CN1651529A - Nano-external wall paint and its production method - Google Patents
Nano-external wall paint and its production method Download PDFInfo
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- CN1651529A CN1651529A CN 200510008925 CN200510008925A CN1651529A CN 1651529 A CN1651529 A CN 1651529A CN 200510008925 CN200510008925 CN 200510008925 CN 200510008925 A CN200510008925 A CN 200510008925A CN 1651529 A CN1651529 A CN 1651529A
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Abstract
A nano-paint for external wall is proportionally prepared from filming acrylic acid emulsion, pigment, talk powder, filming aid, defoaming agent, water and the hydrated calcium silicate powder which is prepared from flyash and calcium lime by dynamic hydrothermal synthesis method.
Description
(1), technical field
The present invention relates to a kind of building coating and production method thereof.
(2), background technology
Existing building coating generally contains filming emulsion (base-material), pigment, filler, film coalescence aid, defoamer and water etc., and wherein filler mostly is inert substances such as talcum powder.Fillers such as existing talcum powder mainly play the covering effect, and the performance of coating depends primarily on the performance of base-material.The domestic and international at present research to high-performance coating mainly concentrates on to adopt to have on the base-material of premium properties, but the price of Chang Yinqi costliness can not be produced and use it in large quantities.Because the limitation of existing base-material, performances such as existing building ADHESION OF PAINTS power, abrasion resistance, alkali resistance, water tolerance, ageing resistance and stain resistance are also unsatisfactory, await further to improve.On the other hand, flyash is the solid industrial residue, have the advantages that extensively be easy to get, but the main approach that utilizes of flyash is confined to produce aspects such as cement, building block, aerating fly ash hollow brick at present, lower for utilization ratios such as the low activity ash of inferior quality, wet ash discharges, these undressed flyash are because activity is relatively poor, if directly as paint filler, not only can not improve the performance of coating, also can cause the coating property instability.
At present in the industrial production of silicate building material, the emphasis that people pay close attention to is to steam to press under higher pressure to generate the higher hydrated calcium silicate of crystallization degree, as products such as Tobemolai stone, mirabilitum crystallina pomegranate stone, afwillites, think that its mechanical property is better, and at lower pressure, the short very low hydrated product of constant voltage time hydro-thermal synthetic crystallization degree, as C-S-H gel, CSH (B) etc., do not earn widespread respect and use.
(3), summary of the invention
The purpose of this invention is to provide a kind of nano-external wall paint and production method thereof, solve the technical problem of powder application coal ash, the sticking power that improves building coating, abrasion resistance, alkali resistance, water tolerance, ageing resistance and anti-fouling performance in coating; And it is too high to solve the high grade paint price, problem that can not large scale application.
The technical scheme of nano-external wall paint of the present invention: it is characterized in that containing in this coating the following component of calculating content by mass percentage:
Acrylic acid or the like filming emulsion: 32.0～34.5%;
Pigment: 4.39～5.50%;
Talcum powder: 5.6～6.8%;
Hydration calcium silicate powder: 8.85～10.25%;
Film coalescence aid: 0.25～0.75%;
Defoamer: 0.3～0.9%;
Water: 41.3～48.6%
Above-mentioned hydration calcium silicate powder is to be siliceous material with flyash, is calcareous material with unslaked lime, and calcium silicon is than CaO: SiO
2Be 1: 1, water-solid ratio is 5: 1,, and the dry powder that form synthetic through dynamic hydro-thermal.
Aforesaid propylene acids filming emulsion is pure acrylic acid emulsion, styrene-propene yogurt liquid or organosilicon-ACRYLIC EMULSION.
Above-mentioned film coalescence aid be the propylene glycol butyl ether or-1-Methoxy-2-propyl acetate contracts.
Above-mentioned defoamer is tributyl phosphate or silicone emulsion.
The dispersion agent that also can contain 0-3% in the above-mentioned coating, dispersion agent are Sodium hexametaphosphate 99 or polyacrylic acid sodium salt.
