A water-based floor coating and a preparation process thereof

Abstract

The application relates to the technical field of coatings, and discloses a water-based floor paint and a preparation process thereof. The water-based floor paint comprises A: 52-65 parts by weight of water-based hydroxyl acrylic resin, 0.1-0.6 parts by weight of amino urea modified carbon nanotubes and 5-15 parts by weight of fillers; and B component comprises 16-23 parts by weight of isocyanate curing agents. A large number of hydrophilic groups such as amino urea and hydrazide are introduced on the surface of the carbon nanotubes, the carbon nanotubes can be better dispersed in the paint, the storage stability is excellent, the dispersibility of the carbon nanotubes in the paint film is good after curing, a continuous conductive path can be formed, the antistatic performance of the paint film is improved, and the mechanical strength and wear resistance are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to a water-based floor paint and a preparation process thereof. BACKGROUND

[0002] Floor paint mainly plays the role of beautifying and decorating, preventing seepage and corrosion, and resisting corrosion, and can be divided into solvent-based paint, water-based paint, and solvent-free paint, etc., among which water-based polyurethane acrylate floor paint is green and environmentally friendly, has no pollution, and is widely used. Ordinary water-based polyurethane acrylate has poor antistatic performance, poor mechanical strength, and poor wear resistance, which is not conducive to its practical application in floor paint.

[0003] The patent for invention with publication number CN111662633B discloses a kind of anti-static wear-resistant polyurethane floor paint and preparation method thereof, which uses polymeric polyol, carbon nanotube, plant polyol, hydroxyl-terminated polysiloxane, aliphatic isocyanate as raw material, and the floor paint prepared has good anti-static, wear-resistant, scratch-resistant and other properties. However, carbon nanotubes have poor dispersibility in water-based paint and are prone to agglomeration, making it difficult to effectively improve the performance of paint film. Surface modification of carbon nanotubes to improve their dispersibility is a research difficulty. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a water-based floor paint and a preparation process thereof, which solves the problem of poor antistatic, strength and other properties of acrylic resin floor paint.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is as follows: a water-based floor paint and a preparation process thereof, the water-based floor paint comprising A component and B component; the A component comprising 52-65 parts by weight of water-based hydroxyl acrylate resin, 0.1-0.6 parts by weight of amino urea modified carbon nanotube, 5-15 parts by weight of filler, 5-8 parts by weight of color paste, 0.4-0.7 parts by weight of defoaming agent, 0.3-0.5 parts by weight of leveling agent, and 0.3-0.5 parts by weight of film-forming aid; the B component comprising 16-23 parts by weight of isocyanate curing agent.

[0006] The preparation process of the water-based floor paint is as follows:

[0007] (1) Add acidified carbon nanotubes, N,N-dicyclohexyl carbodiimide and 4-dimethylamino pyridine to N,N-dimethylformamide, ultrasonically disperse in a nitrogen atmosphere, stir and activate, then add hexamethylene diamino urea, stir and react, filter the product, wash it with water and ethanol, and dry to obtain amino urea modified carbon nanotubes.

[0008] (2) adding water, water-based hydroxyl acrylic resin, amino urea modified carbon nanotube, filler, color paste, defoaming agent, leveling agent, film forming aid into the container, shearing and dispersing to obtain A component; then adding B component isocyanate curing agent, stirring to obtain water-based floor paint.

[0009] Further, the amount of acidified carbon nanotubes in (1) is 100 parts by weight, N,N-dicyclohexyl carbodiimide is 180-300 parts by weight, 4-dimethylamino pyridine is 160-270 parts by weight, and hexamethylene diamino urea is 400-1500 parts by weight.

[0010] Further, the temperature of ultrasonic dispersion in (1) is 20-35℃, and the time is 20-40 min.

[0011] Further, the temperature of stirring and activation in (1) is 20-35℃, and the time is 2-4 h.

[0012] Further, the temperature of stirring and reaction in (1) is 20-40℃, and the time is 18-24 h.

[0013] Further, the filler in (2) includes calcium carbonate, titanium white or fumed white carbon black.

[0014] Further, the film forming aid in (2) includes alcohol ester twelve, dipropylene glycol methyl ether or dipropylene glycol butyl ether.

