CN104151998A - Anti-scrubbing composite antibacterial metal paint and preparation method thereof - Google Patents
Anti-scrubbing composite antibacterial metal paint and preparation method thereof Download PDFInfo
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- CN104151998A CN104151998A CN201410414543.8A CN201410414543A CN104151998A CN 104151998 A CN104151998 A CN 104151998A CN 201410414543 A CN201410414543 A CN 201410414543A CN 104151998 A CN104151998 A CN 104151998A
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Abstract
The invention relates to an anti-scrubbing composite antibacterial metal paint and a preparation method. The paint is composed of the following components in percentage by weight: 10 to 30% of modified polyester resin, 10 to 30% of modified epoxy resin, 5 to 20% of modified styrene-acrylic emulsion, 1 to 15% of coupling agent, 10 to 40% of nano titanium dioxide sol, and 5 to 20% of antibacterial metal ion solution. The invention solves the problems that the application and antibacterial effect of titanium dioxide photocatalyst are confined by environment, the metal ion paint is easy to fade, the antibacterial effect cannot last for a long time, and the scrubbing resistant performance of the metal based antibacterial paint is not good.
Description
Technical field
The present invention relates to metallic paint and antibiotic paint field, especially a kind of washability composite antibacterial metallic paint and preparation method thereof.
Background technology
Along with scientific and technological development, the progress of production technique and growth in the living standard, and national governments more and more pay attention to environmental problem, ecological environment material nd becomes the material that market needs most, and novel antibacterial material is one of closely-related ecological environment material nd such as that recently rise and the sound development mankind and environment in the world in recent years.Meanwhile, it is high that sheet metal had both had ferrous materials physical strength, the performance of easy-formation, and low cost, high practicability, quick for installation, convenient transportation has again ornamental and erosion resistance concurrently.Be subject to the favor of building, household electrical appliances, electromechanics, communications and transportation, upholstery, office furniture and other industry.Therefore, antibacterial metal sheet material has wide market outlook.At present the production technique of antibacterial metal sheet material is divided into two classes: the first kind is that antibacterial metal is entrained in metal interalloy and prepares antibacterial metal sheet material, process for adding a certain amount of antibacterial metal Cu in plain metal sheet material forming forward direction, Ag, Zn etc., control the technique of casting, forging and stamping, rolling and heat treatment process and manufacture antibacterial metal roll bending.This complex process, cost of investment is large, is difficult to guarantee size, the form in antibacterial metal metallic matrix, separates out to even dispersion and the volume percent of precipitated phase, the mechanical property of plain metal and corrosion resistance is had to larger impact simultaneously.Equations of The Second Kind is antibiotic paint to be coated to sheet metal surface prepare antibacterial metal sheet material, and process, for to use various coating means to be coated to sheet metal surface antibiotic paint, forms the coating with anti-microbial property on its surface, thereby manufactures antibacterial metal sheet material.This technique is simple, and cost of investment is less, this process quilt widespread use.Antibiotic paint is by adding and have antibacterial and can be prepared from the antiseptic-germicide of the middle stable existence of filming for physics blending method and Chemical bond method, antiseptic-germicide is mainly divided into two kinds, inorganic antiseptic (agent of TiO 2 series photocatalysis antibacterial, metal ion antibacterial agent etc.) and some organic antibacterial agents.Organic antibacterial agent easily decomposes, validity period is short, and poor heat resistance easily produces resistance, and skin is had to stimulation, difficult degradation, environment is had to pollution, is eliminated gradually.Wherein because the advantages such as inorganic antibacterial coating broad-spectrum antimicrobial effect is good, validity period is long, and good heat resistance, does not produce resistance, safe, nontoxic are widely used.But at present there is the factors such as not good, the antibacterial ageing abrasion resistance long and sheet metal surface antimicrobial coating of antibacterial effect is poor in antibiotic paint, seriously restricted its range of application.Therefore preparation has the important directions that the antibiotic paint of outstanding wash-resistant property and anti-microbial property is current research invention.
Summary of the invention
The deficiencies such as not good, the antibacterial ageing abrasion resistance long and sheet metal surface antimicrobial coating of antibacterial effect that the present invention is directed to current antibiotic paint is poor provide a kind of washability composite antibacterial metallic paint and preparation method thereof.The use that has solved TiO 2 series photocatalysis antibacterial coating is subject to environmental restraint and antibacterial effect, and the easy to change and antibacterial effect of metal ion coating ageing, for the problems such as wash-resistant property of metal base antibiotic paint.
