CN117625020B - Hydrophilic coating, preparation method and device - Google Patents
Hydrophilic coating, preparation method and device Download PDFInfo
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- CN117625020B CN117625020B CN202210983271.8A CN202210983271A CN117625020B CN 117625020 B CN117625020 B CN 117625020B CN 202210983271 A CN202210983271 A CN 202210983271A CN 117625020 B CN117625020 B CN 117625020B
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- 238000000576 coating method Methods 0.000 title claims abstract description 87
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 96
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- -1 amino, hydroxyl Chemical group 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 42
- 239000011521 glass Substances 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000012360 testing method Methods 0.000 description 23
- 238000002791 soaking Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002309 gasification Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 239000012780 transparent material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Classifications
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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
-
- 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
- B05D1/62—Plasma-deposition of organic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The specific embodiment of the invention provides a hydrophilic coating, a preparation method and a device, wherein the preparation method of the hydrophilic coating is characterized in that siloxane monomer I containing amino, hydroxyl or carboxyl and ether monomer II are mixed and then gasified and introduced into a plasma reactor, plasma discharge is carried out, and plasma polymerization is carried out on the surface of a substrate to form the hydrophilic coating.
Description
Technical Field
The invention belongs to the field of plasma chemistry, and particularly relates to a hydrophilic coating, a preparation method and a device.
Background
Transparent materials (e.g., glass, plastic) find wide use in industrial and agricultural production and in everyday life as well as in the military field, such as goggles, laser goggles, lenses for telescopes and various camera devices, various mechanical viewing windows, sports goggles, bathroom glass, chemical or biological masks, vehicle windshields and rearview mirrors, blast protection devices, helmets, solar panels, viewing windows for measuring instruments, glass covers, glass walls for greenhouses, and the like. However, in winter, glasses can make us "look flower in fog"; in cold winter, the fog on the surface of the windshield can greatly influence the visibility of people and even cause accidents. The atomization problem brings a plurality of inconveniences to the work and life of people, and the research and development of anti-fog technology and anti-fog materials are focused by scientific and enterprise industries.
The provision of an anti-fog coating on the surface of a transparent material is a common anti-fog means, and the anti-fog coating is generally of two types, one is that a hydrophilic surface is formed on the surface of the transparent material, water drops spread on the hydrophilic surface to form a film, and the other is that a hydrophobic surface is formed on the surface of the transparent material, and the water drops bead and roll on the hydrophobic surface. The latter has the disadvantage that atomization still occurs when a large amount of water vapor is rapidly condensed. The former forms a uniform water film to eliminate the diffuse reflection phenomenon of light rays and achieve the purpose of anti-fog.
At present, the technical improvement of the hydrophilic anti-fog coating is mainly focused on the traditional liquid phase treatment method, including a gel-sol method, a layer-by-layer self-assembly method, a free radical solution polymerization method and the like. These methods generally use spray or spin coating methods to apply glue to the substrate surface and then cure using heat or UV radiation. In the liquid phase treatment method, there is a disadvantage that: the presence of solvents, reaction media, may react with the substrate, destroying the substrate structure, and creating a potential hazard.
Plasma Enhanced Chemical Vapor Deposition (PECVD) is a chemical vapor deposition process, uses plasma generated by glow discharge to activate monomers under low pressure to generate high-activity monomer free radicals or ion fragments, and deposits the high-activity monomer free radicals or ion fragments on the surface of a substrate to react to form a film, and has high deposition rate; the method has the advantages of good film forming quality, fewer pinholes and difficult cracking, does not need a liquid phase solvent in the reaction process, and does not damage a substrate, so that a PECVD technology is adopted to provide a better choice for preparing the hydrophilic anti-fog coating, and a hydrophilic monomer can be adopted to prepare the good hydrophilic anti-fog coating through PECVD, but the hydrophilic coating prepared by the common hydrophilic monomer can be easily combined with water molecules, so that the hydrophilic performance of the film layer is easily attenuated after the hydrophilic coating contacts with the water molecules.
