CN115772349B - Water-based acrylic coating and preparation method and application thereof - Google Patents
Water-based acrylic coating and preparation method and application thereof Download PDFInfo
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- CN115772349B CN115772349B CN202211418278.1A CN202211418278A CN115772349B CN 115772349 B CN115772349 B CN 115772349B CN 202211418278 A CN202211418278 A CN 202211418278A CN 115772349 B CN115772349 B CN 115772349B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 89
- 239000003973 paint Substances 0.000 claims abstract description 37
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 32
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000002562 thickening agent Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 6
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000080 wetting agent Substances 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000010276 construction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- -1 polyoxyethylene-oxypropylene-oxyethylene Polymers 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 239000003899 bactericide agent Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000007797 corrosion Effects 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000006076 specific stabilizer Substances 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 3
- 239000013530 defoamer Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229920002023 Pluronic® F 87 Polymers 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention provides a water-based acrylic acid coating, a preparation method and application thereof. The water-based acrylic paint comprises the following components in parts by weight: 30-55 parts of water-based acrylic resin, 8-20 parts of filler, 1-4 parts of compound stabilizer, 0.5-1.5 parts of dispersing agent, 0.1-0.5 part of wetting agent, 0.1-0.5 part of defoamer, 1-4 parts of film forming auxiliary agent, 0.1-1 part of thickener, 0-12 parts of other additives and the balance of water; wherein the filler is hydrophobic flaky filler, needle-shaped filler and intangible filler; the compound stabilizer consists of an amphiphilic block copolymer and a siloxane oligomer containing epoxy groups. According to the invention, the hydrophobic flaky filler, the needle-shaped filler and the amorphous filler are added for filling, so that a compatible layered water-blocking wall is formed, and meanwhile, the compatibility of the filler and the acrylic matrix is improved by matching with a specific stabilizer, so that the early water resistance of the water-based acrylic coating is improved together.
Description
Technical Field
The invention relates to the technical field of water-based anti-corrosion paint, in particular to a water-based acrylic paint, a preparation method and application thereof.
Background
The water-based acrylic acid paint has the characteristics of simple construction, quick drying, high cost performance and the like, and has wide application in the industrial field, such as containers, steel structures and automobile parts. Under the condition of sufficient drying, the water-based acrylic coating has good water resistance and can meet the test requirement. However, in an actual construction environment, particularly in the south, the air humidity is high in the plum rain season, and therefore, early water resistance, that is, water resistance in the case of insufficient drying is also an important factor affecting its wide use. The water-based acrylic coating belongs to a single-component coating, and a paint film has no crosslinking reaction and is slower to dry in a high-humidity environment, so that the early water resistance of the water-based acrylic coating is insufficient. Most of the workpieces are placed in the open air after construction, and if continuous rainy days are met, the water-based acrylic paint is easy to foam and fall off under the condition of insufficient drying, so that performance defects are caused. For example, container lines are all continuous, with boxes from the top-coat drying house exit to the yard for about 2-3 hours, and if continuous rain is encountered, blisters tend to form in the high film thickness sections. For steel structures, similar scenes are common, the workpiece cannot move, and the workpiece is always rained after construction is finished for 2-3 hours.
The early water resistance of the aqueous acrylic paint is an important index for evaluating the construction performance of the aqueous acrylic paint and is also an important factor for limiting the construction of the aqueous acrylic paint. Therefore, the improvement of the early water resistance of the water-based acrylic paint is of great importance. At present, an acrylic matrix is modified or a hydrophobic filler is introduced to construct a hydrophobic barrier, so that the early water resistance of the paint is ensured, such as a Chinese patent CN 111849289A-water-based anti-corrosion paint, and a preparation method and application thereof. Modification of the acrylic acid group, however, increases production costs, and early water resistance has yet to be further improved.
Therefore, there is a need to provide an aqueous acrylic coating which is simple to prepare and has excellent early water resistance.
