679A (en) * | 2009-08-25 | 2010-02-03 | 江南大学 | Method for preparing antibacterial filter screen |
| CN101717920A (en) * | 2009-12-29 | 2010-06-02 | 浙江大学 | Method for preparing composite Ag-Ti oxide antibacterial film by magnetron sputtering |
-
2011
- 2011-03-24 CN CN 201110072018 patent/CN102115977B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1387760A (en) * | 2001-05-30 | 2003-01-01 | 纪祖煌 | Bactericidal nano-silver cloth and its making process and use |
| CN1414168A (en) * | 2001-10-26 | 2003-04-30 | 青岛大学 | Bactericidal and for infrared radiation fabric or fibre and its preparation method |
| CN1888168A (en) * | 2006-07-19 | 2007-01-03 | 万薛平 | Health yarn containing germanium and producing method thereof |
| CN101608246A (en) * | 2009-07-20 | 2009-12-23 | 西安工程大学 | A kind of method for preparing antibacterial silver-plating leather |
| CN101637679A (en) * | 2009-08-25 | 2010-02-03 | 江南大学 | Method for preparing antibacterial filter screen |
| CN101717920A (en) * | 2009-12-29 | 2010-06-02 | 浙江大学 | Method for preparing composite Ag-Ti oxide antibacterial film by magnetron sputtering |
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