CN106634366A - Smooth antibacterial leather coating and preparation method thereof - Google Patents
Smooth antibacterial leather coating and preparation method thereof Download PDFInfo
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- CN106634366A CN106634366A CN201610870836.6A CN201610870836A CN106634366A CN 106634366 A CN106634366 A CN 106634366A CN 201610870836 A CN201610870836 A CN 201610870836A CN 106634366 A CN106634366 A CN 106634366A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses smooth antibacterial leather coating and a preparation method thereof. The coating is prepared from, by weight, 1-2 parts of ethoxylated alkylphenol ammonium sulfate, 0.7-1 part of hexafluoroacetylacetone, 1.7-2 parts of polyvinylpyrrolidone, 0.8-1 part of polyacrylamide, 1.6-2 parts of stannous chloride, 0.1-0.13 part of triethanolamine, 190-200 parts of methyl methacrylate, 3-4 parts of lauryl sodium sulfate, 0.1-0.2 part of hexamine, 0.2-0.3 part of ammonium persulfate, 6-7 parts of 20-25% formaldehyde solution, 16-20 parts of zinc acetate, 4-7 parts of silver nitrate, 0.2-0.3 part of n-salicylanilide, 0.1-0.2 part of nickel aminosulfonate, 1-2 parts of molybdenum boride, 0.3-1 part of acetylated, wool grease and 1-2 parts of ditetradecyl carbonate. The smooth antibacterial leather coating is excellent in antibacterial performance, moisture permeability and water resistance, and leather coated with the leather coating is great in antibacterial performance and excellent in hygienic property.
Description
Technical field
The present invention relates to leather coating technical field, more particularly to a kind of smooth type antibacterial leather coating and its preparation side
Method.
Background technology
Leather finishing agent/spinning coating agent is a kind of macromolecule compound for being spread evenly across leather/textile surface.It
One or more layers film is formed in leather/fabric face by adhesive effect.Therefore, coating material quality, not only directly affects
Product appearance, quality, and decides the performance of product to a great extent.Polyacrylate dispersion has the flexible richness of film forming
It is flexible, it is the leather-like spinning coating of for being widely used at present the features such as coating is fast light, ageing-resistant, wet-rub resistance can be excellent
Material.But, the presence of some polar groups in conventional polypropylene acid esters emulsion, and product storing, transports, using process
In affected by environmental condition, often occur go mouldy, the phenomenon such as bacteria breed, raw material are not only wasted when serious, and
The important propagating source of disease can be become, human health is endangered.At the same time, coating material defines one in leather/fabric face
Layer fine and close film, the sweat that Severe blockage human body is distributed diffuses to the passage in the external world, causes the health of leather goods/textile
Performance suffers extreme influence, and snugness of fit declines.In recent years, with the continuous improvement of human living standard, research and development are anti-
Leather/weaving that bacterium property is prominent, sanitation performance is excellent is extremely urgent with coating material.
It is that target exploitation nano-ZnO and nanometer ZO/Ag are compound to improve the antibiotic property of polyacrylate coatings, sanitation performance
The antibiotic property of particle, prevents coating breed bacteria, goes mouldy；It is huge using nanometer ZO and nano-ZnO/Ag compound particles
Specific surface area, improves the sanitation performance of coating.
