CN106634369A - Hard antibacterial leather coating and preparation method thereof - Google Patents
Hard antibacterial leather coating and preparation method thereof Download PDFInfo
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- CN106634369A CN106634369A CN201610871026.2A CN201610871026A CN106634369A CN 106634369 A CN106634369 A CN 106634369A CN 201610871026 A CN201610871026 A CN 201610871026A CN 106634369 A CN106634369 A CN 106634369A
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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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a hard antibacterial leather coating. The coating is prepared from the following raw materials: 1-2 parts of calcium aluminate, 0.1-0.2 parts of trichloroisocyanuric acid, 1.7-2 parts of polyvinylpyrrolidone, 0.8-1 part of polyacrylamide, 1.6-2 parts of stannous chloride, 0.1-0.13 parts of triethanolamine, 190-200 parts of methyl methacrylate, 3-4 parts of sodium dodecyl sulfate, 0.1-0.2 parts of urotropine, 0.2-0.3 parts of ammonium persulfate, 6-7 parts of a 20%-25% formaldehyde solution, 16-20 parts of zinc acetate, 4-7 parts of silver nitrate, 0.1-0.2 parts of diphenylmethane diisocyanate, 0.1-0.3 parts of diphenyl imidazoline, 1-2 parts of ammonium polyphosphate, 0.1-0.3 parts of manganese isooctanoate and 1-2 parts of molybdenum disulfide. The coating has good antibacterial property and excellent moisture permeability and water resistance, and leather coated with emulsion of the coating is excellent in antibacterial property and hygienic performance.
Description
Technical field
The present invention relates to leather coating technical field, more particularly to a kind of hard antibacterial leather coating and preparation method thereof.
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 hard antibacterial leather coating and its preparation
Method.
The present invention is achieved by the following technical solutions：
A kind of hard antibacterial leather coating, it is made up of the raw material of following weight parts：
Calcium aluminate 1-2, sym-closene 0.1-0.2, polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, protochloride
Tin 1.6-2, triethanolamine 0.1-0.13, methyl methacrylate 190-200, lauryl sodium sulfate 3-4, methenamine 0.1-
0.2nd, formalin 6-7 of ammonium persulfate 0.2-0.3,20-25%, zinc acetate 16-20, silver nitrate 4-7, diphenyl methane two are different
Cyanate 0.1-0.2, diphenyl-imidazole quinoline 0.1-0.3, APP 1-2, manganese iso-octoate 0.1-0.3, molybdenum bisuphide 1-2.
A kind of preparation method of described hard 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 calcium aluminate, molybdenum bisuphide are mixed, ball milling；
（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, in being sent to ptfe autoclave, the microwave hydrothermal 20- at 160-170 DEG C
30 minutes, normal temperature is cooled to, is filtered, must be precipitated；
（4）Above-mentioned APP is added in the deionized water of its weight 10-13 times, above-mentioned ball milling material is added, is stirred,
Above-mentioned precipitation is added, it is 80-90 DEG C to rise high-temperature, and insulated and stirred to water is dry, in being placed in baking oven, is dried 1-2 at 50-60 DEG C little
When, obtain modified zinc oxide；
（5）Above-mentioned diphenyl-imidazole quinoline is taken, in being added to the absolute ethyl alcohol of its weight 17-20 times, is stirred；
（6）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, by precipitate with deionized water wash 3-4 time, be added to the ethanol solution of above-mentioned diphenyl-imidazole quinoline
In, it is 80-90 DEG C to rise high-temperature, and insulated and stirred 17-20 minute, discharging cooling, suction filtration washes filter cake 2-3 time, is placed in baking oven
In, 10-17 minutes are dried at 90-100 DEG C, obtain Ag doping modified zinc oxide；
（7）Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, is stirred, add acetic acid or ammonia
Water, regulation pH is 6-7, adds above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, obtains modified dispersion liquid；
（8）Above-mentioned ammonium persulfate is added in the deionized water of its weight 17-20 times, is stirred；
（9）The 60-70% of above-mentioned methyl methacrylate weight is taken, is mixed with lauryl sodium sulfate, be added to above-mentioned modified point
In dispersion liquid, it is 76-80 DEG C to rise high-temperature, insulated and stirred 10-14 minute, remaining methyl methacrylate and over cure is added dropwise respectively
Sour aqueous ammonium, insulation reaction 120-130 minute after completion of dropping, discharging adds remaining each raw material, stirs to normal temperature, obtains institute
State coating.
A kind of described hard antibacterial leather coating, the using method of the coating is：Surpassed using the front coating by the present invention
Sonication 20-30 minutes, leather surface, air drying, in 76-80 DEG C, 80bar are sprayed under the pressure of 0.2MPa with spray gun
Under conditions of press, spray again afterwards the present invention coating, air drying, 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 into 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 of the present invention can form the coating of hard, and peel strength is high.
Specific embodiment
A kind of hard antibacterial leather coating, it is made up of the raw material of following weight parts：
Calcium aluminate 1, sym-closene 0.1, polyvinylpyrrolidone 1.7, polyacrylamide 0.8, stannous chloride 1.6, three second
Hydramine 0.1, methyl methacrylate 190, lauryl sodium sulfate 3, methenamine 0.1, ammonium persulfate 0.2,20% formaldehyde it is molten
Liquid 6, zinc acetate 16, silver nitrate 4, methyl diphenylene diisocyanate 0.1, diphenyl-imidazole quinoline 0.1, APP 1, isooctyl acid
Manganese 0.1, molybdenum bisuphide 1.
