CN117946579B

CN117946579B - Waterborne polyurethane anti-slip floor coating and preparation method thereof

Info

Publication number: CN117946579B
Application number: CN202410158185.2A
Authority: CN
Inventors: 杜卫国; 杜磊; 戴正辉
Original assignee: Shenzhen Longmai New Materials Technology Co ltd
Current assignee: Shenzhen Longmai New Materials Technology Co ltd
Priority date: 2024-02-04
Filing date: 2024-02-04
Publication date: 2025-01-14
Anticipated expiration: 2044-02-04
Also published as: CN117946579A

Abstract

The invention relates to the technical field of coating compositions, and particularly discloses a waterborne polyurethane anti-slip floor coating and a preparation method thereof. The floor coating comprises, by weight, 10-55 parts of a waterborne polyurethane dispersion, 2-8 parts of a pigment, 0.5-2 parts of trimethylolpropane and 25-40 parts of water, 10-25 parts of a waterborne isocyanate curing agent and 4-10 parts of a film forming auxiliary agent, and 0.5-1.5 parts of a dispersing agent, 0.1-1 part of a defoaming agent, 0.1-1 part of a wetting agent and 0.1-1 part of a leveling agent. The coating prepared by the invention has the advantages of wear resistance, skid resistance, good durability and high environmental friendliness.

Description

Waterborne polyurethane anti-slip floor coating and preparation method thereof

Technical Field

The invention relates to the technical field of coating compositions, in particular to a waterborne polyurethane anti-slip floor coating and a preparation method thereof.

Background

In cold winter or humid, open air environments, people need to perform construction in buildings, roads and places of activity, such as outdoor vehicles or work sites. Operators often construct on the roof, the upper part of the equipment, the ground or the platform, and the skid resistance becomes one of the prominent and important safety problems due to the phenomena of low temperature, icing and the like. Among the various modes of the anti-skid treatment, the anti-skid coating is a relatively convenient and effective mode, can be used on various surface states, can also endow different colors on the surface of an object, and plays a role in beautifying and decorating. The anti-slip coating is a functional material, and has the functions of improving the friction of the surface of an object, forming an anti-slip surface with a high friction coefficient, increasing the friction of the surface of the object, reducing the sliding performance of personnel, vehicles and other objects on the surface of the object, reducing the occurrence of sliding and falling accidents of the personnel and avoiding property loss.

The classification of the anti-slip paint is mostly classified by the kind of resin, including epoxy anti-slip paint, polyurethane anti-slip paint, alkyd anti-slip paint, chlorinated rubber anti-slip paint, and the like. The coating composition is classified into one-component, two-component and multi-component anti-slip coatings. The single-component anti-slip coating has only one component, the film-forming resin and the anti-slip material are packaged in one component, the construction is convenient, but the performance is not good with two components. The two-component anti-skid paint is one of the most commonly used, resin and curing agent are packaged separately, the anti-skid material can be placed in one component of the paint, the two components are mixed together during construction, and then the construction is carried out, and the paint currently comprises epoxy polyamide anti-skid paint, polyurethane anti-skid paint and the like. Most of the prior art uses a two-component epoxy system, and the curing agent is usually amine which can react with epoxy chemically, and the thermosetting system is hard and wear-resistant after reaction, and can be used on steel and concrete. The multicomponent antiskid coating is prepared by packaging film-forming resin, curing agent, antiskid granules and the like separately, mechanically mixing the materials when in use, or immediately spraying the antiskid granules after coating the coating, so that the antiskid granules are firmly embedded in a coating film.

The polyurethane has good anti-skid performance, and the static friction coefficient of the coating film in a dry state, a wet state and an oil wet state is more than 0.45, so that the polyurethane can be used for occasions with high requirements on the anti-skid performance, such as offshore oil production platforms, high-voltage transmission line towers, microwave towers, aircraft carrier decks, and floors of buildings such as parking lots, workshops, hospitals, sidewalks, overpasses, sports grounds and swimming pools, and has good anti-skid effect. The anti-slip particles are important components in the anti-slip coating, and can be divided into two types according to the materials of the anti-slip particles, namely, synthetic organic materials such as polyvinyl chloride, polyethylene, polypropylene resin particles, polyurethane resin particles, rubber particles and other inert high polymer materials, and inorganic materials such as silica powder, quartz sand, glass flakes, silicon carbide, crystalline alumina, mica and the like.

