CN101016431A - Nano antibacterial water woodenware paint and preparing method thereof - Google Patents
Nano antibacterial water woodenware paint and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a preparing method of single component nanometer antibiotic water-based woodware paint, which is characterized by the following: the three diverse water-based polyurethane resin emulsion, water-based acrylic acid modified polyurethane resin emulsion and nanometer water-based acrylic resin emulsion are mixed with diverse ratio as film forming matter; it drops the cost of this product and possesses merits of low VOC value, blocking resistance, fish tail tolerant, pollution tolerant, yellowed tolerant and good blocking; the organic swelled ground prefabricated sol is the carrier of compositing type inorganic antibacterial agent, it incorporates multiple inorganic nanometer composition. This invention is easy to process, which can resolve craft problems of sedimentation, discoloration and birdnesting.
Description
[technical field]
The present invention relates to a kind of coating, particularly a kind of monocomponent nanocomposite antibacterial aqueous woodware paint and preparation method thereof.
[background technology]
Mostly be the solvent-borne type wood lacquer at present traditional wood lacquer, based on solvent borne polyurethane and pyroxylin(e)finish.This wood lacquer since organic volatile total amount (VOC) than higher, environmental pollution is bigger, influences people's health.Particularly along with being extensive use of of computer, people's mode of life become gradually outer family into indoor be lead after, easilier cause serious " indoor environmental pollution ".
In the world, the use of solvent-borne type wood lacquer has been subjected to strict restriction.Europe has been completely forbidden in 2004 and has been produced and sold solvent-thinned paint.China also plans to completely forbid in 2008 the solvent-borne type wood lacquer.And aqueous woodware paint has become the favorite in market because of free from environmental pollution, has boundless market outlook.
The aqueous woodware paint that exists at present on the market has two types of single component and two-packs.Be double-component aqueous wood paint as what domestic patent application 200410075486.1,02125991.7 introduced, this double-component aqueous wood paint performance generally is better than single-component water-based wood lacquer, but cost an arm and a leg, and two kinds of components must be pressed specified proportion before use and mix, the cross-linking and curing reaction film forming takes place by it.Construction and use very inconveniently, higher to workmen's competency profiling, two kinds of components mix too early, blending ratio is improper or mix and inhomogeneously all can cause serious quality problems, so limited its application.So adopt the single component type on the market more.Be the single aqueous wood lacquer as what domestic patent application 02100113.8,200510065482.X, 02125992.5,03141382.X, 200510102460.6 introduced.
Also more and more become the focus that the user pays close attention to because whether the raising of people's living standard, the aqueous woodware paint of Gong choosing have " antibiotic " effect.(real is sharp titanium crystal form nano titanium dioxide to have adopted nano titanium oxide among patent application 200410075486.1, the 200410065860.X, also claim photocatalyst) be main antibiotic composition, its shortcoming is to issue the reaction of third contact of a total solar or lunar eclipse catalyst in UV-light (comprising the ultraviolet band in the natural light) irradiation, and can cause degraded to the organic component that comprises coating itself.
Adopted organic antibacterial agent in the patent application 02120734.8, its shortcoming is poor stability, easily degraded, is easy to generate hazard residue.And adopt the mixed dispersion liquid of nano-silver powder and photocatalyst powder in the patent 200510102460.6 is antimicrobial component, its subject matter is the galactic pole easy oxidation discoloration, the sedimentation of also easily reuniting of poor stability, nano-silver powder and nanometer titanium dioxide titanium valve, especially inapplicable to finish paint varnish.
[summary of the invention]
The object of the present invention is to provide a kind of with low cost, easy to use, the green environment protection water soluble woodenware paint of antibacterial and antimildew function good stability.
For realizing above-mentioned technical purpose, the present invention adopts following technical scheme to realize, a kind of nano antibacterial water woodenware paint, comprise that the mixture with aqueous polyurethane resin emulsion, aqueous acrylic modified ester-polyurethane resin emulsion and nano aqueous Emulsion acrylic resin is the film forming matter of composition, and the nano composite inorganic antiseptic-germicide.