Disclosure of Invention
The invention aims to overcome the defects of poor early water resistance and high production cost of the existing water-based acrylic coating and provide the water-based acrylic coating which is simple to prepare and excellent in early water resistance. According to the invention, the hydrophobic flaky filler, the needle-shaped filler and the amorphous filler are added for filling, and meanwhile, the compatibility of the filler and the acrylic matrix is improved by matching with a specific stabilizer, so that the early water resistance of the water-based acrylic coating is improved together.
Another object of the present invention is to provide a method for producing the aqueous acrylic paint.
It is another object of the present invention to provide the use of the aqueous acrylic paint in the construction or anti-corrosive field.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the water-based acrylic paint comprises the following components in parts by weight, based on 100 parts by weight:
wherein the filler is hydrophobic flaky filler, needle-shaped filler and intangible filler;
the compound stabilizer consists of an amphiphilic block copolymer and a siloxane oligomer containing epoxy groups.
The water-based acrylic coating is a thermoplastic coating, has no crosslinking reaction, and can be self-dried to form a film only after moisture volatilizes, so that the early water resistance is important under the condition of insufficient drying.
According to the invention, the water blocking performance of the water-based acrylic coating is improved by adding the filler with specific combination, so that the early water resistance can be improved, and specifically: according to the invention, the hydrophobic modified flaky filler is taken as a main body, so that on one hand, the hydrophobicity of the flaky filler can improve the water resistance, and on the other hand, the flaky filler can be well and tightly stacked, the external water infiltration path is prolonged, and the purpose of blocking water is achieved. However, the hydrophobic lamellar filler alone is not enough to meet the harsh construction environment, and the ideal regular arrangement cannot be achieved by only adding the filler, so that some gap defects always exist, and the water resistance is affected. Therefore, the invention also adds a small amount of nano needle-shaped filler and amorphous filler to fill the gaps left by irregular arrangement of the flaky filler. The combination and collocation of the three fillers obviously enhances the compactness of the coating film and reduces the risk of early water resistance and easy foaming.
However, if a compact 'water-blocking wall' structure is to be formed, a large amount of hydrophobic flaky filler needs to be added, and after the flaky filler is subjected to hydrophobic modification, the dispersibility and compatibility of the flaky filler in the water-based acrylic acid coating system are poor, and phenomena such as uneven dispersion, aggregation and the like are easy to occur, so that the 'water-blocking wall' structure is uneven, and the water-resistant effect of the coating is poor.
The inventors of the present invention have found through a great deal of research that the dispersion uniformity and stability of the hydrophobic platy filler in an aqueous solution can be significantly improved, for example, after adding a specific stabilizer to the above aqueous acrylic coating system. The stabilizer of the invention is a compound stabilizer composed of an amphiphilic block copolymer and a siloxane oligomer containing epoxy groups. The amphiphilic block copolymer can have a bridging effect and help the hydrophobic flaky filler to be better dispersed in the aqueous acrylic emulsion; the epoxy silane oligomer can exist stably in an aqueous system for a long time, and the unique chemical structure of the epoxy silane oligomer can be effectively anchored on the surface of the hydrophobic flaky filler, so that the dispersibility and the storage stability of the epoxy silane oligomer in an aqueous phase are enhanced.
Preferably, in the filler, the weight ratio of the hydrophobic flaky filler: needle-like filler: amorphous filler = 1: (0.2-0.5): (0.2-0.5). The hydrophobic flaky filler is used as a main body, so that a water-blocking wall main body with a compact multi-layer structure can be formed, and the coating has excellent early water resistance; the needle-shaped filler and the amorphous filler fill the pores of the multilayer structure, and simultaneously, the 'water-blocking wall' structure is firmer, so that the early water-blocking performance is more durable and stable. However, the addition amount of the needle-like filler and the amorphous filler is too large, and the needle-like filler and the amorphous filler are easily accumulated on the surface of the lamellar structure of the hydrophobic lamellar filler, so that the compactness of the lamellar structure is reduced, and the early water resistance of the coating is further reduced. In the proportion range of the dosage, the prepared water-based acrylic paint has excellent early water resistance and more durable and stable water resistance.
