CN111849275A

CN111849275A - Preparation method and application of water-based two-component electric heating coating

Info

Publication number: CN111849275A
Application number: CN202010368772.6A
Authority: CN
Inventors: 孙姜楠
Original assignee: Ningbo Yuanshenghe New Material Technology Co Ltd
Current assignee: Ningbo Yuanshenghe New Material Technology Co Ltd
Priority date: 2020-05-02
Filing date: 2020-05-02
Publication date: 2020-10-30
Anticipated expiration: 2040-05-02
Also published as: CN111849275B

Abstract

The application discloses a preparation method and application of a water-based two-component electric heating coating. The water-based two-component electric heating coating comprises: the composite material comprises water-based high polymer resin and a curing agent thereof, a conductive material, a photo-thermal conversion reinforcing agent, an auxiliary agent and water; the synergistic effect of the conductive material and the photo-thermal conversion reinforcing agent is utilized to realize the reinforcing effect of electric conduction and heat conduction; the electrothermal coating with a cross-linking structure formed by the water-based resin and the water-based curing agent has excellent adhesive force and strong durability and aging resistance, and can be widely sprayed, roll-coated or printed on the surfaces of glass, floors, wood, plastic films and the like to prepare the heat-generating material.

Description

Preparation method and application of water-based two-component electric heating coating

Technical Field

The invention relates to the technical field of paint preparation, in particular to a preparation method and application of a water-based two-component electric heating paint.

Background

The electric heating coating is a functional coating which disperses conductive materials in polymer resin and then is sprayed or roll-printed on a plastic film, the coating can convert electric energy into heat energy in the electrifying process, and has the advantages of high electric heating conversion efficiency, environmental protection and energy saving. Under the current diversified heating situation, the electric heating products represented by the film cannot meet the increasingly harsh market demands, and more products with heating forms, such as electric heating wood boards, electric heating glass, electric heating floors and the like, are urgently needed to meet the indoor and outdoor demands. This places greater demands on the selected resin, such as better adhesion and stability, better resistance to aging and use.

The aqueous two-component conductive resin is mixed with a curing agent through resin, and then is sprayed, roll-coated or printed on the surfaces of glass, floors, wood, plastic films and the like, and a conductive network of cross-linked resin is formed after curing, so that the aqueous two-component conductive resin has higher adhesive force, durability and aging resistance, can be widely applied to flexible or rigid surfaces, further improves the application field of electric heating materials, and fills the gap of the prior art.

The invention discloses an electrothermal coating (CN 201610456534.4) which relates to a coating for heating indoor and outdoor buildings, is coated on indoor walls, desks and outdoor sentries, can realize heating by using safe voltage, meets different temperature rise requirements through controlling resistivity, and can reach the performance of 5-20 ℃ higher than the ambient temperature, thereby the invention also provides a processing method of the electrothermal coating. The method is realized by the following technical scheme: the material comprises the following materials in parts by weight: 40 to 60 portions of film forming material, 15 to 30 portions of pigment and filler, 1 to 2 portions of auxiliary agent and 20 to 30 portions of solvent, the materials are put into a ball mill according to a certain proportion and are fully mixed and ground to prepare the coating with the fineness range of 30 to 60 mu m, namely the electrothermal coating.

A high-temperature electrothermal coating and a preparation method (ZL 201710900191.0) thereof are disclosed, wherein the high-temperature electrothermal coating comprises the following components in percentage by weight: 30-60% of organic carrier; 5-15% of nano conductive carbon black; 5-15% of graphite; 0.1 to 15 percent of auxiliary agent; 10-40% of a solvent; the organic carrier comprises the following components in percentage by weight: 30-40% of a solvent; 15-30% of phenolic epoxy resin; 15-35% of bisphenol A type epoxy resin; 3-10% of dicyandiamide latent curing agent; 0.1-5% of substituted urea curing accelerator. By adopting the formula, the prepared high-temperature electric heating coating can ensure that the long-term use temperature is 100-150 ℃, the heating temperature is uniform, and the power recession cannot occur after long-term use. In addition, the preparation method has the advantages of simple preparation process, no pollution and low cost, and is suitable for large-scale industrial production.

A novel electrothermal coating and a preparation method (ZL 201711370283.9) thereof, wherein the ink comprises the following components in parts by mass: 10-20 parts of graphite; 2-10 parts of conductive carbon black; 10-15 parts of carbon nanotube dispersion liquid; 7-15 parts of graphene dispersion liquid; 0.5-2 parts of silicon carbide whisker; 0.5-2 parts of tin oxide; 0.5-2 parts of nickel-iron spinel; 16-37 parts of a water-based resin linking agent; 20-40 parts of water; and 2.3-8 parts of an auxiliary agent. The invention relates to an electrothermal slurry containing the conductive composition and a preparation method thereof. In addition, the conductive ink disclosed by the invention has the advantages of high heating uniformity, high electrothermal conversion efficiency, high heating speed, light weight, good flexibility, strong adhesive force, good weather resistance, good aging resistance, high safety, environmental friendliness and the like, can be used as a heating product for buildings, and can be further processed into various electrothermal heating products.

A preparation method (CN 201910679219.1) of a composite carbon-based electric heating coating, the invention uses polyacrylonitrile and zinc acetate as raw materials to obtain porous carbon nanofibers, then mixes the porous carbon nanofibers with mussel mucin liquid and adds catechol oxidase for ultrasonic oscillation to obtain reaction filter residue, then mixes the reaction filter residue with silver nitrate solution for high-temperature sintering to obtain self-made composite carbon-based filler, and finally blends and shears the self-made composite carbon-based filler with resin and other additives to prepare the composite carbon-based electric heating coating, the oxidized dopa group and the unoxidized dopa group are crosslinked to form a high molecular network polymer which is absorbed on the inner pores and the surface of the porous carbon nanofibers and has metal ion chelation, a layer of carbon nanometer conduction band network is generated between the interfaces of metal silver and the porous carbon nanofibers, the electric conductivity of the composite material is increased, the electric heating coating prepared by the invention has good electric heating performance, the temperature rise is fast, the temperature is high, and the method has wide application prospect.

An electrothermal coating (CN 201510198538.2) comprising the following components: a titanium manganese iron mixed matrix, an induction semi-conductive medium, a flame retardant and an adhesive. The electric heating coating provided by the invention is a gray-brown viscose coating in appearance, is nontoxic and tasteless, can generate heat through the induction of electrodes at two ends, can continuously dissipate heat, does not transmit electricity, is convenient to use, safe and reliable, is durable, has no aging phenomenon after 48h high-temperature test, has long service life, can not cause power supply short circuit, has low power consumption, can not generate dryness and stuffy heat sensation, is an ideal product for replacing other electric heaters, is generally suitable for industries such as family heating, incubation, edible fungus production places, crab culture and the like, and is also suitable for the fields of electric heating murals, electric heating chafing dishes, electric heating pots and the like.

The above documents mainly adopt materials with conductive properties, such as carbon materials, metals and oxides thereof, to carry out grinding preparation, and the problem of poor grinding dispersion effect of the materials does not exist, and meanwhile, because the heat conduction and conductive materials have high conductive efficiency and high heat conduction efficiency, the heat dissipation rate in the electric heating process is high, so that the problem of poor efficiency is brought; therefore, the material with the photothermal conversion is introduced, the material absorbs heat in the heat conduction process and then emits high-energy infrared rays, so that the heating efficiency is improved, the heat loss is reduced, the electric heat conversion effect of the photothermal conversion material is realized, and the electric conduction performance and the heat preservation effect are improved.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method and application of a water-based two-component electric heating coating.

The purpose of the invention is realized by the following technical scheme:

the viscosity of the water-based double-component electric heating coating is 500-10000 mPa & s, the pH value is 5.0-7.5, and the surface tension is 25-45 mN/m; the curing temperature of the water-based two-component electric heating coating is 60-180 ℃, the curing time is 45-120 min, the resistivity of the coating after curing and film forming is 50-500 omega-cm, the thermal conductivity is 1.0-2.5W/(m-K), the reflectivity at 900-2500 nm is more than 20%, and the adhesive force is 0 grade.

