CN1478830A - Ageing resistant colour paste for aqueous building external wall paint and its preparation method - Google Patents
Ageing resistant colour paste for aqueous building external wall paint and its preparation method Download PDFInfo
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- CN1478830A CN1478830A CNA021422648A CN02142264A CN1478830A CN 1478830 A CN1478830 A CN 1478830A CN A021422648 A CNA021422648 A CN A021422648A CN 02142264 A CN02142264 A CN 02142264A CN 1478830 A CN1478830 A CN 1478830A
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Abstract
An antiageing distemper of water paint for external wall of building is prepared from nano TiO2, organic pigment, wet disperser, multifunctional disperser, moisture-retentive agent, stabilizer, defoaming agent and bactericide through stirring and ball grinding. Its advantages are high effect and high compatibility to paint.
Description
Technical field
The present invention relates to a kind of paint additive and preparation method thereof, specifically, relate to a kind of water building outer wall coating material with ageing-resistant mill base and preparation method thereof.The present invention relates to by formulated a kind of water building outer wall coating material such as nano titania level ultra-fine micropowder, pigment dyestuff powder, multiple auxiliary agent and water with ageing-resistant mill base and preparation method thereof.
Background technology
Whitewash promptly becomes colored paint after adding the mill base modulation.The water building outer wall coating material colored paint is owing to stand wind and weather out of doors for a long time, exposure in sunshine, the mal-conditions such as cold and hot conversion of alternation of wetting and drying and temperature, phenomenons such as final coating loss of gloss can occur, fades, variable color, cause that the original color of metope shoals, deepening, in addition colourless fully, and different directions metope aberration is bigger, morbid state such as metope grows dim, irregular colour, this has had a strong impact on the decorative effect of coating.Use through secular experimental study and engineering, people progressively recognize, catabiosis such as the fading of building external paint, variable color mainly be since the ultraviolet ray that contains in the sunlight coating is filmed in the result of effect of granules of pigments.
Except that visible light and infrared rays, also has ultraviolet ray in the sunlight.Press the wavelength size, ultraviolet ray can be divided into shortwave UVC 190nm-280nm, medium wave UVB 280nm-320nm and long wave UVA 320nm-400nm.Ultraviolet wavelength is short more, and energy is strong more, and is serious more to organic destruction.By table 1 as seen, than long light-wave energy molecule is produced vibrates and rotates and the generation heat, and ultraviolet (UV) A, UVB, UVC can produce destruction to chemical bond such as C-H, C-C, C-Cl in the organism and the material with identical bond energy, thereby causes that organism, macromolecular compound are degraded into small molecules.Basic chemical bond is C-C key and c h bond etc. in the pigment dyestuff molecule of pigment coloration, and the uviolizing meeting makes in the coating pigment molecule structure be destroyed, and decomposes, is degraded to other material, makes colored paint lose color or colour-change in appearance.This long term finally cause coating loss of gloss, fade, catabiosis such as variable color.
Table 1 light wavelength and energy and common organic compounds chemistry bond energy
| Wavelength/nm | ????200 | ????300 | ????400 | ????500 | ????700 | ????800 |
| Luminous energy kJmol -1 | ????598 | ????397 | ????301 | ????238 | ????171 | ????146 |
| The chemistry key name | ????O-H | ????C-H | ????C-C | ????C-Cl | ????N-N | ????O-O |
| Bond energy/kJmol -1 | ????462 | ????413 | ????347 | ????326 | ????158 | ????138 |
Also be not directed at present the effective ways that improve pigment dyestuff mill base ageing resistance, in order to improve the ageing resistance of colored paint, general way is to select those anti-mill bases of being made by the good pigment of the aging resistance of pigment own in the use, as pigment Violet 23, Pigment red 254 etc., but the most price of these mill bases is very expensive, and practicality is not strong.For preventing or reducing the extensive method that adopts of paint aging is to add UV light stabilizing agent in coating, rely in the coating as the Switzerland Ciba company of refining and to add the ageing-resistant performance that Tinuvin1130 ultraviolet absorbers and Tinuvin292 hindered amine as light stabilizer increase coating, Switzerland Clariant company relies on and adds the ageing-resistant performance that the Saduvoy3225Dispersion UV light stabilizing agent improves coating in the coating.