The present invention solves the technical scheme that its technical problem adopts: this washability composite antibacterial metallic paint, by following recipe ingredient, formed, with mass parts, count: modified polyester resin 10～30%, modified epoxy 10～30%, modifying cinepazid emulsion 5～20%, coupling agent 1～15%, nano titanic oxide sol 10～40%, antibacterial metal ions solution 5～20%, wherein in nano titanic oxide sol, the content of titanium dioxide is 0.5～25%, and in antibacterial metal ions solution, the content of antibacterial metal ions is 10
-4～10
-1mol/L.
A preparation method for washability composite antibacterial metallic paint, is comprised of following steps:
1) a certain amount of metal-salt is dissolved in the solvent that a certain amount of organic solvent or organic solvent mix with deionized water, wherein the volume ratio of organic solvent and deionized water is 10:1～1:10, rapid stirring until metal salt solid dissolve completely, make antibacterial metal ions solution, wherein the content of antibacterial metal ions is 10
-4～10
-1mol/L;
2) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, to above-mentioned antibacterial metal ions solution, slowly add a certain amount of modifying cinepazid emulsion, coupling agent to be stirred to evenly, prepare the first solution;
3) getting a certain amount of titanate adds and is dissolved in a certain amount of organic solvent, deionized water or organic solvent and deionized water mixed solvent, wherein the volume ratio of organic solvent and deionized water is 5:1～1:5, under the state stirring, slowly drip certain density rare nitric acid to constant pH value 4～6, then continue to stir to obtain nano titanic oxide sol until solution becomes glue, wherein the content of titanium dioxide is 0.5～25%;
4) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, a certain amount of modified epoxy and modified polyester resin are added to the Nano titanium dioxide colloidal sol of above-mentioned preparation, be stirred to evenly, prepare the second solution;
5) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, the first solution is slowly added in the second solution, be stirred to evenly, prepare washability composite antibacterial metallic paint.
As preferably, described metal-salt is silver salt, mantoquita or zinc salt.
As preferably, described modifying cinepazid emulsion is silicone modified styrene-acrylate emulsion, be that vinylbenzene, acrylate and organosilane monomer are by the anionic emulsion being polymerized, its technical characteristic comprises: outward appearance: sub-translucent milky white liquid, solid content (%): 48 ± 2, pH value: 7.0-9.0, minimum film forming reference temperature (MFT): 21 ℃, viscosity: 1000-3000cps, Calcium ion stability: by (5%CaCL2 solution 1:5).
Inventing useful effect is: by metal ion doped titanium dioxide, prepare nano combined titanium dioxide antibacterial paint, overcome the deficiency of traditional optically catalytic TiO 2 coating, the activity and the range of application that improve photocatalysis antibacterial, be extended to visible region by the effective wavelength of photocatalysis antibacterial performance; There is metal ion simultaneously and there is good sterilization effect, can directly contact and be killed with bacterium, no matter at photoirradiation or without under optical condition, all there is excellent anti-microbial property.Machine-inorganic hybridization high molecular polymer in coating, it forms the binary synergic nano interface structure of wetting ability and lipophilicity two-phase coexistent in nano-area, thus can formation marvellous super amphiphilic in surface.Lipophilicity can form more firm chemical bond and have excellent sticking power with oxide compound or the oxyhydroxide of metallic surface, and by cross-linking and curing reaction, generate the reticulated structure of high strength, densification, simultaneously its super amphiphilic can rapidly solidified composite nano titanium dioxide particle, greatly strengthen wash-resistant property and the anti-microbial property of metallic substrate surface antimicrobial coating.
