CN106085173A - A kind of functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat and preparation method thereof - Google Patents
A kind of functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat and preparation method thereof Download PDFInfo
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- CN106085173A CN106085173A CN201610407826.9A CN201610407826A CN106085173A CN 106085173 A CN106085173 A CN 106085173A CN 201610407826 A CN201610407826 A CN 201610407826A CN 106085173 A CN106085173 A CN 106085173A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
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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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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Abstract
The invention discloses a kind of functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat and preparation method thereof, specifically: on substrate, first coat polyurethane ester modified enhancing tack coat, it is then coated with polyurethane and super-hydrophobic compound transition zone, obtain polyurethane/polyurethane and silicon dioxide transition zone composite coating, finally coat micro-nano super-hydrophobic layer, form polyurethane/polyurethane titanium dioxide silicon/silicon dioxide functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.The preparation method technique that the present invention provides is simple, easily operates, and normal pressure is carried out, cost is relatively low, prepared functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat can be used on marine surface coating, vehicle glass surface, the water proof anti-soil of the transparent materials such as mobile phone screen surface.
Description
Technical field
The invention belongs to abrasion-resistant clear and be combined super hydrophobic functional coating technology field, be mainly concerned with one and prepare with methyl
Trimethoxy silane is carrier, in conjunction with the preparation side of polyurethane-modified functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat
Method.
Background technology
Super hydrophobic surface refers to the surface that contact angle is more than 150 °, roll angle is less than 10 ° with water.In nature, Folium Nelumbinis
Surface has natural super-hydrophobic coat, and there are micro-nano structure and low-surface energy substance in its surface.Super-hydrophobic coat have antifouling,
The characteristics such as antifreeze, automatically cleaning, drag reduction, application is extensive.
Transparent hydrophobic coating has transparent and super-hydrophobic double grading concurrently, can be used on the window of skyscraper, vehicle
The water proof anti-soil aspect of the transparent materials such as the face glass of windshield and solaode.Over the past two years, nano-structured coating
Waterproof mobile phone becomes the focus of mobile phone industry, and nanostructured transparent hydrophobic coating can be phone housing, sound equipment and flexible electronic
Product provides waterproof coat, and does not affect its appearance color and feel.
In recent years, the preparation method of abrasion-resistant clear super hydrophobic surface, properity etc. had been carried out detailed grinding by researcher
Study carefully.Knowable to conventional result of study, most of preparation methoies there is also experiment condition harshness, complex steps, high in cost of production are asked
Topic, it is impossible to through engineering approaches is applied.The super hydrophobic material put goods on the market there is also as low in surface fine structure intensity, the most aging,
The shortcomings such as pollution easy to wear, easy, service life are short, limit the extensive degree of its application.
Patent documentation CN101875785A discloses one and prepares super-hydrophobic coat with porous polymethyl siloxane for raw material
Method, but super-hydrophobic coat mechanicalness prepared by the method is poor, and wearability is strong, is easily scraped, and practicality is poor.Patent
Document CN104371535A discloses a kind of wear-resistant white carbon black and strengthens the preparation method of polyurethane super-hydrophobic coat, its feature
For: coating is strengthened polyurethane elastomer by white carbon black and forms, and coating surface has orderly micro-convex structure, and coating surface is static with water
Contact angle, more than 160 °, has certain wearability, but price is relatively costly, and performance the most highly stable do not have transparent
Property, using value is less.Patent documentation CN103964701A discloses a kind of SiO2/ politef hydridization super-hydrophobic coat
Preparation method, by silane coupler at suitable temperature and pH value condition, hydrolyzes and anti-with Ludox in alcohol aqueous solvent
Should, make silica particle surface grafting organic group；Ludox after modification adds certain volume PTFE emulsion and
Auxiliary agent is made homogeneous mixture system and is aged certain time wait coating problems；Preparation coating.But it is super that the method is prepared
Hydrophobic coating anti-wear performance is not strong, and light transmission is poor, poor durability, is unfavorable for application.