Preferably, the hydrophobic flaky filler is modified by a long-chain silane coupling agent and acid, and the modification method of the hydrophobic flaky filler comprises the following steps:
s1, adding acid into an aqueous solution of a long-chain silane coupling agent to adjust the pH to 2-4, and then carrying out a pre-hydrolysis reaction for 10-30 min to obtain a pre-hydrolysis solution;
s2, uniformly mixing the flaky filler and the prehydrolysis liquid prepared in the step S1 at the temperature of 60-70 ℃, continuously reacting for 2-4 hours, drying and crushing to obtain the hydrophobic flaky filler.
Conventional platy fillers may be used in the present invention, including but not limited to at least one of talc or mica powder.
The acid is an organic acid or an inorganic acid including, but not limited to, at least one of sulfuric acid, nitric acid or acetic acid, and more preferably sulfuric acid. The concentration of the sulfuric acid is 5-10wt%. The sulfuric acid has high concentration, is easy to volatilize and releases heat violently in the prehydrolysis process, so that the concentration of the sulfuric acid is in the range, the prehydrolysis efficiency can be improved under the condition of ensuring safety, and the time cost is reduced.
Preferably, the alkyl chain of the long-chain silane coupling agent has a linear alkyl chain with more than or equal to 9 carbon atoms, and the long-chain silane coupling agent is more preferably at least one of n-octyl triethoxysilane or dodecyl triethoxysilane.
Both conventional needle-shaped fillers and amorphous fillers can be used in the present invention.
The needle-like fillers include, but are not limited to, nano needle-like wollastonite; the amorphous filler includes, but is not limited to, at least one of precipitated barium sulfate or precipitated calcium carbonate.
Preferably, in the compound stabilizer, the weight ratio of the amphiphilic block copolymer: epoxy silane oligomer=1:0.8 to 1.2, more preferably 1:1.
Preferably, the compound stabilizer is prepared according to a method comprising the following steps:
s1, regulating the pH value of an aqueous solution of an amphiphilic block copolymer to 3-5 by sulfuric acid with the concentration of 1-5 wt% to obtain an amphiphilic block copolymer dispersion;
s2, adding epoxy silane oligomer into the amphiphilic block copolymer dispersion liquid obtained in the step S1, and uniformly mixing to obtain the compound stabilizer.
Preferably, the amphiphilic block copolymer is polyoxyethylene-oxypropylene-oxyethylene (PEO-PPO-PEO).
In the step S1, the temperature of the amphiphilic segmented copolymer dissolved in water is 15-25 ℃ in the preparation process of the aqueous solution of the amphiphilic segmented copolymer, and the aqueous solution of the amphiphilic segmented copolymer needs to be kept stand for at least 8 hours so as to be completely dissolved.
Preferably, the epoxy silane oligomer is an epoxy group-containing siloxane oligomer. The epoxy silane oligomer is at least one of Michaemap CoattO Sil MP200, LD-3168 epoxy silane oligomer or PU118 epoxy silane oligomer.
Preferably, the aqueous acrylic resin is at least one of styrene-acrylic emulsion or pure acrylic emulsion.
Preferably, the dispersant is a nonionic dispersant.
Preferably, the wetting agent is a polyether modified siloxane.
Preferably, the defoaming agent is at least one of an organosilicon defoaming agent, an ether defoaming agent or a mineral oil defoaming agent.
Preferably, the film forming aid is an alcohol ester film forming aid, including but not limited to alcohol ester twelve.
Preferably, the thickener is a polyurethane thickener.
The present invention may also add corresponding other functional additives (other additives) as desired, including but not limited to at least one of leveling agents, flash rust agents, pigments, or bactericides.
The leveling agent includes, but is not limited to, silicone; the flash rust agent includes, but is not limited to, at least one of an aminocarboxylate, a nitrate, or a nitrite; the pigment includes, but is not limited to, at least one of titanium dioxide or carbon black; including but not limited to silver-based bactericides or isothiazolinone derivatives.
The preparation method of the water-based acrylic acid coating is also in the protection scope of the invention, and comprises the following steps:
and mixing and grinding water, a dispersing agent, a wetting agent, a defoaming agent and a filler uniformly to obtain inorganic slurry, mixing the aqueous acrylic resin, the inorganic slurry, a compound stabilizer, a film forming auxiliary agent and other additives uniformly, and adding a thickening agent to adjust the viscosity to 80-100KU to obtain the aqueous acrylic coating.
