CN105925151B - A kind of composite antibacterial coating - Google Patents
A kind of composite antibacterial coating Download PDFInfo
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- CN105925151B CN105925151B CN201610290773.7A CN201610290773A CN105925151B CN 105925151 B CN105925151 B CN 105925151B CN 201610290773 A CN201610290773 A CN 201610290773A CN 105925151 B CN105925151 B CN 105925151B
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- 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
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- 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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Abstract
The present invention provides a kind of composite antibacterial coating, includes following components：The polymer emulsion of 55 mass parts, 15~20 mass parts Cu-Mn-F doping MgO nano antibacterial agent, 10~15 mass parts Ag-ZnTiO3Nano antibacterial agent, the organic antibacterial agent of 2~4 mass parts, the toughener of 0.6~1 mass parts, the emulsifier of 0.5~0.8 mass parts, the coupling agent of 0.5~0.8 mass parts, the stabilizer of 0.4~0.6 mass parts and 8~10 mass parts solvent.
Description
Technical field
The present invention relates to antimicrobial technology field more particularly to a kind of refrigerator composite antibacterial coating.
Background technique
Plastics, such as drawer, fruit and vegetable box of the refrigerator inside for food containers itself do not have antibacterial and antibacterial effect,
Therefore, in the long-term use process since the storage of food can breed bacterium, mould.How refrigerator inside food containers are solved
Antibacterial action be a problem to be solved always.
It is carried out disinfection processing using disinfectant to food containers, often there is disinfectant residual, be used for a long time and endanger to human body
Evil is very big.Presently commercially available some antimicrobial refrigerators usually make refrigerator generate antibacterial using silver ion plating membrane coat or antibiotic plastic
Effect, prevents the growth of bacterium, the generation of accumulation and peculiar smell.But dissolution can occur in use for silver ion antimicrobial agent now
As so that antibacterial activity gradually decreases；Antibiotic plastic due to antibacterial agent is dispersed in plastics inner and cannot make its adequately with
Bacterium contacts and reduces activity.Therefore, the problem not high for the generally existing antibacterial activity of current antimicrobial refrigerator, develops one kind
The refrigerator that stability is good, antibacterial activity is high is of great practical significance with composite antibacterial coating.
Summary of the invention
The main purpose of the present invention is to provide a kind of composite antibacterial coating, stability is good, antibacterial activity is high, can be used as
The coating of refrigerator inner pressurd vessel, so that refrigerator has preferable antibacterial effect.
To achieve the above objectives, the present invention provides a kind of composite antibacterial coating, includes following components：Polymer emulsion, Cu-
Mn-F adulterates MgO nano antibacterial agent, Ag-ZnTiO3It is nano antibacterial agent, organic antibacterial agent, toughener, emulsifier, coupling agent, steady
Determine agent and solvent.
Preferably, the content of each component is：The Cu-Mn-F doping of the polymer emulsion of 55 mass parts, 15~20 mass parts
The Ag-ZnTiO of MgO nano antibacterial agent, 10~15 mass parts3Nano antibacterial agent, the organic antibacterial agent of 2~4 mass parts, 0.6~1
The toughener of mass parts, the emulsifier of 0.5~0.8 mass parts, the coupling agent of 0.5~0.8 mass parts, 0.4~0.6 mass parts
The solvent of stabilizer and 8~10 mass parts.
Preferably, the polymer emulsion is the mixture of polylactic acid and acrylic acid ester emulsion, polylactic acid and acrylate
The weight ratio of lotion is 6: 5.The organic antibacterial agent is octadecyl triphenyl phosphonium chloride.The toughener is that adipic acid two is pungent
Rouge.The emulsifier is industrial concentrating soya lecithin.The coupling agent is methyl dodecyl diethoxy silane.The stabilization
Agent is triphenyl phosphite.The solvent is isooctanol.
