CN115109513A - Water-based single-component antibacterial child white board paint and preparation method thereof - Google Patents
Water-based single-component antibacterial child white board paint and preparation method thereof Download PDFInfo
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a water-based single-component antibacterial children whiteboard paint which comprises the following raw materials in parts by weight: 55-75 parts of water-based resin, 10-15 parts of modified nano zinc oxide synergistic bentonite composite modifier, 5-10 parts of hydrophobic modified nano stabilizer, 3-8 parts of wetting dispersant, 2-6 parts of film-forming assistant, 1-4 parts of interface modified coupling agent and 80-100 parts of water. The children white board paint is a paint formed by taking water-based resin as a base material, selecting omega-dihydroxy polymethylsiloxane resin, and matching with a modified nano zinc oxide synergistic bentonite composite modifier, a hydrophobic modified nano stabilizer and other auxiliary agents, such as a wetting dispersant, a film-forming assistant, an interface modified coupling agent and the like, and has excellent waterproof and antibacterial stability.
Description
Technical Field
The invention relates to the technical field of child white board paints, in particular to a water-based single-component antibacterial child white board paint and a preparation method thereof.
Background
Paint is a chemical mixture coating that can be firmly covered on the surface of an object for protection, decoration, marking and other special purposes. The 'coating process' book which is relatively authoritative in the Chinese coating world is defined in the way that the coating is a material which can be coated on the surface of an object by different construction processes to form a continuous solid film with firm adhesion and certain strength. The film thus formed is generally called a coating film, also called a paint film or a coating. White board paints generally use oily products, which do not meet the requirements on environmental protection, particularly on children's paint layers and on odor and VOC, and therefore aqueous paint products need to be adopted.
The existing water-based paint is used on a child whiteboard, in order to improve smell and VOC, an inorganic environment-friendly material is used for replacing an organic raw material, so that the product is poor in waterproof performance and easy to breed germs on the surface of the product in a humid environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a water-based single-component antibacterial children whiteboard paint and a preparation method thereof, so as to solve the problems in the background art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a water-based single-component antibacterial children whiteboard paint which comprises the following raw materials in parts by weight:
55-75 parts of water-based resin, 10-15 parts of modified nano zinc oxide synergistic bentonite composite modifier, 5-10 parts of hydrophobic modified nano stabilizer, 3-8 parts of wetting dispersant, 2-6 parts of film forming additive, 1-4 parts of interface modified coupling agent and 80-100 parts of water.
Preferably, the children whiteboard paint comprises the following raw materials in parts by weight:
60 parts of water-based resin, 12.5 parts of modified nano zinc oxide synergistic bentonite composite modifier, 7.5 parts of hydrophobic modified nano stabilizer, 5.5 parts of wetting dispersant, 4 parts of film-forming assistant, 2.5 parts of interface modified coupling agent and 90 parts of water.
Preferably, the aqueous resin is a silicone hydrophobic resin and is an alpha, omega-dihydroxypolymethylsiloxane resin with the viscosity of 2500-3000 mpa.s.
Preferably, the preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
s01: adding 10-15 parts of nano zinc oxide into 30-40 parts of water, then adding 2-5 parts of lanthanum sulfate solution and 3-6 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 300-;
s02: adding 10-20 parts of sodium alginate into 40-50 parts of water, then adding 1-5 parts of 1, 4-naphthalenedicarboxylic acid, stirring and mixing fully, finally adding a phosphoric acid buffer solution, and adjusting the pH value to 5.5 to obtain a modified solution;
s03: adding 5-10 parts of bentonite into 35-45 parts of the modification solution, then adding 8-12 parts of modified nano zinc oxide, stirring at 60-70 ℃ for 35-45min at the stirring speed of 500-1000r/min, finishing stirring, washing with water, filtering and drying to obtain the modified nano zinc oxide synergistic bentonite composite modifier.
Preferably, the mass fraction of the lanthanum sulfate solution is 5-10%.
Preferably, the dispersion type graphene is obtained by sending graphene into a ball mill for ball milling for 20-30min, the ball milling rotation speed is 1500r/min at 1000-.
