CN108996915A - A kind of hydrophobic composite, preparation method, purposes and the glass containing it - Google Patents
A kind of hydrophobic composite, preparation method, purposes and the glass containing it Download PDFInfo
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- CN108996915A CN108996915A CN201810981040.7A CN201810981040A CN108996915A CN 108996915 A CN108996915 A CN 108996915A CN 201810981040 A CN201810981040 A CN 201810981040A CN 108996915 A CN108996915 A CN 108996915A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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- Surface Treatment Of Glass (AREA)
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention provides a kind of hydrophobic composites, the hydrophobic composite includes the basal layer that surface is coated with the hydroxyl modified of organic fluoride coating, the substrate surface of the hydroxyl modified is deposited with fluorinated carbon material, and the organic fluoride in the organic fluoride coating is connected by chemical bond with the basal layer of hydroxyl modified；The present invention is by introducing hydroxyl and depositing fluorinated carbon material in substrate surface, organic fluoride coating is introduced by graft reaction again, the synergistic effect of the two is utilized, so that the fluorine atom density of substrate surface further increases, the hydrophobic layer of formation is more dense, the static contact angle of obtained hydrophobic composite can reach 120 ° or more, and compared to the hydrophobic capability improving 10% or so of other products, hydrophobic performance has a clear superiority.
Description
Technical field
The invention belongs to hydrophobic material field more particularly to a kind of hydrophobic composite, preparation method, purposes and contain
Its glass.
Background technique
Fluorine-containing composite material or coating etc. have in many fields and potentially answer because it is with lower surface free energy
Waterproof material with value, such as surfaces such as mobile phone, automobile, optical instrument, glasses or liquid crystal displays uses, in mobile phone
Surface can effectively improve the smooth feeling of mobile phone using hydrophobic fluorine-containing composite material, be coated on ophthalmic lens surface hydrophobic
Fluorine-containing coat can scratch to avoid glasses, effectively extend the service life of glasses, coat fluorine-containing painting on optical instrument camera lens surface
Layer can be cleared up to avoid it because polluting and being difficult to, cause camera lens to scratch, avoid the damage of optical lens, building curtain wall and
Fluorine-containing composite material is applied in the performances such as glass pane, it can be made to keep cleaning for a long time, the number of glass cleaning is reduced, avoid height
Idle job is dangerous, applies fluorine-containing composite material on the surfaces such as automobile rearview mirror and windshield, it is possible to reduce rainwater is in glass table
The stop in face, slides water droplet quickly, avoids influencing driving sight.
Currently, preparing the method for fluorine-containing composite material or coating in the prior art because its step is complicated, cumbersome, condition
Harshness, so that it is limited in the application on the surfaces such as mobile phone, automobile, glasses, liquid crystal display or optical instrument, for example,
CN103068764A discloses a kind of new method using Perfluoropolyether silanes compositions-treated substrate, and especially it can be used
There can be the material of antimicrobial property in processing ceramics or glass etc., what is obtained has antimicrobial property and table
Containing certain density silver ion is contained in chemically reinforced glass on face coated with low surface energy coat, the synergy of the two makes
The antimicrobial properties and hydrophobic performance that must be obtained are excellent, can be used for antimicrobial shelf, desktop, hospital, laboratory with
And other places for needing to handle microorganism；A kind of preparation side of wear-resistant hydrophobic glass is disclosed in CN102503164A
Method includes the following steps: that (A) prepares SiO2Resin mixed sols: by hydrolyst, solvent, sol precursor according to certain
Volume ratio is mixed and stirred for, and obtains colloidal sol, is then again stirring evenly and then adding into the resin of specific epoxide number and curing agent described
In colloidal sol, SiO is obtained2/ resin mixed sols；(B) glass pre-treatment: using cerium rouge to glass polishing, glass is removed
Then glass surface contaminants clean glass using the mixed solution of sulfuric acid and hydrogen peroxide, formed to have in glass surface and be lived
The hydroxyl group of property；(C) SiO is plated in glass surface2/ resin compounded film: by prepared SiO2/ resin mixed sols is passing through
The glass surface plated film of pre-treatment；(D) solidify: SiO will be coated with2The glass heat treatment of/resin compounded film is solidified；(E) it repairs
Decorations agent modification: modification silane and solvent are mixed to get dressing agent, then by dressing agent in the glass surface for being coated with composite film
Form hydrophobic modification agent film layer；(F) it post-processes: the glass of the hydrophobic modification agent film layer room temperature number in dustfree environment will be coated with
10~60min of hour or heat treatment, obtains wear-resistant hydrophobic glass；However, above-mentioned preparation method is complex, what is obtained is hydrophobic
Material or coating hydrophobic performance are still lower, still need to be further improved.