A kind of preparation method of described hard 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 calcium aluminate, molybdenum bisuphide are mixed, ball milling；
（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, and in being sent to ptfe autoclave, microwave hydrothermal 20 minutes at 160 DEG C are cooled to often
Temperature, filters, and must precipitate；
（4）Above-mentioned APP is added in the deionized water of 10 times of its weight, above-mentioned ball milling material is added, is stirred, plus
Enter above-mentioned precipitation, it is 80 DEG C to rise high-temperature, and insulated and stirred to water is dry, in being placed in baking oven, is dried 1 hour at 50 DEG C, obtains modified oxygen
Change zinc；
（5）Above-mentioned diphenyl-imidazole quinoline is taken, in being added to the absolute ethyl alcohol of 17 times of its weight, is stirred；
（6）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 is washed 3 times, in being added to the ethanol solution of above-mentioned diphenyl-imidazole quinoline, rise high-temperature
For 80 DEG C, insulated and stirred 17 minutes, discharging cooling, suction filtration washes filter cake 2 times, in being placed in baking oven, 10 points is dried at 90 DEG C
Clock, obtains Ag doping modified zinc oxide；
（7）Above-mentioned polyacrylamide is added in the deionized water of 80 times of its weight, is stirred, add acetic acid or ammoniacal liquor,
It is 6 to adjust pH, adds above-mentioned Ag doping modified zinc oxide, ultrasound 20 minutes to obtain modified dispersion liquid；
（8）Above-mentioned ammonium persulfate is added in the deionized water of 17 times of its weight, is stirred；
（9）The 60% of above-mentioned methyl methacrylate weight is taken, is mixed with lauryl sodium sulfate, be added to above-mentioned modified dispersion
In liquid, it is 76 DEG C to rise high-temperature, and insulated and stirred 10 minutes, is added dropwise respectively remaining methyl methacrylate and ammonium persulfate is water-soluble
Liquid, insulation reaction 120 minutes after completion of dropping, discharging adds remaining each raw material, stirs to normal temperature, obtains the coating.
A kind of described hard antibacterial leather coating, the using method of the coating is：Surpassed using the front coating by the present invention
Sonication 20 minutes, with spray gun leather surface, air drying, in 76 DEG C, the condition of 80bar are sprayed under the pressure of 0.2MPa
Lower flatiron, sprays again afterwards the coating of the present invention, air drying, 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 hard antibacterial leather coating, it is characterised in that it is made up of the raw material of following weight parts：
Calcium aluminate 1-2, sym-closene 0.1-0.2, polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, protochloride
Tin 1.6-2, triethanolamine 0.1-0.13, methyl methacrylate 190-200, lauryl sodium sulfate 3-4, methenamine 0.1-
0.2nd, formalin 6-7 of ammonium persulfate 0.2-0.3,20-25%, zinc acetate 16-20, silver nitrate 4-7, diphenyl methane two are different
Cyanate 0.1-0.2, diphenyl-imidazole quinoline 0.1-0.3, APP 1-2, manganese iso-octoate 0.1-0.3, molybdenum bisuphide 1-2.
2. a kind of preparation method of hard 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 calcium aluminate, molybdenum bisuphide are mixed, ball milling；
（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, in being sent to ptfe autoclave, the microwave hydrothermal 20- at 160-170 DEG C
30 minutes, normal temperature is cooled to, is filtered, must be precipitated；
（4）Above-mentioned APP is added in the deionized water of its weight 10-13 times, above-mentioned ball milling material is added, is stirred,
Above-mentioned precipitation is added, it is 80-90 DEG C to rise high-temperature, and insulated and stirred to water is dry, in being placed in baking oven, is dried 1-2 at 50-60 DEG C little
When, obtain modified zinc oxide；
（5）Above-mentioned diphenyl-imidazole quinoline is taken, in being added to the absolute ethyl alcohol of its weight 17-20 times, is stirred；
（6）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, by precipitate with deionized water wash 3-4 time, be added to the ethanol solution of above-mentioned diphenyl-imidazole quinoline
In, it is 80-90 DEG C to rise high-temperature, and insulated and stirred 17-20 minute, discharging cooling, suction filtration washes filter cake 2-3 time, is placed in baking oven
In, 10-17 minutes are dried at 90-100 DEG C, obtain Ag doping modified zinc oxide；
（7）Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, is stirred, add acetic acid or ammonia
Water, regulation pH is 6-7, adds above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, obtains modified dispersion liquid；
（8）Above-mentioned ammonium persulfate is added in the deionized water of its weight 17-20 times, is stirred；
（9）The 60-70% of above-mentioned methyl methacrylate weight is taken, is mixed with lauryl sodium sulfate, be added to above-mentioned modified point
In dispersion liquid, it is 76-80 DEG C to rise high-temperature, insulated and stirred 10-14 minute, remaining methyl methacrylate and over cure is added dropwise respectively
Sour aqueous ammonium, insulation reaction 120-130 minute after completion of dropping, discharging adds remaining each raw material, stirs to normal temperature, obtains institute
State coating.
3. a kind of hard 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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| CN201610871026.2A CN106634369A (en) | 2016-09-30 | 2016-09-30 | Hard antibacterial leather coating and preparation method thereof |
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| CN201610871026.2A CN106634369A (en) | 2016-09-30 | 2016-09-30 | Hard antibacterial leather coating and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860519A (en) * | 2016-06-06 | 2016-08-17 | 淮南曹庵润龙塑业有限公司 | Hard polyamide mold material and preparing method thereof |
| 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 CN201610871026.2A patent/CN106634369A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105860519A (en) * | 2016-06-06 | 2016-08-17 | 淮南曹庵润龙塑业有限公司 | Hard polyamide mold material and preparing method thereof |
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Application publication date: 20170510 |