Summary of the invention
The technical problem to be solved is: provide a kind of functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat
Preparation method, the method with MTMS as carrier, the light transmission of its excellence, resistance to ag(e)ing and good insulation
Property and mechanical strength solve that simple silicon dioxide super-hydrophobic coat transparency is not high enough, mechanical strength is low and resistance to ag(e)ing is poor
Etc. shortcoming；By polyurethane-modified, the painting with super-hydrophobicity, strongly adherent, high-transmittance and high-wearing feature finally given
Layer, this coating can pass through Best-Effort request plated film, spin-coating, brush, the method such as spraying is coated on base material.
The present invention solves its technical problem and uses following scheme:
The preparation method of the functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat that the present invention provides, specifically: first
Substrate coats polyurethane ester modified enhancing tack coat, is then coated with polyurethane and super-hydrophobic compound transition zone, obtains
Polyurethane/polyurethane and silicon dioxide transition zone composite coating, finally coating micro-nano super-hydrophobic layer, form polyurethane/poly-ammonia
Ester-titanium dioxide silicon/silicon dioxide functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
The present invention can use following methods to coat polyurethane ester modified enhancing tack coat on substrate:
(1) preparation modification enhancing tack coat solution:
Polyurethane is dissolved in organic solvent, fully dissolves after stirring, obtain modified enhancing tack coat solution；
(2) utilize painting method that modification strengthens tack coat solution to be coated on substrate, coat 1-3 time, under room temperature, be dried 5
～10 minutes, obtain modified enhancing tack coat.
The present invention can use following methods to prepare polyurethane/polyurethane and silicon dioxide transition zone composite coating:
(1) polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthening tack coat solution with micro-nano super-hydrophobic layer Matrix Solution is 1:5～1:20 according to volume ratio
Mixing, obtains polyurethanes and silicon dioxide mixed transition layer solution after stirring；
(2) painting method is utilized to be coated to change with MTMS mixed transition layer solution by polyurethanes
Property strengthens on tack coat, coats 1～3 time, is dried 5～10 minutes, obtains polyurethane/polyurethane and silicon dioxide transition under room temperature
Layer composite coating.
It is multiple that the present invention can use following methods to prepare polyurethane/polyurethane titanium dioxide silicon/silicon dioxide functionally gradient
Conjunction structure abrasion-resistant clear super-hydrophobic coat:
(1) micro-nano super-hydrophobic layer Matrix Solution is prepared:
1) MTMS is dissolved in the acetone that concentration is 99%, is sufficiently stirred at normal temperatures making it dissolve,
Form solution,
2) oxalic acid solution that concentration is 0.001mol is joined in above-mentioned solution, after reacting 36～48 hours, form hydrolysis
Pre-polymers,
3) add catalyst ammonia water, make hydrolysis pre-polymers be condensed 8～48 hours, form gel；This gel is dissolved in
In organic solvent, form micro-nano super-hydrophobic layer Matrix Solution；
(2) gradient composite structure transparent hydrophobic coating is formed:
Utilize painting method that micro--super-hydrophobic layer Matrix Solution of receiving is coated to polyurethane/polyurethane and silicon dioxide transition
On layer composite coating, coat 1～3 time, be dried 5～10 minutes under room temperature, obtain gradient composite structure transparent hydrophobic coating, its
For polyurethane/polyurethane titanium dioxide silicon/silicon dioxide functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
In the inventive method, can be by resistance to for polyurethane/polyurethane-silica/silicon dioxide functionally gradient composite construction
Mill transparent hydrophobic coating carries out heat treatment, reacts, prepares the adhesive property between coating and substrate, each layer of coating more
Good functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
In the inventive method, described process of thermal treatment is: anneal at 100～200 DEG C, and annealing time is 2 little
Time.
In the inventive method, the described organic solvent dissolving polyurethane is acetone, and the volume fraction of polyurethane is 10%-
50%.
In the inventive method, described painting method is Best-Effort request plated film, spin-coating or brushing method, Qi Zhongti
Drawing coating speed is 50-300mm/min.
Functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat prepared by the said method that the present invention provides, its surface has
There is a coarse structure of super-hydrophobic coat: contact angle >=150 °, roll angle≤5 °；Surface roughness is 332.5nm, has good
Hydrophobic performance；This functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat, at marine surface, vehicle glass surface or Mobile phone screen
Application in the water proof anti-soil of the transparent material in scene plot face.
Functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat prepared by the said method that the present invention provides, its surface machine
Tool is functional, is resistant to silk scarf friction under 30 5Kpa pressure；Light transmission is good, average visible photopic light transmitance >=90%；Should
Functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat, saturating on marine surface, vehicle glass surface or mobile phone screen surface
Application in the water proof anti-soil of bright material.
Functionally gradient composite construction of the present invention is polyurethane-modified enhancing tack coat, polyurethanes and dioxy
SiClx mixed transition layer and silicon dioxide super-hydrophobic micro-nano composite coating.
The base material of present invention coating is polymer, metal or Inorganic Non-metallic Materials, the shape no requirement (NR) to substrate.
The present invention use substrate material surface masking after, can again with same method secondary masking or repeatedly masking obtain
To the coating that thickness is different.
The present invention compared with prior art has a following main advantage:
(1) preparation method technique is simple, easily operates, carries out under normal pressure, and cost is relatively low.
(2) the transparent hydrophobic coating nano surface granule prepared is uniform, and its structure comprises micrometer structure and nanostructured,
Its surface roughness is about 332.5nm, modified enhancing caking property, satisfactory mechanical property, with silk scarf friction 30 under 5Kpa pressure
Still there is after secondary ultra-hydrophobicity.
(3) transparent hydrophobic coating prepared has good hydrophobic performance, contact angle more than 150 °, roll angle is less than
10 °, self-cleaning property is excellent.
(4) transparent hydrophobic coating prepared has good light transmission, and average visible photopic light transmitance is more than 90%.
(5) prepare and there is the solution of hydrophobic group be suitable for large area masking, and to the kind of base material and surface configuration
Do not limit.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained abrasion-resistant clear super hydrophobic surface field emission scanning electron microscope figure.
Fig. 2 is embodiment 1 gained abrasion-resistant clear super hydrophobic surface atomic force micrograph.
Fig. 3 is embodiment 2 gained abrasion-resistant clear super hydrophobic surface contact angle state diagram.
Fig. 4 is embodiment 2 gained abrasion-resistant clear super hydrophobic surface through the contact angle after 30 times that rubs with silk scarf under 5Kpa pressure
State diagram.
Fig. 5 is embodiment 3 gained abrasion-resistant clear super-hydrophobic visible light transmissivity curve chart.
Fig. 6 is embodiment 4 gained abrasion-resistant clear super hydrophobic surface contact angle state diagram.
Fig. 7 is embodiment 5 gained abrasion-resistant clear super hydrophobic surface contact angle state diagram.
Fig. 8 is embodiment 6 gained abrasion-resistant clear super hydrophobic surface contact angle state diagram.
Detailed description of the invention:
The present invention relates to the preparation method of a kind of functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.Described coating has
Having wear-resisting, transparent and super-hydrophobic multiple performance, and each performance is excellent, it is mainly by three graded composite functional structure layer structures
Becoming, be respectively as follows: bottom polyurethane ester modified enhancing tack coat, intermediate layer is polyurethanes and methyl trimethoxy oxygen
Base silane mixed transition layer, surface is the super-hydrophobic three layer function coatings of MTMS.The preparation method of this coating
It is: on substrate, first coat polyurethane ester modified enhancing tack coat, be then coated with polyurethane and super-hydrophobic compound transition
Layer, finally coating micro-nano super-hydrophobic layer, form polyurethane/polyurethane-silica/silicon dioxide functionally gradient composite junction
Structure abrasion-resistant clear super-hydrophobic coat.
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but does not limit the present invention.
Field emission scanning electron microscope figure is obtained by HIT's Hitachi S-4800 type field emission scanning electron microscope.
Contact angle is recorded by Germany's Kr ü ssEasydrop DSA 20 type optical video contact angle tester.
