CN1274775C - Calcium silicate hydrate nano coating and its production method - Google Patents
Calcium silicate hydrate nano coating and its production method Download PDFInfo
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Abstract
The present invention relates to calcium silicate hydrate nano paint and a production method thereof. The calcium silicate hydrate nano paint contains components of the following mass percentage content: 37.0 to 39.0% of film forming emulsion, 5.07 to 6.20% of pigment, 6.50 to 7.50% of talcum powder, 10.15 to 11.0% of calcium silicate hydrate powder, 0.38 to 0.88% of film forming additive, 0.4 to 0.9% of defoaming agent and 34.52 to 40.50% of water. The calcium silicate hydrate powder uses diatomite of low cost as a siliceous material and also uses quick lime as a calcareous material to prepare calcium silicate hydrate nano powder with low crystallinity and a large specific surface area by adopting a dynamic hydrothermal synthesis method. In the present invention, the nano calcium silicate hydrate is used as a filling material for architectural paint for obviously enhancing the adhesive force, scrubbing resistance, alkali resistance, water resistance, aging resistance and stain resistance of the paint. The cost of the present invention is only a bit higher than that of ordinary paint, and in addition, the present invention is favorable to environment protection.
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.Diatomite belongs to silicoide, have characteristics inexpensive, that be easy to get, but the present main approach that utilizes is confined to produce aspects such as building slab, because primary diatomite mineral activity is relatively poor, if directly as paint filler, not only can not improve the performance of coating, also can cause the coating property problem of unstable.
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 calcium silicate hydrate nano coating and production method thereof, solve and in coating, use diatomite, improve the technical problem of sticking power, abrasion resistance, alkali resistance, water tolerance, ageing resistance and the anti-fouling performance of building coating; And it is too high to solve the high grade paint price, problem that can not large scale application.
The technical scheme of calcium silicate hydrate nano coating 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: 37.0～39.0%;
Pigment: 5.07～6.20%;
Talcum powder: 6.50～7.50%;
Hydration calcium silicate powder: 10.15～11.0%;
Film coalescence aid: 0.38～0.88%;
Defoamer: 0.4～0.9%;
Water: 34.52～40.5%
Above-mentioned hydration calcium silicate powder is to be siliceous material with diatomite, is calcareous material with unslaked lime, and calcium silicon is 1: 1 than (mol ratio), and water-solid ratio is 5: 1,, and the dry powder that form synthetic through 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 is propylene glycol butyl ether or a 1-Methoxy-2-propyl acetate that contracts.
Above-mentioned defoamer is tributyl phosphate or silicone emulsion.
The dispersion agent that also contains 0-3% in the above-mentioned coating, dispersion agent are Sodium hexametaphosphate 99 or polyacrylic acid sodium salt.
The thickening material that also contains 0-0.8% in the above-mentioned coating, thickening material are Natvosol or organobentonite.
The softening agent that also contains 0-0.2% in the above-mentioned coating, softening agent are dibutyl phthalate or phosphoric acid ester.
The flow agent that also contains 0-0.6% in the above-mentioned coating, flow agent are colloidal silica or polyvinyl alcohol.
Also 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 calcium silicate hydrate nano coating is characterized in that step is as follows:
(1), the hydration calcium silicate powder of purchasing earlier, with diatomite is siliceous material, is calcareous material with unslaked lime, and calcium silicon ratio is 1: 1, water-solid ratio is 5: 1, keep the temperature of (100-150) ± 5 ℃ in the hydrothermal synthesis reaction still, constant temperature time is 3h-10h, and the heating-up time is 2h, temperature fall time is 4h, discharging, filtration in the temperature below 100 ℃, are dried the powder that makes to constant weight standby;
(2), batching and pre-mixing; By the various components of proportioning weighing, 1/4th and water of dispersion agent is mixed, stir, pour pigment, 1/3rd defoamer, talcum powder and hydration calcium silicate powder then successively into, reinforced while stirring, make 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 ammoniacal liquor, 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, stirs at a slow speed can stop after 6-10 minute stirring, and the coating that makes is put into containers for future use.
The present invention improves the mechanism of coating property: select for use the diatomite mineral that extensively are easy to get as raw material, adopt dynamic hydro-thermal synthesis process, make diatomite under hydrothermal condition, make SiO
2Be dissolved in the solution, rigid shell is broken, and silicon-oxy tetrahedron depolymerization, hydrolysis produce activated silica, is 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 great specific surface area of hydration calcium silicate powder can provide powder and high-polymer molecular very big contact area, after being added into coating, be easy to generate high-intensity novel substance with 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.
