CN104893484B - A kind of double thin antibacterial coating easy to clean and its preparation method and application - Google Patents
A kind of double thin antibacterial coating easy to clean and its preparation method and application Download PDFInfo
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- CN104893484B CN104893484B CN201510342117.2A CN201510342117A CN104893484B CN 104893484 B CN104893484 B CN 104893484B CN 201510342117 A CN201510342117 A CN 201510342117A CN 104893484 B CN104893484 B CN 104893484B
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Abstract
The present invention relates to paint field easy to clean, disclose a kind of double preparation method dredging antibacterial coating easy to clean, the method includes: chitosan is placed in glacial acetic acid aqueous solution by (1), carries out ultrasonic agitation, and high-speed stirred is completely dissolved to chitosan the most again；(2) under ultrasonic agitation, dripping silver nitrate aqueous solution, stir after dropping in the chitosan solution that step (1) obtains, then decompression is distilled off glacial acetic acid and water；(3) being mixed with Ludox, fluorine-containing polyester polymers by step (2) products therefrom, high-speed stirred is uniform, carries out ultrasonic agitation the most again.Also disclose the double thin antibacterial coating easy to clean and the application in kitchen appliance product thereof prepared by said method.The coating of the present invention is easy to clean, acid and alkali-resistance, scratch-resistant, antibacterial, can be widely applied to kitchen appliance product.
Description
Technical field
The present invention relates to a kind of coating easy to clean, in particular it relates to a kind of double thin antibacterial coating easy to clean
Preparation method, double thin antibacterial coating easy to clean and this pair of thin antibacterial coating easy to clean prepared by the method exist
Application in kitchen appliance product.
Background technology
Along with expanding economy, growth in the living standard, people are more and more higher for the requirement of material, right
Requirement in the performance easy to clean of material is also more and more higher, especially for having the most clear of anti-microbial property
The demand of clean material grows with each passing day.
Current kitchen appliance material can meet the electrical equipment basic demand for material, but, right
In the requirement easy to clean that user is the strongest, current technology is but difficult to.Range hood, kitchen range,
Household electrical appliances conventional in the kitchens such as microwave oven are long-time, altofrequency contact oil smoke, acid-base material, various flavoring agent,
Cause outer surface and inner bag to speckle with greasy dirt, contact with greasy dirt due to range hood, kitchen range, microwave oven etc.
Material be mostly metal material or surface carries out the metal material processed that dusts, the surface of these materials
Can be relatively big, cause greasy dirt relatively big with the cohesive force of material, be difficult to the surface making greasy dirt from kitchen appliance material
Depart from, bring the biggest puzzlement to user, be that consumer uses kitchen appliance product for a long time
One pain spot.
The method that the user of kitchen appliance clears up main employing for this type of greasy dirt at present is to use by force
The alkaline cleaner of power coordinates the cleaning supplies that the hardness such as steel wire lump are big, in the effect of bigger cleaning action power
Lower cleaning, though this type of method can clean the material surface of kitchen appliance to a certain extent, but stronger
Alkalescence and during cleaning bigger scraping power the most often make material surface occur scratching, corrosion etc. existing
As, affect the outward appearance of product, even can affect serviceability, to product bring permanent, cannot repair
Damage；And this kind of traditional method cleaning is difficult, the longest, it is impossible to meet user convenient, easily
Clean requirement.
Along with day by day improving and the enhancing of health of people consciousness of living standard, from the simple pursuit in past
The taste of food pursues health, nutrition, delicious food till now, and people are for the antibiotic property of cooking food utensil
Increasing requirement can be there has also been.The household electrical appliances such as range hood, kitchen range, microwave oven, are all that people live
In the most frequently used come cooking food electrical equipment, therefore, people are natural, and the anti-microbial property for this electric appliances has more
Many expectations.The rarely seen antibacterial report being related to this electric appliances of current technology.Visible, have easy to clean
If with the kitchen appliance of anti-microbial property it is achieved that will largely to meet consumer easy clean, healthy
Demand.
Summary of the invention
The invention aims to overcome the drawbacks described above of prior art, it is provided that a kind of easy to clean, antibacterial
Double preparation methoies dredging antibacterial coating easy to clean, prepared by the method double dredges antibacterial coating easy to clean, with
And the application that this coating is in kitchen appliance product.
On the one hand, the invention provides a kind of double preparation method dredging antibacterial coating easy to clean, described method
Including:
(1) chitosan is placed in glacial acetic acid aqueous solution, carries out ultrasonic agitation, the most again high-speed stirred
It is completely dissolved to chitosan；
(2) under ultrasonic agitation, in the chitosan solution that step (1) obtains, silver nitrate is dripped water-soluble
Liquid, stirs after dropping, and then decompression is distilled off glacial acetic acid and water；
(3) step (2) products therefrom is mixed with Ludox, fluorine-containing polyester polymers, high-speed stirred
Uniformly, ultrasonic agitation is carried out the most again.
Preferably, the condition of ultrasonic agitation includes: frequency is 20-25KHz.