For further realizing technique scheme, this nano antibacterial water woodenware paint comprises following component (W/W): aqueous polyurethane emulsion 10-20%, aqueous acrylic modified ester-polyurethane resin emulsion 10-20% and nano aqueous Emulsion acrylic resin 30-60%, nanometer is mixed composite inorganic antimicrobial agent 0.5-3.0% and the anti-heavy thickening material 0.1-0.3% of nanometer, the nanometer 1.0-3.0% of anti-the stain resistant agent, nanometer aging-resistant agent 1.0-3.0%, nano double is dredged agent 1.0-3.0%, nano wearproof stiffening agent 1.0-3.0%, wetting dispersing agent 0.5-1.0%, defoamer 0.2-0.4%, flow agent 0.2-0.4%.
For further realizing above-mentioned technical purpose, described nano composite inorganic antiseptic-germicide is a carrier with the prefabricated colloidal sol of organic expander soil, includes nanometer silver, nano zine oxide, nano aluminium oxide, nano titanium oxide and nano silicon composition.
Another object of the present invention is to, a kind of preparation method of nano antibacterial water woodenware paint is provided.
For realizing above-mentioned technical purpose, the present invention adopts following technical scheme to realize that a kind of preparation method of nano antibacterial water woodenware paint comprises the steps:
(1) preparation composite Nano inorganic antiseptic: add an amount of Silver Nitrate, zinc nitrate and reductive agent, stablizer in the pure water simultaneously; fully after the reaction; the organobentonite that adds 5% (W/W); heating in water bath to 50 ℃; be added into nano zine oxide, nano titanium oxide (wherein the anatase crystal type mass percent is no more than 2.5%), nano aluminium oxide and nano silicon; the inflated with nitrogen protection; 1500-2000rpm high-speed stirring 3-4 hour; stir and finish the back cooling; airtight leaving standstill 12 hours, gel is stand-by.
(2) will meet the aqueous polyurethane emulsion of ratio, aqueous acrylic modified ester-polyurethane resin emulsion, the mixing of nano aqueous Emulsion acrylic resin, stir rotating speed 600-700rpm 10 minutes.
(3) water, wetting agent and defoamer are mixed stirring, add composite Nano inorganic antiseptic, anti-agent, nanometer aging-resistant agent, the thin agent of nano double and the nano wearproof stiffening agent of staining of nanometer successively, stirred rotating speed 700-800rpm 15 minutes.
(4) above-mentioned slip through sand mill or three Kun machines be ground to≤10 microns, filter through 500 mesh standard sieves.
(5) in the emulsion that step (4) gained mixed solution adding step (2) is made, high-speed stirring 10 minutes, rotating speed 1000-1200rpm.
(6) add the anti-heavy thickening material of nanometer, flow agent, other auxiliary agents successively, stirred rotating speed 900-1000rpm 30 minutes.
(7) finish to stir, filter packing leave standstill finished product.
The present invention with three kinds of different aqueous polyurethane resin emulsions, aqueous acrylic modified ester-polyurethane resin emulsion and the nano aqueous Emulsion acrylic resin be mixed in varing proportions as film forming matter, when successfully realizing reducing product cost, also have low VOC value, antiblocking, damage resistant, anti-pollution, anti-xanthochromia and the good characteristics of closure.In three kinds of emulsions, aqueous polyurethane emulsion film forming fullness ratio, hardness of paint film and scratch resistant performance are good, but cost and VOC value are higher; Aqueous acrylic modified polyaminoester emulsion is wear-resisting, thermally-stabilised and freeze-thaw resistance is outstanding, but anti-xanthochromia and anti-fouling performance are poor slightly; Nano aqueous ACRYLIC EMULSION VOC with low cost, zero, snappiness, anti-pollution and closure are good, but hardness and wear resisting property are lower, and the three is mixed assembly by a certain percentage, have complementary advantages, the equilibrium of realization each side is to ensure the up to standard comprehensively of product performance.
