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CN107354251B - A kind of long acting antibiotic leather and preparation method thereof - Google Patents

A kind of long acting antibiotic leather and preparation method thereof Download PDF

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Publication number
CN107354251B
CN107354251B CN201710723701.1A CN201710723701A CN107354251B CN 107354251 B CN107354251 B CN 107354251B CN 201710723701 A CN201710723701 A CN 201710723701A CN 107354251 B CN107354251 B CN 107354251B
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nano silver
gallic acid
preparation
acid modification
solution
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CN107354251A (en
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刘公岩
李开军
向俊
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SHENZHEN CITY ZUOYOU SOFA Co.,Ltd.
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Sichuan University
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    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C13/00Manufacture of special kinds or leather, e.g. vellum
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00Chemical treatment prior to tanning
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00Chemical treatment prior to tanning
    • C14C1/04Soaking
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00Chemical treatment prior to tanning
    • C14C1/06Facilitating unhairing, e.g. by painting, by liming
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00Chemical treatment prior to tanning
    • C14C1/08Deliming; Bating; Pickling; Degreasing
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00Surface finishing of leather
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/04Mineral tanning
    • C14C3/06Mineral tanning using chromium compounds
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/08Chemical tanning by organic agents
    • C14C3/10Vegetable tanning
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/08Chemical tanning by organic agents
    • C14C3/16Chemical tanning by organic agents using aliphatic aldehydes
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/28Multi-step processes
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

The present invention provides a kind of preparation methods of long acting antibiotic leather, it is after tanning, before washing, the Nano silver solution of gallic acid modification is added, additional amount is the 50~120% of animal fur weight, the partial size of the nano silver of the gallic acid modification is 4~10nm, and the concentration of the nano silver of gallic acid modification is 150~5000ppm in the Nano silver solution of the gallic acid modification.Gained long acting antibiotic leather of the invention still has very outstanding antibacterial effect after the solution for being 1g/L through the soap concentration carrying out washing treatment that at least 3 times each times are 60 minutes at 40 DEG C.Preparation method of the invention is simple, and technique requirement is not harsh, easy to implement.

Description

A kind of long acting antibiotic leather and preparation method thereof
Technical field
The invention belongs to antibacterial leather preparation technical fields, and in particular to a kind of long acting antibiotic leather and preparation method thereof.
Background technique
Nano silver has Durability of antimicrobial effect and broad-spectrum sterilization as anti-biotic material, is not likely to produce bacterial drug resistance, environmental protection The advantages that less toxic, has been widely used in the fields such as biological medicine and textile finishing (Hu Yunrui, nano silver and its composite antibacterial The research of material, 2013, South China Science & Engineering University Ph.D. Dissertation).
In numerous methods for preparing nano silver, chemical reduction method is because easy to operate, cost is relatively low, it is extensive raw to be convenient for The advantages such as production are widely used.Used reducing agent is mostly the (Li Ze such as sodium borohydride, reproducibility glucose and oximes reducing agent State, CN103691967A).
Although chemical reduction method is easy to operate, reducing agent chemical substance is most of all to have toxicity, remains in nanometer It is difficult to remove in silver-colored system, on the one hand security risk is brought to the application of nano silver colloidal sol, on the other hand but also large-scale Production nano silver increases cost.Further, since nanometer silver surface can be higher, its aggregate and precipitate is easily led to, so that it is anti-to influence it Bacterium performance.Therefore additional addition stabilizer is needed to improve the stability of solution of nano silver.There are commonly small molecule stabilizers, such as Sodium citrate;Macromolecule stabilizer, such as polyethylene glycol.But current stabilizer largely plays dispersion nano-Ag particles Effect, without real covalent modification on the surface of nano silver, cannot provide nano silver colloidal sol permanent stability.
