CN107987675A - A kind of wear-resisting super hydrophobic coating composition and its preparation method and application - Google Patents

A kind of wear-resisting super hydrophobic coating composition and its preparation method and application Download PDF

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Publication number
CN107987675A
CN107987675A CN201711342372.2A CN201711342372A CN107987675A CN 107987675 A CN107987675 A CN 107987675A CN 201711342372 A CN201711342372 A CN 201711342372A CN 107987675 A CN107987675 A CN 107987675A
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nano
dispersion liquid
hydrophobic
binding
coating composition
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CN201711342372.2A
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Chinese (zh)
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葛骅
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杭州纳微生物化学有限公司
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Priority to CN201711342372.2A priority Critical patent/CN107987675A/en
Publication of CN107987675A publication Critical patent/CN107987675A/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5007Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
    • C04B41/501Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing containing carbon in the anion, e.g. carbonates
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    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D127/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16Homopolymers or copolymers of vinylidene fluoride
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00Metallic substrate
    • B05D2202/10Metallic substrate based on Fe
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00Metallic substrate
    • B05D2202/20Metallic substrate based on light metals
    • B05D2202/25Metallic substrate based on light metals based on Al
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/29Mixtures
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/112Deposition methods from solutions or suspensions by spraying
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/346Clay
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

The present invention relates to a kind of wear-resisting super hydrophobic coating composition and its preparation method and application.Said composition includes nano material dispersion liquid and binding material dispersion liquid.Nano material dispersion liquid is formed by nano-particle material, hydrophobic silane coupling agent and volatile solvent, wherein nano particle is due to its mutual coarse structure of the effect formation with micro-nano double scales, this structure disperses is in the solution of hydrophobic silane coupling agent, there are hydrophobic silane coupling agent one or more groups to form covalent key connection with micro-nano dual coarse structure, while also at least have hydrophobic group containing one.The super-hydrophobic coat formed through this super hydrophobic coating composition maintains permanently effective superhydrophobic characteristic;The combination power between super-drainage structure and matrix is enhanced using binding material in coating composition, enhances the protecting effect of coating;The processing technology of super-hydrophobic coat is simple and convenient, is conducive to the construction of large area.

Description

A kind of wear-resisting super hydrophobic coating composition and its preparation method and application
Technical field
Preparation and applied technical field the invention belongs to super hydrophobic surface, and in particular to a kind of wear-resisting super hydrophobic coating group Compound and its preparation method and application.
Background technology
From Univ Bonn Germany Barthlott research groups the 1990s report that lotus leaf surface has first it is super Since hydrophobic property research, this surface characteristic is also widely referred to as " lotus leaf effect ".Super hydrophobic surface generally refers to the surface of solids It is more than 150 ° with the contact angle of water droplet and roll angle is less than 10 °.Since the contact area of super hydrophobic surface and water is very small, water droplet It cannot easily be tumbled in its superficial residence from surface.Therefore, super hydrophobic surface not only has self-cleaning function, but also has The function such as anticorrosion, waterproof, drag reduction, antifog, anti-ice, has in fields such as aviation, navigation, the energy, electronics, building, anti-corrosion, heat transfers Have wide practical use.
What the superhydrophobic characteristic of the surface of solids was mainly determined by two factors, low surface free energy and suitably coarse Degree.Conventional super hydrophobic coating mixes scattered form with nano particle using fluorine-containing or silicon low surface free energy resin more.Such as Patent CN10378880A and CN103865372A are proposed fluorin modified crylic acid ester and silicane coupling agent surface grafted two The scattered method that super hydrophobic coating is made of silicon oxide nanoparticle mixing, such method is although simple and practicable, but its coating is resistance to Mill property is poor, and superhydrophobic characteristic easily loses under the action of of short duration wind erosion or friction, and practical performance is not strong.In order to make coating Wearability is effectively improved, and patent CN104910776A is proposed a kind of strengthens coating abrasion performance using binding material Method.Substrate surface is coated in after binding material is dissolved first, nano material dispersion liquid is coated with after dry, it is sharp after to be dried Nano material is partially submerged into tack coat with the method for heating or pressurization, then the nano particle bonded loosely is gone divided by obtained Super-hydrophobic coat with certain wearability., can not be in short-term but it is more to prepare step needed for the method for this super-hydrophobic coat In or obtained by simple one-step method, therefore it is greatly limited in commercial Application.
