CN105017871A - Ultraviolet-proof exterior wall coating and preparation method therefor - Google Patents
Ultraviolet-proof exterior wall coating and preparation method therefor Download PDFInfo
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- CN105017871A CN105017871A CN201510409810.7A CN201510409810A CN105017871A CN 105017871 A CN105017871 A CN 105017871A CN 201510409810 A CN201510409810 A CN 201510409810A CN 105017871 A CN105017871 A CN 105017871A
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Abstract
The invention discloses ultraviolet-proof exterior wall coating and a preparation method therefor. The preparation method comprises: coating a nano titanium dioxide surface with a layer of acrylate polymer to obtain nano titanium dioxide/acrylate polymer to obtain compound emulsion; and then, sufficiently mixing the compound emulsion with acrylate polymer exterior wall emulsion to obtain mixed emulsion, and adding pigments, auxiliaries and water into the mixed emulsion. According to the coating, the nano titanium dioxide surface is coated with one layer of acrylate polymer, so that dispersion and stability of nano titanium dioxide in coating are remarkably improved, and therefore, nano titanium dioxide aggregates are avoided, and anti-ultraviolet property of the aggregates is greatly reduced or even avoided. The coating not only has characteristics such as excellent water resistance, excellent alkali resistance, excellent scrubbing resistance and the like of the acrylate polymer exterior wall coating, but also has improved hardness and anti-ultraviolet property, so that the service life of the coating is prolonged; and the preparation method is simple, low in production cost and beneficial for industrial production.
Description
Technical field
The present invention relates to a kind of exterior coating, particularly relate to a kind of antiultraviolet exterior coating and preparation method thereof; Belong to materials synthesis and Paint preparation technology technical field.
Background technology
Light in environment, heat, water, oxygen, inorganic salt, organic solvent and pollutent etc. are all the principal elements impelling filmogen to degrade.In these factors, sunlight uv-radiation causes filmogen degraded topmost, is also modal factor.Exterior coating, from that time used, just starts its irreversible degradation process.Therefore, strengthen the ultraviolet resistance of exterior coating necessary, most simple effective method is in exterior coating, add the additive with ultraviolet resistance, is mainly organic uv screener and inorganic UV shield agent.
The shielding of now widely used organic uv has O-hydroxyl-diphenyl ketone, o-hydroxy triazole, o-hydroxy triazine, salicylate, benzoic ether, laurate and oxanilide etc., but adds the ultraviolet resistance that organic ultraviolet screening agent improves coating and there is a lot of drawback.First, organic uv screener has certain toxicity; Secondly, organic uv screener has selectivity to ultraviolet absorption; Finally, along with the prolongation of time, organic uv screener ultraviolet resistance can weaken gradually and even disappears.
Mineral-type ultraviolet screening agent mainly contains nano titanium oxide, nano silicon and nano zine oxide etc.Nano titanium oxide due to the advantage such as stable chemical nature, nontoxic, cheap and ultraviolet screener performance be strong, and enjoys people to pay close attention to.
Nano titanium oxide ultraviolet screener performance is very strong, and particle diameter is less, and ultraviolet screener performance is stronger, the titanium dioxide shielding ultraviolet rays hardly of submicron order.Nano titanium oxide ultraviolet screener performance is determined jointly by its receptivity and scattering power.Nano titanium oxide to ultraviolet absorption mainly due to its semiconductor property.Under uviolizing, after electronics is excited by valence band in the process of conduction band transitions, cause ultraviolet absorption.Nano titanium oxide not only possesses the ultraviolet performance of absorption, also has the performance of scatters ultraviolet.Ultraviolet is a kind of hertzian wave in essence, when action of ultraviolet radiation is to nano titanium oxide in medium, because nano-titania particle size is less than ultraviolet wavelength, electronics in nano-titania particle is forced to vibrate (its vibrational frequency is identical with incident light wave frequency), become secondary wave source, to all directions emitting electromagnetic wave, ultraviolet scattering that Here it is.
At present, handlebar nano titanium oxide uses the example in antiultraviolet exterior coating.Chinese invention patent application CN102604498A adds rutile type nano titanic oxide to improve the ultraviolet resistance of exterior wall latex paint in water-soluble latex paint for exposed wall, rutile type nano titanic oxide particle diameter used is 20nm, specific surface area is large and show that hydrophilic oleophobic is very easily reunited in the polymer, and coacervate will reduce the ultraviolet resistance of rutile type nano titanic oxide greatly.And the poor compatibility of rutile type nano titanic oxide and polymkeric substance, interface can produce space, has air and enters, and under the irradiation of UV-light, the photocatalysis of rutile type nano titanic oxide can be degraded the polymkeric substance of surrounding.
