CN108004762A - One kind is with Nanometer Copper anti bacteria natural silk product and preparation method thereof - Google Patents
One kind is with Nanometer Copper anti bacteria natural silk product and preparation method thereof Download PDFInfo
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
- D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
Abstract
The invention discloses one kind with Nanometer Copper anti bacteria natural silk product and preparation method thereof, comprise the following steps：Silk product immerse the buffer solution containing monascus ruber in, then add mantoquita acid solution, after immersion carry out reducing agent reduction treatment, finally through over cleaning, be dried to obtain with Nanometer Copper anti bacteria natural silk product；While the present invention can improve the broad spectrum antibacterial performance of silk fiber and its fabric, the harm to human body is avoided, also avoids the pollution to environment.The preparation method of the present invention is simple, is easy to mass production, and gained anti bacteria natural silk fibre has excellent antibiotic property, and anti-microbial property is lasting.
Description
Technical field
The present invention relates to a kind of antimicrobial natural macromolecular fibre, and in particular to a kind of anti bacteria natural silk product with Nanometer Copper
And preparation method.
Background technology
At present, domestic and international antibacterial textile treatment technology is broadly divided into two kinds：Anti-bacterial fibre is first made, then makes again
Into all kinds of antibiotic fabrics；Fabric is subjected to post processing processing to obtain anti-microbial property with various antiseptics.Comparatively, first
Fabric anti-bacterial effect obtained by kind of method is lasting, washability is good but with high content of technology, difficulty is big, the wide, anti-bacterial fibre that is related to field
Production process is more complicated, it is high that antiseptic is required.And the working process process of second method is fairly simple, but three in production
Useless more, its washability and durable antibacterial effect are poor.But since second method is easy to process, and alternative antibacterial
Agent scope is wide.Textile either raw fibre, or yarn or fabric, or even ready-made clothes can be resisted by afterfinish method
Bacterium effect, therefore in all kinds of antibiotic fabrics listed at present, with the in the majority of final finishing processing.
In the prior art, the method for final finishing processing includes：
Antiseptic thermal fixation is applied into the Nonstack spun, prefecture yes in fiber surface, such as Japan using reaction resin
The diphenyl ether anti-bacteium deodorization finishing agent such as sanityze.Itself to cellulose without affinity, need to be with 2D resins or cyanaldehyde resin
Spell and use, its durability can be improved, its deodorization Antibacterial Mechanism is the function of the cell membrane and cell membrane that suppress microorganism.
Fiber surface is fixed in antiseptic absorption.Represent the Odoyte of for example inside and outside cotton of commodity.
Hydroxyl separating methanol reaction using the trimethoxy and fiber surface of organosilicon quaternary ammonium salt makes antiseptic fixed.This
Method since antiseptic is completely fixed, antibacterial action by the active part of antiseptic and the contact condition of bacterial cell surface and
It is fixed.Such as the Cransil that the Viosil that Japanese Japan is spun, storehouse are spun, the DC5700 of Dow corning company etc..
Silver-colored zinc Nano-meter SiO_2 is arranged and carried using nano silver2It is whole after the antibacterial that arrangement, chitosan finishing etc. carry out silk
Reason.
Antiseptic used in textile finishing mainly has quaternary ammonium salt, organosilicon quaternary ammonium salt, chitin, shell to gather after general
Extract etc. of sugar, inorganic salts and natural goods, but there are broad-spectrum antibacterial property is poor, washing fastness mostly for presently commercially available antiseptic
Not good enough, the problems such as security is unreliable.Although in anti-bacterial textile finishing agent, silver system have more by force with wide antibacterial action,
It is that U.S.'s Natural Resources Protection Council (NRDC) announced the use of limitation nano silver on the textile in 2014.This be because
Gradually realize for people, silver is simultaneously not so good as the so safe of people's imagination.On the one hand, silver ion or nano silver enter people by skin
In vivo, and silver compound except silver nitrate it is substantially all insoluble, so internal Heavy Metal Accumulation can be caused, so have for a long time
Damage health.
