CN114437604B - Nanoparticle modified water-based white wood sealing primer and preparation method and application thereof - Google Patents
Nanoparticle modified water-based white wood sealing primer and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a nanoparticle modified water-based whitewood ware sealing primer and a preparation method and application thereof. The nanoparticle modified waterborne white wood sealing primer comprises a component A and a component B; the component A comprises the following components: nano modified core-shell aqueous dispersion, wetting agent, dispersing agent, pH regulator, defoaming agent, titanium dioxide, far infrared ceramic powder, talcum powder, calcium carbonate, nano modified boron nitride, core film-forming aid, shell film-forming aid, water, leveling agent, mildew preventive, grinding aid and thickening agent; the component B comprises the following components: hydrophilic modified aromatic polyisocyanate, dehydrating agent and cosolvent. The nano particle modified water-based white woodware seal primer provided by the invention is matched with a far infrared baking device for use, so that the formed coating has better performances such as polishing property, adhesive force, expansion rib resistance and the like, the baking time is greatly shortened, and the photo-thermal conversion efficiency of the coating can be obviously improved.
Description
Technical Field
The invention belongs to the technical field of wood coatings, and relates to a nanoparticle modified water-based whiteware seal primer and a preparation method and application thereof, in particular to a nanoparticle modified water-based whiteware seal primer for a far infrared baking device and a preparation method and application thereof.
Background
The application performance of the double-component water-based woodenware primer on the market is good, but the primer still has problems in use. Firstly, the coating hardness is slow to build and poor in polishing property, so that the construction efficiency and the matching property are influenced; and the coating is slow to dry, the water vapor permeability resistance is slow to establish, and the expansion rib resistance is poor.
The large amounts of water and slow drying film-forming aids in aqueous coatings are the root cause of the above problems. Particularly, water with high specific heat can cause the overall temperature rise speed of the water-based coating to be much slower than that of common solvent-based coatings in the baking and drying process, thereby causing the solid drying and the hardness rise speed of the coating to be slow. The method adopts the core-shell structure water-based dispersion, reduces the dosage of the film-forming additive, and is a method for effectively improving the speed of the water-based paint on the actual drying and hardness.
From the drying mode, the air convection heating technology is the most common forced drying mode in the water-borne wood paint industry. In recent years, the far infrared heating technology has attracted more and more attention in the baking and drying of the water-based wood lacquer due to the characteristics of being healthier, more efficient and more energy-saving.
The research on far infrared technology in the coating industry is mostly focused on the research on far infrared heating element equipment and functional coatings added with far infrared nano materials, such as the research on far infrared emission, heat dissipation, heat preservation and other functions. For example, patent CN1493626A discloses a far infrared coating containing silicon carbide, which contains silicon carbide, iron oxide, cobalt oxide, manganese oxide, aluminum oxide, chromium oxide, nickel oxide, etc. as main components. Patent CN110776798A discloses a heat-insulating and heat-preserving far infrared negative oxygen ion water-based fluorocarbon coating and a preparation method thereof. The water-based paint patents related to far infrared absorption add nano far infrared particles into the paint in a dispersing mode, are a physical modification mode, do not chemically modify a film forming substance, hardly ensure the dispersing degree of a nano material, have limited heat transfer effect of synergy between the film forming substance and a pigment and filler, finally have limited effect on improving the integral photo-thermal conversion efficiency of a coating, and do not reflect the improvement of the mechanical performance of the coating by the nano far infrared particles. Therefore, it is a problem to be solved to provide a water-based paint for use with a far infrared baking device.
Disclosure of Invention
The invention mainly aims to provide a nanoparticle modified water-based whiteware seal primer and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a nanoparticle modified water-based whiteware seal primer, which comprises a component A and a component B;
the component A comprises the following components in parts by weight: 30.0-50.0 parts of nano modified core-shell aqueous dispersion, 0.1-0.5 part of wetting agent, 0.1-0.5 part of dispersing agent, 0.1-0.3 part of pH regulator, 0.1-0.5 part of defoaming agent, 10-20 parts of titanium dioxide, 1-10 parts of far infrared ceramic powder, 5-10 parts of talcum powder, 5-10 parts of calcium carbonate, 0.2-2 parts of nano modified boron nitride, 2-4 parts of core film-forming additive, 1-3 parts of shell film-forming additive, 5-10 parts of water, 0.1-0.5 part of flatting agent, 0.1-0.3 part of mildew inhibitor, 1-3 parts of polishing additive and 0.5-1.5 parts of thickening agent;
the component B comprises the following components in parts by weight: 65.0 to 80.0 portions of hydrophilic modified aromatic polyisocyanate, 0.1 to 0.3 portion of dehydrating agent and 20.0 to 35.0 portions of latent solvent.