Chinese invention patent application CN102134424A first prepares Mg-Al hydrotalcite and nano titanium oxide composite granule, is then dispersed in styrene acrylic exterior wall coating, and the coating obtained has certain ultraviolet resistance.Although hydrotalcite and nano titanium oxide compound can strengthen the ultraviolet resistance of nano titanium oxide, the compatibility problem of nano titanium oxide and polymkeric substance does not still solve.The dispersiveness of nanoparticle in coating and stability problem are nano paint key issues to be solved.
Summary of the invention
The object of the invention is the deficiency for above-mentioned antiultraviolet exterior coating, provide a kind of ultraviolet resistance excellent, and the exterior coating of the hardness of paint film, scrub performance excellence.
The object of the invention is also to provide the preparation method that a kind of production cost is low, technique simply, easily realizes the antiultraviolet exterior coating of suitability for industrialized production.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of antiultraviolet exterior coating, according to the mass fraction, its raw material comprises following component:
Acrylate polymer emulsion 25 ~ 40
Nano titanium oxide/acrylic ester polymer composite emulsion 5 ~ 15
Color stuffing 15 ~ 25
Frostproofer 1.2 ~ 1.5
Wetting agent 0.1 ~ 0.2
Film coalescence aid 1.2 ~ 1.8
Dispersion agent 0.3 ~ 0.6
Defoamer 0.1 ~ 0.4
Thickening material 0.1 ~ 0.4
Sanitas 0.1 ~ 0.3
PH adjusting agent 0.1 ~ 0.2
Deionized water 20 ~ 40
Described acrylate polymer emulsion be admittedly containing 40% benzene emulsion, pure-acrylic emulsion, vinyl acetate emulsion, tertiary acrylic emulsion or organosilicon crylic acid latex;
Described nano titanium oxide/acrylic ester polymer composite emulsion latex particle take nano titanium oxide as core, and acrylic ester polymer is the nucleocapsid structure of shell, prepares as follows:
(1) modified nano-titanium dioxide is prepared
According to the mass fraction, by ultrasonic disperse after 0.25 ~ 5 part of nano titanium oxide and 20 ~ 200 parts of solvent, 0.1 ~ 5 part of silane coupling agent is added, 60 ~ 80 DEG C of reaction 1 ~ 6h, centrifugal, with absolute ethanol washing, centrifugal, washing, dries, obtains modified nano-titanium dioxide; Described solvent is methyl alcohol, ethanol, Virahol or acetone; Described silane coupling agent is the one in γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane or vinyltriethoxysilane;
(2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, be dispersed in by 0.25 ~ 5 part of modified nano-titanium dioxide in the mixed solution of 20 ~ 50 parts of acrylate monomers and 0.5 ~ 2 part of assistant for emulsifying agent, ultrasonic disperse, joins in emulsifier aqueous solution, wherein the amount of emulsifying agent is 0.5 ~ 2 part, the amount of deionized water is 40 ~ 80 parts, stirs, ultrasonic disperse, be warming up to 60 ~ 80 DEG C, add 0.25 ~ 5 part of initiator, insulation 2 ~ 6h, obtains nano titanium oxide/acrylic ester polymer composite emulsion; Described acrylate monomer is one or more in methyl methacrylate, Tert-butyl Methacrylate, acrylamide, butyl acrylate, acrylic acid-2-ethyl ester, Hydroxyethyl acrylate, methacrylic acid and vinylformic acid; Described assistant for emulsifying agent is n-Hexadecane, hexadecanol, Pentyl alcohol or hexalin; Described emulsifying agent is one or more in sodium oleate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, tween 80, polysorbas20, alkylphenol polyoxyethylene-10 sorbitan monostearate, polyoxyethylene 20 sorbitan trioleate and polyoxyethylene 20 sorbitan monostearate; Described initiator is the one in hydrogen peroxide, Potassium Persulphate, ammonium persulphate or Potassium Persulphate-sodium bisulfite.
Preferably, described color stuffing is one or more in titanium dioxide, dicalcium powder, talcum powder, barium sulfate, mica powder and kaolin; Described frostproofer is ethylene glycol or propylene glycol; Described wetting agent is PE-100, ethanol, propylene glycol or glycerine.
Preferably, described be power by ultrasonic disperse after 0.25 ~ 5 part of nano titanium oxide and 20 ~ 200 parts of solvent is 400 ~ 800W ultrasonic disperse, 5 ~ 30min.
Preferably, described oven dry dries 12 ~ 24h at 50 ~ 100 DEG C.