Preferably, the preparation method of the Cu-Mn-F doping MgO nano antibacterial agent is：Preparing the mass ratio of the material is 1:
0.03: 0.05: 0.05 magnesium nitrate hexahydrate, Gerhardite, four acetate hydrate manganese, ammonium fluoride；First by six nitric hydrates
Magnesium is dissolved in deionized water, forms the first solution；Gerhardite, four acetate hydrate manganese, ammonium fluoride are sequentially added described
First solution is mixing uniformly to form the second solution；Second solution is added in a certain amount of surfactant, is stirred evenly
Third solution is formed afterwards；The use of the pH value that urea adjusts the third solution is 9.5, precipitation reaction occurs, continues stirring to obtain
Mixture；The mixture is stirred under heated condition, removal excessive moisture obtains jelly；After drying the jelly, grinding,
The Cu-Mn-F doping MgO nano antibacterial agent is obtained after calcining.
Preferably, the Ag-ZnTiO3The preparation method of nano antibacterial agent is：Preparing the mass ratio of the material is 1: 0.03: 1
Zinc nitrate hexahydrate, silver nitrate, butyl titanate；First zinc nitrate hexahydrate and silver nitrate are dissolved in deionized water, form the 4th
Solution；Butyl titanate is added in the 4th solution, the 5th solution is formed；5th solution is placed in agitating device
In microwave device, it is 11 that ammonium hydroxide, which is then added, and adjusts pH value, after precipitation reaction occurs, continues stirring and one timing of microwave radiation
Between, obtain reaction product；It is centrifugated the reaction product and obtains solid product；After drying the solid product, grinding, calcining
Obtain the Ag-ZnTiO3Nano antibacterial agent.
The present invention also provides a kind of methods for preparing the composite antibacterial coating, include the following steps：
(1) solvent, coupling agent are uniformly mixed, obtain the 6th mixed liquor；
(2) polylactic acid, acrylate, Cu-Mn-F are adulterated into MgO nano antibacterial agent, Ag-ZnTiO3Nano antibacterial agent has
Machine antibacterial agent is added in the 6th mixed liquor, stirs evenly and obtains the 7th mixed liquor；
(3) toughener, stabilizer, emulsifier are added in the 7th mixed liquor, stirring to obtain composite antibacterial coating.
The composite antibacterial coating of the invention when in use, is uniformly applied to the plastic substrates such as drawer or the partition of refrigerator
Surface, composite antibacterial coating can be formed in foregoing plastics matrix surface at room temperature by drying.
Composite antibacterial coating provided by the invention is added to Cu-Mn-F dopen Nano MgO and Ag-ZnTiO3Nano-antibacterial
Agent has the advantages that property is stable, antibacterial activity is high, nano-class antibacterial agent can it is fully dispersed in a polymer matrix, thus
Assign coating excellent anti-microbial property.The composite antibacterial coating selects octadecyl triphenyl phosphonium chloride as organic anti-bacterial
Agent acts synergistically with inorganic antiseptic, further improves the anti-microbial property of the composite antibacterial coating.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1 provides a kind of Cu-Mn-F doping MgO nano antibacterial agent, is prepared by following steps：
(1) prepare the magnesium nitrate hexahydrate of 25.6g, the Gerhardite of 0.12g, 1.23g four acetate hydrate manganese,
The ammonium fluoride of 0.19g；
(2) magnesium nitrate hexahydrate is added in the deionized water of 200ml, is turned in 40 DEG C of water-bath, in 400r/min
Lower stirring to the magnesium nitrate hexahydrate of speed is completely dissolved, to form the first solution；
(3) Gerhardite, four acetate hydrate manganese, ammonium fluoride are sequentially added described under same stirring condition
One solution is mixing uniformly to form the second solution；
(4) second solution is added in 1g surfactant polyethylene 4000, improve revolving speed makes to gather to 600r/min
Ethylene glycol 4000 is completely dissolved, and forms third solution；
(5) the use of the pH value that urea adjusts the third solution is 9.5, precipitation reaction occurs, in 40 DEG C of water-bath,
Continue to stir 2h acquisition mixture under the revolving speed of 600r/min；
(6) it improves bath temperature to 90 DEG C, revolving speed and improves to 800r/min and continue to stir 4h to the mixture, go to remove water
Jelly is obtained after point；
(7) jelly is dried into 6h at 100 DEG C, is then ground to powder, finally calcined 4h at 400 DEG C and obtain
The Cu-Mn-F adulterates MgO nano antibacterial agent.