The water-based two-component electric heating coating comprises the following components in parts by mass:

the water-based polymer resin is a hydroxyl acrylic emulsion (dispersion) or a water-based epoxy emulsion, and the preferable hydroxyl acrylic emulsion is Changxing 1194-D and Hamming, D, moderate FS-2460AF, the hydroxyl value of which is 1.5-4.5 wt%, the water-based epoxy emulsion is Changxing W34310, Hounsfield PZ3961-1 and Dow 3002, and the epoxy equivalent weight of which is 1000-1500;

the water-based curing agent is a water-dispersible isocyanate curing agent, amino resin and a water-based epoxy curing agent with active hydrogen, the preferable water-dispersible isocyanate curing agent is Bayer H-3800 and Wanhua chemical 268, the NCO content of the water-dispersible isocyanate curing agent is 10.2-20.4%, the amino resin is Meiguo CyMEL amino resin 303LF and 1158, the water-based epoxy curing agent is Tao 805 and Hensmei 36, and the active hydrogen equivalent of the water-based epoxy curing agent is 110-140.

The used conductive material is a composition of conductive carbon black, graphite, graphene and carbon nano tubes, and the preferable conductive material has a particle size of 5-100 micrometers and a specific surface area of 30-60 m²The specific weight ratio is/g, the conductivity is 5-15S/cm, and the oil absorption value is 250-300 mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 5-50 micrometers, the thermal conductivity of the composite powder is 2.0-4.5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is more than 25%;

The dispersant is a commercial carbon black dispersant which is easily purchased on the market, such as XR-81331 of Hiran new material company, KMT-3017 dispersant produced by Kenin new material company of Foshan, KYC-9366 dispersant of Keying group, byk-190 of Germany Bike chemical, Surfynol CT-171 dispersant of Yingchuang Delosol, DS-172 dispersant of Tianjin He Pufel new material, and SP-717 dispersant of Dongguan Chengni chemical industry;

the leveling agent is organic silicon leveling agent, such as TEGO-440, TEGO-2100, byk-331, byk-333;

the defoaming agent is polyether modified siloxane, such as TEGO-901w, TEGO-904w, TEGO-810, TEGO-825;

the thickening agent is any one or the combination of more than two of fumed silica, organic bentonite and hydroxypropyl cellulose, and the preferable composition is a mixture of 1: 1: 1;

the cosolvent used is preferably any one or a combination of more than two of isopropanol, propylene glycol and propylene glycol methyl ether, and the preferred mixture is a mixture with a volume ratio of 1: 1: 1.

the preparation method of the water-based two-component electric heating coating comprises the following steps:

preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then performing mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after 24-36 h of mechanochemical stripping, then adding the composite powder into ferric nitrate solution, performing oscillation reaction for 24-36 h, adsorbing and loading the loaded composite powder by iron ions through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 24-48 h, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor for 6-8 h under the condition of 250-300 ℃ under the protection of nitrogen, increasing the calcining temperature to 400-450 ℃, calcining for 2-3 h in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

The boron nitride is of a multilayer structure, the particle size of a lamella of the boron nitride is 1.0-2.5 micrometers, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.5-1: 0.75; the concentration of the ferric nitrate solution is 0.5-1.0 mol/L, the mass concentration of the composite powder in the ferric nitrate is 10-25%, the concentration of the cerium nitrate solution is 0.5-1.0 mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 5-10%; the boron nitride composite powder contains 5-7.5% of iron element, the photothermal conversion enhancer precursor contains 5-10 wt% of cerium element, the photothermal conversion enhancer precursor contains 3-5% of iron element and 7-12 wt% of cerium element;

(II) preparation of aqueous conductive Material Dispersion

Uniformly dispersing the conductive material, the photo-thermal conversion reinforcing agent, the dispersing agent, the defoaming agent, the cosolvent and the like, adding the mixture into a sand mill, grinding for 2-8 hours until the particle size is below 5 mu m, and preparing aqueous conductive material dispersion liquid;

(III) preparation of aqueous conductive polymer resin A component

Adding the aqueous conductive material dispersion liquid with a certain proportion into aqueous high polymer resin according to a certain proportion, then adding a leveling agent and a rheological aid, and stirring and dispersing for 1-8 h to obtain an aqueous conductive high polymer resin component A; the mass dispersion of the waterborne conductive material in the waterborne conductive polymer resin A component is 20-50%;

Preparation of (IV) aqueous conductive curing agent B component

Adding the rest aqueous conductive material dispersion liquid into an aqueous curing agent according to a certain proportion, and stirring and dispersing for 1-8 h to obtain an aqueous conductive curing agent resin B component;

(V) preparation of water-based two-component electric heating coating

Mixing the component A and the component B according to the proportion of 1: 1.5-1: 3, mixing the components in proportion to prepare the water-based double-component electric heating coating.

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is kept stand for defoaming, then water is added to adjust viscosity, and the two-component electric heating coating is prepared, is sprayed, rolled or printed on the surfaces of glass, floors, wood, plastic films and the like, and is used for electrified heating products.

Compared with the prior art, the invention has the following positive effects:

the reticular polymer conductive coating formed by the crosslinking reaction of the resin and the curing agent has good adhesive force and stability, and good aging resistance and usability; the conductive coating of the reticular polymer formed by the cross-linking reaction of the resin and the curing agent fixes the conductive material inside the coating from the microstructure, so that the wanted displacement is difficult to occur, and the resistance inside the coating is guaranteed to be wanted to be stable in the process of electrifying and heating; the reticular polymer conductive coating formed by the crosslinking reaction of the resin and the curing agent has rich group structures, can be sprayed, roll-coated or printed on the surfaces of glass, floors, wood, plastic films and the like, and greatly widens the application range of the conductive coating. The photo-thermal conversion reinforcing agent and the carbon black, graphite, graphene and carbon nano tubes in the heat conduction material have a synergistic enhancement effect, boron nitride in the photo-thermal conversion material absorbs conduction electrons in the heating process by utilizing the synergistic effect of the heat conduction components of the heat conduction material and the photo-thermal conversion reinforcing material, and the electronic conversion effect of the tungsten ferrite and the cerium tungstate is utilized, so that the conversion of electric energy and heat is realized, and meanwhile, the self-heating and far infrared absorption reflection functions of the tungsten ferrite and the cerium tungstate are utilized, so that the heat effect of the electrothermal coating is improved, and the electric heating efficiency and the heat conduction performance conductivity of the electrothermal coating are improved; the problems that the conventional material heat and electricity conducting material is high in electric conductivity, fast in heat transfer and high in loss rate are solved.

Drawings

FIG. 1 is an X-ray diffraction pattern of a photothermal conversion enhancer of the present application;

FIG. 2 is a scanning electron micrograph of the present photothermal conversion enhancer.

Detailed Description

The following provides a preparation method of the water-based two-component electric heating coating and a specific implementation mode of the application of the water-based two-component electric heating coating.

Example 1

the aqueous polymer resin is hydroxy acrylic emulsion (dispersoid) or aqueous epoxy emulsion, the preferable hydroxy acrylic emulsion is Changxing 1194-D, and the hydroxyl value is 4.5 wt%;

the water-based curing agent is a water-dispersible isocyanate curing agent, an amino resin and a water-based epoxy curing agent with active hydrogen, and the preferred water-dispersible isocyanate curing agent is Wanhua chemical 268, and the NCO content of the water-dispersible isocyanate curing agent is 20.4%.

