CN101343449A - Preparation method for visible light responding functional paint - Google Patents
Preparation method for visible light responding functional paint Download PDFInfo
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- CN101343449A CN101343449A CNA2008101389613A CN200810138961A CN101343449A CN 101343449 A CN101343449 A CN 101343449A CN A2008101389613 A CNA2008101389613 A CN A2008101389613A CN 200810138961 A CN200810138961 A CN 200810138961A CN 101343449 A CN101343449 A CN 101343449A
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Abstract
The invention relates to a preparation method of visible-light responsive functional coating. The visible-light responsive functional coating is composed of styrene-acrylic emulsion, coating nanometer titanium dioxide and isophorone diisocyanate. The preparation of the styrene-acrylic emulsion adopts a polymerization technology of semicontinuous core-shell emulsion, and hydroxyl functional group monomer is used in the raw materials of the shell monomer; the coating nanometer titanium dioxide adopts the process synthetic route which is not calcinated under the high temperature under the assistance of polypropylene glycol and microwave; when being used, the styrene-acrylic emulsion and the coating nanometer titanium dioxide are mixed together, and the blend of the styrene-acrylic emulsion and the coating nanometer titanium dioxide is evenly mixed with the isophorone diisocyanate. The inhibitory rate of the functional coating under the sunlight or the daylight lamp is higher.
Description
Technical field
The present invention relates to a kind of preparation method of visible light-responded functional coating, be specifically related to a kind of preparation method who produces the fancy veneer veneer core-board coating of bacteriostatic action in the visible region.
Background technology
Fancy veneer veneer core-board claims the veneer core-board again, is a kind of of Decorative veneered woodbased panel.Fancy veneer veneer core-board is veneer and core-board base material assembly, the hot pressing that natural rare tree or other self-sow timber are obtained through slicing, rotary-cut etc. or colds pressing and the sheet material made.
China is the big country of the core-board decorations of fancy veneer veneer and furniture production and application, the also annual simultaneously coating accordingly that consume in a large number, along with the raising day by day of decorations and furniture output, the usage quantity of fancy veneer veneer core-board coating also increases year by year.
The kind of coating is more, and wherein, transparent coating coating not only plays a protective role to fancy veneer; the native texture and the color and luster that more can keep this material; prolong its work-ing life, beautify and improve its commodity value, also be decorations and make the normal method that adopts of medium-to-high grade furniture.
At present, fancy veneer veneer core-board transparent coating uses the most solvent type polyurethane coating, this coating paint film strong adhesion, the hardness height, wear resistance is strong, water-tolerant, low temperature flexibility, weathering resistance, alkali resistance, elasticity excellence and curing of coating temperature range are extensive, but its volatile organic matter (VOCs) quantity discharged is higher, serious to operator and ecological environmental pollution, in addition, China exports a large amount of furniture to American-European countries every year, there is strict standard-required in these countries to the furniture content of harmful, and this also brings stern challenge to China's furniture manufacturing industry.
Aqueous high molecular water miscible liquid coating is nontoxic with it, nothing is fired, the distinguishing feature of non-environmental-pollution, the developing direction that is undoubtedly fancy veneer veneer core-board transparent coating, along with improving constantly of people's living standard, people are also developed towards multi-functional direction the consumers demand of this coating.Publication number be CN1644639 patent disclosure a kind of aqueous woodware paint with bactericidal function, comprise A, B two portions component, the weight percent of each component of A part is: film coalescence aid 5.5-8.0, dispersion agent 0.3-0.5, wetting agent 0.2-0.4, solubility promoter 0.8-1.2, pure water 2.0-3.0, flow agent 0.2-0.5, thickening material 0.1-0.2, tensio-active agent 0.1-0.2, defoamer 0.2-0.5, the mixture 1.2-1.5 of nano silicon and nano titanium oxide, the weight percent of each component of B part is: aqueous polyurethane emulsion 75.0-85.0, water-based wax emulsion 4.0-5.0, this aqueous woodware paint has the function of bactericidal, but the composition and the preparation method of undeclared its main component aqueous polyurethane emulsion of this patent do not do further qualification to the nano titanium oxide with bactericidal function yet.