On the basis of existing technology, the present invention needs for the technical problems in the prior art, to provide a kind of letter
Single method for effectively preparing hydrophobic fluorine-containing composite material and corresponding hydrophobic composite further improve common used material such as
Hydrophobic performance, crocking resistance anti-pollution and translucency performance of glass material etc., moreover, preparation method needs have
It is easy to operate, the advantages of easy to use and suitable large-scale promotion.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide it is a kind of simply and effectively prepare it is hydrophobic fluorine-containing
The method of composite material and corresponding hydrophobic composite, the further hydrophobic performance for improving common used material such as glass material,
Crocking resistance anti-pollution and translucency performance etc., moreover, the preparation method need to have it is easy to operate, it is easy to use and
The advantages of being suitble to large-scale promotion.
For this purpose, one of the objects of the present invention is to provide a kind of hydrophobic composite, the hydrophobic composite
The basal layer of the hydroxyl modified of organic fluoride coating is coated with including surface.
The substrate surface of the hydroxyl modified is deposited with fluorinated carbon material.
Organic fluoride in the organic fluoride coating is connected by chemical bond with the basal layer of hydroxyl modified.
The present invention is by introducing hydroxyl and depositing fluorinated carbon material in substrate surface, then is introduced by graft reaction organic
Fluoride coating, so that the fluorinated carbon material of substrate surface deposition is closely coated, so that the fluorine of substrate surface is former
Sub- density further increases, and the hydrophobic layer of formation is more dense, can obtain a kind of composite material that hydrophobic performance is excellent.
In the present invention, there is synergy, due to fluorinated carbon material between fluorinated carbon material and organic fluoride coating
Substrate surface is only adsorbed on by intermolecular force, is dredged by what is obtained in the depositing fluorinated carbon material of substrate surface merely
Water material, with increasing for access times, hydrophobic performance decline is violent, merely by coating organic fluoride in substrate surface
The hydrophobic material that coating obtains due to the factors such as intramolecular repulsion and steric hindrance influence, surface fluorine atom density usually compared with
Low, hydrophobic performance is not generally also high, in substrate surface while depositing fluorinated carbon material and after coating organic fluoride coating, by
In organic fluoride coating for fluorinated carbon material restriction effect and fluorinated carbon material for fluorine atom in organic fluoride
Attract and the presence of stabilizing effect, obtained composite material surface fluorine atom density is higher, is more evenly distributed, and hydrophobic performance and makes
It can be further increased with the service life.
Preferably, the organic fluoride in the organic fluoride coating is perfluor silane, perfluorocarboxylic acid or perfluorinated sulfonic acid
In any one or at least two mixture, such as mixture, perfluorinated sulfonic acid and the perfluor of perfluor silane and perfluorocarboxylic acid
Mixture or the mixture of perfluor silane, perfluorinated sulfonic acid and perfluorocarboxylic acid of carboxylic acid etc..
Preferably, the perfluor silane be perfluorododecyl trichlorosilane, it is perfluorododecyl trimethoxy silane, complete
In fluorine octyltri-ethoxysilane or perfluoro decyl trimethoxy silane any one or at least two mixture, for example,
Mixture, perfluorododecyl trichlorosilane and the perfluor of perfluorododecyl trichlorosilane and perfluoro capryl triethoxysilane
Mixture or perfluoro capryl triethoxysilane, the perfluoro decyl trimethoxy silane and perfluor of dodecyltrimethoxysilane
The mixture etc. of dodecyltrichlorosilane.
Preferably, the perfluorinated sulfonic acid is perfluor -1- fourth sulfonic acid, the own sulfonic acid of perfluor -1-, the pungent sulfonic acid of perfluor -1- or perfluor -
In 1- last of the ten Heavenly stems sulfonic acid any one or at least two mixture, for example, perfluor -1- fourth sulfonic acid and the own sulfonic acid of perfluor -1- is mixed
Close the mixture or perfluor -1- fourth sulfonic acid, the own sulfonic acid of perfluor -1- and perfluor-of object, the pungent sulfonic acid of perfluor -1- and perfluor -1- last of the ten Heavenly stems sulfonic acid
The mixture etc. of the pungent sulfonic acid of 1-.