The content of the invention
It is an object of the invention to overcome the shortcomings of the prior art, there is provided a kind of preparation method is simple, has good The super hydrophobic coating composition and its technique for applying of wearability.
In order to achieve the above object, the present invention adopts the technical scheme that:
Super hydrophobic coating composition includes two component of nano material dispersion liquid and binding material dispersion liquid.By nano material point After dispersion liquid is mixed in proportion with binding material dispersion liquid, the side such as brushing, dip-coating, spin coating, roller coat, spraying and showering can be passed through Method is coated on the matrix surfaces such as glass, metal, ceramics, timber, paper, cloth, plastics, ultimately forms wear-resisting super-hydrophobic coat.
The nano material dispersion liquid is mainly mixed by nano-particle material, hydrophobic silane coupling agent and volatile solvent Conjunction forms, and nano particle forms the coarse structure with micro-nano double scales, this structure point due to its mutual effect It is dispersed in the solution containing hydrophobic silane coupling agent;Wherein hydrophobic silane coupling agent has one or more groups and micro-nano Meter Shuan Chong coarse structures form covalent key connection, while also at least have hydrophobic group containing one;Pass through hydrophobicity silicon Covalent key connection between alkane coupling agent and micro-nano dual coarse structure, adds this coarse structure in solution and coating Stability, therefore assign the more preferable wearability of super-hydrophobic coat.
The binding material dispersion liquid is mainly mixed scattered form by binding material with its good solvent.
Preferably, the size of micro-nano dual coarse structure is 0.03-5 microns.
Preferably, the nano-particle material includes the one or more in the following:Titanium dioxide, calcium carbonate, two Silica, zinc oxide, kaolin, aluminium oxide and polytetrafluoroethylene (PTFE), wherein nano particle can be it is non-modified or By modified, its particle diameter distribution is 10-1000 nanometers.
Preferably, the hydrophobic silane coupling agent includes the one or more in the following:Cetyl trimethoxy Base silane, isobutyl triethoxy silane, trimethoxysilane, dodecyl triethoxysilane, dodecyl three Methoxy silane, octyl group trimethoxy silane, n-octytriethoxysilane, perfluoro capryl triethoxysilane, ten trifluoros are pungent Base trimethoxy silane, 17 fluorine decyl triethoxysilanes and 17 fluorine decyl trimethoxy silanes.
Preferably, the volatile solvent includes the one or more in the following:Acetone, methanol, ethanol and isopropyl Alcohol.
Preferably, the binding material includes the one or more in the following:Fluorocarbon resin, epoxy resin, alkyd Resin, organic siliconresin or polyurethane resin;Its described good solvent for acetone, dimethylbenzene, ethyl acetate, butanone, n-hexane and One or more in dimethylformamide.
Preferably, the binding material dispersion liquid can also contain defoamer, accelerating agent, anti-settling agent, levelling agent, pigment Deng auxiliary agent.
A kind of preparation method of above-mentioned wear-resisting super hydrophobic coating composition is provided, is included the following steps:
Step (1), add nano-particle material and hydrophobic silane coupling agent in volatile solvent, using mechanical agitation Dispersing mode is handled 5-90 minutes, while can also use ultrasonic disperse mode aid in treatment, forms nano material dispersion liquid, its The mass fraction of middle nano-particle material is 0.1-10%, and the mass fraction of hydrophobic silane coupling agent is 0.1-10%;
Step (2), mix binding material with its good solvent, and temperature control is at 10-40 DEG C, mechanical agitation 10-90 minutes, Binding material dispersion liquid is formed, the wherein mass fraction of binding material is 5-50%.