Preferably, the number-average molecular weight of chitosan is 20000-300000, more preferably
100000-200000。
Preferably, the concentration of glacial acetic acid aqueous solution is 0.05-0.15mol/L, relative to the shell of 1 weight portion
Polysaccharide, the consumption of glacial acetic acid aqueous solution is 3-7 weight portion.
Preferably, in step (2), the condition of decompression distillation includes: temperature is 40-50 DEG C, and pressure is
0.05-0.09MPa。
Preferably, the gross weight of Ludox and fluorine-containing polyester polymers and chitosan and the gross weight of silver nitrate
Ratio be 1:0.05-0.3, the weight ratio of Ludox and fluorine-containing polyester polymers is 1:0.5-2.5, chitosan with
The weight ratio of silver nitrate is 9-24:1.
Preferably, described Ludox is the titanium dioxide that the alcoholic solution of tetraethyl orthosilicate generates in acid condition
The ethanol solution of Ludox, more preferably tetraethyl orthosilicate generate under conditions of pH value is 2-4 two
Silica sol.
Preferably, the preparation method of described fluorine-containing polyester polymers includes: existed by fluorine-containing beta-unsaturated esters monomer
In the presence of organic solvent, under an inert atmosphere, it is polymerized by initiator.
Preferably, described fluorine-containing beta-unsaturated esters monomer is fluorinated acrylate and/or fluorine-containing vinyl acetate.
Preferably, described organic solvent is Isosorbide-5-Nitrae-dioxane, DMF, dimethyl Asia
At least one in sulfone, oxolane and ethanol.
Preferably, described initiator is azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline hydrochloride
With at least one in benzoyl peroxide.
Second aspect, the invention provides double thin antibacterial coating easy to clean prepared by method as above.
The third aspect, the invention provides double thin antibacterial coating easy to clean as above and produces at kitchen appliance
Application in product.
Double thin antibacterial coating easy to clean prepared by the method using the present invention, due to containing Ludox, permissible
Give the preferable acid and alkali-resistance of coating, scraping and wiping resistance performance and hydrophobic, oleophobic performance, and can be made this
The coating surface that bright coating is formed is micro-coarse, improves hydrophobic, oleophobic performance further；Owing to containing
The polymer that fluorine beta-unsaturated esters monomer aggregates into, can give hydrophobic, oleophobic performance that coating is excellent；By
In the antibacterial being composited containing chitosan and silver ion, chitosan is a kind of natural materials, has good
Good anti-microbial property, is added on compound to chitosan and silver ion in coating, material can be made simultaneously to have concurrently
Easy to clean and antibacterial performance.
Therefore, the spray painting of the present invention can form coating easy to clean after metal material surface, and this is coated with
Layer can effectively reduce the adhesion of greasy dirt, thus reaches the easy of kitchen appliance product external surfaces and inner bag
Cleaning effect, it is not necessary to use the cleaning appliance of the high rigidity such as cleaning agent and steel wire lump, only uses soft clear
Clean cloth or cleaning cotton can easily wipe greasy dirt, even if using the clear of the high rigidity such as cleaning agent and steel wire lump
Clean apparatus, the coating of the present invention also can be protected metal material not to be corroded, swipe, and have good resisting
Bacterium performance, it is possible to greatly meet people for healthy tight demand.Prepared by the method for the present invention double thin
Antibacterial coating easy to clean can be widely applied to kitchen appliance product.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of double preparation method dredging antibacterial coating easy to clean, the method bag
Include:
(1) chitosan is placed in glacial acetic acid aqueous solution, carries out ultrasonic agitation, the most again high-speed stirred
It is completely dissolved to chitosan；
(2) under ultrasonic agitation, in the chitosan solution that step (1) obtains, silver nitrate is dripped water-soluble
Liquid, stirs after dropping, and then decompression is distilled off glacial acetic acid and water；
(3) step (2) products therefrom is mixed with Ludox, fluorine-containing polyester polymers, high-speed stirred
Uniformly, ultrasonic agitation is carried out the most again.
In the present invention, ultrasonic agitation can be carried out in ultrasonic stirrer, and the condition of ultrasonic agitation is preferably wrapped
Include: frequency is 20-25KHz.
In the present invention, for the speed of high-speed stirred without particular/special requirement, it can be the conventional high speed in this area
Stir speed (S.S.), such as, high-speed stirred can be carried out on magnetic stirring apparatus, and speed can be
800-1200rpm。
In step of the present invention (1), the time of ultrasonic agitation is preferably 10-20min.
In step of the present invention (2), stir after dropping and preferably stir under 800-1200rpm
10-15min。
In step of the present invention (3), the time of high-speed stirred is preferably 5-15min, the time of ultrasonic agitation
It is preferably 3-7min.
