CN111234641B - Water-based acrylic energy-storage luminescent paint and preparation method thereof - Google Patents
Water-based acrylic energy-storage luminescent paint and preparation method thereof Download PDFInfo
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- CN111234641B CN111234641B CN202010209648.5A CN202010209648A CN111234641B CN 111234641 B CN111234641 B CN 111234641B CN 202010209648 A CN202010209648 A CN 202010209648A CN 111234641 B CN111234641 B CN 111234641B
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
Abstract
The invention relates to the field of coatings, and particularly relates to a water-based acrylic energy-storage luminescent coating and a preparation method thereof. The water-based acrylic energy storage luminous paint comprises the following components in parts by weight: 20-30 parts of water, 0.1-0.3 part of dispersing agent, 0.1-0.3 part of wetting agent, 0.01-0.1 part of defoaming agent, 10-30 parts of rare earth doped aluminate type long-acting luminescent powder, 5-10 parts of luminescent powder pretreating agent, 30-50 parts of acrylic emulsion, 0-20 parts of filler, 0.2-0.5 part of thickening agent A and 0.2-0.5 part of thickening agent B. The water-based acrylic energy-storage luminescent coating provided by the invention has the advantages that the water-based acrylic energy-storage luminescent coating is limited in compatibility, the hydrolysis stability of luminescent powder is improved, the obtained water-based acrylic energy-storage luminescent coating is low in VOC content and non-flammable, the construction is safe and convenient, the paint film adhesion is strong, the weather resistance is good, the luminescent intensity is high, and the afterglow time is over 12 hours.
Description
Technical Field
The invention relates to the field of coatings, and particularly relates to a water-based acrylic energy-storage luminescent coating and a preparation method thereof.
Background
The traditional luminescent coating is mostly prepared by taking ZnS and Cu type luminescent powder as a luminescent material, the afterglow of the luminescent material can only reach 1-2h, and the luminescent material is easy to deteriorate and lose efficacy after being irradiated by ultraviolet rays or being contacted with oxygen. The existing paint sometimes adds deuterium and Pm into the paint for prolonging afterglow147And the like, but the radioactive elements are harmful to human bodies, so the luminescent paint is gradually eliminated by the market.
In recent years, rare earth doped alkaline earth metal aluminates (e.g., SrMgAl) have been discovered2O4Eu+2Dy3+) The luminescent material has the advantages of long glow time of more than 12 hours, good heat resistance and oxidation resistance stability, and no chemical change when being heated to 500 ℃ in the air. Therefore, such luminescent materials are beginning to be widely used for preparing luminescent coatings.
However, the long-acting luminous europium-activated alkaline earth metal aluminate type luminescent powder has partial hydrolysis phenomenon in aqueous solution, the water extraction liquid is strong in alkalinity, the pH value can reach 10-12, and the hydrolysis product contains polyvalent metal ions, so that emulsion breaking and coating gelling are easily caused. Therefore, if the problems of dispersion and stability of the luminescent powder in water are not solved, the coating can have the phenomena of overhigh consistency and poor construction performance after being stored for a period of time, thereby limiting the use of products.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the prepared coating has too high consistency and poor construction performance after being stored for a period of time due to the hydrolysis of the long-acting luminous europium-activated alkaline earth metal aluminate type luminescent powder in an aqueous solution in the prior art, and provide the water-based acrylic energy-storage luminescent coating and the preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the water-based acrylic energy-storage luminescent coating comprises the following components in parts by weight:
20-30 parts of water, 0.1-0.3 part of dispersing agent, 0.1-0.3 part of wetting agent, 0.01-0.1 part of defoaming agent, 10-30 parts of rare earth doped aluminate type long-acting luminescent powder, 5-10 parts of luminescent powder pretreating agent, 30-50 parts of acrylic emulsion, 0-20 parts of filler, 0.2-0.5 part of thickening agent A and 0.2-0.5 part of thickening agent B.