In above-described preparation method, the processing time of nano material dispersion liquid is with hydrophobic silane in step (1) Coupling agent was modified subject to the time of nano material completely.Nano material is formed after modification in nano material dispersion liquid The coarse structure of 0.03-5 micron-scales, and hydrophobic silane coupling agent is grafted on its surface by covalent bond.
In the binding material dispersion liquid described in step (2), defoamer, accelerating agent, anti-settling agent, levelling can also be contained The auxiliary agents such as agent, pigment.
A kind of technique for applying of above-described wear-resisting super hydrophobic coating composition, includes the following steps:
Step (3), in coating in use, nano material dispersion liquid and binding material dispersion liquid are mixed in proportion, temperature At 10-40 DEG C, mechanical agitation 10-120 minutes, forms uniform mixed solution for control.
According to needed for application, those skilled in the art can be voluntarily to the proportionate relationship of nano material dispersion liquid and binding material Adjust.
Matrix surface to be coated, is carried out dust removal, degreasing processing until clean and after drying by step (4), by brushing, Mixed solution described in step (3) is coated in matrix surface by the methods of dip-coating, spin coating, roller coat, spraying or showering, it is dry or Super-hydrophobic coat is formed after curing.
Described matrix is glass, metal, ceramics, timber, paper, cloth or plastics.
Beneficial effects of the present invention are mainly manifested in:The super-hydrophobic coat formed through this super hydrophobic coating composition maintains Permanently effective superhydrophobic characteristic;Binding material is used to enhance the combination between super-drainage structure and matrix in coating composition Power, enhances the protecting effect of coating;Added in coating composition using hydrophobic silane coupling agent micro-nano dual coarse The stability of structure, so as to improve the wearability of super-hydrophobic coat;The processing technology of super-hydrophobic coat is simple and convenient, is conducive to The construction of large area.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the dual coarse structure of 1 floating coat surface micronano rank of the embodiment of the present invention.
Fig. 2 is the contact angle state diagram before the experiment of gained coating rub resistance to water in the embodiment of the present invention 1.
Fig. 3 is the contact angle state diagram after the experiment of gained coating rub resistance to water in the embodiment of the present invention 1.
Fig. 4 is the contact angle state diagram before the experiment of gained coating rub resistance to water in the embodiment of the present invention 2.
Fig. 5 is the contact angle state diagram after the experiment of gained coating rub resistance to water in the embodiment of the present invention 2.
Embodiment
Following embodiments further illustrate present disclosure, but should not be construed as limiting the invention.
Embodiment 1
It is prepared by nano material dispersion liquid:By three ethoxy of 1.5g hydrophobicity aerosils (R972) and 1.0g perfluoro capryls Base silane is added in 27.5g aqueous isopropanols, mechanical agitation 30 minutes, up to nano material dispersion liquid;It is micro-nano dual coarse The size of structure is 0.03-3 microns.
It is prepared by binding material dispersion liquid:6.0g epoxy resin (EPO-TEK301) is added in 24.0g acetone, mechanical agitation 40 minutes up to binding material dispersion liquid;
Technique for applying:Above nano material dispersion liquid and binding material dispersion liquid are mixed, mechanical agitation is mixed after twenty minutes Close uniform.By obtained mixed solution by the air cannon that pressure is 40psi, sprayed 3 times with the distance of 20cm and the speed of 8cm/s In on clean glass plate, then by glass plate be dried at room temperature for 1 it is small when after cure in 65 DEG C of baking oven 2 it is small when, finally Super-hydrophobic coat is obtained in glass surface.
Test result:The surface of coating has the dual coarse structure (attached drawing 1) of micro-nano-scale, its static contact angle is 164 ° (attached drawings 2), roll angle are 3 °;Rubbed experiment (load 10N/100mm2, rub 1000 times, rotating speed 100r/min) after, Its static contact angle is 158 ° (attached drawings 3), and roll angle is 5 °.