Preferably, the described ultrasonic disperse preparing nano titanium oxide/acrylic ester polymer composite emulsion be all ultrasonic power be 400 ~ 800W disperse 10 ~ 60min; The described stirring preparing nano titanium oxide/acrylic ester polymer composite emulsion stirs 5 ~ 30min under rotating speed is 100 ~ 400rpm condition.
Preferably, described dispersion agent is sodium lauryl sulphate, polyoxyethylene alkyl phenyl ether, 2-amino-2-methyl-1-propanol, sodium oleate, sodium polyacrylate or polyisobutene maleic acid sodium salt; Film coalescence aid is ethylene glycol, propylene glycol, hexylene glycol, propandiol butyl ether, butyl glycol ether, xylyl alcohol or 2-Butoxyethyl acetate.
Preferably, described defoamer is butanols, 1,2-PD, octanol, tributyl phosphate, emulsification dimethyl silicone oil, emulsification polymethylphenyl siloxane fluid, polyoxyethylene polyoxypropylene tetramethylolmethane ether or polyoxyethylene polyoxy propyl alcohol amidogen ether.
Preferably, described thickening material is dibutyl phthalate, Walocel MT 20.000PV, Natvosol, methylcellulose gum, xanthan gum, XG-60, XG-903, SN-612 or TT-935.
Preferably, described sanitas is the one in BIT, BIT/MIT, CMIT/MIT or DBNPA; Described pH adjusting agent is one or more in AMP-95, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
The preparation method of described antiultraviolet exterior coating, comprises the steps:
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared;
(2) antiultraviolet exterior coating is prepared in the steps below:
1) take material by formula, under 500 ~ 1500rpm stirs, add deionized water, wetting agent, dispersion agent, pH stablizer, defoamer successively, fully stir 10 ~ 60min, obtain prepolymerization material;
2) under 500 ~ 1500rpm stirs, add the color stuffing of formula ratio in described prepolymerization material, after mixing, 1000 ~ 2000rpm stirs 30 ~ 90min, obtains color stuffing dispersion pulp;
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in acrylic ester polymer exterior wall emulsion, frostproofer is slowly added in above-mentioned mixed emulsion under 300 ~ 600rpm stirs, stir 10 ~ 30min, the mixed solution obtained is added color stuffing dispersion pulp, then under 500 ~ 1000rpm stirs, add defoamer, film coalescence aid, stir 10 ~ 60min;
4) regulate pH to 8 ~ 9 by pH adjusting agent, add thickening material, 500 ~ 1000rpm stirs 10 ~ 60min, obtains antiultraviolet exterior coating.
Compared with prior art, the present invention has following outstanding effect:
1) in antiultraviolet exterior coating of the present invention, at nano titanium oxide Surface coating one deck acrylic ester polymer, the consistency of itself and polymkeric substance can be strengthened, excellent dispersion in coating, excellent in stability, keep nano-scale dispersion.
2) antiultraviolet exterior coating of the present invention adds the nano titanium oxide/acrylic ester polymer composite particles with nucleocapsid structure, not only can strengthen coating ultraviolet resistance, can also strengthen the hardness of coating, intensity and wear resistance etc.
3), in antiultraviolet exterior coating of the present invention, nano titanium oxide/acrylic ester polymer composite particles shell adopts the filmogen acrylic ester polymer that exterior coating is conventional, can not affect the scrub performance of dry film.
4) antiultraviolet exterior coating of the present invention is not containing poisonous ultraviolet screening agent, is conducive to environment protection and construction safety.
Accompanying drawing explanation
Fig. 1 is the TEM figure of nano titanium oxide in embodiment 1/acrylic ester polymer composite emulsion.
Fig. 2 is the SEM figure of nano titanium oxide in embodiment 1/acrylic ester polymer composite emulsion.
Fig. 3 is the SEM-EDS figure of nano titanium oxide in embodiment 1/acrylic ester polymer composite emulsion.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described, it should be noted that, embodiment does not form the restriction to application claims protection domain.
Embodiment 1
In mass fraction, the formula of antiultraviolet exterior coating consists of:
Prepare antiultraviolet exterior coating according to the following steps:
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
1) modified nano-titanium dioxide is prepared
According to the mass fraction, after being mixed with 200 parts of ethanol by 5 parts of nano titanium oxides, 800W ultrasonic disperse 35 minutes, adds 5 parts of vinyltriethoxysilanes, 80 DEG C of reaction 6h, centrifugal, with absolute ethanol washing, centrifugal, washing repetition 3 times, 100 DEG C dry 12h after obtain modified nano-titanium dioxide.