The embodiment of the invention also provides a preparation method of the nanoparticle modified water-based whiteware seal primer, which comprises the following steps:
mixing a thickening agent with water, adding a wetting agent, a dispersing agent, a defoaming agent, titanium dioxide, nano-scale modified boron nitride, far infrared ceramic powder, talcum powder, calcium carbonate and a polishing auxiliary agent, mixing and grinding the mixture, then mixing the mixture with the nano-modified core-shell aqueous dispersion, and finally adding a pH regulator, a core film-forming auxiliary agent, a shell film-forming auxiliary agent, a leveling agent and a mildew-proof auxiliary agent, and uniformly mixing to form the component A;
mixing hydrophilic modified aromatic polyisocyanate with a cosolvent, and adding a dehydrating agent to form the component B;
and uniformly mixing the component A and the component B to form the nanoparticle modified water-based whiteware seal primer.
The embodiment of the invention also provides a coating which is formed by baking the nanoparticle modified waterborne chinaware sealing primer through far infrared.
The embodiment of the invention also provides the application of the nanoparticle modified waterborne balsawood seal primer matched with the seal primer of a far infrared baking device.
Compared with the prior art, the invention has the beneficial effects that:
(1) the nano particle modified water-based white wood sealing primer provided by the invention has the advantages that the actual drying speed is higher, the hardness and the strength of the coating are quickly established, the coating is ensured to have better polishing property, and the production efficiency is improved;
(2) the nanoparticle modified waterborne white wood sealing primer provided by the invention has better thick coating property, reduces the condition of wrinkling and even cracking of a thick film, and reduces the energy consumption of comprehensive application in the process of forming a coating;
(3) the coating formed by far infrared baking of the nanoparticle modified waterborne white wood sealing primer has excellent expansion-tendon resistance and adhesive force.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1a to 1b are pictures of sandpaper when polishing the coating layers formed in example 1 of the present invention and comparative example 1, respectively;
FIGS. 2a to 2c are graphs of surface temperatures at different times for the formation of the coating layers in example 1 of the present invention and comparative example 1, respectively.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specifically, as one aspect of the technical scheme of the invention, the nano particle modified water-based whiteware seal primer comprises a component A and a component B;
the component A comprises the following components in parts by weight: 30.0-50.0 parts of nano modified core-shell aqueous dispersion, 0.1-0.5 part of wetting agent, 0.1-0.5 part of dispersing agent, 0.1-0.3 part of pH regulator, 0.1-0.5 part of defoaming agent, 10-20 parts of titanium dioxide, 1-10 parts of far infrared ceramic powder, 5-10 parts of talcum powder, 5-10 parts of calcium carbonate, 0.2-2 parts of nano modified boron nitride, 2-4 parts of core film-forming additive, 1-3 parts of shell film-forming additive, 5-10 parts of water, 0.1-0.5 part of flatting agent, 0.1-0.3 part of mildew inhibitor, 1-3 parts of polishing additive and 0.5-1.5 parts of thickening agent;
the component B comprises the following components in parts by weight: 65.0 to 80.0 portions of hydrophilic modified aromatic polyisocyanate, 0.1 to 0.3 portion of dehydrating agent and 20.0 to 35.0 portions of latent solvent.
In some preferred embodiments, the nano-modified core-shell aqueous dispersion consists of nano-ZrO 2 Modified aqueous dispersion with a core-shell structure, wherein the aqueous dispersion with the core-shell structure comprises nano SiO as a core structure 2 A modified core structure resin.
In some preferred embodiments, the wetting agent includes any one or a combination of two or more of an organic small molecule surfactant, a silicone wetting agent, an acetylenic diol wetting agent, and an organofluorine wetting agent, and is not limited thereto.
In some preferred embodiments, the dispersant includes any one of amine group-or carboxyl group-containing polymer copolymers, and is not limited thereto.
In some preferred embodiments, the pH adjusting agent includes any one of AMP-95, ammonia, DMEA, and is not limited thereto.
In some preferred embodiments, the defoaming agent includes any one or a combination of two or more of a silicone defoaming agent, an acetylene glycol-based defoaming agent, and an acrylic polymer-based defoaming agent, and is not limited thereto.
In some preferred embodiments, the far infrared ceramic powder is prepared by a liquid-phase coprecipitation method, and the far infrared emissivity of the far infrared ceramic powder is above 90% at normal temperature.
In some preferred embodiments, the far infrared ceramic powder is a white powder prepared by a liquid phase coprecipitation method, and is formed by mixing a plurality of substances with excellent far infrared absorption and an activating agent mainly comprising a rare earth material, the average particle size reaches the nanometer level, the mixing ratio is selected through targeted optimization, and the far infrared emissivity is over 90% at normal temperature.
In some preferred embodiments, the nanoscale modified boron nitride includes any one or a combination of two or more of amino-modified nano boron nitride, carboxyl-modified nano boron nitride, and hydroxyl-modified nano boron nitride, and is not limited thereto.