Current nanometer silver antimicrobial method of modifying mainly has two kinds：When first synthesizing nano-silver, then modified silk
Material surface；Another kind is directly in silk material surface fabricated in situ nano silver.However, both approaches common issue is to receive
Meter Yin is only attached on silk material surface, its amount of sticking is low, it is poor to cohere fastness, can not meet application request, therefore into one
Step application is extremely restricted.
The content of the invention
The present invention seeks to disclose a kind of method for simply and easily preparing antimicrobial natural silk product, assign natural high
Molecular fiber antibacterial functions, overcome the shortage of prior art, there is provided a kind of anti-bacterial fibre for loading Nanometer Copper and preparation method thereof, is opened up
Open up its application field；In the antimicrobial natural silk fiber of the present invention, the compound of copper all can dissolve, and the copper into human body also can be with
Metabolism to excrete, on the other hand, copper is that content is only second to iron and zinc in human body, and the 3rd is occupied in trace element
Biological element, and human body and silver element is not required, so, it is standby anti-that antimicrobial natural silk fiber of the invention overcomes existing silvery
The problem of bacterium fiber and defect.
To reach above-mentioned purpose, the technical scheme is that,
A kind of preparation method with Nanometer Copper anti bacteria natural silk product, comprises the following steps, and silk product, which immerses, contains monascus
In the buffer solution of bacterium, mantoquita acid solution is then added, reducing agent reduction treatment is carried out after immersion, finally through over cleaning, dry
To with Nanometer Copper anti bacteria natural silk product.
In above-mentioned technical proposal, the mantoquita is copper nitrate, the one or more in copper sulphate, copper acetate；The mantoquita
Acid in acid solution is sulfuric acid, one kind in phosphoric acid, hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid；In the mantoquita acid solution, mantoquita
Mass concentration be 3%-20%.
In above-mentioned technical proposal, in the buffer solution containing monascus ruber, the mass concentration of monascus ruber is 0.5%-
0.8%；The buffer solution is phosphate buffer.
In above-mentioned technical proposal, the time of the immersion is 20-30 minutes, and temperature is 10 DEG C -15 DEG C；The immersion when
Between for 0.5-12 it is small when, temperature be 0 DEG C -5 DEG C.
In above-mentioned technical proposal, the silk is mulberry silk, tussah silk, wild silk yarn, ricinus silk, spider silk, regeneration silkworm
One or more in silk；The silk product for silk fiber, degumming or non-degumming silk, raw silk, twisted silk, litzendraht wire,
One or more in knitted fabric, woven fabric, non-woven cloth, braid.
In above-mentioned technical proposal, the reducing agent is sodium borohydride, sodium ascorbate, hydrazine hydrate, glucose, Vitamin C
One kind in acid, sugar, sodium citrate, hydrogen peroxide, effectively stable reduction effect can be obtained using reducing agent.
The invention also discloses what is prepared according to the above-mentioned preparation method with Nanometer Copper anti bacteria natural silk product to carry nanometer
Copper anti bacteria natural silk product；The nano copper particle absorption is in silk fiber surface and inside；It is described to carry Nanometer Copper anti bacteria natural silk
In product, the mass content of Nanometer Copper is 5%-20%；The particle diameter of the Nanometer Copper is 1-200nm.
Application of the Nanometer Copper anti bacteria natural silk product in anti-microbial is prepared is carried the invention also discloses above-mentioned.
The invention also discloses a kind of preparation method of the compound cotton thread of antibacterial, comprise the following steps, boiled silk, which immerses, to be contained
Have in the buffer solution of monascus ruber, then add mantoquita acid solution, reducing agent reduction treatment is carried out after immersion, finally by clear
Wash, be dried to obtain with Nanometer Copper anti bacteria natural silk；Then Nanometer Copper anti bacteria natural silk and the cleaning blended preparation antibacterial of cotton thread will be carried
Compound cotton thread, can be used for wound hemostasis etc., and in the compound cotton thread of general antibacterial, the mass fraction of cotton thread is 75%-80%, blended
Mode is the prior art.