Disclosure of Invention
The specific embodiment of the invention provides a hydrophilic coating with the hydrophilic performance less influenced by water molecules, a preparation method and a device, and the specific scheme is as follows:
a method of preparing a hydrophilic coating comprising the steps of:
providing a substrate, and placing the substrate in a plasma reactor; the monomer I and the monomer II are mixed and then gasified and introduced into a plasma reactor, plasma discharge is carried out, and plasma polymerization is carried out on the surface of the substrate to form the hydrophilic coating;
wherein the monomer I has a structure shown in the following formula (1),
In the formula (1), X is amino, hydroxyl or carboxyl, L 1 is alkylene of C 1-C30 or substituted alkylene of C 1-C30, wherein the substituent of the substituted alkylene is hydroxyl, amino or carboxyl, carbon-carbon connection bonds of the alkylene of C 1-C30 or the substituted alkylene of C 1-C30 are provided with-O-, -S-or-NH-, and R 1、R2 or R 3 are independently alkyl of C 1-C5 respectively;
The monomer II has a structure shown in the following formula (2),
R7—R5—O—L2—O—R4—R6
(2)
In the formula (2), L 2 is C 2-C10 alkylene or C 2-C10 substituted alkylene, wherein the substituent of the substituted alkylene is hydroxyl, R 4 and R 5 are respectively and independently a connecting bond, C 1-C4 alkylene, and R 6 and R 7 are respectively and independently methyl or epoxy.
Alternatively, L 1 is alkylene of C 1-C4 and R 1、R2 or R 3 are each independently methyl, ethyl or propyl.
Alternatively, the monomer I is selected from the group consisting of compounds of the following structural formulas (1-1) to (1-12):
alternatively, the monomer I has a structure represented by the following formula (3),
In the formula (3), R 1、R2 or R 3 are respectively methyl, ethyl or propyl independently, and n is 0, 1,2, 3 or 4.
Alternatively, the monomer I is selected from the group consisting of compounds of the following structural formulas (1-13) to (1-16):
alternatively, the monomer II is selected from the group consisting of compounds of the following structural formulas (2-1) to (2-20):
alternatively, the monomer II is selected from the group consisting of compounds of the following structural formulas (2-21) to (2-30):
Alternatively, the molar ratio of monomer I to monomer II is 3:1 to 1:3.
Optionally, the monomer I and the monomer II are mixed and then gasified and introduced into the plasma reactor, and oxygen is introduced at the same time.
Optionally, the flow rate of the mixed gas of the monomer I and the monomer II is 20-200 mu L/min, and the flow rate of oxygen is 20-200 sccm.
Optionally, the plasma is pulse plasma, the pulse plasma is generated by applying pulse voltage discharge, wherein the discharge power is 10-300W, the pulse frequency is 20Hz-10kHz, the pulse duty ratio is 40-80%, and the plasma discharge time is 100-36000 s.
Optionally, the substrate is metal, ceramic, plastic, glass, electronic device or optical instrument.
A hydrophilic coating prepared by the method of preparing a hydrophilic coating as described in any of the above.
A device having a hydrophilic coating as described above on at least part of its surface.
According to the preparation method of the hydrophilic coating, the siloxane monomer I containing amino, hydroxyl or carboxyl and the ether monomer II containing amino, hydroxyl or carboxyl and having the structure shown in the formula (1) are mixed and then gasified and introduced into a plasma reactor, plasma discharge is carried out, plasma polymerization is carried out on the surface of a substrate to form the hydrophilic coating, and the hydrophilic coating prepared by the method has excellent hydrophilic antifogging property, is little influenced by water molecules, and can still keep better hydrophilic property after contact reaction with the water molecules.
Detailed Description
The specific embodiment of the invention provides a preparation method of a hydrophilic coating, which comprises the following steps:
providing a substrate, and placing the substrate in a plasma reactor; the monomer I and the monomer II are mixed and then gasified and introduced into a plasma reactor, plasma discharge is carried out, and plasma polymerization is carried out on the surface of the substrate to form the hydrophilic coating;
wherein the monomer I has a structure shown in the following formula (1),
In the formula (1), X is amino, hydroxyl or carboxyl, L 1 is C 1-C30 alkylene or C 1-C30 substituted alkylene, wherein the substituted alkylene is that the alkylene carries a substituent, the substituent is hydroxyl, amino or carboxyl, carbon-carbon connection bonds of the C 1-C30 alkylene or the C 1-C30 substituted alkylene are provided with-O-, -S-or-NH-, and R 1、R2 or R 3 are independently alkyl of C 1-C5 respectively;
The monomer II has a structure shown in the following formula (2),
R7—R5—O—L2—O—R4—R6
(2)
In formula (2), L 2 is C 2-C10 alkylene or C 2-C10 substituted alkylene, which means that the alkylene has a substituent thereon, the substituent is a hydroxyl group, R 4 and R 5 are each independently a bond, C 1-C4 alkylene, R 6 and R 7 are each independently methyl or epoxy, and in some embodiments R 6 and R 7 are epoxy, considering that the hydrophilic coating retains better hydrophilic properties after contact reaction with water molecules.