Embodiment 2 provides a kind of Ag-ZnTiO3Nano antibacterial agent is prepared by following steps：
(1) prepare the butyl titanate of the zinc nitrate hexahydrate of 44.6g, the silver nitrate of 0.85g, 51.1g；
(2) zinc nitrate hexahydrate and silver nitrate are added in 50ml deionized water, at room temperature under the revolving speed of 400r/min
Stirring to zinc nitrate hexahydrate and silver nitrate is completely dissolved, and forms the 4th solution；
(3) butyl titanate is added dropwise in the 4th solution under the revolving speed of 800r/min, forms the 5th solution；
(4) the 5th solution is placed in the microwave device with agitating device, mixing speed 800r/min, Microwave Frequency
Rate is 2.45GHz, be then added dropwise under stiring ammonium hydroxide adjust pH value be 11, occur precipitation reaction after, continue stirring and it is micro-
Wave radiation 30min, obtains reaction product；
(5) it is centrifugated the reaction product under the speed of 8000r/mim and obtains solid product；
(6) solid product is dried into 6h at 100 DEG C, is then ground to powder, finally calcined 5h at 400 DEG C and obtain
To the Ag-ZnTiO3Nano antibacterial agent.
Embodiment 3 provides a kind of composite antibacterial coating, is prepared by following steps：
(1) the coupling agent methyl dodecyl diethoxy silane of the solvent isooctanol of 10 mass parts, 0.6 mass parts is existed
Container high speed stirs 20min and obtains the 6th mixed liquor；
(2) Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 15 mass parts is adulterated MgO nanometers
The Ag-ZnTiO of antibacterial agent, 15 mass parts3The organic antibacterial agent octadecyl triphenyl phosphonium chloride of nano antibacterial agent, 3 mass parts
It is added in the 6th mixed liquor, keeps the revolving speed of 3000r/min to stir 10min, obtain the 7th mixed liquor；
(3) by the toughener adipic acid dibutyl ester of 0.7 mass parts, the stabilizer triphenyl phosphite of 0.4 mass parts, 0.7
The emulsifier industry concentrating soya lecithin of mass parts is added in the 7th mixed liquor, stirs 30 under the revolving speed of 4000r/min
Minute obtains the composite antibacterial coating.
Embodiment 4 provides a kind of composite antibacterial coating, is prepared by following steps：
(1) the coupling agent methyl dodecyl diethoxy silane of the solvent isooctanol of 9 mass parts, 0.7 mass parts is existed
Container high speed stirs 20min and obtains the 6th mixed liquor；
(2) Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 18 mass parts is adulterated MgO nanometers
The Ag-ZnTiO of antibacterial agent, 12 mass parts3The organic antibacterial agent octadecyl triphenyl phosphonium chloride of nano antibacterial agent, 2 mass parts
It is added in the 6th mixed liquor, keeps the revolving speed of 3000r/min to stir 10min, obtain the 7th mixed liquor；
(3) by the toughener adipic acid dibutyl ester of 0.6 mass parts, the stabilizer triphenyl phosphite of 0.5 mass parts, 0.8
The emulsifier industry concentrating soya lecithin of mass parts is added in the 7th mixed liquor, stirs 30 under the revolving speed of 4000r/min
Minute obtains the composite antibacterial coating.
