CN107254237A - A kind of coating being made up of superelevation roughness particle - Google Patents
A kind of coating being made up of superelevation roughness particle Download PDFInfo
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- CN107254237A CN107254237A CN201710621361.1A CN201710621361A CN107254237A CN 107254237 A CN107254237 A CN 107254237A CN 201710621361 A CN201710621361 A CN 201710621361A CN 107254237 A CN107254237 A CN 107254237A
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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
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- 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
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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
- 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
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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
- 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
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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
-
- 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
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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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention provides a kind of super open coat being made up of superelevation roughness particle, it is prepared from by following component：Particle, protectiveness particle, adhesive and the auxiliary agent of non-smooth structure with raised or hole.Wherein former three volume ratio is (0.1 7):(1‑7):(1‑10)." lotus leaf effect " technical know-how is applied, super-hydrophobic, superoleophobic under water or super-double-hydrophobic surface coating is produced, further improves the performance of coating and overcomes existing super open coat easily to go to pot such as structure, defect short life.Obtained coating has super thin property (super-hydrophobic, superoleophobic under water or super-amphiphobic) and self-cleaning property, and with fabulous rub resistance, it is adaptable to coating substrate material be glass, plastics, rubber, fabric, paper, metal, cement, ceramic material or or covered the above-mentioned materials of other coatings.
Description
Technical field
The invention belongs to the coating technology preparation field in applied chemistry engineering, more particularly, to one kind by superelevation roughness
The coating that particle is constituted.
Background technology
Coating is a kind of conventional process being surface-treated for material, can reach effective protection materials and is not corroded,
So as to significantly improve the effect in materials'use life-span.Hydrophobic coating can be such that material completely cuts off in itself with extraneous moisture, for building,
The isostructural protection of industrial equipment, pipeline, precision optical machinery plays an important role.And in recent years, as people are to quality of life
It is required that continuous improvement and environmental protection and awareness of saving energy continuous enhancing, super-hydrophobic coat technique has extremely strong automatically cleaning because of it
Function and obtained rapid development.
So-called super-hydrophobic coat refers to that the contact angle with water is more than 150 °, and roll angle is less than 10 ° of surface.However, mesh
Before the commercial hydrophobic coating developed generally there is following both sides problem：
(1) it is that hydrophobicity is not enough, existing hydrophobic coating is mainly the change by chemical property, i.e. surface increase is hydrophobic
Group, to reach hydrophobic effect.The hydrophobic angle of the limit that this method can reach is only 112 degree, is much unable to reach more than 150
The super-hydrophobic effect of degree.
(2) hydrophobic material can be caused because the addition of the materials such as element fluorine, anthracene, naphthalene, phenol is with certain toxicity to environment
Pollution, endangers the health of user.In addition, existing hydrophobic coating generally also has the defects such as easy aging, long preparation period.
Structure hydrophobic material is the novel nano-material researched and developed based on Researches on Biomimetic Materials " lotus-effect ", that is, simulates lotus leaf
Rough surface structure obtains the properties such as its hydrophobic, automatically cleaning.The equation developed according to Wenzel based on Young's equation：cosθ1
=r (уSV-уSL)/уLV, wherein, θ1For the contact angle between apparent contact angle, i.e. liquid-solid.R is liquid-solid
The ratio between real contact area and apparent contact area, y are the table between solid phase (S), liquid phase (L) and saturated vapor phase (V) each phase
Face tension force.For hydrophobic material surface, the surface tension perseverance between liquid-solid is more than between solid phase and saturated vapor
Surface tension, i.e. (уSV-уSL)/уLVFor negative value.
As shown from the above formula, when Coating Surface Roughness increase, i.e. the real contact area increase of solid phase and liquid phase,
And apparent contact area keeps constant, therefore r value increases in formula, so as to cause contact angle further to increase, reaches super thin
Water effect.In addition to super-hydrophobic coat, same principle is also applied for super oleophobic coating.According to GB/T 26490-2011, surpass
Oleophobic refers to that the contact angle with oil is more than 120 °.