Recently, Luo Quanqing et al. is used as reduction using the gallic acid of antibiotic property and low toxicity as stabilizer, sodium borohydride Agent be prepared for a kind of nano silver colloidal sol be used to arrange leather antibacterial (Luo Quan is clear etc., gallic acid modify nano silver preparation and Its antibacterial applications, Chinese leather, 2016,45,5-9).Although gallic acid chemical modification provides excellent steady to nanometer silver surface It is qualitative, but the reaction condition of 0 DEG C of the addition needs due to strong reducing property sodium borohydride, severe reaction conditions, preparation cost are higher And be not suitable for large-scale production.Moreover, prepared nano silver partial size is larger, and average grain diameter is greater than 10nm, has been difficult Equably infiltrate into inside leather entirely, can only dip-coating on the surface of leather carry out antibiotic finish, gained leather is difficult resistance to repeatedly clear It washes.
Although the relationship of size and the antibiotic property to different bacterium for nano silver, though at present without very specific fixed By better anti-microbial property can not being brought (such as " nano silver partial size and anti-but it is appreciated that the smaller nano silver of partial size The relationship of bacterium performance ").So, it while meeting aforementioned stable, is prepared to how to select suitable nano silver Long acting antibiotic leather, it appears more difficult.
In this respect, TaiWan, China patent TW 200714554 has carried out good try, using partial size be 1~ On the basis of the nano silver of 90nm, by the addition of stabilization agent and interfacial agent, obtain on fabric and leather with anti- The aqueous solution of the contg. nano-silver dispersing particles of bacterium effect.But, the patent is when preparing leather, equally exists that stability is insufficient to ask Topic, is difficult resistance to multiple washing.
105038550 A of Chinese patent CN prepares the leather with antibacterial functions also with nano silver.But, It is verified, though the leather has the function of antibacterial, deodorization etc., it is not washable, only after a common soap water washing, and anti-microbial property Just it substantially deteriorates.
In addition, N.Lkhagvajav is in its paper " Characterization and antimicrobial Though being also obtained on performance of nano silver coatings on leather materials " extraordinary Antibacterial leather, but the antibiotic property of its same gained leather is equally highly unstable.Although there is scholar to have studied anti-microbial property more Excellent leather, if M. (KOIZHAIGANOVA) KAYGUSUZ is in its paper " Antimicrobial Nano-Ag- The leather provided in TiO2Coating for Lining Leather ", but regrettably, it is this kind of to attempt also without solution skin The problem of long acting antibiotic stability of leather.
2013/0078451 A1 of United States Patent (USP) US by by nano silver and sub-nanometer silicon dioxide coating in leather surface, Obtain antibacterial leather.This leather does not have long acting antibiotic stability equally.
Summary of the invention
In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a kind of preparation sides of long acting antibiotic leather Method the method includes being soaked for animal fur, fleshing, main immersion, liming depilation, first wash, deliming, takes off Rouge, second wash, pickling, tanning, third time washing and retanning procedures, which is characterized in that after tanning, third time is washed Before, the Nano silver solution of gallic acid modification is added, additional amount is the 50~120% of animal fur weight, the galla turcica The partial size of the nano silver of acid modification is 4~10nm, and gallic acid modification receives in the Nano silver solution of the gallic acid modification The concentration of meter Yin is 150~5000ppm;The Nano silver solution of gallic acid modification the preparation method comprises the following steps:
The water soluble silver salt of 1 molar part is uniformly mixed in water with the gallic acid not less than 1 molar part, then slowly It is added in the aqueous solution of pH=9~12,10~60mi n is stirred to react at 20~60 DEG C, after reaction by solution system PH value be adjusted to neutrality, heptamethylene diamine, which is added, makes it to final concentration of 10~14mM, add butylamine make its to final concentration of 8~ 15mM, the Nano silver solution of final obtained gallic acid modification.
Preferably, the additional amount of the Nano silver solution of the gallic acid modification is the 100% of animal fur weight.
Preferably, the concentration of the nano silver of gallic acid modification is 150 in the Nano silver solution of the gallic acid modification ~500ppm.
Preferably, when preparing the Nano silver solution of gallic acid modification, the water is deionized water or distilled water.
In tanning, tanning agent used includes at least one of metal tanning agents, vegetable tanning agent, aldehyde tanning agent.
Preferably, the metal tanning agents are chrome tanning agent.
Preferably, the extremely final concentration of 12mM of the heptamethylene diamine.
Preferably, the extremely final concentration of 9mM of the butylamine.
Preferably, when preparing the Nano silver solution of gallic acid modification, the pH=11 of the aqueous solution.