Embodiment 5 provides a kind of composite antibacterial coating, is prepared by following steps：
(1) the coupling agent methyl dodecyl diethoxy silane of the solvent isooctanol of 8 mass parts, 0.8 mass parts is existed
Container high speed stirs 20min and obtains the 6th mixed liquor；
(2) Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 20 mass parts is adulterated MgO nanometers
The Ag-ZnTiO of antibacterial agent, 10 mass parts3The organic antibacterial agent octadecyl triphenyl phosphonium chloride of nano antibacterial agent, 4 mass parts
It is added in the 6th mixed liquor, keeps the revolving speed of 3000r/min to stir 10min, obtain the 7th mixed liquor；
(3) by the toughener adipic acid dibutyl ester of 0.8 mass parts, the stabilizer triphenyl phosphite of 0.5 mass parts, 0.6
The emulsifier industry concentrating soya lecithin of mass parts is added in the 7th mixed liquor, stirs 30 under the revolving speed of 4000r/min
Minute obtains the composite antibacterial coating.
Embodiment 6 provides a kind of composite antibacterial coating, is prepared by following steps：
(1) the coupling agent methyl dodecyl diethoxy silane of the solvent isooctanol of 9 mass parts, 0.5 mass parts is existed
Container high speed stirs 20min and obtains the 6th mixed liquor；
(2) Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 17 mass parts is adulterated MgO nanometers
The Ag-ZnTiO of antibacterial agent, 13 mass parts3The organic antibacterial agent octadecyl triphenyl phosphonium chloride of nano antibacterial agent, 3 mass parts
It is added in the 6th mixed liquor, keeps the revolving speed of 3000r/min to stir 10min, obtain the 7th mixed liquor；
(3) by the toughener adipic acid dibutyl ester of 0.7 mass parts, the stabilizer triphenyl phosphite of 0.6 mass parts, 0.5
The emulsifier industry concentrating soya lecithin of mass parts is added in the 7th mixed liquor, stirs 30 under the revolving speed of 4000r/min
Minute obtains the composite antibacterial coating.
For the performance of each composite antibacterial coating of comparative example 3-6, the composite antibacterial coating uniform is sprayed
The surface with plastic basis material is applied, after drying at room temperature, carries out the test of correlated performance.The adhesion strength of its floating coat according to
GB9153-88 standard testing；The anti-microbial property test of coating uses JISZ2801 standard testing, with Escherichia coli for tested bacterium
Kind.Test result is as shown in table 1.
The main performance index of each embodiment coating of table 1
| Test item | Unit | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Appearance | - | Without peeling | Without peeling | Without peeling | Without peeling |
| Adhesion strength | MPa | 2.2 | 2.1 | 2.3 | 2.4 |
| Antimicrobial efficiency | % | 99.5 | 99.5 | 99.8 | 99.7 |
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (5)
1. a kind of composite antibacterial coating, which is characterized in that the component comprising following content：The polymer emulsion of 55 mass parts, 15
The Cu-Mn-F of~20 mass parts adulterates the Ag-ZnTiO of MgO nano antibacterial agent, 10~15 mass parts3Nano antibacterial agent, 2~4 matter
Measure the organic antibacterial agent of part, the toughener of 0.6~1 mass parts, the emulsifiers of 0.5~0.8 mass parts, 0.5~0.8 mass parts
The solvent of coupling agent, the stabilizer of 0.4~0.6 mass parts and 8~10 mass parts.
2. composite antibacterial coating according to claim 1, which is characterized in that the polymer emulsion is polylactic acid and propylene
The weight ratio of the mixture of acid esters lotion, polylactic acid and acrylic acid ester emulsion is 6:5, the organic antibacterial agent is octadecyl three
Ben Ji phosphonium chloride, the toughener are adipic acid dibutyl ester, and the emulsifier is industrial concentrating soya lecithin, and the coupling agent is
Methyl dodecyl diethoxy silane, the stabilizer are triphenyl phosphite, and the solvent is isooctanol.