Furthermore, the average particle diameter of the nano boron nitride adopted by the nano modified boron nitride is below 60nm, and the specific surface area is less than 40m 2 /g。
In some preferred embodiments, the core coalescent includes any one or a combination of two or more of PM, DPM, PPh, and is not limited thereto.
In some preferred embodiments, the shell coalescent includes any one or a combination of two or more of Dpnb, DPM, PPh, and is not limited thereto.
In some preferred embodiments, the leveling agent includes any one or a combination of two or more of an acrylic copolymer leveling agent, an organosilicon leveling agent, and a fluorocarbon leveling agent, and is not limited thereto.
In some preferred embodiments, the mildewcide includes any one or a combination of two or more of TBZ, TPN, TMTD, and is not limited thereto.
In some preferred embodiments, the grinding aid includes any one or a combination of two or more of zinc stearate, calcium stearate, and magnesium stearate, and is not limited thereto.
In some preferred embodiments, the thickener includes any one or a combination of two or more of attapulgite, polyamide wax, nonionic hydrophobically modified polyurethane thickener, fumed silica, organically modified montmorillonite clay, and is not limited thereto.
In some preferred embodiments, the hydrophilically-modified aromatic polyisocyanate is a sulfonate hydrophilically-modified aromatic polyisocyanate, and is not limited thereto. In some preferred embodiments, the dehydrating agent includes triethyl orthoformate and/or p-toluenesulfonic acid isocyanate, and is not limited thereto.
In some preferred embodiments, the co-solvent comprises, without limitation, urethane-grade PMA and/or PM.
In some preferred embodiments, the mass ratio of the A component to the B component is 7-9: 1.
Another aspect of the embodiments of the present invention also provides a preparation method of the foregoing nanoparticle-modified water-based whiteware primer sealer, including:
mixing a thickening agent with water, adding a wetting agent, a dispersing agent, a defoaming agent, titanium dioxide, nano-scale modified boron nitride, far infrared ceramic powder, talcum powder, calcium carbonate and a grinding aid, mixing and grinding, then mixing with the nano-modified core-shell aqueous dispersion, and finally adding a pH regulator, a core film-forming aid, a shell film-forming aid, a leveling agent and a mildew-proof aid, and uniformly mixing to form the component A;
mixing hydrophilic modified aromatic polyisocyanate with a cosolvent, and adding a dehydrating agent to form the component B;
and uniformly mixing the component A and the component B to form the nanoparticle modified water-based whiteware seal primer.
In some preferred embodiments, the method of preparing the nano-modified core-shell aqueous dispersion comprises:
so as to contain nano SiO 2 The first mixed reaction system of the dispersion liquid, the first carboxyl monomer, the first hydroxyl monomer, the initiator and the chain transfer agent reacts for 1h at the temperature of 130- 2 Modifying a core structure resin;
so as to contain the nano SiO 2 Reacting a second mixed reaction system of the modified nuclear structure resin, a second carboxyl monomer, a second hydroxyl monomer, a functional monomer, an initiator and a chain transfer agent at the temperature of 130-140 ℃ for 1h, cooling to the temperature of 75 ℃, adding a neutralizing agent, and dispersing at a high speed to obtain the aqueous dispersion with the core-shell structure;
uniformly stirring and mixing the zirconium source and the graphene oxide dispersion liquid, and reacting at 105-115 ℃ for 8h to prepare the nano ZrO 2 Compounding graphene oxide;
subjecting the nano ZrO to 2 And uniformly mixing the composite graphene oxide with the core-shell structure aqueous dispersion, and reacting for 8 hours at 50-60 ℃ to obtain the nano modified core-shell aqueous dispersion.
In some preferred embodiments, the nano-sized SiO 2 The dispersion liquid is obtained by dispersing nano silicon dioxide colloid in propylene glycol butyl ether by ultrasonic.
In some preferred embodiments, the first carboxyl monomer includes any one or a combination of two or more of methyl methacrylate, butyl methacrylate, and butyl acrylate, and is not limited thereto.
In some preferred embodiments, the first hydroxyl monomer includes any one or a combination of two or more of hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate, and is not limited thereto.
In some preferred embodiments, the initiator includes any one or a combination of two or more of AIBN, BPO, DTBP, and is not limited thereto.
In some preferred embodiments, the chain transfer agent includes any one or a combination of two or more of tert-dodecyl mercaptan TDM, mercaptomercaptan ME, pentene compounds, AMSD, and is not limited thereto.
In some preferred embodiments, the second carboxyl monomer includes any one of ethyl acrylate, n-butyl acrylate, isooctyl acrylate, lauryl acrylate, or a combination of two or more thereof, and is not limited thereto.
In some preferred embodiments, the second hydroxyl monomer includes any one or a combination of two or more of hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate, and is not limited thereto.
In some preferred embodiments, the functional monomer includes any one or a combination of two or more of isobornyl methacrylate, glycidyl methacrylate, and alkyl acrylate phosphate, and is not limited thereto.