The conductive material is a composition of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferred conductive material is conductive carbon black with the particle diameter of 100 microns and the specific surface area of 30m²The electric conductivity is 15S/cm, and the oil absorption value is 250mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 50 micrometers, the thermal conductivity of the composite powder is 2.0W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is 25.9%;

The dispersant is a commercially available carbon black dispersant, such as XR-81331 from Hiran New materials, Inc.;

the flatting agent is organic silicon flatting agent, such as TEGO-440;

the defoaming agent is polyether modified siloxane, such as TEGO-901 w;

the thickening agent is fumed silica;

a preferred co-solvent used is isopropanol.

preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then carrying out mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after the mechanochemical stripping is carried out for 36h, then adding the composite powder into ferric nitrate solution, carrying out oscillation reaction for 36h, adsorbing iron ions on the loaded composite powder through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 48h, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor at 300 ℃ for 8h under the protection of nitrogen, increasing the calcining temperature to 450 ℃, calcining for 3h in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

The boron nitride is of a multilayer structure, the grain diameter of a lamella of the boron nitride is 2.5 microns, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.75; the concentration of the ferric nitrate solution is 1.0mol/L, the mass concentration of the composite powder in the ferric nitrate is 25%, the concentration of the cerium nitrate solution is 1.0mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 10%; the boron nitride composite powder contains 7.5% of iron element, 10% of cerium element in the photo-thermal conversion enhancer precursor, 5% of iron element and 12% of cerium element in the photo-thermal conversion enhancer precursor; (II) preparation of aqueous conductive Material Dispersion

Uniformly dispersing the conductive material, the photo-thermal conversion reinforcing agent, the dispersing agent, the defoaming agent, the cosolvent and the like, adding the mixture into a sand mill, grinding for 8 hours until the particle size is below 5 mu m, and preparing aqueous conductive material dispersion liquid;

(III) preparation of aqueous conductive polymer resin A component

Adding the aqueous conductive material dispersion liquid with a certain proportion into aqueous high polymer resin according to a certain proportion, then adding a leveling agent and a rheological aid, and stirring and dispersing for 8 hours to obtain an aqueous conductive high polymer resin component A; the mass dispersion of the aqueous conductive material in the aqueous conductive polymer resin A component is 50 percent;

Preparation of (IV) aqueous conductive curing agent B component

Adding the rest aqueous conductive material dispersion liquid into an aqueous curing agent according to a certain proportion, and stirring and dispersing for 8 hours to obtain an aqueous conductive curing agent resin B component;

(V) preparation of water-based two-component electric heating coating

Mixing the component A and the component B according to the proportion of 1: 2.5, and preparing the aqueous two-component electric heating coating.

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is placed still for defoaming, then water is added to adjust the viscosity, and the two-component electric heating coating is prepared, the coating is printed on the surface of glass, and the water-based two-component electric heating coating is used for electrifying heating products.

The viscosity of the water-based double-component electric heating coating is 10000mPa & s, the pH value is 7.5, and the surface tension is 45 mN/m; the curing temperature of the water-based two-component electric heating coating is 180 ℃, the curing time is 45min, the resistivity of the coating after curing and film forming is 50 omega cm, the thermal conductivity is 1.0W/(m.K), the reflectivity at 900-2500 nm is 22%, and the adhesive force is 0 grade.

Example 2

the water-based polymer resin is a hydroxyl acrylic emulsion (dispersion) or a water-based epoxy emulsion, the preferable hydroxyl acrylic emulsion is Hamming, D.D. FS-2460AF, and the hydroxyl value is 1.5 wt%;

The water-based curing agent is a water-dispersible isocyanate curing agent, an amino resin and a water-based epoxy curing agent with active hydrogen, and the preferable water-dispersible isocyanate curing agent is Bayer H-3800 and the NCO content of the water-dispersible isocyanate curing agent is 20.4%.

The conductive material is a composition of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferred conductive material is graphite with a particle size of 5 microns and a specific surface area of 30m²The electric conductivity is 5S/cm, and the oil absorption value is 300mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 5 micrometers, the thermal conductivity of the composite powder is 4.5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is 29%;

the dispersant is KMT-3017 dispersant produced by new material company of Fushan city, which is a commercial carbon black dispersant, easily available on the market;

the leveling agent is an organic silicon leveling agent, preferably TEGO-2100;

the defoaming agent is polyether modified siloxane, preferably TEGO-904 w;

the thickening agent is organic bentonite;

the preferred co-solvent used is propylene glycol.

Preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then carrying out mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after 24h of mechanochemical stripping, then adding the composite powder into ferric nitrate solution, carrying out oscillation reaction for 24h, adsorbing and loading the composite powder on iron ions through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 24 hours, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor for 6 hours under the condition of 250 ℃ under the protection of nitrogen, increasing the calcining temperature to 400 ℃, calcining for 2 hours in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

the boron nitride is of a multilayer structure, the grain diameter of a lamella of the boron nitride is 1.0 micron, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.5; the concentration of the ferric nitrate solution is 0.5mol/L, the mass concentration of the composite powder in the ferric nitrate is 10%, the concentration of the cerium nitrate solution is 0.5mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 5%; the boron nitride composite powder contains 5% of iron element, 5% of cerium element in the photo-thermal conversion enhancer precursor, 3% of iron element and 7% of cerium element in the photo-thermal conversion enhancer precursor;

(II) preparation of aqueous conductive Material Dispersion

Uniformly dispersing the conductive material, the photo-thermal conversion reinforcing agent, the dispersing agent, the defoaming agent, the cosolvent and the like, adding the mixture into a sand mill, grinding for 2 hours until the particle size is below 5 mu m, and preparing aqueous conductive material dispersion liquid;

(III) preparation of aqueous conductive polymer resin A component

Adding the aqueous conductive material dispersion liquid with a certain proportion into aqueous high polymer resin according to a certain proportion, then adding a leveling agent and a rheological aid, and stirring and dispersing for 1h to obtain an aqueous conductive high polymer resin component A; the mass dispersion of the aqueous conductive material in the aqueous conductive polymer resin A component is 20 percent;

preparation of (IV) aqueous conductive curing agent B component

(V) preparation of water-based two-component electric heating coating

Mixing the component A and the component B according to the proportion of 1: 1.5, and preparing the aqueous two-component electric heating coating.

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is kept stand for defoaming, then water is added to adjust viscosity, and the two-component electric heating coating is prepared, is sprayed on the surface of a floor, and is used for electrifying and heating products.

The viscosity of the water-based double-component electric heating coating is 500mPa & s, the pH value is 5.0, and the surface tension is 25 mN/m; the curing temperature of the water-based two-component electric heating coating is 60 ℃, the curing time is 45min, the resistivity of the coating after curing and film forming is 500 omega cm, the heat conductivity is 1.0W/(m.K), the reflectivity is 22% at 900-2500 nm, and the adhesive force is 0 grade.

Example 3

the water-based polymer resin is hydroxy acrylic emulsion (dispersoid) or water-based epoxy emulsion, the preferable water-based epoxy emulsion is Changxing W34310, and the epoxy equivalent is 1000;

the waterborne curing agent is a water dispersible isocyanate curing agent, amino resin and a waterborne epoxy curing agent with active hydrogen, and the preferred amino resin is American CyMEL amino resin 303 LF.

The conductive material is a composition of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferable conductive material is a graphene sheet layer with the particle diameter of 5 microns and the specific surface area of 30m²The electric conductivity is 15S/cm, and the oil absorption value is 300mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 35 micrometers, the thermal conductivity of the composite powder is 3.5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is 26%;

The dispersant is a commercial carbon black dispersant which is easily purchased in the market, such as KYC-9366 dispersant of Keying group;

the leveling agent is organic silicon leveling agent, such as byk-331;

the defoaming agent is polyether modified siloxane, such as TEGO-810;

the thickening agent is hydroxypropyl cellulose;

the preferred co-solvent used is propylene glycol methyl ether.

preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then carrying out mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after 30h of mechanochemical stripping, then adding the composite powder into ferric nitrate solution, carrying out oscillation reaction for 30h, adsorbing and loading the composite powder on iron ions through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 30h, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor at 300 ℃ for 8h under the protection of nitrogen, increasing the calcining temperature to 450 ℃, calcining for 2h in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

The boron nitride is of a multilayer structure, the grain diameter of a lamella of the boron nitride is 1.5 microns, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.75; the concentration of the ferric nitrate solution is 1.0mol/L, the mass concentration of the composite powder in the ferric nitrate is 15%, the concentration of the cerium nitrate solution is 0.75mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 10%; the boron nitride composite powder contains 6.5% of iron element, the photo-thermal conversion enhancer precursor contains 8.5% of cerium element, the photo-thermal conversion enhancer precursor contains 5% of iron element and 11.5% of cerium element;