In the present invention, in order to make chitosan preferably dissolve formation chitosan solution, chitosan preferably employs
Chitosan powder, the number-average molecular weight of chitosan is preferably 20000-300000, more preferably
100000-200000。
In the present invention, for the concentration of glacial acetic acid aqueous solution without particular/special requirement, can use commonly used in the art
The concentration of the glacial acetic acid aqueous solution of concentration, such as glacial acetic acid aqueous solution can be 0.05-0.15mol/L.Right
In the amount of glacial acetic acid aqueous solution also without particular/special requirement, as long as chitosan can be completely dissolved, such as,
Relative to the chitosan of 1 weight portion, the consumption of glacial acetic acid aqueous solution can be 3-7 weight portion.
In the present invention, in order to enable chitosan and silver ion to be preferably compounded to form antibacterial, step (2)
In, preferably it is slowly added dropwise during dropping silver nitrate.
In the present invention, chitosan is preferably 9-24:1 with the weight ratio of silver nitrate.For silver nitrate aqueous solution
Concentration without particular/special requirement, the silver nitrate aqueous solution of this area normal concentration, such as, nitric acid can be used
The concentration of silver aqueous solution can be 0.05-0.15mol/L.
In step of the present invention (2), for decompression distillation without particular/special requirement, as long as in energy removing system
Glacial acetic acid and water, such as, the condition of decompression distillation may include that temperature is 40-50 DEG C, pressure
For 0.05-0.09MPa.
In the present invention, the gross weight of Ludox and fluorine-containing polyester polymers and chitosan and the gross weight of silver nitrate
The ratio of amount is preferably 1:0.05-0.3, and Ludox is preferably with the weight ratio of fluorine-containing polyester polymers
1:0.5-2.5。
In the present invention, Ludox is preferably the dioxy that the alcoholic solution of tetraethyl orthosilicate generates in acid condition
The ethanol solution of SiClx colloidal sol, more preferably tetraethyl orthosilicate generates under conditions of pH value is 2-4
Silicon dioxide gel.For the preparation method of Ludox without particular/special requirement, can use commonly used in the art
Various methods, such as, may include that under 800-1200rpm, and tetraethyl orthosilicate joins excess second
In alcohol, obtain the ethanol solution of tetraethyl orthosilicate, then under 200-500rpm, to tetraethyl orthosilicate
Ethanol solution in drip acid solution, regulation pH value to 2-4, i.e. can get transparent Ludox.
For acid solution without particular/special requirement, as long as pH value can be regulated and do not affects reaction system,
Such as can use hydrochloric acid solution or salpeter solution, for the concentration of acid solution without particular/special requirement, permissible
Using concentration commonly used in the art, this is known to those skilled in the art, does not repeats them here.
In the present invention, for the preparation method of fluorine-containing polyester polymers without particular/special requirement, ability can be used
The various methods that territory is conventional, such as, preparation method may include that fluorine-containing beta-unsaturated esters monomer organic
In the presence of solvent, under an inert atmosphere, it is polymerized by initiator.Specifically may include that fluorine-containing
Beta-unsaturated esters monomer is dissolved in organic solvent, under an inert atmosphere, at 70-90 DEG C, adds 1/4 amount
Initiator, the most again dropping residue 3/4 amount initiator, isothermal reaction 5-7h, then heat to
85-110 DEG C is continued reaction 10-20min.
In the present invention, the initiator of 1/4 amount is disposable addition, and the initiator of residue 3/4 amount is dropping
Enter reaction system, in order to enable fluorine-containing beta-unsaturated esters monomer to be preferably polymerized, the initiation of residue 3/4 amount
Agent is preferably slowly added dropwise into reaction system.It will be understood by those skilled in the art that 1/4 amount, 3/4 amount
It is for the total amount of initiator.
In the present invention, inert atmosphere can be passed through nitrogen in reaction system and/or noble gas is formed,
To discharge the oxygen in reaction system, prevent free radical aerobic in polymerization process from terminating.
In the present invention, fluorine-containing beta-unsaturated esters monomer is preferably 1:1.3-2 with the weight ratio of organic solvent, fluorine-containing
Beta-unsaturated esters monomer is preferably 1:0.01-0.04 with the weight ratio of initiator total amount.
In the present invention, fluorine-containing beta-unsaturated esters monomer is preferably fluorinated acrylate and/or fluorine-containing vinyl acetate.
In the present invention, organic solvent is preferably Isosorbide-5-Nitrae-dioxane, DMF, dimethyl
At least one in sulfoxide, oxolane and ethanol.
In the present invention, initiator is preferably azo-bis-isobutyrate hydrochloride (V50), azo two isobutyl imidazoles
At least one in quinoline hydrochlorate (VA044) and benzoyl peroxide.
Second aspect, the invention provides double thin antibacterial coating easy to clean prepared by method as above.
In the present invention, " double thin " refers to both hydrophobic and oleophobic, and the double of the present invention dredge antibacterial coating easy to clean,
Owing to containing Ludox, the preferable acid and alkali-resistance of coating, scraping and wiping resistance performance and hydrophobic, oleophobic can be given
Performance, and the coating surface that the coating of the present invention can be made to be formed is micro-coarse, improve further hydrophobic,
Oleophobic performance；Due to the polymer aggregated into containing fluorine-containing beta-unsaturated esters monomer, coating can be given excellent
Hydrophobic, oleophobic performance；Due to the antibacterial being composited containing chitosan and silver ion, chitosan is
A kind of natural materials, has good anti-microbial property, is added on compound to chitosan and silver ion in coating,
Material can be made to have easy to clean and antibacterial performance concurrently simultaneously.