In some embodiments, the L 1 is an alkylene group of C 1-C4, and may be, for example, methylene, ethylene, propylene or butylene, and the R 1、R2 or R 3 are, independently, methyl, ethyl or propyl, respectively.
In some embodiments, the alkylene is a linear alkylene, and in some embodiments, the alkylene is a branched alkylene, such as an alkylene having a methyl, ethyl, or the like branch.
In the preparation method of the hydrophilic coating of the specific embodiment of the invention, L 1 is alkylene of C 1-C30 or substituted alkylene of C 1-C30, with or without-O-, C-and C-linkages between the alkylene of C 1-C30 or the substituted alkylene of C 1-C30 -S-or-NH-, refers to an alkylene group of C 1-C30 or a substituted alkylene group of C 1-C30 in some embodiments, at least part of the carbon-carbon bonds are provided with-O- -alkylene of C 1-C30 or substituted alkylene of C 1-C30 of S-or-NH-.
In some embodiments, the monomer I is selected from the group consisting of compounds of the following structural formulas (1-1) to (1-12):
In some embodiments, monomer I has a structure represented by the following formula (3),
In formula (3), R1, R2 or R3 are each independently methyl, ethyl or propyl, n is 0,1, 2,3 or 4, and specifically, for example, the monomer I may be selected from compounds of the following structural formulae (1-13) to (1-16):
In some embodiments, the monomer II is selected from the group consisting of compounds of the following structural formulas (2-1) to (2-20):
in some embodiments, the monomer II is selected from compounds of the following formulas (2-21) to (2-30):
In some embodiments, the molar ratio of monomer I to monomer II is 3:1 to 1:3.
In some embodiments, the monomer I and the monomer II are mixed and gasified and introduced into the plasma reactor, and one or more of helium, argon, nitrogen, oxygen and hydrogen are introduced, in some embodiments, the monomer I and the monomer II are mixed and gasified and introduced into the plasma reactor, and oxygen is introduced, in some embodiments, the flow rate of the mixed gas of the monomer I and the monomer II is 20-200 mu L/min, specifically, 20μL/min、30μL/min、40μL/min、50μL/min、60μL/min、70μL/min、80μL/min、80μL/min、90μL/min、100μL/min、110μL/min、120μL/min、130μL/min、140μL/min、150μL/min、160μL/min、170μL/min、180μL/min、190μL/min or 200 mu L/min and the like, the flow rate of the oxygen is 20-200 sccm, specifically, 20sccm、30sccm、40sccm、50sccm、60sccm、70sccm、80sccm、90sccm、100sccm、110sccm、120sccm、130sccm、140sccm、150sccm、160sccm、170sccm、180sccm、190sccm or 200sccm and the like, in consideration of better hydrophilicity.
In some embodiments, the substrate is metal, ceramic, plastic, glass, electronic equipment or optical instrument, and in some embodiments, the substrate is glass in consideration of super-hydrophilicity. In some embodiments, the substrate is a transparent material, and may specifically be, for example, a lens of glasses, goggles, laser goggles, telescope and lenses of various imaging devices, various mechanical viewing windows, moving diving goggles, bathroom glass, chemical or biological masks, vehicle windshields and rearview mirrors, explosion-proof treatment protection devices, helmets, solar panels, viewing windows of measuring instruments, glass covers, glass walls of greenhouses, and the like.
In order to further enhance the binding force between the plasma coating and the substrate, in some embodiments, the substrate is pretreated by plasma before the coating, for example, in an inert gas, oxygen or hydrogen atmosphere, the plasma discharge power is 20-500W, and the discharge mode is continuous and the continuous discharge time is 1-60 min. In view of the superior hydrophilicity, in some embodiments, the pretreatment is performed using a plasma discharge in an oxygen atmosphere.