Embodiment
Below the invention will be further described:
Embodiment 1:
A washability metal antibacterial coating, its formula is comprised of following weight per-cent: modified polyester resin 19%, modified epoxy 21%, modifying cinepazid emulsion 13%, coupling agent 7%, nano titanic oxide sol 28%, metal ion solution 12%.Its preparation method comprises the following steps:
1) take the Silver Nitrate that is equivalent to 0.001mol quality, join in 20ml ethanol and 80ml deionized water mixed solvent, rapid stirring until metal salt solid dissolve completely, make contain metal ion organic/deionized water mixing solutions;
2) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, to above-mentioned antibacterial metal ions solution, slowly add a certain amount of modifying cinepazid emulsion, coupling agent to be stirred to evenly, prepare the first solution;
3) 15ml tetrabutyl titanate is added in 50ml ethanol, under agitation condition, slowly drip certain density rare nitric acid to solution pH value in 5 left and right, then continue to stir until solution becomes homogeneous transparent colloidal sol;
4) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, a certain amount of modified epoxy and modified polyester resin are added to the Nano titanium dioxide colloidal sol of above-mentioned preparation, be stirred to evenly, prepare the second solution;
5) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, the first solution is slowly added in the second solution, be stirred to evenly, prepare washability composite antibacterial metallic paint.
Embodiment 2:
A washability metal antibacterial coating, its formula is comprised of following weight per-cent: modified polyester resin 15%, modified epoxy 23%, modifying cinepazid emulsion 9%, coupling agent 9%,, nano titanic oxide sol 31%, metal ion solution 13%,
Its preparation method comprises the following steps:
1) take the cupric nitrate that is equivalent to 0.001mol quality, join in 20ml propandiol butyl ether and 80ml alcohol mixed solvent, rapid stirring until metal salt solid dissolve completely, make contain metal ion organic/deionized water mixing solutions;
2) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, to above-mentioned antibacterial metal ions solution, slowly add a certain amount of modifying cinepazid emulsion, coupling agent to be stirred to evenly, prepare the first solution;
3) 15ml tetrabutyl titanate is added in 50ml deionized water, under agitation condition, slowly drip certain density rare nitric acid to solution pH value in 5 left and right, then continue to stir until solution becomes homogeneous transparent colloidal sol;
4) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, a certain amount of modified epoxy and modified polyester resin are added to the Nano titanium dioxide colloidal sol of above-mentioned preparation, be stirred to evenly, prepare the second solution;
5) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, the first solution is slowly added in the second solution, be stirred to evenly, prepare washability composite antibacterial metallic paint.
Embodiment 3:
A washability metal antibacterial coating, its formula is comprised of following weight per-cent: modified polyester resin 17%, modified epoxy 19%, modifying cinepazid emulsion 12%, coupling agent 8%,, nano titanic oxide sol 30%, metal ion solution 14%.Its preparation method comprises the following steps:
1) take the zinc nitrate that is equivalent to 0.001mol quality, join in 20ml ethanol, 20ml propandiol butyl ether and 60ml deionized water mixed solvent, rapid stirring until metal salt solid dissolve completely, make contain metal ion organic/deionized water mixing solutions;
2) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, to above-mentioned antibacterial metal ions solution, slowly add a certain amount of modifying cinepazid emulsion, coupling agent to be stirred to evenly, prepare the first solution;
3) 15ml tetrabutyl titanate is added in 35ml ethanol and 15ml deionized water mixed solvent, under agitation condition, slowly drip certain density rare nitric acid to solution pH value in 5 left and right, then continue to stir until solution becomes homogeneous transparent colloidal sol;
4) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, a certain amount of modified epoxy and modified polyester resin are added to the Nano titanium dioxide colloidal sol of above-mentioned preparation, be stirred to evenly, prepare the second solution;
5) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, the first solution is slowly added in the second solution, be stirred to evenly, prepare washability composite antibacterial metallic paint.
With reference to GB/T9266-2009 washability experiment and the antibacterial test experience of ISO22196-2011, verify the wash-resistant property of metallic surface antimicrobial coating, the antibiotic rate that result is presented at through antibacterial metal sheet material after 2000 times scrub is greater than 90%.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (4)
1. a washability composite antibacterial metallic paint, is comprised of following recipe ingredient, with mass parts, counts:
Modified polyester resin 10～30%, modified epoxy 10～30%, modifying cinepazid emulsion 5～20%, coupling agent 1～15%, nano titanic oxide sol 10～40%, antibacterial metal ions solution 5～20%, wherein in nano titanic oxide sol, the content of titanium dioxide is 0.5～25%, in antibacterial metal ions solution, the content of antibacterial metal ions is 10
-4～10
-1mol/L.
