CN1460697A - Weatherability self-cleaning external wall coating material and its preparation method - Google Patents
Weatherability self-cleaning external wall coating material and its preparation method Download PDFInfo
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Abstract
The present invention relates to an ultraweatherability self-cleaning paint for outer wall, and its composition contains pigment filling material, moistening dispersing agent, defoaming agent, thickening agent A, B and C, polymer emulsion, anti-mildew bactericide, film-forming adjuvant and water, etc. Said emulsion paint has the water-proofing property, good dirt resistance and anti-ageing property. In particular, the anatase titanium dioxide powder body is added, it make said paint has self-cleaning function. The invention also provides preparation method.
Description
Technical field:
The present invention relates to a kind of super Weather-proof self-cleaning exterior coating and preparation method thereof, particularly relate to a kind of light-catalyzed reaction that utilizes, decompose pollutent and dichloride in anatase type TiO attached to coating surface
2The micronized characteristic of powder is with anatase titanium dioxide sodium rice TiO
2Powder joins in the coating, makes a kind of novel aqueous silicon of maximization, high stratification skin that is applicable to and the third surpasses the latex coating of Weather-proof self-cleaning, the invention belongs to the building coating field.
Background technology:
Through making great efforts for many years, the production technology of esters of acrylic acid latex coating is ripe, in low architectural being used widely, the driving cycle can be satisfied requirement in 5 years～10 years basically.And along with expanding economy, the building of many large-and-medium size cities to maximize, high stratification development, the performance requriements of coating is progressively improved.It is sticking that existing acrylic coating exists high temperature easily to return, the defective of splitting fragile under low temperature and be difficult to meet the demands.At present, this class buildings furring brick or cladding glass are decorated, furring brick or cladding glass, and the high-altitude degeneration that brings because of the ageing of binders harm such as hidden danger and city light pollution of hurting sb.'s feelings are prohibited in some scope by relevant department and to be used.
The object of the invention is to provide a kind of super weather-proof, super anti-staining property, high tint retention and oligosaprobic high-performance and low-cost emulsion for architecture coating, particularly makes the third super weather-proof exterior coating of water-based silicon have self-cleaning function by add the nanometer anatase titania powder in this coating.
Summary of the invention:
The weight percent of its component of the super Weather-proof self-cleaning exterior coating of the present invention is as follows:
Pigment 20～30%
Filler 5～10%
Wetting dispersing agent 0.4～0.8%
Defoamer 0.3～0.5%
Thickening material A 0.2～0.3%
Thickening material B 0.1～0.2%
Thickening material C 0.4～0.6%
Antimildew disinfectant 0.2～0.6%
Frostproofer 2.0～2.5%
Help knot agent 1.0～2.0%
PH conditioning agent 0.1～0.2%
Polymer emulsion 30.0～40.0%
All the other are tap water
Pigment is Rutile type Titanium Dioxide and dichloride in anatase type TiO
2Collocation is used, and Rutile type Titanium Dioxide has good weather resistance, and its optimum amount is 15～22%.Dichloride in anatase type TiO
2Be white powder, the special composite structure of this powder helps the separation and the transportation of photic current carrier, thereby has very high photocatalytic activity, long service life.The consumption of nanoparticle is very crucial, if add quantity not sufficient, does not then have the effect of expection; Dosage is too much, is not only a kind of waste, can play side effect on the contrary, makes the coating products downgrade, and its optimum amount is 5～8%.
Filler is a kaolin, sericite, and wollastonite etc., the use of filler not only can reduce cost, and can give coating some special performances.Make coating have certain thixotropy as kaolinic sheet structure, thereby improve the stability in storage of coating; The sheet structure of sericite is to ultraviolet ray, microwave, infrared rays have good shielding effect strengthened coating resistance to deterioration, weathering resistance indexs such as uvioresistant, but the consumption of filler is unsuitable excessive, is good between 25～35% with the pigment volume concentration (PVC) (PVC) of guarantee system.
Used general wetting dispersing agent and defoamer in the present invention's prescription, wetting dispersing agent adopts polypropylene acid aqueous ammonium, as the GA-40 of Ciba company polyacrylic acid aqueous ammonium, and the SN-5040 of Henkel company, H100 etc.; Defoamer adopts mineral oil antifoam agent, NXZ as Henkel company, the hydrophobic solid of BYK company and broken bubble polysiloxane mixture defoamer BYK-022, BYK-024, the organic silicone oil CF-246 defoamers of BLACKBURN company etc., its effect is the coating system that color stuffing is effectively disperseed and form stable, a no bubble and shrinkage cavity defect.