At present, super-hydrophobic coat is typically using resin as adhesive, by micron-nanometer composite particles or only with nanometer
Grain is as filler, so as to realize super-hydrophobic.Wherein nano particle is modified by ground surface energy material mostly.Using the technical side
Case has such as patent CN200810061480.7, CN201210466649.3, a CN201210286775.0,
CN201310460822.3 etc., and foreign countries Super Ever Dry and Neverwet super hydrophobic coating.Wherein, resin is often
Selection be elastic resin to improve wearability, but the shear strength of elastic resin is too low, is not appropriate for conventional coating and uses.
Patent CN201610392566.2 uses the porous stratum reticulare of addition to protect super-hydrophobic coat, greatly strengthen the mechanicalness of coating
Can, but but add difficulty in terms of construction and occur in that obvious limitation.Except micron-nanometer composite particles coating it
Outside, super-hydrophobic particle is built also by sol gel processing, coating, such as CN201510508485.X is then built again.So
And, it is more fragile that the mechanical structure of the coating that this method is constituted is commonly angled relative to former scheme.
In fact, that both the above technical scheme wears no resistance main reason is that the spy of nano particle and gel in itself
Property.Because nano particle is excessively tiny, it is difficult in embedded resin, it is difficult to increase its attachment by implementing second layer adhesive again
Power, therefore adhesive force is much smaller compared with micron level particle, is easily come off to cause coating to lose super-hydrophobicity by polishing.With receiving
Rice grain is compared, and the particle after gel after grinding is in micron order, and adhesive force is preferable.However, due to being produced after sol-gel
Raw gel porosity is higher, and without crystal structure, thus gel rubber material mechanical strength than same non-porous crystalline structural wood
The mechanical strength of material is much lower, is easily broken, and causes not wear-resisting.In addition, because superelevation roughness surface roughness itself is high, institute
Frictional force during with solid contact is bigger, also causes it to be easier to damage.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is a kind of preparation method that super open coat is made up of superelevation roughness particle of offer, with
Solving the surface such as existing super-hydrophobic coat, super hydrophilic, super-amphiphobic needs the mechanical low intensity of the coating of superelevation asperity structure, life-span
The problem of short, difficult preparation.The present invention by the particle with superelevation roughness by adhesive in substrate material surface, with wearability
Particle reinforced coating mechanical strength, can directly be made the super open coat with practicality.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of coating being made up of superelevation roughness particle, is prepared from by following component：
Particle, protectiveness particle, adhesive and the auxiliary agent of non-smooth structure with raised or hole；
Wherein, the particle of the non-smooth structure, protectiveness particle, the volume ratio of adhesive are (0.1-7):(1-7):
(1-10), be preferably (0.1-2):(1-4):(2-7).
The coating being made up of superelevation roughness particle provided herein, " lotus leaf effect " technical know-how is answered
With producing that structure is super-hydrophobic, superoleophobic under water or super-double-hydrophobic surface coating, the performance for further improving coating simultaneously overcomes existing
Super open coat easily goes to pot such as structure, defect short life.
It is preferred that, the protectiveness particle is selected from silica, aluminum oxide, zirconium dioxide, titanium dioxide, carborundum, carbon
Change carbide, boron nitride, the more preferably one kind of silicon nitride, silica or aluminum oxide such as tungsten, titanium carbide.
It is preferred that, the auxiliary agent accounts for the particle, protectiveness particle, bonding of the non-smooth structure with raised or hole
The 0.01%-10% of agent quality sum, preferably 0.1%-3%, it is furthermore preferred that the auxiliary agent is selected from anti-ultraviolet ageing agent, silane
One kind in coupling agent, water-repelling agent.
It is preferred that, the particle size range of the particle of the non-smooth structure with raised or hole is preferably 0.1-100 μm,
More preferably 0.5-20 μm.
It is preferred that, the surface of the particle of the non-smooth structure with raised or hole has 1nm-100nm projection
Or the non-smooth structure of hole, aeroge or dry gel particle more preferably with 2-100nm holes, still more preferably
, the particle of the non-smooth structure with raised or hole is that as obtained by chemical attack, surface has 10-100nm flowers
Flap or tip-like raised metal or polymeric particles；
It is preferred that, the surface of the particle is modified by surface, and the preferred surface, which is modified, is selected from hydrophobic oleophilic oil, parent
One kind in water oleophobic, three kinds of surfaces characteristic of hydrophobic oleophobic.