(II) preparation of aqueous conductive Material Dispersion

Uniformly dispersing the conductive material, the photo-thermal conversion reinforcing agent, the dispersing agent, the defoaming agent, the cosolvent and the like, adding the mixture into a sand mill, grinding for 6 hours until the particle size is below 5 mu m, and preparing aqueous conductive material dispersion liquid;

(III) preparation of aqueous conductive polymer resin A component

Adding the aqueous conductive material dispersion liquid with a certain proportion into aqueous high polymer resin according to a certain proportion, then adding a leveling agent and a rheological aid, and stirring and dispersing for 6 hours to obtain an aqueous conductive high polymer resin component A; the mass dispersion of the aqueous conductive material in the aqueous conductive polymer resin A component is 45 percent;

Preparation of (IV) aqueous conductive curing agent B component

Adding the rest aqueous conductive material dispersion liquid into an aqueous curing agent according to a certain proportion, and stirring and dispersing for 6 hours to obtain an aqueous conductive curing agent resin component B;

(V) preparation of water-based two-component electric heating coating

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is kept stand for defoaming, then water is added to adjust viscosity, and the two-component electric heating coating is prepared, the coating is roll-coated on the surface of wood, and the water-based two-component electric heating coating is used for electrifying heating products.

The viscosity of the water-based double-component electric heating coating is 5000mPa & s, the pH value is 7.2, and the surface tension is 35 mN/m; the curing temperature of the water-based two-component electric heating coating is 80 ℃, the curing time is 120min, the resistivity of the coating after curing and film forming is 350 omega cm, the heat conductivity is 2.5W/(m.K), the reflectivity at 900-2500 nm is 24%, and the adhesive force is 0 grade.

Example 4

the water-based polymer resin is hydroxy acrylic emulsion (dispersoid) or water-based epoxy emulsion, the preferable water-based epoxy emulsion is Hensmei PZ3961-1, and the epoxy equivalent is 1200;

The waterborne curing agent is a water dispersible isocyanate curing agent, amino resin and a waterborne epoxy curing agent with active hydrogen, and the preferred amino resin is American CyMEL amino resin 1158.

The conductive material is a composition of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferred conductive material is carbon nanotubes with the length of 25 microns and the specific surface area of 30m²The electric conductivity is 10S/cm, and the oil absorption value is 300mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 25 micrometers, the thermal conductivity of the composite powder is 4.5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is more than 27.9%;

the dispersant is a commercial carbon black dispersant which is easily purchased in the market, such as byk-190 of German Bick chemistry;

the leveling agent is organic silicon leveling agent, such as byk-333;

the defoaming agent is polyether modified siloxane, such as TEGO-825;

the thickening agent is a composition of fumed silica, organic bentonite and hydroxypropyl cellulose, and the mass ratio of the thickening agent to the organic bentonite is preferably 1: 1: 1;

the cosolvent used is preferably a mixture of isopropanol, propylene glycol and propylene glycol methyl ether, preferably in a volume ratio of 1: 1: 1.

preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then carrying out mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after the mechanochemical stripping is carried out for 36h, then adding the composite powder into ferric nitrate solution, carrying out oscillation reaction for 36h, adsorbing iron ions on the loaded composite powder through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 48h, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor for 6h under the protection of nitrogen at 300 ℃, increasing the calcining temperature to 450 ℃, calcining for 3h in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

the boron nitride is of a multilayer structure, the grain diameter of a lamella of the boron nitride is 2.5 microns, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.75; the concentration of the ferric nitrate solution is 0.5mol/L, the mass concentration of the composite powder in the ferric nitrate is 15%, the concentration of the cerium nitrate solution is 1.0mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 10%; the boron nitride composite powder contains 7.5% of iron element, 8% of cerium element in the photo-thermal conversion enhancer precursor, 4% of iron element and 11% of cerium element in the photo-thermal conversion enhancer precursor; (II) preparation of aqueous conductive Material Dispersion

(III) preparation of aqueous conductive polymer resin A component

Adding the aqueous conductive material dispersion liquid with a certain proportion into aqueous high polymer resin according to a certain proportion, then adding a leveling agent and a rheological aid, and stirring and dispersing for 6 hours to obtain an aqueous conductive high polymer resin component A; the mass dispersion of the aqueous conductive material in the aqueous conductive polymer resin A component is 40 percent;

preparation of (IV) aqueous conductive curing agent B component

(V) preparation of water-based two-component electric heating coating

Mixing the component A and the component B according to the proportion of 1: 2.0 proportion, and preparing the aqueous two-component electric heating coating.

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is placed still for defoaming, then water is added to adjust the viscosity, and the two-component electric heating coating is prepared, is roll-coated on the surface of a plastic film, and is used for electrifying and heating products.

The viscosity of the water-based two-component electric heating coating is 7000 mPa.s, the pH value is 7.0, and the surface tension is 30 mN/m; the curing temperature of the water-based two-component electric heating coating is 80 ℃, the curing time is 90min, the resistivity of the coating after curing and film forming is 300 omega cm, the heat conductivity is 1.5W/(m.K), the reflectivity at 900-2500 nm is 23%, and the adhesive force is 0 grade.

Example 5

the water-based polymer resin is hydroxy acrylic acid emulsion (dispersoid) or water-based epoxy emulsion, the preferable water-based epoxy emulsion is Dow WB3002, and the epoxy equivalent is 1500;

the waterborne curing agent is a water dispersible isocyanate curing agent, amino resin and a waterborne epoxy curing agent with active hydrogen, the preferred waterborne epoxy curing agent is Dow 805, and the equivalent weight of the active hydrogen of the waterborne epoxy curing agent is 110.

The conductive material is a composition of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferred conductive material is conductive carbon black with the particle size of 50 microns and the specific surface area of 40m²The electric conductivity is 10S/cm, and the oil absorption value is 250mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 35 micrometers, the thermal conductivity of the composite powder is 3.5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is 26.7%;

The dispersant is a commercial carbon black dispersant which is easily purchased in the market, such as Surfynol CT-171 dispersant winning the Chuangdegusai;

the leveling agent is organic silicon leveling agent, such as byk-333;

the defoaming agent is polyether modified siloxane, such as TEGO-810;

the thickening agent is a combination of fumed silica, organic bentonite and hydroxypropyl cellulose, and the preferable combination is a combination with a mass ratio of 1: 1: 1;

the cosolvent used is preferably a combination of isopropanol, propylene glycol and propylene glycol methyl ether, and the preferred mixture is a mixture of isopropanol, propylene glycol and propylene glycol methyl ether in a volume ratio of 1: 1: 1.

preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then carrying out mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after the mechanochemical stripping is carried out for 36h, then adding the composite powder into ferric nitrate solution, carrying out oscillation reaction for 36h, adsorbing iron ions on the loaded composite powder through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 48h, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor for 6h under the protection of nitrogen at 300 ℃, increasing the calcining temperature to 450 ℃, calcining for 2h in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

The boron nitride is of a multilayer structure, the grain diameter of a lamella of the boron nitride is 1..5 microns, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.5; the concentration of the ferric nitrate solution is 1.0mol/L, the mass concentration of the composite powder in the ferric nitrate is 25%, the concentration of the cerium nitrate solution is 0.5mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 10%; the boron nitride composite powder contains 6.5% of iron element, the photothermal conversion enhancer precursor contains 7.8% of cerium element, the photothermal conversion enhancer precursor contains 3.5% of iron element and 9.2% of cerium element;

(II) preparation of aqueous conductive Material Dispersion

(III) preparation of aqueous conductive polymer resin A component

Preparation of (IV) aqueous conductive curing agent B component

(V) preparation of water-based two-component electric heating coating

The viscosity of the water-based double-component electric heating coating is 6500mPa & s, the pH value is 7.5, and the surface tension is 40 mN/m; the curing temperature of the water-based two-component electric heating coating is 120 ℃, the curing time is 45min, the resistivity of the coating after curing and film forming is 350 omega cm, the heat conductivity is 2.0W/(m.K), the reflectivity at 900-2500 nm is 24.3%, and the adhesive force is 0 grade.