Further, the luminescent powder pretreating agent comprises the following components in parts by weight:
20-30 parts of E-12 epoxy resin, 20-30 parts of cosolvent, 15-25 parts of methyl methacrylate, 15-25 parts of butyl acrylate, 0-4 parts of methacrylic acid, 0-4 parts of acrylic acid, 2-4 parts of maleic anhydride, 2-4 parts of allyl polyoxyethylene ether, 1-3 parts of initiator, 5-10 parts of neutralizer and 150 parts of softened water.
Further, in the above-mentioned case,
the initiator is at least one of benzoyl peroxide and azobisisobutyronitrile; and/or the presence of a gas in the gas,
the neutralizing agent is at least one of ammonia water or volatile amine; and/or the presence of a gas in the gas,
the cosolvent is at least one of propylene glycol methyl ether, propylene glycol ethyl ether and dipropylene glycol methyl ether.
Furthermore, the content of water-soluble substances in the softened water is less than 100ppm, and the conductivity is less than 20 mu s/cm.
Further, the luminescent powder pretreating agent is prepared according to the following steps:
mixing epoxy resin and a solvent in a nitrogen atmosphere, and preserving heat for 2-3h at the temperature of 110-130 ℃ to dissolve the epoxy resin to obtain an epoxy resin solution;
mixing unsaturated monomers and dividing into two parts, firstly adding the mixed unsaturated monomers 2/5-3/5 in the total weight of the mixed unsaturated monomers into an epoxy resin solution, dropwise adding for 0.5-1.0h, and preserving heat for 1.0-1.5 h;
adding the rest mixed unsaturated monomer into the epoxy resin solution, dropwise adding for 0.5-1.0h, and keeping the temperature for 1.5-2.0h to obtain an epoxy grafted acrylic resin solution;
mixing an emulsifier, a neutralizer and an epoxy resin solution added with an unsaturated monomer, adding the neutralizer and softened water into the epoxy grafted acrylic resin solution, and stirring and emulsifying for 1-2 hours to obtain the light-emitting powder pretreating agent.
Further, the acrylic emulsion comprises the following components in parts by weight:
5-10 parts of methyl methacrylate, 10-15 parts of styrene, 25-30 parts of butyl acrylate, 0.5-1.5 parts of acrylic acid, 0.5-1 part of anionic emulsifier, 0.5-1 part of nonionic emulsifier, 0.5-1 part of reactive emulsifier, 0.1-0.3 part of initiator, 0.3-1.0 part of neutralizer and 45-55 parts of softened water.
Further, in the above-mentioned case,
the anionic emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether sodium sulfate, fatty alcohol-polyoxyethylene phosphate sodium and lauryl alcohol sodium sulfate; and/or the presence of a gas in the gas,
the nonionic emulsifier is at least one of alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene ether and polyoxyethylene-polyoxypropylene block polyether; and/or the presence of a gas in the gas,
the reactive emulsifier is sodium styrene sulfonate, sodium 2-methallyl sulfonate and sodium allyl-2-hydroxypropyl ether sulfonate; and/or the presence of a gas in the gas,
the initiator is at least one of potassium persulfate and ammonium persulfate; and/or the presence of a gas in the gas,
the neutralizing agent is at least one of ammonia water, 2-amino-2-methyl-1-propanol (AMP-95), N-dimethylethanolamine and triethylamine.