[0015] The present application adopts the above technical solution, and has the beneficial technical effects that: the hexamethylene diamino urea is subjected to amidation reaction with the carboxyl on the surface of the acidified carbon nanotube to obtain the hexamethylene diamino urea grafted to the surface of the carbon nanotube, then the water-based hydroxyl acrylic resin, the amino urea modified carbon nanotube, the filler, the film forming aid and the like are used as A component, and the isocyanate curing agent is used as B component to obtain the water-based floor paint.

[0016] The present application introduces a large amount of hydrophilic groups such as amino urea and hydrazide on the surface of the carbon nanotube, significantly improves the surface hydrophilicity of the carbon nanotube, can be better dispersed in the A component of the water-based floor paint, has excellent storage stability, and after curing, the dispersion of the carbon nanotube in the paint film is good, a continuous conductive path can be formed, which is beneficial to improve the antistatic performance of the paint film and improve the mechanical properties.

[0017] The hydrazide group on the surface of the carbon nanotube in the present application has active amino group, which can react with the isocyanate curing agent, so that the carbon nanotube and the hydroxyl acrylic resin are chemically bonded by the isocyanate curing agent, the interfacial bonding strength between the carbon nanotube and the acrylic resin is enhanced, the crosslinking degree in the paint film is improved, which is beneficial to improve the water resistance of the paint film, and the tensile strength is improved, the frictional mass loss is reduced, and the mechanical strength and wear resistance are better. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is an infrared spectrogram of the amino urea modified carbon nanotube of Example 1. DETAILED DESCRIPTION

[0019] The technical solutions of the present application are further described below in conjunction with the drawings and examples, but are not limited thereto, any modification or equivalent replacement to the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application shall be covered in the protection scope of the present application.

[0020] The aqueous hydroxyl acrylic resin is model WL-AD396, Xiamen Kandilon Trading Co., Ltd. The isocyanate curing agent is model Basonat HI100ap, Qianhai Jishengya (Shenzhen) Technology Co., Ltd. The carbon nanotube is model TOB-TNT-M, specification 8-15 nm, Shenzhen Liyouxin Energy Technology Co., Ltd.

[0021] The hexamethylene diamino urea is prepared according to the method of the reference journal J Incl Phenom Macrocycl Chem (2012) 74:257-263, document Synthesis and extraction abilities of mono-formylated calix[4]-1,3-aza-crown and its hydrazone derivatives. 58 mL of hydrazine monohydrate is added to 600 mL of dichloromethane, 0.3 mol of hexamethylene diisocyanate is added in an ice water bath, and then stirred for 3 h at 25℃, the precipitate is dried after filtration, to obtain hexamethylene diamino urea, with the structural formula .

[0022] 300 mL of mixed acid of concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 70% is added to the carbon nanotube, ultrasonic dispersion is performed for 30 min, then heated to 80℃, and condensed reflux is performed for 24 h, the solution is poured into water, washed with water after filtration, and dried to obtain acidified carbon nanotube.

[0023] Example 1

[0024] (1) 2 g of acidified carbon nanotube, 3.6 g of N,N-dicyclohexyl carbodiimide, and 3.2 g of 4-dimethylamino pyridine are added to 0.6 L of N,N-dimethyl formamide, ultrasonic dispersion is performed for 20 min in a nitrogen atmosphere at 25℃, stirring activation is performed for 4 h, then 8 g of hexamethylene diamino urea is added, stirring reaction is performed for 18 h at 40℃, the product is washed with water and ethanol after filtration, and dried to obtain amino urea modified carbon nanotube. Figure 1The infrared spectrum of the aminourea-modified carbon nanotubes shows a value of 3397 cm⁻¹. -1 It is the absorption peak of -NH2 in hydrazide, 1651 cm⁻¹ -1 It is the absorption peak of the carbonyl group (-C=O-) in the amide bond, at 1511 cm⁻¹. -1 It is a urea group Characteristic peak, 2847cm -1 The absorption peak of the methylene group indicates that hexamethylenediaminourea is grafted onto the surface of the carbon nanotube.