The thickening material that also can contain 0-0.8% in the above-mentioned coating, thickening material are Natvosol or organobentonite.
The softening agent that also can contain 0-0.2% in the above-mentioned coating, softening agent are dibutyl phthalate or phosphoric acid ester.
The flow agent that also can contain 0-0.6% in the above-mentioned coating, flow agent are colloidal silica or polyvinyl alcohol.
Also can contain the pH regulator agent of 0-0.2% in the above-mentioned coating, the pH regulator agent is ammoniacal liquor or sodium bicarbonate aqueous solution.
The production method of this nano-external wall paint is characterized in that production stage is as follows:
(1), prepares hydration calcium silicate powder earlier, with flyash is siliceous material, with unslaked lime is calcareous material, calcium silicon ratio is 1: 1, water-solid ratio is 5: 1, keep the temperature of (100-150) ± 5 ℃ in reactor, through intensification 2h, constant temperature 3h-10h, cooling, discharging, filtration, drying, dynamically the synthetic hydration calcium silicate powder of hydro-thermal is standby;
(2), batching and pre-mixing; By the various components of proportioning weighing, 1/4th and the water mixing with dispersion agent stirs, and pours pigment, 1/3rd defoamer, talcum powder and the hydration calcium silicate powder for preparing then successively into, and is reinforced while stirring, makes mill base;
(3), grind dispersion; The mill base that has made is sent into sand mill, carry out again grinding, stirring, measure fineness with Hegman grind gage and stop to grind to 25-30 μ m;
(4), simultaneously, the acrylic acid or the like filming emulsion that weighs up is regulated the pH value to 6-8 with the pH regulator agent, add film coalescence aid while stirring at the sand mill dispersive;
(5), be in harmonious proportion; After mill base is scattered, stir at a slow speed, add the emulsion for preparing in above-mentioned (4) while stirring with stirrer; Add various auxiliary agents simultaneously, the defoamer remaining 2/3rds adds wherein, can stop to stir after stirring 6-10min at a slow speed, and the coating that makes is put into containers for future use.
Through experimental results show that with modern test method such as X diffraction analysis instrument XRD, nitrogen adsorption method BET, scanning electron microscope sem, transmission electron microscope TEM:
(a), by hydro-thermal synthesis process, under 120 ℃ constant temperature and pressure, steam and press 7h can obtain hydration calcium silicate powder than bigger serface, by the transmissioning electric mirror test analysis, the powder crystal granularity is minimum, can reach nano level; The TEM image shows that powder is the granuloplastic loose aggregates about 50nm, has estimated the grain fineness number size by the Scherrer formula, and granularity is between 40～60nm.
(b), by XRD analysis, under the steaming compacting degree of 7h, its composition is with CSH (B), C
2SH (C) is the continuous mixed phase of the hydrated calcium silicate of primary product, and the product of 4h is C
2SH (A), C
3AH
6, the product of 10h is C
2SH (C), holder shellfish mullite.
(c), along with constant temperature steams the prolongation of pressure time, the specific surface area of powder is the trend that is growth at 4h～7h, and when constant voltage time is increased to 10h, specific surface area descends on the contrary: this is because the long-pending difference of the ratio table of the type of the hydrated calcium silicate that generates; Pore volume is along with the prolongation of constant voltage time is to be to increase earlier the trend that afterwards reduces.