Preferably, the perfluorocarboxylic acid is perfluor caproic acid, perfluoro-pelargonic acid, perfluoro decanoate, perfluor undecanoic acid or perfluor 12
In acid any one or at least two mixture, for example, mixture of perfluor caproic acid and perfluoro decanoate, perfluor undecanoic acid
With the mixture of perfluor lauric acid/dodecanoic acid or the mixture of perfluor caproic acid, perfluoro-pelargonic acid and perfluoro decanoate etc..
Preferably, the fluorinated carbon material is fluorinated graphene and/or fluorographite.
Preferably, the partial size of the fluorinated carbon material be 10~100nm, for example, 12nm, 15nm, 20nm, 25nm,
The fluorinated carbon material of 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 95nm etc., above-mentioned partial size can more stably sink
Product does not influence fluorinated carbon material for the stabilization of organic fluoride coating in substrate surface.
Preferably, the basal layer of the hydroxyl modified is by reacting silane coupling agent with basal layer, in substrate surface
The silane for introducing hydroxyl obtains.
Preferably, the silane coupling agent is hexadecyl trimethoxy silane, isobutyl ethyl triethoxy silicane, metering system
In acryloxypropylethoxysilane trimethoxy silane or vinyltrimethoxysilane any one or at least two mixture, such as
For hexadecyl trimethoxy silane and the mixture of methacryloxypropyl trimethoxy silane, isobutyl group triethoxy
Mixture or isobutyl ethyl triethoxy silicane, the methacryloxypropyl trimethoxy silicon of silicon and vinyltrimethoxysilane
Alkane and the mixture of vinyltrimethoxysilane etc..
Preferably, the basal layer is glass.
The second object of the present invention is to provide a kind of preparation method of hydrophobic composite, and the preparation method includes such as
Lower step:
Step (1), silane coupling agent and fluorinated carbon material are dispersed in the first organic solvent, and it is molten to obtain cleaning coating
Liquid is coated onto substrate surface, obtains the basal layer of hydroxyl modified；
Step (2) disperses organic fluoride and fluorinated carbon material in a second organic solvent, to obtain post-treatment coatings
Solution is coated onto the substrate surface of hydroxyl modified obtained in step (1), obtains to surface and is coated with organic fluoride painting
The basal layer of the hydroxyl modified of layer；
Step (3) adds the basal layer for the hydroxyl modified that surface obtained in step (2) is coated with organic fluoride coating
Heat and/or radiation treatment, obtain the hydrophobic composite.
Preferably, count by weight percentage, the content of silane coupling agent in coating solution is cleaned described in step (1)
For 0.5~2wt%, for example, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.4wt%,
1.6wt%, 1.7wt%, 1.8wt% or 1.9wt% etc..
Preferably, count by weight percentage, the content of fluorinated carbon material in coating solution is cleaned described in step (1)
For 0.05~0.2wt%, for example, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.12wt%,
0.13wt%, 0.14wt%, 0.15wt%, 0.16wt%, 0.17wt%, 0.18wt% or 0.19wt% etc.
Preferably, silane coupling agent described in step (1) is hexadecyl trimethoxy silane, isobutyl group triethoxy
Any one in silicon, methacryloxypropyl trimethoxy silane or vinyltrimethoxysilane or at least two
It is the mixture of mixture, for example, hexadecyl trimethoxy silane and methacryloxypropyl trimethoxy silane, different
Mixture or isobutyl ethyl triethoxy silicane, the methacryloxy third of butyl triethoxysilicane and vinyltrimethoxysilane
Base trimethoxy silane and the mixture of vinyltrimethoxysilane etc..
Preferably, basal layer described in step (1) is glass.
Preferably, the first organic solvent described in step (1) is ethyl alcohol and/or isopropanol.
Preferably, fluorinated carbon material described in step (1) and step (2) is fluorinated graphene and/or fluorographite.
Preferably, the partial size of fluorinated carbon material described in step (1) and step (2) be 10~100nm be, for example, 12nm,
15nm, 20nm, 25nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 95nm etc..
Preferably, roller coating, spin coating or blade coating are applied to described in step (1) and step (2).
Preferably, ultrasonic disperse is separated into described in step (1) and step (2).
Preferably, count by weight percentage, the content of fluorinated carbon material is in post-treatment solution described in step (2)
0.1~0.5wt%, for example, 0.15wt%, 0.20wt%, 0.25wt%, 0.30wt%, 0.35wt%, 0.40wt%,
0.45wt% or 0.48wt% etc..