The third aspect, the invention provides double thin antibacterial coating easy to clean as above and produces at kitchen appliance
Application in product.
The double thin antibacterial coating easy to clean of the present invention, when actually used, can be sprayed on kitchen appliance product
Surfaces externally and internally, and at 150-250 DEG C solidify 10-20 minute, to form coating, for coating
Thickness, without particular/special requirement, can select according to actual needs, generally 1-15 μm.
Embodiment
The present invention is further illustrated for below example, but and is not so limited the present invention.
In the examples below, ultrasonic agitation at ultrasonic stirrer (purchased from the double limited public affairs of good instrument in Ningbo City
Department, model SJIA-150W, frequency is 20-25KHz, automatic frequency tracking) in carry out.
Embodiment 1
The present embodiment is for illustrating that the double of the present invention dredge antibacterial coating easy to clean and preparation method thereof.
(1) preparation of Ludox: under 1000rpm, the tetraethyl orthosilicate of 18 weight portions is joined
In the ethanol of 20 weight portions, obtain the ethanol solution of tetraethyl orthosilicate, the most at 300 rpm, Xiang Zheng
Dripping the hydrochloric acid solution of 17wt% in the ethanol solution of silester, dropping to pH value is 3, obtains
Bright Ludox.
(2) preparation of fluorine-containing polyester polymers: by the hexafluorobutyl acrylate of 15 weight portions (purchased from breathing out
Your Bin Xuejiafu chemistry of silicones company limited) it is placed in equipped with in the condensation reaction bulb with agitating device, add 20
Isosorbide-5-Nitrae-the dioxane of weight portion and the dimethyl sulfoxide of 20 weight portions, dissolve hexafluorobutyl acrylate
After, it is passed through nitrogen and removes the oxygen in reaction bulb, at 70 DEG C, add the initiator of 0.075 weight portion
V50 (purchased from Jinan Bei Di new material company limited, lower same), is slowly added dropwise 0.225 weight portion the most again
V50, isothermal reaction 6h, then heat to 90 DEG C continue reaction 15min, prepare fluorine-containing polyester
Thing.
(3) preparation of complex antimicrobials: (Australia is new purchased from Jiangsu by the Chitosan powder of 0.18 weight portion
Biological engineering company limited, food stage chitosan, number-average molecular weight 130000-170000) it is placed in 0.1mol/L
Glacial acetic acid aqueous solution in, ultrasonic agitation 15min, then stir to chitosan complete under 1000rpm
Dissolve；In chitosan solution, silver nitrate aqueous solution (its of 0.1mol/L is slowly dripped under ultrasonic agitation
In, silver nitrate is 0.02 weight portion), under 1000rpm, stir 15min after dropping, then exist
45 DEG C, under 0.07MPa decompression glacial acetic acid and water are distilled off, obtain recombination chitosan/Ag antibacterial.
(4) double preparations dredging antibacterial coating easy to clean: respectively step (1), (2), (3) are prepared
Ludox, fluorine-containing polyester polymers, recombination chitosan/Ag antibacterial mixing, stirs under 1000rpm
10min, then in ultrasonic agitation 5min, obtains double thin antibacterial coating A1 easy to clean.
Embodiment 2
The present embodiment is for illustrating that the double of the present invention dredge antibacterial coating easy to clean and preparation method thereof.
(1) preparation of Ludox: at 800 rpm the tetraethyl orthosilicate of 20 weight portions is joined 22
In the ethanol of weight portion, obtain the ethanol solution of tetraethyl orthosilicate, the most at 200 rpm, to positive silicon
Dripping the salpeter solution of 25wt% in the ethanol solution of acetoacetic ester, dropping to pH value is 2, obtains transparent
Ludox.
(2) preparation of fluorine-containing polyester polymers: the Hexafluorobutyl mathacrylate of 20 weight portions (is purchased
From Harbin Xue Jiafu chemistry of silicones company limited) it is placed in the reaction bulb equipped with condensation and agitating device, add
Enter ethanol and the DMF of 20 weight portions of 10 weight portions, by methacrylic acid hexafluoro fourth
After ester dissolves, it is passed through nitrogen and removes the oxygen in reaction bulb, at 75 DEG C, add 0.05 weight portion
Initiator VA044 (purchased from Jinan Bei Di new material company limited, lower same), is slowly added dropwise 0.15 the most again
The VA044 of weight portion, isothermal reaction 7h, then heat to 95 DEG C and continue reaction 10min, prepare and contain
Fluorine polyester polymers.