Thickening material A is a Natvosol, for example CellosizeER-4400, the Cellosize ER-15000 etc. of Natvosol NATROSOL 250 HBR, the NATROSOL PLUS 330 of U.S. HERCULES company and U.S. associating carbonization company limited, its effect is to increase the viscosity of water with the dispersion efficiency that improves color stuffing, the final viscosity that increases coating, and optimum amount is 0.2～0.3%; Thickening material B is a magnesium aluminum silicate, for example hydrated magnesium aluminum silicate ATTAGEL50 or the ATTAGEL40 and the concavo-convex sample soil of the colloidal state inorganic mineral type thickening material etc. of lattice Asia-Pacific group are pacified by the U.S., its effect is to bring sag resistance for system, control viscosity, dispersing property is good, improve the levelling property of coating, optimum amount 0.1～0.2%; Thickening material C is the rheology modified thickening material of non-ionic type no-solvent polyurethane class, for example Rohm﹠amp; The RM2020 of Haas company, water/the propylene glycol of vulcabond such as RM-8W/Virahol (3: 2: 1) solution, the Pu-75 of BASF AG for example, Pu-85 etc., its effect is to adjust viscosity and the rheological of coating under different shear actions, and optimum amount is 0.4～0.6%.
Three kinds of thickening materials are used, and can effectively adjust the rheological behaviour of coating under basic, normal, high shearing rate, to obtain good leveling property, not sagging, excellent storage stability, easy working exterior wall latex coating.
Antimildew disinfectant is 2-n-octyl-4-isothiazoline-3-ketone benzoglyoxaline, Isothizole derivatives, the methylolurea 1 of Pvrogiven company, 6 dihydroxyl-2-5 dioxane etc., its effect be prevent in the coating storage process become morally degenerate and application after the mildew of filming.
Frostproofer is ethylene glycol, propylene glycol, glycerol etc., and helping the knot agent is 2,2,4-trimethylammonium-1, and 3-pentanediol first and second butyric esters, phenylcarbinol, propylene glycol phenylate etc., the PH conditioning agent is ammoniacal liquor, soda ash (NaCO
3) or the organic Ammonia ester of a kind of lower molecular weight class PH conditioning agent 2-amino-2-methyl-1-propanol of U.S. ANGUS company, its effect is respectively the freeze-thaw stability that increases coating, the pH value that helps film forming and regulate coating is to increase the stability of coating system.
Polymer emulsion in the present invention prescription is different from pure third, the benzene emulsion that is usually used in exterior coating now on the market, but a kind of organo-siloxane monomer and acrylic ester monomer copolymerization that utilizes chemical copolymerization method that unsaturated link(age) will be arranged, introduce the modification organosilicon crylic acid latex of siloxanes on main polymer chain, optimum amount is 30～40% of a lacquer total amount.
The production method of the super Weather-proof self-cleaning exterior coating of the present invention coating is:
(1) pre-mixing: take by weighing various materials in the paint cylinder by standard formula, open stirring, under stirring at low speed (300～400 rev/mins), be sequentially added into tap water, wetting dispersing agent, defoamer, pigment, filler and thickening material A;
(2) high speed dispersion: carrying out at a high speed in homogenizer, (1200～1500 rev/mins) disperse.The color stuffing particle is dispersed into simple particle under the effect of homogenizer high shear rate, and obtains the stably dispersing state under the effect of dispersing auxiliary system.The high speed dispersion time was at 20～30 minutes.Add thickening material B then, middling speed (800～1000 rev/mins) is disperseed, and disperses 5～8 minutes;
(3) paint: when face is added material when reaching desired fineness, add polymer emulsion, defoamer, PH conditioning agent, thickening material C and other auxiliary agents, this process low speed in the paint cylinder carries out (300～400 rev/mins), to obtain having the coating of appropriate viscosity and good stability;
(4) filter and package.