Embodiments of the present invention are methods of preparing hydrophilic coatings, in some embodiments, the thickness of the coating is from 1 to 1000nm, such as 1nm、5nm、10nm、20nm、30nm、40nm、50nm、100nm、150nm、200nm、250nm、300nm、350nm、400nm、450nm、500nm、600nm、700nm、800nm、900nm、1000nm and the like. In some embodiments, the thickness of the coating is 1-100nm as an ultra-thin transparent nano-coating.
In some embodiments, the temperature in the cavity of the plasma reactor is controlled to be 20-80 ℃ during the reaction, and specifically, for example, 20 ℃,30 ℃, 40 ℃,50 ℃, 60 ℃, 70 ℃ or 80 ℃ and the like; the pressure in the chamber is below 1000 millitorr, further below 500 millitorr, and further below 100 millitorr; the gasification temperature after mixing of monomer I and monomer II is 50-180deg.C, specifically, for example, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, etc., and gasification is performed under vacuum condition. The plasma is a pulsed plasma, in some embodiments, generated by applying a pulsed voltage discharge, wherein the pulsed discharge power is 10W to 300W, which may be, for example, 10W、20W、30W、40W、50W、70W、80W、100W、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W or 300W, etc., in some embodiments, 60W to 100W for better hydrophilicity; the pulse frequency is 20Hz-10kHz, and can be 20Hz、30Hz、40Hz、50Hz、60Hz、70Hz、80Hz、90Hz、100Hz、200Hz、300Hz、400Hz、500Hz、600Hz、700Hz、800Hz、900Hz、1KHz、5KHz or 10KHz, etc; the pulse duty cycle is 0.1% to 85%, specifically, for example, may be 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, etc., in some embodiments, the pulse duty cycle is 40% to 80%, further the pulse duty cycle is 45% to 75%; the plasma discharge time is 100s-36000s, and may be 100s、500s、1000s、1800s、2000s、1000s、2000s、3000s、4000s、5000s、6000s、7000s、7200s、10800s、14400s、18000s、21600s、25200s、28800s、32400s or 36000s, for example.
In some embodiments, the plasma discharge mode may be any of various existing discharge modes, such as electrodeless discharge (e.g. rf inductively coupled discharge, microwave discharge), single electrode discharge (e.g. corona discharge, plasma jet formed by unipolar discharge), double electrode discharge (e.g. dielectric barrier discharge, bare electrode rf glow discharge), and multi-electrode discharge (e.g. discharge using floating electrode as the third electrode).
The specific embodiment of the invention also provides a hydrophilic coating, which is prepared by the preparation method of the hydrophilic coating.
The hydrophilic coating according to embodiments of the present invention has excellent hydrophilicity and retention of hydrophilic properties after soaking in water, and in some embodiments, the water contact angle of the hydrophilic coating before soaking in water is 20 ° or less, further 15 ° or less, further 10 ° or less, and in some embodiments, the water contact angle of the hydrophilic coating after soaking in water is 30 ° or less, further 20 ° or less, and the water contact angle change rate of the hydrophilic coating before soaking is not more than 400%, further not more than 300%, further not more than 200%, further not more than 150% as compared with the water contact angle before soaking, as measured according to GB/T3047-2013.
Embodiments of the present invention also provide a device having a hydrophilic coating as described above on at least a portion of a surface of the device, and in some embodiments, a portion or all of a surface of the device is deposited with a hydrophilic coating as described above.
The invention is further illustrated by the following examples.
Examples
Description of the test methods
Coating thickness test: detection was performed using a U.S. FILMETRICS F-UV-film thickness gauge.
Coating water contact angle: the test was performed according to the GB/T3047-2013 standard.
Coating light transmittance and color difference: according to GB11186.3-1989, the method uses a spectrocolorimeter to detect, and delta E in the test result represents chromatic aberration,T represents light transmittance; l, a, b denote three color channels in the Lab color model, L denotes brightness, a denotes red-green, and b denotes yellow-blue.