The composite inorganic antiseptic-germicide that the present invention uses is carrier with the prefabricated colloidal sol of organic expander soil, contain multiple inorganic nano composition, not only have environmental protection, broad-spectrum antimicrobial and the strong advantage of antibacterial persistence, easy hybrid process has also solved the technology difficult problem of free settling in the common inorganic antiseptic process of manufacture, easy to change and easy reunion.
The present invention has used and has comprised that the anti-heavy thickening material of nanometer, the anti-stain resistant agent of nanometer, nanometer aging-resistant agent, nano double dredge the multiple nano functional auxiliary agent of agent, nano wearproof stiffening agent etc., has the advantage of many-sided performances such as improving product hardness, wear-resisting, ageing-resistant, water-fast, heat-resisting, acid and alkali-resistance.Owing to select for use the nano functional auxiliary agent to be zero VOC and mineral-type product, further improved the environmental-protecting performance of product.
The user is different according to environment for use and operational condition, and other auxiliary agent that can add one or more different contents in the present invention uses.Can be made into coloured enamel such as adding pigment and dyestuff, add matting agent and can be used as mute lac varnish, can add siccative when under southern wet environment, using, under northern cold condition, use and add frostproofer etc. when transporting.
[embodiment]
The present invention is further illustrated below in conjunction with embodiment.
Embodiment one:
Below be that an enforcement (finish paint) preparation prescription is formed (W/W):
Aqueous polyurethane resin emulsion 20%
Aqueous acrylic modified ester-polyurethane resin emulsion 20%
Nano aqueous Emulsion acrylic resin 40%
Composite Nano inorganic antiseptic 0.5%
The anti-heavy thickening material 0.2% of nanometer
The anti-stain resistant agent 1.0% of nanometer
Nanometer aging-resistant agent 1.0%
Nano double is dredged agent 1.0%
Nano wearproof stiffening agent 2.0%
Wetting dispersing agent 0.8%
Defoamer 0.4%
Flow agent 0.4%
Emulsifying wax 0.8%
Water 12%
The preparation technology of the foregoing description is:
(1) three kinds of emulsions is mixed in proportion, stirred rotating speed 600-700rpm 10 minutes.
(2) water, wetting agent and defoamer are mixed stirring, add composite Nano inorganic antiseptic, anti-agent, nanometer aging-resistant agent, the thin agent of nano double and the nano wearproof stiffening agent of staining of nanometer successively, stirred rotating speed 700-800rpm 15 minutes.
(3) above-mentioned slip through sand mill or three Kun machines be ground to≤10 microns, filter through 500 mesh standard sieves.
(4) (3) gained mixed solution is added in (1) emulsion high-speed stirring 10 minutes, rotating speed 1000-1200rpm.
(5) add nanometer anti-heavy thickening material, flow agent and emulsifying wax successively, stirred rotating speed 900-1000rpm 30 minutes.
(6) finish to stir, filter packing leave standstill finished product.
The preparation method of above-mentioned composite Nano inorganic antiseptic component is: add an amount of Silver Nitrate, zinc nitrate and reductive agent, stablizer in the pure water simultaneously; fully after the reaction; the organobentonite that adds 5% (W/W); heating in water bath to 50 ℃; be added into nano zine oxide, nano titanium oxide (wherein the anatase crystal type mass percent is no more than 2.5%), nano aluminium oxide and nano silicon; the inflated with nitrogen protection; 1500-2000rpm high-speed stirring 3-4 hour; stir and finish the back cooling; airtight leaving standstill 12 hours, gel gets final product.The preparation method of composite Nano inorganic antiseptic component is identical in following examples.