Further, the acrylic emulsion is obtained according to the following steps:
mixing the softened water accounting for 3/4-4/5 of formula amount, an aqueous solution of an emulsifier and various unsaturated monomers, and stirring at a high speed for 15min to obtain a monomer pre-emulsion;
adding the rest softened water, the aqueous solution of the emulsifier and the monomer pre-emulsion of 1/3-1/5 into a reaction vessel, heating to 75 +/-2 ℃, adding a part of aqueous solution of the initiator under the nitrogen atmosphere, and keeping the temperature until the liquid is blue;
dropwise adding the residual monomer pre-emulsion into the blue mixed solution, simultaneously dropwise adding an aqueous solution of an initiator, finishing adding within 1-2h, and preserving heat until no reflux exists;
adding an aqueous solution of an initiator into the mixed solution without reflux, heating to 85 ℃, and keeping the temperature for 0.5 h;
cooling to 50-60 deg.C, adding neutralizer to adjust pH to 7-8, filtering and discharging.
Further, the dispersant is a block copolymer containing pigment-philic groups; and/or, the wetting agent is a surfactant that can significantly reduce static and dynamic surface tension; and/or the defoaming agent is polyether modified organic silicon resin; and/or the presence of a gas in the gas,
the filler is at least one of talcum powder, precipitated barium sulfate, calcined kaolin, superfine heavy calcium and light calcium carbonate; and/or the presence of a gas in the gas,
the thickener A is a polyurethane associative thickener; and/or the presence of a gas in the gas,
the thickener B is at least one of magnesium aluminum silicate and bentonite.
A method for preparing the water-based acrylic energy storage luminous paint according to any one of the above schemes, comprising the following steps:
mixing water, a dispersing agent, a wetting agent and a luminescent powder pretreating agent, uniformly stirring, adding rare earth doped aluminate type long-acting luminescent powder, dispersing at a high speed, and grinding to obtain color paste; and adding a thickening agent into the color paste, uniformly stirring, and filtering to obtain a finished product.
The technical scheme of the invention has the following advantages:
1. the water-based acrylic energy-storage luminescent coating provided by the invention has the advantages that the water-based acrylic energy-storage luminescent coating is limited in compatibility, the hydrolysis stability of luminescent powder is improved, the obtained water-based acrylic energy-storage luminescent coating is low in VOC content and non-flammable, the construction is safe and convenient, the paint film adhesion is strong, the weather resistance is good, the luminescent intensity is high, and the afterglow time is over 12 hours.
2. According to the water-based acrylic energy-storage luminescent coating provided by the invention, by aiming at the characteristic that alkaline earth metal aluminate type luminescent powder is easy to hydrolyze and the prepared water-based coating has poor stability, the compatibility of the luminescent powder pretreating agent is limited, so that the luminescent powder pretreating agent can react with the luminescent powder to form an organic coating layer, the hydrolysis stability of the luminescent powder pretreating agent is improved, and the stability of the water-based acrylic energy-storage luminescent coating is further improved. The water-based acrylic energy-storage luminous paint provided by the invention has good adhesive force on the surfaces of cement, steel, aluminum alloy, wood, PVC plastic and other base materials, and the formed paint film has good water resistance, alkali resistance and weather resistance, high luminous brightness and long afterglow time, can be widely applied to aspects of safety channels, mine tunnels, traffic signs, fire-fighting equipment, electrical switches and the like, and can be used as an emergency mark under the condition of power failure or no illumination at night.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The invention provides a water-based acrylic energy storage luminescent coating which comprises the following components in parts by weight:
20-30 parts of water, 0.1-0.3 part of dispersing agent, 0.1-0.3 part of wetting agent, 0.01-0.1 part of defoaming agent, 10-30 parts of rare earth doped aluminate type long-acting luminescent powder, 5-10 parts of luminescent powder pretreating agent, 30-50 parts of acrylic emulsion, 0-20 parts of filler, 0.2-0.5 part of thickening agent A and 0.2-0.5 part of thickening agent B.
The light-emitting powder pretreating agent comprises the following components in parts by weight:
20-30 parts of E-12 epoxy resin, 20-30 parts of cosolvent, 15-25 parts of methyl methacrylate, 15-25 parts of butyl acrylate, 0-4 parts of methacrylic acid, 0-4 parts of acrylic acid, 2-4 parts of maleic anhydride, 2-4 parts of allyl polyoxyethylene ether, 1-3 parts of initiator, 5-10 parts of neutralizer and 150 parts of softened water.