2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, 5 parts of modified nano titanium oxides are dispersed in the mixed solution of 25 parts of acrylamides, 25 parts of butyl acrylates and 2 parts of hexadecanols, 400W ultrasonic disperse 60min, join in sodium oleate and the tween 80 aqueous solution, wherein the amount of sodium oleate is 1.3 parts, the amount of tween 80 is 0.7 part, the amount of deionized water is 80 parts, 400rpm stirs 30min, 400W ultrasonic disperse 10min, is transferred to four-hole boiling flask, be warming up to 60 DEG C, add 0.5 part of ammonium persulphate, insulation 6h, obtains nano titanium oxide/acrylic ester polymer composite emulsion.
(2) antiultraviolet exterior coating is prepared
1) take material by formula, under 1500rpm stirs, add deionized water, PE-100, sodium lauryl sulphate, AMP-95, butanols successively, fully stir 10min, obtain prepolymerization material.
2) under 1500rpm stirs, in above-mentioned prepolymerization material, add titanium dioxide, the talcum powder of formula ratio, mix rear 2000rpm high-speed stirring 30min, obtain color stuffing dispersion pulp.
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in benzene emulsion, ethylene glycol is slowly added in above-mentioned mixed emulsion under 600rpm stirs, stir 10min, the mixed solution obtained is added color stuffing dispersion pulp, then under 1000rpm stirs, add butanols, ethylene glycol, stir 10min.
4) regulate pH to 8 with ammoniacal liquor, add dibutyl phthalate, 1000rpm stirs 10min and obtains antiultraviolet exterior coating.
Embodiment 2
In mass fraction, the formula of antiultraviolet exterior coating consists of:
Prepare antiultraviolet exterior coating according to the following steps:
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
1) modified nano-titanium dioxide is prepared
According to the mass fraction, 400W ultrasonic disperse 20 minutes after 3.2 parts of nano titanium oxides are mixed with 150 parts of Virahols, add 1.2 parts of vinyltrimethoxy silanes, 70 DEG C of reaction 3.5h, centrifugal, with absolute ethanol washing, centrifugal, washing repetition 3 times, 50 DEG C dry 24h after obtain modified nano-titanium dioxide.
2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, 3.2 parts of modified nano-titanium dioxides are dispersed in the mixed solution of 40 parts of methyl methacrylates and 1.8 parts of n-Hexadecanes, 500W ultrasonic disperse 50min, join in sodium lauryl sulphate and the tween 80 aqueous solution, wherein the amount of sodium lauryl sulphate is 1.2 parts, the amount of tween 80 is 0.6 part, the amount of deionized water is 80 parts, 100rpm stirs 25min, 600W ultrasonic disperse 20min, is transferred to four-hole boiling flask, be warming up to 75 DEG C, add 0.4 part of Potassium Persulphate, insulation 3h, obtains nano titanium oxide/acrylic ester polymer composite emulsion.
(2) antiultraviolet exterior coating is prepared
1) take material by formula, under 1300rpm stirs, add deionized water, ethanol, polyoxyethylene alkyl phenyl ether, AMP-95,1,2-PD successively, fully stir 20min, obtain prepolymerization material.
2) under 1300rpm stirs, in above-mentioned prepolymerization material, add titanium dioxide, the mica powder of formula ratio, mix rear 1700rpm high-speed stirring 40min, obtain color stuffing dispersion pulp.
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in pure-acrylic emulsion, ethylene glycol is slowly added in above-mentioned mixed emulsion under 500rpm stirs, stir 10min, the mixed solution obtained is added color stuffing dispersion pulp, then under 800rpm stirs, 1 is added, 2-propylene glycol, propylene glycol, stir 20min.
4) regulate pH to 8 with ammoniacal liquor, add Walocel MT 20.000PV, 800rpm stirs 20min, obtains antiultraviolet exterior coating.
Embodiment 3
In mass fraction, the formula of antiultraviolet exterior coating consists of:
Prepare antiultraviolet exterior coating according to the following steps:
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
1) modified nano-titanium dioxide is prepared
According to the mass fraction, by 600W ultrasonic disperse after 2.25 parts of nano titanium oxides and 110 parts of methanol mixed 10 minutes, add 2.25 parts of γ-methacryloxypropyl trimethoxy silane, 60 DEG C of reaction 3.5h, centrifugal, with absolute ethanol washing, centrifugal, washing repetition 3 times, 75 DEG C dry 18h after obtain modified nano-titanium dioxide.
2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, 2.25 parts of modified nano-titanium dioxides are dispersed in the mixed solution of 20 parts of acrylate, 14.1 parts of Tert-butyl Methacrylates, 0.9 part of vinylformic acid and 1.25 parts of Pentyl alcohols, 800W ultrasonic disperse 30min, join in aqueous solution sodium oleate, wherein the amount of sodium oleate is 1.25 parts, the amount of deionized water is 70 parts, 250rpm stirs 20min, 800W ultrasonic disperse 20min, be transferred to four-hole boiling flask, be warming up to 70 DEG C, add 0.3 part of hydrogen peroxide, insulation 4h, obtains nano titanium oxide/acrylic ester polymer composite emulsion.
