CN106905754A - A kind of super hydrophobic coating anti-wear additive and preparation method thereof, super-hydrophobic wear-resistant paint and super-hydrophobic transparent coating - Google Patents
A kind of super hydrophobic coating anti-wear additive and preparation method thereof, super-hydrophobic wear-resistant paint and super-hydrophobic transparent coating Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/63—Additives non-macromolecular organic
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- C08K5/42—Sulfonic acids; Derivatives thereof
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- C09D127/00—Coating 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
- C09D127/02—Coating 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
- C09D127/12—Coating 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
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/65—Additives macromolecular
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- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The present invention relates to a kind of super hydrophobic coating anti-wear additive and preparation method thereof, super-hydrophobic wear-resistant paint and super-hydrophobic transparent coating.The anti-wear additive is made up of the component of following mass percent：Nano diamond 10%~20%, surfactant 1%~2%, balance of pH adjusting agent and solvent；The addition of the pH adjusting agent makes the pH value of anti-wear additive be 3~10.Nano diamond is dispersed in anti-wear additive, and by anti-wear additive addition super hydrophobic coating, Nano diamond is readily dispersed in coating；After gained coating is coated to surface of solids solidification, Nano diamond is fixed in coating；Because the granularity of Nano diamond is small, hardness is high, when super-hydrophobic coat thickness is very thin, the hardness of coating can be also increased substantially, while not reducing the translucency of coating, enable that gained coating keeps good surface roughness and ultra-hydrophobicity for a long time, increase the service life.
Description
Technical field
The invention belongs to super-hydrophobic coat technical field, and in particular to a kind of super hydrophobic coating anti-wear additive and its system
Preparation Method, also relates to a kind of super-hydrophobic wear-resistant paint using the anti-wear additive and the super-hydrophobic wear-resistant paint formed
Super-hydrophobic transparent coating.
Background technology
The microcosmic of lotus leaf surface is reported first from late 1990s Univ Bonn Germany Barthlott research group
Since structure, the super-hydrophobicity in the extreme wetting behavior that the surface of solids has, also known as " lotus leaf effect ", causes researcher
Great interest.Super hydrophobic surface generally refers to the surface of solids with the contact angle of water more than 150 °, and advancing contact angle and retrogressing connect
Surface of the difference of feeler less than 5 °.Because super hydrophobic surface is very small with the contact area of water droplet, water droplet can not be on its surface
Stabilization is stopped, and is easily tumbled from surface.Therefore, super hydrophobic surface not only has a self-cleaning function, but also with anticorrosion, anti-
The function such as water, drag reduction, antifog, anti-ice, has wide in fields such as building, navigation, aviation, the energy, electronics, anti-corrosion, heat transfers
Application prospect.
The super-hydrophobic characteristic of the surface of solids is together decided on by the hydrophobicity and roughness of material, low surface free energy and suitable
Suitable roughness is two indispensable factors.At present, solid material surface coating super hydrophobic coating is typically employed in be formed
The mode of super-hydrophobic coat improves the hydrophobicity of material surface；Super hydrophobic coating forms super-hydrophobic coat typically has low-surface-energy
Hydrophobic surface, suitable surface roughness and low slide angle.But, it is local sharp when super hydrophobic surface is rubbed
Bulge-structure is more easily damaged, and causes the reduction of hydrophobic property, therefore super-hydrophobic coat of the exploitation with high rigidity is very necessary.
Meanwhile, most application field such as transit equipment such as solar panels, construction window, aviation/space flight/navigation/road surface is used
Form, optical frames are first-class, it is desirable to which super-hydrophobic coat has the transparency.Hydrophobicity and the transparency are often the characteristics of a pair of competitions,
It is especially prominent on rough surface.Hydrophobicity requirement material surface has low surface energy, but low-surface-energy is material modified generally
Coating surface can be made to be in different gloss to light through different degrees of influence is produced；When coating layer thickness is larger, this shadow
Sound is particularly evident.
In the prior art, in order to form transparent hydrophobic wear-resistant coating, some super hydrophobic coatings introduce silica dioxide granule
To improve the hardness of coating, but the Mohs' hardness of silica is 7, and the hardness and machinery that still can not greatly improve coating are steady
It is qualitative, if increase coating layer thickness can influence the translucency of coating.Also super hydrophobic coating introduces carbon black, although anti-wear performance is
Improve, but coating is opaque, it is impossible to take into account wearability and translucency.