Nano material itself has the features such as size is little, and surface energy is high, is thus susceptible to reunion, bad dispersibility.In addition, receiving
In the preparation process of nano composite material, nano material is poor with the compatibility of the relatively low polymeric matrix of surface energy, and the two is mutually mixed
It is difficult to compatible during conjunction, space easily occurs in interface, there is phenomenon of phase separation.In order that nano material is evenly dispersed in polymer matrix
It is essential to its modifying surface in body.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of smooth type antibacterial leather coating and its system
Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of smooth type antibacterial leather coating, it is made up of the raw material of following weight parts：
Ethoxylated alkylphenol ammonium sulfate 1-2, hexafluoroacetylacetone 0.7-1, polyvinylpyrrolidone 1.7-2, polyacrylamide
0.8-1, stannous chloride 1.6-2, triethanolamine 0.1-0.13, methyl methacrylate 190-200, lauryl sodium sulfate 3-4,
Methenamine 0.1-0.2, formalin 6-7 of ammonium persulfate 0.2-0.3,20-25%, zinc acetate 16-20, silver nitrate 4-7, n-
Salicylanilide 0.2-0.3, nickel sulfamic acid 0.1-0.2, molybdenum boride 1-2, acetylated lanolin 0.3-1, double ten four carbon alcohols esters
1-2。
A kind of preparation method of described smooth type antibacterial leather coating, comprises the following steps：
（1）Above-mentioned zinc acetate, methenamine are mixed, in being added to the deionized water of compound weight 60-100 times, stirring is equal
It is even, it is liquid a；
（2）Above-mentioned molybdenum boride is added in the deionized water of its weight 37-40 times, ultrasonic 1-2 minutes, adds ethoxylation alkane
Base phenol ammonium sulfate, stirs, and obtains dispersion soln；
（3）Above-mentioned polyvinylpyrrolidone is added in its weight 20-30 times, 70-75% ethanol solution, is stirred,
Mix with above-mentioned liquid a, ultrasonic 20-30 minutes, add above-mentioned dispersion soln, 100-200 rev/min of stirring 10-15 minute, be sent to
In ptfe autoclave, the microwave hydrothermal 20-30 minutes at 160-170 DEG C, normal temperature is cooled to, adds above-mentioned sulfamic acid
Nickel, stirs, and filters, and precipitate with deionized water, ethanol are washed 3-4 time successively, in being placed in baking oven, is dried, and obtains modified oxygen
Change zinc；
（4）Above-mentioned modified zinc oxide, stannous chloride are mixed, in being added to the absolute ethyl alcohol of compound weight 100-120 times, is surpassed
Sound 3-5 minutes, above-mentioned silver nitrate, triethanolamine are added, stirred, the formalin of above-mentioned 20-25%, completion of dropping is added dropwise
After be centrifuged off supernatant, precipitate with deionized water, ethanol are washed 3-4 time successively, in being placed in baking oven, at 90-100 DEG C do
Dry 10-17 minutes, obtain Ag doping modified zinc oxide；
（5）Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, above-mentioned hexafluoroacetylacetone is added,
Stir, add acetic acid or ammoniacal liquor, regulation pH is 6-7, adds above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, is obtained
Modified dispersion liquid；
（6）Above-mentioned ammonium persulfate is added in the deionized water of its weight 17-20 times, is stirred；
（7）Above-mentioned lauryl sodium sulfate is taken, in being added to the deionized water of its weight 3-4 times, is stirred, add acetylation
Lanolin, it is 60-70 DEG C to rise high-temperature, insulated and stirred 10-15 minute, adds n- salicylanilides, is stirred to normal temperature, obtains fat point
Dispersion liquid；
（8）The 60-70% of above-mentioned methyl methacrylate weight is taken, is mixed with fat dispersion liquid, be added to above-mentioned modified dispersion liquid
In, it is 76-80 DEG C to rise high-temperature, insulated and stirred 10-14 minute, remaining methyl methacrylate and ammonium persulfate is added dropwise respectively
The aqueous solution, insulation reaction 120-130 minute after completion of dropping, discharging adds remaining each raw material, stirs to normal temperature, obtains the painting
Material.
Described a kind of smooth type antibacterial leather coating, the using method of the coating is：Using the front coating by the present invention
Ultrasonically treated 20-30 minutes, with spray gun leather surface is sprayed under the pressure of 0.2MPa, air drying, 76-80 DEG C,
Press under conditions of 80bar, spray the coating of the present invention, air drying again afterwards, you can.
