CN113621277A - Water-based anticorrosive paint for aluminum products and preparation method thereof - Google Patents
Water-based anticorrosive paint for aluminum products and preparation method thereof Download PDFInfo
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- CN113621277A CN113621277A CN202111005429.6A CN202111005429A CN113621277A CN 113621277 A CN113621277 A CN 113621277A CN 202111005429 A CN202111005429 A CN 202111005429A CN 113621277 A CN113621277 A CN 113621277A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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Abstract
The invention relates to a water-based anticorrosive paint for aluminum products, which comprises a primer, a pre-emulsified dispersion liquid, an initiator, a neutralizer and a mildew preventive. The bottom material comprises the following components in parts by weight: 1-3 parts of main emulsifier, 4-6 parts of phosphate ester emulsifier, 0.4-0.6 part of pH value stabilizer and 290-300 parts of aqueous solution containing 0.5 percent of ammonia. The pre-emulsified dispersion comprises the following components in parts by weight: 1-1.5 parts of emulsifier, 220-240 parts of styrene, 150-170 parts of butyl acrylate, 5-15 parts of acrylic acid, 20-30 parts of MQ resin containing vinyl, 10-20 parts of monohydroxyethyl acrylate phosphate and 160-170 parts of deionized water. The invention also relates to a method for preparing the water-based anticorrosive paint.
Description
Technical Field
The invention relates to the field of anticorrosive coatings, in particular to a water-based anticorrosive coating for aluminum products and a preparation method thereof.
Background
The metal aluminum is a very active metal, and aluminum alloy can form a layer of compact oxide film on the surface in a natural state, wherein the oxide film is aluminum oxide which is a main component, but the stability of the oxide film in acid and alkali environments is extremely poor. Since the oxide film exists on the surface of a workpiece made of aluminum or an aluminum alloy (hereinafter referred to as an aluminum product), the adhesion between a functional coating formed on the surface of the aluminum product and the aluminum product is extremely poor. In order to solve the technical problem, the existing technical scheme is that a water-based adhesion promoter is added into a water-based anticorrosive paint to improve the adhesion between a functional coating and an aluminum product. However, the technical problems existing in the prior technical scheme are as follows: as the functional coating is built up over time, the adhesion promoter gradually migrates out of the coating, thereby gradually losing its effectiveness, and eventually still causing the coating to peel off the surface of the aluminum article.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a water-based anticorrosive coating for an aluminum product, which has excellent adhesion with the surface of the aluminum product on the basis of ensuring the anticorrosive performance.
On the one hand, the invention provides a water-based anticorrosive paint for aluminum products, which has ideal performance such as corrosion resistance to coated aluminum products and steel products, and besides the corrosion resistance, a coating formed by curing the water-based anticorrosive paint has good coating film adhesion to substrates (the substrates are metal products such as aluminum products and steel products). The water-based anticorrosive coating not only has water dilutability, but also does not contain heavy metals, so that the water-based anticorrosive coating is easy to manufacture, store, transport and use, and has diluted storage stability. The coating equipment using the aqueous anticorrosive paint is easy to clean, and the cleaning liquid is also easy and economical to handle. The aqueous corrosion resistant coating is applied to and thermally cured on a substrate to provide corrosion resistance to the substrate.
The water-based anticorrosive paint comprises:
(A) a primer;
(B) pre-emulsifying the dispersion;
(C) an initiator;
(D) a neutralizing agent;
(E) and (4) a mildew preventive.
Wherein the bottom material comprises the following components in parts by weight: 1-3 parts of main emulsifier, 4-6 parts of phosphate ester emulsifier, 0.4-0.6 part of pH value stabilizer, and 290-300 parts of ammonia water (aqueous solution containing 0.5% of ammonia).
Wherein the pre-emulsified dispersion liquid comprises the following components in parts by weight: 1-1.5 parts of emulsifier, 220-240 parts of styrene, 150-170 parts of butyl acrylate, 5-15 parts of acrylic acid, 20-30 parts of MQ resin containing vinyl, 10-20 parts of monohydroxyethyl acrylate phosphate and 160-170 parts of deionized water.
The MQ resin refers to polyorganosiloxane with a highly crosslinked space network structure, the vinyl-containing MQ resin has a-Si-O-Si-structure and a vinyl functional group, and the vinyl-containing MQ resin has excellent performances of weather resistance, heat resistance, stain resistance, chemical stability and the like, and can be used in combination with styrene, acrylic acid and derivatives thereof to remarkably improve the adhesiveness and corrosion resistance of the water-based anticorrosive paint.