It is preferred that, the surface of the particle for the non-smooth structure being modified by the hydrophobic oleophilic oil surface can, be less than under normal temperature
72mN/m, more than 27mN/m；The surface of the particle for the non-smooth structure being modified by the hydrophobic oleophobic surface can be at normal temperatures
Less than 27mN/m.
It is preferred that, hydrophilic radical is contained on the surface of the particle for the non-smooth structure being modified by the hydrophilic and oleophobic surface,
The hydrophilic radical is selected from carboxylic acid group, sulfonic group, phosphoric acid, amino, quaternary ammonium group, ehter bond, hydroxyl, the carboxylate of oxy radical composition
With one kind in block polyether.
It is preferred that, the particle diameter of the protectiveness particle is 0.1-1000 μm, more preferably 1-50 μm.
It is furthermore preferred that surface modification treatment is passed through on the surface of the protectiveness particle, the surface, which is modified, to be included：Hydrophobic parent
Oily, hydrophilic and oleophobic, three kinds of surfaces of hydrophobic oleophobic are modified.
It is preferred that, described adhesive is high molecular polymer, and molecular weight is more than 100.
Preferred adhesive be selected from silicones, fluorine resin, acrylic resin, epoxy resin, polyethylene, polypropylene,
Polystyrene, fluorinated polyether, nylon, polycarbonate, polyurethane, butadiene-styrene rubber, nitrile rubber, silicon rubber, butadiene rubber, fluorine rubber
One kind in glue, neoprene, isoprene rubber, the rubber of fourth third, polyurethane and polyureas.
It is preferred that, the coating being made up of superelevation roughness particle is protected it is furthermore preferred that the coating surface also has
Sheath, it is preferred that it is even that the material of the protective layer is selected from fluorinated polyether, fluorine ester, PFPE ester, fluorinated silicone oil, perfluor silane
One or more of combinations in connection agent, perfluoropropene hydrochlorate, perfluor phosphoric acid and ester, perfluorocarboxylic acid, perfluorinated thiol.
Compared with prior art, beneficial effects of the present invention are：
(1) coating provided herein being made up of superelevation roughness particle, technique is simple, and raw material are easy to get, cost
It is moderate, available for fields such as building external paint, automobile automatically cleaning car paint, hull abrasionproof drag reductions.
(2) coating provided herein being made up of superelevation roughness particle can have super-hydrophobicity and less rolling
Dynamic angle, it is possible to achieve self-cleaning function, and the matrix material of the coating can be glass, plastics, rubber, fabric, paper, gold
Category, cement, ceramic material, or the above-mentioned material of other coatings has been covered, have a wide range of application.
(3) the features such as coating provided herein being made up of superelevation roughness particle has intensity height and long lifespan.
(4) coating provided herein being made up of superelevation roughness particle can not only realize super-hydrophobic, certain bar
The function of superoleophobic under water and super-amphiphobic can also be realized under part.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The accompanying drawing used required in embodiment or description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 prepares the technique stream of the super open coat with superelevation roughness particle for the present invention by being layered the method for spraying
Cheng Tu；
Fig. 2 prepares the technique stream of the super open coat with superelevation roughness particle for the present invention by mixing the method for spraying
Cheng Tu；
Fig. 3 is an embodiment of the present invention, and by being layered, spraying constitutes protective layer and layering spraying constitutes super thin layer, painting
Rotating fields schematic diagram.
Fig. 4 is an embodiment of the present invention, and layering spraying constitutes protective layer and mixing spraying constitutes super thin layer, coating knot
Structure schematic diagram.
Fig. 5 is an embodiment of the present invention, and the super thin mixed coating of protection is directly constituted by mixing spraying, coating structure
Schematic diagram.
Fig. 6 is an embodiment of the present invention, and super thin layer is only built by mixing spraying, coating structure schematic diagram.