Preferably, organic fluoride described in step (2) is any in perfluor silane, perfluorocarboxylic acid or perfluorinated sulfonic acid
It is a kind of or at least two mixture, such as the mixture of perfluor silane and perfluorocarboxylic acid, perfluorinated sulfonic acid and perfluorocarboxylic acid it is mixed
Close object or perfluor silane, perfluorinated sulfonic acid and the mixture of perfluorocarboxylic acid etc..
Preferably, the perfluor silane be perfluorododecyl trichlorosilane, it is perfluorododecyl trimethoxy silane, complete
In fluorine octyltri-ethoxysilane or perfluoro decyl trimethoxy silane any one or at least two mixture, for example,
Mixture, perfluorododecyl trichlorosilane and the perfluor of perfluorododecyl trichlorosilane and perfluoro capryl triethoxysilane
Mixture or perfluoro capryl triethoxysilane, the perfluoro decyl trimethoxy silane and perfluor of dodecyltrimethoxysilane
The mixture etc. of dodecyltrichlorosilane.
Preferably, the perfluorinated sulfonic acid is perfluor -1- fourth sulfonic acid, the own sulfonic acid of perfluor -1-, the pungent sulfonic acid of perfluor -1- or perfluor -
In 1- last of the ten Heavenly stems sulfonic acid any one or at least two mixture, for example, perfluor -1- fourth sulfonic acid and the own sulfonic acid of perfluor -1- is mixed
Close the mixture or perfluor -1- fourth sulfonic acid, the own sulfonic acid of perfluor -1- and perfluor-of object, the pungent sulfonic acid of perfluor -1- and perfluor -1- last of the ten Heavenly stems sulfonic acid
The mixture etc. of the pungent sulfonic acid of 1-.
Preferably, the perfluorocarboxylic acid is perfluor caproic acid, perfluoro-pelargonic acid, perfluoro decanoate, perfluor undecanoic acid or perfluor 12
In acid any one or at least two mixture, for example, mixture of perfluor caproic acid and perfluoro decanoate, perfluor undecanoic acid
With the mixture of perfluor lauric acid/dodecanoic acid or the mixture of perfluor caproic acid, perfluoro-pelargonic acid and perfluoro decanoate etc..
Preferably, the second organic solvent described in step (2) is ethyl alcohol and/or isopropanol.
Preferably, the time of heating described in step (3) and/or radiation treatment be 1~10min, for example, 2min,
3min, 4min, 5min, 6min, 7min, 8min or 9min etc..
Preferably, heating described in step (3) and/or radiation treatment are to be irradiated using infrared light supply or under sunlight
Irradiation.
The third object of the present invention is to provide a kind of purposes of hydrophobic composite, the hydrophobic composite tool
There is excellent hydrophobic performance, the waterproof coating that can be used as mobile phone, automobile, eyeglass, display screen or surface optical device uses.
The fourth object of the present invention is to provide a kind of glass, and the glass surface contains the hydrophobic composite.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Compared with prior art, the invention has the benefit that
The present invention is by introducing hydroxyl and depositing fluorinated carbon material in substrate surface, then is introduced by graft reaction organic
The synergistic effect of the two is utilized in fluoride coating, so that the fluorine atom density of substrate surface further increases, formation is dredged
Water layer is more dense, and the static contact angle of obtained hydrophobic composite can reach 120 ° or more, hydrophobic compared to other products
Capability improving 10% or so, hydrophobic performance has a clear superiority.
Detailed description of the invention
Fig. 1 is the SEM photograph for the hydrophobic composite 6 that the embodiment of the present invention 6 obtains.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
Hydrophobic composite 1 is made by the steps:
Step (1) receives the fluorinated graphene that 1g hexadecyl trimethoxy silane and 0.1g average grain diameter are 15nm
Rice corpuscles is dispersed in 99g ethyl alcohol, and carrying out ultrasonic treatment 20min using the ultrasonic cleaner that power is 200W keeps its dispersion equal
It is even, cleaning coating solution is obtained, is spin-coated on silicate glass surface using spin coater, it is dry, obtain the base of hydroxyl modified
Bottom；
The own sulfonic acid of 1g perfluor -1-, 0.7g perfluorododecyl trimethoxy silane and 0.3g are averaged grain by step (2)
Diameter be 15nm fluorinated graphene nanoparticle be dispersed in 100g isopropanol, using power be 200W ultrasonic cleaner into
Row ultrasonic treatment 20min makes it be uniformly dispersed, and obtains post-treatment coatings solution, is scratched the hydroxyl obtained in step (1)
The substrate surface of modification obtains to surface and is coated with the basal layer of the hydroxyl modified of organic fluoride coating；
Step (3) puts the basal layer for the hydroxyl modified that surface obtained in step (2) is coated with organic fluoride coating
It is placed under the infrared lamp that power is 100W and carries out heating and radiation treatment 10min, obtain the hydrophobic composite 1.