The content of the invention
It is an object of the invention to provide a kind of super hydrophobic coating anti-wear additive, can be significantly in addition super hydrophobic coating
The hardness of coating is improved, while not reducing the translucency of coating.
Second object of the present invention is to provide a kind of preparation method of super hydrophobic coating anti-wear additive.
Third object of the present invention is to provide a kind of super-hydrophobic wear-resistant paint using above-mentioned anti-wear additive.
Fourth object of the present invention is to provide a kind of super-hydrophobic transparent formed using above-mentioned super-hydrophobic wear-resistant paint and applied
Layer.
In order to realize the above object the technical solution adopted in the present invention is：
A kind of super hydrophobic coating anti-wear additive, is made up of the component of following mass percent：Nano diamond 10%
~20%, surfactant 1%~2%, balance of pH adjusting agent and solvent；The addition of the pH adjusting agent makes wear-resisting addition
The pH value of agent is 3~10.
The average grain diameter of the Nano diamond is 10~100nm.The Nano diamond is by isostatic pressing method or detonation
Prepared by method, its purity >=99.95%.
The surfactant is calgon, neopelex, lauryl sodium sulfate, polyacrylic acid
Any one in sodium, AEO, APES, sorbitan fatty acid ester or combination.
The pH adjusting agent is triethanolamine, NaOH, potassium hydroxide or oxalic acid.The effect of pH adjusting agent is that regulation is resistance to
The pH value for grinding additive is 3~10.
Weight/mass percentage composition of the pH adjusting agent in anti-wear additive is 0.01%~1%.
The solvent is water, ethanol, isopropanol or butanone.Described water is deionized water.
Diamond Mohs' hardness is 10, and hardness highest, Nano diamond has the double grading of diamond and nano particle concurrently,
It is good with opposed polarity media compatibility and carbon surface is easily influenceed by chemical modification, can be uniformly distributed in variety carrier.
Super hydrophobic coating anti-wear additive of the invention, by Nano diamond, surfactant, pH adjusting agent and solvent
Compounding is formed, and Nano diamond is dispersed in anti-wear additive；By the anti-wear additive add super hydrophobic coating in, nanometer
Diamond is readily dispersed in coating；Gained coating is coated to the surface of solids, and after dry solidification, Nano diamond is fixed on painting
In layer；Because the granularity of Nano diamond is small, hardness is high, when super-hydrophobic coat thickness is very thin, painting can be also increased substantially
The hardness of layer, while not reducing the translucency of coating so that gained coating can for a long time keep good surface roughness and super thin
Aqueous energy, increases the service life.
A kind of preparation method of above-mentioned super hydrophobic coating anti-wear additive, comprises the following steps：
1) take surfactant, pH adjusting agent add solvent in, in the emulsified dispersion of 5000~10000rpm speed conditions,
Obtain mixed liquor；
2) under ultrasound condition, by Nano diamond add step 1) gained mixed liquor in, continue emulsion dispersion, obtain final product.
The Nano diamond is prepared using isostatic pressing method or Detonation Process.Isostatic pressing method or Detonation Process are prepared into gained in advance
Nano diamond disperses to carry out bulk processing in deionized water, low-temperature vacuum drying is carried out after separation of solid and liquid, it is to avoid nm of gold
Hard rock directly dries the secondary agglomeration for causing.
In above-mentioned preparation method, emulsion dispersion is carried out using explosion-proof high-shear emulsion machine.Step 1) in, the emulsion dispersion
Time be 10~20min.Step 2) in, Nano diamond is added after finishing, continue time of emulsion dispersion for 10~
20min。
Step 2) in, when Nano diamond is added, while carrying out high-shear emulsifying dispersion and ultrasonic disperse, prevent nanometer
Diamond powder is deposited in container bottom.The power of the ultrasound is 800~900W.
Step 2) in, removal of impurities is gone into the filter filtering that the mixed liquor aperture after lasting emulsion dispersion is 0.1~0.2 μm
Matter, filtrate is the anti-wear additive.
The preparation method of super hydrophobic coating anti-wear additive of the invention, is to disperse surfactant, pH adjusting agent
After in a solvent, Nano diamond emulsion dispersion is added；The preparation method can make Nano diamond be evenly distributed on wear-resisting adding
Plus in agent, during by anti-wear additive addition super hydrophobic coating, Nano diamond is easily dispersed uniformly, is difficult to reunite；Formed
Coating in, Nano diamond is evenly distributed so that coating have more homogeneous hardness, translucency and super-hydrophobicity.