Chinese patent 202010587275.5 discloses an antistatic wear-resistant polyurethane floor coating and a preparation method thereof. The antistatic wear-resistant polyurethane floor coating consists of a component A, a component B and a component C according to the mass ratio of (2-3) to (4-5), wherein the component A consists of a polymeric polyol, a carbon nano tube, a dispersing agent, a defoaming agent, a leveling agent, a wetting agent, a chain extender, a catalyst and color paste, the component B consists of a plant polyol, hydroxyl-terminated polysiloxane and aliphatic isocyanate, and the component C is wear-resistant aggregate. The polyurethane floor coating disclosed by the invention has small construction thickness, and the formed floor has the performances of permanent antistatic performance, super wear resistance, scratch resistance, skid resistance, chemical corrosion resistance and the like, and can be applied to industrial plants with high load and high traffic flow.

Chinese patent 201811525843.8 discloses a polyurethane texture anti-slip floor coating which comprises, by weight, 15-25 parts of 1, 6-hexamethylene diisocyanate, 15-25 parts of methyl 2, 6-diisocyanato caproate, 30-45 parts of butanediol, 10-20 parts of butyl acetate, 8-10 parts of organic bentonite, 8-10 parts of kaolin, 1-5 parts of color paste, 0.1-0.5 part of EFKA-2040, 0.1-0.5 part of EFKA-3650 and 0.1-0.5 part of EFKA-4310, wherein the B comprises, by weight, 30-40 parts of hydroxyl-containing fluorine resin, 0.5-1 part of zinc naphthenate and 0.5-1 part of lead naphthenate, and the weight ratio of the A component to the B component is 4:1. The polyurethane texture anti-slip floor coating prepared by the invention is a novel floor coating, and is green and environment-friendly, excellent in weather resistance, good in wear resistance, strong in anti-slip property and good in chemical resistance.

The anti-slip granules are indispensable in anti-slip paint, wherein inorganic fillers such as SiC, al ₂O₃ and the like have high hardness, good wear resistance and high temperature resistance, so the anti-slip granules are widely applied in the prior art. However, the inorganic filler has poor compatibility with the organic resin, and the dispersion stability of SiC in the aqueous coating material is also poor. This causes that it is extremely easy to settle in the paint, thereby affecting the uniformity of the paint and the adhesive force of the paint film, and the phenomenon of excessively serious settlement causes insufficient protrusion of the surface of the paint film and reduced anti-skid performance.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the present invention is to solve the technical problem of a waterborne polyurethane anti-skid floor coating and a preparation method thereof

SiC has excellent properties of large hardness, high strength, high modulus, high temperature resistance, corrosion resistance, and the like, and has been widely used as one of high-performance reinforcing fillers for advanced composite materials. However, it belongs to an inorganic material, has poor compatibility with a coating matrix resin, cannot truly play a role in skid resistance and toughness improvement, even causes deterioration of coating properties, and is very easy to form hydrogen bonds to generate agglomeration although a large number of hydroxyl groups exist on the surface due to small particle size and high surface energy, further reduces dispersibility in the coating, and is therefore necessary for modification of SiC. According to the invention, the inventor firstly conducts grafting on SiC and azodiisobutyronitrile through free radical initiation, hydrophilic groups are introduced into the surface of the SiC and then hydrophobic long chains are introduced through reaction with NaH and 1-bromohexadecane, so that amphiphilic SiC is obtained, when the amphiphilic SiC is dispersed in an aqueous solution, hydrophilic groups can well adsorb water molecules, steric hindrance is formed between long alkyl chains and the long alkyl chains, agglomeration among the SiC is well reduced, and therefore dispersibility of the SiC in the aqueous solution is improved.

The invention provides an aqueous polyurethane anti-slip floor coating which comprises, by weight, 10-55 parts of an aqueous polyurethane dispersion, 2-8 parts of a pigment, 0.5-2 parts of trimethylolpropane and 25-40 parts of water, 10-25 parts of an aqueous isocyanate curing agent and 4-10 parts of a film forming auxiliary agent, and component C which comprises, by weight, 2-8 parts of modified SiC, 0.5-1.5 parts of a dispersing agent, 0.1-1 part of a defoaming agent, 0.1-1 part of a wetting agent and 0.1-1 part of a leveling agent.

Further, the pigment is one of carbon black, titanium dioxide, iron oxide red, iron oxide yellow, phthalocyanine green and phthalocyanine blue.

Further, the film forming auxiliary agent is one or a mixture of more of dipropylene glycol butyl ether, propylene glycol methyl ether and dodecanol ester.