It is an advantage of the invention that：Zinc oxide particles are evenly dispersed into the ethanol solution of stannous chloride by the present invention first
In, Sn2+ will promptly be adsorbed onto zinc oxide surface；Then, the ethanol solution of Ag (TEA) 2+ is added in above-mentioned reactant liquor,
Sn2+ can occur ion-exchange reactions with Ag (TEA) 2+ for adding so that Ag+ absorption forms silver-colored kind in zinc oxide surface；Reaction
In the later stage, formalin is gradually added dropwise in solution and is persistently stirred, make Ag be reduced into Ag particles；
Preferably, being introduced in polyacrylate can effectively prevent water to ZnO/Ag compound particles resistance to water of the present invention itself
Molecule infiltration is in film, and then the water absorption rate of reduction laminated film, improves its resistance to water；
ZnO/Ag compound particles of the present invention have good anti-microbial property, and under illumination condition, ZnO surfaces produce substantial amounts of
Electronics and hole, the electronics that nanometer Ag capture is generated, obtain Ag-, and then, Ag- reacts with the oxygen molecule of ZnO adsorptions, raw
Into superoxide ion;Superoxide ion further reacts with water, generates perhydroxyl radical and hydrogen peroxide;The H2O of hole and ZnO adsorptions or
HO- ionic reactions, form the activity hydroxy with strong oxidizing property, and activity hydroxy mutually merges generation hydrogen peroxide.Activity hydroxy
Oxidability is most strong in water body oxidant, and can degrade many organic matters；Additionally, oxidant superoxide ion, hydrogen peroxide, mistake
Hydroxyl etc. can destroy biological cell by the effect of the large biological molecules such as oxidation reaction and protein, enzyme, lipid and nucleic acid
Structure, so as to kill bacterium.In course of reaction, silver ion plays catalytic active center, and itself is not consumed.Nanometer Ag
Because granularity is minimum, specific surface area big, surface energy is higher, is easily adsorbed by various bacteriums, so just constrains the work of bacterium
It is dynamic, the disorderly imbalance of living environment of bacterium is made, suppress it to breathe, ultimately result in bacterium and occur " contact is dead ".
After there is the coating of the present invention good antibiotic property, excellent water vapor permeability and resistance to water, gained emulsion to cover with paint, lacquer, colour wash, etc.
Leather antibacterial is good, sanitation performance is excellent；The coating surface smoothness of the formation of the present invention is good, and comfortable feel, stability is strong.
Specific embodiment
A kind of smooth type antibacterial leather coating, it is made up of the raw material of following weight parts：
Ethoxylated alkylphenol ammonium sulfate 1, hexafluoroacetylacetone 0.7, polyvinylpyrrolidone 1.7, polyacrylamide 0.8, chlorine
Change stannous 1.6, triethanolamine 0.1, methyl methacrylate 190, lauryl sodium sulfate 3, methenamine 0.1, ammonium persulfate
0.2nd, 20% formalin 6, zinc acetate 16, silver nitrate 4, n salicylanilides 0.2, nickel sulfamic acid 0.1, molybdenum boride 1, acetyl
Change lanolin 0.3, double ten four carbon alcohols esters 1.