The present invention improves the mechanism of coating property: select for use the solid industrial residue flyash that extensively is easy to get as raw material, adopt dynamic hydro-thermal synthesis process, make flyash under hydrothermal condition, rigid shell is broken, SiO
2Be dissolved in the solution, silicon-oxy tetrahedron depolymerization, hydrolysis produce activated silica,, be easier to and alkaloids water generation reaction Calucium Silicate powder (C-S-H) such as unslaked lime.Through intensification, constant temperature, cooling, discharging, filtration, drying, make the nanometer hydration calcium silicate powder of ultra-fine, porous, bigger serface.With acrylic acid or the like filming emulsion, pigment, talcum powder, film coalescence aid, defoamer and water appropriate combination after, the specific surface area that hydration calcium silicate powder is bigger can provide powder and high-polymer molecular very big contact area, after being added into coating, be easy to and adjacent substance reaction, help with coating in other component combine closely, can prepare the exterior coating of excellent property.If select suitable constant temperature time, can under the situation of less energy-consumption as far as possible, excite the activity of hydration calcium silicate powder, and this active filler can improve the performance of coating.
Beneficial effect: part filler of the present invention adopts the solid slag of safety non-toxic, has widened the range of application of flyash in the building material field, and has helped protecting environment.More weak and the rational steaming compacting degree (lower pressure, short constant voltage time) of utilization of the present invention has reduced energy consumption, has reduced production cost.The present invention with the nanometer hydration calcium silicate powder as filler, the instead of part talcum powder, greatly reduce the cost of coating, make the filler of coating also have activity, significantly improve ADHESION OF PAINTS power, abrasion resistance, alkali resistance, water tolerance, ageing resistance and anti-fouling performance, under the situation that adopts general filmogen, can improve the quality of coating greatly, make exterior coating cheap, that performance satisfies high request.The nanometer hydration calcium silicate powder has the bad gelatinous material of mass crystallization, fine with other composition consistency in the coating, surface drying time, sticking power, abrasion resistance, alkali resistance, water tolerance, ageing resistance and the anti-fouling performance of this nano-external wall paint all are largely increased.Especially the washability number of times reaches more than 10000 times; Artificial ageing resistance be do not have in 800 hours bubble, peel off, crackle, no efflorescence, variable color; Anti-pollution index＜1%, these performances have all surpassed the national premium grads index of current specifications defined.In addition the present invention has also shortened the surface drying time of coating greatly, and execution of coating efficient is improved greatly.
The test result that coating property of the present invention improves:
Wherein with the nanometer hydration calcium silicate powder of 10h, the effect of (be meant by flyash and unslaked lime and do raw material in the prepared nanometer hydration calcium silicate powder of the dynamic hydro-thermal reaction constant temperature of autoclave back warp 10h) made coating is best, and its The performance test results is as follows:
| The performance title | Test result |
| Condition in container | Stir the no lump in back, be even attitude |
| Application property | It is accessible to brush two roads |
| Appearance of film | Normally |
| Surface drying time | 15±3min |
| Water tolerance (h) | 2040 |
| Alkali resistance (h) | 696 |
| Acid resistance (h) | 624 |
| Washability (inferior) | 12200 |
| Anti-contamination (%) | 0.46 |
| Sticking power (level) | 2 |
| Freeze-thawing resistant (inferior) | 110 |
| Artificial ageing resistance | Do not have in 800 hours bubble, peel off, 0 grade in crackle; No efflorescence, variable color |
The The performance test results such as the following table of other contrast coating:
| The H-06 emulsion paint does not have lump, evenly brush the accessible normal 1h42min 240h in two roads do not have do not have damaged grinning effect 12% after unusual 120h does not have unusually-2500 time-repeatedly 3 circulations do not have caking condense the phenomenon circulation do not have for 10 times unusual- | Auspicious continent, Chongqing emulsion paint be the accessible normal 1h46min 96h in uniform state brushing two roads do not have do not have damaged grinning effect after unusual 48h does not have unusually-1500 time--3 circulations do not have the caking phenomenon circulation of condensing does not repeatedly have for 10 times unusual | Three Gorges board emulsion paint uniform stirring do not have the accessible normal 1h45min 384h in lump brushing two roads film 23.9% 3 grades-circulation of the unchanged 240h of deliquescing 288h unchanged 6000 times break down for 5 times- | (GB/T9755-2001) " exterior wall coating material of synthetic resin emulsion " high-class product index uniform stirring do not have lump brushing two roads accessible normal＜2h 96h 48h-＞2000＜15%--circulation 5 times 600 hours | |
| Condition in container | ||||
| Application property | ||||
| Appearance of film | ||||
| Surface drying time | ||||
| Water tolerance | ||||
| Alkali resistance | ||||
| Acid resistance | ||||
| Washability 〉= | ||||
| Anti-contamination | ||||
| Sticking power | ||||
| Freeze-thawing resistant | ||||
| Temp. variation resistant | ||||
| Ageing resistance |
(4), description of drawings
Fig. 1 is preparation technology's schema of calcium silicate hydrate nano exterior coating of the present invention;
Fig. 2 is the technological process of production figure of hydration calcium silicate powder.