The method that adding UV light stabilizing agent in coating increases ageing resistance mainly is in order to increase the ageing-resistant performance of coating itself, and is main at whitewash, very limited to the ageing resistance raising of pigment dyestuff.And for colored paint, the ageing resistance of pigment dyestuff is very different more than coating itself, and the ageing-resistant performance of coating own is good more, and this contradiction is sharp-pointed more.In aqueous architectural coating is produced, press for a kind of mill base of ageing-resistant performance excellence.
Last decade comes, and progressively gos deep into and raising in the research of the ultra tiny material of 1-100nm for the particle size that is referred to as nano material, has promoted the development of nano material subject and nanosecond science and technology.Nano material has quantum size effect, small-size effect, surface effects and macro quanta tunnel effect.Nano material is because small-size effect makes it have the optical characteristics that conventional massive material does not possess, and all with the size of nanoparticle very strong dependence arranged as the energy waste in optical nonlinearity, photoabsorption, luminous reflectance, the optical transmission process etc.Studies show that nano-titanium dioxide powder has strong absorption to wavelength in the UV-light of 200-400nm, therefore, lay the foundation with ageing-resistant mill base for utilizing nano titanium oxide preparation water building outer wall coating material.Among the present invention, in the production process of mill base, add nano material, make nano material be coated on the granules of pigments surface, to ultraviolet shielding effect, improve the ageing-resistant performance of mill base greatly by nano material by certain technology.
Summary of the invention
The objective of the invention is to research and develop a kind of building coating additive, it can improve the ageing-resistant performance of coating.
Another object of the present invention provides the ageing-resistant mill base of a kind of water building outer wall coating material, and this ageing-resistant mill base can improve guarantor's light tint retention energy of colored paint largely, reaches 1000h temper(ing) variable color one-level.
Another object of the present invention provides a kind of method of producing described water building outer wall coating material with ageing-resistant mill base, produce the ageing-resistant mill base of water building outer wall coating material with the inventive method, used nanometer level titanium dioxide powder, solved in the prior art nanoparticle and very easily assembled agglomerating problem.
A further object of the present invention provides a kind of coating that contains water building outer wall coating material of the present invention with ageing-resistant mill base.Water building outer wall coating material of the present invention is added in the toning process of coating material production with ageing-resistant mill base, and its latex and water soluble resin with routine has good consistency.For example, the nano assistant that the present invention is prepared adds pure acrylate dope, can greatly improve the ageing-resistant performance of pure acrylate dope.
According to the present invention, provide a kind of water building outer wall coating material ageing-resistant mill base, this mill base comprises nanometer level titanium dioxide powder, pigment, dispersion agent, wetting Agent for Printing Inks, sterilant, defoamer, stablizer and deionized water, and wherein the particle diameter of titanium dioxide powder is the 1-100 nanometer.
According to the present invention, provide a kind of water building outer wall coating material ageing-resistant mill base, in the gross weight of mill base, it comprises:
Nanometer level titanium dioxide powder 0.5-6%
Pigment 35-50%
Dispersion agent 2.5-10%;
Wetting Agent for Printing Inks 3-8%;
Sterilant 0.05-0.3%;
Defoamer 0.01-0.5%;
Stablizer 0.1-2%;
The deionized water surplus.
The ageing-resistant mill base of water building outer wall coating material according to the present invention, its performance is:
| Particle diameter | ＜3μm |
| Viscosity | 2100-2400mPa·s |
| PH value | 7-10 |
| State | The thickness slurry |
According to the present invention, provide a kind of water building outer wall coating material ageing-resistant mill base, in the gross weight of mill base, it comprises:
Nanometer level titanium dioxide powder 2-3.5%
Pigment 43-47%
Dispersion agent 4.7-6.8%;
Wetting Agent for Printing Inks 4-6%;
Sterilant 0.1-0.15%;
Defoamer 0.2-0.5%;
Stablizer 0.5-1%;
The deionized water surplus.
Water building outer wall coating material of the present invention is alkalescence with ageing-resistant mill base, and the pH value is 7-10, is preferably 8-9.The pH value is controlled by pH value conditioning agent.Can be used for pH value conditioning agent of the present invention and comprise AMP-95, sodium hydroxide, potassium hydroxide and ammoniacal liquor, preferred AMP-95.