Nano titanium oxide is a kind of little brilliant degree, the photochemical catalytic oxidation agent of bigger serface, bacterial oxidation can be become carbonic acid gas and water, and self is nontoxic, yet, titanium dioxide energy gap big (3.2eV), nano titanium oxide can only utilize in the sunlight 3～4% UV-light (wavelength is less than 380nm), bring into play its photocatalytic oxidation, and indoor sunlight is more weak, irradiation time is shorter, this has seriously restricted the effective utilization of nano titanium oxide to visible light, therefore, in water-borne coatings, add visible light-responded nano titanium dioxide photocatalysis antiseptic-germicide, the absorption that is about to titanium dioxide extends to the visible region of sunlight and fluorescent lamp etc., is the key that corresponding water-borne coatings is effectively brought into play its bacteriostatic action.
Summary of the invention
The objective of the invention is to: remedy the deficiencies in the prior art, a kind of preparation method of visible light-responded functional coating is provided, a kind of preparation method who produces the fancy veneer veneer core-board coating of bacteriostatic action in the visible region promptly is provided.
Visible light-responded functional coating of the present invention is made up of benzene emulsion, clad nano titanium dioxide and isophorone diisocyanate three components, and its preparation may further comprise the steps:
1. the preparation of benzene emulsion: earlier with butyl acrylate 10～20 mass parts, vinylbenzene 50～60 mass parts, methyl methacrylate 20～30 mass parts, vinylformic acid 2～5 mass parts blend, 1/5 of mix monomer gross weight is joined in the reactor, begin to stir, add distilled water 100 mass parts, add polyoxyethylene octylphenol ether 1.0～2.0 mass parts, fatty alcohol-polyoxyethylene ether 1.0～2.0 mass parts, be heated to 60～70 ℃, the initiator initiation reaction that adds 0.15～0.25 mass parts, when monomer-free refluxes, reheat to 75～80 ℃, 2h drips off remaining mix monomer, add initiator 0.25～0.35 mass parts more successively, hydroxy functional group monomer 3～10 mass parts, methyl methacrylate 10～20 mass parts, be warming up to 80～85 ℃, be incubated 2～3 hours, adjust pH is 6～7, and cooling discharge gets benzene emulsion;
Described polyoxyethylene octylphenol ether and fatty alcohol-polyoxyethylene ether, the polyoxyethylated polymerization degree are 5～20;
Described initiator is selected from: Potassium Persulphate, Sodium Persulfate or ammonium persulphate;
Described hydroxy functional group monomer is selected from: N hydroxymethyl acrylamide, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, methacrylic acid-beta-hydroxy ethyl ester or methacrylic acid-β-hydroxypropyl acrylate;
2. the preparation of clad nano titanium dioxide: in the ethanol of 50 mass parts, add polypropylene glycol 0.1～0.5 mass parts and titanic acid ester 5～10 mass parts earlier, begin to stir, the deionized water that adds 100 mass parts, adding acid-conditioning solution pH value is 1～4, the aqueous solution is heated to 45～70 ℃, when white precipitate or gel generation, microwave azeotropic distillation 10～40min with 300～600W, cooling discharge, the powder that obtains again with aluminum nitrate 8～15 mass parts blend of 0.01mol/L, be 8 with the ammoniacal liquor adjust pH, ageing 0.5h, microwave drying get clad nano titanium dioxide;
Described polypropylene glycol, molecular weight is selected from: 400,600,1000 or 1500;
Described titanic acid ester is selected from: titanium ethanolate, isopropyl titanate or butyl (tetra) titanate;
Described acid is selected from: hydrochloric acid, nitric acid, hydrofluoric acid or sulfuric acid;
When 3. using, with 100: 1～3 blend of pressing mass ratio of benzene emulsion and clad nano titanium dioxide, the functional coating that mixes visible light-respondedly by mass ratio 100: 1～10 blend and the isophorone diisocyanate of benzene emulsion and clad nano titanium dioxide again.
The preparation of benzene emulsion of the present invention belongs to semicontinuous core-shell emulsion polymerization technology, owing to used the hydroxy functional group monomer in the shell monomer raw material, the synthetic benzene emulsion polymer end of the chain contains activity hydroxy; Its viscosity is 200～600mPa.s; Because adopted polyoxyethylene octylphenol ether and fatty alcohol-polyoxyethylene ether to be fit to the compound emulsifying agent that ratio is formed in synthetic, building-up process is stable, does not produce cohesion; Be more than 6 months storage period.
