Antifouling paint for ceramic tile surface and preparation method thereof

Abstract

The invention discloses an antifouling paint for ceramic tile surfaces and a preparation method thereof, and belongs to the technical field of paints.The antifouling paint is prepared from, by weight, 30-50 parts of waterborne acrylic emulsion, 10-20 parts of antifouling filler, 0.2-0.5 part of defoaming agent, 0.1-0.3 part of flatting agent and 50-80 parts of deionized water; the preparation method comprises the following steps: mixing the water-based acrylic emulsion and the deionized water, stirring at a constant speed for 10 minutes, sequentially adding the defoaming agent, the flatting agent and the anti-fouling filler, and uniformly stirring to obtain the anti-fouling paint for the ceramic tile surface. The perfluoroalkyl structure on the anti-fouling filler structure can endow the coating with excellent hydrophobic and anti-fouling performance, the introduced cationic quaternary ammonium salt structure can kill bacteria attached to the surface of the coating, and the introduced fluorine element is cooperated to improve the anti-fouling effect.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to an antifouling coating for a tile surface and a preparation method thereof. Background Art

[0002] Ceramic tiles are plate-shaped or block-shaped ceramic products made of clay and other inorganic non-metallic raw materials through molding, sintering and other processes. They have the advantages of good anti-freeze and anti-fouling, low water absorption, good acid and alkali resistance, bright and gorgeous, easy to maintain, and long service life. They are favored by more and more consumers and are widely used in bathrooms, kitchens, balconies, exterior wall decoration, etc. They are usually formed by dry pressing, extrusion or other molding methods at room temperature, then dried and fired at a certain temperature.

[0003] Commercially available decorative materials such as polished tiles and porcelain tiles are popular for their wear resistance, corrosion resistance, high strength, smooth surface, rich and lifelike patterns and colors. However, many tiny pores are formed on their surfaces during the firing process. Due to surface adsorption and capillary action, the surface of the tiles is easily contaminated and difficult to clean, which seriously affects the cleanliness and appearance of the tiles. This requires anti-fouling coatings to be used. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an antifouling coating for a tile surface and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: An antifouling coating for a tile surface comprises the following raw materials in parts by weight: 30-50 parts of water-based acrylic emulsion, 10-20 parts of antifouling filler, 0.2-0.5 parts of defoaming agent, 0.1-0.3 parts of leveling agent, and 50-80 parts of deionized water; The anti-fouling filler is prepared by the following steps: Step S1, adding perfluorooctanol, mercaptopropionic acid and methanesulfonic acid to toluene in sequence, heating to 100-110° C. under a nitrogen atmosphere, keeping the temperature and reacting for 6-8 hours, and after the reaction, washing the reaction product with a saturated sodium bicarbonate aqueous solution for 2-3 times to obtain an intermediate 1, wherein the amount ratio of perfluorooctanol, mercaptopropionic acid, methanesulfonic acid and toluene is controlled to be 1-2 g: 0.2-0.5 g: 0.02-0.04 g: 5-8 mL; In step S1, perfluorooctanol and mercaptopropionic acid undergo an esterification reaction to prepare an intermediate 1, the structure of which contains both a perfluoroalkyl structure and a mercapto group.

