CN101613556A - The preparation method of titanium silver-based antimildew and antibacterial emulsion paint interior wall paint - Google Patents
The preparation method of titanium silver-based antimildew and antibacterial emulsion paint interior wall paint Download PDFInfo
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- CN101613556A CN101613556A CN200910100686A CN200910100686A CN101613556A CN 101613556 A CN101613556 A CN 101613556A CN 200910100686 A CN200910100686 A CN 200910100686A CN 200910100686 A CN200910100686 A CN 200910100686A CN 101613556 A CN101613556 A CN 101613556A
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Abstract
The present invention relates to the preparation method of coating, aim to provide a kind of preparation method of titanium silver-based antimildew and antibacterial emulsion paint interior wall paint.Comprise: will be rich in the titanium dioxide nanocrystalline colloidal sol and the tin salt solution thorough mixing of hydroxyl, back flow reaction under water bath condition, then with product centrifugation, the repeptization of washing back in deionized water; Under agitation in colloidal sol, add silver soluble salts solution and reductive agent, stir impel system fully to react after with the product centrifuge washing, and peptization obtains the antibiotic colloidal sol of Ag-carried nanometer titanium dioxide antimildew to deionized water; Under agitation colloidal sol is added and obtain titanium silver-based antimildew and antibacterial emulsion paint interior wall paint in the emulsion paint.The present invention has many outstanding advantages: nontoxic, and do not have for the second time and pollute; Antibacterial effect is obvious, and reusable; Preparation technology is simple, and is easy to operate.
Description
Technical field
The present invention relates to a kind of preparation method's of coating, particularly titanium silver-based antimildew and antibacterial emulsion paint interior wall paint preparation method.
Background technology
Interior wall coating is a kind of important decorating and renovating material, and the building coating kind of external industrially developed country mainly is an emulsion paint, and its output generally accounts for 50% of ultimate production.Wherein, the U.S. is based on development pure acrylic acid emulsion paint and vinyl acetate emulsion lacquer, and Japan is based on styrene-acrylic latex paint, and every Western Europe country is based on vinyl acetate between to for plastic or tertiary ethylene carbonate modified vinyl acetate emulsion coating.In China's dope for inner wall of architecture, present low-grade polyvinyl alcohol coating still accounts for larger specific gravity, accounts for 40% of coating ultimate production; Because its inferior quality, output will descend gradually in recent years, and the more excellent building coating of quality has obtained development faster, mainly contain polyvinyl acetate lacquer, polyester acid ethylene-acrylate emulsion paint etc.Interior wall coating is owing to the indoor solar radiation that lacks, and corner or moist easy breed bacteria in place and mould make on the interior wall coating coating mildew to occur.Abroad after the eighties in 20th century, mildew-resistant, antibiotic, de-odorised aqueous latex paint functionalization product appear in beginning in a large number.Domestic research and the production that this class coating is also arranged at present.
Yet, common mildew-resistant, antibiotic emulsion paint product, lower to the restraining effect of some bacterium, the usage quantity that needs to strengthen antimildew and antibacterial agent could obtain the ideal effect, causes the cost of interior wall coating to increase; Simultaneously, in coating, divide breaking up to produce sedimentation, must stir again during use, but still be difficult to guarantee to be uniformly dispersed because traditional antimildew and antibacterial agent product mostly is larger particles, so its mildew-resistant, antibacterial effect instability.And to some novel nano mildew-proof antiseptic-germicides, but exist and easily reunite, the problem that long dispersion stability is relatively poor.The development of the antimildew and antibacterial agent of long-acting, broad-spectrum, and the long-term dispersion in coating system is the technical problem that solution is needed in current this field badly.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method of novel titanium silver-based antimildew and antibacterial emulsion paint interior wall paint is provided.