A kind of preparation method of described smooth type antibacterial leather coating, comprises the following steps：
（1）Above-mentioned zinc acetate, methenamine are mixed, in being added to the deionized water of 60 times of compound weight, is stirred, be
Liquid a；
（2）Above-mentioned molybdenum boride is added in the deionized water of 37 times of its weight, ultrasound 1 minute adds ethoxylated alkylphenol
Ammonium sulfate, stirs, and obtains dispersion soln；
（3）Above-mentioned polyvinylpyrrolidone is added in 20 times of its weight, 70% ethanol solution, is stirred, it is and above-mentioned
Liquid a mixes, ultrasound 20 minutes, adds above-mentioned dispersion soln, and 100 revs/min are stirred 10 minutes, are sent to ptfe autoclave
In, microwave hydrothermal 20 minutes at 160 DEG C are cooled to normal temperature, add above-mentioned nickel sulfamic acid, stir, and filter, and will precipitate
Deionized water, ethanol are washed successively 3 times, in being placed in baking oven, are dried, and obtain modified zinc oxide；
（4）Above-mentioned modified zinc oxide, stannous chloride are mixed, in being added to the absolute ethyl alcohol of 100 times of compound weight, ultrasound 3
Minute, above-mentioned silver nitrate, triethanolamine are added, stir, above-mentioned 20% formalin is added dropwise, centrifugation after completion of dropping is removed
Supernatant is removed, precipitate with deionized water, ethanol are washed successively 3 times, in being placed in baking oven, be dried 10 minutes at 90 DEG C, obtain silver-colored
Doping vario-property zinc oxide；
（5）Above-mentioned polyacrylamide is added in the deionized water of 80 times of its weight, above-mentioned hexafluoroacetylacetone, stirring is added
Uniformly, acetic acid or ammoniacal liquor are added, it is 6 to adjust pH, adds above-mentioned Ag doping modified zinc oxide, ultrasound 20 minutes to obtain modified dispersion
Liquid；
（6）Above-mentioned ammonium persulfate is added in the deionized water of 17 times of its weight, is stirred；
（7）Above-mentioned lauryl sodium sulfate is taken, in being added to the deionized water of 3 times of its weight, is stirred, add acetylation sheep
Hair fat, it is 60 DEG C to rise high-temperature, and insulated and stirred 10 minutes adds n salicylanilides, stirs to normal temperature, obtains fat dispersion liquid；
（8）The 60% of above-mentioned methyl methacrylate weight is taken, is mixed with fat dispersion liquid, in being added to above-mentioned modified dispersion liquid, risen
High-temperature is 76 DEG C, and insulated and stirred 10 minutes is added dropwise respectively remaining methyl methacrylate and ammonium persulfate aqueous solution, is added dropwise
Finish rear insulation reaction 120 minutes, discharge, add remaining each raw material, stir to normal temperature, obtain the coating.
A kind of smooth type antibacterial leather coating described in 2, the using method of the coating is：Using the front coating by the present invention
Ultrasonically treated 20 minutes, leather surface, air drying, in 76 DEG C, the bar of 80bar are sprayed under the pressure of 0.2MPa with spray gun
Press under part, spray the coating of the present invention, air drying again afterwards, you can.
Performance test：
Leather after liquid is covered with paint, lacquer, colour wash, etc. is 96.33% to the bacteriostasis rate of Candida albicans, is 80.0% to the bacteriostasis rate of mould.
Claims (3)
1. a kind of smooth type antibacterial leather coating, it is characterised in that it is made up of the raw material of following weight parts：
Ethoxylated alkylphenol ammonium sulfate 1-2, hexafluoroacetylacetone 0.7-1, polyvinylpyrrolidone 1.7-2, polyacrylamide
0.8-1, stannous chloride 1.6-2, triethanolamine 0.1-0.13, methyl methacrylate 190-200, lauryl sodium sulfate 3-4,
Methenamine 0.1-0.2, formalin 6-7 of ammonium persulfate 0.2-0.3,20-25%, zinc acetate 16-20, silver nitrate 4-7, n-
Salicylanilide 0.2-0.3, nickel sulfamic acid 0.1-0.2, molybdenum boride 1-2, acetylated lanolin 0.3-1, double ten four carbon alcohols esters
1-2。
2. a kind of preparation method of smooth type antibacterial leather coating as claimed in claim 1, it is characterised in that including following step
Suddenly：
（1）Above-mentioned zinc acetate, methenamine are mixed, in being added to the deionized water of compound weight 60-100 times, stirring is equal