Embodiment two:
Nano antibacterial water woodenware paint floor finish preparation prescription is formed (W/W):
Aqueous polyurethane resin emulsion 20%
Aqueous acrylic modified ester-polyurethane resin emulsion 20%
Nano aqueous Emulsion acrylic resin 40%
Composite Nano inorganic antiseptic 0.8%
The anti-heavy thickening material 0.2% of nanometer
Nanometer is anti-to stain agent 2.0%
Nanometer aging-resistant agent 1.0%
Nano double is dredged agent 1.0%
Nano wearproof stiffening agent 3.0%
Wetting dispersing agent 1.0%
Defoamer 0.4%
Flow agent 0.3%
Slip(ping)agent 0.5%
Negative ion propellant 0.5%
Water 9.4%
Embodiment three:
Nano antibacterial water woodenware house ornamentation dull finishing coat preparation prescription is formed (W/W):
Aqueous polyurethane resin emulsion 10%
Aqueous acrylic modified ester-polyurethane resin emulsion 10%
Nano aqueous Emulsion acrylic resin 60%
Composite Nano inorganic antiseptic 1.5%
The anti-heavy thickening material 0.2% of nanometer
Nanometer is anti-to stain agent 3.0%
Nanometer aging-resistant agent 3.0%
Nano double is dredged agent 3.0%
Wetting dispersing agent 1.0%
Defoamer 0.2%
Flow agent 0.4%
Negative ion propellant 0.5%
Matting agent 1.0%
Water 6.2%
Embodiment four:
The coloured house ornamentation finish paint preparation of nano antibacterial water woodenware prescription is formed (W/W):
Aqueous polyurethane resin emulsion 15%
Aqueous acrylic modified ester-polyurethane resin emulsion 15%
Nano aqueous Emulsion acrylic resin 30%
Composite Nano inorganic antiseptic 3.0%
The anti-heavy thickening material 0.3% of nanometer
Nanometer is anti-to stain agent 1.0%
Nanometer aging-resistant agent 3.0%
Nano double is dredged agent 1.0%
Nano wearproof stiffening agent 1.0%
Wetting dispersing agent 1.0%
Defoamer 0.4%
Flow agent 0.4%
Softening agent 0.3%
Pigment 15%
Water 13.6%
Embodiment five:
The antifreeze finish paint preparation of nano antibacterial water woodenware paint prescription is formed (W/W):
Aqueous polyurethane resin emulsion 15%
Aqueous acrylic modified ester-polyurethane resin emulsion 15%
Nano aqueous Emulsion acrylic resin 45%
Composite Nano inorganic antiseptic 2.0%
The anti-heavy thickening material 0.3% of nanometer
Nanometer is anti-to stain agent 3.0%
Nanometer aging-resistant agent 1.0%
Nano double is dredged agent 1.0%
Nano wearproof stiffening agent 1.0%
Wetting dispersing agent 0.6%
Defoamer 0.2%
Flow agent 0.4%
Slip(ping)agent 0.5%
Frostproofer 4.5%
Water 8.5%
Embodiment six:
Nano antibacterial water woodenware paint priming paint preparation prescription is formed (W/W):
Nano aqueous Emulsion acrylic resin 80%
Composite Nano inorganic antiseptic 0.5%
The anti-heavy thickening material 0.5% of nanometer
Nanometer is anti-to stain agent 0.5%
Nano silicon 1.5%
Nanometer titanium dioxide 1.0%
Wetting dispersing agent 0.8%
Defoamer 1.0%
Flow agent 0.8%
Grinding aid 2.0%
Water 11.4%
Product anti-microbial property of the present invention is pressed the IC/T897-2002 standard detection by Guangdong microbiological analysis inspection center, to the antibiotic rate of intestinal bacteria (ATC25922) and streptococcus aureus (ATC6358) all 99.9%.
Embodiment seven:
The construction process of nano antibacterial water woodenware paint:
(1) timber polishing:
The wood surface for the treatment of application is used after the preliminary grinding of 200# emery cloth again with the polishing of 1000# emery cloth, makes it smooth smooth, removes the lime-ash of polishing with wet rag, thoroughly cleans and dries the back and prepare japanning.
(2) first road priming paint:
The main effect of the first road priming paint is a back cover.Lacquer liquid is suitable rare during brushing, brushes after can adding 10～30% water latting drown, and lacquer liquid is poured in the timber pore, helps increasing paint film adhesion like this.Lacquer liquid must filter earlier and could use with preceding mistake 200 order tulles, particularly spraying.(apparent temperature and temperature and decide need 2～8h) approximately, and the burr of wood surface being holded up with 1000# sand paper is polished and removed, and makes surperficial essentially smooth to treat to do the back by prime paint.