The preparation method of titanium silver-based antimildew and antibacterial emulsion paint interior wall paint provided by the invention comprises the steps:
(1) will be rich in the titanium dioxide nanocrystalline colloidal sol and the tin salt solution thorough mixing of hydroxyl, back flow reaction under 40～90 ℃ water bath condition, then with product centrifugation, washing back repeptization in deionized water; Wherein the mol ratio of Sn in the tin salt solution and the Ti in the TiO 2 sol is 1: 0.2～1: 5;
(2) under agitation condition, in above-mentioned colloidal sol after tin salt is handled, add the silver soluble salts solution, and add reductive agent, after stirring impels system fully to react, with the product centrifuge washing, and peptization obtains the antibiotic colloidal sol of Ag-carried nanometer titanium dioxide antimildew to deionized water; The mol ratio of Ti is 1: 0.5～20 in Ag in the described soluble silver salt and the TiO 2 sol; Described reductive agent is at least a in formic acid or the sodium formiate, and the mol ratio of reductive agent and silver salt is 1: 0.1～10;
(3) under agitation condition, the antibiotic colloidal sol of above-mentioned Ag-carried nanometer titanium dioxide antimildew is added in the emulsion paint, utilize interparticle electrostatic interaction to impel a year silver-colored TiO 2 sol particle on emulsion particle, to adhere to, realize the dispersion of nano silver-carrying titanium dioxide in emulsion paint, obtain titanium silver-based antimildew and antibacterial emulsion paint interior wall paint; Wherein the interpolation quality of the antibiotic colloidal sol of titanium dioxide antimildew accounts for 1%～15% of emulsion paint quality.
The titanium dioxide nanocrystalline colloidal sol that is rich in hydroxyl described in the step (1) prepares according to the following procedure:
1. under agitation condition, titanium tetrachloride, titanium sulfate or butyl (tetra) titanate are added in 1～10m/m pure diluting solvent doubly in wherein at least a, stir;
2. under 5～95 ℃ of bath temperatures, the mixing solutions of step in 1. dropwise added in 1～500m/m hydrolysising solvent doubly, stirred 0.5～5 hour;
3. colloidal sol is still aging 1 hour～15 days, until being light blue transparent.
As a kind of improvement, described tin salt is at least a in inferior tin of tin protochloride, nitric acid or the stannous sulfate.
As a kind of improvement, the dispersiveness of colloid in water that obtains after, the washing centrifugal in the step (1) for improving regulated its pH value with nitric acid, and the pH value is controlled between 0.5～5.
As a kind of improvement, described silver soluble salts solution is at least a in Silver Nitrate, silver perchlorate or the silver fluoride solution.
As a kind of improvement, the base-material of described emulsion paint is that pure-acrylic emulsion or benzene emulsion are wherein a kind of.
Compared with prior art, the present invention has following beneficial effect:
The present invention utilizes the contained abundant hydroxyl of TiO 2 sol particle by wet chemical method under cold condition, with the effective bonding of stannous ion, and become nano-Ag particles to load on titanium dioxide surface silver ion reduction in situ by tin, these nano particles can be grown up under the further effect of reductive agent subsequently, thereby improve the content of silver, realize the low temperature preparation of year silver-colored titanic oxide material, saved the energy.Add in latex coating with solation simultaneously and carry silver-colored titanium dioxide, impel by electrostatic interaction and carry silver-colored TiO 2 sol particle adhering on emulsion particle, realize the good distribution of nano silver-carrying titanium dioxide in emulsion paint.
The present invention is less demanding to preparation condition, just can carry out at normal temperatures and pressures, need not traditional hot aftertreatment technology, can realize the long-term stability dispersion of antimildew and antibacterial agent in the emulsion paint coating system, has superpower oxidation capacity, can destroy protein of bacteria, decomposing organic matter plays the effect of antimildew and antibacterial.Have many outstanding advantages: 1, nontoxic, do not have for the second time and pollute; 2, antibacterial effect is obvious, and reusable; 3, preparation technology is simple, and is easy to operate.
Description of drawings
Fig. 1 is the transmission electron microscope photo of benzene emulsion particle in the generic latex lacquer;
Fig. 2 is the transmission electron microscope photo that Ag-carried nanometer titanium dioxide is attached to the benzene emulsion particle surface among the present invention; Under identical shooting condition, the color burn of emulsion particle.