The initiator in the luminescent powder pretreating agent can be at least one of benzoyl peroxide and azodiisobutyronitrile; the neutralizing agent can be at least one of ammonia water or volatile amine; the cosolvent can be at least one of propylene glycol methyl ether, propylene glycol ethyl ether and dipropylene glycol methyl ether; wherein the softened water can be deionized water or distilled water, but the content of water-soluble substances in the softened water is required to be less than 100ppm, and the electric conductivity is less than 20 mus/cm.
The light-emitting powder pretreating agent is prepared by the following steps:
mixing epoxy resin and a solvent in a nitrogen atmosphere, and preserving heat for 2-3h at the temperature of 110-130 ℃ to dissolve the epoxy resin to obtain an epoxy resin solution;
mixing unsaturated monomers and dividing into two parts, firstly adding the mixed unsaturated monomers 2/5-3/5 in the total weight of the mixed unsaturated monomers into an epoxy resin solution, dropwise adding for 0.5-1.0h, and preserving heat for 1.0-1.5 h;
adding the rest mixed unsaturated monomer into the epoxy resin solution, dropwise adding for 0.5-1.0h, and keeping the temperature for 1.5-2.0h to obtain an epoxy grafted acrylic resin solution;
and adding a neutralizer and softened water into the epoxy grafted acrylic resin solution, and stirring and emulsifying for 1-2h to obtain the light-emitting powder pretreating agent.
Specifically, the luminescent powder pretreating agent is prepared according to the following steps:
(1) in 1#Adding epoxy resin and a solvent into a reaction container, starting stirring, introducing nitrogen, heating to 110-;
(2) uniformly dripping a first part of mixed unsaturated monomer (containing initiator) into the mixture 1#Dropwise adding into a reaction container for 0.5-1.0h, and keeping the temperature for 1.0-1.5h, wherein the first part of the mixed unsaturated monomer accounts for 2/5-3/5 of the total weight of the mixed unsaturated monomer;
(3) uniformly dripping the rest mixed unsaturated monomer (containing initiator) into the mixture 1#Dropwise adding the mixture into a reaction container for 0.5 to 1.0 hour, and keeping the temperature for 1.5 to 2.0 hours;
(4) adding the formula amount of softened water and a neutralizer into the mixture 2#In a reaction vessel, stirring uniformly, and mixing the mixture 1#The contents of the reaction vessel are transferred to 2#Stirring and emulsifying for 1-2h in a reaction vessel to obtain the semitransparent epoxy modified acrylic emulsion.
The acrylic emulsion comprises the following components in parts by weight:
5-10 parts of methyl methacrylate, 10-15 parts of styrene, 25-30 parts of butyl acrylate, 0.5-1.5 parts of acrylic acid, 0.5-1 part of anionic emulsifier, 0.5-1 part of nonionic emulsifier, 0.5-1 part of reactive emulsifier, 0.1-0.3 part of initiator, 0.3-1.0 part of neutralizer and 45-55 parts of softened water.
Wherein the anionic emulsifier can be at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium fatty alcohol-polyoxyethylene ether sulfate, sodium fatty alcohol-polyoxyethylene phosphate and sodium lauryl sulfate; the nonionic emulsifier can be at least one of alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene ether and polyoxyethylene-polyoxypropylene block polyether; the reactive emulsifier can be sodium styrene sulfonate, sodium 2-methyl allyl sulfonate and sodium allyl-2-hydroxypropyl ether sulfonate; the initiator can be at least one of potassium persulfate and ammonium persulfate; the neutralizer is at least one of ammonia water, 2-amino-2-methyl-1-propanol (AMP-95), N-dimethylethanolamine and triethylamine; the demineralized water in the acrylic emulsion may be deionized or distilled water, but it is desirable that the conductivity be less than 20. mu.s/cm.
