CN109811586A - A kind of method that laser printing prepares super-hydrophobic coat - Google Patents
A kind of method that laser printing prepares super-hydrophobic coat Download PDFInfo
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- CN109811586A CN109811586A CN201910082352.9A CN201910082352A CN109811586A CN 109811586 A CN109811586 A CN 109811586A CN 201910082352 A CN201910082352 A CN 201910082352A CN 109811586 A CN109811586 A CN 109811586A
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Abstract
It is that super-hydrophobic nano compound first is made by hydrolysis, condensation reaction in organosilan and nanoparticle the invention discloses a kind of method that laser printing prepares super-hydrophobic coat；Again by super-hydrophobic nano compound, resin and carbon dust with mixing and ball milling, uniform super-hydrophobic carbon dust is obtained；Then super-hydrophobic carbon dust is packed into selenium drum of laser printer, super-hydrophobic carbon dust is printed on common print paper by laser printer, obtains super-hydrophobic coat.The present invention passes through laser printer types super-hydrophobic coat; speed is fast; precision is high; Computer Design can be passed through; the complicated super-hydrophobic coat of printing speed (such as complicated shape, gradient wetability); and the super-hydrophobic coat of printing preparation has excellent performance (contact angle>155 ° of 5 μ L water droplets, roll angle<8 °), lays a good foundation for scale application.
Description
Technical field
The present invention relates to a kind of preparation method of super-hydrophobic coat more particularly to it is a kind of using laser printing by super-hydrophobic painting
Layer prints to the method that super-hydrophobic coat is prepared on common print paper.
Background technique
Super hydrophobic surface refers to that water droplet is greater than 150 ° in its surface contact angle, and roll angle is lower than 10 ° of surface.Currently, system
There are mainly two types of the approach of standby super hydrophobic surface: (1) modifying low-surface energy substance on micro-nano coarse structure surface；
(2) micro-nano coarse structure is constructed in the material surface with low-surface-energy.Constructing for micro-nano coarse structure mainly passes through
The technological means such as plasma etching, electrostatic spinning, self assembly, vapor deposition and electrochemical deposition, but these technologies there are still
The problems such as preparation method is complicated, higher cost and stability are poor.In patent CN108654960A, using laser ablation method to substrate
Surface carries out micro structured pattern processing, carries out low energyization processing to substrate by fluorine-containing reagent later and obtains super hydrophobic surface.Specially
In sharp CN106517821A, using PDMS as silicon source, multi-walled carbon nanotube is template, constructs nano-tube coating in glass surface,
Then silicic acid anhydride is carried out to it by the cured PDMS of chemical vapor deposition, finally obtains super-hydrophobic coat.The above method
All there are the problems such as preparation process is complicated, and substrate dependence is big, coating hydrophobicity is poor and the stability of coating is not directed to.
In recent years, how to be had received widespread attention by the method constructing super-drainage coating being simple and efficient, be super-hydrophobic table
The application in face is laid a good foundation.Patent CN108043482A disclose a kind of super infiltration Janus paper or the super infiltration pattern of paper base and its
Using having been synthesized in ethyl alcohol and water mixed system by acid catalyzed process specific using ethyl orthosilicate and silicon fluoride as raw material
Sol solutions.Then the sol solutions are deposited in filter paper substrate by ink-jet printing, is formd with good super-hydrophobicity
Surface.However, this method still have environmental pollution, preparation process time-consuming it is long, it is at high cost, be unable to the problems such as scale application.
Spray coating method and ink-jet printing method are simple, but there are self-defects.For example, spray coating method prepares super-hydrophobic coat people
Big for influence factor, coating performance floats larger；After modifying super hydrophobicity, there are problems for ink-jet print water stability, easily stifled
Fill in spray head.Therefore, how super-hydrophobic coat prepared by method simple and fast, with high accuracy, especially quick preparation structure is multiple
Miscellaneous super-hydrophobic coat (such as complicated shape, gradient wetability), is that this field urgently solves the problems, such as.
Summary of the invention
The problems such as the purpose of the present invention is to solve existing super-hydrophobic coat technology of preparing complexity, valuableness, it is especially difficult
The problem of to prepare labyrinth super-hydrophobic sample, provides a kind of laser printing simple and fast, with high accuracy and prepares super-hydrophobic painting
The method of layer.