[0006] Step S2, the intermediate 1 and diallyl dimethyl ammonium chloride were added to tetrahydrofuran, stirred at a uniform speed and benzoin dimethyl ether was added, placed under ultraviolet light and stirred for 30min, then heated to 50°C, the solvent was removed by vacuum rotary evaporation to obtain intermediate 2, the amount of intermediate 1, diallyl dimethyl ammonium chloride, benzoin dimethyl ether and tetrahydrofuran was controlled to be 0.2-0.4mmol: 0.2-0.4mmol: 0.3-0.5mg: 3-5mL; In step S2, benzoin dimethyl ether is used as a photoinitiator and tetrahydrofuran is used as a solvent. The thiol group on the intermediate 1 reacts with the carbon-carbon double bond on diallyldimethylammonium chloride to prepare an intermediate 2, which contains a perfluoroalkyl structure, a quaternary ammonium salt structure, and a carbon-carbon double bond that does not participate in the reaction; Step S3, adding the graphene oxide prepared by Hummer's to a 15% volume fraction ethanol aqueous solution, adjusting the system pH to 4-5, adding γ-methacryloxypropyltrimethoxysilane, stirring at a uniform speed and reacting for 2-4 hours, filtering and washing after the reaction to obtain modified graphene oxide, and controlling the weight ratio of graphene oxide, γ-methacryloxypropyltrimethoxysilane and ethanol aqueous solution to be 1-2:0.3-0.5:10; Step S4, adding the prepared modified graphene oxide and intermediate 2 to toluene, adding 4-dimethylaminopyridine, stirring at a uniform speed and heating to 100-110° C., keeping warm and reacting for 4-6 hours, and obtaining an anti-fouling filler after the reaction is completed, controlling the weight ratio of the modified graphene oxide, intermediate 2 and toluene to be 1-2:0.3-0.5:10-12, and the amount of 4-dimethylaminopyridine is 1-2% of the total weight of the modified graphene oxide and intermediate 2.

[0007] In step S3, the graphene oxide is first modified by a silane coupling agent γ-methacryloxypropyltrimethoxysilane, and then a carbon-carbon double bond is connected to the surface of the graphene oxide. Then, in step S4, under the catalysis of 4-dimethylaminopyridine, the carbon-carbon double bond on the modified graphene oxide is polymerized with the carbon-carbon double bond on the intermediate 2, and then the intermediate 2 is grafted on the surface of the graphene oxide. The perfluoroalkyl structure on the structure of the intermediate 2 can give the coating excellent hydrophobic and anti-fouling properties, and the introduced cationic quaternary ammonium salt structure can kill bacteria attached to the surface of the coating, and the fluorine element introduced synergistically improves the anti-fouling effect.

[0008] Furthermore, the defoaming agent is defoaming agent BYK066N (BYK, Germany), and the leveling agent is silicone polyether copolymer (DOWSIL 57).

[0009] A method for preparing an antifouling coating for a tile surface comprises the following steps: The aqueous acrylic emulsion and deionized water are mixed and stirred at a uniform speed for 5-10 minutes, and then a defoamer, a leveling agent and an antifouling filler are added in sequence and stirred evenly to prepare an antifouling coating for the surface of ceramic tiles.

[0010] Beneficial effects of the present invention: The invention prepares an antifouling coating for a tile surface. The water-based acrylic emulsion is used as a matrix. The antifouling filler is added to give the coating excellent antifouling performance. In the preparation process, the antifouling filler first undergoes an esterification reaction with perfluorooctanol and mercaptopropionic acid to prepare an intermediate 1. Then, the mercapto group on the intermediate 1 reacts with the carbon-carbon double bond on diallyldimethylammonium chloride to prepare an intermediate 2. Then, the graphene oxide is modified by a silane coupling agent gamma-methacryloxypropyltrimethoxysilane, and the carbon-carbon double bond is connected to the surface of the graphene oxide. Then, under the catalysis of 4-dimethylaminopyridine, the carbon-carbon double bond on the modified graphene oxide is polymerized with the carbon-carbon double bond on the intermediate 2, and then the intermediate 2 is grafted on the surface of the graphene oxide. The perfluoroalkyl structure on the structure of the intermediate 2 can give the coating excellent hydrophobic antifouling performance, and the introduced cationic quaternary ammonium salt structure can kill bacteria attached to the surface of the coating, and the antifouling effect is improved in coordination with the introduced fluorine element. DETAILED DESCRIPTION

[0011] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0012] Example 1: An antifouling coating for a tile surface comprises the following raw materials in parts by weight: 30 parts of water-based acrylic emulsion, 10 parts of antifouling filler, 0.2 parts of defoaming agent, 0.1 parts of leveling agent, and 50 parts of deionized water; The method for preparing the antifouling coating for the surface of ceramic tiles comprises the following steps: The aqueous acrylic emulsion and deionized water were mixed and stirred at a uniform speed for 5 minutes, and then a defoamer, a leveling agent and an antifouling filler were added in sequence and stirred evenly to prepare an antifouling coating for the surface of tiles.