In enforcement of the present invention, employed nano-titanium dioxide powder is commercially available, and its key technical indexes is purity 〉=99.9%, median size 10nm, specific surface area 640m
2/ g, thing phase amorphous.The used pigment of the present invention can be mineral dye and pigment dyestuff, comprises phthalocyanine blue pigment Huang, Pigment green, titanium white, network Huang and red lead etc.Can be used for the mixture that dispersion agent of the present invention comprises wetting dispersing agent and multi-functional dispersion agent, it comprises succimide, 2-amino-2-methyl-1-propanol, 3-methacryloxypropyl trimethoxy silane, two [tetra-sodium dialkoxy ester]-2 hydroxy propanoic acid titanium, Diisobutylene maleic acid sodium salt, two (phosphorous acid dilaurate) network four octyloxy titaniums, β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium etc. or their mixture, and preferred dispersing agent is the mixture of succimide and 2-amino-2-methyl-1-propanol.In the gross weight of mill base of the present invention, the amount of dispersion agent is generally 2.5-10%, and wherein the amount of wetting dispersing agent is 2-8%, is preferably 3.5-5.5%, and the amount of multi-functional dispersion agent is 0.5-2%, is preferably 1.2-1.3%.
Can be used for wetting Agent for Printing Inks of the present invention is alcohols material, as 1, and 2-propylene glycol, ethylene glycol, glycerol or propyl carbinol etc.; The amount of wetting Agent for Printing Inks is generally 3-8%, is preferably 4-6%.Sterilant is the sterilant of this area routine, comprise 1,1,2-benzisothiazole-3-ketone, benzoglyoxaline Urethylane, 2,4,5,6-first chlorine m-dicyanobenzene, benzisothiazole ketone, 2-(4-thiazolyl) benzoglyoxaline and 2-n-octyl-4-isothiazoline-3-ketone etc., preferred 1,1, the 2-benzisothiazole-3-ketone; The amount of sterilant is generally 0.01-0.3%, is preferably 0.1-0.15%.Defoamer is this area defoamer commonly used, comprise poly-three normal-butyl phosphoric acid ester, Union carbide A-162, methyl polysiloxane or dimethyl polysiloxane, propanediol polyoxypropylene Soxylat A 25-7 and polyoxyethylene nonyl phenylate etc., preferably poly-three normal-butyl phosphoric acid ester; The amount of defoamer is generally 0.01-0.5%, is preferably 0.2-0.5%.
Can be used for stablizer of the present invention is ether of cellulose, and the available ether of cellulose comprises Natvosol, methyl hydroxyethylcellulose, Vltra tears, Type 3U and propyl group Natvosol.Useful especially in the present invention stablizer is Natvosol and Type 3U.The amount of stablizer is generally 0.1-2%, is preferably 0.5-1%.
In a preferred embodiment of the invention, provide a kind of water building outer wall coating material ageing-resistant mill base, in the gross weight of described mill base, it comprises:
Nano-TiO
2Powder 0.5～6%
Phthalocyanine blue 35～50%
Succimide 2～8%
2-amino-2-methyl-1-propanol 0.5～2%
1,2-propylene glycol 3～8%
1,1,2-[4-morpholinodithio quinoline-3-ketone 0.05～0.3%
Three normal-butyl phosphoesterase 30 .01～0.5%
Natvosol 0.1～2%
Deionized water 30～50%.
In another preferred embodiment of the present invention, provide a kind of water building outer wall coating material ageing-resistant mill base, it comprises:
Nano-TiO
2Powder 2～3.5%
Phthalocyanine blue 43～47%
Succimide 3.5～5.5%
2-amino-2-methyl-1-propanol 1.2～1.3%
1,2-propylene glycol 4～6%
1,1,2-[4-morpholinodithio quinoline-3-ketone 0.1～0.15%
Three normal-butyl phosphoesterase 30 .2～0.5%
Natvosol 0.5～1%
Deionized water 38～42%.