The acrylic emulsion is prepared according to the following steps:
mixing the softened water accounting for 3/4-4/5 of formula amount, an aqueous solution of an emulsifier and various unsaturated monomers, and stirring at a high speed for 15min to obtain a monomer pre-emulsion;
adding the rest softened water, the aqueous solution of the emulsifier and the monomer pre-emulsion of 1/3-1/5 into a reaction vessel, heating to 75 +/-2 ℃, adding a part of aqueous solution of the initiator under the nitrogen atmosphere, and keeping the temperature until the liquid is blue;
dropwise adding the residual monomer pre-emulsion into the blue mixed solution, simultaneously dropwise adding an aqueous solution of an initiator, finishing adding within 1-2h, and preserving heat until no reflux exists;
adding an aqueous solution of an initiator into the mixed solution without reflux, heating to 85 ℃, and keeping the temperature for 0.5 h;
cooling to 50-60 deg.C, adding neutralizer to adjust pH to 7-8, filtering and discharging.
Specifically, the preparation of the acrylic emulsion comprises the following steps:
preparing an initiator and an emulsifier into aqueous solutions respectively. Adding part of softened water, emulsifier solution and various unsaturated monomers into a stirring container, and stirring at high speed for 15min to obtain monomer pre-emulsion.
② adding metered softened water, emulsifier solution and monomer pre-emulsion into a four-neck flask provided with a stirrer, a thermometer, a condenser tube and a dropping funnel. The temperature is increased to 75 +/-2 ℃. Introducing nitrogen, adding partial initiator solution, and keeping the temperature until the liquid is blue.
And thirdly, dropwise adding the residual monomer pre-emulsion into the blue mixed solution, dropwise adding an initiator solution at the same time, finishing the addition for about 1.5 hours, and carrying out heat preservation reaction until no reflux exists.
Supplementing initiator solution, heating to 85 ℃, and reacting for 0.5h under the condition of heat preservation.
Cooling to 50-60 deg.c, adding neutralizer to regulate pH value to 7-8, filtering and discharging.
Preferably, in the water-based acrylic energy storage luminescent coating, the dispersing agent is a block copolymer containing pigment-philic groups; wetting agents are surfactants that can significantly reduce static and dynamic surface tension; the defoaming agent is polyether modified organic silicon resin; the filler is at least one of talcum powder, precipitated barium sulfate, calcined kaolin, superfine heavy calcium and light calcium carbonate; the thickener A is a polyurethane associative thickener; the thickener B is at least one of magnesium aluminum silicate and bentonite.
The preparation method of the water-based acrylic energy-storage luminescent coating comprises the following steps:
mixing water, a dispersing agent, a wetting agent and a luminescent powder pretreating agent, uniformly stirring, adding rare earth doped aluminate type long-acting luminescent powder, dispersing at a high speed, and grinding to obtain color paste; and adding a thickening agent into the color paste, uniformly stirring, and filtering to obtain a finished product.
Wherein, the grinding is carried out by a grinder.
The construction process and the detection method of the water-based luminous paint are as follows:
the luminous paint can be applied by brushing or spraying, and is stirred uniformly before use, and the viscosity can be adjusted by water. The paint film with high brightness can be formed only when the thickness of the paint film reaches more than 100 mu m and the film thickness is relatively uniform, and therefore, the paint film is generally sprayed for 2 to 3 times. The white primer can obviously improve the brightness of the paint film, so the white primer is needed to be precoated for reducing the cost.
The performance of the coating is detected according to the standard of JG/T446-2014 light-storage type luminous coating for buildings.