Embodiment 2
Difference with embodiment 1 is only that the additional amount of hexadecyl trimethoxy silane is 0.6g, fluorine in step (1)
The additional amount of graphite alkene nanoparticle is 0.2g.
Embodiment 2 obtains hydrophobic composite 2.
Embodiment 3
Difference with embodiment 1 is only that the additional amount of hexadecyl trimethoxy silane is 2g, fluorination in step (1)
The additional amount of graphene nano particle is 0.06g.
Embodiment 3 obtains hydrophobic composite 3.
Embodiment 4
Difference with embodiment 1 is only that, the hexadecyl trimethoxy silane in step (1) is replaced with metering system
Acryloxypropylethoxysilane trimethoxy silane.
Embodiment 4 obtains hydrophobic composite 4.
Embodiment 5
Difference with embodiment 1 is only that, the average grain of step (1) and the fluorinated graphene nanoparticle in step (2)
Diameter is 45nm.
Embodiment 5 obtains hydrophobic composite 5.
Embodiment 6
Difference with embodiment 1 is only that the fluorinated graphene nanoparticle in step (1) and step (2) replaces with fluorine
The mixture of graphite alkene nanoparticle and fluorographite, the average grain diameter of mixture are 100nm.
Embodiment 6 obtains hydrophobic composite 6.
Embodiment 7
Difference with embodiment 1 is only that, the own sulfonic acid of perfluor -1- and perfluorododecyl trimethoxy in step (2)
Silane replaces with 1.7g perfluoro decanoate.
Embodiment 7 obtains hydrophobic composite 7.
Embodiment 8
Difference with embodiment 1 is only that the time of heating and radiation treatment is 1min in step (3).
Embodiment 8 obtains hydrophobic composite 8.
Embodiment 9
Difference with embodiment 1 is only that, the average grain of step (1) and the fluorinated graphene nanoparticle in step (2)
Diameter is 5nm.
Embodiment 9 obtains hydrophobic composite 9.
Embodiment 10
Difference with embodiment 1 is only that the fluorinated graphene nanoparticle in step (1) and step (2) replaces with fluorine
Graphite ion, average grain diameter 225nm.
Embodiment 10 obtains hydrophobic composite 10.
Reference examples 1
Hydrophobic composite 11 is made by the steps:
Step (1) receives the fluorinated graphene that 1g hexadecyl trimethoxy silane and 0.1g average grain diameter are 15nm
Rice corpuscles is dispersed in 99g ethyl alcohol, and carrying out ultrasonic treatment 20min using the ultrasonic cleaner that power is 200W keeps its dispersion equal
It is even, cleaning coating solution is obtained, is spin-coated on silicate glass surface using spin coater, it is dry, obtain the base of hydroxyl modified
Bottom；
Step (2), by the basal layer of hydroxyl modified obtained in step (1) be placed in power be 100W infrared lamp under into
Row heating and radiation treatment 10min, obtain the hydrophobic composite 11.
Reference examples 2
Hydrophobic composite 12 is made by the steps:
Step (1), 1g hexadecyl trimethoxy silane is dispersed in 99g ethyl alcohol, the ultrasound for the use of power being 200W
Wave washer, which carries out ultrasonic treatment 20min, makes it be uniformly dispersed, and obtains cleaning coating solution, is spin-coated on silicon using spin coater
Silicate glass surface, it is dry, obtain the basal layer of hydroxyl modified；
The own sulfonic acid of 1g perfluor -1- and 0.7g perfluorododecyl trimethoxy silane are dispersed in 100g isopropyl by step (2)
In alcohol, carrying out ultrasonic treatment 20min using the ultrasonic cleaner that power is 200W makes it be uniformly dispersed, and obtains post-treatment coatings
Solution is scratched the silicate glass for being obtained on silicate glass surface to surface and being coated with organic fluoride coating；
The silicate glass that surface obtained in step (2) is coated with organic fluoride coating is placed in function by step (3)
Heating and radiation treatment 10min are carried out under the infrared lamp that rate is 100W, obtains the hydrophobic composite 12.