Fig. 7 is the electron micrograph of the aerogel particle with superelevation roughness.
Brief description of the drawings：
1- protective layer primers；2- protective layer re-glues；The super thin layer primers of 3-；The super thin layer diaphragms of 4-；5- protects particle；6- surpasses
High roughness particle；The super thin layer adhesives of 7-；Mixed layer adhesive.
Embodiment
Technical scheme is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that following described embodiment is a part of embodiment of the invention, it is rather than whole
Embodiment, is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same
Or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
A kind of coating being made up of superelevation roughness particle, is prepared from by following component：
Particle, protectiveness particle, adhesive and the auxiliary agent of non-smooth structure with raised or hole；
Wherein, the particle of the non-smooth structure, protectiveness particle, the volume ratio of adhesive are (0.1-7):(1-7):
(1-10), be preferably (0.1-2):(1-4):(2-7).
The coating being made up of superelevation roughness particle provided herein, is realized super using superelevation roughness grains
Effect is dredged, using protecting particle reinforced coating wearability and increasing service life, is further enhanced using suitable construction technology
The performances such as intensity, service life and the super thin property of coating.
Wherein, the particle of the non-smooth structure with raised or hole has high roughness, by adhesive in substrate material
Expect surface, coating mechanical strength is strengthened with attrition resistant particulate, the super open coat with practicality can be directly made.
It is preferred that, the protectiveness particle is selected from silica, aluminum oxide, zirconium dioxide, titanium dioxide, carborundum, carbon
Change carbide, boron nitride, the more preferably one kind of silicon nitride, silica or aluminum oxide such as tungsten, titanium carbide.
Protectiveness particle has certain mechanical strength, and the particle of non-smooth structure is played a protective role.
It is preferred that, the auxiliary agent accounts for the particle, protectiveness particle, bonding of the non-smooth structure with raised or hole
The 0.01%-10% of agent quality sum, preferably 0.1%-3%, it is furthermore preferred that the auxiliary agent is selected from anti-ultraviolet ageing agent, silane
One kind in coupling agent, water-repelling agent.
Auxiliary agent is the indispensable component of coating, and it can improve production technology, keeps storage stable, improves construction bar
Part, improves product quality, assigns specific function.It is rationally correct to reduce cost from auxiliary agent, increase economic efficiency.The application's
Additive dosage rationally, improves coating combination property.
It is preferred that, the particle size range of the particle of the non-smooth structure with raised or hole is preferably 0.1-100 μm,
More preferably 0.5-20 μm.
The particle diameter of particle is the smaller the better, helps with reducing its surface energy.When particle diameter is less than 0.1 micron, particle is easily reunited,
It is difficult to disperse, influences coating performance.
It is preferred that, the surface of the particle of the non-smooth structure with raised or hole has 1nm-100nm projection
Or the non-smooth structure of hole, aeroge or dry gel particle more preferably with 2-100nm holes, still more preferably
, the particle of the non-smooth structure with raised or hole is that as obtained by chemical attack, surface has 10-100nm flowers
Flap or tip-like raised metal or polymeric particles.
The particle of non-smooth structure with raised or hole shows with nano level microstructure.The microstructure
The roughness of coating is effectively increased, reduction coating shows energy.And the particle is preferably obtained by chemical attack.
It is preferred that, the surface of the particle is modified by surface, and the preferred surface, which is modified, is selected from hydrophobic oleophilic oil, parent
One kind in water oleophobic, three kinds of surfaces characteristic of hydrophobic oleophobic.
By showing to be modified, coating can further produce hydrophobic, oleophobic or double thin performances.
It is preferred that, the surface of the particle for the non-smooth structure being modified by the hydrophobic oleophilic oil surface can, be less than under normal temperature
72mN/m, more than 27mN/m；The surface of the particle for the non-smooth structure being modified by the hydrophobic oleophobic surface can be at normal temperatures
Less than 27mN/m.
By modified, coating is further improved, and surface be able to can effectively be reduced.