Example 6

the water-based polymer resin is hydroxy acrylic acid emulsion (dispersoid) or water-based epoxy emulsion, the preferable water-based epoxy emulsion is Dow WB3002, and the epoxy equivalent is 1000;

The water-based curing agent is a water-dispersible isocyanate curing agent, an amino resin and a water-based epoxy curing agent with active hydrogen, the preferable water-based epoxy curing agent is Hensmei 36, and the equivalent weight of the active hydrogen of the water-based epoxy curing agent is 140.

Conductive material usedIs a combination of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferred conductive material is graphite with a particle size of 45 microns and a specific surface area of 40m²The specific weight ratio is/g, the conductivity is 12.5S/cm, and the oil absorption value is 280mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 35 micrometers, the thermal conductivity of the composite powder is 2.. 5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is 27.1%;

the dispersant is a commercial carbon black dispersant which is easily purchased in the market, such as a DS-172 dispersant of a new Tianjin Help Philippine material;

the flatting agent is organic silicon flatting agent, such as TEGO-440;

the defoaming agent is polyether modified siloxane, such as TEGO-901 w;

preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then carrying out mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after 28h of mechanochemical stripping, then adding the composite powder into ferric nitrate solution, carrying out oscillation reaction for 28h, adsorbing and loading the composite powder on iron ions through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 28h, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor at 300 ℃ for 8h under the protection of nitrogen, increasing the calcining temperature to 450 ℃, calcining for 3h in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

(III) preparation of aqueous conductive polymer resin A component

Adding the aqueous conductive material dispersion liquid with a certain proportion into aqueous high polymer resin according to a certain proportion, then adding a leveling agent and a rheological aid, and stirring and dispersing for 6 hours to obtain an aqueous conductive high polymer resin component A; the mass dispersion of the aqueous conductive material in the aqueous conductive polymer resin A component is 50 percent;

preparation of (IV) aqueous conductive curing agent B component

(V) preparation of water-based two-component electric heating coating

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is kept stand for defoaming, then water is added to adjust viscosity, and the two-component electric heating coating is prepared, the coating is sprayed on the surface of wood, and the water-based two-component electric heating coating is used for electrifying heating products.

The viscosity of the water-based two-component electric heating coating is 3000mPa & s, the pH is 6..5, and the surface tension is 40 mN/m; the curing temperature of the water-based two-component electric heating coating is 80 ℃, the curing time is 90min, the resistivity of the coating after curing and film forming is 100 omega cm, the thermal conductivity is 2.0W/(m.K), the reflectivity at 900-2500 nm is 21.1%, and the adhesive force is 0 grade.

Example 7

the water-based polymer resin is hydroxyl acrylic emulsion (dispersion) or water-based epoxy emulsion, the preferable hydroxyl acrylic emulsion is Hamming, D.D. FS-2460AF, and the hydroxyl value is 3.5 wt%;

the water-based curing agent is a water-dispersible isocyanate curing agent, an amino resin and a water-based epoxy curing agent with active hydrogen, the preferable water-based epoxy curing agent is Hensmei 36, and the equivalent weight of the active hydrogen of the water-based epoxy curing agent is 110.

The conductive material is a composition of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferred conductive material is conductive carbon black with the particle size of 75 microns and the specific surface area of 35m²The specific weight ratio is/g, the conductivity is 7.5S/cm, and the oil absorption value is 280mL/100 g;

The photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 35 micrometers, the thermal conductivity of the composite powder is 2.5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is 26%;

the dispersant is a commercial carbon black dispersant which is easily purchased in the market, such as SP-717 dispersant of Bocheng chemical engineering in Dongguan;

the leveling agent is organic silicon leveling agent, such as byk-333;

the defoaming agent is polyether modified siloxane, such as TEGO-810;

preparation of photothermal conversion enhancer

The boron nitride is of a multilayer structure, the grain diameter of a lamella of the boron nitride is 1.5 microns, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.75; the concentration of the ferric nitrate solution is 0.85mol/L, the mass concentration of the composite powder in the ferric nitrate is 15%, the concentration of the cerium nitrate solution is 0.5mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 10%; the boron nitride composite powder contains 6.5% of iron element, the photo-thermal conversion enhancer precursor contains 8.5% of cerium element, the photo-thermal conversion enhancer precursor contains 4.5% of iron element and 8.9% of cerium element;

(II) preparation of aqueous conductive Material Dispersion

(III) preparation of aqueous conductive polymer resin A component

Preparation of (IV) aqueous conductive curing agent B component

(V) preparation of water-based two-component electric heating coating

Mixing the component A and the component B according to the proportion of 1: 2, mixing the components in proportion to prepare the water-based double-component electric heating coating.

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is stood for defoaming, then water is added to adjust the viscosity, and the two-component electric heating coating is prepared, the coating is sprayed on the surface of a floor, and the water-based two-component electric heating coating is used for a power-on heating product.

The viscosity of the water-based double-component electric heating coating is 6000mPa & s, the pH value is 7.5, and the surface tension is 35 mN/m; the curing temperature of the water-based two-component electric heating coating is 60 ℃, the curing time is 120min, the resistivity of the coating after curing and film forming is 100 omega cm, the heat conductivity is 1.5W/(m.K), the reflectivity at 900-2500 nm is 22%, and the adhesive force is 0 grade.

Example 8

the water-based polymer resin is hydroxy acrylic acid emulsion (dispersoid) or water-based epoxy emulsion, the preferable hydroxy acrylic acid emulsion is water-based epoxy emulsion Dow 3002, and the epoxy equivalent is 1400;

The water-based curing agent is a water-dispersible isocyanate curing agent, an amino resin and a water-based epoxy curing agent with active hydrogen, and the preferable water-dispersible isocyanate curing agent is Bayer H-3800 and the NCO content of the water-dispersible isocyanate curing agent is 15.9%.

The conductive material is a composition of conductive carbon black, graphite, graphene and carbon nanotubes, and the preferred conductive material is conductive carbon black with the particle size of 50 microns and the specific surface area of 35m²The electric conductivity is 9S/cm, and the oil absorption value is 300mL/100 g;

the photothermal conversion reinforcing agent is boron nitride loaded cerium tungstate and tungsten ferrite composite powder, the particle size of the composite powder is 25 micrometers, the thermal conductivity of the composite powder is 3.5W/(m.K), and the reflectivity of the composite powder at 900-2500 nm is 25.6%;

the leveling agent is organic silicon leveling agent, such as TEGO-2100;

the defoaming agent is polyether modified siloxane, such as TEGO-810;

preparation of photothermal conversion enhancer

Mixing boron nitride and tungsten oxide, then carrying out mechanochemical stripping at 5000-7200 r/min by adopting a dry grinding method, preparing composite powder after 30h of mechanochemical stripping, then adding the composite powder into ferric nitrate solution, carrying out oscillation reaction for 30h, adsorbing and loading the composite powder on iron ions through adsorption, and filtering to obtain boron nitride composite powder; then adding the boron nitride composite powder into a cerium nitrate solution, introducing cerium ions into the boron nitride composite powder through adsorption, after the adsorption time is 30h, preparing a photo-thermal conversion reinforcing agent precursor through centrifugal filtration, calcining the precursor for 6h under the protection of nitrogen at 300 ℃, increasing the calcining temperature to 450 ℃, calcining for 3h in an oxygen atmosphere, and naturally cooling to prepare the photo-thermal conversion reinforcing agent;

the boron nitride is of a multilayer structure, the grain diameter of a lamella of the boron nitride is 1.5 microns, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.75; the concentration of the ferric nitrate solution is 1.0mol/L, the mass concentration of the composite powder in the ferric nitrate is 25%, the concentration of the cerium nitrate solution is 1.0mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 10%; the boron nitride composite powder contains 6.5% of iron element, 10 wt% of cerium element in the photo-thermal conversion enhancer precursor, 4.5% of iron element and 10.4 wt% of cerium element in the photo-thermal conversion enhancer precursor;

(II) preparation of aqueous conductive Material Dispersion

(III) preparation of aqueous conductive polymer resin A component

preparation of (IV) aqueous conductive curing agent B component

(V) preparation of water-based two-component electric heating coating

Mixing the component A and the component B according to the proportion of 1: 2.2, and preparing the aqueous two-component electric heating coating.