Super hydrophobic coating anti-wear additive of the invention, solvent for use can for water or organic solvent (ethanol, isopropanol or
Butanone), the solvent of anti-wear additive according to the solvent polarity of super hydrophobic coating, can be selected, make that it is consistent or polarity is similar,
So that anti-wear additive has good compatibility with super hydrophobic coating, Nano diamond can be evenly spread to super-hydrophobic
In coating.
A kind of super-hydrophobic wear-resistant paint using above-mentioned anti-wear additive.
Described super-hydrophobic wear-resistant paint, is made up of super hydrophobic coating and described anti-wear additive；The super-hydrophobic painting
Material is 100 with the mass ratio of anti-wear additive:10~20.
The super hydrophobic coating is isobutyl triethoxy silane, urethane acrylate, epoxy acrylate, asphalt mixtures modified by epoxy resin
Any one or more in fat, acrylic resin, fluororesin, fluoroacrylic resin, or with it is above-mentioned any one or more
It is the super hydrophobic coating of hydrophobic ingredient.Preferably, the fluororesin is solvent-borne type fluororesin.
Preferably, the solvent of the anti-wear additive is consistent to the solvent of super hydrophobic coating or polarity is similar.
A kind of super-hydrophobic transparent coating formed using above-mentioned super-hydrophobic wear-resistant paint.By the super-hydrophobic wear-resistant paint
The surface of solids is coated uniformly on, solidification obtains final product the super-hydrophobic transparent coating.
When the main hydrophobic ingredient of super hydrophobic coating is isobutyl triethoxy silane, condition of cure is：First 45~
55 DEG C of 20~40min of drying, then dry 1.5~2.5h at 150~170 DEG C.When the main hydrophobic ingredient of super hydrophobic coating is
During fluoroacrylic resin, condition of cure is：Cold curing 6~8 days.
Super-hydrophobic wear-resistant paint of the invention, is added with above-mentioned anti-wear additive；The coating is coated to the surface of solids, does
After dry solidification, Nano diamond is fixed in the coating；The anti-wear additive is well dispersed in itself, and it is mixed with super hydrophobic coating
It is easily dispersed during conjunction uniformly, Nano diamond is also uniformly dispersed in the super-hydrophobic coat of formation；Due to the granularity of Nano diamond
Small, hardness is high, when super-hydrophobic coat thickness is very thin, it may have hardness higher, while not reducing the translucency of coating so that
Gained coating can for a long time keep good ultra-hydrophobicity, increase the service life.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
In specific embodiment, Nano diamond used is prepared using Detonation Process.Prepared by Detonation Process into gained in advance to receive
Rice diamond disperses to carry out bulk processing in deionized water, low-temperature vacuum drying is carried out after separation of solid and liquid, it is to avoid nanometer Buddha's warrior attendant
Stone directly dries the secondary agglomeration for causing.Gained Nano diamond >=99.95%, average grain diameter is 10~100nm.
Embodiment 1
The super hydrophobic coating anti-wear additive of the present embodiment, is made up of the component of following mass percent：Nanometer Buddha's warrior attendant
Stone 10%, calgon 1%, NaOH 0.01%, balance of deionized water；The pH value of the anti-wear additive is 8-
10。
The preparation method of the super hydrophobic coating anti-wear additive of the present embodiment, comprises the following steps：
1) take in calgon, NaOH addition deionized water, use explosion-proof high-shear emulsion machine, turn in 5000rpm
Emulsion dispersion 20min under the conditions of speed, obtains mixed liquor；
2) it is the nanometer of 80nm by average grain diameter under 900W ultrasound conditions while keeping high-shear emulsifying to disperse
Diamond powder is slowly added to step 1) gained mixed liquor in, prevent Nano diamond powder to be deposited in container bottom；Nm of gold
After hard rock powder is all added, emulsion dispersion 20min is continued under 5000rpm speed conditions, after with the filter that aperture is 0.2 μm
Impurity screening, gained filtrate is the anti-wear additive.
The super-hydrophobic wear-resistant paint of the present embodiment, it according to the mass ratio of super hydrophobic coating and anti-wear additive is 100 to be:20
Ratio, by above-mentioned anti-wear additive add super hydrophobic coating in, stir, obtain final product.The super hydrophobic coating is DOW CORNING
6403 impregnating with silane agent (isobutyl triethoxy silane).