It is preferred that, hydrophilic radical is contained on the surface of the particle for the non-smooth structure being modified by the hydrophilic and oleophobic surface,
The hydrophilic radical is selected from carboxylic acid group, sulfonic group, phosphoric acid, amino, quaternary ammonium group, ehter bond, hydroxyl, the carboxylate of oxy radical composition
With one kind in block polyether.
Above-mentioned hydrophilic radical has hydrophilic and oleophobic performance, effectively improves the oleophobic performance of coating.
It is preferred that, the particle diameter of the protectiveness particle is 0.1-1000 μm, more preferably 1-50 μm.
It is furthermore preferred that surface modification treatment is passed through on the surface of the protectiveness particle, the surface, which is modified, to be included：Hydrophobic parent
Oily, hydrophilic and oleophobic, three kinds of surfaces of hydrophobic oleophobic are modified.
Protectiveness particle can be surface-treated, to improve the hydrophobic performance of coating.
It is preferred that, described adhesive is high molecular polymer, and molecular weight is more than 100；
Preferred adhesive be selected from silicones, fluorine resin, acrylic resin, epoxy resin, polyethylene, polypropylene,
Polystyrene, fluorinated polyether, nylon, polycarbonate, polyurethane, butadiene-styrene rubber, nitrile rubber, silicon rubber, butadiene rubber, fluorine rubber
One kind in glue, neoprene, isoprene rubber, the rubber of fourth third, polyurethane and polyureas.
In the coating, adhesive can have different types of selection, to adapt to different types of matrix.
It is preferred that, the coating being made up of superelevation roughness particle is protected it is furthermore preferred that the coating surface also has
Sheath, it is preferred that it is even that the material of the protective layer is selected from fluorinated polyether, fluorine ester, PFPE ester, fluorinated silicone oil, perfluor silane
One or more of combinations in connection agent, perfluoropropene hydrochlorate, perfluor phosphoric acid and ester, perfluorocarboxylic acid, perfluorinated thiol.
Protective layer plays a protective role to coating, improves the mechanical performance and service life of coating.
Embodiment 1 is hydrophobic
With reference to Fig. 3, the schematic diagram indicates that the example coating is main by protective layer primer 1, protective layer re-glue 2, super thin layer
Primer 3, super thin layer diaphragm 4, protection particle 5 and superelevation roughness particle 6 are constituted.
With reference to Fig. 1, in a step 101, substrate material surface processing can use surface sand-blasting, phosphatization, adhesion primer with
And the conventional method such as clean with paint thinner and carry out substrate material surface processing.
In a step 102, epoxy resin and its curing agent are passed through into organic solvent diluting to 10-50wt% respectively first.
Secondly, after the epoxy resin and curing agent after dilution are mixed, by pneumatic spray gun even application on base material,
Solid content thickness forms 1 protective layer primer at 20-30 μm.
In step 103, by 500 mesh corundum in granules (5 protection particle) by sand-blasting gun even application in attachment band
On the base material of oxygen tree fat.
At step 104, the sheet material for having adhered to corundum in granules is placed in dry room temperature environment and solidified 24 hours, or
It is placed in 60 DEG C of baking ovens and solidifies 3 hours.
In step 105, after the epoxy resin and curing agent after dilution will be mixed, uniformly sprayed by pneumatic spray gun
It is coated on base material, thickness forms 2 protective layer re-glues at 5-10 μm.
In step 106, the base material of spraying protective layer re-glue is placed in dry room temperature environment and solidified 24 hours, or
Person, which is placed in 120 DEG C of baking ovens, to be solidified 0.5 hour, is formed by 1,2 and 5 protective layer constituted.
In step 111, then terminal hydroxy group silicones is added into 1-5wt% by organic solvent diluting to 1-50wt%
KH550 silane couplers after uniform stirring.Mixed silicones is sprayed on protective layer, 3 super thin layer primer is constituted.
In step 112, the aerogel particle being modified by HMDS surface is ground to D first90It is less than
15 μm of particle.Then 0.1-15wt% aerogel particle is scattered among organic solvent.Again by this 6 superelevation of aeroge
Roughness particle is by pneumatic spray gun even application on super thin layer surface.