Clad nano titanium dioxide of the present invention: be meant that the surface has coated the nano titanium oxide of aluminium hydroxide, when this clad nano titanium dioxide and benzene emulsion blend, can prevent effectively that the nano titanium oxide of high-ratio surface energy from reuniting; This product cut size is 20～80nm; Show tangible absorption is arranged through ultraviolet-visible light diffuse-reflectance absorption spectrum in the visible region of 400～650nm; Owing to used under polypropylene glycol and the microwave-assisted synthesis route without high-temperature calcination, this is synthetic low for equipment requirements, simple to operate, and synthesis cycle is short, and production efficiency obviously improves; Because used an amount of methyl methacrylate in the raw material, the coating gloss of film obviously improves.
Visible light-responded functional coating of the present invention, it is the benzene emulsion that promptly contains activity hydroxy by three components, clad nano titanium dioxide and isophorone diisocyanate are formed, under the room temperature, the coating that the present invention is made evenly applies the surface of fancy veneer veneer core-board, highly active isocyanate group and benzene emulsion macromole hydroxyl in the isophorone diisocyanate molecule, the reaction of macromole surface hydroxyls such as clad nano titanium dioxide surface hydroxyl and fancy veneer and core-board surface fiber element generates reticulated structure, dry its transparent coating layer of back and wood base composite material strong adhesion, wear resistance is strong, water-tolerant; Compare with solvent borne polyurethane coating, pollution-free to the operator, environmentally friendly; Produce the nano titanium oxide that absorbs owing to contain in the visible region, 24h reaches more than 95% the bacteriostasis rate of intestinal bacteria, subtilis and streptococcus aureus under sunlight or fluorescent lamp.
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to embodiment.
Embodiment 1:
1. the preparation of benzene emulsion: earlier with butyl acrylate 10 mass parts, vinylbenzene 50 mass parts, methyl methacrylate 20 mass parts, vinylformic acid 2 mass parts blend, 1/5 of mix monomer gross weight is joined in the reactor, begin to stir, add distilled water 100 mass parts, add polyoxyethylene octylphenol ether 1.0 mass parts, fatty alcohol-polyoxyethylene ether 1.0 mass parts, be heated to 60 ℃, the Potassium Persulphate initiation reaction that adds 0.15 mass parts, when monomer-free refluxes, reheat to 75 ℃, 2h drips off remaining mix monomer, adds initiator 0.25 mass parts more successively, N hydroxymethyl acrylamide 3 mass parts, methyl methacrylate 10 mass parts are warming up to 80 ℃, be incubated 3 hours, adjust pH is 6, and cooling discharge gets benzene emulsion;
Described polyoxyethylene octylphenol ether, the polyoxyethylated polymerization degree are 6; Described fatty alcohol-polyoxyethylene ether, the polyoxyethylated polymerization degree are 20;
2. the preparation of clad nano titanium dioxide: in the ethanol of 50 mass parts, the adding molecular weight is 400 polypropylene glycol 0.1 mass parts and titanium ethanolate 5 mass parts earlier, begin to stir, the deionized water that adds 100 mass parts, adding hydrochloric acid conditioning solution pH value is 1.0, the aqueous solution is heated to 45 ℃, when white precipitate produces, microwave azeotropic distillation 40min with 300W, cooling discharge, the powder that obtains again with the aluminum nitrate 8 mass parts blend of 0.01mol/L, be 8 with the ammoniacal liquor adjust pH, ageing 0.5h, microwave drying get clad nano titanium dioxide;
When 3. using, benzene emulsion and clad nano titanium dioxide are pressed mass ratio blend in 100: 1, again the functional coating that 100: 3 mixes visible light-respondedly by mass ratio the blend and the isophorone diisocyanate of benzene emulsion and clad nano titanium dioxide.