Silk cleans to obtain boiled silk through degumming, and obtained boiled silk is immersed in the buffer solution containing monascus ruber,
Then it is soaked in mantoquita acid solution and promotes copper ion to the uniformly penetrating inside and outside silk and absorption, then in-situ reducing copper ion
Nanometer Copper is generated, finally the silk after reaction is washed, is dried to obtain with Nanometer Copper anti bacteria natural silk product.
In preferable technical solution, the mantoquita is copper nitrate, mass concentration 5%-20%；In the mantoquita acid solution
Acid is formic acid, and formic acid mass concentration is 90%~98%；The copper ion reduction is using sodium borohydride as reducing agent；It is preferred herein
Under the conditions of, not only preparation time is shorter, while the silk fiber obtained also has excellent anti-microbial property.
Technique according to the invention scheme, first, pure fibroin fiber is obtained by degumming impurity removal process so that
Fiber meets the application requirements such as follow-up textile garment, health care；Secondly, monascus ruber is adsorbed on silk fiber surface and had
Certain infiltration；Then, silk is swollen using acid solution, open silk inside and outside ion infiltration lane, promote copper ion,
Monascus ruber permeates and fixation to silk inner homogeneous；Thirdly, using reducing agent by the copper ion in-situ reducing inside and outside fiber
Into Nanometer Copper, the fibroin fiber of inside and outside dispersed Nanometer Copper is obtained；Finally, elution work is carried out to loading nanometer copper fiber
Skill removes deionization and organic solvent, and then is dried to obtain with Nanometer Copper anti bacteria natural silk product.Present invention incorporates silk in itself
Fluffy and loose structure, while using acid flux material swelling action, effectively open fiber inside and outside ion infiltration lane, will
Metal copper ion introduces fibrous inside, then it be Nanometer Copper directly to reduce copper ion in the original location by the reproducibility of reducing agent, realization
The dispersed and fixation of Nanometer Copper, it is hereby achieved that permanent antibiotic property and water-wash resistance.In contrast to this, the prior art
Only be that Nanometer Copper is bonded to fiber surface, there are load factor is low, fixed intensity is low, disperse non-uniform problem, especially receive
Rice copper characteristic in itself and nano silver and zinc are different, it is difficult to preferably be attached to fiber surface, it more difficult to permeate and be enriched in
Fibrous inside, the present invention first soak acid solution again with monascus ruber processing silk, and in the presence of monascus ruber, mantoquita is preferable
Penetrate into fibrous inside and be colonized after reduction.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
（1）The present invention is directly effectively swollen natural fiber using acid flux material, fully opens ion inside and outside fiber and oozes
Saturating passage, realize Nanometer Copper presoma copper ion to effective infiltration inside natural fiber with it is dispersed；Solve existing
Metal ion can not be introduced the technical barrier inside natural fiber by technology.
（2）The present invention exists on the basis of metal copper ion is dispersed in inside and outside natural fiber in monascus ruber
Under, realize that metal ion in-situ reducing generates Nanometer Copper by reducing agent, the Nanometer Copper of generation is kept good and disperse
Property, while make it that most of Nanometer Copper is bonded to inside silk, Function is lasting, solves functional molecular and fibre knot
Close the problem of fastness is poor.
（3）Nano copper particle diameter prepared by the present invention is between 10~100nm, and particle diameter is small, size uniform, anti-microbial property
Excellent, especially nanometer copper ion and silk material combination power is strong, after adsorbing parcel copper ion using fibroin albumen, in-situ reducing
Into Nanometer Copper, the reunion of nano silver is effectively avoided, and realizes the good dispersion of Nanometer Copper.
（4）The method of the present invention has wide applicability, suitable for degumming and non-degumming silk, raw silk, twisted silk, braiding
The existing silk product such as line, knitted fabric, woven fabric, non-woven cloth, braid；Nanometer Copper anti-biotic material prepared by the present invention, receives
Rice copper is dispersed in inside and outside material, such as fibrous inside and surface, thus with lasting or permanent anti-microbial property.
（5）The method of the present invention is simple, technological process is short, is easy to volume production；Antibacterial copper particle after particularly handling is deeply fine
Dimension is internal, and does not influence the performance of fibrous mechanical property, avoids influence of the prior art to silk mechanical property, solves existing
There is the technical barrier of technology antibiotic property and the reverse ratio of mechanical property.