(5), embodiment
Embodiment one: contain the following component of calculating content by mass percentage in the calcium silicate hydrate nano exterior coating of the present invention:
Pure acrylic acid emulsion: any number between 32.0～34.5%;
Pigment: any number between 4.39～5.50%;
Talcum powder: any number between 5.6～6.8%;
Hydration calcium silicate powder: any number between 8.85～10.25%;
Film coalescence aid: any number between 0.25～0.75%;
Defoamer: any number between 0.3～0.9%;
Water: any number between 41.3～48.6%.
Aforesaid propylene acids filming emulsion can be pure acrylic acid emulsion, styrene-propene yogurt liquid or organosilicon-ACRYLIC EMULSION.This proportioning adopts the pure acrylic acid emulsion, for example: XG-2002 building emulsion tackiness agent.
Above-mentioned film coalescence aid can be the propylene glycol butyl ether or-1-Methoxy-2-propyl acetate contracts.This proportioning adopts the propylene glycol butyl ether.
Above-mentioned defoamer can be tributyl phosphate or silicone emulsion.This proportioning adopts silicone emulsion.
The dispersion agent that also can contain 0-3% in the above-mentioned coating.As Sodium hexametaphosphate 99 or polyacrylic acid sodium salt.This proportioning adopts Sodium hexametaphosphate 99.
Also contain the thickening material that 0-0.8% can be arranged in the above-mentioned coating.As Natvosol or organobentonite.This proportioning adopts Natvosol.
The softening agent that also can contain 0-0.2% in the above-mentioned coating.As dibutyl phthalate or phosphoric acid ester, this proportioning adopts dibutyl phthalate.
The flow agent that also can contain 0-0.6% in the above-mentioned coating.As colloidal silica or polyvinyl alcohol.This proportioning adopts colloidal silica.
Also can contain the pH regulator agent of 0-0.2% in the above-mentioned coating.As ammoniacal liquor or sodium bicarbonate aqueous solution.This proportioning adopts ammoniacal liquor.
Obviously, above-mentioned pigment can be selected random color as required.
Above-mentioned hydration calcium silicate powder is to be siliceous material with flyash, is calcareous material with unslaked lime, and calcium silicon is 1: 1 than (mol ratio), and water-solid ratio is 5: 1, synthetic through hydro-thermal in reactor, and the dry powder that forms.
