CN105925151A - Composite anti-bacterial paint - Google Patents

Composite anti-bacterial paint Download PDF

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Publication number
CN105925151A
CN105925151A CN201610290773.7A CN201610290773A CN105925151A CN 105925151 A CN105925151 A CN 105925151A CN 201610290773 A CN201610290773 A CN 201610290773A CN 105925151 A CN105925151 A CN 105925151A
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mass parts
agent
antibacterial agent
solution
antibacterial
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CN201610290773.7A
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CN105925151B (en
Inventor
魏亮
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Shanghai Ze Tai environmental protection new material Co., Ltd.
Xu Xiaojun
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Ningbo Hi Tech Zone Xia Yuan Technology Co Ltd
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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
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides a composite anti-bacterial paint. The composite anti-bacterial paint is prepared from, by mass, 55 parts of polymer emulsion, 15-20 parts of a Cu-Mn-F doped MgO nanometer antibacterial agent, 10-15 parts of an Ag-ZnTiO3 nanometer antibacterial agent, 2-4 parts of an organic antibacterial agent, 0.6-1 part of a toughening agent, 0.5-0.8 part of an emulsifier, 0.5-0.8 part of a coupling agent, 0.4-0.6 part of a stabilizing agent and 8-10 parts of a solvent.

Description

A kind of composite antibacterial coating
Technical field
The present invention relates to antimicrobial technology field, particularly relate to a kind of refrigerator composite antibacterial coating.
Background technology
Refrigerator inside is for the plastics of food containers, as drawer, fruit and vegetable box etc. itself does not have antibacterial and antibacterial effect, Therefore, can breed bacteria, mycete due to depositing of food during long-term use.How to solve refrigerator inside food to hold The antibacterial action of device is always problem demanding prompt solution.
Using disinfectant to food containers disinfection, often there is disinfectant residual, human body is endangered by life-time service Evil is greatly.More presently commercially available antimicrobial refrigerators, generally utilize silver ion plated film coating or antibiotic plastic that refrigerator is produced antibacterial Effect, prevents the growing of antibacterial, accumulates and the generation of abnormal flavour.But silver ion antimicrobial agent in use can occur dissolution Phenomenon so that antibacterial activity is gradually lowered；Antibiotic plastic can not make it sufficient owing to antibacterial is dispersed in plastics inner Contact with antibacterial and reduce activity.Therefore, generally there is, for current antimicrobial refrigerator, the problem that antibacterial activity is the highest, develop The refrigerator composite antibacterial coating that a kind of good stability, antibacterial activity are high is of great practical significance.
Summary of the invention
Present invention is primarily targeted at a kind of composite antibacterial coating of offer, its good stability, antibacterial activity are high, can make Coating for refrigerator inner pressurd vessel so that refrigerator has preferable antibacterial effect.
For reaching object above, the present invention provides a kind of composite antibacterial coating, comprises following components: polymer emulsion, Cu-Mn-F adulterates MgO nano antibacterial agent, Ag-ZnTiO3Nano antibacterial agent, organic antibacterial agent, toughener, emulsifying agent, Coupling agent, stabilizer and solvent.
Preferably, the content of each component is: the polymer emulsion of 55 mass parts, 15～20 the Cu-Mn-F of mass parts mix Miscellaneous MgO nano antibacterial agent, 10～15 Ag-ZnTiO of mass parts3Nano antibacterial agent, 2～4 mass parts organic antibacterial agent, The toughener of 0.6～1 mass parts, 0.5～0.8 emulsifying agent, 0.5～0.8 coupling agent, 0.4～0.6 mass of mass parts of mass parts The stabilizer of part and the solvent of 8～10 mass parts.
Preferably, described polymer emulsion is the mixture of polylactic acid and acrylic acid ester emulsion, polylactic acid and acrylate The weight ratio of emulsion is 6: 5.Described organic antibacterial agent is octadecyl benzyltriphenylphosphonium chloride.Described toughener is adipic acid two Pungent fat.Described emulsifying agent is industry concentrating soya lecithin.Described coupling agent is methyl dodecyl diethoxy silane.Described Stabilizer is triphenyl phosphite.Described solvent is isooctanol.