Another object of the present invention is that long acting antibiotic leather prepared by the preparation method.
Beneficial effects of the present invention:
1, the present invention gained long acting antibiotic leather through soap concentration be 1g/L solution at 40 DEG C at least 3 times it is each when Between for after 60 minutes carrying out washing treatment, anti-microbial property does not change substantially.
2, preparation method of the invention is simple, and technique requirement is not harsh, easy to implement.
Detailed description of the invention
Fig. 1 is the TEM figure of the Nano silver solution of present invention gained gallic acid modification;
Fig. 2 is the anti-bacterial result figure of the nano silver of present invention gained gallic acid modification;Wherein, (A, D) blank reference sample, Bacteriostasis rate<90% of (B, E) 5ppm Nano silver solution, bacteriostasis rate>99.9% of the Nano silver solution of (C, F) 10ppm;
Fig. 3 is the SEM detection and spectroscopy detection result figure of progress of the invention, wherein (A, C) is not added with gallic acid and repairs The SEM of the sheepskin wet blue leather of the nano silver tanning of decorations schemes and energy spectrum diagram, and (B, D) adds the nano silver tanning of gallic acid modification Sheepskin wet blue leather SEM figure and energy spectrum diagram;
Fig. 4 is to connect containing the nano silver sheepskin wet blue leather that gallic acid is modified to Escherichia coli and staphylococcus aureus Touch germicidal efficiency (A) and inhibition zone (B) result figure;
Fig. 5 is the nano silver sheepskin wet blue leather modified containing gallic acid to Escherichia coli (A) and staphylococcus aureus (B) growth inhibitory effect figure;
Fig. 6 is the nano silver of gallic acid modification and the filling in chrome leather tannery and the fixed schematic diagram of chemistry.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used It is further detailed in the present invention, should not be understood as limiting the scope of the invention, which is skilled in technique Some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
So-called " nano silver " or " gallic acid nano silver " is that described " gallic acid modification is received in following embodiments Meter Yin ".
Embodiment 1
The gallic acid of 1 molar part mix with the silver nitrate of 1 molar part to be made into aqueous solution, is delayed under the conditions of 25 DEG C In the slow water for instilling pH value and being 11, it is protected from light 30min, the pH value of solution system is adjusted to neutrality, heptamethylene diamine, which is added, makes it extremely Final concentration of 10~14mM, adding butylamine makes it to final concentration of 8~15mM, the nano silver of final obtained gallic acid modification Solution.Wherein, argentiferous solid content is 1000ppm.As shown in Figure 1, transmission electron microscope (TEM) scanning result shows the nanometer The average grain diameter of silver is 6nm, and stable at normal temperature can save 180 days or more and deposited phenomenon do not occur.
With Escherichia coli (ATCC25922) and staphylococcus aureus (ATCC6538) for Model of Bacterial.It prepares first dense Degree is respectively 50ppm, 30ppm, 20ppm, and the Nano silver solution of 10ppm, 5ppm, sterile water is as blank referring to sample;Then divide Do not take the above-mentioned solution of 1mL be added to containing bacterial concentration be 5 × 106cfumL-1 5mL LB nutrient solution in, in 37 DEG C of conditions Lower culture is for 24 hours;Then it takes the 20 above-mentioned bacterium solutions of μ L to be applied on agar medium, is cultivated under the conditions of 37 DEG C for 24 hours, utilize plate meter Several methods calculates the minimum nanometer silver concentration for being able to suppress 90% or more bacterium.It is shown to compare with blank sample such as Fig. 2, it is dense The nano silver that degree is 5ppm is respectively less than 90% to the bacteriostasis rate of Escherichia coli and staphylococcus aureus, and the nano silver of 10ppm 99% is above to the bacteriostasis rate of Escherichia coli and staphylococcus aureus, it is thus determined that the minimum of gallic acid modification nano silver Mlc is 10ppm.