The application of the water-based two-component electric heating coating is that the water-based two-component electric heating coating is placed still for defoaming, then water is added to adjust the viscosity, and the two-component electric heating coating is prepared, is printed on the surfaces of plastic films and the like, and is used for electrified heating products.

The viscosity of the water-based double-component electric heating coating is 6000mPa & s, the pH value is 5.0, and the surface tension is 27 mN/m; the curing temperature of the water-based two-component electric heating coating is 60 ℃, the curing time is 100min, the resistivity of the coating after curing and film forming is 100 omega cm, the heat conductivity is 2.0W/(m.K), the reflectivity at 900-2500 nm is 23.5%, and the adhesive force is 0 grade.

Example 9

The embodiment provides a two-component water-based electric heating coating which comprises the following components in parts by mass:

30 parts of a hydroxy acrylic emulsion;

10 parts of blocked isocyanate curing agent;

15 parts of a conductive material;

5 parts of a photothermal conversion enhancer;

3 parts of a dispersing agent;

1 part of a leveling agent;

0.5 part of defoaming agent;

1.5 parts of a rheological additive;

8 parts of a cosolvent;

and 18 parts of water.

In this example, the hydroxyl value of the above-mentioned hydroxyl acrylic emulsion was 3.2%;

in this example, the NCO content of the blocked isocyanate curing agent was 10.2%;

in this embodiment, the conductive material is carbon black, cabot VXC 72R;

in this example, the photothermal conversion enhancer was prepared in the same manner as in example 7;

in the embodiment, the dispersant is byk-190 of German Bick chemistry;

in this embodiment, the leveling agent is byk-333;

In the embodiment, the defoaming agent is TEGO-904 w;

in this embodiment, the rheological additive is AEROSIL R202;

in this embodiment, the cosolvent is a mixed solvent of propylene glycol methyl ether and ethylene glycol propyl ether;

the specific process comprises the following steps:

taking 18 parts of water and 8 parts of cosolvent into a dispersion tank, adding 3 parts of rheological additive, one half of defoamer, conductive material and photo-thermal conversion reinforcing agent, uniformly stirring, transferring into a sand mill, and sanding for 5 hours at the rotating speed of 800rpm until the fineness is less than 15 microns to obtain the water-based conductive material;

taking the water-based conductive material in a dispersion tank, adding one fourth of defoaming agent, flatting agent and 30 parts of hydroxyl acrylic emulsion, and stirring at 800rpm for 2 hours to obtain a component A of the two-component water-based conductive coating;

and (3) putting the water-based conductive material into a dispersion tank, adding one fourth of defoaming agent, flatting agent and 10 parts of blocked isocyanate curing agent, stirring at 600rpm for 2 hours to obtain a component B of the two-component water-based conductive coating.

Usually, A, B components are stored separately, and when required, A, B components are mixed according to the ratio of 1:1.5 for use, and the specific application is as follows:

a, B components are uniformly mixed according to the ratio of 1:1.5, a certain amount of water is added for dilution, the mixture is uniformly sprayed on a glass plate by a spray gun, after the surface is dried, the mixture is cured for 30min at 150 ℃, and an electrothermal coating is prepared, wherein the viscosity of the aqueous two-component electrothermal coating is 6000mPa & s, the pH value is 5.0, and the surface tension is 27 mN/m; the cured film has the resistivity of 450 omega cm, the thermal conductivity of 2.5W/(m.K), the reflectivity of 900-2500 nm of 22.5 percent and the adhesive force of 0 grade.

Example 10

40 parts of a hydroxy acrylic emulsion;

10 parts of amino resin;

28 parts of a conductive material;

5 parts of photothermal conversion enhancer;

5 parts of a dispersing agent;

1 part of a leveling agent;

0.5 part of defoaming agent;

1.5 parts of a rheological additive;

12 parts of a cosolvent;

33 parts of water.

In this example, the hydroxyl value of the above-mentioned hydroxyl acrylic emulsion was 2.5%;

in this embodiment, the amino resin is cyanamide resin CYMEL303 LF;

in this embodiment, the conductive material is graphite of 6000 meshes;

in this example, the photothermal conversion enhancer was the same as in example 7;

in this embodiment, the dispersant is KMT-3017;

in this embodiment, the defoaming agent is TEGO-825;

in the embodiment, the leveling agent is TEGO-440;

in the embodiment, the defoaming agent is TEGO-901 w;

in this embodiment, the rheological additive is organic bentonite;

in this example, the cosolvent is ethylene glycol propyl ether, and other preparation methods and processes are the same as those in example 7.

The specific process comprises the following steps:

adding 33 parts of water and 12 parts of cosolvent into a dispersion tank, adding 3 parts of thickening agent, one half of defoaming agent, graphite and photo-thermal conversion reinforcing material, uniformly stirring, transferring into a sand mill, and sanding for 5 hours at the rotating speed of 1000rpm until the fineness is less than 15 microns to obtain the water-based conductive material;

Taking the water-based conductive material in a dispersion tank, adding one fourth of defoaming agent, flatting agent and 40 parts of hydroxyl acrylic emulsion, and stirring at 800rpm for 2 hours to obtain a component A of the two-component water-based conductive coating;

taking the water-based conductive material, adding one fourth of defoaming agent, flatting agent and 10 parts of amino resin into a dispersion tank, and stirring at 1000rpm for 2 hours to obtain a component B of the two-component water-based conductive coating;

usually, A, B components are stored separately, and when required, A, B components are mixed according to the ratio of 1:2.2 for use, and the specific application is as follows:

a, B components are uniformly mixed according to the ratio of 1:2.2, a certain amount of water is added for dilution, the mixture is rolled on a plate, after the surface is dried, the mixture is cured for 30min at 150 ℃, and the electrothermal coating is prepared, wherein the electrothermal coating is cured into a film, the resistivity is 220 omega cm, the thermal conductivity is 2.2W/(m.K), the reflectivity at 900-2500 nm is 23.1%, and the adhesive force is 0 grade.

Example 11

30 parts of a hydroxy acrylic emulsion;

5 parts of water-dispersible isocyanate curing agent;

28 parts of a conductive material;

8 parts of photothermal conversion reinforcing material;

4 parts of a dispersing agent;

1 part of a leveling agent;

1 part of a defoaming agent;

1 part of rheological additive;

10 parts of a cosolvent;

and 25 parts of water.

In this example, the hydroxyl value of the above-mentioned hydroxyl acrylic emulsion was 3.3%;

in this example, the NCO content of the water-dispersible isocyanate curing agent was 20.4%;

in this embodiment, the conductive material is graphene slurry with 6000 mesh graphite and 5% graphene content;

in the embodiment, the dispersant is KYC-9366;

in this embodiment, the leveling agent is byk-333;

in the embodiment, the defoaming agent is TEGO-810;

in this embodiment, the rheological additive is AEROSIL R202;

in this embodiment, the cosolvent is propylene glycol dimethyl ether and isopropyl alcohol; other procedures the procedure of example 7 was followed.