Other embodiment:
| Raw material (%) | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| The vinylformic acid filming emulsion | ????32.98 | ????33.45 | ?32.5 | ??32.0 | ?34.5 |
| The Z129 ferric oxide red colorant | ????4.89 | ????4.95 | ?4.81 | ??4.39 | ?5.50 |
| 800 order talcum powder | ????6.11 | ????6.19 | ?6.01 | ??6.80 | ?5.60 |
| Hydration calcium silicate powder | ????9.35 | ????9.50 | ?9.23 | ??10.25 | ?8.85 |
| The CA-03 film coalescence aid | ????0.33 | ????0.33 | ?0.33 | ??0.75 | ?0.25 |
| The SP-03 silicon oil foam killer | ????0.39 | ????0.40 | ?0.39 | ??0.30 | ?0.90 |
| The Sodium hexametaphosphate 99 dispersion agent | ????1.95 | ????1.97 | ?1.92 | ??3.00 | ?0.00 |
| The Natvosol thickening material | ????0.61 | ????0.60 | ?0.59 | ??0.00 | ?0.80 |
| The dibutyl phthalate softening agent | ????0.12 | ????0.13 | ?0.13 | ??0.20 | ?0.00 |
| The colloidal silica flow agent | ????0.39 | ????0.40 | ?0.39 | ??0.60 | ?0.00 |
| The agent of ammoniacal liquor pH regulator | ????0.12 | ????0.13 | ?0.13 | ??0.00 | ?0.20 |
| Water | ????42.76 | ????41.95 | ?43.57 | ??41.71 | ?43.40 |
The production method of calcium silicate hydrate nano exterior coating of the present invention:
(1), earlier prepare hydration calcium silicate powder, the proportioning example is as follows:
Doing row II level flyash with Chongqing Power Plant is siliceous material, the SiO of flyash
2Content 42.4%, the consumption 5.8kg of flyash.
With the unslaked lime that originates in Nikkei mountain, Chongqing is calcareous material, and the free GaO content of lime is 85.1%, lime consumption 2.7kg.
The consumption of water is 42.5kg, and the starting material total mass is 8.5kg, and calcium silicon is than GaO: SiO
2(mol ratio) is 1: 1, and water-solid ratio is 5: 1, and said ratio can be adjusted according to selecting raw-material difference for use, and this adjustment technology belongs to those skilled in the art's known technology.
Said components keeps the temperature of (100-150) ± 5 ℃ in reactor, through intensification 2h, constant temperature 3h-10h, cooling 4h, discharging, filtration, and dry to constant weight in the temperature below 100 ℃, and dynamically the synthetic hydration calcium silicate powder of hydro-thermal is standby.
(2) batching and pre-mixing---according to proportioning, be placed on each component that weighs up in the container stand-by.1/4th and a certain amount of water with dispersion agent mixes earlier, under homogenizer, stir, pour pigment, about 1/3rd defoamer, 1/2nd dispersion agent, talcum powder and dynamic hydro-thermal synthetic hydration calcium silicate powder then successively into, reinforced while stirring, make pigment evenly become mill base with fillers dispersed.
(3) grind dispersion---will send into sand mill at the mill base of stir about 20min under the homogenizer, carry out grinding again, and behind the stirring 15min, measure fineness with Hegman grind gage and can stop to grind to 25-30 μ m.
(4) the sand mill dispersive is regulated the pH value to the acrylic acid or the like filming emulsion that weighs up to 6-8 with ammoniacal liquor simultaneously, adds film coalescence aid and softening agent while stirring.
(5) be in harmonious proportion---after mill base is scattered, put into container, stir at a slow speed, add the above-mentioned emulsion for preparing while stirring with stirrer.Add various auxiliary agents simultaneously, defoamer remaining 2/3rds and 1/4th dispersion agent add wherein, stirring (rotating speed of stirrer is 120-400r/min) at a slow speed can stop after 6-10 minute stirring, the coating that makes is packed in the container, obtain having the exterior coating of good application property.
Claims (10)
1, a kind of nano-external wall paint is characterized in that containing in this coating the following component of calculating content by mass percentage:
Acrylic acid or the like filming emulsion: 32.0～34.5%;
Pigment: 4.39～5.50%;
Talcum powder: 5.6～6.8%;
Hydration calcium silicate powder: 8.85～10.25%;
Film coalescence aid: 0.25～0.75%;
Defoamer: 0.3～0.9%;
Water: 41.3～48.6%;
Above-mentioned hydration calcium silicate powder is to be siliceous material with flyash, is calcareous material with unslaked lime, and calcium silicon ratio is 1: 1, and water-solid ratio is 5: 1,, and the dry powder that form synthetic through dynamic hydro-thermal.