Embodiment 2:
1. the preparation of benzene emulsion: earlier with butyl acrylate 20 mass parts, vinylbenzene 60 mass parts, methyl methacrylate 30 mass parts, vinylformic acid 5 mass parts blend, 1/5 of mix monomer gross weight is joined in the reactor, begin to stir, add distilled water 100 mass parts, add polyoxyethylene octylphenol ether 2.0 mass parts, fatty alcohol-polyoxyethylene ether 2.0 mass parts, be heated to 70 ℃, the Sodium Persulfate initiation reaction that adds 0.25 mass parts, when monomer-free refluxes, reheat to 80 ℃, 2h drips off remaining mix monomer, adds Sodium Persulfate 0.35 mass parts more successively, senecioate-hydroxyl ethyl ester 10 mass parts, methyl methacrylate 20 mass parts are warming up to 85 ℃, be incubated 2 hours, adjust pH is 7, and cooling discharge gets benzene emulsion;
Described polyoxyethylene octylphenol ether, the polyoxyethylated polymerization degree are 10; Described fatty alcohol-polyoxyethylene ether, the polyoxyethylated polymerization degree are 10;
2. the preparation of clad nano titanium dioxide: in the ethanol of 50 mass parts, the adding molecular weight is 1000 polypropylene glycol 0.5 mass parts and isopropyl titanate 10 mass parts earlier, begin to stir, the deionized water that adds 100 mass parts, adding nitric acid regulator solution pH value is 4, the aqueous solution is heated to 70 ℃, when white precipitate or gel generation, microwave azeotropic distillation 10min with 600W, cooling discharge, the powder that obtains again with the aluminum nitrate 15 mass parts blend of 0.01mol/L, be 8 with the ammoniacal liquor adjust pH, ageing 0.5h, microwave drying get clad nano titanium dioxide;
When 3. using, with benzene emulsion and clad nano titanium dioxide by weight blend in 100: 3, the functional coating that mixes visible light-respondedly at 100: 10 blend of benzene emulsion and clad nano titanium dioxide and isophorone diisocyanate by weight again.
Embodiment 3:
1. the preparation of benzene emulsion: earlier with butyl acrylate 15 mass parts, vinylbenzene 55 mass parts, methyl methacrylate 25 mass parts, vinylformic acid 3 mass parts blend, 1/5 of mix monomer gross weight is joined in the reactor, begin to stir, add distilled water 100 mass parts, add polyoxyethylene octylphenol ether 1.5 mass parts, fatty alcohol-polyoxyethylene ether 1.5 mass parts, be heated to 65 ℃, the ammonium persulphate initiation reaction that adds 0.20 mass parts, when monomer-free refluxes, reheat to 78 ℃, 2h drips off remaining mix monomer, adds ammonium persulphate 0.30 mass parts more successively, methacrylic acid-beta-hydroxy ethyl ester 7 mass parts, methyl methacrylate 15 mass parts are warming up to 83 ℃, be incubated 2.5 hours, adjust pH is 6.5, and cooling discharge gets benzene emulsion;
Described polyoxyethylene octylphenol ether, the polyoxyethylated polymerization degree are 20; Described fatty alcohol-polyoxyethylene ether, the polyoxyethylated polymerization degree are 6;
2. the preparation of clad nano titanium dioxide: in the ethanol of 50 mass parts, the adding molecular weight is 1500 polypropylene glycol 0.3 mass parts and butyl (tetra) titanate 7 mass parts earlier, begin to stir, the deionized water that adds 100 mass parts, adding hydrofluoric acid regulator solution pH value is 3, the aqueous solution is heated to 65 ℃, when white precipitate produces, microwave azeotropic distillation 25min with 450W, cooling discharge, the powder that obtains again with the aluminum nitrate 12 mass parts blend of 0.01mol/L, be 8 with the ammoniacal liquor adjust pH, ageing 0.5h, microwave drying get clad nano titanium dioxide;
When 3. using, benzene emulsion and clad nano titanium dioxide are pressed mass ratio blend in 100: 2, again the functional coating that 100: 5 mixes visible light-respondedly by mass ratio the blend and the isophorone diisocyanate of benzene emulsion and clad nano titanium dioxide.