(3) priming paint back cover:
Look wood surface roughness difference and can brush 1～2 road priming paint.Irregular especially surface also can be brushed more, brushes twice generally speaking and gets final product, and per pass is 0.5h (preceding do solid work together then brush two roads again) at least at interval.Must not grind Overexertion, utmost point unfairness place of need only polishing gently now is coated with down priming paint one.Place 2h at least behind the back cover, with sand papering level and smooth (the longer better polishing of open assembly time), the most handy 1200-1500# sand paper water mill is tied cunning.But,, must not carry out water mill to the occasion that water might cause warp in wood, be out of shape, comes unglued.The water mill post-flush is clean, just can carry out next application after drying, drying.
(4) priming paint is abundant
Wood surface behind the back cover just can be primed through polishing, cleaning back again, behind the 2h gently polishing be coated with one again, as if wanting water mill, storage period should more longer (more than the 4h).Repeat this process, regrind, be coated with again, till satisfaction.Tu Deyue is many, and fullness ratio is good more, and this step can be accepted or rejected according to customer need.
(5) go up finish paint
On the basis of priming paint, be coated with light top coat top coat or dull finishing coat 1～3 road, be no less than 2 roads usually for well.Be coated with before each road finish paint and must be coated with the sticking power of interlayer with increase with 1200-1500# sand paper preceding one finishing paint of polishing gently.On clear lacquer, be coated with mute lac varnish again and can make coating change mute light type into, may reduce paint film brightness, do not reach maximum brightness and transparency and on mute lac varnish, be coated with clear lacquer.Before the finish paint application, no matter brush still spraying, should construction again after the 200# tulle filters earlier.
(6) spraying application
The paint film of spraying application is more smooth than brushing paint film.Spraying water-based property wood lacquer is existing usefulness after adding the less water latting drown on the basis of former lacquer just, the lacquer liquid behind the latting drown its be coated with-4 glasss of viscosity should be about 18s.After stirring evenly, latting drown should leave standstill 20min at least, application again after bubble to be stirred into disappears substantially.Lacquer liquid must filter through 200 order tulles earlier before the spraying, in order to avoid bring impurity into, influences painting quality.Spraying generally is advisable with two crosses.It is unsuitable excessive to go out the lacquer amount, can not spray too thickly, otherwise be easy to generate disadvantages such as sagging, tangerine peel.If want to increase film thickness, should adopt the method for repeatedly spraying to solve.
The serial nano auxiliary agent that various nano assistants in the component of the present invention can select for use Jiangsu morning twilight Nono-material Science ﹠ Technology Ltd., Beijing initiative nanosecond science and technology company and Guangzhou cloud star scientific instrument company limited to produce or provide.The various product that wetting dispersing agent, defoamer, flow agent are on the market to be used always.Wetting dispersing agent can be selected EFKA series of the TEGO series of the OROTAN series of SN-DISPERSANT series, the U.S. Rhom and Hass of Japanese Nuo Puke company, German Di Gao company, Dutch EFKA company etc. for use.Defoamer can be with the BYK series of German Bi Ke company, the EFKA series of Dutch EFKA company, PLURIOL series of BASF Aktiengesellschaft etc.Flow agent comprises TEGO series of the SUNFYNOL series of RHEOLATE series, U.S.'s gas chemical industry of RM series, the strength brightness company of U.S. Rhom and Hass, German Di Gao company etc.
More than be preferred forms of the present invention, according to content disclosed by the invention, some identical, replacement schemes that those of ordinary skill in the art can expect apparently all should fall into protection scope of the present invention.
Claims (6)
1. a nano antibacterial water woodenware paint is characterized in that, comprises that the mixture with aqueous polyurethane resin emulsion, aqueous acrylic modified ester-polyurethane resin emulsion and nano aqueous Emulsion acrylic resin is the film forming matter of composition, and the nano composite inorganic antiseptic-germicide.