Above-mentioned super-hydrophobic wear-resistant paint is uniformly coated to the glass surface for cleaning up, first 30min is dried at 50 DEG C, so
2h is dried at 160 DEG C afterwards, super-hydrophobic transparent coating is obtained final product.
The contact angle of test gained super-hydrophobic transparent coating is 153 °, has reached super-hydrophobic requirement；Using spectrophotometric
The meter glass of integral light-transmitting rate about 84% to(for) visible ray of the measurement containing coating；It is hard using Mitsubishi UNI pencil series of tests coatings
Degree reaches 9H, and is free of the coating hardness about 5H of anti-wear additive.
Embodiment 2
The super hydrophobic coating anti-wear additive of the present embodiment, is made up of the component of following mass percent：Nanometer Buddha's warrior attendant
Stone 15%, neopelex 1.5%, potassium hydroxide 0.01%, balance of deionized water；The pH of the anti-wear additive
It is 8-10 to be worth.
The preparation method of the super hydrophobic coating anti-wear additive of the present embodiment, comprises the following steps：
1) take in neopelex, potassium hydroxide addition deionized water, use explosion-proof high-shear emulsion machine,
The emulsified dispersion 15min of 8000rpm speed conditions, obtains mixed liquor；
2) it is the nanometer of 50nm by average grain diameter under 900W ultrasound conditions while keeping high-shear emulsifying to disperse
Diamond powder is slowly added to step 1) gained mixed liquor in, prevent Nano diamond powder to be deposited in container bottom；Nm of gold
After hard rock powder is all added, emulsion dispersion 15min is continued under 8000rpm speed conditions, after with the filter that aperture is 0.15 μm
Device impurity screening, gained filtrate is the anti-wear additive.
The super-hydrophobic wear-resistant paint of the present embodiment, it according to the mass ratio of super hydrophobic coating and anti-wear additive is 100 to be:20
Ratio, by above-mentioned anti-wear additive add super hydrophobic coating in, stir, obtain final product.The super hydrophobic coating is DOW CORNING
6403 impregnating with silane agent (isobutyl triethoxy silane).
Above-mentioned super-hydrophobic wear-resistant paint is uniformly coated to the glass surface for cleaning up, first 30min is dried at 50 DEG C, so
2h is dried at 160 DEG C afterwards, super-hydrophobic transparent coating is obtained final product.
The contact angle of test gained super-hydrophobic transparent coating is 151 °, has reached super-hydrophobic requirement；Using spectrophotometric
The meter glass of integral light-transmitting rate about 81% to(for) visible ray of the measurement containing coating；It is hard using Mitsubishi UNI pencil series of tests coatings
Degree reaches 9H, and is free of the coating hardness about 5H of anti-wear additive.
Embodiment 3
The super hydrophobic coating anti-wear additive of the present embodiment, is made up of the component of following mass percent：Nanometer Buddha's warrior attendant
Stone 20%, AEO 2%, triethanolamine 1%, balance of butanone；The pH value of the anti-wear additive is 7-9.
The preparation method of the super hydrophobic coating anti-wear additive of the present embodiment, comprises the following steps：
1) take in AEO, triethanolamine addition butanone, explosion-proof high-shear emulsion machine is used, in 10000rpm
The emulsified dispersion 10min of speed conditions, obtains mixed liquor；
2) it is the nanometer of 20nm by average grain diameter under 900W ultrasound conditions while keeping high-shear emulsifying to disperse
Diamond powder is slowly added to step 1) gained mixed liquor in, prevent Nano diamond powder to be deposited in container bottom；Nm of gold
After hard rock powder is all added, emulsion dispersion 10min is continued under 10000rpm speed conditions, after with the filter that aperture is 0.1 μm
Device impurity screening, gained filtrate is the anti-wear additive.
The super-hydrophobic wear-resistant paint of the present embodiment, it according to the mass ratio of super hydrophobic coating and anti-wear additive is 100 to be:10
Ratio, by above-mentioned anti-wear additive add super hydrophobic coating in, stir, obtain final product.The super hydrophobic coating is Asahi Glass
Solvent-borne type fluororesin LF200, curing agent is isocyanates, and curing agent is 1 with fluororesin mass ratio:10.
Above-mentioned super-hydrophobic wear-resistant paint is uniformly coated to the glass surface for cleaning up, cold curing 7 days is obtained final product super thin
Water clear coat.