In step 113, the base material for having adhered to aerogel particle is placed in dry room temperature environment and solidified 24 hours, or
Person, which is placed in 180 DEG C of baking ovens, to be solidified 0.5 hour.
In step 114, by the PFPE after being diluted by perfluor fluorine carbocyclic ring ether, existed by pneumatic spray gun even application
On base material, thickness forms 4 super thin layer diaphragm at 0.1-0.5 μm, also constitutes by 3, the 4 and 6 super thin layers constituted.
Obtained coating is 162 ° with water contact angle, and roll angle is 1 °.250g counterweights are used by Taber abrasion resistant testers
After the circle of 10f rubber wheels polishing 50,155 ° of the contact angle with water, roll angle is 8 °.
The hydrophobic oleophobic of embodiment 2
With reference to Fig. 4, the schematic diagram indicate coating it is main by protective layer primer 1, it is protective layer re-glue 2, protection particle 5, super
High roughness particle 6 and super thin layer adhesive 7 are constituted.
With reference to Fig. 1, in a step 101, substrate material surface processing can use surface sand-blasting, phosphatization, adhesion primer with
And the conventional method such as clean with paint thinner and carry out substrate material surface processing.
In a step 102, polyurethane resin and its curing agent are passed through into organic solvent diluting to 1-50wt% respectively first.
Secondly, after the epoxy resin and curing agent after dilution are mixed, by pneumatic spray gun even application on base material,
Solid content thickness forms 1 protective layer primer at 3-5 μm.
In step 103,3000 mesh corundum in granules (5 protection particle) are being adhered to by electrostatic gun even application
On the base material of polyurethane resin.
At step 104, the sheet material for having adhered to corundum in granules is placed in dry room temperature environment and solidified 12 hours, or
Person, which is placed in 60 DEG C of baking ovens, to be solidified 1.5 hours.
In step 105, it is uniform by pneumatic spray gun after the polyurethane resin and curing agent after dilution will be mixed
It is sprayed on base material, solid content thickness forms 2 protective layer re-glues at 0.5-2 μm.
In step 106, the base material of spraying protective layer re-glue is placed in dry room temperature environment and solidified 12 hours, or
Person, which is placed in 60 DEG C of baking ovens, to be solidified 1.5 hours, is formed by 1,2 and 5 protective layer constituted.
In step 121, D will be ground to by the silane surface modified aerogel particle of perfluor first90Less than 5 μm
Grain.Then by 0.1-15wt% aerogel particle, 0.1-20wt% terminal hydroxy group silicones and 0.01-1wt% KH550 divide
Dissipate among organic solvent, form mixed liquor.
In step 122, by mixed liquor by pneumatic spray gun even application on super thin layer surface.
In step 123, the base material for having sprayed mixed liquor is placed in dry room temperature environment and solidified 24 hours, Huo Zhefang
Put and solidify 0.5 hour in 180 DEG C of baking ovens, form the super thin layer being made up of 6 and 7.
Obtained coating is 160 ° with water contact angle, and roll angle is 1 °；Contact angle with edible oil is 150 °, and roll angle is
15°.After being enclosed by Taber abrasion resistant testers using 250g counterweight 10f rubber wheels polishing 50,152 ° of the contact angle with water, rolling
Dynamic angle is 8 °；Contact angle with edible oil is 70 °, and oil droplet can not be rolled.
The hydrophobic oleophilic oil of embodiment 3
With reference to Fig. 5, the schematic diagram indicates that coating is mainly glued by protection particle 5, superelevation roughness particle 6 and mixed layer
Mixture 8.
With reference to Fig. 2, in step 201, substrate material surface processing can use surface sand-blasting, phosphatization, adhesion primer with
And the conventional method such as clean with paint thinner and carry out substrate material surface processing.
In step 211, the aerogel particle being modified by HMDS surface is ground to D first90Less than 5
μm particle.Then by 0.1-15wt% aerogel particle, 0.01-60wt% 2000 mesh corundum in granules, 0.1-20wt%
Terminal hydroxy group silicones and 0.01-1wt% KH550 be scattered among organic solvent, form mixed liquor.