Claims (1)
1. the preparation method of visible light-responded functional coating, described functional coating is made up of benzene emulsion, clad nano titanium dioxide and isophorone diisocyanate three components, and step is as follows:
1. the preparation of benzene emulsion
Earlier with butyl acrylate 10～20 mass parts, vinylbenzene 50～60 mass parts, methyl methacrylate 20～30 mass parts, vinylformic acid 2～5 mass parts blend, 1/5 of mix monomer gross weight is joined in the reactor, begin to stir, add distilled water 100 mass parts, add polyoxyethylene octylphenol ether 1.0～2.0 mass parts, fatty alcohol-polyoxyethylene ether 1.0～2.0 mass parts, be heated to 60～70 ℃, the initiator initiation reaction that adds 0.15～0.25 mass parts, when monomer-free refluxes, reheat to 75～80 ℃, 2h drips off remaining mix monomer, adds initiator 0.25～0.35 mass parts more successively, hydroxy functional group monomer 3～10 mass parts, methyl methacrylate 10～20 mass parts are warming up to 80～85 ℃, be incubated 2～3 hours, adjust pH is 6～7, and cooling discharge gets benzene emulsion;
Described polyoxyethylene octylphenol ether and fatty alcohol-polyoxyethylene ether, the polyoxyethylated polymerization degree are 5～20;
Described initiator is selected from: Potassium Persulphate, Sodium Persulfate or ammonium persulphate;
Described hydroxy functional group monomer is selected from: N hydroxymethyl acrylamide, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, methacrylic acid-beta-hydroxy ethyl ester or methacrylic acid-β-hydroxypropyl acrylate;
2. the preparation of clad nano titanium dioxide
In the ethanol of 50 mass parts, add polypropylene glycol 0.1～0.5 mass parts and titanic acid ester 5～10 mass parts earlier, begin to stir, the deionized water that adds 100 mass parts, adding acid-conditioning solution pH value is 1～4, the aqueous solution is heated to 45～70 ℃, when white precipitate or gel generation, microwave azeotropic distillation 10～40min with 300～600W, cooling discharge, the powder that obtains again with aluminum nitrate 8～15 mass parts blend of 0.01mol/L, be 8 with the ammoniacal liquor adjust pH, ageing 0.5h, microwave drying get clad nano titanium dioxide;
Described polypropylene glycol, molecular weight is selected from: 400,600,1000 or 1500;
Described titanic acid ester is selected from: titanium ethanolate, isopropyl titanate or butyl (tetra) titanate;
Described acid is selected from: hydrochloric acid, nitric acid, hydrofluoric acid or sulfuric acid;
When 3. using, with 100: 1～3 blend of pressing mass ratio of benzene emulsion and clad nano titanium dioxide, the functional coating that mixes visible light-respondedly by mass ratio 100: 1～10 blend and the isophorone diisocyanate of benzene emulsion and clad nano titanium dioxide again.
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| CN200810138961A CN100593556C (en) | 2008-08-15 | 2008-08-15 | Preparation method for visible light responding functional paint |
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| CN200810138961A CN100593556C (en) | 2008-08-15 | 2008-08-15 | Preparation method for visible light responding functional paint |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629031B (en) * | 2009-08-17 | 2012-07-04 | 湖北大学 | Photocatalytic functional coating and preparation method thereof |
| CN110157043A (en) * | 2019-05-09 | 2019-08-23 | 江苏理工学院 | A kind of composite assistant and preparation method thereof with improvement polymer ageing-resistant performance |
| CN110157227A (en) * | 2019-05-30 | 2019-08-23 | 陈理抗 | A kind of preparation method of high temperature oxidation resisting metallic paint |
| CN112778847A (en) * | 2021-02-23 | 2021-05-11 | 广东施彩新材料科技有限公司 | Long-acting photosensitive slow-release antibacterial coating and preparation method thereof |
-
2008
- 2008-08-15 CN CN200810138961A patent/CN100593556C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629031B (en) * | 2009-08-17 | 2012-07-04 | 湖北大学 | Photocatalytic functional coating and preparation method thereof |
| CN110157043A (en) * | 2019-05-09 | 2019-08-23 | 江苏理工学院 | A kind of composite assistant and preparation method thereof with improvement polymer ageing-resistant performance |
| CN110157227A (en) * | 2019-05-30 | 2019-08-23 | 陈理抗 | A kind of preparation method of high temperature oxidation resisting metallic paint |
| CN112778847A (en) * | 2021-02-23 | 2021-05-11 | 广东施彩新材料科技有限公司 | Long-acting photosensitive slow-release antibacterial coating and preparation method thereof |
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| CN100593556C (en) | 2010-03-10 |
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