Preferably, the preparation method of the hydrophobically modified nano stabilizer comprises the following steps:
ultrasonically dispersing 5-10 parts of nano silicon dioxide in 40-50 parts of acetone for 10-20min, wherein the ultrasonic power is 300-350W, and washing, filtering and drying for later use after the ultrasonic treatment is finished; adding 3-6 parts of tetramethyldisiloxane into 10-15 parts of ethanol, then adding 2-4 parts of chitosan and 1-3 parts of castor oil, and stirring and fully mixing to obtain a hydrophobic modifier; and (3) mixing the product to be prepared and a hydrophobic modifier according to the weight ratio of 1: (5-9), stirring at 60-65 ℃ for full reaction, finishing stirring, washing with water, and drying to obtain the hydrophobic modified nano stabilizer.
Preferably, the wetting and dispersing agent is one of dyhi 760W and 762W; the film-forming assistant is polyethylene glycol.
The invention also provides a preparation method of the water-based single-component antibacterial children whiteboard paint, which comprises the following steps:
the method comprises the following steps: adding the modified nano zinc oxide synergistic bentonite composite modifier and the hydrophobic modified nano stabilizer into a stirrer to obtain a material to be used;
step two: then adding an interface modification coupling agent, stirring and mixing for 10-20min at the rotating speed of 550-750r/min to obtain a mixed material A;
step three: then sequentially adding the water-based resin and the water, and continuously stirring for 5-10 min;
step four: and adding a wetting dispersant and a film-forming assistant, stirring for 1-5min, and finishing stirring to obtain the water-based single-component antibacterial children whiteboard paint.
Preferably, the interface modification coupling agent comprises the following raw materials in parts by weight: 5-10 parts of coupling agent KH560 and 2-5 parts of rare earth lanthanum chloride.
Compared with the prior art, the invention has the following beneficial effects:
the children white board paint takes water-based resin as a base material, selects omega-dihydroxy polymethylsiloxane resin, and is matched with a nano zinc oxide synergistic bentonite composite modifier subjected to modification treatment, a hydrophobic modified nano stabilizer and other auxiliary agents, such as a wetting dispersant, a film forming aid, an interface modified coupling agent and the like to form a paint vehicle, so that the paint vehicle has excellent waterproof and antibacterial stability;
the modified nano zinc oxide synergistic bentonite composite modifier is modified by dispersing nano zinc oxide in lanthanum sulfate solution, sodium carboxymethylcellulose and water and adding dispersive graphene, the graphene is ground and dispersed, the sheet structure has better dispersity, the dispersity of nano zinc oxide is improved by coordinating with the modified nano zinc oxide, the bentonite has a sheet structure and is dispersed in sodium alginate aqueous solution, the activity of the modified solution is improved by 1, 4-naphthalenedicarboxylic acid, and the sheet-shaped bentonite and the modified nano zinc oxide can generate further synergistic effect, because the sheet-shaped graphene can be inserted into the sheet-shaped bentonite in a penetrating way, the stability of the whole raw material is improved, and the durability and antibacterial property of the product can be obviously improved;
the hydrophobic modified nano stabilizer is prepared by dispersing nano silicon dioxide in acetone, so that modification in a hydrophobic modifier of tetramethyldisiloxane, chitosan and castor oil is facilitated, the tetramethyldisiloxane and the castor oil are used for carrying out hydrophobic surface modification on the nano silicon dioxide, the chitosan can play a role of an auxiliary agent, and the interface contact effect among the nano silicon dioxide, the tetramethyldisiloxane and the castor oil is enhanced, so that the surface modification efficiency is improved, the modified nano silicon dioxide serving as the hydrophobic modified nano stabilizer can be efficiently dispersed in a product system, an efficient hydrophobic environment is provided, and the hydrophobic efficiency is remarkably improved;
after the hydrophobic modified nano stabilizer and the modified nano zinc oxide synergistic bentonite are subjected to composite modification by the interface modified coupling agent, the interface modified coupling agent is matched with the coupling agent KH560 and rare earth lanthanum chloride, the inorganic material and the organic material are subjected to efficient interface modification by the coupling agent KH560, and meanwhile, the lanthanum chloride rare earth material has amphoteric interface property, so that a bridging auxiliary effect is achieved, the raw materials of the optimized and improved product can be efficiently matched, the raw materials are complementary and mutually matched, and the prepared white board paint has excellent hydrophobic and antibacterial lasting effects.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The water-based single-component antibacterial children whiteboard paint comprises the following raw materials in parts by weight:
55-75 parts of water-based resin, 10-15 parts of modified nano zinc oxide synergistic bentonite composite modifier, 5-10 parts of hydrophobic modified nano stabilizer, 3-8 parts of wetting dispersant, 2-6 parts of film forming additive, 1-4 parts of interface modified coupling agent and 80-100 parts of water.