In step 202., by mixed liquor by pneumatic spray gun even application on base material.
In step 203, the base material for having sprayed mixed liquor is placed in dry room temperature environment and solidified 24 hours, Huo Zhefang
Put and solidify 0.5 hour in 180 DEG C of baking ovens, formed by 5, the 6 and 7 super thin mixed layers of protection constituted.
Obtained coating is 160 ° with water contact angle, and roll angle is 1 °.250g counterweights are used by Taber abrasion resistant testers
After the circle of 10f rubber wheels polishing 50,150 ° of the contact angle with water, roll angle is 12 °.
Embodiment 4 is super hydrophilic, superoleophobic under water
With reference to Fig. 6, the schematic diagram indicates that coating is mainly glued by protection particle 5, superelevation roughness particle 6 and super thin layer
Mixture 7.
With reference to Fig. 2, in step 201, substrate material surface processing can use surface sand-blasting, phosphatization, adhesion primer with
And the conventional method such as clean with paint thinner and carry out substrate material surface processing.
In step 221, unmodified aerogel particle is heated to more than 350 DEG C 1 hour in atmosphere first, then
It is ground to D90Particle less than 5 μm.Then by 0.1-15wt% aerogel particle, 0.1-20wt% terminal hydroxy group silicones and
0.01-1wt% KH550 is scattered among organic solvent, forms mixed liquor.
In step 202., by mixed liquor by pneumatic spray gun even application on base material.
In step 203, the base material for having sprayed mixed liquor is placed in dry room temperature environment and solidified 24 hours, Huo Zhefang
Put and solidify 0.5 hour in 180 DEG C of baking ovens, form the super thin layer being made up of 6 and 7.
Obtained coating and water contact angle are 0 °, with the contact angle of edible oil are 152 ° in water.
The coating that the Application No. CN201510508485.X of comparative example 1 patent is obtained.
Coating is 135 ° with water contact angle, and roll angle is 6 °.250g counterweight 10f rubbers are used by Taber abrasion resistant testers
After the circle of rubber tire polishing 10,104 ° of the contact angle with water, roll angle is 35 °.
The coating that the Application No. CN200810061480.7 of comparative example 2 patent is obtained.
Coating is 122 ° with water contact angle, and roll angle is 5 °.250g counterweight 10f rubbers are used by Taber abrasion resistant testers
After the circle of rubber tire polishing 10,105 ° of the contact angle with water, roll angle is 40 °.
The coating that the Application No. CN201210466649.3 of comparative example 3 patent is obtained.
Coating is 123 ° with water contact angle, and roll angle is 5 °.250g counterweight 10f rubbers are used by Taber abrasion resistant testers
After the circle of rubber tire polishing 10,102 ° of the contact angle with water, roll angle is 28 °.
By the contrast of embodiment and comparative example, it can clearly show, coating provided herein, by abrasion
Afterwards, still with good ultra-hydrophobicity.Its protectiveness particle reinforced coating wearability and growth use the longevity, better than existing skill
Art.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that various embodiments above is only used
To illustrate technical scheme, rather than its limitations；It will be understood by those within the art that：Without departing substantially from this hair
In the case of bright spirit and scope, the technical scheme described in foregoing embodiments can be modified, or to wherein
Some or all of technical characteristic carries out equivalent substitution；And these modifications or replacement, do not make the essence of appropriate technical solution
Depart from the scope of various embodiments of the present invention technical scheme；It is, therefore, intended that including belonging to the present invention in the following claims
In the range of all these substitutions and modifications.
Claims (10)
1. a kind of coating being made up of superelevation roughness particle, it is characterised in that be prepared from by following component：
Particle, protectiveness particle, adhesive and the auxiliary agent of non-smooth structure with raised or hole；
Wherein, the particle of the non-smooth structure, protectiveness particle, the volume ratio of adhesive are (0.1-7):(1-7):(1-
10), it is preferably (0.1-2):(1-4):(2-7).