Hydrophobic composite 1~12 obtained in above-described embodiment and reference examples is surveyed by following test method
Examination, and test result is listed in table 1.
(1) pattern test
The VEGA 3LMH type scanning electron microscope (SEM) produced using TESCAN company is respectively to hydrophobic composite 1
~12 surface carries out pattern test, test parameter are as follows: test voltage 1kv~30kV.
(2) hydrophobic performance is tested
According to standard GB/T/T 24368-2009 " glass surface hydrophobic contaminants detect contact angle measurement "
Method test hydrophobic composite 1~12 respectively for the static contact angle of distilled water, with silicate used in embodiment 1
The contact angle (62 °) of glass material compares, and later the immersion of hydrophobic composite 1~12 is placed in power respectively in water and is
Ultrasonic treatment 1h is carried out in the ultrasonic cleaning machine of 200W, the case where when using for a long time to simulate, is used after ultrasonic treatment
The hydrophobic performance of identical method test hydrophobic composite 1~12.
The hydrophobic performance contrast table of 1 hydrophobic composite 1~12 of table
Fig. 1 is the SEM photograph for the hydrophobic composite 6 that the embodiment of the present invention 6 obtains, wherein this it appears that fluorocarbons
Material is limited by organic fluoride coating, uniformly and is closely deposited on silicate glass layer surface.
Comparison between embodiment 1 and embodiment 5~6 and embodiment 9~10 is it is found that work as the average grain of fluorinated carbon material
When diameter is located in the range of 10~100nm, can uniform deposition in substrate surface and limit by organic fluoride coating
Production is used, and when its partial size is excessive or too small, corresponding restriction effect weakens, fluorinated carbon material be easier to from substrate surface from
It goes, hydrophobic performance is deteriorated the hydrophobic composite caused after prolonged use.
Comparison between embodiment 1 and reference examples 1 is it is found that only in the depositing fluorinated carbon material of substrate surface, band
The hydrophobic effect come is general, and obtained composite material is still hydrophilic material, moreover, the substrate surface when long-time uses
Fluorinated carbon material is easy to leave away, and fluorinated carbon material bring hydrophobic performance is caused to disappear substantially.
Comparison between embodiment 1 and reference examples 2 applies it is found that one layer of organic fluoride only ought be coated in substrate surface
When layer, obtained composite material hydrophobic performance is general, and (contact angle is about with hydrophobic material other similar obtained in the prior art
104 ° or so) it compares, performance is without clear superiority.
In conclusion the present invention passes through in substrate surface introducing hydroxyl and depositing fluorinated carbon material, then instead by grafting
Organic fluoride coating should be introduced, the synergistic effect of the two is utilized, so that the fluorine atom density of substrate surface further mentions
The hydrophobic layer of height, formation is more dense, and the static contact angle of obtained hydrophobic composite can reach 120 ° or more, compared to it
The hydrophobic capability improving 10% or so of his product, hydrophobic performance has a clear superiority.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of hydrophobic composite, which is characterized in that the hydrophobic composite includes that surface is coated with organic fluoride painting
The basal layer of the hydroxyl modified of layer；
The substrate surface of the hydroxyl modified is deposited with fluorinated carbon material；
Organic fluoride in the organic fluoride coating is connected by chemical bond with the basal layer of hydroxyl modified.
2. hydrophobic composite according to claim 1, which is characterized in that the Organic fluoride in the organic fluoride coating
Compound is the mixture of any one or at least two in perfluor silane, perfluorocarboxylic acid or perfluorinated sulfonic acid；
Preferably, the perfluor silane is that perfluorododecyl trichlorosilane, perfluorododecyl trimethoxy silane, perfluor are pungent
In ethyl triethoxy silicane alkane or perfluoro decyl trimethoxy silane any one or at least two mixture；
Preferably, the perfluorinated sulfonic acid is perfluor -1- fourth sulfonic acid, the own sulfonic acid of perfluor -1-, the pungent sulfonic acid of perfluor -1- or the perfluor -1- last of the ten Heavenly stems
In sulfonic acid any one or at least two mixture；
Preferably, the perfluorocarboxylic acid is in perfluor caproic acid, perfluoro-pelargonic acid, perfluoro decanoate, perfluor undecanoic acid or perfluor lauric acid/dodecanoic acid
Any one or at least two mixture.