The water-based luminous paint has good stability, is matched with the pre-coating primer for coating, has good adhesive force on the surfaces of base materials such as cement, steel, aluminum alloy, wood, PVC plastic and the like, has good water resistance, alkali resistance and weather resistance of a paint film, high luminous brightness and long afterglow time, can be widely applied to aspects such as safety passages, mine tunnels, traffic signs, fire-fighting equipment, electrical switches and the like, and can be used as emergency marks under the condition of power failure or no illumination at night.
Examples 1 to 5
Examples 1-5 relate to a water-based acrylic energy storage luminescent coating, and the specific formula of the coating is shown in table 1.
TABLE 1. luminescent coating formulations of the examples
Wherein, the specific formula of the luminescent powder pretreating agent E1-E3 in the table 1 is shown in the table 2, and the specific formula of the acrylic emulsion E4-E6 is shown in the table 3.
TABLE 2 phosphor pretreatment formulations of the examples
TABLE 3 acrylic emulsion formulations of the examples
The water-based acrylic paint is prepared according to the following steps:
s1, preparation of luminescent powder pretreatment: adding propylene glycol methyl ether and dipropylene glycol methyl ether into a reaction container provided with a stirrer, a thermometer, a condenser and a dripping tank, starting stirring, adding epoxy resin, heating to 80-90 ℃, and keeping stirring until the epoxy resin is completely dissolved. Introducing nitrogen, heating to 115-125 ℃, and keeping the micro-boiling state. Secondly, mixing the unsaturated monomer and the initiator, dripping the mixture into a reaction container under the protection of nitrogen for about 2 to 3 hours, and carrying out heat preservation reaction at the temperature of 115 ℃ and 125 ℃ for 1 to 2 hours after the dripping is finished. Thirdly, cooling to 60-70 ℃, and adding a neutralizer. Gradually adding water and stirring to obtain copolymer carboxylate colloidal solution as a light-emitting powder pretreating agent.
S2, preparation of acrylic emulsion: dissolving emulsifier and initiator in water separately to prepare solution. Methyl methacrylate, styrene, butyl acrylate, emulsifier solution and deionized water are mixed and stirred to prepare the monomer pre-emulsion. Secondly, adding a part of monomer pre-emulsion, emulsifier solution and deionized water mixture into a four-neck flask provided with a stirrer, a thermometer, a condenser tube and a dropping funnel, and heating to 75 ℃. Introducing nitrogen, adding partial initiator solution, and keeping the temperature until the liquid is blue. Thirdly, dropwise adding the residual monomer pre-emulsion, dropwise adding the initiator solution at the same time, finishing the adding for about 2 hours, and continuously carrying out heat preservation reaction until no reflux exists. Fourthly, the temperature is raised to 85 ℃, a proper amount of initiator is added, and the temperature is kept for 0.5 h. Fifthly, cooling to 50-60 ℃, adding ammonia water to adjust the PH value to 7-9, filtering and discharging.
S3, preparation of the luminous paint: dissolving emulsifier and initiator in water separately to prepare solution. Methyl methacrylate, styrene, butyl acrylate, emulsifier solution and deionized water are mixed and stirred to prepare the monomer pre-emulsion. Secondly, adding a part of monomer pre-emulsion, emulsifier solution and deionized water mixture into a four-neck flask provided with a stirrer, a thermometer, a condenser tube and a dropping funnel, and heating to 75 ℃. Introducing nitrogen, adding partial initiator solution, and keeping the temperature until the liquid is blue. Thirdly, dropwise adding the residual monomer pre-emulsion, dropwise adding the initiator solution at the same time, finishing the adding for about 2 hours, and continuously carrying out heat preservation reaction until no reflux exists. Fourthly, the temperature is raised to 85 ℃, a proper amount of initiator is added, and the temperature is kept for 0.5 h. Fifthly, cooling to 50-60 ℃, adding ammonia water to adjust the PH value to 7-9, filtering and discharging.