The aqueous anticorrosive coating provided by the invention can contain additives and pigments which are conventionally used for preparing coatings, such as a stabilizer, an antioxidant, a leveling agent, an antisettling agent, a light stabilizer, a dispersing agent, a slip agent and the like besides the components.
The water-based anticorrosive paint provided by the invention can be used for the surfaces of aluminum or aluminum-based alloy, iron-based alloy, stainless steel or nickel-based metal, galvanized and aluminized steel plates and stainless steel. The metal surface should be degreased and degreased before coating, and may be degreased using any known method, for example, degreasing in an acidic, alkaline or organic solvent, and further, the metal surface may be subjected to roughening treatment, for example, sand blasting or grinding, for the purpose of further improving adhesion, although these steps are not essential. The aqueous anticorrosive paint can be applied to the metal surface by a conventional coating method, for example, brushing, spraying and the like can be used, and the coating is baked or naturally dried after the application.
The solid content of the water-based anticorrosive paint is about 45 percent.
In another aspect, the present invention also provides a method for preparing the above water-based anticorrosive paint, comprising the following steps:
s1, adding the bottom materials into a three-neck flask, heating to 85-90 ℃ under the stirring state, and keeping the temperature constant;
s2, putting the components of the pre-emulsified dispersion liquid into a pre-emulsifying container, and stirring and dispersing to form stable pre-emulsified dispersion liquid;
s3, adding a part of pre-emulsified dispersion liquid (the mass of the part of pre-emulsified dispersion liquid accounts for no more than 5% of the total mass of the pre-emulsified dispersion liquid) into a three-neck flask containing a base material, stirring, then adding a part of initiator (the mass of the part of initiator accounts for no more than 35% of the total mass of the initiator), and reacting at constant temperature of 85-90 ℃ for no less than 20min until no obvious reflux exists, so as to obtain a solution A;
s4, dropwise adding the rest of pre-emulsified dispersion liquid and the rest of initiator into the solution A, reacting at the constant temperature of 85-90 ℃ for not less than 90min to obtain a solution B, and then cooling;
s6, adding a neutralizing agent to adjust the pH value to 7.0-7.5 when the temperature of the solution B is reduced to be not more than 40 ℃ to obtain a solution C;
and S7, adding the mildew preventive into the solution C, stirring for not less than 5min, filtering through a filter cloth of 200 meshes, and discharging to obtain the water-based anticorrosive paint.
In step S4, the pre-emulsified dispersion and the dropping initiator may be added dropwise into a three-necked bottle in several times or simultaneously, the dropping time of the pre-emulsified dispersion is not less than 240min, and the dropping time of the dropping initiator is not less than 255 min.
In another aspect, the invention relates to a coated aluminum article that is protected with an anti-corrosive coating that is a film deposited and cured from the above-described aqueous anti-corrosive coating.
Styrene in the aqueous anticorrosive coating material provided by the present invention forms a crosslink with a carboxylic acid functional group of acrylic acid and derivatives thereof, which are components constituting a coating film, and it is considered that adhesion is increased by the formation of the crosslink. The inventors have found that, if the substrate is made of a metal material other than aluminum or an aluminum alloy, titanium or a titanium alloy, the specific components of acrylic acid and its derivatives may be: the acrylic acid and any acrylic acid derivative with hydrophilicity are compounded in any proportion, and the adhesive force between the water-based anticorrosive paint and the substrate can reach 0 grade (the adhesive force of the coating is classified according to the adhesive force test of a paint film cross-cut method described in GB/T9286-1988, the adhesive force is divided into 6 grades, the adhesive force of the coating is gradually reduced from 0 grade to 5 grade, and the 5 grade is worst); however, when the substrate is made of aluminum or aluminum alloy, because the surface of the aluminum product is provided with a compact oxide film layer, the specific component proportion of acrylic acid and derivatives thereof has a great influence on the adhesion of the coating formed by the water-based anticorrosive paint on the surface of the aluminum product, and the inventor finds that the specific component proportion of acrylic acid and derivatives thereof has positive or negative influence on the adhesion, so that in order to enable the adhesion of the coating formed by the water-based anticorrosive paint on the surface of the aluminum product to reach 0 level, the inventor conducts cross comparison experiments on different combinations of acrylic acid and derivatives thereof, and the inventor unexpectedly finds that acrylic acid and derivatives thereof consisting of butyl acrylate, acrylic acid and monohydroxyethyl acrylate phosphate can generate a synergistic effect with styrene, so that the adhesion of the coating formed by the water-based anticorrosive paint on the surface of the aluminum product is good, and when the mass fraction of the butyl acrylate in the acrylic acid and the acrylic acid derivatives exceeds 80%, the adhesive force of a coating formed by the water-based anticorrosive paint on the surface of the aluminum product reaches 0 level.
