CN107254237B - Coating composed of ultrahigh-roughness particles - Google Patents

Coating composed of ultrahigh-roughness particles Download PDF

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Publication number
CN107254237B
CN107254237B CN201710621361.1A CN201710621361A CN107254237B CN 107254237 B CN107254237 B CN 107254237B CN 201710621361 A CN201710621361 A CN 201710621361A CN 107254237 B CN107254237 B CN 107254237B
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particles
coating
super
hydrophobic
protective layer
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CN107254237A (en
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卢序
傅怡然
李光武
李福全
郑振叶
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Hong Hitech Beijing Co ltd
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Hong Hitech Beijing Co ltd
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/12—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

The invention provides an ultra-hydrophobic coating consisting of ultra-high roughness particles, which is prepared from the following components: non-smooth structured particles with protrusions or holes, protective particles, binders and auxiliaries. Wherein the volume ratio of the first three is (0.1-7) to (1-10). The lotus effect technical theory is applied to produce the super-hydrophobic, underwater super-oleophobic or super-amphiphobic surface coating, so that the performance of the coating is further improved, and the defects of easy damage to the structure, short service life and the like of the conventional super-hydrophobic coating are overcome. The prepared coating has super-hydrophobicity (super-hydrophobicity, underwater super-oleophobic or super-amphiphobic) and self-cleaning property, and has excellent abrasion resistance, and the coating substrate material is suitable for glass, plastics, rubber, fabric, paper, metal, cement, ceramic materials or the materials covered with other coatings.

Description

Coating composed of ultrahigh-roughness particles
Technical Field
The invention belongs to the technical field of paint preparation in applied chemical engineering, and particularly relates to a coating consisting of ultrahigh-roughness particles.
Background
The coating is a common process for surface treatment of materials, and can effectively protect the materials from corrosion, thereby obviously prolonging the service life of the materials. The hydrophobic coating can isolate the material from external moisture, and plays an important role in protecting structures such as buildings, industrial equipment, pipelines, precision machinery and the like. In recent years, with the increasing demand for living quality and the increasing awareness of environmental protection and energy conservation, the super-hydrophobic coating process has been rapidly developed due to its strong self-cleaning function.
By superhydrophobic coating is meant a surface having a contact angle with water of more than 150 ° and a rolling angle of less than 10 °. However, the commercial hydrophobic coatings currently developed generally have two problems:
(1) the existing hydrophobic coating mainly depends on the change of chemical properties, namely, hydrophobic groups are added on the surface to achieve the hydrophobic effect. The limit hydrophobic angle which can be achieved by the method is only 112 degrees, and the super-hydrophobic effect of more than 150 degrees cannot be achieved.
(2) The hydrophobic material has certain toxicity due to the addition of fluorine, anthracene, naphthalene, phenol and other substances, and can cause pollution to the environment and harm the health of users. In addition, the existing hydrophobic coating generally has the defects of easy aging, long preparation period and the like.
The structural hydrophobic material is a novel nano material developed based on the 'lotus effect' of bionic materials science, namely the rough surface structure of lotus leaves is simulated to obtain the properties of hydrophobicity, self-cleaning and the like. An equation developed based on the young's equation according to Wenzel: cos θ1＝r(уSV-уSL)/уLVWherein, theta1The apparent contact angle is the contact angle between liquid phase and solid phase. r is the ratio of the actual contact area to the apparent contact area of the liquid phase-solid phase, and y is the surface tension between the solid phase (S), the liquid phase (L), and the saturated vapor phase (V). For the surface of the hydrophobic material, the surface tension between the liquid phase and the solid phase is constantly larger than the surface tension between the solid phase and the saturated steam,that is (у)SV-уSL)/уLVIs negative.
From the above formula, when the surface roughness of the coating increases, that is, the actual contact area between the solid phase and the liquid phase increases, but the apparent contact area remains unchanged, so that the value of r in the formula increases, which leads to further increase of the contact angle, and the super-hydrophobic effect is achieved. The same principle applies to superoleophobic coatings in addition to superhydrophobic coatings. According to GB/T26490-2011, superoleophobic means that the contact angle with oil is greater than 120 deg..