Further, the dispersing agent is one or more of Disponer W-18, disponer W-19 and Disponer W-77.

Further, the defoamer is NXZ type defoamer.

Further, the wetting agent is one or a mixture of more of Tego245, tego277 and Tego 4100.

Further, the leveling agent is one or a mixture of more of BYK-3720, BYK-333 and BYK-6410.

The preparation method of the modified SiC comprises the following steps:

Adding 5-15 parts by weight of SiC into 15-50 parts by weight of toluene, stirring and dispersing uniformly to obtain a solution A, adding 10-25 parts by weight of azodiisobutyronitrile into 15-50 parts by weight of toluene, stirring uniformly to obtain a solution B, adding the solution B into the solution A under a nitrogen atmosphere, continuously heating to 60-90 ℃ under the nitrogen atmosphere after the addition is finished, stirring for 2-8 hours, cooling to room temperature after the reaction is finished, filtering, washing residues with toluene, drying to constant weight, adding the residues into a mixed solution (water: concentrated sulfuric acid: acetic acid=1:1) with 60-80 times of volume, heating to 100-130 ℃ and stirring for 16-28 hours, cooling to room temperature after the reaction is finished, adding water for dilution, filtering, washing a filter cake with water, and drying to obtain grafted SiC;

And X2, weighing 1.0-2.5 parts by weight of NaH, rinsing by normal hexane, adding the mixture into 45-100 parts by weight of 1, 4-dioxane to obtain a mixed solution, weighing 4-10 parts by weight of grafted SiC in the step X1, adding 0.8-1.5 parts by weight of 1-bromohexadecane into the mixed solution, stirring and mixing uniformly, heating to 90-120 ℃, stirring for 20-30 hours, cooling to room temperature after the reaction is finished, quenching by adding ice water, filtering, and drying residues to obtain the modified SiC.

A preparation method of an aqueous polyurethane anti-slip floor coating comprises the following steps:

Weighing the raw materials in the component A according to the formula amount, uniformly stirring at 1000-2000 rpm, adding the raw materials in the component B, uniformly mixing at 500-1000 rpm, finally adding the component C, uniformly stirring at 300-850 rpm, and finally filtering through 120-mesh filter cloth to obtain the anti-slip floor coating.

The invention has the beneficial effects that:

1. According to the invention, through grafting and modifying SiC, hydrophilic groups and hydrophobic long chains are simultaneously introduced into the surface of the SiC, so that amphiphilic SiC is obtained, when the amphiphilic SiC is dispersed in an aqueous solution, one side of a hydrophilic group can well adsorb water molecules, and the long alkyl chains form steric hindrance with each other, so that agglomeration among SiC is well reduced, and therefore, the dispersibility of the SiC in the aqueous solution is improved, and the obtained aqueous coating is more uniform;

2. The modified SiC is added into the anti-skid floor coating, so that the anti-skid property and the wear resistance of the coating can be improved well, and the prepared coating is good in durability and high in environmental friendliness.

Detailed Description

The aqueous polyurethane dispersion is Leasys 3900:3900A, a company of Shizhong Ming chemical Co.

The model number of the aqueous isocyanate curing agent is Imprafix 2794XP, which is a fine strength supplier.

SiC, particle size 50nm.

NaH,60wt% was sealed in oil.

Concentrated sulfuric acid, 98wt%.

Comparative example 1

The preparation method comprises the steps of weighing water-based polyurethane dispersoid Leasys-3900A 4.5kg, titanium dioxide 0.5kg, trimethylolpropane 0.1kg and water 4kg, stirring and mixing uniformly at 1500rpm, adding water-based isocyanate curing agent Imprafix 2794XP 1.5kg and dipropylene glycol butyl ether 0.4kg, stirring and mixing uniformly at 850rpm, adding SiC 0.5kg, disponer W-18.1 kg, NZX defoamer 0.05kg, tego 245.1 kg and BYK-333.1 kg, mixing uniformly at 450rpm, and filtering through 120-mesh filter cloth to obtain the floor coating.

Example 1

The preparation method comprises the steps of weighing water-based polyurethane dispersoid Leasys-3900A 4.5kg, titanium dioxide 0.5kg, trimethylolpropane 0.1kg and water 4kg, stirring and mixing uniformly at 1500rpm, adding water-based isocyanate curing agent Imprafix 2794XP 1.5kg and dipropylene glycol butyl ether 0.4kg, stirring and mixing uniformly at 850rpm, adding modified SiC 0.5kg, disponer W-18.1 kg, NZX defoamer 0.05kg, tego 245.1 kg and BYK-333.1 kg, mixing uniformly at 450rpm, and filtering through 120-mesh filter cloth to obtain the floor coating.