[0025] (2) Add 400mL of water, 580g of waterborne hydroxyl acrylic resin, 1g of aminourea-modified carbon nanotubes, 150g of calcium carbonate, 60g of iron oxide red 8811 waterborne pigment, 4g of defoamer BYK-019, 5g of leveling agent BYK-333, and 3g of alcohol ester twelve to a container, and shear and disperse them in a high-speed shearing machine to obtain component A; then add component B 192g of isocyanate curing agent, and stir to obtain waterborne floor coating.

[0026] Example 2

[0027] (1) 2g of acidified carbon nanotubes, 6g of N,N-dicyclohexylcarbodiimide and 5.4g of 4-dimethylaminopyridine were added to 0.8L of N,N-dimethylformamide. The mixture was ultrasonically dispersed at 20°C for 40min under a nitrogen atmosphere and stirred for 4h. Then, 30g of hexamethylenediaminourea was added and the mixture was stirred at 20°C for 24h. After filtration, the product was washed with water and ethanol and dried to obtain aminourea-modified carbon nanotubes.

[0028] (2) Add 400mL of water, 650g of waterborne hydroxyl acrylic resin, 3g of aminourea-modified carbon nanotubes, 50g of fumed silica, 50g of iron oxide red 8811 waterborne pigment, 7g of defoamer BYK-019, 4g of leveling agent BYK-333, and 5g of dipropylene glycol methyl ether to a container, and shear and disperse them in a high-speed shearing machine to obtain component A; then add 230g of component B isocyanate curing agent, and stir to obtain waterborne floor coating.

[0029] Example 3

[0030] (1) 2g of acidified carbon nanotubes, 5g of N,N-dicyclohexylcarbodiimide and 8.4g of 4-dimethylaminopyridine were added to 0.8L of N,N-dimethylformamide. The mixture was ultrasonically dispersed at 35°C for 20min under a nitrogen atmosphere and stirred for 2h. Then 20g of hexamethylenediaminourea was added and the mixture was stirred at 35°C for 24h. After filtration, the product was washed with water and ethanol and dried to obtain aminourea-modified carbon nanotubes.

[0031] (2) Into a container, 300 mL of water, 520 g of water-based hydroxyl acrylic resin, 6 g of amino urea modified carbon nanotube, 70 g of titanium white, 80 g of iron red 8811 water-based color paste, 5 g of defoaming agent BYK-019, 3 g of leveling agent BYK-333, 4.6 g of dipropylene glycol butyl ether were added, and shearing dispersion was performed in a high-speed shearing machine to obtain component A; then 160 g of isocyanate curing agent was added as component B, and after stirring, a water-based floor paint was obtained.

[0032] Comparative Example 1

[0033] (1) Into a container, 400 mL of water, 580 g of water-based hydroxyl acrylic resin, 150 g of calcium carbonate, 60 g of iron red 8811 water-based color paste, 4 g of defoaming agent BYK-019, 5 g of leveling agent BYK-333, 3 g of alcohol ester twelve were added, and shearing dispersion was performed in a high-speed shearing machine to obtain component A; then 192 g of isocyanate curing agent was added as component B, and after stirring, a water-based floor paint was obtained.

[0034] Comparative Example 2

[0035] (1) Into a container, 400 mL of water, 580 g of water-based hydroxyl acrylic resin, 1 g of acidified carbon nanotube, 150 g of calcium carbonate, 60 g of iron red 8811 water-based color paste, 4 g of defoaming agent BYK-019, 5 g of leveling agent BYK-333, 3 g of alcohol ester twelve were added, and shearing dispersion was performed in a high-speed shearing machine to obtain component A; then 192 g of isocyanate curing agent was added as component B, and after stirring, a water-based floor paint was obtained.

[0036] Comparative Example 3

[0037] (1) 2 g of acidified carbon nanotube, 3.6 g of N,N-dicyclohexyl carbodiimide, 3.2 g of 4-dimethylamino pyridine were added to 0.6 L of N,N-dimethyl formamide, ultrasonic dispersion was performed for 20 min in a nitrogen atmosphere at 25°C, stirring activation was performed for 4 h, then 8 g of ethylenediamine was added, and then stirring reaction was performed for 18 h at 40°C, the product was washed with water and ethanol after filtration, and drying was performed to obtain ethylenediamine modified carbon nanotube.