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) above-mentioned hydration calcium silicate powder adopts dynamic hydrothermal synthesis method, and it is the calcium silicate hydrate nano powder of main component that constant temperature can make with the hydrated calcium silicate for 120 ℃, and its particle diameter is about 50nm.This powder has very large specific surface area, and inner porous, help with coating in other component combine closely.
(b) reaction of diatomite and unslaked lime is mainly dissolving-precipitin reaction.Under scanning electron microscope and transmission electron microscope, can observe in the powder that constant temperature 4h and 7h make, residue after starting material dissolve is arranged, there are pit or pit in its surface, also deposits needle-like or fibrous hydrated product, makes its easier and adjacent substance reaction generate high-intensity novel substance.
(c) under 120 ℃ constant temperature and pressure, diatomite and unslaked lime can obtain the hydration calcium silicate powder of bigger specific surface area after dynamically hydro-thermal is synthesized 7h, and its thing phase composite is with CSH (B), C
2SH (C) is the continuous mixture of the hydrated calcium silicate of main phase; Along with the prolongation of constant temperature time, the specific surface area of powder is the trend that is growth at 4h～7h, and when the hydro-thermal generated time extended to 10h, specific surface area descended on the contrary.Constant temperature time is bigger to the influence of hydro-thermal synthetic product, and XRD and TEM test result analysis show, contain Ca (OH) in the powder that raw material makes when constant temperature 4h
2, Ca during constant temperature 7h (OH)
2Reaction finishes.During constant temperature 10h, also has a spot of SiO
2Still unreacted finishes, and illustrates to select suitable constant temperature time, can excite the activity of hydration calcium silicate powder under the situation of less energy-consumption as far as possible, and this active filler can improve the performance of coating.
(d) when hydro-thermal synthesis of nano hydration calcium silicate powder, water-solid ratio can change SiO in the liquid-phase system
2Solubleness.When water-solid ratio is high, form well-crystallized's hydrated calcium silicate easily.When water-solid ratio was low, the dissolving of siliceous raw material was slower, Ca (OH)
2Be deposited on the siliceous raw material particle surface and generate hydrated product, the bad hydrated calcium silicate gel of main formation crystallization this moment.But low excessively water-solid ratio can influence the speed of reaction.The water-solid ratio that the present invention determines is 5: 1, can produce the bad sour calcium of aquation silicon (aluminium) of the huge crystallization of a large amount of specific surface areas.From XRD and TEM test result analysis as can be known: under the experiment condition that this institute adopts, the prepared hydrated calcium silicate product great majority of constant temperature 10h are relatively poor or even material amorphous state of degree of crystallinity, therefore, help with coating in other component merge and reaction and this reason of improving of coating property just.
Beneficial effect: building coating of the present invention selects for use the diatomite cheaply of cheap and easy to get, safety non-toxic as raw material instead of part filler, has widened the range of application of diatomite in the building material field, helps environment protection.Utilize more weak steaming compacting degree (lower pressure, short constant voltage time), adopt dynamic hydrothermal synthesis method, made low-crystallinity, the great calcium silicate hydrate nano powder of specific surface area, saved energy consumption, reduced production cost.The hydrated calcium silicate that obtains after the present invention handles is the superfine powdery material of granularity about 50nm, and under the situation that adopts general filmogen, as filler, the instead of part talcum powder has lowered the coating cost with the nanometer hydration calcium silicate powder.The nanometer hydration calcium silicate powder has activity, be used for building coating, can significantly improve the various performances and the quality of coating, make building coating cheap, that performance satisfies high request, it is too high to have solved the high grade paint price, problem that can not large scale application.Other composition consistency in nanometer hydration calcium silicate powder and the coating is fine, has improved sticking power, abrasion resistance, alkali resistance, water tolerance, ageing resistance and the anti-fouling performance of this nano paint.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 also shortened the surface drying time of coating greatly, 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 7h, the effect of (be meant by diatomite and unslaked lime and do raw material in the prepared nanometer hydration calcium silicate powder of the dynamic hydro-thermal reaction 7h of autoclave back warp) 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) | 4560 |