3. composite antibacterial coating according to claim 2, which is characterized in that prepared by following steps：
(1) solvent, coupling agent are uniformly mixed, obtain the 6th mixed liquor；
(2) polylactic acid, acrylate, Cu-Mn-F are adulterated into MgO nano antibacterial agent, Ag-ZnTiO3Nano antibacterial agent, organic anti-bacterial
Agent is added in the 6th mixed liquor, stirs evenly and obtains the 7th mixed liquor；
(3) toughener, stabilizer, emulsifier are added in the 7th mixed liquor, stirring to obtain composite antibacterial coating.
4. composite antibacterial coating according to claim 1 to 3, which is characterized in that the Cu-Mn-F adulterates MgO nanometers
The preparation method of antibacterial agent is：Preparing the mass ratio of the material is 1:0.03:0.05:0.05 magnesium nitrate hexahydrate, three nitric hydrates
Copper, four acetate hydrate manganese, ammonium fluoride；Magnesium nitrate hexahydrate is dissolved in deionized water, the first solution is formed；By three nitric hydrates
Copper, four acetate hydrate manganese, ammonium fluoride sequentially add first solution, are mixing uniformly to form the second solution；It will be a certain amount of
Second solution is added in surfactant, is mixing uniformly to form third solution；The third solution is adjusted using urea
PH value is 9.5, and precipitation reaction occurs, and continues stirring to obtain mixture；The mixture is stirred under heated condition, removes superfluous water
Separately win to obtain jelly；After drying the jelly, the Cu-Mn-F doping MgO nano antibacterial agent is obtained after grinding, calcining.
5. composite antibacterial coating according to claim 1 to 3, which is characterized in that the Ag-ZnTiO3Nano antibacterial agent
Preparation method be：Preparing the mass ratio of the material is 1:0.03:1 zinc nitrate hexahydrate, silver nitrate, butyl titanate；First by six water
It closes zinc nitrate and silver nitrate is dissolved in deionized water, form the 4th solution；Butyl titanate is added in the 4th solution, is formed
5th solution；5th solution is placed in the microwave device with agitating device, it is 11 that ammonium hydroxide, which is then added, and adjusts pH value, hair
After raw precipitation reaction, continues stirring and microwave radiation certain time, obtain reaction product；The reaction product is centrifugated to obtain
Solid product；After drying the solid product, grinding, calcining obtain the Ag-ZnTiO3Nano antibacterial agent.
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| CN107936662A (en) * | 2017-12-02 | 2018-04-20 | 马晓洁 | A kind of graphene-based antibiotic paint and its preparation method and application |
| CN110499672A (en) * | 2019-09-05 | 2019-11-26 | 沭阳宇涛新型装饰材料有限公司 | A kind of novel wear resistant anion facing paper |
| CN110731350B (en) * | 2019-10-24 | 2021-08-03 | 同曦集团有限公司 | Nano composite antibacterial agent and preparation method thereof |
| CN116463103B (en) * | 2023-05-12 | 2024-05-14 | 佛山市荞鸿新材料有限公司 | Antibacterial mildew-proof sealant and preparation method thereof |
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| CA1239492A (en) * | 1982-10-18 | 1988-07-19 | Donald F. Smith, Jr. | High solids coating compositions containing polycaprolactone polyol reactive diluents |
| DE69001932T2 (en) * | 1989-03-20 | 1993-11-11 | Kansai Paint Co Ltd | Thermosetting resin-based coating. |
| CN1843995A (en) * | 2006-05-12 | 2006-10-11 | 丁文战 | Antibacterial enamel and preparation method thereof |
| CN101411337A (en) * | 2008-11-05 | 2009-04-22 | 广州市未来之窗新材料股份有限公司 | Composite anti-bacteria agent, antibiotic paint and antibiotic aluminum composite board |
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