The children white board paint comprises the following raw materials in parts by weight:
60 parts of water-based resin, 12.5 parts of modified nano zinc oxide synergistic bentonite composite modifier, 7.5 parts of hydrophobic modified nano stabilizer, 5.5 parts of wetting dispersant, 4 parts of film forming assistant, 2.5 parts of interface modified coupling agent and 90 parts of water.
The aqueous resin of this example is a silicone hydrophobic resin, and is an α, ω -dihydroxypolymethylsiloxane resin having a viscosity of 2500-.
The preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
s01: adding 10-15 parts of nano zinc oxide into 30-40 parts of water, then adding 2-5 parts of lanthanum sulfate solution and 3-6 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 300-;
s02: adding 10-20 parts of sodium alginate into 40-50 parts of water, then adding 1-5 parts of 1, 4-naphthalenedicarboxylic acid, stirring and mixing fully, finally adding a phosphoric acid buffer solution, and adjusting the pH value to 5.5 to obtain a modified solution;
s03: adding 5-10 parts of bentonite into 35-45 parts of modification liquid, then adding 8-12 parts of modified nano zinc oxide, stirring at 60-70 ℃ for 35-45min at the stirring speed of 500-1000r/min, finishing stirring, washing with water, and drying to obtain the modified nano zinc oxide synergistic bentonite composite modifier.
The mass fraction of the lanthanum sulfate solution of this example is 5-10%.
The dispersion type graphene is obtained by sending graphene into a ball mill for ball milling for 20-30min, wherein the ball milling rotation speed is 1000-.
The preparation method of the hydrophobically modified nano stabilizer in the embodiment comprises the following steps:
ultrasonically dispersing 5-10 parts of nano silicon dioxide in 40-50 parts of acetone for 10-20min, wherein the ultrasonic power is 300-350W, and finishing the ultrasonic treatment for later use; adding 3-6 parts of tetramethyldisiloxane into 10-15 parts of ethanol, then adding 2-4 parts of chitosan and 1-3 parts of castor oil, and stirring and fully mixing to obtain a hydrophobic modifier; mixing the product to be used and a hydrophobic modifier according to a weight ratio of 1: (5-9), stirring at 60-65 ℃ for full reaction, washing with water, and drying to obtain the hydrophobic modified nano stabilizer.
The wetting dispersant of the embodiment is one of digao 760W and 762W; the film-forming assistant is polyethylene glycol.
The preparation method of the water-based single-component antibacterial children whiteboard paint provided by the embodiment comprises the following steps:
the method comprises the following steps: adding the modified nano zinc oxide synergistic bentonite composite modifier and the hydrophobic modified nano stabilizer into a stirrer to obtain a material to be used;
step two: then adding an interface modification coupling agent, stirring and mixing for 10-20min at the rotating speed of 550-750r/min to obtain a mixed material A;
step three: then sequentially adding the water-based resin and the water, and continuously stirring for 5-10 min;
step four: and adding a wetting dispersant and a film-forming assistant, stirring for 1-5min, and finishing stirring to obtain the water-based single-component antibacterial children whiteboard paint.
The interface modified coupling agent of the embodiment comprises the following raw materials in parts by weight: 5-10 parts of coupling agent KH560 and 2-5 parts of rare earth lanthanum chloride.
Example 1.
The water-based single-component antibacterial children white board paint comprises the following raw materials in parts by weight:
55 parts of water-based resin, 10 parts of modified nano zinc oxide synergistic bentonite composite modifier, 5 parts of hydrophobic modified nano stabilizer, 3 parts of wetting dispersant, 2 parts of film-forming assistant, 1 part of interface modified coupling agent and 80 parts of water.