[0013] The anti-fouling filler is prepared by the following steps: Step S1, perfluorooctanol (647-42-7), mercaptopropionic acid and methanesulfonic acid are added to toluene in sequence, the temperature is raised to 100°C under a nitrogen atmosphere, the temperature is kept and the reaction is carried out for 6 hours, and after the reaction is completed, the reaction product is washed twice with a saturated sodium bicarbonate aqueous solution to obtain an intermediate 1, and the amount ratio of perfluorooctanol, mercaptopropionic acid, methanesulfonic acid and toluene is controlled to be 1g:0.2g:0.02g:5mL; Step S2, the intermediate 1 and diallyl dimethyl ammonium chloride were added to tetrahydrofuran, stirred at a uniform speed and benzoin dimethyl ether was added, placed under ultraviolet light and stirred for 30min, then heated to 50°C, the solvent was removed by vacuum rotary evaporation to obtain intermediate 2, the amount of intermediate 1, diallyl dimethyl ammonium chloride, benzoin dimethyl ether and tetrahydrofuran was controlled to be 0.2mmol: 0.2mmol: 0.3mg: 3mL; Step S3, adding the graphene oxide prepared by Hummer's to a 15% volume fraction ethanol aqueous solution, adjusting the system pH to 4, adding γ-methacryloxypropyltrimethoxysilane, stirring at a uniform speed and reacting for 2 hours, filtering and washing after the reaction to obtain modified graphene oxide, and controlling the weight ratio of graphene oxide, γ-methacryloxypropyltrimethoxysilane and ethanol aqueous solution to be 1:0.3:10; Step S4, adding the prepared modified graphene oxide and intermediate 2 to toluene, adding 4-dimethylaminopyridine, stirring at a uniform speed and heating to 100°C, keeping warm and reacting for 4 hours, and obtaining an anti-fouling filler after the reaction is completed, controlling the weight ratio of the modified graphene oxide, intermediate 2 and toluene to be 1:0.3:10, and the amount of 4-dimethylaminopyridine is 1% of the total weight of the modified graphene oxide and intermediate 2.

[0014] The water-based acrylic emulsion is BASF Joncryl 1980, the defoamer is defoamer BYK066N (Bick, Germany), and the leveling agent is silicone polyether copolymer (DOWSIL 57).

[0015] Example 2: An antifouling coating for a tile surface comprises the following raw materials in parts by weight: 40 parts of water-based acrylic emulsion, 15 parts of antifouling filler, 0.3 parts of defoaming agent, 0.2 parts of leveling agent, and 60 parts of deionized water; The method for preparing the antifouling coating for the surface of ceramic tiles comprises the following steps: The aqueous acrylic emulsion and deionized water are mixed and stirred at a uniform speed for 5-10 minutes, and then a defoamer, a leveling agent and an antifouling filler are added in sequence and stirred evenly to prepare an antifouling coating for the surface of ceramic tiles.