The preparation method of the modified SiC comprises the following steps:

Adding solution B into solution A under nitrogen atmosphere, continuously heating to 80 ℃ under nitrogen atmosphere after the addition is finished, stirring for 6 hours, cooling to room temperature, filtering, washing residues with toluene, drying to constant weight, adding into 60 volumes of mixed solution (water: concentrated sulfuric acid: acetic acid volume ratio=1:1:1), heating to 110 ℃ and stirring for 22 hours, cooling to room temperature, diluting with water, filtering, and drying filter cakes for 6 hours after water washing to obtain grafted SiC;

And X2, weighing 150g of NaH, rinsing with normal hexane, adding the NaH into 6L of 1, 4-dioxane to obtain a mixed solution, weighing 0.8kg of grafted SiC in the step X1, adding 0.1kg of 1-bromohexadecane after stirring and mixing uniformly, heating to 105 ℃, stirring for 24 hours, cooling to room temperature after the reaction is finished, adding ice water for quenching, filtering, and drying residues at 80 ℃ for 8 hours to obtain modified SiC.

Example 2

The preparation method comprises the steps of weighing water-based polyurethane dispersoid Leasys-3900A 4.5kg, titanium dioxide 0.5kg, trimethylolpropane 0.1kg and water 4kg, stirring and mixing uniformly at 1500rpm, adding water-based isocyanate curing agent Imprafix 2794XP 1.5kg and dipropylene glycol butyl ether 0.4kg, stirring and mixing uniformly at 850rpm, adding modified SiC 0.5kg, disponer W-18.1 kg, NZX defoamer 0.01kg, tego 245.1 kg and BYK-333.1 kg, mixing uniformly at 450rpm, and filtering through 120-mesh filter cloth to obtain the floor coating.

The preparation method of the modified SiC comprises the following steps:

Example 3

The preparation method comprises the steps of weighing water-based polyurethane dispersoid Leasys-3900A 4.5kg, titanium dioxide 0.8kg, trimethylolpropane 0.1kg and water 4kg, stirring and mixing uniformly at 1500rpm, adding water-based isocyanate curing agent Imprafix 2794XP 1.5kg and dipropylene glycol butyl ether 0.4kg, stirring and mixing uniformly at 850rpm, adding modified SiC 0.5kg, disponer W-18.1 kg, NZX defoamer 0.05kg, tego 245.1 kg and BYK-333.1 kg, mixing uniformly at 450rpm, and filtering through 120-mesh filter cloth to obtain the floor coating.

The preparation method of the modified SiC comprises the following steps:

Example 4

The preparation method comprises the steps of weighing water-based polyurethane dispersoid Leasys-3900A 4.5kg, titanium dioxide 0.5kg, trimethylolpropane 0.1kg and water 4kg, stirring and mixing uniformly at 1500rpm, adding water-based isocyanate curing agent Imprafix 2794XP 1.5kg and dipropylene glycol butyl ether 0.4kg, stirring and mixing uniformly at 850rpm, adding modified SiC 0.5kg, disponer W-18.1 kg, NZX defoamer 0.05kg, tego 245.1 kg and BYK-333.05 kg, mixing uniformly at 450rpm, and filtering through 120-mesh filter cloth to obtain the floor coating.

The preparation method of the modified SiC comprises the following steps:

Test example 1

The floor coating prepared in the comparative example and the example is subjected to a series of performance tests such as skid resistance, wear resistance, water resistance, chemical resistance and the like, the test method is carried out according to GB/T22374-2018 floor coating material, and the specific test results are shown in Table 1.