The aqueous resin of this example was a silicone hydrophobic resin and was an alpha, omega-dihydroxy polymethylsiloxane resin having a viscosity of 2500 mpa.s.
The preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
s01: adding 10 parts of nano zinc oxide into 30 parts of water, then adding 2 parts of lanthanum sulfate solution and 3 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 300r/min for 20min, then adding 5 parts of dispersed graphene and 1 part of hydrochloric acid, continuing stirring for 10min, finishing stirring, washing with water, and drying to obtain modified nano zinc oxide;
s02: adding 10 parts of sodium alginate into 40 parts of water, then adding 1 part of 1, 4-naphthalenedicarboxylic acid, stirring and mixing fully, finally adding a phosphoric acid buffer solution, and adjusting the pH value to 5.5 to obtain a modified solution;
s03: and adding 5 parts of bentonite into 35 parts of the modification solution, then adding 8 parts of modified nano-zinc oxide, stirring at 60 ℃ for 35min at the stirring speed of 500r/min, finishing stirring, washing with water, and drying to obtain the modified nano-zinc oxide synergistic bentonite composite modifier.
The mass fraction of the lanthanum sulfate solution of this example was 5%.
The dispersion type graphene is prepared by feeding graphene into a ball mill for ball milling for 20min, wherein the ball milling rotation speed is 1000r/min, finishing ball milling, placing the graphene in a hydrochloric acid solution with the mass fraction of 5% for ultrasonic dispersion for 20min, wherein the ultrasonic power is 150W, finishing ultrasonic dispersion, washing with water, and drying.
The preparation method of the hydrophobically modified nano stabilizer in the embodiment comprises the following steps:
ultrasonically dispersing 5 parts of nano silicon dioxide in 40 parts of acetone for 10min, wherein the ultrasonic power is 300W, and finishing the ultrasonic treatment for later use; adding 3 parts of tetramethyldisiloxane into 10 parts of ethanol, then adding 2 parts of chitosan and 1 part of castor oil, and stirring and mixing fully to obtain a hydrophobic modifier; mixing the product to be used and a hydrophobic modifier according to a weight ratio of 1: 5, stirring at 60 ℃ to react fully, washing with water, and drying to obtain the hydrophobic modified nano stabilizer.
The wetting dispersant of this example is digao 760W; the film-forming assistant is polyethylene glycol.
The preparation method of the water-based single-component antibacterial children whiteboard paint provided by the embodiment comprises the following steps:
the method comprises the following steps: adding the modified nano zinc oxide synergistic bentonite composite modifier and the hydrophobic modified nano stabilizer into a stirrer to obtain a material to be used;
step two: then adding an interface modification coupling agent, and stirring and mixing for 10min at the rotating speed of 550r/min to obtain a mixed material A;
step three: then sequentially adding the water-based resin and the water, and continuously stirring for 5 min;
step four: and adding the wetting dispersant and the film-forming assistant, stirring for 1min, and finishing stirring to obtain the water-based single-component antibacterial child white board paint.
The interface modified coupling agent of the embodiment comprises the following raw materials in parts by weight: 5 parts of a coupling agent KH560 and 2 parts of rare earth lanthanum chloride.
Example 2.
The water-based single-component antibacterial children whiteboard paint comprises the following raw materials in parts by weight:
75 parts of water-based resin, 15 parts of modified nano zinc oxide synergistic bentonite composite modifier, 10 parts of hydrophobic modified nano stabilizer, 8 parts of wetting dispersant, 6 parts of film-forming assistant, 4 parts of interface modified coupling agent and 100 parts of water.
The aqueous resin of this example was a silicone hydrophobic resin and was an α, ω -dihydroxypolymethylsiloxane resin having a viscosity of 3000 mpa.s.
The preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
s01: adding 15 parts of nano zinc oxide into 40 parts of water, then adding 5 parts of lanthanum sulfate solution and 6 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 500r/min for 30min, then adding 9 parts of dispersed graphene and 3 parts of hydrochloric acid, continuing stirring for 20min, finishing stirring, washing with water, and drying to obtain modified nano zinc oxide;
s02: adding 20 parts of sodium alginate into 50 parts of water, then adding 5 parts of 1, 4-naphthalenedicarboxylic acid, stirring and mixing fully, finally adding a phosphoric acid buffer solution, and adjusting the pH value to 5.5 to obtain a modified solution;
s03: and adding 10 parts of bentonite into 45 parts of the modification solution, then adding 12 parts of modified nano-zinc oxide, stirring at 70 ℃ for 45min at the stirring speed of 1000r/min, finishing stirring, washing with water, and drying to obtain the modified nano-zinc oxide synergistic bentonite composite modifier.