Characteristics of the present invention are: the base-material of (one) lacquer is the high-weatherability organosilicon crylic acid latex.Organosilicon crylic acid latex is when drying and forming-film, siloxanes hydrolysis, polycondensation, firmly crosslinked cubic network (Si-O-Si-) structure can formed between the polymer molecule and between polymkeric substance and the base material, make paint film have very strong water tolerance and sticking power, and polysiloxane molecule is structure in the shape of a spiral, methyl is outwards arranged and is rotated around the Si-O chain, molecular volume is big, and cohesive energy density(CED) is low, thereby makes emulsion that very strong hydrophobic nature and dirt resistance be arranged.In addition, the bond energy of Si-O is followed the C-O key much larger than the C-C key in the organosilicon crylic acid latex, this makes thermotolerance, weathering resistance, the antioxidant capacity of organosilicon crylic acid latex strengthen, therefore, the water tolerance of this coating, pollution resistance, water-repellancy performance obviously are better than pure acrylic acid coating, this coating has satisfactory stability simultaneously, and the shelf lives can reach more than 1 year.(2) in this prescription except adding traditional Rutile type Titanium Dioxide, also added dichloride in anatase type TiO with special construction
2This powder is composited through special process by ultra tiny inorganic functional material, and particle diameter is little, and specific surface area is big, has very high chemical stability and thermostability.It is added in the coating, can decompose the pollutent attached to coating surface, thereby play self-cleaning effect by light-catalyzed reaction, simultaneously, utilize this phenomenon of the easy efflorescence of anatase thpe white powder, we add a spot of dichloride in anatase type TiO
2, under UV-irradiation, about 1 year micronization takes place, approximately consumed 6～8 microns film thickness in 1 year, the dust that sticks on the body of wall is come off thereupon, body of wall also can keep clean for a long time.Itself has self-cleaning function paint film, and it is crucial that this special performance pollutes serious day by day urban environment to air-borne dust.
Specific embodiment:
Embodiment one:
Prescription is: 22 kilograms in (total amount is 100 kilograms of meters) tap water, ammonium polyacrylate wetting dispersing agent GA-400.6 kilogram, 16 kilograms of Rutile type Titanium Dioxides (CR-828), dichloride in anatase type TiO
28 kilograms of powders, 5 kilograms of kaolin (3000 order), 3 kilograms of sericites (1250 order), 0.4 kilogram of the organic silicone oil defoamer CF-246 of BLACKBURN company, 330 0.3 kilograms of Natvosol thickening material NATROSOL PLUS, 0.1 kilogram of magnesium aluminum silicate thickening material ATTAGEL50,0.4 kilogram of hydrophobic remodeling polyurethane thickener RM2020,0.2 kilogram of PH conditioning agent 2-amino-2-methyl-1-propanol, 0.2 kilogram of sterilant bayer Isothizole derivatives+methylolurea 1,6 dihydroxyl-2-5 dioxane, mould inhibitor Progiven 2-n-octyl-4-isothiazoline-3-ketone benzoglyoxaline, 0.3 kilogram, 2 kilograms of frostproofer propylene glycol, help knot agent 2,2,4-trimethylammonium-1,1.5 kilograms of 3-pentanediol first and second butyric esters, 40 kilograms of organosilicon crylic acid latexs.The blending process step is: 1. at first disperse to add in the cylinder dispersion medium water at stainless steel, start stirrer, accurately take by weighing various materials by prescription then, adding wetting dispersing agent, 1/2 defoamer, thickening material A, frostproofer, Rutile type Titanium Dioxide, dichloride in anatase type TiO under the stirring state at a slow speed
2Powder and other filler low speed (300～400 rev/mins) stirred 5 minutes.2. (1200～1500 rev/mins) dispersion at a high speed in homogenizer.The color stuffing particle is dispersed into simple particle under the high shear rate effect of homogenizer.The fineness of checking pigment slurry is less than 30 μ m.Add thickening material B, middling speed (800～1000 rev/mins) was disperseed 5 minutes, and the slow speed of revolution is so that paint.3. paint.2. the slurry of gained is transferred in the paint cylinder, under low speed (300～400 rev/mins), added polymer emulsion, residue 1/2 defoamer, PH conditioning agent successively, and thickening material C, help knot agent and other auxiliary agents, paint.4. filter with reciprocating sieve, by the customer requirement packing.This product is nontoxic, non-environmental-pollution, levelling property brilliance, strong covering power.After testing, this coating has good water-fast, alkaline resistance properties, and its washability number of times of filming is greater than 3000; Weathering resistance and automatically cleaning ability that superelevation is arranged, artificial ageing resistance were the optimal selections of high stratification building greater than 1000 hours.