The inventor finds that when styrene, butyl acrylate, acrylic acid and monohydroxyethyl acrylate in the water-based anticorrosive paint are main components for forming a film, the adhesion of a coating formed by the water-based anticorrosive paint on the surface of an aluminum product is good, but the weather resistance is weakened, so that the weather resistance of the coating needs to be improved under the condition of keeping the adhesion of the coating.
The component proportion of the primer is based on the components of the pre-emulsified dispersion liquid, and the components of the primer are controlled in consideration of the storage stability of the water-based anticorrosive paint, so that the system of the prepared water-based anticorrosive paint is kept stable. The inventors found that a synergistic effect can be produced by adding a phosphate ester emulsifier, a phosphate ester emulsifier and a main emulsifier to the primer, so that the pre-emulsified dispersion liquid is uniformly dispersed in the aqueous solvent, and the aqueous anticorrosive paint is kept stable during the preparation process by adding ammonia water. Preferably, the main emulsifier is sodium dodecyl benzene sulfonate, the phosphate ester emulsifier is Solvay (SIPOMER) PAM-100, and the pH value stabilizer is sodium carbonate.
The neutralizing agent in the water-based anticorrosive paint is used for adjusting the pH value of the water-based anticorrosive paint so as to improve the stability of the whole system of the water-based anticorrosive paint in the storage process, the pH value of the water-based anticorrosive paint is usually about 6-7 but can be higher than 7, and the neutralizing agent is preferably a diluted solution formed by mixing ammonia water (20% ammonia-containing aqueous solution) with deionized water.
The initiator in the water-based anticorrosive paint is used for initiating free radical polymerization and copolymerization reaction in the pre-emulsified dispersion liquid and is also used for crosslinking curing and macromolecular crosslinking reaction of unsaturated polyester in the pre-emulsified dispersion liquid. The component proportion of the initiator in the aqueous anticorrosive coating is based on the components of the pre-emulsified dispersion, and therefore it is preferable that the initiator is a solution containing potassium persulfate.
Compared with the prior art, the technical scheme of the invention has at least the following beneficial effects:
the coating formed by the water-based anticorrosive paint provided by the invention has excellent weather resistance and corrosion resistance, and when the water-based anticorrosive paint is coated on the surface of an aluminum product, the adhesion between the formed coating and the surface of the aluminum product can be kept excellent for a long time.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The specific component ratios of the aqueous anticorrosive coatings provided in examples 1 to 3 are shown in table 1, and the specific component ratios of the aqueous anticorrosive coatings provided in comparative examples 1 to 4 are shown in table 2.
TABLE 1
TABLE 2
The preparation methods of the water-based anticorrosive coatings provided by the examples 1-3 and the comparative examples 1-4 respectively comprise the following steps:
s1, adding the bottom materials into a three-neck flask, heating to 85-90 ℃ under the stirring state, and keeping the temperature constant;
s2, putting the components of the pre-emulsified dispersion liquid into a pre-emulsifying container, and stirring and dispersing to form stable pre-emulsified dispersion liquid;
s3, adding a part of pre-emulsified dispersion liquid (the mass of the part of pre-emulsified dispersion liquid accounts for 5% of the total mass of the pre-emulsified dispersion liquid) into a three-neck flask containing a base material, stirring, then adding a part of initiator (the mass of the part of initiator accounts for 35% of the total mass of the initiator), and reacting at constant temperature of 85-90 ℃ for not less than 20min until no obvious reflux exists, thus obtaining a solution A;
s4, dropwise adding the rest of pre-emulsified dispersion liquid and the rest of initiator into the solution A, reacting at the constant temperature of 85-90 ℃ for 90min to obtain a solution B, and then cooling;
s6, adding a neutralizing agent to adjust the pH value to 7.0-7.5 when the temperature of the solution B is reduced to 40 ℃ to obtain a solution C;
and S7, adding the mildew preventive into the solution C, stirring for 5min, filtering through a filter cloth of 200 meshes, and discharging to obtain the water-based anticorrosive paint.
Performance testing
The preparation of the paint solution and the preparation of the test panels were carried out in this order before the performance test of the aqueous anticorrosive coatings provided in examples 1 to 3 and comparative examples 1 to 4.