Embodiment
Below the present invention is further described by example.
The preparation method of the Ag-carried nanometer titanium dioxide antimildew and antibacterial agent of the present invention's preparation comprises following several steps:
(1) will be rich in the titanium dioxide nanocrystalline colloidal sol and the tin salt solution thorough mixing of hydroxyl, back flow reaction under 40～90 ℃ water bath condition, then with product centrifugation, washing back repeptization in deionized water; Wherein the mol ratio of Sn in the tin salt solution and the Ti in the TiO 2 sol is 1: 0.2～1: 5;
(2) under agitation condition, in above-mentioned colloidal sol after tin salt is handled, add the silver soluble salts solution, and add reductive agent, after stirring impels system fully to react, with the product centrifuge washing, and peptization obtains the antibiotic colloidal sol of Ag-carried nanometer titanium dioxide antimildew to deionized water; The mol ratio of Ti is 1: 0.5～20 in Ag in the described soluble silver salt and the TiO 2 sol; Described reductive agent is at least a in formic acid or the sodium formiate, and the mol ratio of reductive agent and silver salt is 1: 0.1～10;
(3) under agitation condition, the antibiotic colloidal sol of above-mentioned Ag-carried nanometer titanium dioxide antimildew is added in the emulsion paint, utilize interparticle electrostatic interaction to impel a year silver-colored TiO 2 sol particle on emulsion particle, to adhere to, realize the dispersion of nano silver-carrying titanium dioxide in emulsion paint, obtain titanium silver-based antimildew and antibacterial emulsion paint interior wall paint; Wherein the interpolation quality of the antibiotic colloidal sol of titanium dioxide antimildew accounts for 1%～15% of emulsion paint quality.
Wherein, the anatase type TiO 2 sol of hydroxyl is rich on the surface, is according to the disclosed method preparation of Chinese invention patent " preparation method of titanium dioxide optical catalyst sol " (ZL 200510061118.6), comprises the steps:
1. under agitation condition, titanium tetrachloride, titanium sulfate or butyl (tetra) titanate are added in the pure diluting solvent of 1～10 times (m/m) in wherein at least a, stir; 2. under 5～95 ℃ of bath temperatures, the mixing solutions of step in 1. dropwise added in the hydrolysising solvent of 1～500 times (m/m), stirred 0.5～5 hour; 3. colloidal sol is still aging 1 hour～15 days, until being light blue transparent.
Described pure diluting solvent is a wherein one or more combination of dehydrated alcohol, ethylene glycol, Virahol.
Described hydrolysising solvent is deionized water or distilled water.
When adding mixing solutions in the hydrolysising solvent, can also add mineral acid control hydrolysis speed, described mineral acid can be wherein a kind of or wherein several combination of nitric acid, hydrochloric acid, sulfuric acid, it is 1～5 that the consumption of acid is controlled at the pH value that makes colloidal sol.
Testing data among each embodiment sees Table 1.