Embodiment 2
Long acting antibiotic leather is prepared using the nano silver that 1 gained gallic acid of embodiment is modified:
After the weighing of sheep raw material skin, tanning is carried out according to process for tanning shown in table 1, filling is made and fixes nano silver Sheep wet blue leather;In the process of retanning, the weight of added gallic acid modification Nano silver solution is identical as raw material tare weight, does not eat Nano silver (the calling nano silver in the following text) content of sub- acid modification is 200ppm;After nano silver is filled between leather collagen fiber, skin Nanometer silver chemical is fixed on materials with hide glue fibril by the chrome tanning agent in leather by being covalently complexed;The indigo plant containing nano silver is finally made Wet leather, the characteristic with " nano silver sponge " have long acting antibiotic effect (schematic diagram as shown in FIG. 6).
The obtained wet blue leather of sheepskin containing nano silver is carried out to cut open layer, and utilizes high-resolution electronic flying-spot microscope (SEM) it is scanned its section layer;To be not added with the sheepskin wet blue leather of nano silver as a comparison.As shown in figure 3, addition nanometer It can be seen that apparent nano-Ag particles, power spectrum also show that the letter of silver element on the wet blue leather section layer fiber of silver-colored tanning Number.Should the result shows that, nano silver can be by tanning into inside leather.
By the obtained wet blue leather of sheepskin containing nano silver, it is cut into the round skin sample that quality is 0.1g.First with sterile Water sufficiently cleans skin graft, and being then placed into containing bacterial concentration is 5 × 106cfu·mL-15mL bacterium solution in, at 37 DEG C Under the conditions of cultivate, point, takes the 50 above-mentioned bacterium solutions of μ L to be applied on agar medium, cultivates under the conditions of 37 DEG C in different times For 24 hours, the contact sterilization efficiency of the sample of parchment covering containing nanometer is calculated using the method for plate count;As shown in figure 4, sheepskin containing nano silver Wet blue leather reached 99% or more to the contact sterilization rate of Escherichia coli and staphylococcus aureus in two hours, and showed Apparent inhibition zone;Illustrate that there are efficient bactericidal properties through the tanned wet blue leather of nano silver.
By the obtained wet blue leather of sheepskin containing nano silver, it is cut into the round skin sample that quality is 0.1g.First with sterile Water sufficiently cleans skin graft, is then placed into containing bacterial concentration OD600 (suction of the bacterium solution in 600 nanometers of ultraviolet spectra Receipts value) value be 0.05 10mL bacterium solution in;It is cultivated under the conditions of 37 DEG C, point takes the above-mentioned bacterium solution of 150 μ L and utilizes in different times UV-Vis spectrometer measures its OD600 value.As shown in figure 5, the OD600 value of two kinds of bacteriums does not increase in for 24 hours, explanation The wet blue leather of sheepskin containing nano silver can be by slow release silver ion for sterilization, and inhibits Escherichia coli and golden yellow in long-time Staphylococcic hyperplasia breeding, has long-acting antibacterial functions.
By the obtained wet blue leather of sheepskin containing nano silver, using surface dip-coating nano silver sheepskin wet blue leather as control, Reference standard (GB/T 3921-2008), leather sample wash 3~4 with the solution for being 1g/L containing soap concentration at 40 DEG C It is secondary, every time after sixty minutes, then the leather after washing is evaluated according to the antibacterial evaluation method in embodiment 6, as a result such as Shown in table 2, the finished leather of nano silver tanning is maintained at Escherichia coli and staphylococcus aureus in 2 hours contact sterilization rates 97% or more, and the contact sterilization rate after the finished leather of nano silver dip-coating washing 60min illustrates nano silver tanning less than 60% Leather wash resistant, nanometer galactic longitude chemical action are fixed on materials with hide glue fibril and are not easy to be washed out.
Table 2
Embodiment 3
It weighs after ox-hide acid skin water squeezing, then increases weight 50% as materials benchmark.The technique referring to shown in table 3 carries out tan The ox-hide vegetable leather of filling and fixed nano silver is made in system;After vegetable tanning agent tanning processes, the weight of added Nano silver solution It is the 50% of materials benchmark, the content of nanometer silver of gallic acid modification is 150ppm;When the nano silver filling of gallic acid modification To after between leather collagen fiber, vegatable tannin ingredient contained in the vegetable tanning agent in leather can not have with nanometer silver surface Gallate-based forms hydrogen bond, and then nanometer silver chemical is fixed on materials with hide glue fibril;The vegetable leather containing nano silver is finally made, Characteristic with " nano silver sponge " has long acting antibiotic effect.