Embodiment two:
Certain newly-built commercial building because of belonging to maximization, high stratification building, has adopted this product to carry out external-wall coating.Prescription is (gross weight is in 100 kilograms): 23 kilograms of ammonium polyacrylate wetting dispersing agents of tap water H-1000.5 kilogram, 20 kilograms of Rutile type Titanium Dioxides (CR-828), dichloride in anatase type TiO
25 kilograms of powders, 5 kilograms of kaolin (3000 order), 3 kilograms of sericites, 2 kilograms of wollastonite powder (900 order), 0.4 kilogram of the organic silicone oil mixture defoamer CF-246 of BLACKBURN company, Natvosol thickening material CellosizeER-150000.25 kilogram, 0.1 kilogram of thickening material magnesium aluminum silicate Attgel50,0.2 kilogram of 0.45 kilogram of PH conditioning agent of hydrophobic remodeling polyurethane thickener RM2020 2-amino-2-methyl-1-propanol, 0.2 kilogram of sterilant Progiven bayer Isothizole derivatives+methylolurea 1,6 dihydroxyl-2-5 dioxane, mould inhibitor Progiven 2-n-octyl-4-isothiazoline-3-ketone benzoglyoxaline, 0.4 kilogram, 2 kilograms of frostproofer propylene glycol, help knot agent 2,2,4-trimethylammonium-1,1.5 kilograms of 3-pentanediol first and second butyric esters, 36 kilograms of organosilicon crylic acid latexs.The tap water that adds 20% latex coating amount during construction stirred 10 minutes, and it is mixed, and can use.Before brushing paint, metope is clean, smooth and exsiccant, has scraped matching putty on it, brushes sealing priming paint, with synthetic scrub-brush brush application.The coating that brushing the present invention makes, the sliding as silk of lacquer painting children, the flow leveling brilliance brush easyly, and the alkali resistant mildew resistance is strong, and superior performances such as anti-contamination, scrubbing resistance are not faded in use for a long time.The engineering completion was checked to the building site after 2 years, so coating of the present invention has still light as new of good self-cleaning performance metope.Coating stands Exposure to Sunlight, drenches with rain, the etch of wind, freezing and various chemical substances, still can protect light and protect look, does not peel off, does not damage, and has good alkaline-resisting, anti-industrial gaseous waste, UV resistant, anti-mould, anti-contamination, high-performances such as scrubbing resistance.
Embodiment three:
Certain high-rise office building the 10th buildings～the 22nd building has adopted product of the present invention to carry out external-wall coating, its prescription is 25 kilograms in (total amount is 100 kilograms of meters) tap water, 0.5 kilogram of ammonium polyacrylate wetting dispersing agent H100,16 kilograms of Rutile type Titanium Dioxides (CR-828), dichloride in anatase type TiO
28 kilograms of powders, 5 kilograms of kaolin (3000 order), 3 kilograms of sericites (1250 order), 0.5 kilogram of the organic silicone oil defoamer CF-246 of BLACKBURN company, 330 0.3 kilograms of Natvosol thickening material NATROSOL PLUS, 0.1 kilogram of magnesium aluminum silicate thickening material ATTAGEL50,0.4 kilogram of hydrophobic remodeling polyurethane thickener RM2020,0.2 kilogram of PH conditioning agent 2-amino-2-methyl-1-propanol, 0.2 kilogram of sterilant bayer Isothizole derivatives+methylolurea 1,6 dihydroxyl-2-5 dioxane, mould inhibitor Progiven 2-n-octyl-4-isothiazoline-3-ketone benzoglyoxaline, 0.3 kilogram, 2 kilograms of frostproofer propylene glycol, help knot agent 2,2,4-trimethylammonium-1,1.5 kilograms of 3-pentanediol first and second butyric esters, 37 kilograms of organosilicon crylic acid latexs.And its 1st building～the 9th buildings adopt pure third exterior wall latex paint of our company's production to cover with paint, lacquer, colour wash, etc. simultaneously.Prescription is: 25 kilograms in water, 0.6 kilogram of ammonium polyacrylate dispersion agent GA-40,23 kilograms of Rutile type Titanium Dioxides (CR-828), 6 kilograms in lime carbonate (700 order), 0.5 kilogram of organic silicone oil mixture defoamer CF-246,0.34 kilogram of thickening material A (Natvosol CellosizeER-4400), 0.6 kilogram of thickening material B (hydrophobically modified polyurethanes thickening material RM2020), all the other are his auxiliary agent of tool, 35.0 kilograms of pure-acrylic emulsions.The tap water that adds 20% emulsion paint amount during construction respectively stirred 15 minutes, and it is mixed, and just can use.Before brushing paint, wall all is clean, smooth and exsiccant.Adopt wool cylinder roller coating construction.Engineering completion was sought and visited discovery to this office building after 1 year, and the 10th buildings～22 building metopes are light as newly still, the 1st building～9 building metope colour-darkenings and have tangible grey dirt to stick on the metope.This shows that product of the present invention has super-weathering resistance and self-cleaning function.