3. hydrophobic composite according to claim 1 or 2, which is characterized in that the fluorinated carbon material is fluorographite
Alkene and/or fluorographite；
Preferably, the partial size of the fluorinated carbon material is 10~100nm.
4. hydrophobic composite described according to claim 1~one of 3, which is characterized in that the basal layer of the hydroxyl modified
By reacting silane coupling agent with basal layer, obtained in the silane that substrate surface introduces hydroxyl；
Preferably, the silane coupling agent is hexadecyl trimethoxy silane, isobutyl ethyl triethoxy silicane, methacryloxypropyl
In base propyl trimethoxy silicane or vinyltrimethoxysilane any one or at least two mixture；
Preferably, the basal layer is glass.
5. a kind of preparation method of hydrophobic composite, which is characterized in that the preparation method includes the following steps:
Step (1), silane coupling agent and fluorinated carbon material are dispersed in the first organic solvent, obtain cleaning coating solution,
It is coated onto substrate surface, obtains the basal layer of hydroxyl modified；
Step (2) disperses organic fluoride and fluorinated carbon material in a second organic solvent, it is molten to obtain post-treatment coatings
Liquid is coated onto the substrate surface of hydroxyl modified obtained in step (1), obtains to surface and be coated with organic fluoride coating
Hydroxyl modified basal layer；
Step (3) heats the basal layer that surface obtained in step (2) is coated with the hydroxyl modified of organic fluoride coating
And/or radiation treatment, obtain the hydrophobic composite.
6. preparation method according to claim 5, which is characterized in that count by weight percentage, described in step (1)
The content for cleaning silane coupling agent in coating solution is 0.5~2wt%；
Preferably, count by weight percentage, the content of fluorinated carbon material is in cleaning coating solution described in step (1)
0.05~0.2wt%；
Preferably, silane coupling agent described in step (1) be hexadecyl trimethoxy silane, isobutyl ethyl triethoxy silicane,
In methacryloxypropyl trimethoxy silane or vinyltrimethoxysilane any one or at least two it is mixed
Close object；
Preferably, basal layer described in step (1) is glass；
Preferably, the first organic solvent described in step (1) is ethyl alcohol and/or isopropanol；
Preferably, fluorinated carbon material described in step (1) and step (2) is fluorinated graphene and/or fluorographite；
Preferably, the partial size of fluorinated carbon material described in step (1) and step (2) is 10~100nm；
Preferably, roller coating, spin coating or blade coating are applied to described in step (1) and step (2)；
Preferably, ultrasonic disperse is separated into described in step (1) and step (2).
7. preparation method according to claim 5 or 6, which is characterized in that count by weight percentage, institute in step (2)
The content of fluorinated carbon material is 0.1~0.5wt% in the post-treatment solution stated；
Preferably, organic fluoride described in step (2) is any one in perfluor silane, perfluorocarboxylic acid or perfluorinated sulfonic acid
Or at least two mixture；
Preferably, the perfluor silane is that perfluorododecyl trichlorosilane, perfluorododecyl trimethoxy silane, perfluor are pungent
In ethyl triethoxy silicane alkane or perfluoro decyl trimethoxy silane any one or at least two mixture；
Preferably, the perfluorinated sulfonic acid is perfluor -1- fourth sulfonic acid, the own sulfonic acid of perfluor -1-, the pungent sulfonic acid of perfluor -1- or the perfluor -1- last of the ten Heavenly stems
In sulfonic acid any one or at least two mixture；
Preferably, the perfluorocarboxylic acid is in perfluor caproic acid, perfluoro-pelargonic acid, perfluoro decanoate, perfluor undecanoic acid or perfluor lauric acid/dodecanoic acid
Any one or at least two mixture；
Preferably, the second organic solvent described in step (2) is ethyl alcohol and/or isopropanol.
8. the preparation method according to one of claim 5~7, which is characterized in that heating described in step (3) and/or
The time of radiation treatment is 1~10min；
Preferably, heating described in step (3) and/or radiation treatment are to be irradiated using infrared light supply or shone under sunlight
It penetrates.
9. a kind of purposes of the hydrophobic composite as described in one of Claims 1 to 4, which is characterized in that described hydrophobic compound
Material is used as the waterproof coating of mobile phone, automobile, eyeglass, display screen or surface optical device.