In a preferred embodiment of the invention, the water building outer wall coating material of gained is as follows with the performance of ageing-resistant mill base:
| Particle diameter | ＜3μm |
| Viscosity | 2200mPa·s |
| PH value | 8.5 |
| State | The thickness slurry |
According to the present invention, a kind of method of producing water building outer wall coating material of the present invention with ageing-resistant mill base is provided, this method comprises:
Stablizer is added in the deionized water, mix and make pre-solution;
Dispersion agent, wetting Agent for Printing Inks, sterilant, defoamer are added in the pre-solution, stir and they were mixed in 5-30 minute;
Add nano-TiO
2With the phthalocyanine blue powder, stirred 20-90 minute;
Above-mentioned mixed slurry component was added grinding machine for grinding 5-15 hour, until the soup compound that forms uniform good fluidity;
Add an amount of pH regulator agent soup compound pH value is controlled between the 7-10, make the ageing-resistant mill base of water building outer wall coating material of the present invention.
In the present invention, the stirring of being adopted can be undertaken by stirrer well known in the art, and it mainly is that mixture dispersion agent, wetting Agent for Printing Inks, sterilant, defoamer, stablizer and deionized water are mixed.
After adding titanium dioxide powder and pigment powder, stirred 20-90 minute.Its objective is Nano titanium dioxide is uniformly distributed in the solution, form uniform and stable slurries.
In the grinding steps of the present invention, equipment used is that the field is known, comprises shredder, sand mill and ball mill etc.
Key of the present invention is nanoparticle to be dispersed into evenly stable slurries.For realizing this purpose, must appropriately control following condition: the kind of dispersion agent, the consumption of the consumption of dispersion agent, the consumption of nano powder, PH conditioning agent, the consumption of stablizer and the amount of water.
Can be used for pH value conditioning agent of the present invention and comprise AMP-95, sodium hydroxide, potassium hydroxide and ammoniacal liquor, preferred AMP-95.
In enforcement of the present invention, employed nano-titanium dioxide powder is commercially available, and its key technical indexes is purity 〉=99.9%, median size 10nm, specific surface area 640m
2/ g, thing phase amorphous.The used pigment of the present invention can mineral dye and pigment dyestuff, comprises phthalocyanine blue pigment Huang, Pigment green, titanium white, network Huang and red lead etc.Can be used for the mixture that dispersion agent of the present invention comprises wetting dispersing agent and multi-functional dispersion agent, it comprises succimide, 2-amino-2-methyl-1-propanol, 3-methacryloxypropyl trimethoxy silane, two [tetra-sodium dialkoxy ester]-2 hydroxy propanoic acid titanium, Diisobutylene maleic acid sodium salt, two (phosphorous acid dilaurate) network four octyloxy titaniums, β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium etc. or their mixture, and preferred dispersing agent is the mixture of succimide and 2-amino-2-methyl-1-propanol.In the gross weight of mill base of the present invention, the amount of dispersion agent is generally 2.5-10%, and wherein the amount of wetting dispersing agent is 2-8%, is preferably 3.5-5.5%, and the amount of multi-functional dispersion agent is 0.5-2%, is preferably 1.2-1.3%.
Can be used for wetting Agent for Printing Inks of the present invention is alcohols material, as 1, and 2-propylene glycol, ethylene glycol, glycerol or propyl carbinol etc.; The amount of wetting Agent for Printing Inks is generally 3-8%, is preferably 4-6%.Sterilant is the sterilant of this area routine, comprise 1,1,2-benzisothiazole-3-ketone, benzoglyoxaline Urethylane, 2,4,5,6-first chlorine m-dicyanobenzene, benzisothiazole ketone, 2-(4-thiazolyl) benzoglyoxaline and 2-n-octyl-4-isothiazoline-3-ketone etc., preferred 1,1, the 2-benzisothiazole-3-ketone; The amount of sterilant is generally 0.01-0.3%, is preferably 0.1-0.15%.Defoamer is this area defoamer commonly used, comprise poly-three normal-butyl phosphoric acid ester, Union carbide A-162, methyl polysiloxane or dimethyl polysiloxane, propanediol polyoxypropylene Soxylat A 25-7 and polyoxyethylene nonyl phenylate etc., preferably poly-three normal-butyl phosphoric acid ester; The amount of defoamer is generally 0.01-0.5%, is preferably 0.2-0.5%.
Can be used for stablizer of the present invention is ether of cellulose, and the available ether of cellulose comprises Natvosol, methyl hydroxyethylcellulose, Vltra tears, Type 3U and propyl group Natvosol.Useful especially in the present invention stablizer is Natvosol and Type 3U.The amount of stablizer is generally 0.1-2%, is preferably 0.5-1%.