At present, the super-hydrophobic coating usually uses resin as a binder, and micron-nano composite particles or only nano particles as a filler, so as to realize super-hydrophobicity. The nanoparticles are mostly modified by surface energy substances. The technical proposal is adopted by Super-hydrophobic coatings of patents CN200810061480.7, CN201210466649.3, CN201210286775.0, CN201310460822.3 and the like, and Super Ever Dry and Neverwet abroad. Among them, the resin is often selected to be an elastic resin to improve abrasion resistance, but the shear strength of the elastic resin is too low to be suitable for conventional coating use. Patent CN201610392566.2 adopts the addition of a porous mesh layer to protect the super-hydrophobic coating, which greatly enhances the mechanical properties of the coating, however, the construction aspect increases the difficulty and presents obvious limitations. In addition to micro-nanocomposite particle coatings, super-hydrophobic particles are built by sol-gel principles and then coatings are built, e.g. cn201510508485. x. However, the mechanical structure of the coating formed by this method is generally more fragile than the former solution.
In fact, the main reason for the poor abrasion resistance of the above two solutions is the nature of the nanoparticles and of the gel itself. Because the nano particles are too fine and are difficult to embed into the resin, and the adhesive force of the second layer of adhesive is difficult to increase, the adhesive force is much smaller than that of micron-level particles, and the particles are easy to fall off by grinding, so that the super-hydrophobicity of the coating is lost. Compared with nano particles, the particles after being grinded after the gelation are in micron order, and the adhesive force is better. However, since the porosity of the gel produced after sol-gel is high and the gel has no crystal structure, the mechanical strength of the gel material is much lower than that of the same material with a non-porous crystal structure, and the gel material is easy to break, so that the gel material is not wear-resistant. Furthermore, since the ultra-high roughness surface itself has a high roughness, the friction force upon contact with a solid is greater, also resulting in that it is more easily damaged.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of an ultra-hydrophobic coating formed by ultra-high roughness particles, which aims to solve the problems of low mechanical strength, short service life and difficult preparation of the existing coatings with ultra-hydrophobic, ultra-hydrophilic, ultra-hydrophobic and the like surfaces needing ultra-high roughness structures. The invention uses the particles with ultrahigh roughness on the surface of the substrate material through the adhesive, uses the wear-resistant particles to enhance the mechanical strength of the coating, and can directly prepare the practical super-hydrophobic coating.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a coating consisting of ultra-high roughness particles is prepared from the following components:
non-smooth structured particles with protrusions or holes, protective particles, binders and auxiliaries;
wherein the volume ratio of the non-smooth structure particles, the protective particles and the adhesive is (0.1-7): 1-10, preferably (0.1-2): 1-4): 2-7.
The coating formed by the ultra-high roughness particles provided by the application applies the lotus effect technical theory to manufacture the structural ultra-hydrophobic, underwater ultra-oleophobic or ultra-amphiphobic surface coating, further improves the performance of the coating and overcomes the defects of the existing ultra-hydrophobic coating such as easy damage to the structure, short service life and the like.
Preferably, the protective particles are selected from one of silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, silicon carbide, tungsten carbide, carbide such as titanium carbide, boron nitride, and silicon nitride, and more preferably from silicon dioxide or aluminum oxide.
Preferably, the auxiliary agent accounts for 0.01-10%, preferably 0.1-3% of the mass sum of the particles with the non-smooth structures, the protective particles and the adhesive, and more preferably, the auxiliary agent is selected from one of an ultraviolet aging resistant agent, a silane coupling agent and a hydrophobic agent.
Preferably, the particle size of the non-smooth structured particles having protrusions or holes is in the range of 0.1 to 100 μm, more preferably 0.5 to 20 μm.
Preferably, the surface of the particles with the non-smooth structures with the protrusions or the holes has the non-smooth structures with the protrusions or the holes of 1nm-100nm, more preferably the aerogel or xerogel particles with the holes of 2-100nm, and even more preferably, the particles with the non-smooth structures with the protrusions or the holes are obtained by chemical corrosion, and the surface of the particles with the protrusions or the holes has the metal or polymer particles with the protrusions of 10-100nm petal-shaped or needle-point-shaped;
preferably, the surface of the particle is surface modified, and more preferably, the surface modification is selected from one of three surface characteristics of hydrophobic oleophilic property, hydrophilic oleophobic property and hydrophobic oleophobic property.