2. nano antibacterial water woodenware paint according to claim 1 is characterized in that, the basic recipe of described film forming matter consists of (W/W):
Aqueous polyurethane resin emulsion 10-20%;
Aqueous acrylic modified ester-polyurethane resin emulsion 10-20%;
Nano aqueous Emulsion acrylic resin 30-60%.
3. nano antibacterial water woodenware paint according to claim 1 and 2, it is characterized in that, described nano composite inorganic antiseptic-germicide is a carrier with the prefabricated colloidal sol of organic expander soil, includes nanometer silver, nano zine oxide, nano aluminium oxide, nano titanium oxide and nano silicon.
4. nano antibacterial water woodenware paint according to claim 1 and 2 is characterized in that, comprises following component (W/W):
Aqueous polyurethane emulsion 10-20%;
Aqueous acrylic modified ester-polyurethane resin emulsion 10-20%;
Nano aqueous Emulsion acrylic resin 30-60%;
Nanometer is mixed composite inorganic antimicrobial agent 0.5-3.0%;
The anti-heavy thickening material 0.1-0.3% of nanometer;
The nanometer 1.0-3.0% of anti-the stain resistant agent;
Nanometer aging-resistant agent 1.0-3.0%;
Nano double is dredged agent 1.0-3.0%;
Nano wearproof stiffening agent 1.0-3.0%;
Wetting dispersing agent 0.5-1.0%;
Defoamer 0.2-0.4%;
Flow agent 0.2-0.4%.
5. nano antibacterial water woodenware paint according to claim 4, it is characterized in that, also comprise at least a other auxiliary agents 3.0-24.5%, described other auxiliary agents are emulsifying wax, slip(ping)agent, negative ion propellant, pigment, dyestuff, matting agent, siccative, frostproofer.
6. the preparation method of a nano antibacterial water woodenware paint is characterized in that, comprises the steps:
(1) preparation composite Nano inorganic antiseptic: add an amount of Silver Nitrate, zinc nitrate and reductive agent, stablizer in the pure water simultaneously, fully after the reaction, the organobentonite that adds 5% (W/W), heating in water bath to 50 ℃, be added into nano zine oxide, nano titanium oxide (wherein the anatase crystal type mass percent is no more than 2.5%), nano aluminium oxide and nano silicon, the inflated with nitrogen protection, 1500-2000rpm high-speed stirring 3-4 hour, stir and finish the back cooling, airtight leaving standstill 12 hours, gel is stand-by;
(2) will meet the aqueous polyurethane emulsion of ratio, aqueous acrylic modified ester-polyurethane resin emulsion, the mixing of nano aqueous Emulsion acrylic resin, stir rotating speed 600-700rpm 10 minutes;
(3) water, wetting agent and defoamer are mixed stirring, add composite Nano inorganic antiseptic, anti-agent, nanometer aging-resistant agent, the thin agent of nano double and the nano wearproof stiffening agent of staining of nanometer successively, stirred rotating speed 700-800rpm 15 minutes;
(4) above-mentioned slip through sand mill or three Kun machines be ground to≤10 microns, filter through 500 mesh standard sieves;
(5) in the emulsion that step (4) gained mixed solution adding step (2) is made, high-speed stirring 10 minutes, rotating speed 1000-1200rpm;
(6) add the anti-heavy thickening material of nanometer, flow agent, other auxiliary agents successively, stirred rotating speed 900-1000rpm 30 minutes;
(7) finish to stir, filter packing leave standstill finished product.
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| CNB2007100268886A CN100503753C (en) | 2007-02-06 | 2007-02-06 | Nano antibacterial aqueous woodenware paint and preparing method thereof |
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| CNB2007100268886A CN100503753C (en) | 2007-02-06 | 2007-02-06 | Nano antibacterial aqueous woodenware paint and preparing method thereof |
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| CN100503753C CN100503753C (en) | 2009-06-24 |
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