The application of the water-based acrylic paint in the building or anti-corrosion field is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the hydrophobic flaky filler, the needle-shaped filler and the amorphous filler are added for filling, so that a compatible layered water-blocking wall is formed, and meanwhile, the compatibility of the filler and the acrylic matrix is improved by matching with a specific stabilizer, so that the early water resistance of the water-based acrylic coating is improved together.
The aqueous acrylic coating has excellent storage stability, can be kept at 50 ℃ for at least 25 days without layering and precipitation; and after film formation at 25 ℃ under 50r.h.% humidity, does not foam after soaking in 25 ℃ water for at least 5 days.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
Examples 1 to 11 and comparative examples 1 to 6
Providing a series of aqueous acrylic paint, which is prepared by the following steps:
(1) Adding water, a dispersing agent, a wetting agent, a defoaming agent, pigment and filler into a container according to the formula dosage in tables 1-3, dispersing at a high speed of 1500r/min for 30min, and grinding the mixture to a fineness of less than 40 mu m to obtain inorganic slurry;
(2) Adding the ground inorganic slurry into the aqueous acrylic resin emulsion under the stirring condition of the speed of 1000r/min, and then continuously adding a compound stabilizer, a film forming auxiliary agent and other additives (including a flatting agent, a flash rust agent and a bactericide), and stirring and mixing uniformly;
(3) And finally, adding a thickening agent into the mixed solution obtained in the step (2), adjusting the viscosity to 80-100KU through the thickening agent, and then filtering and packaging to obtain the water-based acrylic paint.
Wherein, the preparation method of the hydrophobically modified platy filler comprises the following steps:
s1, adding 10 parts of long-chain silane coupling agent (dodecyl triethoxysilane) into 40 parts of water, and stirring at the speed of 300r/min for 10min to prepare 20wt% of dispersion; then regulating the pH value of the dispersion liquid to 4.0 by using sulfuric acid with the concentration of 10wt percent, and carrying out prehydrolysis for 10min to obtain prehydrolysis liquid;
s2, adding 50 parts of flaky filler into a reactor, heating to 60-70 ℃, stirring at the speed of 500r/min, slowly spraying the prepared prehydrolysis liquid in the step S1 by using a nozzle atomizer, and continuing to react for 4 hours after the prehydrolysis liquid is added; finally, drying, crushing and separating to obtain the hydrophobic flaky filler.
The preparation method of the compound stabilizer comprises the following steps:
s1, adding an amphiphilic block copolymer (Pluronic F87 purchased from Pasteur) under stirring at a speed of 500r/min, dissolving at 15-25 ℃, and standing for at least 8 hours until the amphiphilic block copolymer is completely dissolved to obtain an amphiphilic block copolymer aqueous solution; then, adjusting the PH=5 by using sulfuric acid with the concentration of 2wt percent to obtain amphiphilic block copolymer dispersion liquid;
s2, adding epoxy silane oligomer (CoatO Sil MP200 purchased from Michaelk corporation) into the amphiphilic block copolymer dispersion liquid obtained in the step S1, stirring for 30min until the mixture is uniformly mixed, and obtaining the compound stabilizer with the concentration of 20 wt%.
Table 1 formulations (parts by weight, total weight 100 parts) of aqueous acrylic paints of examples 1 to 6
Table 2 formulations (weight parts, total weight 100 parts) of the aqueous acrylic paints of examples 7 to 11
Example 12
This example provides an aqueous acrylic paint prepared according to the method of example 2, differing from example 2 in that: the hydrophobic modifier dodecyltriethoxysilane in the hydrophobic platy filler (dodecyltriethoxysilane modified talc) is replaced by the silane coupling agent KH550 (gamma-aminopropyl triethoxysilane) in equal amount.