Preferably, the preparation method of described Cu-Mn-F doping MgO nano antibacterial agent is: the amount ratio preparing material is The magnesium nitrate hexahydrate of 1: 0.03: 0.05: 0.05, Gerhardite, four acetate hydrate manganese, ammonium fluoride；First by six hydration nitre Acid magnesium is dissolved in deionized water, forms the first solution；Gerhardite, four acetate hydrate manganese, ammonium fluoride are sequentially added into Described first solution, is mixing uniformly to form the second solution；A certain amount of surfactant is added described second solution, stirs The 3rd solution is formed after mixing uniformly；The pH value using carbamide to regulate described 3rd solution is 9.5, precipitation occurs, continues Continuous stirring obtains mixture；Stir described mixture under heated condition, remove excessive moisture and obtain jelly；Dry described glue After shape thing, grind, calcine after obtain described Cu-Mn-F adulterate MgO nano antibacterial agent.
Preferably, described Ag-ZnTiO3The preparation method of nano antibacterial agent is: the amount ratio preparing 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, are formed 4th solution；Butyl titanate is added in described 4th solution, form the 5th solution；Described 5th solution is placed in band stirring In the microwave device of device, being subsequently adding ammonia regulation pH value is 11, after there is precipitation, continues stirring microwave spoke Penetrate certain time, obtain product；Described in centrifugation, product obtains solid product；After drying described solid product, Grind, calcining obtains described Ag-ZnTiO3Nano antibacterial agent.
The present invention also provides for a kind of method preparing described composite antibacterial coating, comprises the following steps:
(1) by solvent, coupling agent mix homogeneously, the 6th mixed liquor is obtained；
(2) adulterate MgO nano antibacterial agent, Ag-ZnTiO by polylactic acid, acrylate, Cu-Mn-F3Nano antibacterial agent, Organic antibacterial agent adds in described 6th mixed liquor, and stir acquisition the 7th mixed liquor；
(3) adding in described 7th mixed liquor by toughener, stabilizer, emulsifying agent, stirring obtains composite antibacterial coating.
In use, uniform application is in the plastic substrate such as the drawer of refrigerator or dividing plate for the described composite antibacterial coating of the present invention Surface, dries under room temperature and can form composite antibacterial coating at foregoing plastics matrix surface.
The composite antibacterial coating that the present invention provides with the addition of Cu-Mn-F dopen Nano MgO and Ag-ZnTiO3Nanometer resists Microbial inoculum, has stable in properties, an advantage that antibacterial activity is high, and nano-class antibacterial agent can be well dispersed in polymeric matrix, Thus give the anti-microbial property that coating is excellent.Described composite antibacterial coating selects octadecyl benzyltriphenylphosphonium chloride as organic anti- Microbial inoculum, with inorganic antiseptic synergism, further increases the anti-microbial property of described composite antibacterial coating.
Detailed description of the invention
Hereinafter describe and be used for disclosing the present invention so that those skilled in the art are capable of the present invention.Below describe in excellent Select embodiment to be only used as citing, it may occur to persons skilled in the art that other obvious modification.
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, the four acetate hydrate manganese of 1.23g, The ammonium fluoride of 0.19g；
(2) magnesium nitrate hexahydrate is added in the deionized water of 200ml, turning in the water-bath of 40 DEG C, at 400r/min Lower stirring to the magnesium nitrate hexahydrate of speed is completely dissolved, thus forms the first solution；
(3) Gerhardite, four acetate hydrate manganese, ammonium fluoride are sequentially added into described under same stirring condition One solution, is mixing uniformly to form the second solution；
(4) 1g surfactant polyethylene 4000 is added described second solution, improve rotating speed and make to gather to 600r/min Ethylene glycol 4000 is completely dissolved, and forms the 3rd solution；
(5) pH value using carbamide to regulate described 3rd solution is 9.5, and precipitation occurs, in the water-bath of 40 DEG C, Continue stirring 2h under the rotating speed of 600r/min and obtain mixture；
(6) improve bath temperature to 90 DEG C, rotating speed improve to 800r/min continue to described mixture stir 4h, remove Jelly is obtained after moisture；
(7) described jelly is dried at 100 DEG C 6h, be then ground to powder, at 400 DEG C, finally calcine 4h obtain To described Cu-Mn-F doping MgO nano antibacterial agent.