The method that laser printing of the present invention prepares super-hydrophobic coat, be first by organosilan and nanoparticle by hydrolysis,
Super-hydrophobic nano compound is made in condensation reaction；Again by super-hydrophobic nano compound, resin and carbon dust with mixing and ball milling, obtain
Even super-hydrophobic carbon dust；Then super-hydrophobic carbon dust is packed into selenium drum of laser printer, by laser printer by super-hydrophobic carbon
Powder prints on common print paper, obtains super-hydrophobic coat.
Above-mentioned super-hydrophobic nano compound preparation: being that catalyst, water, organosilan and nanoparticle are added in alcoholic solvent
Son is stirred to react 1 ~ 72 h under 25 ~ 100 °C；Be centrifuged after reaction, dry to get.Organosilan and nanoparticle
Mass ratio is 1:1 ~ 1:50.The additional amount of catalyst is 1 ~ 200 times of organosilan quality.Wherein, organosilan is that perfluor is pungent
Base trichlorosilane, perfluoro capryl trimethoxy silane, perfluoro capryl triethoxysilane, perfluoro decyl trichlorosilane, the perfluor last of the ten Heavenly stems
Base trimethoxy silane, perfluoro decyl triethoxysilane, perfluoro capryl dimethylchlorosilane, perfluoro capryl dimethyl methyl oxygroup
Silane, perfluoro decyl dimethylchlorosilane, perfluoro decyl dimethyl methoxy silane, methyltrimethoxysilane, three second of methyl
Oxysilane, ethyl trichlorosilane, ethyl trimethoxy silane, ethyl triethoxysilane, vinyl trichlorosilane, vinyl
Trimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, octyl trimethoxy silane, dodecyl three
At least one of methoxy silane, hexadecyl trimethoxy silane.Nanoparticle is carbon nanotube, graphene oxide, two
Silica, titanium dioxide, zinc oxide, nano silver, montmorillonite, attapulgite, sepiolite, galapectite, hydrotalcite, vermiculite, mica,
At least one of kaolinite, hectorite, bacteria cellulose, polystyrene, polytetrafluoroethylene (PTFE).Catalyst is hydrochloric acid, nitric acid, sulphur
At least one of acid, acetic acid, oxalic acid, formic acid, benzene sulfonic acid, ammonium hydroxide, ethylenediamine, triethylamine, butylamine.Alcoholic solvent is methanol, second
At least one of alcohol, ethylene glycol, propyl alcohol, isopropanol, glycerol.
In the preparation of the super-hydrophobic carbon dust, the mass ratio of super-hydrophobic nano compound and carbon dust is 1:5 ~ 1:0.2, super thin
The mass ratio of water nano-complex and resin is 1:0.05 ~ 1:0.5；The mixing and ball milling time is 2 ~ 36 h.Wherein, resin includes poly-
The just own ester of styrene, butyl polyacrylate, polyethyl acrylate, polyacrylic acid, polyacrylic acid 2- ethylhexyl, the polyacrylic acid moon
Osmanthus ester, polymethyl methacrylate, polyethyl methacrylate, Vinalac 5920, polyisobutyl methacrylate,
At least one of just own ester of tert-butyl methacrylate, polymethylacrylic acid.
In laser printer types, layout can according to need, and print by computer control that structure is complicated
Super-hydrophobic coat.
For the present invention by laser printer types super-hydrophobic coat, speed is fast, and precision is high, can by Computer Design,
The complicated super-hydrophobic coat of printing speed (such as complicated shape, gradient wetability), and print the super-hydrophobic coat of preparation
(contact angle>155 ° of 5 μ L water droplets, roll angle<8 °) are had excellent performance, are laid a good foundation for scale application.
Specific embodiment
Prepared by the preparation method of super-hydrophobic coat to laser printing of the present invention below by specific embodiment and performance make into
One step explanation.
Embodiment 1
Weigh the SiO that 18.0 g diameters are 100 nm2Nanoparticle is added in 1000 mL wide-mouth bottles, then measures 800 respectively
ML propyl alcohol, 80 mL oxalic acid and 40 mL deionized waters, 10 min of magnetic agitation, 3 min of cell pulverization instrument ultrasound.It measures later
5.0 mL tetraethoxysilanes and 16.0 mL perfluoro decyl dimethylchlorosilanes, are added in wide-mouth bottle, are stirred to react at room temperature
2 h obtain uniform super-hydrophobic SiO2Suspension.Then it is centrifuged 10 min under the conditions of 10000 rpm and collects sediment fraction, and
Dry 6 h obtain super-hydrophobic SiO under 60 °C2；Secondly, by super-hydrophobic SiO2It with mass ratio is 1:1, polystyrene with carbon dust
24 h of powder mixing and ball milling of 5.0 g obtains uniform super-hydrophobic carbon dust, and further the super-hydrophobic carbon dust is sieved 300 mesh,
Then 50 g are weighed to be packed into selenium drum of laser printer, are then printed to the pattern of Computer Design commonly by laser printing
Super-hydrophobic coat is obtained on printing paper.