Table 3 formulations (weight parts, total weight 100 parts) of the aqueous acrylic paints of comparative examples 1 to 7
Performance testing
The properties of the aqueous acrylic coatings obtained in the above examples and comparative examples were characterized, and specific test items, test methods and results are as follows:
1. drying time: the surface drying time and the real drying time of the film forming of the aqueous acrylic paint prepared by the examples and the comparative examples are tested according to the method described in the standard GB/T1728-2020, the surface drying time is within 60min, the real drying time is within 24h, and the research result shows that the formula of the aqueous acrylic paint does not have negative influence on the film forming drying time.
2. Performance of the dried film: the aqueous acrylic paint prepared in the examples and the comparative examples is coated to prepare a film with the thickness of 40 micrometers, and after the film is completely dried, the bending performance of the film is tested according to the method described in the standard GB/T6742-2007, and the bending degree is within 1 mm; the impact performance of the film is tested according to the method described in the standard GB/T1732-2020, and the impact with the height of more than or equal to 50cm can be resisted; the films were tested for adhesion (cross-hatch) according to the method described in standard GB/T9286-2021, which shows that all can reach a level 1. The above results all show that the formulation of the aqueous acrylic coating of the present invention does not degrade the film properties.
3. Storage stability of aqueous acrylic coating: it was placed in a 50 ℃ environment and observed for its stable storage time, and the test results are shown in table 4.
4. Early water resistance test of aqueous acrylic coatings:
early water resistance test, baking for 30min at the temperature of 1:45 ℃ and soaking water at the temperature of 25 ℃ with the film thickness of 80-100 microns;
the early water resistance test is carried out at 2:25 ℃ under 50R.H. condition, the self-drying is carried out for 4 hours, the film thickness is 80-100 micrometers, the water soaking test is carried out at 25 ℃, and the time for starting to generate foaming is observed;
the test results are shown in Table 4.
Table 4 results of Performance test of aqueous acrylic coatings obtained in examples and comparative examples
From the above results, it can be seen that:
the aqueous acrylic coating prepared by the invention has excellent storage stability and early water resistance, can be stably stored at 50 ℃ for more than 25 days, and can be soaked in water at 25 ℃ for at least 5 days without foaming after being formed into a film under the humidity condition of 25 ℃ and 50R.H.
The results of examples 1 to 6 show that the aqueous acrylic paint obtained is excellent in both stability and early water resistance in the above-mentioned range of the amount of the present invention and the selection of the raw materials.
The results of examples 2 and 7 to 9 show that the early water resistance of the water-based acrylic paint tends to increase gradually with the increase of the ratio of the needle-like filler to the amorphous filler, but when the ratio is increased to a certain amount, the water-based acrylic paint tends to accumulate on the lamellar structure surface of the hydrophobic lamellar filler, the compactness of the lamellar structure is lowered, and the early water resistance of the paint is lowered (example 9), and the water-based acrylic paint excellent in early water resistance can be produced in a proper compounding ratio range.
The results of example 2 and examples 10 to 11 show that the amphiphilic block copolymer and the epoxy silane oligomer are in the above ratio range, and the obtained aqueous acrylic coating has better stability and early water resistance.
In example 12, the silane coupling agent with shorter alkyl chain is selected to modify the platy filler, and the early water resistance of the obtained water-based acrylic paint is slightly poorer than that of example 2, which shows that the hydrophobic performance of the long-chain alkyl modified hydrophobic platy filler is better, and the early water resistance of the obtained water-based acrylic paint is more excellent.
Comparative examples 1 to 3 lack filler of any shape, and the early water resistance of the obtained aqueous acrylic paint is remarkably reduced; comparative example 4 did not hydrophobically modify the platy filler, and the early water resistance of the resulting aqueous acrylic coating was also poor; the stabilizers of comparative examples 5 and 6 contained only one component, and comparative example 7 did not add a compounding stabilizer, resulting in uneven dispersion of the hydrophobic platy filler in the aqueous acrylic coating system, uneven water blocking structure, and further resulting in significant decrease in early water resistance, and also significant decrease in storage stability.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The water-based acrylic paint is characterized by comprising the following components in parts by weight, based on 100 parts by weight:
wherein the filler is hydrophobic flaky filler, needle-shaped filler and amorphous filler; the amorphous filler is at least one of precipitated barium sulfate or precipitated calcium carbonate;
the compound stabilizer consists of an amphiphilic block copolymer and an epoxy silane oligomer; the amphiphilic block copolymer is polyoxyethylene-oxypropylene-oxyethylene; the epoxy silane oligomer is at least one of Michaemap CoattO Sil MP200, LD-3168 epoxy silane oligomer or PU118 epoxy silane oligomer.