Soaking water test: and (3) filling half a cup of water at room temperature by using a beaker with the capacity of 500ML, completely soaking a transparent glass sheet with the surface plated with the super-hydrophilic nano coating into the beaker, taking out the beaker after 10 minutes, and carrying out a coating water contact angle test after the water stain on the surface of the sample is completely drained.
Example 1
Placing a substrate transparent glass plate (length: 75mm, width: 26mm, thickness: 1 mm) in a 500L plasma vacuum reaction cavity, continuously vacuumizing the reaction cavity to enable the vacuum degree to reach 80 millitorr, introducing oxygen at the temperature of 50 ℃ in the cavity, and enabling the flow to be 160sccm;
Maintaining the air pressure of the cavity at 80 millitorr, maintaining the oxygen flow at 160sccm, starting the radio frequency plasma discharge, and continuously discharging the radio frequency energy in a discharge time of 600s and a discharge power of 300w;
then, monomer I and monomer II were mixed in a molar ratio of 2.6 according to the structure shown in Table 1 below: 1, after mixing, introducing the mixture into a reaction cavity, wherein the monomer gasification temperature is 110 ℃, the cavity air pressure is 80 millitorr, starting the radio frequency plasma discharge, and the radio frequency energy output mode is pulse, the discharge power, the monomer flow and the oxygen flow are as shown in the following table 1, the pulse frequency is 50Hz, the discharge time is 1800s, the pulse duty ratio is 45%, and a hydrophilic coating is formed on a transparent glass plate;
after the coating preparation is finished, air is introduced to restore the reaction cavity to normal pressure, the cavity is opened, the transparent glass plate is taken out for coating thickness and water contact angle testing, and the testing results are listed in table 1.
TABLE 1 monomer, plasma coating conditions, and related test results for example 1
Example 2
Placing a substrate transparent glass plate (length: 75mm, width: 26mm, thickness: 1 mm) in a 500L plasma vacuum reaction cavity, continuously vacuumizing the reaction cavity to enable the vacuum degree to reach 80 millitorr, introducing oxygen at the temperature of 50 ℃ in the cavity, and enabling the flow to be 160sccm;
Maintaining the air pressure of the cavity at 80 millitorr, maintaining the oxygen flow at 160sccm, starting the radio frequency plasma discharge, and continuously discharging the radio frequency energy in a discharge time of 600s and a discharge power of 300w;
then, monomer I and monomer II were mixed in a molar ratio of 2.6 according to the structure shown in Table 2 below: 1, after mixing, introducing the mixture into a reaction cavity, wherein the monomer gasification temperature is 110 ℃, the cavity air pressure is 80 millitorr, starting the radio frequency plasma discharge, and the radio frequency energy output mode is pulse, the discharge power, the monomer flow and the oxygen flow are as shown in the following table 2, the pulse frequency is 50Hz, the discharge time is 1800s, the pulse duty ratio is 45%, and a hydrophilic coating is formed on a transparent glass plate;
after the coating preparation is finished, air is introduced to restore the reaction cavity to normal pressure, the cavity is opened, the transparent glass plate is taken out for coating thickness and water contact angle testing, and the testing results are listed in table 2.
TABLE 2 monomer, plasma coating conditions, and related test results for example 2
Example 3
Placing a substrate transparent plastic PC board (length: 120mm, width: 50mm, thickness: 3 mm) in a 500L plasma vacuum reaction cavity, continuously vacuumizing the reaction cavity to enable the vacuum degree to reach 80 millitorr, introducing oxygen at the temperature of 50 ℃ in the cavity, and enabling the flow to be 160sccm;
Maintaining the air pressure of the cavity at 80 millitorr, maintaining the oxygen flow at 160sccm, starting the radio frequency plasma discharge, and continuously discharging the radio frequency energy in a discharge time of 600s and a discharge power of 300w;
Then, monomer I and monomer II were mixed in a molar ratio of 2.6 according to the structure shown in Table 3 below: 1, after mixing, introducing the mixture into a reaction cavity, wherein the monomer gasification temperature is 110 ℃, the cavity air pressure is 80 millitorr, starting the radio frequency plasma discharge, and the radio frequency energy output mode is pulse, the discharge power, the monomer flow and the oxygen flow are as shown in the following table 3, the pulse frequency is 50Hz, the discharge time is 1800s, the pulse duty ratio is 45%, and a hydrophilic coating is formed on a transparent glass plate;
After the coating preparation is finished, air is introduced to restore the reaction cavity to normal pressure, the cavity is opened, and the transparent plastic PC board is taken out for coating thickness and water contact angle test, and the test results are listed in Table 3.