[0016] The anti-fouling filler is prepared by the following steps: Step S1, perfluorooctanol (647-42-7), mercaptopropionic acid and methanesulfonic acid are added to toluene in sequence, the temperature is raised to 100°C under a nitrogen atmosphere, the temperature is kept and the reaction is carried out for 6 hours, and after the reaction is completed, the reaction product is washed twice with a saturated sodium bicarbonate aqueous solution to obtain an intermediate 1, and the amount ratio of perfluorooctanol, mercaptopropionic acid, methanesulfonic acid and toluene is controlled to be 1.5g:0.3g:0.03g:6mL; Step S2, the intermediate 1 and diallyl dimethyl ammonium chloride were added to tetrahydrofuran, stirred at a uniform speed and benzoin dimethyl ether was added, placed under ultraviolet light and stirred for 30min, then heated to 50°C, the solvent was removed by vacuum rotary evaporation to obtain intermediate 2, the amount of intermediate 1, diallyl dimethyl ammonium chloride, benzoin dimethyl ether and tetrahydrofuran was controlled to be 0.3mmol: 0.3mmol: 0.4mg: 4mL; Step S3, adding the graphene oxide prepared by Hummer's to a 15% volume fraction ethanol aqueous solution, adjusting the system pH to 4-5, adding γ-methacryloxypropyltrimethoxysilane, stirring at a uniform speed and reacting for 2-4 hours, filtering and washing after the reaction to obtain modified graphene oxide, and controlling the weight ratio of graphene oxide, γ-methacryloxypropyltrimethoxysilane and ethanol aqueous solution to be 1.5:0.4:10; Step S4, adding the prepared modified graphene oxide and intermediate 2 to toluene, adding 4-dimethylaminopyridine, stirring at a uniform speed and heating to 100°C, keeping warm and reacting for 5 hours, and obtaining an anti-fouling filler after the reaction is completed, controlling the weight ratio of the modified graphene oxide, intermediate 2 and toluene to be 1.5:0.4:12, and the amount of 4-dimethylaminopyridine is 2% of the total weight of the modified graphene oxide and intermediate 2.

[0017] The water-based acrylic emulsion is BASF Joncryl 1980, the defoamer is defoamer BYK066N (Bick, Germany), and the leveling agent is silicone polyether copolymer (DOWSIL 57).

[0018] Example 3: An antifouling coating for a tile surface comprises the following raw materials in parts by weight: 45 parts of an aqueous acrylic emulsion, 18 parts of an antifouling filler, 0.4 parts of a defoaming agent, 0.2 parts of a leveling agent, and 80 parts of deionized water; The method for preparing the antifouling coating for the surface of ceramic tiles comprises the following steps: The aqueous acrylic emulsion and deionized water were mixed and stirred at a uniform speed for 10 minutes, and then a defoamer, a leveling agent and an antifouling filler were added in sequence and stirred evenly to prepare an antifouling coating for the surface of ceramic tiles.

[0019] The anti-fouling filler is prepared by the following steps: Step S1, perfluorooctanol (647-42-7), mercaptopropionic acid and methanesulfonic acid are added to toluene in sequence, the temperature is raised to 110° C. under a nitrogen atmosphere, the temperature is kept and the reaction is performed for 8 hours, and after the reaction is completed, the reaction product is washed three times with a saturated sodium bicarbonate aqueous solution to obtain an intermediate 1, and the amount ratio of perfluorooctanol, mercaptopropionic acid, methanesulfonic acid and toluene is controlled to be 2g:0.4g:0.04g:8mL; Step S2, the intermediate 1 and diallyl dimethyl ammonium chloride were added to tetrahydrofuran, stirred at a uniform speed and benzoin dimethyl ether was added, placed under ultraviolet light and stirred for 30min, then heated to 50°C, the solvent was removed by vacuum rotary evaporation to obtain intermediate 2, the amount of intermediate 1, diallyl dimethyl ammonium chloride, benzoin dimethyl ether and tetrahydrofuran was controlled to be 0.4mmol: 0.4mmol: 0.4mg: 4mL; Step S3, adding the graphene oxide prepared by Hummer's to a 15% volume fraction ethanol aqueous solution, adjusting the system pH to 4-5, adding γ-methacryloxypropyltrimethoxysilane, stirring at a uniform speed and reacting for 2-4 hours, filtering and washing after the reaction to obtain modified graphene oxide, and controlling the weight ratio of graphene oxide, γ-methacryloxypropyltrimethoxysilane and ethanol aqueous solution to be 1.8:0.4:10; Step S4, adding the prepared modified graphene oxide and intermediate 2 to toluene, adding 4-dimethylaminopyridine, stirring at a uniform speed and heating to 110°C, keeping warm and reacting for 6 hours, and obtaining an anti-fouling filler after the reaction is completed, controlling the weight ratio of the modified graphene oxide, intermediate 2 and toluene to be 1.8:0.4:12, and the amount of 4-dimethylaminopyridine is 2% of the total weight of the modified graphene oxide and intermediate 2.