The mass fraction of the lanthanum sulfate solution of this example was 10%.
The dispersion type graphene is prepared by feeding graphene into a ball mill for ball milling for 30min, wherein the ball milling rotation speed is 1500r/min, after the ball milling is finished, placing the graphene in a hydrochloric acid solution with the mass fraction of 7% for ultrasonic dispersion for 30min, wherein the ultrasonic power is 200W, and after the ultrasonic dispersion, washing and drying.
The preparation method of the hydrophobically modified nano stabilizer in the embodiment comprises the following steps:
ultrasonically dispersing 10 parts of nano silicon dioxide in 50 parts of acetone for 20min, wherein the ultrasonic power is 350W, and finishing the ultrasonic treatment for later use; adding 6 parts of tetramethyldisiloxane into 15 parts of ethanol, then adding 4 parts of chitosan and 3 parts of castor oil, and stirring and mixing fully to obtain a hydrophobic modifier; mixing the product to be used and a hydrophobic modifier according to a weight ratio of 1: 9, stirring at 65 ℃ to react fully, washing with water, and drying to obtain the hydrophobic modified nano stabilizer.
The wetting and dispersing agent of the present embodiment is dyhi 762W; the film-forming assistant is polyethylene glycol.
The preparation method of the water-based single-component antibacterial children whiteboard paint provided by the embodiment comprises the following steps:
the method comprises the following steps: adding the modified nano zinc oxide synergistic bentonite composite modifier and the hydrophobic modified nano stabilizer into a stirrer to obtain a material to be used;
step two: then adding an interface modification coupling agent, and stirring and mixing at the rotating speed of 750r/min for 20min to obtain a mixed material A;
step three: then sequentially adding the water-based resin and the water, and continuously stirring for 10 min;
step four: and adding a wetting dispersant and a film-forming assistant, stirring for 5min, and finishing stirring to obtain the water-based single-component antibacterial children whiteboard paint.
The interface modified coupling agent of the embodiment comprises the following raw materials in parts by weight: 10 parts of a coupling agent KH560 and 5 parts of rare earth lanthanum chloride.
Example 3.
The water-based single-component antibacterial children whiteboard paint comprises the following raw materials in parts by weight:
60 parts of water-based resin, 12.5 parts of modified nano zinc oxide synergistic bentonite composite modifier, 7.5 parts of hydrophobic modified nano stabilizer, 5.5 parts of wetting dispersant, 4 parts of film-forming assistant, 2.5 parts of interface modified coupling agent and 90 parts of water.
The aqueous resin of this example was a silicone hydrophobic resin and was an alpha, omega-dihydroxypolymethylsiloxane resin having a viscosity of 2750 mpa.s.
The preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
s01: adding 12.5 parts of nano zinc oxide into 35 parts of water, then adding 3.5 parts of lanthanum sulfate solution and 4.5 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 400r/min for 25min, then adding 7 parts of dispersed graphene and 2 parts of hydrochloric acid, continuously stirring for 15min, and after stirring, washing and drying to obtain modified nano zinc oxide;
s02: adding 15 parts of sodium alginate into 45 parts of water, then adding 3 parts of 1, 4-naphthalenedicarboxylic acid, stirring and mixing fully, finally adding a phosphoric acid buffer solution, and adjusting the pH value to 5.5 to obtain a modified solution;
s03: adding 7.5 parts of bentonite into 40 parts of the modification liquid, then adding 10 parts of modified nano-zinc oxide, stirring at 65 ℃ for 40min at the stirring speed of 750r/min, finishing stirring, washing with water, and drying to obtain the modified nano-zinc oxide synergistic bentonite composite modifier.
The mass fraction of the lanthanum sulfate solution of this example was 7.5%.