2, nano-external wall paint according to claim 1 is characterized in that: described acrylic acid or the like filming emulsion is pure acrylic acid emulsion, styrene-propene yogurt liquid or organosilicon-ACRYLIC EMULSION.
3, nano-external wall paint according to claim 1 is characterized in that: described film coalescence aid is propylene glycol butyl ether or a 1-Methoxy-2-propyl acetate that contracts.
4, nano-external wall paint according to claim 1 is characterized in that: described defoamer is tributyl phosphate or silicone emulsion.
5, nano-external wall paint according to claim 1 is characterized in that: also contain the dispersion agent of 0-3% in the described coating, dispersion agent is Sodium hexametaphosphate 99 or polyacrylic acid sodium salt.
6, nano-external wall paint according to claim 1 is characterized in that: also contain the thickening material of 0-0.8% in the described coating, thickening material is Natvosol or organobentonite.
7, nano-external wall paint according to claim 1 is characterized in that: also contain the softening agent of 0-0.2% in the described coating, softening agent is dibutyl phthalate or phosphoric acid ester.
8, nano-external wall paint according to claim 1 is characterized in that: also contain the flow agent of 0-0.6% in the described coating, flow agent is colloidal silica or polyvinyl alcohol.
9, nano-external wall paint according to claim 1 is characterized in that: also contain the pH regulator agent of 0-0.2% in the described coating, the pH regulator agent is ammoniacal liquor or sodium bicarbonate aqueous solution.
10, a kind of production method according to each described nano-external wall paint of claim 1 to 9 is characterized in that production stage is as follows:
(1), prepares hydration calcium silicate powder earlier, with flyash is siliceous material, with unslaked lime is calcareous material, calcium silicon ratio is 1: 1, water-solid ratio is 5: 1, keep the temperature of (100-150) ± 5 ℃ in reactor, through intensification 2h, constant temperature 3h-10h, cooling, discharging, filtration, drying, dynamically the synthetic hydration calcium silicate powder of hydro-thermal is standby;
(2), batching and pre-mixing; By the various components of proportioning weighing, 1/4th and the water mixing with dispersion agent stirs, and pours pigment, 1/3rd defoamer, talcum powder and the hydration calcium silicate powder for preparing then successively into, and is reinforced while stirring, makes mill base;
(3), grind dispersion; The mill base that has made is sent into sand mill, carry out again grinding, stirring, measure fineness with Hegman grind gage and stop to grind to 25-30 μ m;
(4), simultaneously, the acrylic acid or the like filming emulsion that weighs up is regulated the pH value to 6-8 with the pH regulator agent, add film coalescence aid while stirring at the sand mill dispersive;
(5), be in harmonious proportion; After mill base is scattered, stir at a slow speed, add the emulsion for preparing in above-mentioned (4) while stirring with stirrer; Add various auxiliary agents simultaneously, the defoamer remaining 2/3rds adds wherein, can stop to stir after stirring 6-10min at a slow speed, and the coating that makes is put into containers for future use.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510008925 CN1281694C (en) | 2005-02-25 | 2005-02-25 | Nano-external wall paint and its production method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510008925 CN1281694C (en) | 2005-02-25 | 2005-02-25 | Nano-external wall paint and its production method |
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| CN1651529A true CN1651529A (en) | 2005-08-10 |