[0038] (2) Into a container, 400 mL of water, 580 g of water-based hydroxyl acrylic resin, 1 g of ethylenediamine modified carbon nanotube, 150 g of calcium carbonate, 60 g of iron red 8811 water-based color paste, 4 g of defoaming agent BYK-019, 5 g of leveling agent BYK-333, 3 g of alcohol ester twelve were added, and shearing dispersion was performed in a high-speed shearing machine to obtain component A; then 192 g of isocyanate curing agent was added as component B, and after stirring, a water-based floor paint was obtained.

[0039] Comparative Example 4

[0040] (1) 2 g acidified carbon nanotubes, 3.6 g N,N-dicyclohexyl carbodiimide, 3.2 g 4-dimethylamino pyridine were added to 0.6 L N,N-dimethyl formamide, ultrasonic dispersion for 20 min under nitrogen atmosphere at 25 °C, stirring activation for 4 h, then 8 g 4-phenyl amino urea was added, then stirring reaction at 40 °C for 18 h, after filtration, the product was washed with water and ethanol, and dried to obtain amino urea modified carbon nanotubes.

[0041] (2) 400 mL water, 580 g aqueous hydroxyl acrylic resin, 1 g amino urea modified carbon nanotubes, 150 g calcium carbonate, 60 g iron red 8811 aqueous color paste, 4 g defoamer BYK-019, 5 g leveling agent BYK-333, 3 g alcohol ester twelve were added to a container, shearing dispersion in a high speed shearing machine to obtain component A; then 192 g isocyanate curing agent was added to component B, and after stirring, an aqueous floor coating was obtained.

[0042] Storage stability test of the A component of the coating (without adding filler calcium carbonate, fumed silica and titanium dioxide, and without adding color paste): the A component was placed at room temperature for 6 months, and the dispersion of the solution was observed.

[0043] The aqueous floor coating was sprayed on the surface of a tinplate substrate, dried and cured at room temperature, and maintained for 7 days to form a paint film. The performance of the paint film was tested according to the method specified in GB / T 22374-2018 standard. The antistatic performance and wear resistance were tested according to the method specified in SJ / T 11294-2018 standard. The test results are shown in Table 1.

[0044] Table 1 Performance of floor coating

[0045] Dispersibility of A component Water resistance (h) Point-to-point resistance / Ω Tensile strength (MPa) Wear resistance (mass loss mg) Example 1 No sediment 276 2.30 x 10 6 ]] 11.8 32.5 Example 2 No sediment 372 3.71 x 10 5 ]] 14.6 13.8 Example 3 No sediment 324 7.29 x 10 4 ]]> 12.0 19.1 Comparative Example 1 No sediment 192 4.72 x 10 10 ]] 7.2 51.6 Comparative Example 2 A large amount of black sediment 192 6.81 x 10 6 ]]> 8.5 46.4 Comparative Example 3 A small amount of black sediment 252 3.97 x 10 6 ]] 10.3 37.0 Comparative Example 4 A large amount of black sediment 204 5.09 x 10 6 ]]> 8.9 40.3

[0046] As can be seen from the above table, the water resistance of the floor coating of Comparative Example 1 is poor, the point-to-point resistance is large, the antistatic performance is not good, and the tensile strength is low, the frictional mass loss is large, and the mechanical strength and wear resistance are not good.

[0047] The acidified carbon nanotubes were added to the A component of the floor coating of Comparative Example 1. Although the carbon nanotubes were acidified and introduced with carboxyl and other oxygen-containing functional groups on the surface, they were still prone to agglomeration and had poor dispersibility, which easily produced sediment in the A component, affecting the storage stability. After curing, the carbon nanotubes were difficult to uniformly disperse in the paint film of the coating, and it was not conducive to the formation of a conductive path to reduce the point-to-point resistance of the paint film, and the antistatic performance was not good. It was also difficult to effectively improve the mechanical properties of the paint film, resulting in poor mechanical strength and wear resistance.