Embodiment 2 provides a kind of Ag-ZnTiO3Nano antibacterial agent, is prepared by following steps:
(1) zinc nitrate hexahydrate of 44.6g, the silver nitrate of 0.85g, the butyl titanate of 51.1g are prepared；
(2) zinc nitrate hexahydrate and silver nitrate are added in 50ml deionized water, under room temperature under the rotating speed of 400r/min Stir and be completely dissolved to zinc nitrate hexahydrate and silver nitrate, form the 4th solution；
(3) butyl titanate is added dropwise under the rotating speed of 800r/min in described 4th solution, forms the 5th solution；
(4) being placed in the microwave device of band agitating device by described 5th solution, mixing speed is 800r/min, Microwave Frequency Rate is 2.45GHz, and being the most under agitation added dropwise over ammonia regulation pH value is 11, after there is precipitation, continues stirring And microwave radiation 30min, obtain product；
(5) under the speed of 8000r/mim, described in centrifugation, product obtains solid product；
(6) described solid product is dried at 100 DEG C 6h, be then ground to powder, at 400 DEG C, finally calcine 5h Obtain described 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 stirring 20min obtains the 6th mixed liquor；
(2) adulterate MgO by the Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 15 mass parts Nano antibacterial agent, the Ag-ZnTiO of 15 mass parts3Nano antibacterial agent, the organic antibacterial agent octadecyl triphenyl of 3 mass parts Chlorination adds in described 6th mixed liquor, keeps the rotating speed stirring 10min of 3000r/min, it is thus achieved that 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 emulsifying agent industry concentrating soya lecithin of mass parts adds in described 7th mixed liquor, stirs 30 under the rotating speed of 4000r/min Minute obtain described 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 being held Device high speed stirring 20min obtains the 6th mixed liquor；
(2) adulterate MgO by the Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 18 mass parts Nano antibacterial agent, the Ag-ZnTiO of 12 mass parts3Nano antibacterial agent, the organic antibacterial agent octadecyl triphenyl of 2 mass parts Chlorination adds in described 6th mixed liquor, keeps the rotating speed stirring 10min of 3000r/min, it is thus achieved that 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 emulsifying agent industry concentrating soya lecithin of mass parts adds in described 7th mixed liquor, stirs 30 under the rotating speed of 4000r/min Minute obtain described 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 being held Device high speed stirring 20min obtains the 6th mixed liquor；
(2) adulterate MgO by the Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 20 mass parts Nano antibacterial agent, the Ag-ZnTiO of 10 mass parts3Nano antibacterial agent, the organic antibacterial agent octadecyl triphenyl of 4 mass parts Chlorination adds in described 6th mixed liquor, keeps the rotating speed stirring 10min of 3000r/min, it is thus achieved that 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 emulsifying agent industry concentrating soya lecithin of mass parts adds in described 7th mixed liquor, stirs 30 under the rotating speed of 4000r/min Minute obtain described 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 being held Device high speed stirring 20min obtains the 6th mixed liquor；
(2) adulterate MgO by the Cu-Mn-F of the polylactic acid of 30 mass parts, the acrylate of 25 mass parts, 17 mass parts Nano antibacterial agent, the Ag-ZnTiO of 13 mass parts3Nano antibacterial agent, the organic antibacterial agent octadecyl triphenyl of 3 mass parts Chlorination adds in described 6th mixed liquor, keeps the rotating speed stirring 10min of 3000r/min, it is thus achieved that 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 emulsifying agent industry concentrating soya lecithin of mass parts adds in described 7th mixed liquor, stirs 30 under the rotating speed of 4000r/min Minute obtain described composite antibacterial coating.
For the performance of each described composite antibacterial coating of comparative example 3-6, described composite antibacterial coating uniform is sprayed It is coated with the surface with plastic basis material, 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, is tested with escherichia coli Strain.Test result is as shown in table 1.
The main performance index of table 1 each embodiment coating
Test event Unit Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Outward appearance - Without peeling off Without peeling off Without peeling off Without peeling off
Adhesion strength MPa 2.2 2.1 2.3 2.4
Antimicrobial efficiency % 99.5 99.5 99.8 99.7
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology of the industry The personnel simply present invention it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description Principle, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, these change and Improvement both falls within the range of claimed invention.The protection domain of application claims by appending claims and Equivalent defines.

Claims (6)

1. a composite antibacterial coating, it is characterised in that comprise following components: polymer emulsion, Cu-Mn-F adulterate MgO nano antibacterial agent, Ag-ZnTiO3Nano antibacterial agent, organic antibacterial agent, toughener, emulsifying agent, coupling agent, steady Determine agent and solvent.
Composite antibacterial coating the most according to claim 1, it is characterised in that the content of each component is: 55 mass parts Polymer emulsion, 15～20 Cu-Mn-F doping MgO nano antibacterial agent, 10～15 Ag-ZnTiO of mass parts of mass parts3 Nano antibacterial agent, 2～4 mass parts organic antibacterial agent, 0.6～1 mass parts toughener, 0.5～0.8 mass parts emulsifying agent, The coupling agent of 0.5～0.8 mass parts, 0.4～0.6 mass parts stabilizer and the solvent of 8～10 mass parts.