The Specord plus type ultraviolet-visible spectrophotometer that visible light transmissivity is produced by Jena, Germany instrument company is surveyed
?.
Embodiment 1:
A. the modified tack coat solution that strengthens is prepared:
Take the volumetric concentration of 10ml be 40% polyurethane solutions in beaker, volumetric concentration 99% acetone adding 60ml is molten
Liquid, ultrasonic disperse 1 hour, stirs and all dissolves to it for 2 hours, i.e. prepare modification and strengthen tack coat solution.
B. polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthens tack coat solution mix according to the volume ratio of 1:2 with micro-nano super-hydrophobic layer Matrix Solution, stir
After mixing, obtain polyurethanes and silicon dioxide mixed transition layer solution.
C. micro-nano super-hydrophobic layer Matrix Solution is prepared:
(1) the volumetric concentration 99% MTMS solution of 2ml is dissolved in volumetric concentration 99% first of 19.48ml
In alcohol, it is sufficiently stirred at normal temperatures making it dissolve, forms solution；
(2) 1ml oxalic acid is joined in the solution in step (1), stir 30 minutes, be aged 24 hours under room temperature, add
The volumetric concentration of 1.22ml is 75% ammonia spirit, stirs 15 minutes, is aged more than 24 hours, forms gel；
(3) add 20ml methanol, the gel formed in dissolving step (2), ultrasonic after stirring, fully dispersed, formed micro--receive
Rice super-hydrophobic layer solution；
D. functionally gradient wear-resisting composite transparent super-hydrophobic coat is prepared:
(1) cleaning the substrate, first dip-coating modification strengthens tack coat solution, soaks 30 seconds, and the speed of substrate lifting is
0.25 centimetre per second, coat 1 time, then place the substrate in 80 DEG C of baking ovens and solidify 2 hours.
(2) by substrate dip-coating polyurethanes in step (1) and silicon dioxide mixed transition layer solution, 0.5 point is soaked
Clock, the speed of lifting substrate is 0.25 centimetre per second, natural drying.
(3) by substrate dip-coating micro-nano super-hydrophobic layer Matrix Solution in step (2), soak 0.5 minute, substrate lifting
Speed is 0.25 centimetre per second, natural drying.
E. gradient composite structure abrasion-resistant clear super-hydrophobic coat heat treatment:
Substrate in step (3) in D step is annealed under the conditions of 160 DEG C, heating rate be 1 DEG C per minute.
Through above-mentioned steps, products obtained therefrom is functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Through field emission scanning electron microscope and three contourograph tests, as depicted in figs. 1 and 2, this gradient composite structure
The particle diameter on abrasion-resistant clear super-hydrophobic coat surface is about 25nm, and surface roughness is 322.5nm.
Embodiment 2:
A. the modified tack coat solution that strengthens is prepared:
Take the volumetric concentration of 10ml be 40% polyurethane solutions in beaker, volumetric concentration 99% acetone adding 60ml is molten
Liquid, ultrasonic disperse 1 hour, stirs and all dissolves to it for 2 hours, i.e. prepare modification and strengthen tack coat solution.
B. polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthens tack coat solution mix according to the volume ratio of 1:2 with micro-nano super-hydrophobic layer Matrix Solution, stir
After mixing, obtain polyurethanes and silicon dioxide mixed transition layer solution.
C. micro-nano super-hydrophobic layer Matrix Solution is prepared:
(1) the volumetric concentration 99% MTMS solution of 2ml is dissolved in volumetric concentration 99% first of 19.48ml
In alcohol, it is sufficiently stirred at normal temperatures making it dissolve, forms solution；
(2) 1ml oxalic acid is joined in the solution in step (1), stir 30 minutes, be aged 24 hours under room temperature, add
The volumetric concentration of 1.22ml is 75% ammonia spirit, stirs 15 minutes, is aged more than 24 hours, forms gel；
(3) add 20ml methanol, the gel formed in dissolving step (2), ultrasonic after stirring, fully dispersed, formed micro--receive
Rice super-hydrophobic layer solution；
D. functionally gradient wear-resisting composite transparent super-hydrophobic coat is prepared:
(1) cleaning the substrate, first dip-coating modification strengthens tack coat solution, soaks 30 seconds, and the speed of substrate lifting is
0.25 centimetre per second, coat 1 time, then place the substrate in 80 DEG C of baking ovens and solidify 2 hours.