Claims (6)
1. super Weather-proof self-cleaning exterior coating is characterized in that its weight percentages of components is as follows:
Pigment 20～30%,
Filler 5～10%,
Polymer emulsion 30～40%,
Wetting dispersing agent 0.4～0.8%,
Defoamer 0.3～0.5%,
Thickening material A 0.2～0.3%,
Thickening material B 0.1～0.2%,
Thickening material C 0.4～0.6%,
Antimildew disinfectant 0.2～0.6%,
Frostproofer 2.0～2.5%,
Help the knot agent 1.0～2.0%,
PH conditioning agent 0.1～0.2%,
All the other are tap water
2. super Weather-proof self-cleaning exterior coating according to claim 1 is characterized in that pigment is Rutile type Titanium Dioxide and dichloride in anatase type TiO
2Collocation is used, and the optimum amount of Rutile type Titanium Dioxide is 15～22%, dichloride in anatase type TiO
2. its optimum amount is 5～8%.
3. super Weather-proof self-cleaning exterior coating according to claim 1 is characterized in that filler is wherein one or more of kaolin, sericite, wollastonite.
4. super Weather-proof self-cleaning exterior coating according to claim 1, it is characterized in that polymer emulsion is a kind of organo-siloxane monomer and acrylic ester monomer copolymerization that utilizes chemical copolymerization method that unsaturated link(age) will be arranged, introduce the modification organosilicon crylic acid latex of siloxanes on main polymer chain, optimum amount is 30～40% of a lacquer total amount.
5. super Weather-proof self-cleaning exterior coating according to claim 1, it is characterized in that thickening material A is a Natvosol, thickening material B is a magnesium aluminum silicate, thickening material C is the rheology modified thickening material of non-ionic type no-solvent polyurethane class, wetting dispersing agent adopts polypropylene acid aqueous ammonium, defoamer adopts mineral oil antifoam agent, frostproofer is ethylene glycol, propylene glycol or glycerol, helping the knot agent is 2,2,4-trimethylammonium-1,3-pentanediol first and second butyric esters, phenylcarbinol or propylene glycol phenylate, PH conditioning agent are ammoniacal liquor, soda ash (NaCO
3) the organic Ammonia ester of lower molecular weight class PH conditioning agent 2-amino-2-methyl-1-propanol, antimildew disinfectant is 2-n-octyl-4-isothiazoline-3-ketone benzoglyoxaline, Isothizole derivatives+methylolurea 1 or 6 dihydroxyl-2-5 dioxane.
6. the preparation method of super according to claim 1 Weather-proof self-cleaning exterior coating is characterized in that its production stage and method are as follows:
(1) pre-mixing: take by weighing various materials in paint mixing tank by standard formula, open stirrer, under stirring at low speed (300～400 rev/mins), be sequentially added into tap water, wetting dispersing agent, defoamer, pigment, filler and thickening material A;
(2) high speed dispersion: carrying out at a high speed in homogenizer, (1200～1500 rev/mins) disperse.The color stuffing particle is dispersed into simple particle under the effect of homogenizer high shear rate, and obtains the stably dispersing state under the effect of dispersing auxiliary system, the high speed dispersion time was at 20～30 minutes, add thickening material B then, middling speed (800～1000 rev/mins) is disperseed, and disperses 5～8 minutes;
(3) paint: when color stuffing reaches desired fineness, add base-material, defoamer, PH conditioning agent, thickening material C and other auxiliary agents, this process low speed in the paint cylinder carries out (300～400 rev/mins), to obtain having the coating of appropriate viscosity and good stability;
(4) filter and package.
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