| Alkali resistance (h) | 744 |
| Acid resistance (h) | 1560 |
| Washability (inferior) | 19300 |
| Anti-contamination (%) | 0.58 |
| Sticking power (level) | 2 |
| Freeze-thawing resistant (inferior) | 93 |
| 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-O6 emulsion paint | Auspicious continent, Chongqing emulsion paint | Three Gorges board emulsion paint | (GBT9755-2001) " synthetic resin emulsion coating " premium grads index | |
| Condition in container | No lump, evenly | Be uniform state | Evenly stir no lump | Evenly stir no lump |
| Application property | It is accessible to brush two roads | It is accessible to brush two roads | It is accessible to brush two roads | It is accessible to brush two roads |
| Appearance of film | Normally | Normally | Normally | Normally |
| Surface drying time | 1h42min | 1h46min | 1h45min | ＜2h |
| Water tolerance | 240h is no abnormal | 96h is no abnormal | The 384h deliquescing of filming | 96h |
| Alkali resistance | 120h is no abnormal | 48h is no abnormal | The 288h no change | 48h |
| Acid resistance | - | - | The 240h no change | - |
| Washability 〉= | No damaged grinning effect after 2500 times | No damaged grinning effect after 1500 times | 6000 times | ＞2000 times |
| Anti-contamination | 12％ | - | 23.9％ | ＜15％ |
| Sticking power | - | - | 3 grades | - |
| Freeze-thawing resistant | 3 circulations do not have the phenomenon of condensing of luming repeatedly | 3 circulations do not have the phenomenon of condensing of luming repeatedly | - | - |
| Temp. variation resistant | Circulate 10 times no abnormal | Circulate 10 times no abnormal | Circulate and break down for 5 times | Circulate 5 times |
| Ageing resistance | - | - | 600 hours |
(4), description of drawings
Fig. 1 is preparation technology's schema of calcium silicate hydrate nano 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 coating of the present invention:
Acrylic acid or the like filming emulsion: any number between 37.0～39.0%;
Pigment: any number between 5.07～6.20%;
Talcum powder: any number between 6.50～7.50%;
Hydration calcium silicate powder: any number between 10.15～11.0%;
Film coalescence aid: any number between 0.38～0.88%;
Defoamer: any number between 0.4～0.9%;
Water: any number between 34.52～40.5%.
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.
Except that said components, also can contain the dispersion agent of 0-3% in the coating, dispersion agent can be selected Sodium hexametaphosphate 99 or polyacrylic acid sodium salt.
Also can contain the thickening material of 0-0.8% in the above-mentioned coating, thickening material can be selected Natvosol or organobentonite.
The softening agent that also can contain 0-0.2% in the above-mentioned coating, optional dibutyl phthalate of softening agent or phosphoric acid ester.
Also can contain the flow agent of 0-0.6% in the above-mentioned coating, flow agent can be selected 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 can be selected ammoniacal liquor or sodium bicarbonate aqueous solution.
Above-mentioned hydration calcium silicate powder is to be siliceous material with diatomite, 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.
Obviously, above-mentioned pigment can be selected arbitrarily as required.
Other embodiment:
| Raw material (%) | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The vinylformic acid filming emulsion | 37.57 | 37.00 | 39.00 | 37.00 |
| The Z129 ferric oxide red colorant | 5.57 | 5.50 | 6.20 | 5.07 |
| 800 order talcum powder | 6.96 | 6.80 | 6.50 | 7.50 |
| Hydration calcium silicate powder | 10.65 | 10.50 | 11.00 | 10.15 |
| The CA-03 film coalescence aid | 0.38 | 0.38 | 0.88 | 0.58 |
| The SP-03 silicon oil foam killer | 0.44 | 0.43 | 0.90 | 0.40 |
| The Sodium hexametaphosphate 99 dispersion agent | 2.23 | 2.18 | 0.00 | 3.00 |
| The Natvosol thickening material | 0.69 | 0.67 | 0.00 | 0.80 |
| The dibutyl phthalate softening agent | 0.14 | 0.15 | 0.00 | 0.20 |
| The colloidal silica flow agent | 0.44 | 0.44 | 0.00 | 0.60 |
| The agent of ammoniacal liquor pH regulator | 0.14 | 0.15 | 0.00 | 0.20 |
| Water | 34.79 | 35.8 | 35.52 | 34.5 |
The production method of calcium silicate hydrate nano coating of the present invention has five steps:
(1), earlier prepare the nanometer hydration calcium silicate powder, the proportioning example is as follows:
Calcareous material is selected fine grinding quicklime: the free GaO content of lime is 85.1%, and grinding 90min, lime consumption are 4.85kg.