2. the preparation method of washability composite antibacterial metallic paint according to claim 1, is comprised of following steps:
1) a certain amount of metal-salt is dissolved in the solvent that a certain amount of organic solvent or organic solvent mix with deionized water, wherein the volume ratio of organic solvent and deionized water is 10:1～1:10, rapid stirring until metal salt solid dissolve completely, make antibacterial metal ions solution, wherein the content of antibacterial metal ions is 10
-4～10
-1mol/L;
2) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, to above-mentioned antibacterial metal ions solution, slowly add a certain amount of modifying cinepazid emulsion, coupling agent to be stirred to evenly, prepare the first solution;
3) getting a certain amount of titanate adds and is dissolved in a certain amount of organic solvent, deionized water or organic solvent and deionized water mixed solvent, wherein the volume ratio of organic solvent and deionized water is 5:1～1:5, under the state stirring, slowly drip certain density rare nitric acid to constant pH value 4～6, then continue to stir to obtain nano titanic oxide sol until solution becomes glue, wherein the content of titanium dioxide is 0.5～25%;
4) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, a certain amount of modified epoxy and modified polyester resin are added to the Nano titanium dioxide colloidal sol of above-mentioned preparation, be stirred to evenly, prepare the second solution;
5) under the steady temperature of the state of dispersion machine high-speed stirring and 40～70 ℃, the first solution is slowly added in the second solution, be stirred to evenly, prepare washability composite antibacterial metallic paint.
3. the preparation method of washability composite antibacterial metallic paint according to claim 2, is characterized in that: described metal-salt is silver salt, mantoquita or zinc salt.
4. the preparation method of washability composite antibacterial metallic paint according to claim 2, is characterized in that: described modifying cinepazid emulsion is silicone modified styrene-acrylate emulsion.
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| CN107325592A (en) * | 2017-05-19 | 2017-11-07 | 浙江帝恒实业有限公司 | A kind of antiseptic dressing |
| CN107441580A (en) * | 2016-05-03 | 2017-12-08 | B·布莱恩·阿维图姆股份公司 | Medical treatment device including antimicrobial surface coating and the method for the microorganism on the surface for controlling this device |
| CN107891647A (en) * | 2017-12-04 | 2018-04-10 | 成都杰雷遮阳工程有限公司 | A kind of charge garment water repellent fabric |
| CN108064881A (en) * | 2016-11-14 | 2018-05-25 | 佛山市顺德区美的电热电器制造有限公司 | A kind of argentiferous titanium dioxide composite antibacterial agent and preparation method thereof and antibiotic paint and preparation method thereof |
| CN108783675A (en) * | 2018-07-03 | 2018-11-13 | 阜南县创发工艺品有限公司 | A kind of braiding gloves of soft wear resistant pro-skin |
| CN109535583A (en) * | 2017-09-21 | 2019-03-29 | 张家港市沐和新材料技术开发有限公司 | The preparation method of titania modified epoxy styrene-acrylic resin composite material |
| IT202100016025A1 (en) * | 2021-06-18 | 2022-12-18 | Argochem S R L | Antibacterial and antiviral coating for surfaces |
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| CN108064881A (en) * | 2016-11-14 | 2018-05-25 | 佛山市顺德区美的电热电器制造有限公司 | A kind of argentiferous titanium dioxide composite antibacterial agent and preparation method thereof and antibiotic paint and preparation method thereof |
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| CN109535583A (en) * | 2017-09-21 | 2019-03-29 | 张家港市沐和新材料技术开发有限公司 | The preparation method of titania modified epoxy styrene-acrylic resin composite material |
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| CN108783675A (en) * | 2018-07-03 | 2018-11-13 | 阜南县创发工艺品有限公司 | A kind of braiding gloves of soft wear resistant pro-skin |
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| IT202100016025A1 (en) * | 2021-06-18 | 2022-12-18 | Argochem S R L | Antibacterial and antiviral coating for surfaces |
| WO2022264099A1 (en) * | 2021-06-18 | 2022-12-22 | Argochem S.R.L. | Antibacterial and antiviral surface coating |
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| CN104151998B (en) | 2016-06-29 |
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Effective date of registration: 20200107 Address after: 311300 No. 58, sangyuan Road, Qingshanhu street, Lin'an District, Hangzhou City, Zhejiang Province Patentee after: Zhejiang Great-wall Purification Engineering Technology Co., Ltd. Address before: Hangzhou City, Zhejiang province 310011 Xiangyuan Road No. 28 Le Fuzhi Park building 12 9F Patentee before: LINKWELL TECHNOLOGY CO., LTD. |