Embodiment 2
It is prepared by nano material dispersion liquid:By 0.5g hydrophobicity aerosils (R972), 1.0g nano-titanium dioxides (TTP-A10) added with 1.0g hexadecyl trimethoxy silanes in 27.5g ethanol solutions, mechanical agitation 30 minutes, receives to obtain the final product Rice material dispersion liquid;The size of micro-nano dual coarse structure is 0.08-4 microns.
It is prepared by binding material dispersion liquid:8.0g polyurethane resins (KL-540E) are added into 10.0g acetone, 6.0g acetic acid second In the mixed solution of ester and 6.0g dimethylformamides, mechanical agitation 30 minutes is up to binding material dispersion liquid;
Technique for applying:Above nano material dispersion liquid and binding material dispersion liquid are mixed, mechanical agitation is mixed after twenty minutes Close uniform.Obtained mixed solution is brushed on clean iron plate, when drying 2 is small in 120 DEG C of baking oven, finally in iron plate Surface obtains super-hydrophobic coat.
Test result:The surface of coating has the dual coarse structure of micro-nano-scale, its static contact angle is (attached for 172 ° Fig. 4), roll angle is 2 °;Rubbed experiment (load 10N/100mm2, rub 1000 times, rotating speed 100r/min) after, its static state connects Feeler is 152 ° (attached drawings 5), and roll angle is 4 °.
Embodiment 3
It is prepared by nano material dispersion liquid:By 2.5g nanometer polytetrafluoroethylcomposites particle (3M-1600) and 1.5g octyl group trimethoxies Base silane is added in the mixed solution of 16.0g acetone and 10.0g ethanol, mechanical agitation 20 minutes, up to nano material dispersion liquid; The size of micro-nano dual coarse structure is 0.1-5 microns.
It is prepared by binding material dispersion liquid:7.0g Kynoar (V203) is added in 23.0g dimethyl formamide solutions, Mechanical agitation 30 minutes is up to binding material dispersion liquid;
Technique for applying:Above nano material dispersion liquid and binding material dispersion liquid are mixed, mechanical agitation is mixed after twenty minutes Close uniform.Obtained mixed solution is spin-coated on clean aluminium flake, when drying 2.5 is small in 120 DEG C of baking oven, finally in aluminium Piece surface obtains super-hydrophobic coat.
Test result:The surface of coating has the dual coarse structure of micro-nano-scale, its static contact angle is 158 °, rolling Dynamic angle is 3 °;Rubbed experiment (load 10N/100mm2, rub 1000 times, rotating speed 100r/min) after, its static contact angle is 151 °, roll angle is 5 °.
Embodiment 4
It is prepared by nano material dispersion liquid:By ten trifluoro octyl group trimethoxy of 1.5g nano silicon dioxides (TS-530) and 1.0g Silane is added in the mixed solution of 27.5g acetone and 10.0g ethanol, mechanical agitation 20 minutes, up to nano material dispersion liquid;It is micro- The size of the dual coarse structure of nanometer is 0.03-3 microns.
It is prepared by binding material dispersion liquid:7.0g organic siliconresins (OS-903AB) are added into 18.0g acetone and 5.0g diformazans In benzene mixed solution, mechanical agitation 30 minutes is up to binding material dispersion liquid;
Technique for applying:Above nano material dispersion liquid and binding material dispersion liquid are mixed, mechanical agitation is mixed after twenty minutes Close uniform.By obtained mixed solution dip-coating on clean cotton, when drying 1.5 is small in 100 DEG C of baking oven, finally in cotton Cloth surface obtains super-hydrophobic coat.
Test result:The static contact angle of coating surface is 162 °, and roll angle is 4 °;Rubbed experiment (load 10N/ 100mm2, rub 1000 times, rotating speed 100r/min) after, its static contact angle is 153 °, and roll angle is 5 °.