Siliceous material is that Miyi County, Sichuan produces diatomite, grinding 120min, and specific surface area is 3000cm
2/ g, diatomaceous SiO
2Content 68.6%, diatomaceous consumption are 3.65kg.
The consumption of water is 42.5kg, and the starting material total mass is 8.5kg, and calcium silicon is than CaO: SiO
2=1: 1 (mol ratio) water-solid ratio is 5: 1.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 the hydrothermal synthesis reaction still, the heating-up time is 2h, and constant temperature time is 3h-10h, temperature fall time is 4h, after filtration, in the temperature below 100 ℃, dry the nanometer hydration calcium silicate powder that makes to constant weight 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 and disperse---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 simultaneously regulates the pH value to the emulsion that weighs up to 6-8 with ammoniacal liquor, 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 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 building coating of good application property.
Claims (10)
1, a kind of calcium silicate hydrate nano coating is characterized in that containing in this coating the following component of calculating content by mass percentage:
Acrylic acid or the like filming emulsion: 37.0～39.0%;
Pigment: 5.07～6.20%;
Talcum powder: 6.50～7.50%;
Nanometer hydration calcium silicate powder: 10.15～11.00%;
Film coalescence aid: 0.38～0.88%;
Defoamer: 0.4～0.9%;
Water: 34.52～40.50%
Above-mentioned nanometer hydration calcium silicate powder is to be siliceous material with diatomite, is calcareous material with unslaked lime, and calcium silicon ratio is 1: 1 mol ratio, and water-solid ratio is 5: 1,, and the dry powder that form synthetic through hydro-thermal.
2, calcium silicate hydrate nano coating 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, calcium silicate hydrate nano coating 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, calcium silicate hydrate nano coating according to claim 1 is characterized in that: described defoamer is tributyl phosphate or silicone emulsion.
5, calcium silicate hydrate nano coating 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, calcium silicate hydrate nano coating 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, calcium silicate hydrate nano coating 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, calcium silicate hydrate nano coating 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, calcium silicate hydrate nano coating 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 the described calcium silicate hydrate nano coating of claim 5 is characterized in that step is as follows:
(1), prepares the nanometer hydration calcium silicate powder earlier, with diatomite is siliceous material, is calcareous material with unslaked lime, and calcium silicon ratio is 1: 1 mol ratio, water-solid ratio is 5: 1, keep the temperature of (100-150) ± 5 ℃ in the hydrothermal synthesis reaction still, constant temperature time is 3h-10h, and the heating-up time is 2h, temperature fall time is 4h, discharging, filtration in the temperature below 100 ℃, are dried the powder that makes to constant weight standby;
(2), batching and pre-mixing; By the various components of proportioning weighing, 1/4th and water of dispersion agent is mixed, stir, pour pigment, 1/3rd defoamer, talcum powder and nanometer hydration calcium silicate powder then successively into, reinforced while stirring, make 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 ammoniacal liquor, 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, stirs at a slow speed can stop after 6-10 minute stirring, and the coating that makes is put into containers for future use.
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| CN101948649B (en) * | 2010-09-17 | 2012-08-22 | 中国十七冶集团有限公司 | Calcium silicate nanowire composite thermal-insulation 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 |
| CN106009867A (en) * | 2016-07-04 | 2016-10-12 | 中国科学院上海硅酸盐研究所 | Calcium silicate ultrathin nano-sheet composite flame-retardant sound-proof damping coating |
| CN107162010B (en) * | 2017-05-25 | 2019-09-20 | 内蒙古仁创沙漠资源利用研究院有限公司 | The hydrated calcium silicate for synthesizing the method for hydrated calcium silicate and being synthesized by this method |
| CN107365547B (en) * | 2017-08-17 | 2021-05-07 | 珠海市盛西源机电设备有限公司 | Bright water-based epoxy floor paint and preparation method thereof |
| CN108976929A (en) * | 2018-08-28 | 2018-12-11 | 巢湖市兰天大诚门窗幕墙有限公司 | The thermal insulation coatings of composite energy-saving door and window |
| CN110343433A (en) * | 2019-07-15 | 2019-10-18 | 重庆大学 | A kind of nanometer of hydrated calcium silicate insulating moulding coating and preparation method thereof |
| CN111704817B (en) * | 2020-07-31 | 2022-03-25 | 荆州斯米克新材料有限公司 | Water-resistant breathable water-based inorganic coating 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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