| CN1281694C CN1281694C (en) | 2006-10-25 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531470A (en) * | 2010-12-26 | 2012-07-04 | 新疆生产建设兵团建筑工程科学技术研究院有限责任公司 | Waterproof building paint |
| CN103496932A (en) * | 2013-09-25 | 2014-01-08 | 广西科技大学 | Inorganic special historic building wall coating adopting flyash and preparation method thereof |
| CN104109409A (en) * | 2014-07-01 | 2014-10-22 | 芜湖县双宝建材有限公司 | Waterproof acrylate exterior wall coating |
| CN104312241A (en) * | 2014-11-11 | 2015-01-28 | 合肥不老传奇保健科技有限公司 | Sterilizing, anti-algae and anti-aging water-based exterior wall coating and preparation method thereof |
| CN104446303A (en) * | 2014-11-11 | 2015-03-25 | 合肥不老传奇保健科技有限公司 | Anti-crack texture exterior wall coating with modified round grain mortar and preparation method of anti-crack texture exterior wall coating |
| CN104592823A (en) * | 2015-02-03 | 2015-05-06 | 安徽工业大学 | Bismuth nickelate nano-wire multifunctional paint |
| CN106833157A (en) * | 2017-03-04 | 2017-06-13 | 杭州蓝田涂料有限公司 | A kind of granite shell piece water paint and preparation method thereof |
| CN107400420A (en) * | 2016-05-20 | 2017-11-28 | 立邦涂料（中国）有限公司 | A kind of superpower osmosis type metope strengthening agent and its application |
| CN113845806A (en) * | 2021-10-25 | 2021-12-28 | 富思特新材料科技发展股份有限公司 | Building coating with high rain mark resistance and preparation method thereof |
| CN114479585A (en) * | 2020-10-26 | 2022-05-13 | 立邦涂料（中国）有限公司 | Rain mark resistant high-color-retention high-polymer exterior wall coating and preparation method thereof |
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2005
- 2005-02-25 CN CN 200510008925 patent/CN1281694C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531470A (en) * | 2010-12-26 | 2012-07-04 | 新疆生产建设兵团建筑工程科学技术研究院有限责任公司 | Waterproof building paint |
| CN103496932B (en) * | 2013-09-25 | 2015-06-17 | 广西科技大学 | Inorganic special historic building wall coating adopting flyash and preparation method thereof |
| CN103496932A (en) * | 2013-09-25 | 2014-01-08 | 广西科技大学 | Inorganic special historic building wall coating adopting flyash and preparation method thereof |
| CN104109409A (en) * | 2014-07-01 | 2014-10-22 | 芜湖县双宝建材有限公司 | Waterproof acrylate exterior wall coating |
| CN104109409B (en) * | 2014-07-01 | 2016-07-13 | 芜湖县双宝建材有限公司 | A kind of water-proof acrylic acid ester exterior coating |
| CN104312241A (en) * | 2014-11-11 | 2015-01-28 | 合肥不老传奇保健科技有限公司 | Sterilizing, anti-algae and anti-aging water-based exterior wall coating and preparation method thereof |
| CN104446303A (en) * | 2014-11-11 | 2015-03-25 | 合肥不老传奇保健科技有限公司 | Anti-crack texture exterior wall coating with modified round grain mortar and preparation method of anti-crack texture exterior wall coating |
| CN104592823A (en) * | 2015-02-03 | 2015-05-06 | 安徽工业大学 | Bismuth nickelate nano-wire multifunctional paint |
| CN107400420A (en) * | 2016-05-20 | 2017-11-28 | 立邦涂料（中国）有限公司 | A kind of superpower osmosis type metope strengthening agent and its application |
| CN106833157A (en) * | 2017-03-04 | 2017-06-13 | 杭州蓝田涂料有限公司 | A kind of granite shell piece water paint and preparation method thereof |
| CN114479585A (en) * | 2020-10-26 | 2022-05-13 | 立邦涂料（中国）有限公司 | Rain mark resistant high-color-retention high-polymer exterior wall coating and preparation method thereof |
| CN114479585B (en) * | 2020-10-26 | 2023-02-10 | 立邦涂料（中国）有限公司 | Rain mark resistant high-color-retention high-polymer exterior wall coating and preparation method thereof |
| CN113845806A (en) * | 2021-10-25 | 2021-12-28 | 富思特新材料科技发展股份有限公司 | Building coating with high rain mark resistance and preparation method thereof |
| CN113845806B (en) * | 2021-10-25 | 2022-09-02 | 富思特新材料科技发展股份有限公司 | Building coating with high rain mark resistance and preparation method thereof |
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