It is even, it is liquid a；
（2）Above-mentioned molybdenum boride is added in the deionized water of its weight 37-40 times, ultrasonic 1-2 minutes, adds ethoxylation alkane
Base phenol ammonium sulfate, stirs, and obtains dispersion soln；
（3）Above-mentioned polyvinylpyrrolidone is added in its weight 20-30 times, 70-75% ethanol solution, is stirred,
Mix with above-mentioned liquid a, ultrasonic 20-30 minutes, add above-mentioned dispersion soln, 100-200 rev/min of stirring 10-15 minute, be sent to
In ptfe autoclave, the microwave hydrothermal 20-30 minutes at 160-170 DEG C, normal temperature is cooled to, adds above-mentioned sulfamic acid
Nickel, stirs, and filters, and precipitate with deionized water, ethanol are washed 3-4 time successively, in being placed in baking oven, is dried, and obtains modified oxygen
Change zinc；
（4）Above-mentioned modified zinc oxide, stannous chloride are mixed, in being added to the absolute ethyl alcohol of compound weight 100-120 times, is surpassed
Sound 3-5 minutes, above-mentioned silver nitrate, triethanolamine are added, stirred, the formalin of above-mentioned 20-25%, completion of dropping is added dropwise
After be centrifuged off supernatant, precipitate with deionized water, ethanol are washed 3-4 time successively, in being placed in baking oven, at 90-100 DEG C do
Dry 10-17 minutes, obtain Ag doping modified zinc oxide；
（5）Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, above-mentioned hexafluoroacetylacetone is added,
Stir, add acetic acid or ammoniacal liquor, regulation pH is 6-7, adds above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, is obtained
Modified dispersion liquid；
（6）Above-mentioned ammonium persulfate is added in the deionized water of its weight 17-20 times, is stirred；
（7）Above-mentioned lauryl sodium sulfate is taken, in being added to the deionized water of its weight 3-4 times, is stirred, add acetylation
Lanolin, it is 60-70 DEG C to rise high-temperature, insulated and stirred 10-15 minute, adds n- salicylanilides, is stirred to normal temperature, obtains fat point
Dispersion liquid；
（8）The 60-70% of above-mentioned methyl methacrylate weight is taken, is mixed with fat dispersion liquid, be added to above-mentioned modified dispersion liquid
In, it is 76-80 DEG C to rise high-temperature, insulated and stirred 10-14 minute, remaining methyl methacrylate and ammonium persulfate is added dropwise respectively
The aqueous solution, insulation reaction 120-130 minute after completion of dropping, discharging adds remaining each raw material, stirs to normal temperature, obtains the painting
Material.
3. a kind of smooth type antibacterial leather coating according to claim 1,2, it is characterised in that the using method of the coating
For：Using the front coating ultrasonically treated 20-30 minutes by the present invention, leather table is sprayed under the pressure of 0.2MPa with spray gun
Face, air drying, under conditions of 76-80 DEG C, 80bar press, spray again afterwards the present invention coating, air drying, i.e.,
Can.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610870836.6A CN106634366A (en) | 2016-09-30 | 2016-09-30 | Smooth antibacterial leather coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610870836.6A CN106634366A (en) | 2016-09-30 | 2016-09-30 | Smooth antibacterial leather coating and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618892A (en) * | 2004-10-19 | 2005-05-25 | 上海梅盛企业发展有限公司 | Long effect mould proof antibacterial paint and its preparation method |
| CN105925099A (en) * | 2016-05-11 | 2016-09-07 | 滁州职业技术学院 | Anti-flaming antisepsis leather coating and preparation method thereof |
| CN105936788A (en) * | 2016-05-11 | 2016-09-14 | 滁州职业技术学院 | Self-cleaning antibiosis leather coating and preparation method thereof |
-
2016
- 2016-09-30 CN CN201610870836.6A patent/CN106634366A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618892A (en) * | 2004-10-19 | 2005-05-25 | 上海梅盛企业发展有限公司 | Long effect mould proof antibacterial paint and its preparation method |
| CN105925099A (en) * | 2016-05-11 | 2016-09-07 | 滁州职业技术学院 | Anti-flaming antisepsis leather coating and preparation method thereof |
| CN105936788A (en) * | 2016-05-11 | 2016-09-14 | 滁州职业技术学院 | Self-cleaning antibiosis leather coating and preparation method thereof |
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Application publication date: 20170510 |