According to the present invention, also provide a kind of coating that comprises water building outer wall coating material of the present invention with ageing-resistant mill base.Water building outer wall coating material of the present invention is the water-based slurry with ageing-resistant mill base, adds in the toning process of coating material production, and with common latex and water soluble resin good consistency is arranged.
The of the present invention ageing-resistant mill base for preparing is added pure acrylate dope tests through temper(ing), ageing-resistant mill base with do not add the nanometer material with prescription and record aberration Δ E contrast as following table 2 with the experiment of the mill base of explained hereafter.The method of this area routine is adopted in experiment.Senile experiment shows that the ageing-resistant performance of ageing-resistant mill base is very excellent.
The aging resistance of the anti-aging mill base of table 2
| The temper(ing) time | ??250h | ??500h | ??750h | ??1000h | |
| ? ? ??ΔE | Add the mill base of nano material | 0.26-0.38 | ?0.40-0.49 | ?0.72-0.85 | ?1.0-1.13 |
| Do not add the mill base of nano material | 0.52-0.72 | ?1.06-1.21 | ?2.27-2.61 | ?3.80-4.54 | |
Add in the coating of the present invention water building outer wall coating material with the basic consumption of ageing-resistant mill base by the amount that the people adopted of knowing coating technology, and performances such as the storage period that can obtain to be satisfied with, outward appearance, viscosity.
Environment amenable and the aqueous color paste that can excellent compatibility be arranged with various water-borne coatingss such as phenylpropyl water-soluble coating, pure third water-borne coatings, silicone-acrylic water-soluble coating, second third water-borne coatings and common latex and water soluble resin when water building outer wall coating material of the present invention is a kind of the use with ageing-resistant mill base.
Embodiment
Embodiment 1
Press column weight amount % batching:
Nano-TiO
2Powder 2.5
Phthalocyanine blue 45.0
Succimide 4.7
2-amino-2-methyl-1-propanol 1.2
1,2-propylene glycol 5.2
1,1,2-[4-morpholinodithio quinoline-3-ketone 0.1
Three normal-butyl phosphoesterase 30 .4
Natvosol 0.8
Deionized water 40.1
Natvosol with 0.8% mixes until forming even viscous solution through stirring at low speed with 40.1% deionized water, add 4.7% succimide, 1.2% 2-amino-2-methyl-1-propanol, 5.2% 1, the 2-propylene glycol, 0.1% 1,1,2-[4-morpholinodithio quinoline-3-ketone, 0.4% three normal-butyl phosphoric acid ester.Stir and they were mixed in 5 minutes, add nano-TiO then
2Powder, the phthalocyanine blue pigment powder, stirred 30 minutes, at last the mixed slurry component is added ball milling 6-8h in the ball mill, until the soup compound that forms uniform good fluidity, add an amount of AMP-95 the soup compound pH value is controlled between the 8-9, make the ageing-resistant mill base of water building outer wall coating material of the present invention.
Embodiment 2
Press column weight amount % batching:
Nano-TiO
2Powder 6
Pigment Yellow 73 35.0
Succimide 8
2-amino-2-first-1-propyl alcohol 0.5
Glycerol 3
1,1,2-[4-morpholinodithio quinoline-3-ketone 0.3
Three normal-butyl phosphoesterase 30 .5
Type 3U 0.1
Deionized water 46.6
Type 3U is mixed until forming even viscous solution through stirring at low speed with deionized water, add succimide, 2-amino-2-methyl-1-propanol, glycerol, 1,1,2-[4-morpholinodithio quinoline-3-ketone, three normal-butyl phosphoric acid ester.Stir and they were mixed in 5 minutes, add nano-TiO then
2Powder, the phthalocyanine blue pigment powder, stirred 30 minutes, at last the mixed slurry component is added ball milling 5-7h in the ball mill, until the soup compound that forms uniform good fluidity, add an amount of AMP-95 the soup compound pH value is controlled between the 7-8, make the ageing-resistant mill base of water building outer wall coating material of the present invention.