Preferably, the surface energy of the particles with the non-smooth structures, which are subjected to the hydrophobic and oleophilic surface modification, is less than 72mN/m and more than 27mN/m at normal temperature; the surface energy of the particles with the non-smooth structures, which are subjected to the hydrophobic and oleophobic surface modification, is lower than 27mN/m at normal temperature.
Preferably, the surface of the non-smooth structure particles modified by the hydrophilic and oleophobic surface contains hydrophilic groups, and the hydrophilic groups are selected from one of ether bonds consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid, amino groups, quaternary ammonium groups and oxygen-containing groups, hydroxyl groups, carboxylic ester and block polyether.
Preferably, the protective particles have a particle size of 0.1 to 1000 μm, more preferably 1 to 50 μm.
More preferably, the surface of the protective particle is subjected to a surface modification treatment, the surface modification comprising: three surface modifications of hydrophobic oleophylic, hydrophilic oleophobic and hydrophobic oleophobic are carried out.
Preferably, the adhesive is a high molecular polymer with molecular weight greater than 100.
More preferably, the adhesive is one selected from the group consisting of silicone, fluorine-containing resin, acrylic resin, epoxy resin, polyethylene, polypropylene, polystyrene, fluorinated polyether, nylon, polycarbonate, polyurethane, styrene-butadiene rubber, nitrile rubber, silicone rubber, butadiene rubber, fluorine rubber, chloroprene rubber, isoprene rubber, butyl rubber, polyurethane, and polyurea.
Preferably, the coating layer is made of ultra-high roughness particles, more preferably, the surface of the coating layer is further provided with a protective layer, and preferably, the material of the protective layer is selected from one or a combination of more of fluorinated polyether, fluorine ester, perfluoropolyether ester, fluorinated silicone oil, a perfluorosilane coupling agent, perfluoroacrylate, perfluorophosphoric acid and ester, perfluorocarboxylic acid, and perfluorothiol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the coating formed by the ultrahigh-roughness particles is simple in process, easily available in raw materials and moderate in cost, and can be used in the fields of building exterior wall coatings, automobile self-cleaning vehicle paints, ship wear resistance, drag reduction and the like.
(2) The coating formed by the ultra-high roughness particles has super-hydrophobicity and a smaller rolling angle, can realize a self-cleaning function, and the base material of the coating can be glass, plastic, rubber, fabric, paper, metal, cement, ceramic material or the material covered with other coatings, so that the application range is wide.
(3) The coating formed by the ultrahigh-roughness particles has the characteristics of high strength, long service life and the like.
(4) The coating that constitutes by super high roughness granule that this application provided not only can realize super hydrophobic, can also realize underwater super oleophobic and super amphiphobic function under the certain condition.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow diagram of the present invention for preparing an ultraphobic coating with ultra-high roughness particles by a layered spray method;
FIG. 2 is a process flow diagram of the present invention for preparing an ultra-hydrophobic coating with ultra-high roughness particles by a hybrid spray method;
fig. 3 is a schematic view of a coating structure in which a protective layer is formed by layered spraying and an ultra-hydrophobic layer is formed by layered spraying according to an embodiment of the present invention.
FIG. 4 is a schematic view of a coating structure of a protective layer formed by layered spraying and an ultra-hydrophobic layer formed by mixed spraying according to an embodiment of the present invention.
Fig. 5 is a schematic view of a coating structure in which a protective super-hydrophobic hybrid coating is directly formed by hybrid spraying according to an embodiment of the present invention.
FIG. 6 is a schematic view of a coating structure in which only the ultra-hydrophobic layer is formed by hybrid spraying according to an embodiment of the present invention.
Fig. 7 is an electron microscope photograph of aerogel particles having ultra-high roughness.
Description of the drawings:
1-protective layer primer; 2-coating the protective layer with glue; 3-super-hydrophobic layer primer; 4-super-hydrophobic layer protective film; 5-protective particles; 6-ultra high roughness particles; 7-a super-hydrophobic layer adhesive; and mixing the layer adhesive.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A coating consisting of ultra-high roughness particles is prepared from the following components:
non-smooth structured particles with protrusions or holes, protective particles, binders and auxiliaries;
wherein the volume ratio of the non-smooth structure particles, the protective particles and the adhesive is (0.1-7): 1-10, preferably (0.1-2): 1-4): 2-7.
The coating that constitutes by super high roughness granule that this application provided utilizes super high roughness granule to realize super thin effect, utilizes protection granule reinforcing coating wearability and increase life, uses performance such as intensity, life and the super thin nature of suitable construction process further reinforcing coating.