In some preferred embodiments, the neutralizing agent includes any one or a combination of two or more of triethylamine, N-dimethylethanolamine, and ammonia water, and is not limited thereto.
In some preferred embodiments, the zirconium source comprises any one or a combination of two or more of zirconium oxychloride octahydrate, zirconium propoxide, and zirconium tetra-n-butoxide, without limitation thereto.
In some preferred embodiments, the graphene oxide in the graphene oxide dispersion liquid has a lamella diameter of 5-20 μm, a number of layers below 10, and an oxygen content of less than 15%.
In some preferred embodiments, the aqueous dispersion having a core-shell structure has a number average molecular weight of 10000-20000 and a weight average molecular weight of 20000-40000.
In some preferred embodiments, the nano SiO in the first mixed reaction system 2 The mass ratio of the first carboxyl monomer, the first hydroxyl monomer, the initiator and the chain transfer agent is 0.3-1.5:40-60:0.5-2.0:0.5-1.8: 0.5-2.0.
In some preferred embodiments, the second mixed reaction system is nano-SiO 2 Modified core knotThe mass ratio of the structural resin, the second carboxyl monomer, the second hydroxyl monomer, the functional monomer, the initiator and the chain transfer agent is 0.5-1.5:50-70:1.0-2.5:2.0-6.0:0.5-1.8: 0.5-2.0.
In some more specific embodiments, the method for preparing the nanoparticle-modified aqueous white wood sealing primer comprises the following steps:
uniformly mixing deionized water and a thickening agent, dispersing at a high speed of 20-30m/s for 10-15min, sequentially adding a wetting agent, a dispersing agent, a defoaming agent, titanium dioxide, nano-modified boron nitride, far infrared ceramic powder, talcum powder, calcium carbonate and a grinding aid, dispersing at a high speed of 20-30m/s for 25-30min, and filtering to obtain resin-free filler slurry, wherein the grinding fineness is qualified;
weighing a nano modified aqueous dispersion, slowly adding resin-free filler slurry into the nano modified graphene oxide aqueous dispersion under the stirring condition, dispersing at a high speed of 20-30m/s for 10-15min, then slowly adding a pH regulator to regulate the pH value, then adding a core film-forming aid, a shell film-forming aid, a leveling agent and a mildew-proof aid, dispersing at a high speed of 20-30m/s for 10-15min, and finally regulating the viscosity to be qualified by using deionized water to obtain a component A;
slowly adding the urethane-grade cosolvent into the hydrophilic modified aromatic polyisocyanate, dispersing at a high speed of 20-30m/s for 10-15min, adding the dehydrating agent, dispersing at a high speed of 20-30m/s for 10-15min, filtering by using a 200-mesh filter screen, and filling to obtain the component B.
In some more specific embodiments, the method of preparing the aqueous nano-modified core-shell dispersion comprises:
adding a certain amount of nano SiO into a four-neck flask provided with a stirrer, a dropping funnel, a condenser tube and a thermometer 2 Stirring and heating to 130-140 ℃ in ultrasonic liquid in propylene glycol monobutyl ether, uniformly mixing a first carboxyl monomer, a first hydroxyl monomer, an initiator and a chain transfer agent under the condition of constant reaction temperature and stirring speed, wherein the dripping time is about 4 hours, and carrying out heat preservation reaction for 1 hour to obtain the nano SiO 2 Modifying a core structure resin;
and the other contains a second carboxylic acidUniformly mixing a base monomer, a second hydroxyl monomer, a functional monomer, an initiator and a chain transfer agent, and dripping the mixture into the nano SiO within 3 hours 2 Keeping the modified core-shell resin for 1h to obtain hydrophilic core-shell resin, cooling to 75 ℃, adding a neutralizing agent, stirring for 30min, adding water, dispersing for 60min at a high speed, cooling, filtering, and discharging to obtain the core-shell structure aqueous dispersion;
taking a proper amount of ZrOCl 2 ·8H 2 O is a zirconium source, is dissolved in deionized water, is added into 1 percent graphene oxide solution prepared by ultrasonic dispersion, and is evenly stirred under the ultrasonic condition to prepare suspension, so that ZrOCl is obtained 2 ·8H 2 O is evenly attached to the surface of the graphene oxide sheet layer, and the evenly stirred suspension is put into a high-temperature reaction kettle, and ZrOCl is added under the high-temperature condition of 110 +/-5 DEG C 2 ·8H 2 O and graphene oxide react for 8 hours to obtain nano ZrO 2 Compounding graphene oxide;
then taking a proper amount of nano ZrO 2 And compounding graphene oxide, ultrasonically dispersing for 30min, slowly adding the graphene oxide into the aqueous dispersion with the core-shell structure, and stirring at a high speed of 20-30m/s for 30min to obtain the nano modified core-shell aqueous dispersion.
The nano modified core-shell aqueous dispersion comprises double modification of a core and a shell, wherein nano SiO 2 Modified as hard core modifier, nano ZrO 2 The composite graphene oxide is used as a soft shell modifier.