(2) antiultraviolet exterior coating is prepared
1) take material by formula, under 1100rpm stirs, add deionized water, propylene glycol, 2-amino-2-methyl 1-propyl alcohol, AMP-95, octanol successively, fully stir 30min, obtain prepolymerization material.
2) under 1100rpm stirs, in above-mentioned prepolymerization material, add titanium dioxide, the kaolin of formula ratio, mix rear 1500rpm high-speed stirring 50min, obtain color stuffing dispersion pulp.
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in vinyl acetate emulsion, ethylene glycol is slowly added in above-mentioned mixed emulsion under 450rpm stirs, stir 20min, the mixed solution obtained is added color stuffing dispersion pulp, then under 750rpm stirs, add octanol, hexylene glycol, stir 30min.
4) regulate pH to 8 with ammoniacal liquor, add Natvosol, 750rpm stirs 30min, obtains antiultraviolet exterior coating.
Embodiment 4
In mass fraction, the formula of antiultraviolet exterior coating consists of:
Prepare antiultraviolet exterior coating according to the following steps:
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
1) modified nano-titanium dioxide is prepared
According to the mass fraction, 400W ultrasonic disperse 30 minutes after 2 parts of nano titanium oxides are mixed with 150 parts of ethanol, add 1.8 parts of vinyltriethoxysilanes, 65 DEG C of reaction 4h, centrifugal, with absolute ethanol washing, centrifugal, washing repetition 3 times, 70 DEG C dry 18h after obtain modified nano titanium oxide.
2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, 2 parts of modified nano titanium oxides are dispersed in 20 parts of methyl methacrylates, 18.8 parts of acrylic acid-2-ethyl esters, in the mixed solution of 1.2 parts of vinylformic acid and 0.5 part of hexadecanol, 400W ultrasonic disperse 20min, join in lauryl sodium sulfate aqueous solution, wherein the amount of sodium lauryl sulphate is 1.2 parts, the amount of deionized water is 70 parts, 200rpm stirs 17min, 800W ultrasonic disperse 40min, be transferred to four-hole boiling flask, be warming up to 70 DEG C, add 0.35 part of ammonium persulphate, insulation 4h, obtain nano titanium oxide/acrylic ester polymer composite emulsion.
(2) antiultraviolet exterior coating is prepared
1) take material by formula, under 1000rpm stirs, add deionized water, PE-100, sodium oleate, AMP-95, tributyl phosphate successively, fully stir 40min, obtain prepolymerization material.
2) under 1000rpm stirs, in above-mentioned prepolymerization material, add formula ratio titanium dioxide, barium sulfate, mix rear 1500rpm and stir 70min, obtain color stuffing dispersion pulp.
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in tertiary acrylic emulsion, frostproofer is slowly added in above-mentioned mixed emulsion under 400rpm stirs, stir 30min, the mixed solution obtained is added color stuffing dispersion pulp, then under 750rpm stirs, add tributyl phosphate, propandiol butyl ether, stir 40min.
4) regulate pH to 9 with sodium hydroxide, add methylcellulose gum, 750rpm stirs 40min, obtains antiultraviolet exterior coating.
Embodiment 5
In mass fraction, the formula of antiultraviolet exterior coating consists of:
Prepare antiultraviolet exterior coating according to the following steps:
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
1) modified nano-titanium dioxide is prepared
According to the mass fraction, after being mixed with 50 parts of ethanol by 0.9 part of nano titanium oxide, 700W ultrasonic disperse 10 minutes, adds 1 part of vinyltrimethoxy silane, 60 DEG C of reaction 3.5h, centrifugal, with absolute ethanol washing, centrifugal, washing repetition 3 times, 60 DEG C dry 20h after obtain modified nano-titanium dioxide.
2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, 0.9 part of modified nano-titanium dioxide is dispersed in the mixed solution of 15 parts of methyl methacrylates, 14.1 parts of Tert-butyl Methacrylates and 0.5 part of n-Hexadecane, 500W ultrasonic disperse 35min, join in lauryl sodium sulfate aqueous solution, wherein the amount of emulsifying agent is 1.2 parts, the amount of deionized water is 60 parts, 300rpm stirs 15min, 700W ultrasonic disperse 30min, be transferred to four-hole boiling flask, be warming up to 75 DEG C, add 0.25 part of Potassium Persulphate, insulation 4h, obtains nano titanium oxide/acrylic ester polymer composite emulsion.