[0020] The water-based acrylic emulsion is BASF Joncryl 1980, the defoamer is defoamer BYK066N (Bick, Germany), and the leveling agent is silicone polyether copolymer (DOWSIL 57).

[0021] Example 4: An antifouling coating for a tile surface comprises the following raw materials in parts by weight: 50 parts of water-based acrylic emulsion, 20 parts of antifouling filler, 0.5 parts of defoaming agent, 0.3 parts of leveling agent, and 80 parts of deionized water; The method for preparing the antifouling coating for the surface of ceramic tiles comprises the following steps: The aqueous acrylic emulsion and deionized water were mixed and stirred at a uniform speed for 10 minutes, and then a defoamer, a leveling agent and an antifouling filler were added in sequence and stirred evenly to prepare an antifouling coating for the surface of ceramic tiles.

[0022] The anti-fouling filler is prepared by the following steps: Step S1, adding perfluorooctanol (647-42-7), mercaptopropionic acid and methanesulfonic acid to toluene in sequence, heating to 110°C under a nitrogen atmosphere, keeping the temperature and reacting for 8 hours, and after the reaction, washing the reaction product with a saturated sodium bicarbonate aqueous solution for 3 times to obtain an intermediate 1, wherein the amount ratio of perfluorooctanol, mercaptopropionic acid, methanesulfonic acid and toluene is controlled to be 2g:0.5g:0.04g:8mL; Step S2, the intermediate 1 and diallyl dimethyl ammonium chloride were added to tetrahydrofuran, stirred at a uniform speed and benzoin dimethyl ether was added, placed under ultraviolet light and stirred for 30min, then heated to 50°C, the solvent was removed by vacuum rotary evaporation to obtain intermediate 2, the amount of intermediate 1, diallyl dimethyl ammonium chloride, benzoin dimethyl ether and tetrahydrofuran was controlled to be 0.4mmol: 0.4mmol: 0.5mg: 5mL; Step S3, adding the graphene oxide prepared by Hummer's to a 15% volume fraction ethanol aqueous solution, adjusting the system pH to 5, adding γ-methacryloxypropyltrimethoxysilane, stirring at a uniform speed and reacting for 4 hours, filtering and washing after the reaction to obtain modified graphene oxide, and controlling the weight ratio of graphene oxide, γ-methacryloxypropyltrimethoxysilane and ethanol aqueous solution to be 2:0.5:10; Step S4, adding the prepared modified graphene oxide and intermediate 2 to toluene, adding 4-dimethylaminopyridine, stirring at a uniform speed and heating to 110°C, keeping warm and reacting for 6 hours, and obtaining an anti-fouling filler after the reaction is completed, controlling the weight ratio of the modified graphene oxide, intermediate 2 and toluene to be 2:0.5:12, and the amount of 4-dimethylaminopyridine is 2% of the total weight of the modified graphene oxide and intermediate 2.

[0023] The water-based acrylic emulsion is BASF Joncryl 1980, the defoamer is defoamer BYK066N (Bick, Germany), and the leveling agent is silicone polyether copolymer (DOWSIL 57).

[0024] Comparative Example 1: Compared with Example 1, this comparative example uses graphene oxide instead of the anti-fouling filler.

[0025] Comparative Example 2: This comparative example is a water-based acrylic paint produced by a certain company on the market.