(3) preparation of complex antimicrobials: (Australia is new purchased from Jiangsu by the Chitosan powder of 0.09 weight portion
Biological engineering company limited, food stage chitosan, number-average molecular weight 100000-150000) it is placed in
In the glacial acetic acid aqueous solution of 0.05mol/L, ultrasonic agitation 10min, stirs the most at 800 rpm to shell
Polysaccharide is completely dissolved；In chitosan solution, the silver nitrate of 0.05mol/L is slowly dripped under ultrasonic agitation
Aqueous solution (wherein, silver nitrate is 0.01 weight portion), stirs 10min at 800 rpm after dropping,
Then 40 DEG C, under 0.05MPa decompression glacial acetic acid and water are distilled off, obtain recombination chitosan/Ag and resist
Microbial inoculum.
(4) double preparations dredging antibacterial coating easy to clean: respectively step (1), (2), (3) are prepared
Ludox, fluorine-containing polyester polymers, recombination chitosan/Ag antibacterial mixing, stirs at 800 rpm
15min, then ultrasonic agitation 7min, obtain double thin antibacterial coating A2 easy to clean.
Embodiment 3
The present embodiment is for illustrating that the double of the present invention dredge antibacterial coating easy to clean and preparation method thereof.
(1) preparation of Ludox: under 1200rpm, the tetraethyl orthosilicate of 15 weight portions is joined
In the ethanol of 18 weight portions, obtain the ethanol solution of tetraethyl orthosilicate, the most at 500 rpm, Xiang Zheng
Dripping the hydrochloric acid solution of 17wt% in the ethanol solution of silester, dropping to pH value is 4, obtains
Bright Ludox.
(2) preparation of fluorine-containing polyester polymers: (purchase pungent for methacrylic acid ten trifluoro of 24 weight portions
From Harbin Xue Jiafu chemistry of silicones company limited) it is placed in the reaction bulb equipped with condensation and agitating device, add
Enter the dimethyl sulfoxide of 36 weight portions, after the methacrylic acid ten pungent dissolving of trifluoro, be passed through nitrogen and remove
Oxygen in reaction bulb, at 90 DEG C, adds the benzoyl peroxide of 0.18 weight portion (purchased from Dongying
Hai Jing Chemical Co., Ltd. of city, lower same), it is slowly added dropwise the benzoyl peroxide of 0.54 weight portion the most again,
Isothermal reaction 5h, then heats to 110 DEG C and continues reaction 10min, prepare fluorine-containing polyester polymers.
(3) preparation of complex antimicrobials: (Australia is new purchased from Jiangsu by the Chitosan powder of 0.28 weight portion
Biological engineering company limited, food stage chitosan, number-average molecular weight 160000-200000) it is placed in
In the glacial acetic acid aqueous solution of 0.15mol/L, ultrasonic agitation 20min, then stir under 1200rpm to
Chitosan is completely dissolved；In chitosan solution, the nitric acid of 0.15mol/L is slowly dripped under ultrasonic agitation
Silver aqueous solution (wherein, silver nitrate is 0.02 weight portion), stirs after dropping under 1200rpm
10min, then 50 DEG C, under 0.09MPa decompression glacial acetic acid and water are distilled off, obtain Composite Shell and gather
Sugar/Ag antibacterial.
(4) double preparations dredging antibacterial coating easy to clean: respectively step (1), (2), (3) are prepared
Ludox, fluorine-containing polyester polymers, recombination chitosan/Ag antibacterial mixing, stirs under 1200rpm
5min, then ultrasonic agitation 3min, obtain double thin antibacterial coating A3 easy to clean.
Embodiment 4
The present embodiment is for illustrating that the double of the present invention dredge antibacterial coating easy to clean and preparation method thereof.
(1) preparation of Ludox: under 1000rpm, the tetraethyl orthosilicate of 13 weight portions is joined
In the ethanol of 15 weight portions, obtain the ethanol solution of tetraethyl orthosilicate, the most at 500 rpm, Xiang Zheng
Dripping the hydrochloric acid solution of 17wt% in the ethanol solution of silester, dropping to pH value is 4, obtains
Bright Ludox.
(2) preparation of fluorine-containing polyester polymers: the dodecafluorhe-ptylacrylate of 28 weight portions (is purchased from
Harbin Xue Jiafu chemistry of silicones company limited) it is placed in the reaction bulb equipped with condensation and agitating device, add
The DMF of 37 weight portions, after being dissolved by dodecafluorhe-ptylacrylate, is passed through nitrogen and removes
Oxygen in dereaction bottle, at 70 DEG C, adds the initiator V50 of 0.14 weight portion, delays
Slow initiator V50, the isothermal reaction 5h dripping 0.42 weight portion, then heats to 85 DEG C and continues reaction
20min, prepares fluorine-containing polyester polymers.