Embodiment 3
Press column weight amount % batching:
Nano-TiO
2Powder 0.5
Titanium white 50.0
Succimide 2
2-amino-2-methyl-1-propanol 2
Ethylene glycol 8
1,1,2-[4-morpholinodithio quinoline-3-ketone 0.05
Three normal-butyl phosphoesterase 30 .01
Methyl hydroxyethylcellulose 2
Deionized water 35.5
Methyl hydroxyethylcellulose is mixed until forming even viscous solution through stirring at low speed with deionized water, add succimide, 2-amino-2-methyl-1-propanol, ethylene glycol, 1,1,2-[4-morpholinodithio quinoline-3-ketone, three normal-butyl phosphoric acid ester.Stir and they were mixed in 30 minutes, add nano-TiO then
2Powder, the phthalocyanine blue pigment powder, stirred 90 minutes, at last the mixed slurry component is added ball milling 13-15h in the ball mill, until the soup compound that forms uniform good fluidity, add an amount of AMP-95 the soup compound pH value is controlled between the 9-10, make the ageing-resistant mill base of water building outer wall coating material of the present invention.
Claims (10)
1, the ageing-resistant mill base of a kind of water building outer wall coating material, it is characterized in that: in the gross weight of described mill base, it comprises:
Nanometer level titanium dioxide powder 0.5-6%
Pigment 35-50%
Dispersion agent 2.5-10%;
Wetting Agent for Printing Inks 3-8%;
Sterilant 0.05-0.3%;
Defoamer 0.01-0.5%;
Stablizer 0.1-2%;
The deionized water surplus.
2, the ageing-resistant mill base of water building outer wall coating material as claimed in claim 1 is characterized in that described pigment comprises phthalocyanine blue, Pigment Yellow 73, Pigment green, titanium white, network Huang and red lead.
3, the ageing-resistant mill base of water building outer wall coating material as claimed in claim 1 is characterized in that described dispersion agent is to comprise succimide, 2-amino-2-methyl-1-propanol, 3-methacryloxypropyl trimethoxy silane, two [tetra-sodium dialkoxy ester]-2 hydroxy propanoic acid titanium, Diisobutylene maleic acid sodium salt, two (phosphorous acid dilaurate) network four octyloxy titaniums, β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium etc. or their mixture.
4, the ageing-resistant mill base of water building outer wall coating material as claimed in claim 1 is characterized in that described wetting Agent for Printing Inks is an alcohols material.
5, the ageing-resistant mill base of water building outer wall coating material as claimed in claim 1, it is characterized in that described sterilant comprises 1,1,2-benzisothiazole-3-ketone, benzoglyoxaline Urethylane, 2,4,5,6-first chlorine m-dicyanobenzene, benzisothiazole ketone, 2-(4-thiazolyl) benzoglyoxaline or 2-n-octyl-4-isothiazoline-3-ketone.
6, the ageing-resistant mill base of water building outer wall coating material as claimed in claim 1 is characterized in that described defoamer comprises poly-three normal-butyl phosphoric acid ester, Union carbide A-162, methyl polysiloxane or dimethyl polysiloxane, propanediol polyoxypropylene Soxylat A 25-7 and polyoxyethylene nonyl phenylate.
7, the ageing-resistant mill base of water building outer wall coating material as claimed in claim 1 is characterized in that described stablizer is an ether of cellulose.
8, as the ageing-resistant mill base of each described water building outer wall coating material of claim 1-7, it is characterized in that described mill base also comprises the pH regulator agent.
9, a kind of water building outer wall coating material is with the preparation method of ageing-resistant mill base, and it comprises the steps:
Stablizer is added in the deionized water, mix and make pre-solution;
Dispersion agent, wetting Agent for Printing Inks, sterilant, defoamer are added in the pre-solution, stir and they were mixed in 5-30 minute;
Add nano-TiO
2With the phthalocyanine blue powder, stirred 20-90 minute;
Above-mentioned mixed slurry component was added grinding machine for grinding 5-15 hour, until the soup compound that forms uniform good fluidity;
Add an amount of pH regulator agent soup compound pH value is controlled between the 7-10, make the ageing-resistant mill base of water building outer wall coating material of the present invention.
10, method as claimed in claim 10 is characterized in that described pH regulator agent comprises AMP-95, sodium hydroxide, potassium hydroxide and ammoniacal liquor.
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| CNA021422648A CN1478830A (en) | 2002-08-29 | 2002-08-29 | Ageing resistant colour paste for aqueous building external wall paint and its preparation method |
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