Composite antibacterial coating the most according to claim 2, it is characterised in that described polymer emulsion be polylactic acid and The mixture of acrylic acid ester emulsion, polylactic acid is 6: 5 with the weight ratio of acrylic acid ester emulsion, and described organic antibacterial agent is 18 Alkyl triphenyl phosphonium chlorination, described toughener is adipic acid dibutyl ester, and described emulsifying agent is industry concentrating soya lecithin, described Coupling agent is methyl dodecyl diethoxy silane, and described stabilizer is triphenyl phosphite, and described solvent is isooctanol.
Composite antibacterial coating the most according to claim 3, it is characterised in that prepared by following steps:
(1) by solvent, coupling agent mix homogeneously, the 6th mixed liquor is obtained；
(2) adulterate MgO nano antibacterial agent, Ag-ZnTiO by polylactic acid, acrylate, Cu-Mn-F3Nano antibacterial agent, Organic antibacterial agent adds in described 6th mixed liquor, and stir acquisition the 7th mixed liquor；
(3) adding in described 7th mixed liquor by toughener, stabilizer, emulsifying agent, stirring obtains composite antibacterial coating.
5. according to the arbitrary described composite antibacterial coating of claim 1-4, it is characterised in that described Cu-Mn-F adulterates The preparation method of MgO nano antibacterial agent is: prepare the magnesium nitrate hexahydrate that amount ratio is 1: 0.03: 0.05: 0.05 of material, three Nitric hydrate copper, four acetate hydrate manganese, ammonium fluoride；Magnesium nitrate hexahydrate is dissolved in deionized water, forms the first solution； Gerhardite, four acetate hydrate manganese, ammonium fluoride are sequentially added into described first solution, are mixing uniformly to form second molten Liquid；A certain amount of surfactant is added described second solution, is mixing uniformly to form the 3rd solution；Use carbamide regulates The pH value of described 3rd solution is 9.5, and precipitation occurs, and continues stirring and obtains mixture；Institute is stirred under heated condition State mixture, remove excessive moisture and obtain jelly；After drying described jelly, grind, calcine after obtain described Cu-Mn-F Doping MgO nano antibacterial agent.
6. according to the arbitrary described composite antibacterial coating of claim 1-4, it is characterised in that described Ag-ZnTiO3Nanometer The preparation method of antibacterial is: prepare the zinc nitrate hexahydrate that amount ratio is 1: 0.03: 1 of material, silver nitrate, butyl titanate； First zinc nitrate hexahydrate and silver nitrate are dissolved in deionized water, form the 4th solution；Butyl titanate is added described 4th molten In liquid, form the 5th solution；Described 5th solution is placed in the microwave device of band agitating device, is subsequently adding ammonia regulation PH value is 11, after there is precipitation, continues stirring microwave radiation certain time, obtains product；Centrifugation Described product obtains solid product；After drying described solid product, grind, calcine and obtain described Ag-ZnTiO3Nanometer Antibacterial.
CN201610290773.7A 2016-04-29 2016-04-29 A kind of composite antibacterial coating Active CN105925151B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110731350A (en) * 2019-10-24 2020-01-31 同曦集团有限公司 nanometer composite antibacterial agent and its preparation method
CN116463103A (en) * 2023-05-12 2023-07-21 广东裕鑫新材料科技有限公司 Antibacterial mildew-proof sealant and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3363798D1 (en) * 1982-10-18 1986-07-03 Union Carbide Corp High solids coating compositions containing polycaprolactone polyol reactive diluents and a process for preparing a cured film coating thereof
EP0388858A1 (en) * 1989-03-20 1990-09-26 Kansai Paint Co., Ltd. Heat-curable resinous coating composition
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3363798D1 (en) * 1982-10-18 1986-07-03 Union Carbide Corp High solids coating compositions containing polycaprolactone polyol reactive diluents and a process for preparing a cured film coating thereof
EP0388858A1 (en) * 1989-03-20 1990-09-26 Kansai Paint Co., Ltd. Heat-curable resinous coating composition
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110731350A (en) * 2019-10-24 2020-01-31 同曦集团有限公司 nanometer composite antibacterial agent and its preparation method
CN110731350B (en) * 2019-10-24 2021-08-03 同曦集团有限公司 Nano composite antibacterial agent and preparation method thereof
CN116463103A (en) * 2023-05-12 2023-07-21 广东裕鑫新材料科技有限公司 Antibacterial mildew-proof sealant 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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