Wherein the preparation of the painting solution comprises the following steps:
s1, adding the water-based anticorrosive paint into a reaction vessel, and adding a defoaming agent BYK 024 under the condition of keeping low-speed stirring;
s2, adjusting the stirring speed to 1500r/min, keeping stirring for not less than 15min, sampling, scraping a glass plate, and testing that no fish eyes exist;
s3, adding a defoaming agent BYK 028 into the reaction container, adjusting the stirring speed to 1000r/min, stirring for not less than 15min, sampling, scraping a glass plate, and testing that no fish eyes exist;
s4, dissolving polyurethane thickener PUR 62 of German Mingling in a solvent compounded by dipropylene glycol butyl ether and dipropylene glycol methyl ether, adding deionized water, stirring to obtain uniform slurry, slowly adding the slurry into a reaction vessel, adjusting the stirring speed to 600r/min, and keeping stirring for not less than 10 min;
s5, adding sodium nitrite aqueous solution into the reaction container, and stirring for not less than 5 min;
s6, adding a substrate wetting agent Tego 245 of Digao company into the reaction vessel, and stirring for not less than 5 min;
s7, adding a leveling agent BYK 333 (BYK company) into the reaction container, and stirring for not less than 5 min;
s8, filtering the solution in the reaction container through 200-mesh filter cloth and discharging to obtain the painting solution.
The aqueous anticorrosive coatings provided in examples 1 to 3 and comparative examples 1 to 4 were prepared into corresponding coating solutions, respectively, by the above-described method.
Wherein the substrate for preparing the test sample is 10 × 10cm2The pure aluminum plate is degreased by alkaline solution before coating, rinsed by water and then immersed into cleaning solution. And taking the pure aluminum plate out of the cleaning solution, rinsing the pure aluminum plate by using deionized water, and drying the pure aluminum plate. The cleaned pure aluminum sheet may be dipped into the coating solution for coating, then removed and drained of excess coating solution on the surface, sometimes with gentle shaking, and then baked immediately or air dried at room temperature or pre-cured at an appropriate temperature until the coating is dry to the touch and then baked, with the coating solution curing to form a coating on the surface of the pure aluminum sheet. But in order to control the thickness error of the coating on each substrate to be less than 3 percent, the prior paint gun is preferably used for spraying the paint solution on the surface of the pure aluminum plate, the thickness of the wet film is kept to be about 80 mu m, the pure aluminum plate is naturally dried for 7 days in a constant temperature and humidity machine, the temperature is kept to be 23-25 ℃, and the relative humidity is kept to be 48-52 percentAnd curing the painting solution on the surface of the pure aluminum plate to form a coating.
Test panels were prepared by coating the paint solutions of examples 1-3 and comparative examples 1-4, respectively, on pure aluminum panels using the method described above.
The test panels were tested according to the test methods described in the following standards:
1. the hardness of the coating of the test panels was tested according to the "pencil method for coating hardness" described in GB/T6739-;
2. the adhesion of the coating of the test panel was tested according to the "paint adhesion test (cross-hatch method)" described in GB/T9286-1988;
3. the water resistance of the coating of the test panel was tested according to the "paint film water resistance test method (immersion method)" described in GB/T5209-1985;
4. the salt water resistance (sodium chloride solution, mass fraction of sodium chloride is 5%) of the coating of the test sample is tested according to the 'determination of salt water resistance of marine paint' described in GB/T10834-2008;
5. the corrosion resistance of the coating of the test sample in an acetic acid solution (the mass fraction of acetic acid is 5%) and a sodium bicarbonate solution (the mass fraction of sodium bicarbonate is 5%) is tested according to the determination of alkali resistance of the architectural coating described in GB/T9265-1988;
5. the coating of the test panel was tested for its resistance to wiping with an alcohol solution (95% by mass of ethanol) according to "determination of films resistant to wet heat, salt spray and weathering (manually accelerated) as described in GB/T1765-1979 (1989)";
6. the corrosion resistance of the coating of the test panel in salt spray was tested according to "determination of resistance to wet heat, salt spray, weathering (manual acceleration) of the paint film" described in GB/T1765-1979 (1989), the coating of the test panel being tested according to the standard salt spray test ASTM B-117, the test panel being placed in a container kept at a constant temperature and exposed to a dilute salt spray of 5% by weight salt solution, and the time at which traces of corrosion of the substrate occurred being recorded;
7. the coatings of the test panels were subjected to an artificial accelerated weathering test according to "artificial weathering and exposure to artificial radiation of paints and varnishes" described in GB/T23987-.