Embodiment 5
It is prepared by nano material dispersion liquid:By 0.03g nano-calcium carbonates (TH-2500) and 1.0g isobutyl triethoxy silanes Add in 28.97g methanol solutions, ultrasonic disperse 20 minutes, up to nano material dispersion liquid;The ruler of micro-nano dual coarse structure Very little is 0.2-4 microns.
It is prepared by binding material dispersion liquid:1g defoamers (BYK-057), 6.0g alkyd resins (BC-6501-80) are added In 18.0g acetone and 5.0g dimethylbenzene mixed solutions, mechanical agitation 30 minutes is up to binding material dispersion liquid;
Technique for applying:Above nano material dispersion liquid and binding material dispersion liquid are mixed, 40 DEG C of mechanical agitations 10 minutes After be uniformly mixed.By obtained mixed solution dip-coating in clean ceramic surface, dried in 90 DEG C of baking oven 3.0 it is small when, most Eventually super-hydrophobic coat is obtained in ceramic surface.
Test result:The static contact angle of coating surface is 167 °, and roll angle is 6 °;Rubbed experiment (load 10N/ 100mm2, rub 1000 times, rotating speed 100r/min) after, its static contact angle is 162 °, and roll angle is 7 °.
Embodiment 6
It is prepared by nano material dispersion liquid:3g nano zine oxides (PZT-30) and 1.0g trimethoxysilanes are added In 16g methanol solutions, ultrasonic disperse 20 minutes, up to nano material dispersion liquid;The size of micro-nano dual coarse structure is 0.06-5 microns.
It is prepared by binding material dispersion liquid:1g pigment (K3840SQ), 6.0g organic siliconresins (OS-903AB) are added In 18.0g acetone and 5.0g dimethylbenzene mixed solutions, mechanical agitation 30 minutes is up to binding material dispersion liquid;
Technique for applying:Above nano material dispersion liquid and binding material dispersion liquid are mixed, 40 DEG C of mechanical agitations 10 minutes After be uniformly mixed.By obtained mixed solution dip-coating on clean paper, when drying 2.0 is small in 100 DEG C of baking oven, finally exist Paper surface obtains super-hydrophobic coat.
Test result:The static contact angle of coating surface is 159 °, and roll angle is 2 °;Rubbed experiment (load 10N/ 100mm2, rub 1000 times, rotating speed 100r/min) after, its static contact angle is 152 °, and roll angle is 4 °.
Embodiment 7
It is prepared by nano material dispersion liquid:By 1g nano kaolines (Polarite 403A) and 1.0g dodecyl trimethoxies Base silane is added in 18g methanol solutions, ultrasonic disperse 20 minutes, up to nano material dispersion liquid;Micro-nano dual coarse structure Size be 0.07-4 microns.
It is prepared by binding material dispersion liquid:7.0g organic siliconresins (OS-903AB) are added into 18.0g acetone and 5.0g diformazans In benzene mixed solution, mechanical agitation 30 minutes is up to binding material dispersion liquid;
Technique for applying:Above nano material dispersion liquid and binding material dispersion liquid are mixed, 40 DEG C of mechanical agitations 10 minutes After be uniformly mixed.By obtained mixed solution dip-coating on clean plastic plate, when drying 2.0 is small in 100 DEG C of baking oven, most Eventually super-hydrophobic coat is obtained in plastic sheet surface.
Test result:The static contact angle of coating surface is 171 °, and roll angle is 3 °;Rubbed experiment (load 10N/ 100mm2, rub 1000 times, rotating speed 100r/min) after, its static contact angle is 162 °, and roll angle is 5 °.
It is that the present invention is not limited only to above-described embodiment, as long as meeting for limitation of the invention that above-described embodiment, which is not, Application claims, belong to protection scope of the present invention.