In the invention, in the synthesis process of the core layer and the shell layer of the core-shell aqueous dispersion, different nano far infrared particles are introduced for chemical modification, so that the dispersibility and stability of the nano material are improved, the photo-thermal conversion efficiency and the heat conduction efficiency are improved, the cross-linking curing gradient of the core layer and the shell layer is reasonably adjusted, the internal and external curing drying of the aqueous wood coating is more uniform, and the problem of thick film cracking caused by no drying in the surface and the inside is reduced.
Another aspect of the embodiments of the present invention also provides a coating layer formed by far infrared baking of the aforementioned nanoparticle-modified waterborne balsawood blocking primer.
When the modified water-based white wood ware sealing primer is used together with special far infrared drying equipment, compared with unmodified products of the same type, the baking time can be greatly shortened. The coating can quickly establish hardness and strength, so that the performances of the coating, such as the sanding property, the adhesive force, the expansion rib resistance and the like, are obviously improved. Through repeated evaluation and test of customers, on the premise of ensuring the quality of the coating, when the modified water-based whitewood ware sealing primer disclosed by the invention and the traditional water-based whitewood ware sealing primer both adopt a far infrared baking process, the photo-thermal conversion efficiency of the coating can be obviously improved, and the comprehensive application energy consumption can be reduced by more than 40%. Compared with the traditional air blast air convection type baking process adopted by the traditional water-based whitewood ware sealing primer, the modified water-based whitewood ware sealing primer disclosed by the invention has the advantage that the comprehensive application energy consumption can be reduced by 60-70%.
The invention also provides application of the nanoparticle modified water-based whiteware seal coat in matching with a seal coat of a far infrared baking device.
Further, the far infrared wavelength range emitted by the far infrared baking device is 7-15 μm.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
The preparation method of the nano modified core-shell aqueous dispersion in the following examples and comparative examples comprises the following steps:
adding a certain amount of nano SiO into a four-neck flask provided with a stirrer, a dropping funnel, a condenser tube and a thermometer 2 Stirring and heating to 130-140 ℃ in ultrasonic liquid in propylene glycol butyl ether, uniformly mixing methyl methacrylate, hydroxyethyl acrylate, AIBN and tert-dodecyl mercaptan TDM for about 4 hours under the condition of constant reaction temperature and stirring speed,keeping the temperature for reaction for 1 hour to obtain nano SiO 2 Modifying a core structure resin; wherein the nano SiO 2 The mass ratio of the methyl methacrylate to the hydroxyethyl acrylate to the AIBN to the tert-dodecyl mercaptan is 1: 50: 1;
then another mixture containing ethyl acrylate, hydroxypropyl acrylate, isobornyl methacrylate, AIBN and mercaptothiol is uniformly mixed and dripped into the nano SiO within 3 hours 2 Keeping the modified core-shell resin for 1h to obtain hydrophilic core-shell resin, cooling to 75 ℃, adding a neutralizing agent, stirring for 30min, adding water, dispersing for 60min at a high speed, cooling, filtering, and discharging to obtain the aqueous dispersion with the core-shell structure; wherein the nano SiO 2 The mass ratio of the modified nuclear structure resin, the ethyl acrylate, the hydroxypropyl acrylate, the isobornyl methacrylate, the AIBN and the mercaptomercaptan is 1: 60: 2: 4: 1;
taking a proper amount of ZrOCl 2 ·8H 2 O is a zirconium source, is dissolved in deionized water, is added into 1 percent graphene oxide solution prepared by ultrasonic dispersion, and is evenly stirred under the ultrasonic condition to prepare suspension, so that ZrOCl is obtained 2 ·8H 2 O is evenly attached to the surface of the graphene oxide sheet layer, and the evenly stirred suspension is put into a high-temperature reaction kettle, and ZrOCl is added under the high-temperature condition of 110 +/-5 DEG C 2 ·8H 2 O and graphene oxide react for 8 hours to obtain nano ZrO 2 Compounding graphene oxide;
then taking a proper amount of nano ZrO 2 And (3) compounding graphene oxide, ultrasonically dispersing for 30min, slowly adding the graphene oxide into the aqueous dispersion with the core-shell structure, and stirring at a high speed of 20-30m/s for 30min to obtain the nano modified core-shell aqueous dispersion.