Wherein, the particles with the non-smooth structure of the bulges or the holes have high roughness, and the abrasion-resistant particles are used for enhancing the mechanical strength of the coating on the surface of the substrate material through the adhesive, so that the super-hydrophobic coating with practicability can be directly prepared.
Preferably, the protective particles are selected from one of silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, silicon carbide, tungsten carbide, carbide such as titanium carbide, boron nitride, and silicon nitride, and more preferably from silicon dioxide or aluminum oxide.
The protective particles have a certain mechanical strength and protect particles with non-smooth structures.
Preferably, the auxiliary agent accounts for 0.01-10%, preferably 0.1-3% of the mass sum of the particles with the non-smooth structures, the protective particles and the adhesive, and more preferably, the auxiliary agent is selected from one of an ultraviolet aging resistant agent, a silane coupling agent and a hydrophobic agent.
The assistant is an indispensable component of the paint, can improve the production process, keep the storage stability, improve the construction conditions, improve the product quality and endow special functions. The reasonable and correct selection of the auxiliary agent can reduce the cost and improve the economic benefit. The additive is reasonable in addition amount, and the comprehensive performance of the coating is improved.
Preferably, the particle size of the non-smooth structured particles having protrusions or holes is in the range of 0.1 to 100 μm, more preferably 0.5 to 20 μm.
The smaller the particle size, the better the surface energy of the particles is reduced. When the particle size is less than 0.1 micron, the particles are easy to agglomerate and not easy to disperse, and the performance of the coating is affected.
Preferably, the surface of the particles with the non-smooth structures with the protrusions or the holes has the non-smooth structures with the protrusions or the holes of 1nm-100nm, more preferably the aerogel or xerogel particles with the holes of 2-100nm, and even more preferably, the particles with the non-smooth structures with the protrusions or the holes are obtained by chemical corrosion, and the surface of the particles is provided with metal or polymer particles with the protrusions of 10-100nm petal-shaped or needle-point-shaped.
The surface of the non-smooth structured particles having projections or holes has a microscopic structure of a nanometer order. The microstructure effectively increases the roughness of the coating, decreasing the apparent energy of the coating. And the particles are preferably obtained by chemical etching.
Preferably, the surface of the particle is surface modified, and more preferably, the surface modification is selected from one of three surface characteristics of hydrophobic oleophilic property, hydrophilic oleophobic property and hydrophobic oleophobic property.
The coating can further produce hydrophobic, oleophobic or amphiphobic properties by showing modification.
Preferably, the surface energy of the particles with the non-smooth structures, which are subjected to the hydrophobic and oleophilic surface modification, is less than 72mN/m and more than 27mN/m at normal temperature; the surface energy of the particles with the non-smooth structures, which are subjected to the hydrophobic and oleophobic surface modification, is lower than 27mN/m at normal temperature.
After the modification, the coating is further improved, and the surface energy can be effectively reduced.
Preferably, the surface of the non-smooth structure particles modified by the hydrophilic and oleophobic surface contains hydrophilic groups, and the hydrophilic groups are selected from one of ether bonds consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid, amino groups, quaternary ammonium groups and oxygen-containing groups, hydroxyl groups, carboxylic ester and block polyether.
The hydrophilic group has hydrophilic and oleophobic performances, and the oleophobic performance of the coating is effectively improved.
Preferably, the protective particles have a particle size of 0.1 to 1000 μm, more preferably 1 to 50 μm.
More preferably, the surface of the protective particle is subjected to a surface modification treatment, the surface modification comprising: three surface modifications of hydrophobic oleophylic, hydrophilic oleophobic and hydrophobic oleophobic are carried out.
The protective particles may be surface treated to enhance the hydrophobic properties of the coating.
Preferably, the adhesive is a high molecular polymer with molecular weight more than 100;
more preferably, the adhesive is one selected from the group consisting of silicone, fluorine-containing resin, acrylic resin, epoxy resin, polyethylene, polypropylene, polystyrene, fluorinated polyether, nylon, polycarbonate, polyurethane, styrene-butadiene rubber, nitrile rubber, silicone rubber, butadiene rubber, fluorine rubber, chloroprene rubber, isoprene rubber, butyl rubber, polyurethane, and polyurea.