(2) by substrate dip-coating polyurethanes in step (1) and silicon dioxide mixed transition layer solution, 0.5 point is soaked
Clock, the speed of lifting substrate is 0.25 centimetre per second, natural drying.
(3) by substrate dip-coating micro-nano super-hydrophobic layer Matrix Solution in step (2), soak 0.5 minute, substrate lifting
Speed is 0.25 centimetre per second, natural drying.
E. gradient composite structure abrasion-resistant clear super-hydrophobic coat heat treatment:
Substrate in step (3) in D step is annealed under the conditions of 160 DEG C, heating rate be 1 DEG C per minute.
Through above-mentioned steps, products obtained therefrom is functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Recording through contact angle tester, as shown in Figure 3, prepared abrasion-resistant clear super-hydrophobic coat, its contact angle is
152.4 °, the contact angle shown in Fig. 4, after wearability test.
Embodiment 3:
A. the modified tack coat solution that strengthens is prepared:
Take the volumetric concentration of 10ml be 40% polyurethane solutions in beaker, volumetric concentration 99% acetone adding 60ml is molten
Liquid, ultrasonic disperse 1 hour, stirs and all dissolves to it for 2 hours, i.e. prepare modification and strengthen tack coat solution.
B. polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthens tack coat solution mix according to the volume ratio of 1:2 with micro-nano super-hydrophobic layer Matrix Solution, stir
After mixing, obtain polyurethanes and silicon dioxide mixed transition layer solution.
C. micro-nano super-hydrophobic layer Matrix Solution is prepared:
(1) the volumetric concentration 99% MTMS solution of 2ml is dissolved in volumetric concentration 99% first of 19.48ml
In alcohol, it is sufficiently stirred at normal temperatures making it dissolve, forms solution；
(2) 1ml oxalic acid is joined in the solution in step (1), stir 30 minutes, be aged 24 hours under room temperature, add
The volumetric concentration of 1.22ml is 75% ammonia spirit, stirs 15 minutes, is aged more than 24 hours, forms gel；
(3) add 20ml methanol, the gel formed in dissolving step (2), ultrasonic after stirring, fully dispersed, formed micro--receive
Rice super-hydrophobic layer solution；
D. functionally gradient wear-resisting composite transparent super-hydrophobic coat is prepared:
(1) cleaning the substrate, first dip-coating modification strengthens tack coat solution, soaks 30 seconds, and the speed of substrate lifting is
0.25 centimetre per second, coat 1 time, then place the substrate in 80 DEG C of baking ovens and solidify 2 hours.
(2) by substrate dip-coating polyurethanes in step (1) and silicon dioxide mixed transition layer solution, 0.5 point is soaked
Clock, the speed of lifting substrate is 0.25 centimetre per second, natural drying.
(3) by substrate dip-coating micro-nano super-hydrophobic layer Matrix Solution in step (2), soak 0.5 minute, substrate lifting
Speed is 0.25 centimetre per second, natural drying.
E. gradient composite structure abrasion-resistant clear super-hydrophobic coat heat treatment:
Substrate in step (3) in D step is annealed under the conditions of 160 DEG C, heating rate be 1 DEG C per minute.
Through above-mentioned steps, products obtained therefrom is functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Light transmittance is recorded through ultraviolet-visible spectrophotometer, as shown in Figure 5, the super-hydrophobic painting of prepared abrasion-resistant clear
Layer visible light transmissivity curve chart.
Embodiment 4:
A. the modified tack coat solution that strengthens is prepared:
Take the volumetric concentration of 10ml be 10% polyurethane solutions in beaker, volumetric concentration 99% acetone adding 60ml is molten
Liquid, ultrasonic disperse 1 hour, stirs and all dissolves to it for 2 hours, i.e. prepare modification and strengthen tack coat solution.
B. polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthens tack coat solution mix according to the volume ratio of 1:2 with micro-nano super-hydrophobic layer Matrix Solution, stir
After mixing, obtain polyurethanes and silicon dioxide mixed transition layer solution.
C. micro-nano super-hydrophobic layer Matrix Solution is prepared:
(1) the volumetric concentration 99% MTMS solution of 2ml is dissolved in volumetric concentration 99% first of 19.48ml
In alcohol, it is sufficiently stirred at normal temperatures making it dissolve, forms solution；
(2) 1ml oxalic acid is joined in the solution in step (1), stir 30 minutes, be aged 24 hours under room temperature, add
The volumetric concentration of 1.22ml is 75% ammonia spirit, stirs 15 minutes, is aged more than 24 hours, forms gel；
(3) add 20ml methanol, the gel formed in dissolving step (2), ultrasonic after stirring, fully dispersed, formed micro--receive
Rice super-hydrophobic layer solution；
D. functionally gradient wear-resisting composite transparent super-hydrophobic coat is prepared:
(1) cleaning the substrate, first dip-coating modification strengthens tack coat solution, soaks 30 seconds, and the speed of substrate lifting is
0.25 centimetre per second, coat 1 time, then place the substrate in 80 DEG C of baking ovens and solidify 2 hours.
(2) by substrate dip-coating polyurethanes in step (1) and silicon dioxide mixed transition layer solution, 0.5 point is soaked
Clock, the speed of lifting substrate is 0.25 centimetre per second, natural drying.
(3) by substrate dip-coating micro-nano super-hydrophobic layer Matrix Solution in step (2), soak 0.5 minute, substrate lifting
Speed is 0.25 centimetre per second, natural drying.
E. gradient composite structure abrasion-resistant clear super-hydrophobic coat heat treatment:
Substrate in step (3) in D step is annealed under the conditions of 160 DEG C, heating rate be 1 DEG C per minute.
Through above-mentioned steps, products obtained therefrom is functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Record such as accompanying drawing 6 through contact angle tester: embodiment 4 gained abrasion-resistant clear super hydrophobic surface contact angle state diagram.
Embodiment 5:
A. the modified tack coat solution that strengthens is prepared:
Take the volumetric concentration of 10ml be 50% polyurethane solutions in beaker, volumetric concentration 99% acetone adding 60ml is molten
Liquid, ultrasonic disperse 1 hour, stirs and all dissolves to it for 2 hours, i.e. prepare modification and strengthen tack coat solution.
B. polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthens tack coat solution mix according to the volume ratio of 1:2 with micro-nano super-hydrophobic layer Matrix Solution, stir
After mixing, obtain polyurethanes and silicon dioxide mixed transition layer solution.
C. micro-nano super-hydrophobic layer Matrix Solution is prepared:
(1) the volumetric concentration 99% MTMS solution of 2ml is dissolved in volumetric concentration 99% first of 19.48ml
In alcohol, it is sufficiently stirred at normal temperatures making it dissolve, forms solution；
(2) 1ml oxalic acid is joined in the solution in step (1), stir 30 minutes, be aged 24 hours under room temperature, add
The volumetric concentration of 1.22ml is 75% ammonia spirit, stirs 15 minutes, is aged more than 24 hours, forms gel；
(3) add 20ml methanol, the gel formed in dissolving step (2), ultrasonic after stirring, fully dispersed, formed micro--receive
Rice super-hydrophobic layer solution；
D. functionally gradient wear-resisting composite transparent super-hydrophobic coat is prepared:
(1) cleaning the substrate, first dip-coating modification strengthens tack coat solution, soaks 30 seconds, and the speed of substrate lifting is
0.25 centimetre per second, coat 3 times, then place the substrate in 80 DEG C of baking ovens and solidify 2 hours.
(2) by substrate dip-coating polyurethanes in step (1) and silicon dioxide mixed transition layer solution, 0.5 point is soaked
Clock, the speed of lifting substrate is 0.25 centimetre per second, natural drying.