(2) antiultraviolet exterior coating is prepared
1) take material by formula, under 500rpm stirs, add deionized water, PE-100, sodium polyacrylate, AMP-95, emulsification dimethyl silicone oil successively, fully stir 50min, obtain prepolymerization material.
2) under 500rpm stirs, in above-mentioned prepolymerization material, add titanium dioxide, the kaolin of formula ratio, mix rear 1000rpm and stir 80min, obtain color stuffing dispersion pulp.
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in organosilicon crylic acid latex, propylene glycol is slowly added in above-mentioned mixed emulsion under 300rpm stirs, stir 30min, the mixed solution obtained is added color stuffing dispersion pulp, then under 500rpm stirs, add emulsification dimethyl silicone oil, butyl glycol ether, stir 50min.
4) regulate pH to 8.5 with potassium hydroxide, add xanthan gum, 500rpm stirs 50min, obtains antiultraviolet exterior wall
Coating.
Embodiment 6
In mass fraction, the formula of antiultraviolet exterior coating consists of:
Benzene emulsion 40
Nano titanium oxide/acrylic ester polymer composite emulsion 15
Titanium dioxide 6
Talcum powder 15
Propylene glycol 1.2
PE-1000.2
2-Butoxyethyl acetate 1.2
Polyisobutene maleic acid sodium salt 0.3
Polyoxyethylene polyoxy propyl alcohol amidogen ether 0.4
TT-9350.4
DBNPA0.2
AMP-950.05
Ammoniacal liquor 0.05
Deionized water 20
Prepare antiultraviolet exterior coating according to the following steps
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
1) modified nano-titanium dioxide is prepared
According to the mass fraction, by 500W ultrasonic disperse after 0.25 part of nano titanium oxide and 20 parts of methanol mixed 5 minutes, 0.1 part of vinyltrimethoxy silane is added, 60 DEG C of reaction 1h, centrifugal, with absolute ethanol washing, centrifugal, washing repetition 3 times, 80 DEG C dry 16h after obtain modified nano-titanium dioxide.
2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, 0.25 part of modified nano titanium oxide is dispersed in 10 parts of methyl methacrylates, in 10 parts of acrylic acid-2-ethyl esters and 0.5 portion of hexalin mixed solution, 600W ultrasonic disperse 10min, join in Sodium dodecylbenzene sulfonate and the polyoxyethylene 20 sorbitan trioleate aqueous solution, wherein the amount of Sodium dodecylbenzene sulfonate is 0.3 part, the amount of polyoxyethylene 20 sorbitan trioleate is 0.2 part, the amount of deionized water is 40 parts, 200rpm stirs 5min, 600W ultrasonic disperse 10min, be transferred to four-hole boiling flask, be warming up to 80 DEG C, add 0.25 part of Potassium Persulphate-sodium bisulfite, insulation 2h, obtain nano titanium oxide/acrylic ester polymer composite emulsion.
(2) antiultraviolet exterior coating is prepared
1) take material by formula, under 750rpm stirs, add deionized water, PE-100, polyisobutene maleic acid sodium salt, AMP-95, polyoxyethylene polyoxy propyl alcohol amidogen ether successively, fully stir 60min, obtain prepolymerization material.
2) under 750rpm stirs, add in above-mentioned prepolymerization material in the titanium dioxide of formula ratio, talcum powder, mix rear 1250rpm and stir 90min, obtain color stuffing dispersion pulp.
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in benzene emulsion, propylene glycol is slowly added in above-mentioned mixed emulsion under 600rpm stirs, stir 30min, the mixed solution obtained is added color stuffing dispersion pulp, then under moderate-speed mixer, add polyoxyethylene polyoxy propyl alcohol amidogen ether, 2-Butoxyethyl acetate, stir 60min.
4) regulate pH to 9 with ammoniacal liquor, add TT-935,700rpm stirs 60min, obtains antiultraviolet exterior coating.
Test specification
Prepared by nano titanium oxide/acrylic ester polymer composite emulsion to embodiment 1 and antiultraviolet exterior coating is tested:
TEM: sample deionized water is diluted to solid containing about 0.3%, drops on 400 order carbon film copper mesh, test for TEM after seasoning.Use transmission electron microscope TECNAI 12 (Dutch FEI electron optics company limited), during operation, acceleration voltage is 80KV.
SEM: sample deionized water is diluted to solid containing about 0.3%, drops on the masking foil on conductive resin, test for SEM after seasoning.Use the NOVA NANOSEM 430 high power scanning electronic microscope of Holland, its acceleration voltage is 20KV, and the scanning period is 100s, and pulsimeter digit rate is 2000cps, and operating distance is 34mm.