In the coating, the binder can be chosen in different kinds to suit different kinds of substrates.
Preferably, the coating layer is made of ultra-high roughness particles, more preferably, the surface of the coating layer is further provided with a protective layer, and preferably, the material of the protective layer is selected from one or a combination of more of fluorinated polyether, fluorine ester, perfluoropolyether ester, fluorinated silicone oil, a perfluorosilane coupling agent, perfluoroacrylate, perfluorophosphoric acid and ester, perfluorocarboxylic acid, and perfluorothiol.
The protective layer plays a role in protecting the coating, improves the mechanical property of the coating and prolongs the service life of the coating.
Example 1 hydrophobing
Referring to fig. 3, the schematic indicates that the example coating consists essentially of a protective layer primer 1, a protective layer size 2, an ultraphobic layer primer 3, an ultraphobic layer protective film 4, protective particles 5, and ultra-high roughness particles 6.
Referring to fig. 1, in step 101, the surface treatment of the base material may be performed by conventional methods such as surface blasting, phosphating, primer adhesion, and scrubbing with a paint thinner.
In step 102, the epoxy resin and the curing agent thereof are first diluted to 10-50 wt% respectively by an organic solvent. Secondly, after the diluted epoxy resin and the curing agent are mixed, the mixture is uniformly sprayed on a substrate material through a pneumatic spray gun, and the thickness of the solid content is 20-30 mu m, so that a 1 protective layer primer is formed.
In step 103, 500 mesh corundum particles (5 protective particles) are uniformly sprayed on the substrate to which the epoxy resin has been attached by a sand blast gun.
In step 104, the plate with the corundum particles attached is placed in a dry room temperature environment for curing for 24 hours, or placed in an oven at 60 ℃ for curing for 3 hours.
In step 105, the diluted epoxy resin and the curing agent are mixed and then evenly sprayed on the substrate material by a pneumatic spray gun, and the thickness is 5-10 μm, so as to form 2 protective layer compound glue.
In step 106, the substrate coated with the protective layer coating is placed in a dry room temperature environment to be cured for 24 hours, or placed in an oven at 120 ℃ to be cured for 0.5 hour, so as to form a protective layer consisting of 1, 2 and 5.
In step 111, the hydroxyl-terminated silicone resin is diluted to 1-50wt% by an organic solvent, and then 1-5 wt% of a KH550 silane coupling agent is added and uniformly stirred. And spraying the mixed silicon resin on the protective layer to form the 3-super-hydrophobic layer primer.
In step 112, the aerogel particles surface-modified with hexamethyldisilazane are first milled to D90Particles smaller than 15 μm. Then 0.1 to 15wt% of aerogel particles are dispersed in an organic solvent. Then the 6 ultra-high roughness particles of aerogel are evenly sprayed on the surface of the ultra-sparse layer by a pneumatic spray gun.
In step 113, the substrate with the attached aerogel particles is placed in a dry room temperature environment to be cured for 24 hours, or placed in an oven at 180 ℃ to be cured for 0.5 hour.
In step 114, the perfluoropolyether diluted by the perfluorocarbon cyclic ether is uniformly sprayed on the substrate material by a pneumatic spray gun, the thickness is 0.1-0.5 μm, and a 4-super-hydrophobic layer protective film is formed, and a super-hydrophobic layer consisting of 3, 4 and 6 is also formed.
The contact angle between the prepared coating and water is 162 degrees, and the rolling angle is 1 degree. After 50 circles of polishing by a Taber abrasion tester by using a 250g weight 10f rubber wheel, the contact angle with water is 155 degrees, and the rolling angle is 8 degrees.
Example 2 hydrophobic oleophobic
Referring to fig. 4, the schematic indicates that the coating consists essentially of protective layer primer 1, protective layer size 2, protective particles 5, ultra-high roughness particles 6, and ultra-sparse layer binder 7.
Referring to fig. 1, in step 101, the surface treatment of the base material may be performed by conventional methods such as surface blasting, phosphating, primer adhesion, and scrubbing with a paint thinner.
In step 102, the polyurethane resin and the curing agent thereof are first diluted to 1-50wt% by an organic solvent, respectively. Secondly, after the diluted epoxy resin and the curing agent are mixed, the mixture is uniformly sprayed on a substrate material through a pneumatic spray gun, and the thickness of the solid content is 3-5 mu m, so that a 1 protective layer primer is formed.