(3) preparation of complex antimicrobials: (Australia is new purchased from Jiangsu by the Chitosan powder of 0.048 weight portion
Biological engineering company limited, food stage chitosan, number-average molecular weight 160000-200000) it is placed in 0.1mol/L
Glacial acetic acid aqueous solution in, ultrasonic agitation 20min, then stir to chitosan complete under 1200rpm
Dissolve；In chitosan solution, silver nitrate aqueous solution (its of 0.1mol/L is slowly dripped under ultrasonic agitation
In, silver nitrate is 0.002 weight portion), under 1200rpm, stir 10min after dropping, then exist
45 DEG C, under 0.07MPa decompression glacial acetic acid and water are distilled off, obtain recombination chitosan/Ag antibacterial.
(4) double preparations dredging antibacterial coating easy to clean: respectively step (1), (2), (3) are prepared
Ludox, fluorine-containing polyester polymers, recombination chitosan/Ag antibacterial mixing, stirs under 1000rpm
10min, then ultrasonic agitation 5min, obtain double thin antibacterial coating A4 easy to clean.
Embodiment 5
The present embodiment is for illustrating that the double of the present invention dredge antibacterial coating easy to clean and preparation method thereof.
(1) preparation of Ludox: at 800 rpm the tetraethyl orthosilicate of 21 weight portions is joined 23
In the ethanol of weight portion, obtain the ethanol solution of tetraethyl orthosilicate, the most at 300 rpm, to positive silicon
Dripping the hydrochloric acid solution of 17wt% in the ethanol solution of acetoacetic ester, dropping to pH value is 3, obtains transparent
Ludox.
(2) preparation of fluorine-containing polyester polymers: the dodecafluoroheptyl methacrylate of 13 weight portions (is purchased
From Harbin Xue Jiafu chemistry of silicones company limited) it is placed in the reaction bulb equipped with condensation and agitating device, add
Enter Isosorbide-5-Nitrae-dioxane and the ethanol of 20 weight portions of 12 weight portions, by dodecafluoroheptyl methacrylate
After dissolving, it is passed through nitrogen and removes the oxygen in reaction bulb, at 80 DEG C, add drawing of 0.02 weight portion
Send out agent VA044 and the benzoyl peroxide of 0.0013 weight portion, be slowly added dropwise 0.06 weight portion the most again
Initiator VA044 and the benzoyl peroxide of 0.0039 weight portion, isothermal reaction 7h, then heat up
Continue reaction 15min to 95 DEG C, prepare fluorine-containing polyester polymers.
(3) preparation of complex antimicrobials: (Australia is new purchased from Jiangsu by the Chitosan powder of 0.09 weight portion
Biological engineering company limited, food stage chitosan, number-average molecular weight 100000-150000) it is placed in
In the glacial acetic acid aqueous solution of 0.05mol/L, ultrasonic agitation 15min, then stir under 1000rpm to
Chitosan is completely dissolved；In chitosan solution, the nitric acid of 0.05mol/L is slowly dripped under ultrasonic agitation
Silver aqueous solution (wherein, silver nitrate is 0.01 weight portion), stirs after dropping under 1000rpm
15min, then 50 DEG C, under 0.05MPa decompression glacial acetic acid and water are distilled off, obtain Composite Shell and gather
Sugar/Ag antibacterial.
(4) double preparations dredging antibacterial coating easy to clean: respectively step (1), (2), (3) are prepared
Ludox, fluorine-containing polyester polymers, recombination chitosan/Ag antibacterial mixing, stirs under 1000rpm
10min, then in ultrasonic agitation 5min, obtains double thin antibacterial coating A5 easy to clean.
Embodiment 6
The present embodiment is for illustrating that the double of the present invention dredge antibacterial coating easy to clean and preparation method thereof.
(1) preparation of Ludox: at 800 rpm the tetraethyl orthosilicate of 15 weight portions is joined 16
In the ethanol of weight portion, obtain the ethanol solution of tetraethyl orthosilicate, the most at 200 rpm, to positive silicon
Dripping the salpeter solution of 25wt% in the ethanol solution of acetoacetic ester, dropping to pH value is 2, obtains transparent
Ludox.
(2) preparation of fluorine-containing polyester polymers: the trifluoroethyl methacrylate of 24 weight portions (is purchased
From Harbin Xue Jiafu chemistry of silicones company limited) it is placed in the reaction bulb equipped with condensation and agitating device, add
Enter the dimethyl sulfoxide of 40 weight portions, after trifluoroethyl methacrylate is dissolved, be passed through nitrogen and remove
Oxygen in reaction bulb, at 75 DEG C, adds the initiator V50 of 0.24 weight portion, the slowest
Drip the V50 of 0.72 weight portion, isothermal reaction 6h, then heat to 90 DEG C and continue reaction 15min,
Prepare fluorine-containing polyester polymers.
(3) preparation of complex antimicrobials: (Australia is new purchased from Jiangsu by the Chitosan powder of 0.09 weight portion
Biological engineering company limited, food stage chitosan, number-average molecular weight 130000-170000) it is placed in
In the glacial acetic acid aqueous solution of 0.15mol/L, ultrasonic agitation 10min, stirs the most at 800 rpm to shell
Polysaccharide is completely dissolved；In chitosan solution, the silver nitrate of 0.15mol/L is slowly dripped under ultrasonic agitation
Aqueous solution (wherein, silver nitrate is 0.01 weight portion), stirs 10min at 800 rpm after dropping,
Then 40 DEG C, under 0.09MPa decompression glacial acetic acid and water are distilled off, obtain recombination chitosan/Ag and resist
Microbial inoculum.