The results of the above tests are shown in table 3.
TABLE 3
According to the test results in table 3, it can be judged that:
1. styrene, butyl acrylate, acrylic acid and monohydroxyethyl acrylate in the water-based anticorrosive paint have a synergistic effect, and the adhesion force between the water-based anticorrosive paint and an aluminum product can be improved under the condition of ensuring the corrosion resistance of the coating;
2. the water-based anticorrosive paint is added with the MQ resin containing vinyl, and the MQ resin containing vinyl is combined with styrene, butyl acrylate, acrylic acid and monohydroxyethyl acrylate phosphate, so that the adhesion, corrosion resistance and weather resistance of the coating can be obviously improved;
3. the water-based anticorrosive paint is added with the emulsifier containing the phosphate ester, so that the weather resistance of the coating can be obviously improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A water-based anticorrosive paint for aluminum products is characterized in that,
the water-based anticorrosive paint comprises a bottom material, pre-emulsified dispersion liquid, an initiator, a neutralizer and a mildew preventive; the base material comprises the following components in parts by weight: 1-3 parts of main emulsifier, 4-6 parts of phosphate ester emulsifier, 0.4-0.6 part of pH value stabilizer, 290-300 parts of aqueous solution containing 0.5% of ammonia;
the pre-emulsified dispersion liquid comprises the following components in parts by weight: 1-1.5 parts of emulsifier, 220-240 parts of styrene, 150-170 parts of butyl acrylate, 5-15 parts of acrylic acid, 20-30 parts of MQ resin containing vinyl, 10-20 parts of monohydroxyethyl acrylate phosphate and 160-170 parts of deionized water.
2. The water-based anticorrosive paint of claim 1, wherein the main emulsifier is sodium dodecyl benzene sulfonate, the phosphate ester emulsifier is Solvay PAM-100, and the pH stabilizer is sodium carbonate.
3. The water-based anticorrosive paint according to claim 1, wherein the initiator is potassium persulfate and deionized water in a mass ratio of 1: 39 and compounding.
4. The water-based anticorrosive paint according to claim 1, wherein the neutralizing agent is a 20% ammonia-containing aqueous solution and deionized water in a mass ratio of 17: 23, compounding.
5. The water-based anticorrosive paint as claimed in claim 1, wherein the mildew inhibitor is Hofmann CP-15 and deionized water in a mass ratio of 1: 9 and (4) compounding.
6. A method for preparing the aqueous anticorrosive coating according to any one of claims 1 to 5, characterized by comprising the steps of:
s1, adding the bottom materials into a three-neck flask, heating to 85-90 ℃ under the stirring state, and keeping the temperature constant;
s2, putting the components of the pre-emulsified dispersion liquid into a pre-emulsifying container, and stirring and dispersing to form stable pre-emulsified dispersion liquid;
s3, adding part of the pre-emulsified dispersion liquid into a three-necked bottle containing a base material, stirring, then adding part of the initiator, and reacting at a constant temperature of 85-90 ℃ for not less than 20min until no obvious reflux exists to obtain a solution A;
s4, dropwise adding the rest of pre-emulsified dispersion liquid and the rest of initiator into the solution A, reacting at the constant temperature of 85-90 ℃ for not less than 90min to obtain a solution B, and then cooling;
s6, when the temperature of the solution B is reduced to be not more than 40 ℃, adding the neutralizer to adjust the pH value to 7.0-7.5 to obtain a solution C;
and S7, adding the mildew preventive into the solution C, stirring for not less than 5min, and filtering through a 200-mesh filter cloth to discharge.
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| CN105885745A (en) * | 2015-04-15 | 2016-08-24 | 广州都邦材料科技有限公司 | Silicon-fluorine modified polyacrylate pressure-sensitive adhesive emulsion for PVC high-temperature-resistant adhesive tape, preparation method and application |
| CN105218725A (en) * | 2015-09-23 | 2016-01-06 | 南通瑞普埃尔生物工程有限公司 | A kind of preparation method of high adhesive force heavy-duty coating acrylate copolymer emulsion |
| CN105153828A (en) * | 2015-09-25 | 2015-12-16 | 南通瑞普埃尔生物工程有限公司 | Acrylic ester copolymer emulsion used for high-water-resistance heavy anti-corrosion coating and preparation method thereof |
| CN105153343A (en) * | 2015-09-29 | 2015-12-16 | 南通瑞普埃尔生物工程有限公司 | Acrylate copolymeric mini-emulsion for heavy anti-corrosion coating and preparation method of acrylate copolymeric mini-emulsion |
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