In step 103, 3000 mesh corundum particles (5 protective particles) are uniformly sprayed on the base material to which the polyurethane resin has been attached by an electrostatic spray gun.
In step 104, the plate with the corundum particles attached is placed in a dry room temperature environment for curing for 12 hours, or placed in an oven at 60 ℃ for curing for 1.5 hours.
In step 105, the diluted polyurethane resin and the curing agent are mixed and then evenly sprayed on the substrate material through a pneumatic spray gun, and the thickness of the solid content is 0.5-2 μm, so that 2 protective layer compound glue is formed.
In step 106, the substrate coated with the protective layer coating is placed in a dry room temperature environment for curing for 12 hours, or placed in an oven at 60 ℃ for curing for 1.5 hours, so as to form a protective layer consisting of 1, 2 and 5.
In step 121, the perfluorosilane surface-modified aerogel particles are first milled to D90Particles smaller than 5 μm. Then 0.1-15wt% of air is condensedGlue particles, 0.1-20wt% of hydroxyl-terminated silicone resin and 0.01-1wt% of KH550 are dispersed in an organic solvent to form a mixed solution.
In step 122, the mixed liquor is sprayed uniformly onto the superhydrophobic surface by a pneumatic spray gun.
In step 123, the substrate sprayed with the mixed solution is placed in a dry room temperature environment to be cured for 24 hours, or placed in an oven at 180 ℃ to be cured for 0.5 hour, and the ultra-hydrophobic layer composed of 6 and 7 is formed.
The contact angle of the prepared coating and water is 160 degrees, and the rolling angle is 1 degree; the contact angle with edible oil is 150 degrees, and the rolling angle is 15 degrees. After a Taber abrasion resistance tester polishes the mixture for 50 circles by using a 250g weight 10f rubber wheel, the contact angle between the mixture and water is 152 degrees, and the rolling angle is 8 degrees; the contact angle with edible oil is 70 degrees, and oil drops can not roll.
Example 3 hydrophobic oleophilic
Referring to fig. 5, the schematic indicates that the coating is mainly composed of protective particles 5, ultra-high roughness particles 6, and a mixed layer binder 8.
Referring to fig. 2, in step 201, the surface treatment of the base material may be performed by conventional methods such as surface blasting, phosphating, primer adhesion, and scrubbing with a paint thinner.
In step 211, the aerogel particles surface-modified with hexamethyldisilazane are first milled to D90Particles smaller than 5 μm. Then 0.1-15wt% of aerogel particles, 0.01-60 wt% of 2000-mesh corundum particles, 0.1-20wt% of hydroxyl-terminated silicon resin and 0.01-1wt% of KH550 are dispersed in an organic solvent to form a mixed solution.
In step 202, the mixed liquid is sprayed uniformly onto the substrate material by a pneumatic spray gun.
In step 203, the substrate coated with the mixed solution is placed in a dry room temperature environment to be cured for 24 hours, or placed in an oven at 180 ℃ to be cured for 0.5 hour, so as to form a protective ultra-hydrophobic mixed layer consisting of 5, 6 and 7.
The contact angle of the prepared coating and water is 160 degrees, and the rolling angle is 1 degree. After being polished for 50 circles by a Taber abrasion tester by using a 250g weight 10f rubber wheel, the contact angle of the rubber wheel with water is 150 degrees, and the rolling angle is 12 degrees.
Example 4 Superhydrophilic, Underwater Superoleophobic
Referring to fig. 6, the schematic indicates that the coating is mainly composed of protective particles 5, ultra-high roughness particles 6, and ultra-sparse layer binder 7.
Referring to fig. 2, in step 201, the surface treatment of the base material may be performed by conventional methods such as surface blasting, phosphating, primer adhesion, and scrubbing with a paint thinner.
In step 221, unmodified aerogel particles are first heated in air to 350 ℃ or above for 1 hour, then milled to D90Particles smaller than 5 μm. Then dispersing 0.1-15wt% of aerogel particles, 0.1-20wt% of hydroxyl-terminated silicon resin and 0.01-1wt% of KH550 in an organic solvent to form a mixed solution.
In step 202, the mixed liquid is sprayed uniformly onto the substrate material by a pneumatic spray gun.