TABLE 3 monomer, plasma coating conditions, and related test results for example 3
From the results of examples 1 and 3, it is evident that the plasma coatings of monomer I and monomer II formed on the transparent glass plate have super hydrophilicity compared to the transparent plastic PC plate, and that the plasma coatings of monomer I and monomer II are more suitable for glass substrates as super hydrophilicity coatings compared to the plastic PC plate.
Comparative examples 1 to 2
Placing a substrate transparent glass plate (length: 75mm, width: 26mm, thickness: 1 mm) in a 500L plasma vacuum reaction cavity, continuously vacuumizing the reaction cavity to enable the vacuum degree to reach 80 millitorr, introducing oxygen at the temperature of 50 ℃ in the cavity, and enabling the flow to be 160sccm;
Maintaining the air pressure of the cavity at 80 millitorr, maintaining the oxygen flow at 160sccm, starting the radio frequency plasma discharge, and continuously discharging the radio frequency energy in a discharge time of 600s and a discharge power of 300w;
Then, monomers with the structures shown in the following table 4 are introduced into a reaction cavity, the gasification temperature of the monomers is 110 ℃, the air pressure of the cavity is kept at 80 millitorr, the radio frequency plasma discharge is started, the energy output mode of the radio frequency is pulse, the discharge power, the monomer flow and the oxygen flow are shown in the following table 4, the pulse frequency is 50Hz, the discharge time is 1800s, the pulse duty ratio is 45%, and a hydrophilic coating is formed on a transparent glass plate;
after the coating preparation is finished, air is introduced to restore the reaction cavity to normal pressure, the cavity is opened, the transparent glass plate is taken out for coating thickness and water contact angle testing, and the testing results are listed in table 4.
Table 4 monomer of comparative examples 1-2, plasma coating conditions and related test results
Comparative example 3
Placing a substrate transparent glass plate (length: 75mm, width: 26mm, thickness: 1 mm) in a 500L plasma vacuum reaction cavity, continuously vacuumizing the reaction cavity to enable the vacuum degree to reach 80 millitorr, introducing oxygen at the temperature of 50 ℃ in the cavity, and enabling the flow to be 160sccm;
Maintaining the air pressure of the cavity at 80 millitorr, maintaining the oxygen flow at 160sccm, starting the radio frequency plasma discharge, and continuously discharging the radio frequency energy in a discharge time of 600s and a discharge power of 300w;
then, monomer I and monomer II with the structures shown in the following table 5 are respectively introduced into a reaction cavity in a mode of mixed spraying at the flow rates of 80 mu L/min and 20 mu L/min, the gasification temperature of the monomer is 110 ℃, the air pressure of the cavity is kept at 80 millitorr, the radio frequency plasma discharge is started, the energy output mode of the radio frequency is pulse, the discharge power and the oxygen flow are shown in the following table 5, the pulse frequency is 50Hz, the discharge time is 1800s, the pulse duty ratio is 45%, and a hydrophilic coating is formed on a transparent glass plate;
after the coating preparation is finished, air is introduced to restore the reaction cavity to normal pressure, the cavity is opened, the transparent glass plate is taken out for coating thickness and water contact angle testing, and the testing results are listed in table 5.
TABLE 5 monomer of comparative example 3, plasma coating conditions and related test results
The uncoated glass sheets, 1-1, 1-3, 1-5, 1-7, 1-8, 1-9 of example 1, and the coatings of comparative examples 1-3 were selected for the water soaking test, and the color difference and transmittance of the coatings before water soaking were tested, and the results are shown in Table 6 below.