Example 1
Uniformly mixing deionized water and a thickening agent, dispersing at a high speed of 20-30m/s for 10-15min, sequentially adding a wetting agent, a dispersing agent, a defoaming agent, titanium dioxide, nano-modified boron nitride, far infrared ceramic powder, talcum powder, calcium carbonate and a grinding aid, dispersing at a high speed of 20-30m/s for 25-30min, grinding to obtain qualified fineness, and filtering to obtain resin-free filler slurry;
weighing the nano modified core-shell aqueous dispersion, slowly adding the resin-free filler slurry into the nano modified core-shell aqueous dispersion under the stirring condition, dispersing at a high speed of 20-30m/s for 10-15min, then slowly adding the pH regulator, then adding the core film-forming aid, the shell film-forming aid, the leveling agent and the mildew-proof aid, dispersing at a high speed of 20-30m/s for 10-15min, and finally regulating the viscosity to be qualified by using deionized water to obtain a component A;
slowly adding the cosolvent into the sulfonate hydrophilic modified aromatic polyisocyanate, dispersing at a high speed of 20-30m/s for 10-15min, adding the dehydrating agent, dispersing at a high speed of 20-30m/s for 10-15min, filtering by using a 200-mesh filter screen, and filling to obtain the component B.
And (3) uniformly mixing the component A and the component B (the mass ratio of the component A to the component B is 8: 1) to form the nanoparticle modified waterborne white wood sealing primer.
The dosage and the like of each component in the nanoparticle modified waterborne white wood sealing primer are shown in table 1, and the performance of the formed coating is shown in tables 4 and 5.
Example 2
The method is the same as example 1, except that the amount of each component is used, (the mass ratio of the component A to the component B is 9: 1)
See table 1 for details and the properties of the resulting coatings are shown in table 4.
Example 3
The method is the same as example 1, except that the amount of each component is used, (the mass ratio of the component A to the component B is 7: 1)
See table 1 for details and the properties of the resulting coatings are shown in table 4.
Example 4
The process was the same as example 1 except that the amounts of the components, as specified in Table 1, were varied and the properties of the resulting coatings are shown in Table 4.
Example 5
The process was the same as in example 1 except that the amounts of the components, as specified in Table 2, were varied and the properties of the resulting coatings are shown in Table 4.
Example 6
The process was the same as in example 1 except that the amounts of the components, as specified in Table 2, were varied and the properties of the resulting coatings are shown in Table 4.
Example 7
The process was the same as in example 1 except that the amounts of the components, as specified in Table 2, were varied and the properties of the resulting coating were as shown in Table 4.
TABLE 1 contents of respective components in examples 1 to 4
TABLE 2 contents of components in examples 5 to 7
Comparative example 1
The method is the same as example 1, except that the far infrared ceramic powder was not added, the amounts of the respective components are specified in table 3, and the properties of the formed coating are shown in table 4.
Comparative example 2
The method is the same as example 1, except that the far infrared ceramic powder is not added, the nano-scale modified boron nitride is replaced by the micro-scale boron nitride, the amounts of the components are detailed in table 3, and the properties of the formed coating are shown in table 4.
Comparative example 3
The process is the same as example 1 except that the nano-modified core-shell aqueous dispersion is replaced with a commercially available aqueous dispersion, the amounts of the components are specified in table 3, and the properties of the resulting coating are shown in tables 4 and 5.
Comparative example 4
The method is the same as example 1, except that the nano-modified core-shell aqueous dispersion is a self-synthesized aqueous dispersion without nano-modification (i.e., "aqueous dispersion with core-shell structure"), the amounts of the components are shown in table 3, and the properties of the formed coating are shown in table 4.
TABLE 3 contents of components in comparative examples 1 to 4
TABLE 4 Properties of the coatings formed in examples 1 to 7 and comparative examples 1 to 4
TABLE 5 comparison of the applied Integrated energy consumption of example 1 and comparative example 3
The test method employed in this specification is as follows:
the actual dry time is tested according to the actual dry method in GB/T1728-2020 standard.
The visual observation phenomenon after the scratch coating is removed by the full force of the fingernail when the early-stage hardness is baked for 60min serves as the basis for judging and comparing, and the test results can be recorded as no scratch, scratch and scratch.
The hardness is tested according to the GB/T6739-2006 standard, and the baking time is 90 min;
the adhesive force is tested according to the ASTM D3359-2002 standard, and the baking time is 90 min;
the sanding property is tested according to the GB/T1770-2008 standard for baking time of 90min, and the amount of the sandpaper with the sandpaper adhered thereon after sanding is taken as a judgment basis;
the expansion rib resistance adopts visual observation as a judgment and comparison basis, and the experimental result can be recorded as the presence of expansion ribs or the absence of expansion ribs.
The thick coating property adopts visual observation as a judgment basis, the wrinkling phenomenon caused by the dryness of the surface and the inside is mainly observed, and the experimental result can be recorded as no abnormity and local wrinkling. The dry film thickness was 120. mu.m.
The test items shown in table 2 above were all wood boards. Except for the early hardness and final hardness, which were pre-applied with a water-borne UV primer on the wood board, other test items were pre-applied with a clear water-borne two-component sealer primer on the wood board. The dry film thickness of examples 1 to 7 and comparative examples 1 to 4 was controlled to 55. + -.5. mu.m. The data in table 4 show that the modified waterborne woodware seal primer prepared according to examples 1-7 is superior to the waterborne woodware seal primer prepared according to comparative examples 1-4 in the aspects of hardness, adhesion, anti-expansion property, sanding property and the like, and particularly, the advantages of the solid dry time, the early hardness, the final pencil hardness and the sanding property are more obvious. With example 1 having the best overall performance.