Table 1 test results table of anti-slip floor coating

As can be seen from the test results of the anti-slip floor coating of example 1 and comparative example 1, the addition of the modified SiC improves the anti-slip and wear resistance of the coating to a certain extent, probably because although the high hardness of SiC itself brings a certain wear-resistant anti-slip effect to the coating, siC is not well dispersed in an aqueous solution due to its nature and is extremely easy to agglomerate, which also causes SiC to be extremely easy to settle in the coating, so the flatness of the surface of comparative example 1 is far less than that of example 1, while the improvement of the anti-slip and wear resistance of example 1 is probably due to the fact that hydrophilic groups and hydrophobic long chains are simultaneously introduced on the surface of SiC by grafting and modifying the SiC, so that amphiphilic SiC is obtained, the hydrophilic groups can be well adsorbed on one side of the hydrophilic groups when the SiC is dispersed in an aqueous solution, and the long alkyl chains form steric hindrance with each other, so that agglomeration between SiC is well reduced, and the dispersibility in an aqueous solution is improved, and the performance of the obtained aqueous coating is also greatly improved. The difference between the properties of example 1 and example 3 is that the viscosity is increased due to the deterioration of the dispersibility of the paint when the amount of titanium pigment is too large, the flatness of the surface of the coating is deteriorated, and the abrasion-resistant and anti-slip properties are affected, while the difference between example 1 and example 2 is that the surface of the paint is easily formed into holes when the amount of the antifoaming agent is too small, which may lead to the uneven surface of the coating, and thus the abrasion resistance is poor and the impact resistance is not strong, while the difference between example 1 and example 4 is that shrinkage holes occur when the amount of the leveling agent is too small, and the coating properties are affected.

The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.

Claims

1. A waterborne polyurethane anti-skid floor coating, characterized in that it comprises component A, component B and component C; wherein component A comprises the following raw materials in parts by weight: 10-55 parts of waterborne polyurethane dispersion, 2-8 parts of pigment, 0.5-2 parts of trihydroxypropane, and 25-40 parts of water; component B comprises the following raw materials in parts by weight: 10-25 parts of waterborne isocyanate curing agent, 4-10 parts of film-forming aid; component C comprises the following raw materials in parts by weight: 2-8 parts of modified SiC, 0.5-1.5 parts of dispersant, 0.1-1 parts of defoamer, 0.1-1 parts of wetting agent, and 0.1-1 parts of leveling agent;

The preparation method of the modified SiC comprises the following steps:

X1 weighs 5-15 parts by weight of SiC and disperses it in 15-50 parts by weight of toluene, stirs and disperses it evenly to obtain solution A; weighs 10-25 parts by weight of azobisisobutyronitrile and adds it to 15-50 parts by weight of toluene, stirs and disperses it evenly to obtain solution B; adds solution B to solution A under a nitrogen atmosphere, and continues to heat to 60-90°C under a nitrogen atmosphere after the addition is complete, stirs for 2-8 hours, and after the reaction is completed, cools to room temperature, filters, washes the residue with toluene, dries to constant weight, and adds it to a 60-80 times volume mixed solution, in which the volume ratio of water: concentrated sulfuric acid: acetic acid is 1:1:1, heats to 100-130°C and stirs for 16-28 hours, and after the reaction is completed, cools to room temperature, dilutes with water, filters, and washes the filter cake with water and then dries it to obtain grafted SiC;

X2: Weigh 1.0-2.5 parts by weight of NaH, rinse with n-hexane, and add to 45-100 parts by weight of 1,4-dioxane to obtain a mixed solution. Weigh 4-10 parts by weight of the grafted SiC in step X1, add to the mixed solution, stir and mix evenly, then add 0.8-1.5 parts by weight of 1-bromohexadecane, heat to 90-120°C and stir for 20-30 hours. After the reaction is completed, cool to room temperature, add ice water to quench, filter, and dry the residue to obtain modified SiC.

2. The coating according to claim 1, characterized in that the pigment is one of carbon black, titanium dioxide, red iron oxide, yellow iron oxide, phthalocyanine green and phthalocyanine blue.

3. The coating according to claim 1, characterized in that the film-forming aid is a mixture of one or more of dipropylene glycol butyl ether, propylene glycol methyl ether and dodecyl alcohol ester.

4. The coating according to claim 1, wherein the dispersant is a mixture of one or more of Disponer W-18, Disponer W-19 and Disponer W-77.

5. The coating according to claim 1, wherein the defoamer is a NXZ type defoamer.

6. The coating according to claim 1, characterized in that the wetting agent is a mixture of one or more of Tego245, Tego277, and Tego4100.

7. The coating according to claim 1, characterized in that the leveling agent is a mixture of one or more of BYK-3720, BYK-333, and BYK-6410.

8. A method for preparing the coating according to any one of claims 1 to 7, characterized in that it comprises the following steps:

Weigh the raw materials in component A according to the formula, stir evenly at 1000-2000 rpm, then add the raw materials in component B, mix evenly at 500-1000 rpm, finally add component C, stir and mix evenly at 300-850 rpm, and finally filter through 120-mesh filter cloth to obtain the anti-slip floor coating.