Brief description of the drawings
Fig. 1 is one untreated mulberry silk fiber of embodiment（Degumed silk）Scanning electron microscope (SEM) photograph；
Fig. 2 is one antimicrobial treatment mulberry silk fiber of embodiment（Degumed silk）Section transmission electron microscope picture.
Embodiment
The invention will be further described with reference to the accompanying drawings and embodiments：
Embodiment one
90% aqueous formic acid of configuration quality fraction, then adds copper nitrate into formic acid solution, and lucifuge magnetic agitation 5min is molten
Solution, configuration quality concentration are 5% copper nitrate formic acid solution；At 15 DEG C, it is 0.5% that natural degummed mulberry silk is immersed mass concentration
Monascus ruber phosphate buffer in, add above-mentioned copper nitrate formic acid solution after twenty minutes, lucifuge stands 1h, 4 DEG C of temperature；
Sodium borohydride, lucifuge stirring 0.5h are added into the solution of immersion silk；By the abundant water washing of gained silk, it is after natural drying
Obtain antibacterial mulberry silk fiber product；After testing, nanometer copper content about 9.5wt% in fiber；Carry out X-ray diffraction test, X-ray
2 θ of the angle of diffraction is 43.53 °, 50.24 °, 74.91 °, 89.88 °, these characteristic diffraction angles are with copper standard with reference to card 01-085-
The peak value of 1326 card numbers is consistent, thus determines that Nanometer Copper is largely present in inside silk, and transmissioning electric mirror test, which is also observed, to be seen
Fiber cross-sectional has even copper to disperse；Before processing silk tensile strength is 420MPa, is 411Mpa after processing, reaches before processing
More than 97%.
It is as shown in Figure 1 untreated boiled silk scanning electron microscope (SEM) photograph, as seen from the figure, silk fiber surface is smooth；Fig. 2 is anti-
The section transmission electron microscope picture on bacterium processing degummed mulberry silk surface, visible silk carries the nanometer of diameter about 30nm or so in figure
Copper, transmissioning electric mirror test observation see that fiber cross-sectional has even copper to disperse；X-ray diffraction test chart spectrum is shown as
Nanometer Copper characteristic diffraction peak at 43.53 °, 50.24 °, 74.91 °, 89.88 °.Illustrate that the method for the present invention successfully bears copper particle
It is loaded on silk fiber, most copper particle is not easily runed off, can be seen that from the anti-microbial property after washing in fibrous inside.
Embodiment two
98% aqueous formic acid of configuration quality fraction, then adds Salzburg vitriol, lucifuge magnetic agitation into formic acid solution
15min dissolves, and configuration quality concentration is 10% copper sulphate formic acid solution；At 10 DEG C, natural degummed mulberry silk fiber is immersed into matter
Measure in the monascus ruber phosphate buffer that concentration is 0.8%, above-mentioned copper sulphate formic acid solution is added after 30 minutes, lucifuge is quiet
Put 5h, 2 DEG C of temperature；Sodium borohydride, lucifuge stirring 0.5h are added into the solution of immersion silk；Gained degummed mulberry silk is abundant
Water washing, up to antibacterial degummed mulberry silk after natural drying；After testing, nanometer copper content about 15wt% in fiber；Mechanical property is surveyed
Bright tensile strength of taking temperature reaches more than the 95% of before processing.
Antibacterial test uses People's Republic of China's textile industry standard-antibiosis knitting product（FZ/T 73023 —
2006）In antibiotic fabric test method：Vibrate flask method.
Antibacterial effect test is carried out to embodiment one, two gained anti bacteria natural silk fiber of embodiment, while is tested without antibacterial
The anti-microbial property of the silk fiber of processing, the results are shown in Table 1, the results showed that, the degumming and non-degummed mulberry silk after antimicrobial treatment are equal
Excellent anti-microbial property is shown, after 50 standard wash, anti bacteria natural silk still retains more than 85% antibacterial effect, explanation
Antibacterial fastness is high.