Comparative examples 1 to 6
Comparative examples 1 to 6 relate to a water-based acrylic energy storage luminescent coating, and comparative examples 1 to 6 differ from example 1 only in the coating formulation, wherein the specific formulation of the luminescent coating of comparative examples 1 to 6 is shown in table 4.
TABLE 4 formulation of comparative luminescent coatings
The formula of the light-emitting powder pretreating agent E1 in Table 4 is the same as that of the examples, the specific formula of the light-emitting powder pretreating agent C1-C2 is shown in Table 5, the formula of the acrylic emulsion E4 in Table 4 is the same as that of the examples, and the specific formula of the acrylic emulsion C3-C4 is shown in Table 6.
TABLE 5 pretreatment of the phosphor powders for each pair of ratios
TABLE 6 acrylic emulsion formulations for each pair of ratios
Test examples
The performances of the aqueous acrylic acid energy storage luminescent coatings of examples 1-5 and comparative examples 1-6 were tested according to the JG/T446-2014 standard of light storage luminescent coatings for buildings, and the test results are shown in tables 7 and 8.
TABLE 7 test results of the aqueous acrylic energy-storing luminescent coatings of the examples
TABLE 8 test results of various comparative aqueous acrylic energy-storage luminescent coatings
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The water-based acrylic energy-storage luminescent coating is characterized by comprising the following components in parts by weight:
20-30 parts of water, 0.1-0.3 part of dispersant, 0.1-0.3 part of wetting agent, 0.01-0.1 part of defoaming agent, 10-30 parts of rare earth doped aluminate type long-acting luminescent powder, 5-10 parts of luminescent powder pretreating agent, 30-50 parts of acrylic emulsion, 0-20 parts of filler, 0.2-0.5 part of thickening agent A and 0.2-0.5 part of thickening agent B; the light-emitting powder pretreating agent comprises the following components:
20-30 parts of E-12 epoxy resin, 20-30 parts of cosolvent, 15-25 parts of methyl methacrylate, 15-25 parts of butyl acrylate, 0-4 parts of methacrylic acid, 0-4 parts of acrylic acid, 2-4 parts of maleic anhydride, 2-4 parts of allyl polyoxyethylene ether, 1-3 parts of initiator, 5-10 parts of neutralizer and 100 parts of softened water and 150 parts of organic solvent.
2. The aqueous acrylic energy-storing luminescent coating material of claim 1,
the initiator is at least one of benzoyl peroxide and azobisisobutyronitrile; and/or the presence of a gas in the gas,
the neutralizing agent is at least one of ammonia water or volatile amine; and/or the presence of a gas in the gas,
the cosolvent is at least one of propylene glycol methyl ether, propylene glycol ethyl ether and dipropylene glycol methyl ether.
3. The aqueous acrylic energy-storing luminescent paint as claimed in claim 1 or 2, wherein the content of water-soluble substances in the softened water is less than 100ppm, and the electrical conductivity is less than 20 μ s/cm.
4. The water-based acrylic energy storage luminous paint as claimed in any one of claims 1 to 3, characterized in that the luminous powder pretreating agent is prepared according to the following steps:
mixing epoxy resin and a solvent in a nitrogen atmosphere, and preserving heat for 2-3h at the temperature of 110-130 ℃ to dissolve the epoxy resin to obtain an epoxy resin solution;
mixing unsaturated monomers and dividing into two parts, firstly adding the mixed unsaturated monomers 2/5-3/5 in the total weight of the mixed unsaturated monomers into an epoxy resin solution, dropwise adding for 0.5-1.0h, and preserving heat for 1.0-1.5 h;
adding the rest mixed unsaturated monomer into the epoxy resin solution, dropwise adding for 0.5-1.0h, and keeping the temperature for 1.5-2.0h to obtain an epoxy grafted acrylic resin solution;
mixing an emulsifier, a neutralizer and an epoxy resin solution added with an unsaturated monomer, adding the neutralizer and softened water into the epoxy grafted acrylic resin solution, and stirring and emulsifying for 1-2 hours to obtain the light-emitting powder pretreating agent.