The data in table 5 show that the modified aqueous white wood sealer primer prepared according to example 1 reduces the comprehensive application energy consumption by 43.0% under the conditions of the far infrared baking process, compared to the aqueous white wood sealer primer prepared according to comparative example 3. Compared with the traditional blast convection type baking process, the comprehensive application energy consumption is reduced by 63.5 percent.
The modified aqueous woodenware seal primer of example 1 and the aqueous woodenware seal primer of comparative example 3 were applied to the boards with a dry film thickness of 60 μm and were simultaneously baked in a far infrared oven at a temperature of 65 ℃ for 80min, with the coating of comparative example 3 being significantly sticky when sanded, (see figure 1a), while the coating of example 1 being essentially non-sticky (see figure 1 b).
The modified aqueous white woodenware seal primer of example 1 and the aqueous white woodenware seal primer of comparative example 3 were coated on a wood board with a dry film thickness of 60 μm, and simultaneously baked in a far infrared oven at 65 ℃ for 0min, 5min and 20min, the surface temperature rise rate of example 1 on the right side was significantly higher than that of comparative example 3 on the left side (see fig. 2a to 2 c).
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solutions of the present invention are not limited to the above specific embodiments, and any technical modifications made according to the technical solutions of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the scope of the claims.
Claims (30)
1. The nanoparticle modified water-based whiteware seal primer is characterized by comprising a component A and a component B in a mass ratio of 7-9: 1;
the component A comprises the following components in parts by weight: 30.0-50.0 parts of nano modified core-shell aqueous dispersion, 0.1-0.5 part of wetting agent, 0.1-0.5 part of dispersing agent, 0.1-0.3 part of pH regulator, 0.1-0.5 part of defoaming agent, 10-20 parts of titanium dioxide, 1-10 parts of far infrared ceramic powder, 5-10 parts of talcum powder, 5-10 parts of calcium carbonate, 0.2-2 parts of nano modified boron nitride, 2-4 parts of core film-forming additive, 1-3 parts of shell film-forming additive, 5-10 parts of water, 0.1-0.5 part of flatting agent, 0.1-0.3 part of mildew inhibitor, 1-3 parts of polishing additive and 0.5-1.5 parts of thickening agent;
the component B comprises the following components in parts by weight: 65.0 to 80.0 portions of hydrophilic modified aromatic polyisocyanate, 0.1 to 0.3 portion of dehydrating agent and 20.0 to 35.0 portions of latent solvent;
wherein the preparation method of the nano modified core-shell aqueous dispersion comprises the following steps:
so as to contain nano SiO 2 The first mixed reaction system of the dispersion liquid, the first carboxyl monomer, the first hydroxyl monomer, the initiator and the chain transfer agent reacts for 1h at the temperature of 130- 2 Modified core structure resin, wherein the resin contains nano SiO 2 The dispersion liquid is obtained by dispersing nano silicon dioxide colloid in propylene glycol butyl ether by ultrasonic;
so as to contain the nano SiO 2 Reacting a second mixed reaction system of the modified nuclear structure resin, the second carboxyl monomer, the second hydroxyl monomer, the functional monomer, the initiator and the chain transfer agent at the temperature of 130-140 ℃ for 1h, cooling to 75 ℃, and addingAnd a neutralizing agent is dispersed at a high speed to prepare an aqueous dispersion with a core-shell structure, wherein the number average molecular weight of the aqueous dispersion with the core-shell structure is 10000-20000, and the weight average molecular weight of the aqueous dispersion with the core-shell structure is 20000-40000;
stirring and mixing the zirconium source and the graphene oxide dispersion liquid uniformly, and reacting for 8 hours at 105-115 ℃ to prepare the nano ZrO 2 Compounding graphene oxide;
subjecting the nano ZrO to 2 The composite graphene oxide and the aqueous dispersion with the core-shell structure are uniformly mixed and react for 8 hours at 50-60 ℃ to prepare the nano modified core-shell aqueous dispersion.
2. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the wetting agent comprises any one or the combination of more than two of an organic small molecular surfactant, an organosilicon wetting agent, an alkyne diol wetting agent and an organic fluorine wetting agent.
3. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the dispersant comprises any one of macromolecular copolymers containing amino or carboxyl.
4. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the pH regulator comprises any one of AMP-95, ammonia water and DMEA.
5. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the defoaming agent comprises any one or the combination of more than two of organosilicon defoaming agent, acetylene glycol defoaming agent and acrylic polymer defoaming agent.
6. The nanoparticle modified waterborne white wood sealer primer according to claim 1, wherein: the far infrared ceramic powder is prepared by adopting a liquid phase coprecipitation method, and the far infrared emissivity of the far infrared ceramic powder is more than 90% at normal temperature.