The anti-microbial property of the mulberry silk fiber before and after the processing of table 1
Embodiment three
80% trifluoroacetic acid ethanol solution of configuration quality fraction, then adds copper fluoride, lucifuge magnetic agitation 30min into solution
Dissolving, configuration quality concentration are 10% copper fluoride trifluoroacetic acid solution；At 15 DEG C, it is dense that degumming natural tussah silk is immersed into quality
Spend in the monascus ruber phosphate buffer for 0.6%, add above-mentioned copper fluoride trifluoroacetic acid solution after twenty minutes, lucifuge is quiet
Put 2h, 1 DEG C of temperature；Sodium citrate, lucifuge stirring 1h are added into the solution of immersion silk；Gained degumming natural tussah silk is filled
Divide washing, up to antibacterial silk tussah fibre after natural drying.After testing, nanometer copper content about 12wt% in fiber；Carry out X-ray
Diffraction test, find Nanometer Copper be largely present in inside silk, X-ray diffraction test chart spectrum show as 43.53 °,
Nanometer Copper characteristic diffraction peak at 50.24 °, 74.91 °, 89.88 °, transmissioning electric mirror test, which is also observed, sees that fiber cross-sectional has uniformly
Nanometer Copper disperses；Tensile strength reaches more than the 93% of before processing；Escherichia coli inhibiting rate reaches 99.3%, and withered grass bacterium inhibiting rate reaches
To 97.3%, gold-coloured staphylococci inhibiting rate reaches 97.2%, and after 50 standard wash, anti bacteria natural silk still retains more than 85%
Antibacterial effect, illustrate antibacterial fastness height.
Example IV
50% phosphoric acid methanol solution of configuration quality fraction, then adds copper nitrate into solution, and lucifuge magnetic agitation 5min dissolves,
Configuration quality concentration is 15% copper nitrate phosphoric acid solution；At 15 DEG C, it is 0.6% that natural mulberry silk woven fabric is immersed mass concentration
Monascus ruber phosphate buffer in, add above-mentioned copper nitrate phosphoric acid solution after twenty minutes, lucifuge stands 5h, 5 DEG C of temperature；
Hydrazine hydrate, lucifuge stirring 0.8h are added into the solution of immersion fabric；Gained silk fabrics is fully washed, after natural drying to obtain the final product
Antibacterial Light of Mulberry Silk Fabrics；After testing, nanometer copper content about 10wt% in fabric；Escherichia coli inhibiting rate reaches 98.1%, withered
Careless bacterium inhibiting rate reaches 97.3%, and gold-coloured staphylococci inhibiting rate reaches 97.9%, and after 50 standard wash, anti bacteria natural silk is still
Retain more than 82% antibacterial effect, illustrate antibacterial fastness height.
Embodiment five
50% aqueous formic acid of configuration quality fraction, then adds copper chloride into formic acid solution, and lucifuge magnetic agitation 10min is molten
Solution, configuration quality concentration are 10% copper chloride formic acid solution；At 10 DEG C, it is by natural ricinus silk raw silk immersion mass concentration
In 0.6% monascus ruber phosphate buffer, above-mentioned copper chloride formic acid solution is added after twenty minutes, and lucifuge stands 12h, temperature
3 DEG C of degree；Hydrogen peroxide, lucifuge stirring 1h are added into the solution of immersion silk；Gained raw silk is fully washed, after natural drying i.e.
Obtain antibacterial castor silkworm raw silk product；After testing, nanometer copper content about 13wt% in fiber；Tensile strength reach the 94% of before processing with
On；Escherichia coli inhibiting rate reaches 97.4%, and withered grass bacterium inhibiting rate reaches 96.7%, and gold-coloured staphylococci inhibiting rate reaches 95.8%,
After 50 standard wash, anti bacteria natural silk still retains more than 80% antibacterial effect, illustrates antibacterial fastness height.