The specific process comprises the following steps:

taking 25 parts of water and 3 parts of isopropanol into a dispersion tank, adding 1 part of rheological additive, one half of defoaming agent, conductive material and photo-thermal conversion reinforcing agent, uniformly stirring, transferring into a sand mill, and sanding for 5 hours at the rotating speed of 800rpm until the fineness is less than 15 microns to obtain the water-based conductive material;

Taking 10 parts of water dispersible isocyanate curing agent, adding 7 parts of propylene glycol dimethyl ether, dispersing agent, defoaming agent and conductive graphite, stirring uniformly, transferring to a sand mill, and sanding for 5 hours at the rotating speed of 800rpm until the fineness is less than 15 mu m to obtain a component B of the two-component waterborne conductive coating;

A. the component B needs to be stored separately, and when the component B needs to be used, A, B components are mixed according to the ratio of 1:3 for use, and the specific application is as follows:

a, B components are uniformly mixed according to the ratio of 1:3, a certain amount of water is added for dilution, the mixture is printed on a PET film, the PET film is dried by a drying tunnel and is cured for 30min at 150 ℃, and the electrothermal coating is prepared, and has the resistivity of 240 omega cm after curing film forming, the thermal conductivity of 2.0W/(m.K), the reflectivity of 900-2500 nm of 22.9 percent and the adhesive force of 0 level.

Example 12

50 parts of water-based epoxy emulsion;

20 parts of a water-based epoxy curing agent;

48 parts of heat conduction material;

the photothermal conversion reinforcing material accounts for 8 parts;

8 parts of a dispersing agent;

1.5 parts of a leveling agent;

0.8 part of defoaming agent;

1 part of rheological additive;

15 parts of a cosolvent;

35 parts of water.

In this example, the epoxy equivalent of the aqueous epoxy resin was 1100;

in this embodiment, the active hydrogen equivalent of the aqueous epoxy curing agent is 140;

in this embodiment, the conductive material is a mixture of conductive carbon black and graphene slurry, wherein 40 parts of conductive carbon black and 8 parts of graphene slurry are used; the conductive carbon black is cabot VXC72R, and the graphene content in the graphene slurry is 5%;

In this example, the photothermal conversion enhancing material was prepared in example 7;

in the embodiment, the dispersant is byk-180 of German Bick chemistry;

in the embodiment, the leveling agent is TEGO-2100;

in the embodiment, the defoaming agent is TEGO-904W;

in this embodiment, the rheological additive is AEROSIL R202;

in this example, the cosolvent is a mixed solvent of isopropyl alcohol and propylene glycol butyl ether, and the rest is the same as that in example 7.

The specific process comprises the following steps:

taking 35 parts of water and 15 parts of cosolvent into a dispersion tank, adding 1 part of rheological additive, one half of defoamer, conductive carbon black and graphene slurry, uniformly stirring, transferring into a sand mill, and sanding for 5 hours at the rotating speed of 800rpm until the fineness is less than 15 microns to obtain the water-based conductive material;

taking the water-based conductive material into a dispersion tank, adding one fourth of defoaming agent, flatting agent and 50 parts of water-based epoxy emulsion, and stirring at 800rpm for 2 hours to obtain a component A of the two-component water-based conductive coating;

taking the water-based conductive material to be placed in a dispersion tank, adding one fourth of defoaming agent, flatting agent and 20 parts of water-based epoxy curing agent, stirring at 800rpm for 2 hours to obtain a component B of the two-component water-based conductive coating;

A. The component B needs to be stored separately, and when the component B needs to be used, A, B components are mixed according to the ratio of 1:2.5 for use, and the specific application is as follows:

a, B components are uniformly mixed according to the ratio of 1:1.5, a certain amount of water is added for dilution, the mixture is uniformly sprayed on fireproof flame-retardant cloth by a spray gun, and after the surface is dried, the mixture is cured for 45min at 80 ℃ to prepare the electrothermal coating, the electric resistivity of the electrothermal coating after curing film forming is 150 omega cm, the thermal conductivity is 2.1W/(m K), the reflectivity at 900-2500 nm is 23.2%, and the adhesive force is 0 level.

Comparative example 1

Comparative example 1 the process of example 7 was followed except that the photothermal conversion enhancer was a mixture of boron nitride and tungsten oxide, and the resulting material was not ground. The cured film has the resistivity of 5000 omega cm, the thermal conductivity of 0.5W/(m.K), the reflectivity of 900-2500 nm of 5.8 percent and the adhesive force of I level.

Comparative example 2

Comparative example 2 the process of example 7 was followed except that the photothermal conversion enhancer was a mixture obtained by grinding boron nitride and tungsten oxide as raw materials and mixing them with cerium tungstate. The cured film has the resistivity of 5500 omega cm, the thermal conductivity of 2.1W/(m.K), the reflectivity of 23.2 percent at 900-2500 nm and the adhesive force of 0 grade.

Comparative example 3

Comparative example 3 the same procedure as in example 7 was followed, except that the photothermal conversion enhancer was changed to a mixture of boron nitride powder, tungsten ferrite, and cerium tungstate. The cured film has the resistivity of 7890 omega-cm, the thermal conductivity of 1.5W/(m-K), the reflectivity of 12.2% at 900-2500 nm and the adhesive force of I level.

Comparative example 4

Comparative example 4 a photothermal conversion enhancer was obtained by following the same procedure as in example 7 except that the precursor was calcined at 300 ℃ for 6 hours under nitrogen protection and then calcined at 450 ℃ for 3 hours; the cured film has the resistivity of 5600 omega-cm, the thermal conductivity of 0.5W/(m-K), the reflectivity of 900-2500 nm of 5% and the adhesive force of I grade.

Comparative example 5

Comparative example 5 the photothermal conversion enhancer was prepared in the same manner as in example 7, except that the precursor was calcined at 300 ℃ for 6 hours under oxygen protection, the calcination temperature was raised to 450 ℃ and the precursor was calcined in an oxygen atmosphere for 3 hours, followed by natural cooling; the cured film has the resistivity of 17890 omega cm, the thermal conductivity of 1.1W/(m.K), the reflectivity of 10.2 percent at 900-2500 nm and the adhesive force of I level.

Comparative example 6

Comparative example 6 the photothermal conversion enhancer was prepared in the same manner as in example 7, except that the precursor was calcined at 300 ℃ for 6 hours under oxygen protection, the calcination temperature was raised to 450 ℃ and the precursor was calcined in a nitrogen atmosphere for 3 hours, followed by natural cooling; the cured film has a resistivity of 9800 omega cm, a thermal conductivity of 0.1W/(m.K), a reflectance of 4.2% at 900-2500 nm, and an adhesion of class I.

Comparative example 7

Comparative example 7 the photothermal conversion enhancer was prepared in the same manner as in example 7 except that the precursor was calcined at 350 ℃ for 6 hours under nitrogen protection, the calcination temperature was raised to 350 ℃, and the precursor was further calcined in an oxygen atmosphere for 3 hours, followed by natural cooling; the cured film has a resistivity of 9000 Ω & cm, a thermal conductivity of 0.4W/(m & K), a reflectance of 5.1% at 900-2500 nm, and an adhesion of class I.

Comparative example 8

Comparative example 8 the same procedure as in example 7 was followed, except that the conductive material was a single one, and the photothermal conversion enhancer was used. The cured film has a resistivity of 10000 Ω & cm, a thermal conductivity of 0.2W/(m & K), a reflectance of 900 to 2500nm of 5.1%, and an adhesion of 0 grade.

Comparative example 9

Comparative example 9 the same procedure as in example 7 was followed except that the photothermal conversion enhancer was boron nitride. The cured film has the resistivity of 10000 omega cm, the thermal conductivity of 2.0W/(m.K), the reflectivity of 900-2500 nm of 3.1 percent and the adhesive force of I grade.

Comparative example 10

Comparative example 10 the same procedure was followed as in example 7 except that the photothermal conversion enhancer was tungsten oxide. The cured film has the resistivity of 15000 omega cm, the thermal conductivity of 0.3W/(m.K), the reflectivity of 900-2500 nm of 7.1 percent and the adhesive force of I level.

Comparative example 11

Comparative example 11 the same procedure was followed as in example 7 except that the photothermal conversion enhancer was tungsten ferrite. The cured film has the resistivity of 40000 omega cm, the thermal conductivity of 0.5W/(m.K), the reflectivity of 900-2500 nm of 6.1 percent and the adhesive force of I grade.

Comparative example 12

Comparative example 12 the same procedure as in example 7 was followed except that the photothermal conversion enhancer was cerium tungstate. The cured film has the resistivity of 11000 omega-cm, the thermal conductivity of 0.5W/(m.K), the reflectivity of 900-2500 nm of 8.1 percent and the adhesive force of I level.