The dispersion type graphene is prepared by feeding graphene into a ball mill for ball milling for 25min, wherein the ball milling rotation speed is 1250r/min, after the ball milling is finished, placing the graphene in a hydrochloric acid solution with the mass fraction of 6% for ultrasonic dispersion for 25min, wherein the ultrasonic power is 175W, and after the ultrasonic dispersion, washing and drying.
The preparation method of the hydrophobically modified nano stabilizer of the embodiment comprises the following steps:
ultrasonically dispersing 7.5 parts of nano silicon dioxide in 45 parts of acetone for 15min, wherein the ultrasonic power is 325W, and finishing the ultrasonic treatment for later use; adding 4.5 parts of tetramethyldisiloxane into 12.5 parts of ethanol, then adding 3 parts of chitosan and 2 parts of castor oil, and stirring and mixing fully to obtain a hydrophobic modifier; mixing the product to be used and a hydrophobic modifier according to a weight ratio of 1: 7, stirring at 62.5 ℃ to react fully, washing with water, and drying to obtain the hydrophobic modified nano stabilizer.
The wetting dispersant of this example is digao 760W; the film-forming assistant is polyethylene glycol.
The preparation method of the water-based single-component antibacterial children whiteboard paint provided by the embodiment comprises the following steps:
the method comprises the following steps: adding the modified nano zinc oxide synergistic bentonite composite modifier and the hydrophobic modified nano stabilizer into a stirrer to obtain a material to be used;
step two: then adding an interface modification coupling agent, and stirring and mixing for 15min at the rotating speed of 600r/min to obtain a mixed material A;
step three: then sequentially adding the water-based resin and the water, and continuously stirring for 7.5 min;
step four: and adding the wetting dispersant and the film-forming assistant, stirring for 3min, and finishing stirring to obtain the water-based single-component antibacterial child white board paint.
The interface modified coupling agent of the embodiment comprises the following raw materials in parts by weight: 7.5 parts of a coupling agent KH560 and 3.5 parts of rare earth lanthanum chloride.
Comparative example 1.
The difference from the embodiment 3 is that the modified nano zinc oxide synergistic bentonite composite modifier is replaced by nano zinc oxide.
Comparative example 2.
Unlike example 3, no hydrophobically modified nano-stabilizer was added.
Comparative example 3.
The difference from example 3 is that the hydrophobically modified nano-stabiliser was prepared without treatment with a hydrophobic modifier.
Comparative example 4.
The difference from example 3 is that the hydrophobically modified nano-stabiliser is replaced by nano-silica.
Comparative example 5.
Unlike example 3, the hydrophobic modifier of the hydrophobically modified nano-stabilizer was not added with chitosan.
Comparative example 6.
Unlike example 3, no treatment with an interface modifying coupling agent was used.
Comparative example 7.
Measuring the contact angle of the coating to water by using a contact angle measuring instrument, and carrying out antibacterial performance test according to GB/T21866-2008 'antibacterial property measuring method and antibacterial effect of antibacterial coating (paint film)':
the results of measuring the properties of examples 1 to 3 and comparative examples 1 to 7 are as follows
From examples 1 to 3 and comparative examples 1 to 7,
the product of the embodiment 3 has excellent hydrophobic and antibacterial lasting effects, and can still reach more than 99% after 1 month of antibacterial test, and the comparative examples 2-5 show that the hydrophobic property of the product is deteriorated to a certain extent without adding the hydrophobic modified nano stabilizer and by replacing the hydrophobic modified nano stabilizer with nano silicon dioxide, the hydrophobic property of the product is different, meanwhile, the hydrophobic modified nano stabilizer has different preparation methods and different hydrophobic effects, the hydrophobic modified nano stabilizer prepared by the method of the invention has the most obvious hydrophobic effect on the product, and the comparative examples 6-7 show that the interface modified coupling agent and the hydrophobic modified nano stabilizer are cooperated to jointly enhance the hydrophobic effect of the product through the treatment of the interface modified coupling agent;
the antibacterial and bacteriostatic properties are shown;
the modified nano zinc oxide synergistic bentonite composite modifier is replaced by nano zinc oxide, the antibacterial performance of the product is basically the same, but after 7 days/1 month, the antibacterial performance of the product is obviously reduced, meanwhile, the hydrophobic modified nano stabilizer is not added, the interface modified coupling agent is not used for treatment, the antibacterial stability of the product has an obvious reduction trend, in addition, the hydrophobic modified nano stabilizer is different in preparation method and different in antibacterial stability, the hydrophobic modified nano stabilizer prepared by the method has the best antibacterial stability, and the antibacterial long-acting stability of the product can be obviously improved by matching the hydrophobic modified nano stabilizer and the modified nano zinc oxide synergistic bentonite composite modifier with the interface modified coupling agent.
The preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
s01: adding 12.5 parts of nano zinc oxide into 35 parts of water, then adding 3.5 parts of lanthanum sulfate solution and 4.5 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 400r/min for 25min, then adding 7 parts of dispersed graphene and 2 parts of hydrochloric acid, continuously stirring for 15min, and after stirring, washing and drying to obtain modified nano zinc oxide;
s02: adding 15 parts of sodium alginate into 45 parts of water, then adding 3 parts of 1, 4-naphthalenedicarboxylic acid, stirring and mixing fully, finally adding a phosphoric acid buffer solution, and adjusting the pH value to 5.5 to obtain a modified solution;
s03: adding 7.5 parts of bentonite into 40 parts of the modification liquid, then adding 10 parts of modified nano-zinc oxide, stirring at 65 ℃ for 40min at the stirring speed of 750r/min, finishing stirring, washing with water, and drying to obtain the modified nano-zinc oxide synergistic bentonite composite modifier.
The mass fraction of the lanthanum sulfate solution was 7.5%.
And (3) sending the dispersed graphene into a ball mill for ball milling for 25min, wherein the ball milling rotation speed is 1250r/min, finishing ball milling, placing the ball mill into a hydrochloric acid solution with the mass fraction of 6%, performing ultrasonic dispersion for 25min, wherein the ultrasonic power is 175W, finishing ultrasonic dispersion, washing and drying to obtain the dispersed graphene.
The product performance is further researched by the modified nano zinc oxide synergistic bentonite composite modifier;
experimental example 1.
The same as example 3, except that no dispersed graphene was added.
Experimental example 2.
The same procedure as in example 3 was repeated except that the graphene material of the dispersion-type graphene was replaced with carbon nanotubes, and the dispersibility was performed.
Experimental example 3.
The same as in example 3, except that the dispersed graphene was replaced by graphene without any treatment.
Experimental example 4.
The same as example 3 except that the modified solution was not treated;
the preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
adding 12.5 parts of nano zinc oxide into 35 parts of water, then adding 3.5 parts of lanthanum sulfate solution and 4.5 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 400r/min for 25min, then adding 7 parts of dispersed graphene and 2 parts of hydrochloric acid, continuing stirring for 15min, after stirring, adding 7.5 parts of bentonite, stirring at the temperature of 65 ℃ for 40min, wherein the stirring rotating speed is 750r/min, and finally washing and drying to obtain the nano zinc oxide synergistic bentonite composite modifier.
From the experimental examples 1-4, it can be seen that the antibacterial performance after 7 days and 1 month without adding the dispersion type graphene and the antibacterial performance without adding the modified nano zinc oxide synergistic bentonite composite modifier both have a significant deterioration trend, but the antibacterial change without adding the modified nano zinc oxide synergistic bentonite composite modifier is significant, and meanwhile, the carbon nanotube replacement finds that the long-term antibacterial effect deterioration trend is still significant, and it can be known that the graphene and the bentonite have a synergistic effect and cooperate with each other to enhance the antibacterial stability of the product, and the other raw materials are used for replacement, so that the significant effect of the invention cannot be achieved;
meanwhile, after the graphene is subjected to the preparation method of the dispersion type graphene, the antibacterial stability of the product is improved, and the treatment of the modification liquid is improved; the modified nano zinc oxide synergistic bentonite composite modifier prepared by the method has an obvious effect on the antibacterial stability of the product, and the effect of the invention cannot be achieved by other methods.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The water-based single-component antibacterial children whiteboard paint is characterized by comprising the following raw materials in parts by weight:
55-75 parts of water-based resin, 10-15 parts of modified nano zinc oxide synergistic bentonite composite modifier, 5-10 parts of hydrophobic modified nano stabilizer, 3-8 parts of wetting dispersant, 2-6 parts of film forming additive, 1-4 parts of interface modified coupling agent and 80-100 parts of water.