(3) by substrate dip-coating micro-nano super-hydrophobic layer Matrix Solution in step (2), soak 0.5 minute, substrate lifting
Speed is 0.25 centimetre per second, natural drying.
E. gradient composite structure abrasion-resistant clear super-hydrophobic coat heat treatment:
Substrate in step (3) in D step is annealed under the conditions of 160 DEG C, heating rate be 1 DEG C per minute.
Through above-mentioned steps, products obtained therefrom is functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Record such as accompanying drawing 7 through contact angle tester: embodiment 5 gained abrasion-resistant clear super hydrophobic surface contact angle state diagram.
Embodiment 6:
A. the modified tack coat solution that strengthens is prepared:
Take the volumetric concentration of 10ml be 40% polyurethane solutions in beaker, volumetric concentration 99% acetone adding 60ml is molten
Liquid, ultrasonic disperse 1 hour, stirs and all dissolves to it for 2 hours, i.e. prepare modification and strengthen tack coat solution.
B. polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthens tack coat solution mix according to the volume ratio of 1:2 with micro-nano super-hydrophobic layer Matrix Solution, stir
After mixing, obtain polyurethanes and silicon dioxide mixed transition layer solution.
C. micro-nano super-hydrophobic layer Matrix Solution is prepared:
(1) the volumetric concentration 99% MTMS solution of 2ml is dissolved in volumetric concentration 99% first of 19.48ml
In alcohol, it is sufficiently stirred at normal temperatures making it dissolve, forms solution；
(2) 1ml oxalic acid is joined in the solution in step (1), stir 30 minutes, be aged 24 hours under room temperature, add
The volumetric concentration of 1.22ml is 75% ammonia spirit, stirs 15 minutes, is aged more than 24 hours, forms gel；
(3) add 20ml methanol, the gel formed in dissolving step (2), ultrasonic after stirring, fully dispersed, formed micro--receive
Rice super-hydrophobic layer solution；
D. functionally gradient wear-resisting composite transparent super-hydrophobic coat is prepared:
(1) cleaning the substrate, first dip-coating modification strengthens tack coat solution, soaks 30 seconds, and the speed of substrate lifting is
0.50 centimetre per second, coat 3 times, then place the substrate in 80 DEG C of baking ovens and solidify 2 hours.
(2) by substrate dip-coating polyurethanes in step (1) and silicon dioxide mixed transition layer solution, 0.5 point is soaked
Clock, the speed of lifting substrate is 0.50 centimetre per second, natural drying.
(3) by substrate dip-coating micro-nano super-hydrophobic layer Matrix Solution in step (2), soak 0.5 minute, substrate lifting
Speed is 0.50 centimetre per second, natural drying.
E. gradient composite structure abrasion-resistant clear super-hydrophobic coat heat treatment:
Substrate in step (3) in D step is annealed under the conditions of 160 DEG C, heating rate be 1 DEG C per minute.
Through above-mentioned steps, products obtained therefrom is functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Record such as accompanying drawing 8 through contact angle tester: embodiment 6 gained abrasion-resistant clear super hydrophobic surface contact angle state diagram.
Functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat prepared by above-described embodiment, it is at marine surface, automobile
Application in the water proof anti-soil of the transparent material on glass surface or mobile phone screen surface.
Claims (10)
1. the preparation method of a functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat, it is characterised in that the method is: first
On substrate, first coat polyurethane ester modified enhancing tack coat, be then coated with polyurethane and super-hydrophobic compound transition zone,
To polyurethane/polyurethane and silicon dioxide transition zone composite coating, finally coating micro-nano super-hydrophobic layer, formation polyurethane/poly-
Urethane-titanium dioxide silicon/silicon dioxide functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Preparation method the most according to claim 1, is characterized in that using following methods to coat polyurethane on substrate
Ester modified enhancing tack coat:
(1) preparation modification enhancing tack coat solution:
Polyurethane is dissolved in organic solvent, fully dissolves after stirring, obtain modified enhancing tack coat solution；
(2) utilize painting method that modification strengthens tack coat solution to be coated on substrate, coat 1-3 time, under room temperature, be dried 5～10
Minute, obtain modified enhancing tack coat.