10. a kind of glass, which is characterized in that the glass surface contains the hydrophobic composite wood as described in one of Claims 1 to 4
Material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810981040.7A CN108996915A (en) | 2018-08-27 | 2018-08-27 | A kind of hydrophobic composite, preparation method, purposes and the glass containing it |
| PCT/CN2018/119542 WO2020042415A1 (en) | 2018-08-27 | 2018-12-06 | Hydrophobic composite material, preparation method and use therefor, and glass containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810981040.7A CN108996915A (en) | 2018-08-27 | 2018-08-27 | A kind of hydrophobic composite, preparation method, purposes and the glass containing it |
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| Publication Number | Publication Date |
|---|---|
| CN108996915A true CN108996915A (en) | 2018-12-14 |
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|---|---|---|---|
| CN201810981040.7A Pending CN108996915A (en) | 2018-08-27 | 2018-08-27 | A kind of hydrophobic composite, preparation method, purposes and the glass containing it |
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| Country | Link |
|---|---|
| CN (1) | CN108996915A (en) |
| WO (1) | WO2020042415A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746125A (en) * | 2019-11-01 | 2020-02-04 | 深圳南科氟光纳米科技有限责任公司 | Hydrophobic glass and preparation method thereof |
| CN111077600A (en) * | 2020-01-07 | 2020-04-28 | 重庆金山医疗技术研究院有限公司 | Lens glass, endoscope, and lens glass processing method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3539887B1 (en) * | 2018-03-16 | 2021-05-26 | Schott AG | Hollow body, in particular for packaging a pharmaceutical composition, having a layer of glass and a surface region with a contact angle for wetting with water |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002524313A (en) * | 1998-09-07 | 2002-08-06 | ザ、プロクター、エンド、ギャンブル、カンパニー | Superhydrophobic coated substrate |
| CN1762610A (en) * | 2001-04-02 | 2006-04-26 | 松下电器产业株式会社 | Water-repellent film and method for preparing the same, and ink-jet head and ink-jet type recording device using the same |
| CN101544476A (en) * | 2008-03-28 | 2009-09-30 | 皮尔金顿集团有限公司 | Super-hydrophobic transparent coating and preparation method thereof |
| CN104402242A (en) * | 2014-11-17 | 2015-03-11 | 上海交通大学 | Preparation method for superhydrophobic rigid carbon film |
| CN102606872B (en) * | 2012-02-17 | 2015-08-19 | 清华大学 | A kind of method being reduced frictional coefficient by finishing |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863154B (en) * | 2012-10-18 | 2014-07-16 | 齐鲁工业大学 | Method for preparing super-hydrophobicity surfaces |
| WO2014133466A1 (en) * | 2013-02-28 | 2014-09-04 | Nanyang Technological University | Ionic liquid electrolyte and fluorinated carbon electrode |
| US10400137B2 (en) * | 2014-11-12 | 2019-09-03 | Sumitomo Chemical Company, Limited | Water-repellant and oil-repellant coating composition and transparent film |
-
2018
- 2018-08-27 CN CN201810981040.7A patent/CN108996915A/en active Pending
- 2018-12-06 WO PCT/CN2018/119542 patent/WO2020042415A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002524313A (en) * | 1998-09-07 | 2002-08-06 | ザ、プロクター、エンド、ギャンブル、カンパニー | Superhydrophobic coated substrate |
| CN1762610A (en) * | 2001-04-02 | 2006-04-26 | 松下电器产业株式会社 | Water-repellent film and method for preparing the same, and ink-jet head and ink-jet type recording device using the same |
| CN101544476A (en) * | 2008-03-28 | 2009-09-30 | 皮尔金顿集团有限公司 | Super-hydrophobic transparent coating and preparation method thereof |
| CN102606872B (en) * | 2012-02-17 | 2015-08-19 | 清华大学 | A kind of method being reduced frictional coefficient by finishing |
| CN104402242A (en) * | 2014-11-17 | 2015-03-11 | 上海交通大学 | Preparation method for superhydrophobic rigid carbon film |
Non-Patent Citations (2)
| Title |
|---|
| 强亮生: "《"新型功能材料制备技术与分析表征方法》", 30 June 2017, 哈尔滨工业大学出版社 * |
| 朴正杰等: "氟化石墨的加工技术及其应用新进展", 《化工新型材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746125A (en) * | 2019-11-01 | 2020-02-04 | 深圳南科氟光纳米科技有限责任公司 | Hydrophobic glass and preparation method thereof |
| CN111077600A (en) * | 2020-01-07 | 2020-04-28 | 重庆金山医疗技术研究院有限公司 | Lens glass, endoscope, and lens glass processing method |
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| WO2020042415A1 (en) | 2020-03-05 |
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