Table 1:
| The specific embodiment sequence number | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 |
| Tin protochloride | ??√ | ??√ | ??√ | ??√ | |||
| The inferior tin of nitric acid | ??√ | ??√ | ??√ | ??√ | |||
| Stannous sulfate | ??√ | ??√ | ??√ | ??√ | |||
| Silver Nitrate | ??√ | ??√ | ??√ | ??√ | |||
| Silver perchlorate | ??√ | ??√ | ??√ | ??√ | |||
| Silver fluoride | ??√ | ??√ | ??√ | ??√ | |||
| Formic acid | ??√ | ??√ | ??√ | ??√ | |||
| Sodium formiate | ??√ | ??√ | ??√ | ??√ | |||
| Emulsion paint (is base-material with the pure-acrylic emulsion) | ??√ | ??√ | ??√ | ||||
| Emulsion paint (is base-material with the benzene emulsion) | ??√ | ??√ | ??√ | ??√ | |||
| Bath temperature | ??40℃ | ??50℃ | ??60℃ | ??70℃ | ??80℃ | ??85℃ | ??90℃ |
| The pH value of solution | ??0.5 | ??1.5 | ??2.4 | ??3.2 | ??5.0 | ??4.6 | ??3.8 |
| The mol ratio of Sn and Ti in the colloidal sol | ??1∶0.2 | ??1∶0.5 | ??1∶1 | ??1∶2 | ??1∶3 | ??1∶4 | ??1∶5 |
| The mol ratio of Ag and Ti in the solution | ??1∶0.5 | ??1∶2 | ??1∶4 | ??1∶12 | ??1∶8 | ??1∶20 | ??1∶16 |
| The mol ratio of reductive agent and silver salt | ??1∶0.1 | ??1∶1 | ??1∶2 | ??1∶3 | ??1∶5 | ??1∶10 | ??1∶7 |
| The addition of the antibiotic colloidal sol of titanium dioxide antimildew accounts for the per-cent of emulsion paint quality | ??1％ | ??3％ | ??6％ | ??9％ | ??11％ | ??15％ | ??13％ |
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (5)
1, a kind of preparation method of titanium silver-based antimildew and antibacterial emulsion paint interior wall paint comprises the steps:
(1) will be rich in the titanium dioxide nanocrystalline colloidal sol and the tin salt solution thorough mixing of hydroxyl, back flow reaction under 40～90 ℃ water bath condition, then with product centrifugation, washing back repeptization in deionized water; Wherein the mol ratio of Sn in the tin salt solution and the Ti in the TiO 2 sol is 1: 0.2～1: 5;
(2) under agitation condition, in above-mentioned colloidal sol after tin salt is handled, add the silver soluble salts solution, and add reductive agent, after stirring impels system fully to react, with the product centrifuge washing, and peptization obtains the antibiotic colloidal sol of Ag-carried nanometer titanium dioxide antimildew to deionized water; The mol ratio of Ti is 1: 0.5～20 in Ag in the described soluble silver salt and the TiO 2 sol; Described reductive agent is at least a in formic acid or the sodium formiate, and the mol ratio of reductive agent and silver salt is 1: 0.1～10;
(3) under agitation condition, the antibiotic colloidal sol of above-mentioned Ag-carried nanometer titanium dioxide antimildew is added in the emulsion paint, utilize interparticle electrostatic interaction to impel a year silver-colored TiO 2 sol particle on emulsion particle, to adhere to, realize the dispersion of nano silver-carrying titanium dioxide in emulsion paint, obtain titanium silver-based antimildew and antibacterial emulsion paint interior wall paint; Wherein the interpolation quality of the antibiotic colloidal sol of titanium dioxide antimildew accounts for 1%～15% of emulsion paint quality;
The titanium dioxide nanocrystalline colloidal sol that is rich in hydroxyl described in the step (1) prepares according to the following procedure:
1. under agitation condition, titanium tetrachloride, titanium sulfate or butyl (tetra) titanate are added in 1～10m/m pure diluting solvent doubly in wherein at least a, stir;
2. under 5～95 ℃ of bath temperatures, the mixing solutions of step in 1. dropwise added in 1～500m/m hydrolysising solvent doubly, stirred 0.5～5 hour;
3. colloidal sol is still aging 1 hour～15 days, until being light blue transparent.
According to the preparation method of the described titanium silver-based antimildew and antibacterial emulsion paint interior wall paint of claim 1, it is characterized in that 2, described tin salt is at least a in inferior tin of tin protochloride, nitric acid or the stannous sulfate.
3, according to the preparation method of the described titanium silver-based antimildew and antibacterial emulsion paint interior wall paint of claim 1, it is characterized in that, the dispersiveness of colloid in water that obtains after, the washing centrifugal in the step (1) for improving regulated its pH value with nitric acid, and the pH value is controlled between 0.5～5.
According to the preparation method of the described titanium silver-based antimildew and antibacterial emulsion paint interior wall paint of claim 1, it is characterized in that 4, described silver soluble salts solution is at least a in Silver Nitrate, silver perchlorate or the silver fluoride solution.