2. the coating according to claim 1 being made up of superelevation roughness particle, it is characterised in that the protectiveness particle
Selected from the carbide such as silica, aluminum oxide, zirconium dioxide, titanium dioxide, carborundum, tungsten carbide, titanium carbide, boron nitride, nitrogen
One kind of SiClx, preferably silica or aluminum oxide.
3. the coating according to claim 1 being made up of superelevation roughness particle, it is characterised in that the auxiliary agent accounts for described
Particle, protectiveness particle, the 0.01%-10% of adhesive quality sum of non-smooth structure with raised or hole, be preferably
0.1%-3%, it is preferred that the one kind of the auxiliary agent in anti-ultraviolet ageing agent, silane coupler, water-repelling agent.
4. the coating according to claim 1 being made up of superelevation roughness particle, it is characterised in that it is described have it is raised or
The particle size range of the particle of the non-smooth structure of hole is preferably 0.1-100 μm, preferably 0.5-20 μm.
5. the coating according to claim 1 being made up of superelevation roughness particle, it is characterised in that it is described have it is raised or
The surface of the particle of the non-smooth structure of hole has 1nm-100nm projection or the non-smooth structure of hole, it is however preferred to have
The aeroge or dry gel particle of 2-100nm holes, it is furthermore preferred that the particle of the non-smooth structure with raised or hole
It is that as obtained by chemical attack, surface has 10-100nm petal-shapeds or tip-like raised metal or polymeric particles；
It is preferred that, the surface of the particle is modified by surface, and the preferred surface is modified selected from hydrophobic oleophilic oil, hydrophilic dredged
One kind in oil, three kinds of surfaces characteristic of hydrophobic oleophobic.
6. the coating according to claim 5 being made up of superelevation roughness particle, it is characterised in that pass through the hydrophobic parent
It is less than 72mN/m under the surface energy of the particle for the non-smooth structure that oil meter face is modified, normal temperature, more than 27mN/m；By described hydrophobic
The surface of the particle for the non-smooth structure that oleophobic surface is modified can be less than 27mN/m at normal temperatures.
7. the coating according to claim 5 being made up of superelevation roughness particle, it is characterised in that by described hydrophilic thin
Hydrophilic radical is contained on the surface of the particle for the non-smooth structure that oil meter face is modified, the hydrophilic radical be selected from carboxylic acid group, sulfonic group,
One kind in phosphoric acid, amino, quaternary ammonium group, ehter bond, hydroxyl, carboxylate and the block polyether of oxy radical composition.
8. the coating according to claim 1 being made up of superelevation roughness particle, it is characterised in that the protectiveness particle
Particle diameter be 0.1-1000 μm, preferably 1-50 μm；
It is preferred that, surface modification treatment is passed through on the surface of the protectiveness particle, and the surface, which is modified, to be included：Hydrophobic oleophilic oil, parent
Water oleophobic, three kinds of surfaces of hydrophobic oleophobic are modified.
9. the coating according to claim 1 being made up of superelevation roughness particle, it is characterised in that described adhesive is height
Molecularly Imprinted Polymer, molecular weight is more than 100；
It is preferred that adhesive be selected from silicones, fluorine resin, acrylic resin, epoxy resin, polyethylene, polypropylene, polyphenyl second
Alkene, fluorinated polyether, nylon, polycarbonate, polyurethane, butadiene-styrene rubber, nitrile rubber, silicon rubber, butadiene rubber, fluorubber, chlorine
One kind in buna, isoprene rubber, the rubber of fourth third, polyurethane and polyureas.
10. the coating being made up of superelevation roughness particle according to claim any one of 1-9, it is characterised in that described
Coating surface also has protective layer, it is preferred that the material of the protective layer is selected from fluorinated polyether, fluorine ester, PFPE ester, fluorination
One or more in silicone oil, perfluor silane coupler, perfluoropropene hydrochlorate, perfluor phosphoric acid and ester, perfluorocarboxylic acid, perfluorinated thiol
Combination.
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|---|---|---|---|
| CN201710621361.1A CN107254237B (en) | 2017-07-27 | 2017-07-27 | Coating composed of ultrahigh-roughness particles |
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