Claims (10)

1. a kind of wear-resisting super hydrophobic coating composition, it is characterised in that said composition includes nano material dispersion liquid and binding material Dispersion liquid;
Nano material dispersion liquid is mainly formed by nano-particle material, hydrophobic silane coupling agent and volatile solvent;Its Middle nano particle forms the coarse structure with micro-nano double scales due to its mutual effect;Hydrophobic silane is coupled There are one or more groups to form covalent key connection with micro-nano dual coarse structure for agent, while also at least have containing one Hydrophobic group;
Binding material dispersion liquid is mainly mixed scattered form by binding material with its good solvent.
2. a kind of preparation method of wear-resisting super hydrophobic coating composition, it is characterised in that this method is specifically:
The preparation of nano material dispersion liquid is to add nano-particle material and hydrophobic silane coupling agent in volatile solvent, is adopted Disperseed with mechanical agitation or ultrasonic disperse;
The preparation of binding material dispersion liquid is to mix binding material with its good solvent, and temperature control is at 10-40 DEG C, mechanical agitation 10-90 minutes.
3. the preparation method described in a kind of wear-resisting super hydrophobic coating composition according to claim 1 or claim 2, its It is characterized in that nano-particle material includes the one or more in the following:Titanium dioxide, calcium carbonate, silica, oxidation Zinc, kaolin, aluminium oxide and polytetrafluoroethylene (PTFE), wherein nano particle can be non-modified or process is modified, Its particle diameter distribution is 10-1000 nanometers.
4. the preparation method described in a kind of wear-resisting super hydrophobic coating composition according to claim 1 or claim 2, its It is characterized in that hydrophobic silane coupling agent includes the one or more in the following:Hexadecyl trimethoxy silane, isobutyl Ethyl triethoxy silicane alkane, trimethoxysilane, dodecyl triethoxysilane, dodecyltrimethoxysilane, Octyl group trimethoxy silane, n-octytriethoxysilane, perfluoro capryl triethoxysilane, ten trifluoro octyl group trimethoxy silicon Alkane, 17 fluorine decyl triethoxysilanes and 17 fluorine decyl trimethoxy silanes.
5. the preparation method described in a kind of wear-resisting super hydrophobic coating composition according to claim 1 or claim 2, its It is characterized in that volatile solvent includes the one or more in the following:Acetone, methanol, ethanol and isopropanol.
6. the preparation method described in a kind of wear-resisting super hydrophobic coating composition according to claim 1 or claim 2, its It is characterized in that binding material includes the one or more in the following:Fluorocarbon resin, epoxy resin, alkyd resin, organosilicon Resin or polyurethane resin;Good solvent is one in acetone, dimethylbenzene, ethyl acetate, butanone, n-hexane and dimethylformamide Kind is a variety of.
7. the preparation method described in a kind of wear-resisting super hydrophobic coating composition according to claim 1 or claim 2, its The mass fraction for being characterized in that nano-particle material in nano material dispersion liquid is 0.1-10%, the matter of hydrophobic silane coupling agent Amount fraction is 0.1-10%.
A kind of 8. wear-resisting super hydrophobic coating composition according to claim 1, it is characterised in that micro-nano dual coarse knot The size of structure is 0.03-5 microns.
9. the application of wear-resisting super hydrophobic coating composition according to claim 1, it is characterised in that disperse nano material Liquid and binding material dispersion liquid are mixed in required ratio, and at 10-40 DEG C, mechanical agitation 10-120 minutes, forms equal temperature control Even mixed solution;By mixed solution by being coated in matrix table the methods of brushing, dip-coating, spin coating, roller coat, spraying or showering Face, wear-resisting super-hydrophobic coat is formed after dry or curing.
10. application according to claim 9, it is characterised in that described matrix is glass, metal, ceramics, timber, paper, cloth Material or plastics.
CN201711342372.2A 2017-12-15 2017-12-15 A kind of wear-resisting super hydrophobic coating composition and its preparation method and application CN107987675A (en)

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