Contact angle and roll angle: water contact angle=166 °, roll angle=5 ° are measured with 5 μ L water droplets.
Embodiment 2
15.0 g attapulgites are weighed, are added in 1000 mL wide-mouth bottles, then measure 660 mL isopropanols, 60 mL hydrochloric acid respectively
With 30 mL deionized waters, 10 min of magnetic agitation, 3 min of cell pulverization instrument ultrasound.4.0 mL aminopropyl, three ethoxy is measured later
Base silane and 12.0 mL perfluoro capryl triethoxysilanes, are added in wide-mouth bottle, be stirred to react at room temperature 2 h obtain it is uniform
Super-hydrophobic attapulgite suspension.Then it is centrifuged 15 min under the conditions of 8000 rpm and collects sediment fraction, and under 80 °C
Dry 5 h obtain super-hydrophobic attapulgite；Secondly, with mass ratio being 3:1, polyacrylic acid fourth by super-hydrophobic attapulgite and carbon dust
36 h of powder mixing and ball milling of 4.0 g of ester obtains uniform super-hydrophobic carbon dust, further by the super-hydrophobic carbon dust sieving 300
Then mesh weighs 50 g and is packed into selenium drum of laser printer, then printed to the pattern of Computer Design by laser printing
Super-hydrophobic coat is obtained on common print paper.
Contact angle and roll angle: water contact angle=155 °, roll angle=7 ° are measured with 5 μ L water droplets.
Embodiment 3
10.0 g galapectites are weighed, are added in 1000 mL wide-mouth bottles, then measure 440 mL methanol, 40 mL acetic acid and 20 respectively
ML deionized water, 10 min of magnetic agitation, 3 min of cell pulverization instrument ultrasound.3.0 mL γ-glycidyl ether oxygen third is measured later
Base trimethoxy silane and 8.0 mL perfluoro decyl trichlorosilanes, are added in wide-mouth bottle, are stirred to react 2 h at room temperature and obtain
One super-hydrophobic galapectite suspension.Then it is centrifuged 12 min under the conditions of 9000 rpm and collects sediment fraction, and under 70 °C
Dry 6 h obtain super-hydrophobic galapectite；Secondly, with mass ratio being 1:3, polyethyl acrylate by super-hydrophobic galapectite and carbon dust
30 h of powder mixing and ball milling of 6.0 g obtains uniform super-hydrophobic carbon dust, and further the super-hydrophobic carbon dust is sieved 300 mesh,
Then 50 g are weighed to be packed into selenium drum of laser printer, are then printed to the pattern of Computer Design commonly by laser printing
Super-hydrophobic coat is obtained on printing paper.
Contact angle and roll angle: water contact angle=156 °, roll angle=10 ° are measured with 5 μ L water droplets.
Embodiment 4
Weigh 12.0 g sepiolites, be added in 1000 mL wide-mouth bottles, then measure respectively 520 mL ethylene glycol, 50 mL ammonium hydroxide and
30 mL deionized waters, 10 min of magnetic agitation, 3 min of cell pulverization instrument ultrasound.4.0 mL methyltriethoxy silanes are measured later
Alkane and 10.0 mL perfluoro decyl triethoxysilanes, are added in wide-mouth bottle, are stirred to react 2 h at room temperature and obtain uniform surpass
Hydrophobic sepiolite suspension.Then it is centrifuged 10 min under the conditions of 10000 rpm and collects sediment fraction, and is dry under 100 °C
4 h obtain super-hydrophobic sepiolite；Secondly, with mass ratio being 1:1, the just own ester 10.0 of polyacrylic acid by super-hydrophobic sepiolite and carbon dust
16 h of powder mixing and ball milling of g obtains uniform super-hydrophobic carbon dust, further by 300 mesh of super-hydrophobic carbon dust sieving, then
It weighs 50 g to be packed into selenium drum of laser printer, the pattern of Computer Design is then printed to by common print by laser printing
Super-hydrophobic coat is obtained on paper.
Contact angle and roll angle: water contact angle=158 °, roll angle=8 ° are measured with 5 μ L water droplets.