The effects of the embodiment are as follows:

The above examples 1 to 12 and comparative examples 1 to 12 were subjected to performance tests according to the following test methods.

The samples were tested for performance as follows: the resistivity is tested by adopting a BEST-121-paint film surface resistivity tester according to the GJB8806-2015 paint film high-temperature resistivity test method; the thermal conductivity test adopts a Linesis LFA 1000 laser thermal conductivity tester, the thickness of a sample is less than 3 mm, a wafer with the diameter of 5CM is tested, the adhesive force is measured according to a GB 1720-1979 paint film adhesive force measuring method, the reflection rate is measured according to a Lambda 35 ultraviolet-visible spectrometer, and the reflection rate of the coating material in the wavelength range of 400-2500 nm is tested. In the XRD test, a D/max-2550PC X-ray polycrystalline diffractometer is adopted to carry out structural characterization on the photo-thermal conversion reinforcing agent, the surface morphology of the prepared photo-thermal conversion reinforcing agent is detected by a field emission scanning electron microscope of SU-8010 model, and the detection voltage is 3 kv.

FIG. 1 is an XRD pattern of the photothermal conversion enhancer obtained in example 7, wherein the crystal forms of the respective components are shown in the figure, and the pattern shows diffraction peaks of boron nitride shown in # and absorption peaks of the desired crystal forms of cerium tungstate (. apprxeq.) and tungsten ferrite (. tangle-solidup.) are detected. And diffraction peaks of impurities such as residual cerium nitrate, tungsten oxide and ferric nitrate are not formed in the spectrum, so that the obtained structure is explained as a prepared material. In addition, a single powder structure is not formed in the graph of fig. 2, a compound of a boron nitride structure and cerium tungstate and tungsten ferrite is formed, and cerium tungstate and tungsten ferrite structures with structures such as globes and the like are not remained, so that the preparation method adopted by the application can be used for synthesizing the corresponding photo-thermal conversion enhancer.

In the corresponding embodiments 1 to 12, the photo-thermal conversion reinforcing agent is introduced, and has a synergistic enhancement effect with carbon black, graphite, graphene and carbon nano tubes in the heat conducting material, boron nitride in the photo-thermal conversion material absorbs and conducts electrons in the heating process through the synergistic effect of the heat conducting component of the heat conducting material and the photo-thermal conversion reinforcing material, and the electronic conversion effect of tungsten ferrite and cerium tungstate is utilized, so that the conversion of electric energy and heat is realized, and meanwhile, due to the self-heating and far infrared absorption and reflection functions of the tungsten ferrite and the cerium tungstate, the heat effect of the electrothermal coating is improved, and the electric heating efficiency and the heat conducting performance conductivity of the electrothermal coating are improved; the problems that the conventional material heat and electricity conducting material is high in electric conductivity, rapid in heat transfer and high in loss rate when used are solved; meanwhile, by means of loading boron nitride, the excellent electric conduction and heat conduction transmission channel of the boron nitride is utilized, the synergistic effect enhancement effect of the tungsten ferrite and the cerium tungstate with the photo-thermal conversion effect is achieved, the excellent electric conduction and heat conduction performance of the tungsten ferrite and the cerium tungstate is improved, the excellent far infrared emission capability of the tungsten ferrite and the cerium tungstate is maintained, and the heating efficiency of the electric heating coating is improved.

In comparative examples 1 to 3, since single boron nitride is mixed with the material and no load is applied, the heat-conducting electron channel is wide, so that the photo-thermal conversion enhancement efficiency is poor, the electric conductivity is poor, the infrared reflectivity is low, and the effect of the electric-conducting coating is poor; the comparative examples 4-7 adopt different photo-thermal conversion reinforcing agent calcining processes, and due to the conversion of various crystal forms in the calcining process, the products produced by different processes are different, so that the photo-thermal conversion effect is poor, and the performance of the photo-thermal conversion reinforcing agent and a conductive material is poor; the comparative examples 8-12 adopt a single material and a heat conduction material, but the coating has only heat conduction performance or only far infrared performance, so that the coating is difficult to have a photo-thermal conversion effect after load compounding, the finally prepared coating has a poor electric heating effect and high resistivity.

The above embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, it should be understood that the above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. The preparation method and the application of the water-based two-component electric heating coating are characterized in that the viscosity of the water-based two-component electric heating coating is 500-10000 mPa.s, the pH value is 5.0-7.5, and the surface tension is 25-45 mN/m; the curing temperature of the water-based two-component electric heating coating is 15-45 ℃, the curing time is 45-120 min, the resistivity of the coating after curing and film forming is 50-500 omega-cm, the thermal conductivity is 1.0-2.5W/(m-K), the reflectivity at 900-2500 nm is more than 20%, and the adhesive force is 0 grade.

2. The preparation method and application of the water-based two-component electric heating coating material as claimed in claim 1, wherein the water-based two-component electric heating coating material comprises the following components in parts by mass:

the water-based polymer resin is hydroxyl acrylic acid emulsion (dispersion) or water-based epoxy emulsion, the preferable hydroxyl acrylic acid emulsion is Changxing 1194-D and Haiming, D, courtey FS-2460AF, and the water-based epoxy emulsion is Changxing W34310, Hounsfield PZ3961-1 and Dow WB 3002;

The waterborne curing agent is a water dispersible isocyanate curing agent, amino resin and a waterborne epoxy curing agent with active hydrogen, the preferred water dispersible isocyanate curing agent is Bayer H-3800 and Wanhua chemical 268, the amino resin is American CyMEL amino resin 303LF and 1158, and the waterborne epoxy curing agent is Tao's 805 and Hensmei 36;

3. the preparation method and application of the water-based two-component electric heating paint according to claim 1, characterized in that the preparation method of the water-based two-component electric heating paint comprises the following steps:

preparation of photothermal conversion enhancer

The boron nitride is of a multilayer structure, the particle size of a lamella of the boron nitride is 1.0-2.5 micrometers, and the mass ratio of the boron nitride to the tungsten oxide is 1: 0.5-1: 0.75; the concentration of the ferric nitrate solution is 0.5-1.0 mol/L, the mass concentration of the composite powder in the ferric nitrate is 10-25%, the concentration of the cerium nitrate solution is 0.5-1.0 mol/L, and the mass concentration of the boron nitride composite powder in the cerium nitrate solution is 5-10%; the boron nitride composite powder contains 5-7.5% of iron, 5-10 wt% of cerium in the photo-thermal conversion enhancer precursor, 3-5% of iron and 7-12 wt% of cerium in the photo-thermal conversion enhancer precursor;

(II) preparation of aqueous conductive Material Dispersion

Uniformly dispersing the conductive material, the photo-thermal conversion reinforcing agent, the dispersing agent, the defoaming agent, the cosolvent and the like, adding the mixture into a sand mill, grinding for 2-8 hours until the particle size is below 5 mu m, and preparing a water-based conductive material dispersion liquid;

(III) preparation of aqueous conductive polymer resin A component

Adding the aqueous conductive material dispersion liquid with a certain proportion into aqueous high polymer resin according to a certain proportion, then adding a flatting agent and a rheological aid, and stirring and dispersing for 1-8 h to obtain an aqueous conductive high polymer resin component A; the mass dispersion of the aqueous conductive material in the aqueous conductive polymer resin A component is 20-50%;

Preparation of (IV) aqueous conductive curing agent B component

(V) preparation of water-based two-component electric heating coating

Mixing the component A and the component B according to a certain proportion to prepare the water-based double-component electric heating coating;

the mixing ratio of the component A and the component B is 1: 1.15-1: 3.0.

4. the preparation method and application of the water-based two-component electrothermal coating according to claim 1, wherein the application of the water-based two-component electrothermal coating is to prepare the two-component electrothermal coating by standing and defoaming the water-based two-component electrothermal coating, then adding water to adjust viscosity, and spraying, rolling or printing the coating on the surfaces of glass, floors, wood, plastic films and the like, wherein the water-based two-component electrothermal coating is used for electrically heating products.