[0048] Each embodiment utilizes the amidation reaction of hexamethylene diamino urea with the carboxyl groups on the surface of acidified carbon nanotubes to introduce a large number of amino urea groups on the surface of the carbon nanotubes. ) and acylhydrazine ( The presence of hydrophilic groups significantly enhances the surface hydrophilicity of carbon nanotubes, allowing for better dispersion in component A of the coating. This results in excellent storage stability and, after curing, good dispersion of carbon nanotubes in the paint film, forming continuous conductive pathways. This improves the antistatic properties and mechanical properties of the paint film. Furthermore, the active amino groups of the hydrazide groups on the carbon nanotube surface react with the isocyanate groups of the isocyanate curing agent, thereby forming chemical bonds between the isocyanate curing agent and the hydroxyl acrylic resin. This strengthens the interfacial bonding strength between the carbon nanotubes and the acrylic resin, increasing the degree of crosslinking within the paint film. This improves the water resistance of the paint film and enhances its mechanical and abrasion resistance, resulting in higher tensile strength and lower frictional mass loss.

[0049] Compared with Example 1, Comparative Examples 2 and 3 used ethylenediamine and 4-phenylaminourea, respectively, to perform amidation reactions on acidified carbon nanotubes. The modification effect on carbon nanotubes was not good, and the antistatic properties, mechanical strength and wear resistance were lower than those of Example 1.

[0050] While the specific embodiments of the present invention have been described above, they are not intended to limit the scope of protection of the present invention. Based on the technical solutions of the present invention, various modifications or variations that can be made by those skilled in the art without creative effort are still within the scope of protection of the present invention.

Claims

1. An aqueous floor coating, characterized in that, The water-based floor paint comprises an A component and a B component; the A component comprises 52-65 parts by weight of a water-based hydroxyl acrylic resin, 0.1-0.6 parts by weight of an amino urea modified carbon nanotube, 5-15 parts by weight of a filler, 5-8 parts by weight of a color paste, 0.4-0.7 parts by weight of an antifoaming agent, 0.3-0.5 parts by weight of a leveling agent, and 0.3-0.5 parts by weight of a film forming aid; The B component comprises 16-23 parts by weight of an isocyanate curing agent. The preparation process of the amino urea modified carbon nanotube is: acidified carbon nanotube, N,N-dicyclohexyl carbodiimide, 4-dimethylamino pyridine are added into N,N-dimethyl formamide, ultrasonic dispersion in nitrogen atmosphere, stirring activation, then adding hexamethylene diamino urea with structural formula , stirring reaction, after filtering, the product is washed with water and ethanol, dried, to obtain the amino urea modified carbon nanotube.

2. The aqueous floor coating of claim 1, wherein, The filler comprises calcium carbonate, titanium white powder or fumed white carbon black.

3. The aqueous floor coating of claim 1, wherein, The film forming aid comprises alcohol ester dodecane, dipropylene glycol methyl ether or dipropylene glycol butyl ether.

4. The aqueous floor coating of claim 1, wherein, The acidified carbon nanotube is used in an amount of 100 parts by weight, N,N-dicyclohexyl carbodiimide is used in an amount of 180-300 parts by weight, 4-dimethylamino pyridine is used in an amount of 160-270 parts by weight, and hexamethylene diamino urea is used in an amount of 400-1500 parts by weight.

5. The aqueous floor coating of claim 1, wherein, The temperature for ultrasonic dispersion is 20-35°C, and the time is 20-40 min.

6. The aqueous floor coating of claim 1, wherein, The temperature for stirring activation is 20-35°C and the time is 2-4 h.

7. The aqueous floor coating of claim 1, wherein, The temperature for stirring reaction is 20-40°C and the time is 18-24 h.

8. A process for the preparation of an aqueous floor coating as claimed in any one of claims 1 to 7, characterized in that, The preparation process comprises the following steps: adding water, a water-based hydroxyl acrylic resin, an amino urea modified carbon nanotube, a filler, a color paste, an antifoaming agent, a leveling agent and a film forming aid into a container, shearing and dispersing to obtain the A component; then adding a B component isocyanate curing agent, and stirring to obtain the water-based floor paint.

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