Claims (10)
1. a kind of method that laser printing prepares super-hydrophobic coat is that organosilan and nanoparticle are first passed through hydrolysis, condensation
It reacts and super-hydrophobic nano compound is made；Again by super-hydrophobic nano compound, resin and carbon dust with mixing and ball milling, obtain uniform
Super-hydrophobic carbon dust；Then super-hydrophobic carbon dust is packed into selenium drum of laser printer, is beaten super-hydrophobic carbon dust by laser printer
It prints on common print paper, obtains super-hydrophobic coat.
2. a kind of method that laser printing prepares super-hydrophobic coat as described in claim 1, it is characterised in that: super-hydrophobic nano is multiple
It closes object preparation: being that catalyst, water, organosilan and nanoparticle are added in alcoholic solvent, it is stirred to react 1 under 25 ~ 100 °C ~
72 h；Be centrifuged after reaction, dry to get.
3. a kind of method that laser printing prepares super-hydrophobic coat as claimed in claim 2, it is characterised in that: the organosilan
For perfluoro capryl trichlorosilane, perfluoro capryl trimethoxy silane, perfluoro capryl triethoxysilane, perfluoro decyl trichlorine silicon
Alkane, perfluoro decyl trimethoxy silane, perfluoro decyl triethoxysilane, perfluoro capryl dimethylchlorosilane, perfluoro capryl two
Methylmethoxysilane, perfluoro decyl dimethylchlorosilane, perfluoro decyl dimethyl methoxy silane, methyl trimethoxy oxygroup silicon
Alkane, methyltriethoxysilane, ethyl trichlorosilane, ethyl trimethoxy silane, ethyl triethoxysilane, vinyl trichlorine
Silane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysila,e, octyl trimethoxy silane,
At least one of dodecyltrimethoxysilane, hexadecyl trimethoxy silane.
4. a kind of method that laser printing prepares super-hydrophobic coat as claimed in claim 2, it is characterised in that: the nanoparticle
For carbon nanotube, graphene oxide, silica, titanium dioxide, zinc oxide, nano silver, montmorillonite, attapulgite, sepiolite,
Galapectite, hydrotalcite, vermiculite, mica, kaolinite, hectorite, bacteria cellulose, polystyrene, in polytetrafluoroethylene (PTFE) at least
It is a kind of.
5. a kind of method that laser printing prepares super-hydrophobic coat as claimed in claim 2, it is characterised in that: organosilan with receive
The mass ratio of rice corpuscles is 1:1 ~ 1:50.
6. a kind of method that laser printing prepares super-hydrophobic coat as claimed in claim 2, it is characterised in that: catalyst is salt
At least one of acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, benzene sulfonic acid, ammonium hydroxide, ethylenediamine, triethylamine, butylamine, catalyst
Additional amount be 1 ~ 200 times of organosilan quality.
7. a kind of method that laser printing prepares super-hydrophobic coat as described in claim 1, it is characterised in that: alcoholic solvent is first
At least one of alcohol, ethyl alcohol, ethylene glycol, propyl alcohol, isopropanol, glycerol.
8. a kind of method that laser printing prepares super-hydrophobic coat as described in claim 1, it is characterised in that: super-hydrophobic carbon dust
In preparation, the mass ratio of super-hydrophobic nano compound and carbon dust is 1:5 ~ 1:0.2, the quality of super-hydrophobic nano compound and resin
Than for 1:0.05 ~ 1:0.5；The mixing and ball milling time is 2 ~ 36 h.
9. a kind of method that laser printing prepares super-hydrophobic coat as described in claim 1 or 8, it is characterised in that: the resin
Including the just own ester of polystyrene, butyl polyacrylate, polyethyl acrylate, polyacrylic acid, polyacrylic acid 2- ethylhexyl, poly- third
Olefin(e) acid lauryl, polymethyl methacrylate, polyethyl methacrylate, Vinalac 5920, polymethylacrylic acid
At least one of just own ester of isobutyl ester, tert-butyl methacrylate, polymethylacrylic acid.
10. a kind of method that laser printing prepares super-hydrophobic coat as described in claim 1, it is characterised in that: laser printer
When printing, super-hydrophobic carbon dust is printed on common print paper according to the pattern of design.
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| CN113338047A (en) * | 2021-05-25 | 2021-09-03 | 青岛大学 | TiO on surface of cotton fabric2-BC/PDMS hydrophobic coating and preparation method thereof |
| CN113457954A (en) * | 2021-07-14 | 2021-10-01 | 宁波齐云新材料技术有限公司 | System and method for processing super-hydrophobic surface by laser |
| WO2023247576A1 (en) | 2022-06-22 | 2023-12-28 | Organograph Ab | An electron conducting coating |
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