7. The nanoparticle modified waterborne white wood sealer primer according to claim 1, wherein: the nanoscale modified boron nitride comprises any one or combination of more than two of amino-modified nano boron nitride, carboxyl-modified nano boron nitride and hydroxyl-modified nano boron nitride, the average particle size of the nano boron nitride adopted by the nanoscale modified boron nitride is below 60nm, and the specific surface area of the nano boron nitride is less than 40m 2 /g。
8. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the core film-forming aid comprises any one or the combination of more than two of PM, DPM and PPh.
9. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the shell film-forming assistant comprises one or the combination of more than two of Dpnb, DPM and PPh.
10. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the flatting agent comprises any one or the combination of more than two of an acrylic copolymer flatting agent, an organic silicon flatting agent and a fluorocarbon flatting agent.
11. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the mildew preventive comprises any one or the combination of more than two of TBZ, TPN and TMTD.
12. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the grinding aid comprises any one or the combination of more than two of zinc stearate, calcium stearate and magnesium stearate.
13. The nanoparticle modified waterborne white wood sealer primer according to claim 1, wherein: the thickening agent comprises one or the combination of more than two of attapulgite, polyamide wax, nonionic hydrophobic modified polyurethane thickening agent, fumed silica and organic modified montmorillonite clay.
14. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the hydrophilic modified aromatic polyisocyanate is sulfonate hydrophilic modified aromatic polyisocyanate.
15. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the dehydrating agent comprises triethyl orthoformate and/or p-toluenesulfonic acid isocyanate.
16. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the co-solvent comprises a urethane grade PMA and/or PM.
17. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the first carboxyl monomer comprises any one or the combination of more than two of methyl methacrylate, butyl methacrylate and butyl acrylate.
18. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the first hydroxyl monomer comprises any one or the combination of more than two of hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate.
19. The nanoparticle modified waterborne white wood sealer primer according to claim 1, wherein: the initiator comprises any one or the combination of more than two of AIBN, BPO and DTBP.
20. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the chain transfer agent comprises any one of tert-dodecyl mercaptan and a pentene compound or a combination of the two.
21. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the second carboxyl monomer comprises any one or the combination of more than two of ethyl acrylate, n-butyl acrylate, isooctyl acrylate and lauryl acrylate.
22. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the second hydroxyl monomer comprises any one or the combination of more than two of hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate.
23. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the functional monomer comprises any one or the combination of more than two of isobornyl methacrylate, glycidyl methacrylate and alkyl acrylate phosphate.
24. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the neutralizing agent comprises one or the combination of more than two of triethylamine, N-dimethylethanolamine and ammonia water.
25. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the zirconium source comprises any one or the combination of more than two of zirconium oxychloride octahydrate, zirconium propanol and zirconium tetra-n-butoxide.
26. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: the graphene oxide dispersion liquid comprises graphene oxide, wherein the diameter of a sheet layer of the graphene oxide in the graphene oxide dispersion liquid is 5-20 mu m, the number of layers is less than 10, and the oxygen content is lower than 15%.
27. The nanoparticle modified waterborne white wood sealer primer according to claim 1, wherein: nano SiO in the first mixed reaction system 2 The mass ratio of the first carboxyl monomer, the first hydroxyl monomer, the initiator and the chain transfer agent is 0.3-1.5:40-60:0.5-2.0:0.5-1.8: 0.5-2.0.
28. The nanoparticle-modified waterborne white wood seal primer according to claim 1, characterized in that: nano SiO in the second mixed reaction system 2 The mass ratio of the modified nuclear structure resin, the second carboxyl monomer, the second hydroxyl monomer, the functional monomer, the initiator and the chain transfer agent is 0.5-1.5:50-70:1.0-2.5:2.0-6.0:0.5-1.8: 0.5-2.0.
29. The method for preparing the nanoparticle-modified aqueous white wood sealing primer according to any one of claims 1 to 28, comprising:
mixing a thickening agent with water, adding a wetting agent, a dispersing agent, a defoaming agent, titanium dioxide, nano-scale modified boron nitride, far infrared ceramic powder, talcum powder, calcium carbonate and a polishing auxiliary agent, mixing and grinding the mixture, then mixing the mixture with the nano-modified core-shell aqueous dispersion, and finally adding a pH regulator, a core film-forming auxiliary agent, a shell film-forming auxiliary agent, a leveling agent and a mildew inhibitor, and uniformly mixing to form a component A;
mixing hydrophilic modified aromatic polyisocyanate with cosolvent, and adding dehydrating agent to form component B;
and uniformly mixing the component A and the component B to form the nanoparticle modified water-based whiteware seal primer.
30. A coating, characterized by: the coating is formed by baking the nanoparticle modified waterborne white wood sealing primer according to any one of claims 1 to 28 through far infrared, wherein the wavelength of the adopted far infrared light is 7 to 15 microns.
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