Embodiment six
30% aqueous sulfuric acid of configuration quality fraction, then adds copper nitrate, lucifuge magnetic agitation 20min dissolvings, match somebody with somebody into solution
Put the copper nitrate sulfuric acid solution that mass concentration is 10%；At 15 DEG C, it is 0.6% that natural mulberry silk litzendraht wire is immersed mass concentration
In monascus ruber phosphate buffer, above-mentioned copper fluoride trifluoroacetic acid solution is added after 25 minutes, lucifuge stands 24h, temperature 4
℃；Sodium borohydride, lucifuge stirring 0.5h are added into the solution of immersion silk fabric；Gained silk litzendraht wire is fully washed,
Up to antibacterial mulberry silk litzendraht wire after vacuum drying；After testing, nanometer copper content about 6wt% in fibrage line；Escherichia coli press down
Rate processed reaches 99.2%, and withered grass bacterium inhibiting rate reaches 98.8%, and gold-coloured staphylococci inhibiting rate reaches 99.1%, by 50 standards
After washing, anti bacteria natural silk still retains more than 90% antibacterial effect, illustrates antibacterial fastness height.
Embodiment seven
98% aqueous formic acid of configuration quality fraction, then adds Salzburg vitriol, lucifuge magnetic agitation into formic acid solution
15min dissolves, and configuration quality concentration is 10% copper sulphate formic acid solution；At 10 DEG C, natural degummed mulberry silk fiber is immersed into matter
Measure in the monascus ruber phosphate buffer that concentration is 0.8%, above-mentioned copper sulphate formic acid solution is added after 30 minutes, lucifuge is quiet
Put 5h, 2 DEG C of temperature；Sodium borohydride, lucifuge stirring 0.5h are added into the solution of immersion silk；Gained degummed mulberry silk is abundant
Water washing, up to antibacterial degummed mulberry silk after natural drying；Cotton thread after antibacterial degummed mulberry silk and ultraviolet disinfection is blended
To the compound cotton thread of antibacterial, the wherein mass fraction of cotton thread is 78%, is tested for animal wound hemostasis, and blood coagulation speed improves 30%,
Usage time extends 40% than existing gauze and does not occur infection sign.
Comparative example one
98% aqueous formic acid of configuration quality fraction, then adds Salzburg vitriol, lucifuge magnetic agitation into formic acid solution
15min dissolves, and configuration quality concentration is 10% copper sulphate formic acid solution；At 15 DEG C, natural degummed mulberry silk fiber is immersed into phosphorus
In phthalate buffer, above-mentioned copper sulphate formic acid solution is added after 30 minutes, lucifuge stands 5h, 24 DEG C of temperature；To immersion silk
Solution in add sodium borohydride, lucifuge stirring 0.5h；It is to obtain the final product anti-after natural drying by the abundant water washing of gained degummed mulberry silk
Bacterium degummed mulberry silk；Mechanics Performance Testing shows that tensile strength reaches the 80% of before processing, after testing, nanometer copper content in fiber
About 0.1wt%；；Escherichia coli inhibiting rate 45.5%, withered grass bacterium inhibiting rate reach 36.5%, and gold-coloured staphylococci inhibiting rate reaches
24.1%, after 50 standard wash, anti bacteria natural silk is almost without fungistatic effect.
Comparative example two
98% aqueous formic acid of configuration quality fraction, then adds Salzburg vitriol, lucifuge magnetic agitation into formic acid solution
15min dissolves, and configuration quality concentration is 20% copper sulphate formic acid solution；At 15 DEG C, natural degummed mulberry silk fiber is immersed into matter
Measure in the monascus ruber phosphate buffer that concentration is 1.2%, above-mentioned copper sulphate formic acid solution is added after 30 minutes, lucifuge is quiet
Put 5h, 24 DEG C of temperature；Sodium borohydride, lucifuge stirring 0.5h are added into the solution of immersion silk；Gained degummed mulberry silk is filled
Divide water washing, up to antibacterial degummed mulberry silk after natural drying；Mechanics Performance Testing shows that tensile strength reaches before processing
60%, after testing, nanometer copper content about 2wt% in fiber；Escherichia coli inhibiting rate reaches 65.5%, and withered grass bacterium inhibiting rate reaches
56.5%, gold-coloured staphylococci inhibiting rate reaches 44.1%, and after 50 standard wash, anti bacteria natural silk retains 10% fungistatic effect.