(4) double preparations dredging antibacterial coating easy to clean: respectively step (1), (2), (3) are prepared
Ludox, fluorine-containing polyester polymers, recombination chitosan/Ag antibacterial mixing, stirs at 800 rpm
15min, then ultrasonic agitation 7min, obtain double thin antibacterial coating A6 easy to clean.
Experimental example
It is thick not that the double thin antibacterial coating A1-A6 easy to clean embodiment obtained is sprayed on 1.5mm respectively
On rust steel substrate, and solidifying 15 minutes at 200 DEG C, form coating, the thickness of coating is 8 μm,
Obtain surface-coated cated stainless steel substrate B1-B6, and make with the stainless steel substrate of not sprayed coating
For comparison D1, test as follows.
1, property easy to clean: (COFCO likes delicious by edible oil (good fortune one-level soybean oil near the house), soy sauce
Special grade soy), cooking wine (six must occupy refined cooking wine), vinegar (5 years five grain old vinegars of Chen family), edible
Salt (middle salt green iodine salt) presses 2:4:1:2:1 mix homogeneously, respectively at coating surface, the D1 of B1-B6
Surface drip 5mL, after the flavouring agent on surface all being dried at 200 DEG C, at 25 DEG C cool down 30 minutes,
Immerse in clear water after 5 minutes, use power wiping B1-B6, D1 of 10N by the daily life of a family with textile rag
Surface, then observes the spot situation on surface, the results are shown in Table 1.
2, acid and alkali-resistance:
It is (1) acidproof: in the coating of B1-B6, draw the circle of a diameter of 10mm respectively with marking pen,
With dropper, the acetic acid solution of 1wt% is dropped in circle, till dripping full circle, at 25 DEG C, place 24
After hour, observe the internally coated change of circle, and record, the results are shown in Table 1.
It is (2) alkaline-resisting: in the coating of B1-B6, draw the circle of a diameter of 10mm respectively with marking pen,
With dropper, the sodium hydroxide solution of 0.5wt% is dropped in circle, till dripping full circle, transfer at 25 DEG C
After putting 24 hours, observe the internally coated change of circle, and record, the results are shown in Table 1.
3, scratch-resistant: according to GB/T 6739-1996, hardness-testing device is put down gently respectively B1-B6's
Coating surface, holds pulley both sides, pushes away forward 10mm with the speed of 10cm/s, observes coating table
Whether face is scraped off, and according to the order of pencil hardness, by firmly progressively testing to soft, record pencil completely will not
The maximum hardness on scratch-resistant coatings surface, as the scratch-resistant hardness of coating, the results are shown in Table 1.
4, antibiotic property: carry out reality according to People's Republic of China (PRC) light industry standard QB/T 2591-2003
Test, the bacterium solution of the bacterium solution of staphylococcus aureus, colon bacillus is dripped the most respectively at B1-B6
Coating surface, the surface of D1, initial dripping quantity is designated as the clump count on " 0 " sample time of contact,
Bacterium amount after cultivating 24 hours be designated as 24 hours cultivating after clump count on sample, antibiotic rate=(" 0 "
Clump count on time of contact sample within-24 hours, cultivate after clump count on sample)/" 0 " time of contact
Clump count × 100% on sample, staphylococcus aureus the results are shown in Table 2, the knot of colon bacillus
Fruit is shown in Table 3.
Table 1
Table 2
Table 3
As it can be seen from table 1 double coatings dredging the formation of antibacterial coating easy to clean of the present invention have good
Property easy to clean, acidproof, alkaline-resisting, scratch-resistant.
From table 2 and table 3 it can be seen that double coatings dredging the formation of antibacterial coating easy to clean of the present invention have
Good antibiotic property.
The spray painting of the present invention can form coating easy to clean after metal material surface, and this coating is permissible
Effectively reduce the adhesion of greasy dirt, thus reach the effect easy to clean of kitchen appliance product external surfaces and inner bag
Really, it is not necessary to use the high rigidity such as cleaning agent and steel wire lump cleaning appliance, only use soft cleaning cloth or
Person's cleaning cotton can easily wipe greasy dirt, even if using the Clean-of the high rigidity such as cleaning agent and steel wire lump
Tool, the coating of the present invention also can be protected metal material not to be corroded, swipe, and have good antibiotic property
Can, it is possible to greatly meet people for healthy tight demand.Prepared by the method for the present invention double thin antibacterial
Coating easy to clean can be widely applied to kitchen appliance product.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. double preparation method dredging antibacterial coating easy to clean, it is characterised in that described method includes:
(1) chitosan is placed in glacial acetic acid aqueous solution, carries out ultrasonic agitation, the most again high-speed stirred
It is completely dissolved to chitosan；
(2) under ultrasonic agitation, in the chitosan solution that step (1) obtains, silver nitrate is dripped water-soluble
Liquid, stirs after dropping, and then decompression is distilled off glacial acetic acid and water；
(3) step (2) products therefrom is mixed with Ludox, fluorine-containing polyester polymers, high-speed stirred
Uniformly, ultrasonic agitation is carried out the most again；
Described Ludox is the silicon dioxide gel that the alcoholic solution of tetraethyl orthosilicate generates in acid condition；
Wherein, the gross weight of the gross weight of Ludox and fluorine-containing polyester polymers and chitosan and silver nitrate it
It is 1:0.5-2.5 than the weight ratio for 1:0.05-0.3, Ludox and fluorine-containing polyester polymers, chitosan and nitre
The weight ratio of acid silver is 9-24:1.