[0026] The properties of the coatings prepared in Examples 1-4 and Comparative Examples 1-2 were tested, and the results are shown in Table 1 below: Test method: Referring to the test method disclosed in GB / T 5370-2007 "Shallow sea immersion test method for antifouling paint samples", the coatings prepared in Examples 1-4 and Comparative Examples 1-2 were coated on the surface of tiles (50mmX50mmX3mm), and then placed in a sea area with a seawater tidal current of 2m / s for shallow sea immersion test. The test period was 12 months.

[0027] Table 1 It can be seen from Table 1 above that the coatings prepared in Examples 1-4 of the present invention have excellent water resistance and anti-fouling properties.

[0028] The above contents are merely examples and explanations of the concept of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An antifouling coating for a tile surface, characterized in that: The method comprises the following raw materials in parts by weight: 30-50 parts of water-based acrylic emulsion, 10-20 parts of antifouling filler, 0.2-0.5 parts of defoaming agent, 0.1-0.3 parts of leveling agent, and 50-80 parts of deionized water; The anti-fouling filler is prepared by the following steps: Step S1, adding perfluorooctanol, mercaptopropionic acid and methanesulfonic acid to toluene in sequence, heating to 100-110° C. under a nitrogen atmosphere, keeping the temperature and reacting for 6-8 hours, and after the reaction, washing the reaction product with a saturated sodium bicarbonate aqueous solution for 2-3 times to obtain an intermediate 1; Step S2, the intermediate 1 and diallyldimethylammonium chloride were added to tetrahydrofuran, stirred at a uniform rate and benzoin dimethyl ether was added, placed under ultraviolet light and stirred for 30min, then heated to 50 ° C, the solvent was removed by vacuum rotary evaporation to obtain intermediate 2; Step S3, adding the graphene oxide prepared by Hummer's to a 15% volume fraction ethanol aqueous solution, adjusting the system pH to 4-5, adding γ-methacryloxypropyltrimethoxysilane, stirring at a uniform speed and reacting for 2-4 hours, filtering and washing after the reaction to obtain modified graphene oxide; Step S4, adding the prepared modified graphene oxide and intermediate 2 into toluene, adding 4-dimethylaminopyridine, stirring at a uniform speed and heating to 100-110° C., keeping the temperature and reacting for 4-6 hours, and obtaining the antifouling filler after the reaction is completed.

2. The antifouling coating for tile surface according to claim 1, characterized in that: The defoamer is defoamer BYK066N, and the leveling agent is silicone polyether copolymer.

3. The antifouling coating for tile surface according to claim 1, characterized in that: In step S1, the dosage ratio of perfluorooctanol, mercaptopropionic acid, methanesulfonic acid and toluene is controlled to be 1-2 g: 0.2-0.5 g: 0.02-0.04 g: 5-8 mL.

4. The antifouling coating for tile surface according to claim 1, characterized in that: In step S2, the dosage ratio of intermediate 1, diallyldimethylammonium chloride, benzoin dimethyl ether and tetrahydrofuran is controlled to be 0.2-0.4 mmol: 0.2-0.4 mmol: 0.3-0.5 mg: 3-5 mL.

5. The antifouling coating for tile surface according to claim 1, characterized in that: In step S3, the weight ratio of graphene oxide, γ-methacryloxypropyltrimethoxysilane and ethanol aqueous solution is controlled to be 1-2:0.3-0.5:

10.

6. The antifouling coating for tile surface according to claim 1, characterized in that: In step S4, the weight ratio of modified graphene oxide, intermediate 2 and toluene is controlled to be 1-2:0.3-0.5:10-12, and the amount of 4-dimethylaminopyridine is 1-2% of the total weight of modified graphene oxide and intermediate 2.

7. The method for preparing an antifouling coating for a tile surface according to claim 1, characterized in that: The steps include: The aqueous acrylic emulsion and deionized water are mixed and stirred at a uniform speed for 5-10 minutes, and then a defoamer, a leveling agent and an antifouling filler are added in sequence and stirred evenly to prepare an antifouling coating for the surface of ceramic tiles.

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