Claims (10)
1. a kind of preparation method with Nanometer Copper anti bacteria natural silk product, it is characterised in that comprise the following steps, silk product leaching
Enter in the buffer solution containing monascus ruber, then add mantoquita acid solution, reducing agent reduction treatment is carried out after immersion, is finally passed through
Clean, be dried to obtain with Nanometer Copper anti bacteria natural silk product.
2. the preparation method of Nanometer Copper anti bacteria natural silk product is carried according to claim 1, it is characterised in that the mantoquita is
One or more in copper nitrate, copper sulphate, copper acetate；Acid in the mantoquita acid solution is sulfuric acid, phosphoric acid, hydrochloric acid, formic acid,
One kind in acetic acid, trifluoroacetic acid；In the mantoquita acid solution, the mass concentration of mantoquita is 3%-20%.
3. the preparation method of Nanometer Copper anti bacteria natural silk product is carried according to claim 1, it is characterised in that described containing red
In the buffer solution of Aspergillus, the mass concentration of monascus ruber is 0.5%-0.8%；The buffer solution is phosphate buffer.
4. the preparation method of Nanometer Copper anti bacteria natural silk product is carried according to claim 1, it is characterised in that the immersion
Time is 20-30 minutes, and temperature is 10 DEG C -15 DEG C；When the time of the immersion is 0.5-12 small, temperature is 0 DEG C -5 DEG C.
5. the preparation method of Nanometer Copper anti bacteria natural silk product is carried according to claim 1, it is characterised in that the silk is
One or more in mulberry silk, tussah silk, wild silk yarn, ricinus silk, regenerated silk.
6. the preparation method of Nanometer Copper anti bacteria natural silk product is carried according to claim 1, it is characterised in that the silk system
Product are silk fiber, degumming or non-degumming silk, raw silk, twisted silk, litzendraht wire, knitted fabric, woven fabric, non-woven cloth, braiding
The one or more of thing.
7. the preparation method of Nanometer Copper anti bacteria natural silk product is carried according to claim 1, it is characterised in that the reducing agent
For one kind in sodium borohydride, sodium ascorbate, hydrazine hydrate, glucose, ascorbic acid, sugar, sodium citrate, hydrogen peroxide.
What 8. according to claim 1 prepared by the preparation method with Nanometer Copper anti bacteria natural silk product carries Nanometer Copper antibacterial silkworm
Squeeze.
9. a kind of preparation method of the compound cotton thread of antibacterial, it is characterised in that comprise the following steps, boiled silk, which immerses, contains red yeast rice
In the buffer solution of mould, mantoquita acid solution is then added, reducing agent reduction treatment is carried out after immersion, finally through over cleaning, drying
Obtain carrying Nanometer Copper anti bacteria natural silk；Then Nanometer Copper anti bacteria natural silk and the blended preparation antibacterial composite cotton fabric of cleaning cotton thread will be carried
Line.
10. application of the Nanometer Copper anti bacteria natural silk product in anti-microbial is prepared is carried described in claim 8.
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| CN111670907A (en) * | 2020-06-18 | 2020-09-18 | 湖南国发精细化工科技有限公司 | Fenobucarb pesticide stabilizer and fenobucarb pesticide |
| CN112376265A (en) * | 2020-11-12 | 2021-02-19 | 上海普榭尔科技有限公司 | Method for preparing antimicrobial treatment agent for textiles |
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| CN115652625B (en) * | 2022-11-15 | 2024-03-12 | 中南大学湘雅三医院 | Non-woven fabric with nano copper and shikonin and preparation method thereof |
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| CN108004762B (en) | 2019-12-10 |
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Effective date of registration: 20221128 Address after: 517 Huanzhu Road, Wuxing District, Huzhou City, Zhejiang Province 313000 Patentee after: Huzhou Jinyu Silk Technology Co.,Ltd. Address before: 545006 No. 268 East Ring Road, the Guangxi Zhuang Autonomous Region, Liuzhou Patentee before: GUANGXI University OF SCIENCE AND TECHNOLOGY |