Method the most according to claim 1, wherein, the condition of ultrasonic agitation includes: frequency is
20-25KHz。
Method the most according to claim 1, wherein, the number-average molecular weight of chitosan is
20000-300000。
Method the most according to claim 3, wherein, the number-average molecular weight of chitosan is
100000-200000。
5. according to the method described in claim 3 or 4, wherein, the concentration of glacial acetic acid aqueous solution is
0.05-0.15mol/L, relative to the chitosan of 1 weight portion, the consumption of glacial acetic acid aqueous solution is 3-7 weight
Part.
6. according to the method described in any one in claim 1-4, wherein, in step (2), subtract
The condition of pressure distillation includes: temperature is 40-50 DEG C, and pressure is 0.05-0.09MPa.
7. according to the method described in any one in claim 1-4, wherein, described Ludox is just
The silicon dioxide gel that the ethanol solution of silester generates under conditions of pH value is 2-4.
8. according to the method described in any one in claim 1-4, wherein, described fluorine-containing polyester gathers
The preparation method of compound includes: by fluorine-containing beta-unsaturated esters monomer in the presence of an organic, at inert atmosphere
Under, it is polymerized by initiator.
Method the most according to claim 8, wherein, described fluorine-containing beta-unsaturated esters monomer is fluorine-containing
Acrylate and/or fluorine-containing vinyl acetate.
Method the most according to claim 8, wherein, described organic solvent be Isosorbide-5-Nitrae-dioxane,
At least one in N,N-dimethylformamide, dimethyl sulfoxide, oxolane and ethanol.
11. methods according to claim 8, wherein, described initiator is azo two 2,2-Dimethylaziridine salt
At least one in hydrochlorate, azo two isobutyl imidazoline hydrochloride and benzoyl peroxide.
What in 12. claim 1-11 prepared by method described in any one double dredges antibacterial coating easy to clean.
The double thin antibacterial coating easy to clean application in kitchen appliance product described in 13. claim 12.
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| CN108610919B (en) * | 2016-12-26 | 2021-03-30 | 3M创新有限公司 | Preparation method of durable and easy-to-clean antibacterial coating composition |
| CN108129902A (en) * | 2018-03-12 | 2018-06-08 | 常州五荣化工有限公司 | A kind of preparation method of moisture-proof, antibiotic type putty paste |
| CN108950573B (en) * | 2018-07-28 | 2019-11-08 | 苏州速腾电子科技有限公司 | A kind of process of surface treatment of valve |
| WO2020024083A1 (en) * | 2018-07-28 | 2020-02-06 | 苏州速腾电子科技有限公司 | Surface treatment process for valve |
| CN110499091B (en) * | 2019-08-16 | 2021-04-27 | 安徽省优亲科技发展有限公司 | Nano-silver-chitosan modified polyphenyl sulfonamide antibacterial coating and preparation method thereof |
| CN112940396B (en) * | 2021-02-03 | 2023-04-07 | 珠海格力新材料有限公司 | Melt-blown polypropylene with amphiphobic effect and preparation method and application thereof |
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| CN101125934A (en) * | 2007-09-30 | 2008-02-20 | 四川大学 | Method for preparing chitosan/nylon composite antibacterial film containing silver ion |
| CN101899251A (en) * | 2010-08-10 | 2010-12-01 | 上海琥达投资发展有限公司 | Paint for coating surface of sanitary ware made of composite materials and preparation method thereof |
| CN103555184A (en) * | 2013-10-23 | 2014-02-05 | 三棵树涂料股份有限公司 | Super-amphiphobic nano composite finish varnish, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125934A (en) * | 2007-09-30 | 2008-02-20 | 四川大学 | Method for preparing chitosan/nylon composite antibacterial film containing silver ion |
| CN101899251A (en) * | 2010-08-10 | 2010-12-01 | 上海琥达投资发展有限公司 | Paint for coating surface of sanitary ware made of composite materials and preparation method thereof |
| CN103555184A (en) * | 2013-10-23 | 2014-02-05 | 三棵树涂料股份有限公司 | Super-amphiphobic nano composite finish varnish, and preparation method thereof |
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Inventor after: Zhao Li Inventor before: Zhao Li Inventor before: Xue Xiaoshan Inventor before: Zheng Wenqiang |