5. The aqueous acrylic energy-storing luminescent coating as claimed in claim 1, wherein the acrylic emulsion comprises the following components in parts by weight:
5-10 parts of methyl methacrylate, 10-15 parts of styrene, 25-30 parts of butyl acrylate, 0.5-1.5 parts of acrylic acid, 0.5-1 part of anionic emulsifier, 0.5-1 part of nonionic emulsifier, 0.5-1 part of reactive emulsifier, 0.1-0.3 part of initiator, 0.3-1.0 part of neutralizer and 45-55 parts of softened water.
6. The aqueous acrylic energy-storing luminescent paint of claim 5,
the anionic emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether sodium sulfate, fatty alcohol-polyoxyethylene phosphate sodium and lauryl alcohol sodium sulfate; and/or the presence of a gas in the gas,
the nonionic emulsifier is at least one of alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene ether and polyoxyethylene-polyoxypropylene block polyether; and/or the presence of a gas in the gas,
the reactive emulsifier is sodium styrene sulfonate, sodium 2-methallyl sulfonate and sodium allyl-2-hydroxypropyl ether sulfonate; and/or the presence of a gas in the gas,
the initiator is at least one of potassium persulfate and ammonium persulfate; and/or the presence of a gas in the gas,
the neutralizing agent is at least one of ammonia water, 2-amino-2-methyl-1-propanol (AMP-95), N-dimethylethanolamine and triethylamine.
7. The water-based acrylic energy-storing luminescent coating as claimed in claim 5 or 6, wherein the acrylic emulsion is obtained by the following steps:
mixing the softened water accounting for 3/4-4/5 of formula amount, an aqueous solution of an emulsifier and various unsaturated monomers, and stirring at a high speed for 15min to obtain a monomer pre-emulsion;
adding the rest softened water, the aqueous solution of the emulsifier and the monomer pre-emulsion of 1/3-1/5 into a reaction vessel, heating to 75 +/-2 ℃, adding a part of aqueous solution of the initiator under the nitrogen atmosphere, and keeping the temperature until the liquid is blue;
dropwise adding the residual monomer pre-emulsion into the blue mixed solution, simultaneously dropwise adding an aqueous solution of an initiator, finishing adding within 1-2h, and preserving heat until no reflux exists;
adding an aqueous solution of an initiator into the mixed solution without reflux, heating to 85 ℃, and keeping the temperature for 0.5 h;
cooling to 50-60 deg.C, adding neutralizer to adjust pH to 7-8, filtering and discharging.
8. The aqueous acrylic energy storing luminescent paint according to any one of claims 1 to 7, wherein the dispersant is a block copolymer containing pigment-philic groups; and/or, the wetting agent is a surfactant that can significantly reduce static and dynamic surface tension; and/or the defoaming agent is polyether modified organic silicon resin; and/or the presence of a gas in the gas,
the filler is at least one of talcum powder, precipitated barium sulfate, calcined kaolin, superfine heavy calcium and light calcium carbonate; and/or the presence of a gas in the gas,
the thickener A is a polyurethane associative thickener; and/or the presence of a gas in the gas,
the thickener B is at least one of magnesium aluminum silicate and bentonite.
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| CN111574896A (en) * | 2020-06-09 | 2020-08-25 | 广东青筑科技有限公司 | Water-based energy-storage luminescent coating and preparation method and construction method thereof |
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| CN113214824A (en) * | 2021-05-11 | 2021-08-06 | 齐齐哈尔北方集团北方化学工业有限责任公司 | Composite energy-storage luminescent material, water-based energy-storage luminescent coating and preparation method thereof |
| CN113201181A (en) * | 2021-05-19 | 2021-08-03 | 哈尔滨理工大学 | Preparation method of field enhanced nonlinear conductive polyethylene composite insulating material |
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