EDS:EDS is for being connected on SEM.
Adopt the ultraviolet resistance of accelerated deterioration instrument test paint film, ultraviolet source is the fluorescent tube of UVA-340nm specification, and irradiation intensity is 0.60W/m
2;
The hardness of paint film is measured by GB/T 6739-2006;
The water tolerance of paint film is measured by GB 5209-1985;
The alkali resistance of paint film is measured by GB 9274-1988;
The scrub resistance of paint film is measured by GB/T9266-88.
Nano titanium oxide is all distributed on acrylate polymer microspheres as seen from Figure 1, excellent dispersion, acrylic ester polymer smooth surface as seen from Figure 2, nano titanium oxide is not on its surface, and Fig. 3 shows in this complex microsphere containing titanium elements, illustrate that nano titanium oxide is distributed in acrylate polymer microspheres inside, its structure is take nano titanium oxide as core, and acrylic ester polymer is the nucleocapsid structure of shell.
Table 1 antiultraviolet exterior coating the performance test results
The data declaration of table 1 coating stability in storage of the present invention is good, and the hardness of paint film is high, be conducive to resisting physical damage; Water tolerance, resistance to acids and bases and scrub performance are excellent; Ultraviolet resistance has exceeded the standard (600h) of premium grads.
Detection case all exceedes the standard of premium grads, compared with Chinese invention patent application CN102134424A, CN102134424A gained coating to have started yellow, efflorescence for more than 200 hour, in the prior art, nano titanium oxide is directly added in coating, because nano titanium oxide particle diameter is little, reference area is large, and rich surface hydroxyl etc. is very easily reunited in coating, and the ultraviolet screener performance of coacervate reduces greatly.Products obtained therefrom performance of the present invention is better than CN102134424A far away.
It is emphasized that, the present invention is not only at nano titanium oxide Surface coating one deck acrylic ester polymer, and the present invention is by conservative control cladding process and whole antiultraviolet exterior coating formula system, add to nano titanium oxide surface again in exterior coating after coated, the acrylic ester polymer on nano titanium oxide surface participates in the film forming of exterior coating, this synergy not only makes the UV resistance excellent performance of paint film, can also improve the hardness of paint film, scrub performance etc., specific performance detection case is in table 1.
Claims (10)
1. an antiultraviolet exterior coating, is characterized in that, according to the mass fraction, its raw material comprises following component:
Acrylate polymer emulsion 25 ~ 40
Nano titanium oxide/acrylic ester polymer composite emulsion 5 ~ 15
Color stuffing 15 ~ 25
Frostproofer 1.2 ~ 1.5
Wetting agent 0.1 ~ 0.2
Film coalescence aid 1.2 ~ 1.8
Dispersion agent 0.3 ~ 0.6
Defoamer 0.1 ~ 0.4
Thickening material 0.1 ~ 0.4
Sanitas 0.1 ~ 0.3
PH adjusting agent 0.1 ~ 0.2
Deionized water 20 ~ 40
Described acrylate polymer emulsion be admittedly containing 40% benzene emulsion, pure-acrylic emulsion, vinyl acetate emulsion, tertiary acrylic emulsion or organosilicon crylic acid latex;
Described nano titanium oxide/acrylic ester polymer composite emulsion latex particle take nano titanium oxide as core, and acrylic ester polymer is the nucleocapsid structure of shell, prepares as follows:
(1) modified nano-titanium dioxide is prepared
According to the mass fraction, by ultrasonic disperse after 0.25 ~ 5 part of nano titanium oxide and 20 ~ 200 parts of solvent, 0.1 ~ 5 part of silane coupling agent is added, 60 ~ 80 DEG C of reaction 1 ~ 6h, centrifugal, with absolute ethanol washing, centrifugal, washing, dries, obtains modified nano-titanium dioxide; Described solvent is methyl alcohol, ethanol, Virahol or acetone; Described silane coupling agent is the one in γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane or vinyltriethoxysilane;
(2) nano titanium oxide/acrylic ester polymer composite emulsion is prepared
According to the mass fraction, be dispersed in by 0.25 ~ 5 part of modified nano-titanium dioxide in the mixed solution of 20 ~ 50 parts of acrylate monomers and 0.5 ~ 2 part of assistant for emulsifying agent, ultrasonic disperse, joins in emulsifier aqueous solution, wherein the amount of emulsifying agent is 0.5 ~ 2 part, the amount of deionized water is 40 ~ 80 parts, stirs, ultrasonic disperse, be warming up to 60 ~ 80 DEG C, add 0.25 ~ 5 part of initiator, insulation 2 ~ 6h, obtains nano titanium oxide/acrylic ester polymer composite emulsion; Described acrylate monomer is one or more in methyl methacrylate, Tert-butyl Methacrylate, acrylamide, butyl acrylate, acrylic acid-2-ethyl ester, Hydroxyethyl acrylate, methacrylic acid and vinylformic acid; Described assistant for emulsifying agent is n-Hexadecane, hexadecanol, Pentyl alcohol or hexalin; Described emulsifying agent is one or more in sodium oleate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, tween 80, polysorbas20, alkylphenol polyoxyethylene-10 sorbitan monostearate, polyoxyethylene 20 sorbitan trioleate and polyoxyethylene 20 sorbitan monostearate; Described initiator is the one in hydrogen peroxide, Potassium Persulphate, ammonium persulphate or Potassium Persulphate-sodium bisulfite.