In step 203, the substrate sprayed with the mixed solution is placed in a dry room temperature environment to be cured for 24 hours, or placed in an oven at 180 ℃ to be cured for 0.5 hour, and the ultra-hydrophobic layer composed of 6 and 7 is formed.
The contact angle of the prepared coating with water is 0 degree, and the contact angle with edible oil in water is 152 degrees.
Comparative example 1 the coating obtained in patent application No. cn201510508485. x.
The contact angle of the coating and water is 135 degrees, and the rolling angle is 6 degrees. After being polished for 10 circles by a Taber abrasion tester by using a 250g weight 10f rubber wheel, the contact angle of the rubber wheel with water is 104 degrees, and the rolling angle is 35 degrees.
Comparative example 2 the coating obtained in patent application No. CN 200810061480.7.
The contact angle of the coating and water is 122 degrees, and the rolling angle is 5 degrees. After being polished for 10 circles by a Taber abrasion tester by using a 250g weight 10f rubber wheel, the contact angle of the rubber wheel with water is 105 degrees, and the rolling angle is 40 degrees.
Comparative example 3 application No. CN 201210466649.3.
The contact angle between the coating and water is 123 degrees, and the rolling angle is 5 degrees. After being polished for 10 circles by a Taber abrasion tester by using a 250g weight 10f rubber wheel, the contact angle with water is 102 degrees, and the rolling angle is 28 degrees.
By comparing the examples with the comparative examples, it can be clearly shown that the coating provided by the application still has good superhydrophobic performance after being worn. The protective particles enhance the wear resistance and prolong the service life of the coating, which is superior to the prior art.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.

Claims (1)

1. A coating composed of ultra-high roughness particles is characterized in that the coating is composed of a protective layer primer, a protective layer compound adhesive, protective particles, ultra-high roughness particles and an ultra-sparse layer adhesive;
the preparation method of the coating consisting of the ultrahigh-roughness particles comprises the following steps:
step 101: performing surface treatment on the substrate material by adopting a conventional method, wherein the conventional method comprises surface sand blasting, phosphating, primer adhesion and scrubbing by using a paint thinner;
step 102: firstly, respectively diluting polyurethane resin and a curing agent thereof to 1-50wt% through an organic solvent; secondly, mixing the diluted polyurethane resin and a curing agent, and uniformly spraying the mixture on a substrate material by a pneumatic spray gun, wherein the solid content is 3-5 mu m, so as to form a protective layer primer;
step 103: uniformly spraying the protective particles on the base material to which the polyurethane resin is attached by an electrostatic spray gun; the protective particles are 3000-mesh corundum particles;
step 104: placing the plate to which the corundum particles are attached in a dry room temperature environment for curing for 12 hours, or placing the plate in a 60 ℃ oven for curing for 1.5 hours;
step 105: mixing the diluted polyurethane resin and a curing agent, and uniformly spraying the mixture on a substrate material by a pneumatic spray gun, wherein the solid content is 0.5-2 mu m, so as to form a protective layer compound adhesive;
step 106: placing the substrate material sprayed with the protective layer compound glue in a dry room temperature environment for curing for 12 hours, or placing the substrate material in a 60 ℃ oven for curing for 1.5 hours to form a protective layer consisting of protective layer primer glue, protective layer compound glue and protective particles;
step 121: firstly, grinding aerogel particles subjected to surface modification by perfluorosilane to D90Particles smaller than 5 μm, then dispersing 0.1-15wt% of aerogel particles, 0.1-20wt% of hydroxyl-terminated silicone resin and 0.01-1wt% of KH550 in an organic solvent to form a mixed solution;
step 122: uniformly spraying the mixed solution on the surface of the protective layer through a pneumatic spray gun;
step 123: placing the substrate material sprayed with the mixed solution in a dry room temperature environment for curing for 24 hours, or placing the substrate material in a 180 ℃ oven for curing for 0.5 hour to form a super-hydrophobic layer consisting of super-high roughness particles and a super-hydrophobic layer adhesive;
the contact angle of the prepared coating and water is 160 degrees, and the rolling angle is 1 degree; the contact angle of the oil and the edible oil is 150 degrees, and the rolling angle is 15 degrees; after a Taber abrasion resistance tester polishes the mixture for 50 circles by using a 250g weight 10f rubber wheel, the contact angle between the mixture and water is 152 degrees, and the rolling angle is 8 degrees; the contact angle with edible oil is 70 degrees, and oil drops can not roll.
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