Comparative example 1
With " Luo Quan is clear etc., and gallic acid modifies the preparation and its antibacterial applications of nano silver, Chinese leather, and 2016,45,5- 9 " gained leather organizes 1 as a comparison in;2 are organized as a comparison with Chinese patent CN105038550 A embodiment 3;With “Characterization and antimicrobial performance of nano silver coatings on Leather obtained by leather materials " organizes 3 as a comparison;With " Antimicrobial Nano-Ag-TiO2Coating For Lining Leather " organizes 4 as a comparison;Not add referring to embodiment 2 but heptamethylene diamine and butylamine as contrast groups 5.Ginseng According to the test method in embodiment 2 about anti-microbial property after washing, above-mentioned 1~contrast groups of contrast groups, 5 gained leather is examined It surveys, as a result as follows:
Contrast groups 1 are after 3 washings, antibacterial effect decline 27%, after 4 washings, antibacterial effect decline 33%;
Contrast groups 2 are after 3 washings, antibacterial effect decline 38%, after 4 washings, antibacterial effect decline 62%;
Contrast groups 3 are after 3 washings, antibacterial effect decline 34%, after 4 washings, antibacterial effect decline 59%;
Contrast groups 4 are after 3 washings, antibacterial effect decline 35%, after 4 washings, antibacterial effect decline 59%.
Contrast groups 5 are after 3 washings, antibacterial effect decline 24%, after 4 washings, antibacterial effect decline 45%.
The present invention hardly reduces after 3 times and 4 times washings, the present invention and above-mentioned five groups of contrast groups in comparison, With long-acting stabilization anti-microbial property.

Claims (9)

1. a kind of preparation method of long acting antibiotic leather, the method includes being soaked for animal fur, fleshing, main leaching Water, liming depilation, first wash, deliming, degreasing, second wash, pickling, tanning, third time washing and retanning procedures, It is characterized in that, after tanning, before third time is washed, the Nano silver solution of gallic acid modification is added, additional amount is animal The partial size of the 50~120% of fur weight, the nano silver of the gallic acid modification is 4~10nm, the gallic acid modification Nano silver solution in gallic acid modification nano silver concentration be 150~500ppm;The nanometer of the gallic acid modification Silver-colored solution the preparation method comprises the following steps:
The water soluble silver salt of 1 molar part is uniformly mixed in water with the gallic acid not less than 1 molar part, is then slowly added into Into the aqueous solution of pH=9~12,10~60min is stirred to react at 20~60 DEG C, after reaction by the pH of solution system Value is adjusted to neutrality, and heptamethylene diamine, which is added, makes it to final concentration of 10~14mM, and adding butylamine makes it to final concentration of 8~15mM, The Nano silver solution of final obtained gallic acid modification.
2. preparation method according to claim 1, which is characterized in that the Nano silver solution of the gallic acid modification adds Enter 100% that amount is animal fur weight.
3. preparation method according to claim 1, which is characterized in that in the Nano silver solution for preparing gallic acid modification When, the water is deionized water or distilled water.
4. preparation method according to claim 1, which is characterized in that in tanning, tanning agent used include metal tanning agents, At least one of vegetable tanning agent, aldehyde tanning agent.
5. the preparation method according to claim 4, which is characterized in that the metal tanning agents are chrome tanning agent.
6. preparation method according to claim 1, which is characterized in that the extremely final concentration of 12mM of the heptamethylene diamine.
7. preparation method according to claim 1 or 6, which is characterized in that the extremely final concentration of 9mM of the butylamine.
8. preparation method according to claim 1, which is characterized in that in the Nano silver solution for preparing gallic acid modification When, the pH=11 of the aqueous solution.
9. the long acting antibiotic leather being prepared by preparation method according to any one of claims 1 to 8, which is characterized in that institute Long acting antibiotic leather is stated in the solution for being 1g/L through the soap concentration washup that at least 3 times each times are 60 minutes at 40 DEG C After reason, 99% or more is maintained in 2 hours contact sterilization rates for Escherichia coli and staphylococcus aureus.
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