TABLE 6 results of bubble test, color difference and transmittance test
As can be seen from the results in table 6, the plasma coatings prepared from the monomers i and ii of examples 1 and 2 have smaller water droplet angle change rate after soaking in water than the corresponding monomers of comparative examples 1 and 2, indicating that the plasma coatings prepared from the monomer combinations are less affected by water molecules and still maintain better hydrophilic performance after contact reaction with water molecules; compared with the comparative example 3 in which the monomer I and the monomer II enter the reaction cavity through different inlet openings to carry out the plasma coating, in the embodiment 1, the monomer I and the monomer II enter the reaction cavity to carry out the plasma coating after being fully and uniformly mixed in advance, and possibly because the reaction between the monomer I and the monomer II is more complete, the crosslinking reaction occurring during the coating is more complete, the consistency is better, the coating has stronger adhesive capacity and hydrophilicity after soaking water, and the durability of the hydrophilic membrane layer is improved. From the results of examples 1 and 2, it is clear that when monomer II includes epoxy end groups, the coating has relatively better hydrophilic properties after soaking due to better reactivity with monomer I when mixed.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.
Claims (14)
1. A method for preparing a hydrophilic coating, comprising the steps of:
providing a substrate, and placing the substrate in a plasma reactor; the monomer I and the monomer II are mixed and then gasified and introduced into a plasma reactor, plasma discharge is carried out, and plasma polymerization is carried out on the surface of the substrate to form the hydrophilic coating;
wherein the monomer I has a structure shown in the following formula (1),
In the formula (1), X is amino, hydroxyl or carboxyl, L 1 is alkylene of C 1-C30 or substituted alkylene of C 1-C30, wherein the substituent of the substituted alkylene is hydroxyl, amino or carboxyl, carbon-carbon connection bonds of the alkylene of C 1-C30 or the substituted alkylene of C 1-C30 are provided with-O-, -S-or-NH-, and R 1、R2 or R 3 are independently alkyl of C 1-C5 respectively;
The monomer II has a structure shown in the following formula (2),
R7-R5-O-L2-O-R4-R6 (2)
In the formula (2), L 2 is C 2-C10 alkylene or C 2-C10 substituted alkylene, wherein the substituent of the substituted alkylene is hydroxyl, R 4 and R 5 are respectively and independently a connecting bond, C 1-C4 alkylene, and R 6 and R 7 are respectively and independently methyl or epoxy.
2. The method of claim 1, wherein L 1 is an alkylene group of C 1-C4 and R 1、R2 or R 3 are each independently methyl, ethyl or propyl.
3. The method for producing a hydrophilic coating according to claim 2, wherein the monomer i is selected from compounds of the following structural formulae (1-1) to (1-12):
4. the method for producing a hydrophilic coating according to claim 1, wherein the monomer I has a structure represented by the following formula (3),
In the formula (3), R 1、R2 or R 3 are respectively methyl, ethyl or propyl independently, and n is 0, 1,2, 3 or 4.
5. The method for producing a hydrophilic coating according to claim 4, wherein the monomer i is selected from the group consisting of compounds of the following structural formulae (1-13) to (1-16):
6. The method for producing a hydrophilic coating according to claim 1, wherein the monomer ii is selected from compounds of the following structural formulae (2-1) to (2-20):
7. the method of producing a hydrophilic coating according to claim 1, wherein the monomer ii is selected from compounds of the following structural formulae (2-21) to (2-30):
8. The method of claim 1, wherein the molar ratio of monomer I to monomer II is 3:1 to 1:3.
9. The method for producing a hydrophilic coating according to claim 1, wherein the monomer i and the monomer ii are mixed and then gasified and introduced into the plasma reactor while introducing oxygen.
10. The method for preparing a hydrophilic coating according to claim 9, wherein the flow rate of the mixed gas of the monomer I and the monomer II is 20 to 200. Mu.L/min, and the flow rate of the oxygen is 20 to 200sccm.
11. The method of claim 1, wherein the plasma is a pulsed plasma, the pulsed plasma is generated by applying a pulsed voltage discharge, wherein the discharge power is 10W to 300W, the pulse frequency is 20Hz to 10kHz, the pulse duty cycle is 40% to 80%, and the plasma discharge time is 100s to 36000s.
12. The method of claim 1, wherein the substrate is a metal, ceramic, plastic, glass, electronic device, or optical device.
13. A hydrophilic coating, characterized in that it is prepared by the method for preparing a hydrophilic coating according to any one of claims 1 to 12.
14. A device characterized in that at least part of the surface of the device is provided with a hydrophilic coating according to claim 13.
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