The contact angle of test gained super-hydrophobic transparent coating is 155 °, has reached super-hydrophobic requirement；Using spectrophotometric
The meter glass of integral light-transmitting rate about 80% to(for) visible ray of the measurement containing coating；It is hard using Mitsubishi UNI pencil series of tests coatings
Degree reaches 7H, and is free of the coating hardness about 4H of anti-wear additive.
Claims (10)
1. a kind of super hydrophobic coating anti-wear additive, it is characterised in that：It is made up of the component of following mass percent：Nm of gold
Hard rock 10%~20%, surfactant 1%~2%, balance of pH adjusting agent and solvent；The addition of the pH adjusting agent makes
The pH value of anti-wear additive is 3~10.
2. super hydrophobic coating anti-wear additive according to claim 1, it is characterised in that：The surfactant is six
Sodium metaphosphate, neopelex, lauryl sodium sulfate, Sodium Polyacrylate, AEO, alkyl phenol gather
Any one in oxygen vinethene, sorbitan fatty acid ester or combination.
3. super hydrophobic coating anti-wear additive according to claim 1, it is characterised in that：The pH adjusting agent is three second
Hydramine, NaOH, potassium hydroxide or oxalic acid.
4. super hydrophobic coating anti-wear additive according to claim 3, it is characterised in that：The pH adjusting agent is wear-resisting
Weight/mass percentage composition in additive is 0.01%~1%.
5. super hydrophobic coating anti-wear additive according to claim 1, it is characterised in that：The solvent be water, ethanol,
Isopropanol or butanone.
6. a kind of preparation method of super hydrophobic coating anti-wear additive as claimed in claim 1, it is characterised in that：Including with
Lower step：
1) take in surfactant, pH adjusting agent addition solvent, in the emulsified dispersion of 5000~10000rpm speed conditions, obtain mixed
Close liquid；
2) under ultrasound condition, by Nano diamond add step 1) gained mixed liquor in, continue emulsion dispersion, obtain final product.
7. the super-hydrophobic wear-resistant paint of a kind of anti-wear additive using as any one of claim 1-5.
8. super-hydrophobic wear-resistant paint according to claim 7, it is characterised in that：By super hydrophobic coating and described wear-resisting add
Plus agent composition；The super hydrophobic coating is 100 with the mass ratio of anti-wear additive:10~20.
9. super-hydrophobic wear-resistant paint according to claim 8, it is characterised in that：The super hydrophobic coating is the second of isobutyl group three
TMOS, urethane acrylate, epoxy acrylate, epoxy resin, acrylic resin, fluororesin, fluorine-containing tree
Any one or more in fat, or with above-mentioned any one or more super hydrophobic coating as hydrophobic ingredient.
10. a kind of using the super-hydrophobic transparent coating that super-hydrophobic wear-resistant paint is formed as claimed in claim 7.
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| CN201710166732.1A CN106905754B (en) | 2017-03-20 | 2017-03-20 | Wear-resistant additive for super-hydrophobic coating, preparation method of wear-resistant additive, super-hydrophobic wear-resistant coating and super-hydrophobic transparent coating |
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| CN201710166732.1A CN106905754B (en) | 2017-03-20 | 2017-03-20 | Wear-resistant additive for super-hydrophobic coating, preparation method of wear-resistant additive, super-hydrophobic wear-resistant coating and super-hydrophobic transparent coating |
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| CN107964325A (en) * | 2017-10-09 | 2018-04-27 | 江苏海晟涂料有限公司 | A kind of wear-resisting ship coating of impact resistance and preparation method thereof |
| CN109355012A (en) * | 2018-10-31 | 2019-02-19 | 西安近代化学研究所 | A kind of preparation method and application containing Nano diamond fluorine-containing organic silicon hydrophobing agent |
| CN110760256A (en) * | 2019-11-13 | 2020-02-07 | 宁波富纳新材料科技有限公司 | High-hardness wear-resistant anti-fingerprint nano coating for PC material and preparation method thereof |
| CN112300681A (en) * | 2020-10-26 | 2021-02-02 | 清远市蓝林新材料有限公司 | Polyurethane coating for mirror frame surface processing and preparation method thereof |
| CN114269868A (en) * | 2019-08-20 | 2022-04-01 | 信越化学工业株式会社 | Water-and oil-repellent member and method for producing water-and oil-repellent member |
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| CN116554749A (en) * | 2023-05-26 | 2023-08-08 | 江苏大学 | Preparation method of self-repairable high-hydrophobicity high-light-transmittance organic glass film layer |
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