Preparation method the most according to claim 1, is characterized in that using following methods to prepare polyurethane/polyurethane and dioxy
SiClx transition zone composite coating:
(1) polyurethanes and silicon dioxide mixed transition layer solution are prepared:
Modification strengthening tack coat solution with micro-nano super-hydrophobic layer Matrix Solution is that 1:5～1:20 mixes according to volume ratio,
Polyurethanes and silicon dioxide mixed transition layer solution is obtained after stirring；
(2) utilize painting method that polyurethanes and MTMS mixed transition layer solution are coated to modified increasing
On strong tack coat, coat 1～3 time, be dried 5～10 minutes under room temperature, obtain polyurethane/polyurethane and silicon dioxide transition zone is multiple
Close coating.
Preparation method the most according to claim 1, is characterized in that using following methods to prepare polyurethane/polyurethane dioxy
Change silicon/silicon dioxide functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat:
(1) micro-nano super-hydrophobic layer Matrix Solution is prepared:
1) MTMS is dissolved in the acetone that concentration is 99%, is sufficiently stirred at normal temperatures making it dissolve, formed
Solution,
2) oxalic acid solution that concentration is 0.001mol is joined in above-mentioned solution, after reacting 36～48 hours, form hydrolysis pre-polymerization
Zoarium,
3) add catalyst ammonia water, make hydrolysis pre-polymers be condensed 8～48 hours, form gel；This gel is dissolved in organic
In solvent, form micro-nano super-hydrophobic layer Matrix Solution；
(2) gradient composite structure transparent hydrophobic coating is formed:
Utilize painting method that micro--super-hydrophobic layer Matrix Solution of receiving is coated to polyurethane/polyurethane and silicon dioxide transition zone is multiple
Closing in coating, coat 1～3 time, be dried 5～10 minutes, obtain gradient composite structure transparent hydrophobic coating under room temperature, it is poly-
Urethane/polyurethane titanium dioxide silicon/silicon dioxide functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Preparation method the most according to claim 1, is characterized in that polyurethane/polyurethane-silica/silicon dioxide merit
Heat treatment can be carried out by gradient composite structure abrasion-resistant clear super-hydrophobic coat, react, prepare coating and substrate, each layer of coating
Between adhesive property more preferable functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat.
Preparation method the most according to claim 5, it is characterised in that described heat treatment, its technique is: 100～200
Annealing at DEG C, annealing time is 2 hours.
Preparation method the most according to claim 2, it is characterised in that the described organic solvent dissolving polyurethane is acetone,
The volume fraction of polyurethane is 10%-50%.
Preparation method the most according to claim 2, it is characterised in that described painting method is Best-Effort request plated film, rotation
Film or brushing method, wherein lifting coating speed is 50-300mm/min.
9. the functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat prepared according to described method arbitrary in claim 1 to 8,
It is characterized in that its surface has a coarse structure of super-hydrophobic coat: contact angle >=150 °, roll angle≤5 °；Surface roughness is
332.5nm, has good hydrophobic performance；This functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat, at marine surface, vapour
Application in the water proof anti-soil of the transparent material on car glass surface or mobile phone screen surface.
10. the functionally gradient super-hydrophobic painting of composite construction abrasion-resistant clear prepared according to described method arbitrary in claim 1 to 8
Layer, it is characterised in that its surface satisfactory mechanical property, is resistant to silk scarf friction under 30 5Kpa pressure；Light transmission is good, averagely
Visible light transmissivity >=90%；This functionally gradient composite construction abrasion-resistant clear super-hydrophobic coat, at marine surface, vehicle glass table
Application in the water proof anti-soil of the transparent material on face or mobile phone screen surface.
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| CN110956946A (en) * | 2019-11-12 | 2020-04-03 | 哈尔滨工程大学 | Coupling resonance type underwater acoustic covering layer with functional gradient plate |
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