According to the preparation method of the described titanium silver-based antimildew and antibacterial emulsion paint interior wall paint of claim 1, it is characterized in that 5, the base-material of described emulsion paint is that pure-acrylic emulsion or benzene emulsion are wherein a kind of.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892000A (en) * | 2010-07-21 | 2010-11-24 | 广州门德纳米科技有限公司 | Antibacterial mildew-proof hydrophilic coating, aluminum foil and preparation method thereof |
| CN102363685A (en) * | 2011-06-30 | 2012-02-29 | 成都倍大涂料有限公司 | Multifunctional environment-friendly low-carbon interior wall paint and preparation method thereof |
| CN103509395A (en) * | 2013-09-15 | 2014-01-15 | 浙江大学 | Method for preparing slow-release composite antibacterial coating |
| CN104824020A (en) * | 2015-04-07 | 2015-08-12 | 上海上星家居用品有限公司 | Preparation method of nanometer titanium dioxide composite nanometer silver sol |
| CN106519846A (en) * | 2016-11-17 | 2017-03-22 | 重庆文理学院 | Preparation method of antibacterial nano latex paint for interior walls |
| CN106519756A (en) * | 2016-11-17 | 2017-03-22 | 重庆文理学院 | Sterilizing anti-mildew internal wall nano paint |
| 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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| CN1318133C (en) * | 2005-12-02 | 2007-05-30 | 厦门大学 | Method for loading silver nanometer particles onto nanometer titanium dioxide |
| CN1962049A (en) * | 2006-11-10 | 2007-05-16 | 浙江大学 | Method for preparing compound photocatalytic sol doped with metal ion |
| CN100545093C (en) * | 2007-05-09 | 2009-09-30 | 浙江大学 | Codoping titanium dioxide nano sol and preparation method thereof |
| CN101406834B (en) * | 2008-11-04 | 2010-07-07 | 浙江大学 | Method for preparing silver and titanic oxide nano compound material at low temperature |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101892000A (en) * | 2010-07-21 | 2010-11-24 | 广州门德纳米科技有限公司 | Antibacterial mildew-proof hydrophilic coating, aluminum foil and preparation method thereof |
| CN102363685A (en) * | 2011-06-30 | 2012-02-29 | 成都倍大涂料有限公司 | Multifunctional environment-friendly low-carbon interior wall paint and preparation method thereof |
| CN102363685B (en) * | 2011-06-30 | 2013-03-27 | 成都倍大涂料有限公司 | Multifunctional environment-friendly low-carbon interior wall paint and preparation method thereof |
| CN103509395A (en) * | 2013-09-15 | 2014-01-15 | 浙江大学 | Method for preparing slow-release composite antibacterial coating |
| CN103509395B (en) * | 2013-09-15 | 2016-04-20 | 浙江大学 | The preparation method of slow-release composite antibacterial coating |
| CN104824020A (en) * | 2015-04-07 | 2015-08-12 | 上海上星家居用品有限公司 | Preparation method of nanometer titanium dioxide composite nanometer silver sol |
| 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 |
| CN108064881B (en) * | 2016-11-14 | 2024-02-13 | 佛山市顺德区美的电热电器制造有限公司 | Silver-containing titanium dioxide composite antibacterial agent and preparation method thereof, and antibacterial coating and preparation method thereof |
| CN106519846A (en) * | 2016-11-17 | 2017-03-22 | 重庆文理学院 | Preparation method of antibacterial nano latex paint for interior walls |
| CN106519756A (en) * | 2016-11-17 | 2017-03-22 | 重庆文理学院 | Sterilizing anti-mildew internal wall nano paint |
| CN106519756B (en) * | 2016-11-17 | 2019-03-15 | 重庆文理学院 | A kind of sterilization anti-mildew interior wall nano paint |
| CN106519846B (en) * | 2016-11-17 | 2019-05-17 | 重庆文理学院 | A kind of preparation method of antibacterial interior wall nano-latex |
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