2. antiultraviolet exterior coating according to claim 1, is characterized in that, described color stuffing is one or more in titanium dioxide, dicalcium powder, talcum powder, barium sulfate, mica powder and kaolin; Described frostproofer is ethylene glycol or propylene glycol; Described wetting agent is PE-100, ethanol, propylene glycol or glycerine.
3. antiultraviolet exterior coating according to claim 1, is characterized in that, described be power by ultrasonic disperse after 0.25 ~ 5 part of nano titanium oxide and 20 ~ 200 parts of solvent is 400 ~ 800W ultrasonic disperse, 5 ~ 30min.
4. antiultraviolet exterior coating according to claim 1, is characterized in that, described oven dry dries 12 ~ 24h at 50 ~ 100 DEG C.
5. antiultraviolet exterior coating according to claim 1, is characterized in that, the described ultrasonic disperse preparing nano titanium oxide/acrylic ester polymer composite emulsion be all ultrasonic power be 400 ~ 800W disperse 10 ~ 60min; The described stirring preparing nano titanium oxide/acrylic ester polymer composite emulsion stirs 5 ~ 30min under rotating speed is 100 ~ 400rpm condition.
6. antiultraviolet exterior coating according to claim 1, it is characterized in that, described dispersion agent is sodium lauryl sulphate, polyoxyethylene alkyl phenyl ether, 2-amino-2-methyl-1-propanol, sodium oleate, sodium polyacrylate or polyisobutene maleic acid sodium salt; Film coalescence aid is ethylene glycol, propylene glycol, hexylene glycol, propandiol butyl ether, butyl glycol ether, xylyl alcohol or 2-Butoxyethyl acetate.
7. antiultraviolet exterior coating according to claim 1, it is characterized in that, described defoamer is butanols, 1,2-PD, octanol, tributyl phosphate, emulsification dimethyl silicone oil, emulsification polymethylphenyl siloxane fluid, polyoxyethylene polyoxypropylene tetramethylolmethane ether or polyoxyethylene polyoxy propyl alcohol amidogen ether.
8. antiultraviolet exterior coating according to claim 1, it is characterized in that, described thickening material is dibutyl phthalate, Walocel MT 20.000PV, Natvosol, methylcellulose gum, xanthan gum, XG-60, XG-903, SN-612 or TT-935.
9. antiultraviolet exterior coating according to claim 1, is characterized in that, described sanitas is the one in BIT, BIT/MIT, CMIT/MIT or DBNPA; Described pH adjusting agent is one or more in AMP-95, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
10. the preparation method of the antiultraviolet exterior coating described in any one of claim 1-9, is characterized in that comprising the steps:
(1) nano titanium oxide/acrylic ester polymer composite emulsion is prepared;
(2) antiultraviolet exterior coating is prepared in the steps below:
1) take material by formula, under 500 ~ 1500rpm stirs, add deionized water, wetting agent, dispersion agent, pH stablizer, defoamer successively, fully stir 10 ~ 60min, obtain prepolymerization material;
2) under 500 ~ 1500rpm stirs, add the color stuffing of formula ratio in described prepolymerization material, after mixing, 1000 ~ 2000rpm stirs 30 ~ 90min, obtains color stuffing dispersion pulp;
3) nano titanium oxide/acrylic ester polymer composite emulsion is well dispersed in acrylic ester polymer exterior wall emulsion, frostproofer is slowly added in above-mentioned mixed emulsion under 300 ~ 600rpm stirs, stir 10 ~ 30min, the mixed solution obtained is added color stuffing dispersion pulp, then under 500 ~ 1000rpm stirs, add defoamer, film coalescence aid, stir 10 ~ 60min;
4) regulate pH to 8 ~ 9 by pH adjusting agent, add thickening material, 500 ~ 1000rpm stirs 10 ~ 60min, obtains antiultraviolet exterior coating.
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