2. The aqueous single-component antibacterial children whiteboard paint as claimed in claim 1, wherein the children whiteboard paint comprises the following raw materials in parts by weight:
60 parts of water-based resin, 12.5 parts of modified nano zinc oxide synergistic bentonite composite modifier, 7.5 parts of hydrophobic modified nano stabilizer, 5.5 parts of wetting dispersant, 4 parts of film-forming assistant, 2.5 parts of interface modified coupling agent and 90 parts of water.
3. The aqueous one-component antibacterial children whiteboard paint as claimed in claim 1, wherein the aqueous resin is a silicone hydrophobic resin and is an α, ω -dihydroxypolymethylsiloxane resin with a viscosity of 2500-.
4. The water-based single-component antibacterial children whiteboard paint as claimed in claim 1, wherein the preparation method of the modified nano zinc oxide synergistic bentonite composite modifier comprises the following steps:
s01: adding 10-15 parts of nano zinc oxide into 30-40 parts of water, then adding 2-5 parts of lanthanum sulfate solution and 3-6 parts of sodium carboxymethylcellulose, stirring at the rotating speed of 300-;
s02: adding 10-20 parts of sodium alginate into 40-50 parts of water, then adding 1-5 parts of 1, 4-naphthalenedicarboxylic acid, stirring and mixing fully, finally adding a phosphoric acid buffer solution, and adjusting the pH value to 5.5 to obtain a modified solution;
s03: adding 5-10 parts of bentonite into 35-45 parts of modification liquid, then adding 8-12 parts of modified nano zinc oxide, stirring at 60-70 ℃ for 35-45min at the stirring speed of 500-1000r/min, finishing stirring, washing with water, and drying to obtain the modified nano zinc oxide synergistic bentonite composite modifier.
5. The aqueous single-component antibacterial children whiteboard paint as claimed in claim 4, wherein the mass fraction of the lanthanum sulfate solution is 5-10%.
6. The aqueous single-component antibacterial children whiteboard paint as claimed in claim 4, wherein the dispersed graphene is obtained by sending graphene into a ball mill for ball milling for 20-30min, the ball milling rotation speed is 1500r/min and is 1000-.
7. The aqueous single-component antibacterial child white board paint according to claim 1, wherein the preparation method of the hydrophobic modified nano stabilizer comprises the following steps:
ultrasonically dispersing 5-10 parts of nano silicon dioxide in 40-50 parts of acetone for 10-20min, wherein the ultrasonic power is 300-350W, and finishing the ultrasonic treatment for later use; adding 3-6 parts of tetramethyldisiloxane into 10-15 parts of ethanol, then adding 2-4 parts of chitosan and 1-3 parts of castor oil, and stirring and fully mixing to obtain a hydrophobic modifier; and (3) mixing the product to be prepared and a hydrophobic modifier according to the weight ratio of 1: (5-9), stirring at 60-65 ℃ for full reaction, finishing stirring, washing with water, and drying to obtain the hydrophobic modified nano stabilizer.
8. The aqueous one-component antibacterial children whiteboard paint as claimed in claim 1, wherein the wetting dispersant is one of digao 760W and 762W; the film-forming assistant is polyethylene glycol.
9. A method for preparing the aqueous single-component antibacterial children white board paint as claimed in any one of claims 1 to 8, which comprises the following steps:
the method comprises the following steps: adding the modified nano zinc oxide synergistic bentonite composite modifier and the hydrophobic modified nano stabilizer into a stirrer to obtain a material to be used;
step two: then adding an interface modification coupling agent, stirring and mixing for 10-20min at the rotating speed of 550-750r/min to obtain a mixed material A;
step three: then sequentially adding the water-based resin and the water, and continuously stirring for 5-10 min;
step four: and adding a wetting dispersant and a film-forming assistant, stirring for 1-5min, and finishing stirring to obtain the water-based single-component antibacterial children whiteboard paint.
10. The preparation method of the water-based single-component antibacterial children whiteboard paint as claimed in claim 9, wherein the interface modification coupling agent comprises the following raw materials in parts by weight: 5-10 parts of coupling agent KH560 and 2-5 parts of rare earth lanthanum chloride.
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