2. The aqueous acrylic coating according to claim 1, wherein the filler comprises, by weight, a hydrophobic platy filler: needle-like filler: amorphous filler = 1: (0.2-0.5): (0.2-0.5).
3. The aqueous acrylic coating according to claim 1, wherein the hydrophobic platy filler is modified by a long-chain silane coupling agent and an acid, and the modification method of the hydrophobic platy filler comprises the steps of:
s1, adding acid into an aqueous solution of a long-chain silane coupling agent to adjust the pH to 2-4, and then carrying out a pre-hydrolysis reaction for 10-30 min to obtain a pre-hydrolysis solution;
s2, uniformly mixing the flaky filler and the prehydrolysis liquid prepared in the step S1 at the temperature of 60-70 ℃, continuously reacting for 2-4 hours, drying and crushing to obtain the hydrophobic flaky filler.
4. The aqueous acrylic coating according to claim 3, wherein the platy filler is at least one of talc or mica powder; the long-chain silane coupling agent is at least one of n-octyl triethoxysilane or dodecyl triethoxysilane.
5. The aqueous acrylic coating according to claim 1, characterized in that the needle-like filler is nano needle-like wollastonite.
6. The aqueous acrylic coating according to claim 1, wherein in the built stabilizer, the weight ratio of amphiphilic block copolymer: epoxy silane oligomer=1:0.8-1.2.
7. The aqueous acrylic coating according to claim 1, characterized by comprising at least one of the following features (a) - (g):
(a) The water-based acrylic resin is at least one of styrene-acrylic emulsion or pure acrylic emulsion;
(b) The dispersing agent is a nonionic dispersing agent;
(c) The wetting agent is polyether modified siloxane;
(d) The defoaming agent is at least one of an organic silicon defoaming agent, an ether defoaming agent or a mineral oil defoaming agent;
(e) The film forming auxiliary agent is an alcohol ester film forming auxiliary agent;
(f) The thickener is polyurethane thickener;
(g) The other additive is at least one of leveling agent, flash rust agent, pigment or bactericide.
8. The method for producing an aqueous acrylic paint according to any one of claims 1 to 7, comprising the steps of:
and mixing and grinding water, a dispersing agent, a wetting agent, a defoaming agent and a filler uniformly to obtain inorganic slurry, mixing the aqueous acrylic resin, the inorganic slurry, a compound stabilizer, a film forming auxiliary agent and other additives uniformly, and adding a thickening agent to adjust the viscosity to 80-100KU to obtain the aqueous acrylic coating.
9. Use of the aqueous acrylic paint according to any one of claims 1 to 7 in the construction or corrosion protection field.
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| CN102382535A (en) * | 2011-08-19 | 2012-03-21 | 石宇 | Waterproof paint film |
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| CN111876035A (en) * | 2020-07-23 | 2020-11-03 | 何亚艳 | Water-based paint and production process thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102382535A (en) * | 2011-08-19 | 2012-03-21 | 石宇 | Waterproof paint film |
| CN104629508A (en) * | 2015-03-11 | 2015-05-20 | 马清浩 | Water-resistant scrub-resistant internal/external wall latex paint |
| WO2017007439A1 (en) * | 2015-07-03 | 2017-01-12 | Erciyes Universitesi | A superhydrophobic nanocomposite coating method |
| CN109021691A (en) * | 2018-09-30 | 2018-12-18 | 中山市中益油墨涂料有限公司 | A kind of aqueous color crystal glass ink and preparation method thereof |
| CN111876035A (en) * | 2020-07-23 | 2020-11-03 | 何亚艳 | Water-based paint and production process thereof |
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