CN116925606A - Hydrophilic coating, preparation method and device - Google Patents
Hydrophilic coating, preparation method and device Download PDFInfo
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- CN116925606A CN116925606A CN202210320685.2A CN202210320685A CN116925606A CN 116925606 A CN116925606 A CN 116925606A CN 202210320685 A CN202210320685 A CN 202210320685A CN 116925606 A CN116925606 A CN 116925606A
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- 238000000576 coating method Methods 0.000 title claims abstract description 126
- 239000011248 coating agent Substances 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 88
- 238000002834 transmittance Methods 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000011521 glass Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000012780 transparent material Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000004075 alteration Effects 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 22
- 238000005299 abrasion Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000001307 helium Substances 0.000 description 12
- 229910052734 helium Inorganic materials 0.000 description 12
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- -1 hydroxy, amino Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003203 everyday effect Effects 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 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
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 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
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F116/04—Acyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/52—Polymerisation initiated by wave energy or particle radiation by electric discharge, e.g. voltolisation
-
- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
-
- 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
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The coating of the specific embodiment of the application is formed by carrying out plasma polymerization on an olefin monomer, wherein the olefin monomer consists of a carbon-carbon double bond structure and saturated chain groups which are positioned on the carbon-carbon double bond and are selected from hydrogen atoms, halogen atoms, methyl groups, ethyl groups and hydrophilic end groups, and at least two saturated chain groups which are respectively positioned on two carbon atoms of the olefin double bond are arranged on the hydroxyl groups, carboxyl groups or amino hydrophilic end groups, and the coating formed by carrying out plasma polymerization on the olefin monomer with the structure has excellent wear resistance, simultaneously has more excellent hydrophilic performance, has small chromatic aberration and excellent light transmittance, and is very suitable for hydrophilic anti-fog coatings.
Description
Technical Field
The application 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 base material, so that a PECVD technology is adopted to provide a better choice for preparing the hydrophilic anti-fog coating, and the inventor can prepare and obtain the hydrophilic anti-fog coating by utilizing an acrylic acid monomer and adopting PECVD to prepare the hydrophilic coating as disclosed in CN 111501023A.
Disclosure of Invention
The specific embodiment of the application provides a plasma hydrophilic coating which is different from the prior art, and the specific scheme is as follows:
a hydrophilic coating, the coating being a plasma polymerized coating formed from a substrate contacted with a plasma comprising a monomer of formula (1);
in the formula (1), R 1 、R 2 、R 3 And R is 4 Independently selected from a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a group represented by formula (2), and R 1 And R is 3 At least one of them is a group represented by the formula (2), R 2 And R is 4 At least one of them is a group represented by the formula (2);
*-L-X
(2)
in the formula (2), L is C 1 -C 30 Alkylene or C of (2) 1 -C 30 A substituted alkylene group of (a), wherein the substituent of the substituted alkylene group is a hydroxyl group, an amino group or a carboxyl group;
the C is 1 -C 30 Alkylene or C of (2) 1 -C 30 With or without-O-, with or without-O-; -S-or-NH-, and X is hydroxyl, carboxyl or amino.
Optionally, the L is C 1 -C 4 Alkylene groups of (a).
Alternatively, the L is methylene or ethylene.
Optionally, the group of the formula (2) is a structure shown in the formula (3),
in the formula (3), n is 1, 2, 3 or 4.
Optionally, the R 1 And R is 2 Is a hydrogen atom, R 3 And R is 4 Is a group represented by formula (2).
Alternatively, the monomer of formula (1) has a structure represented by formula (4),
in formula (4), x1 and x2 are each independently 1, 2, 3 or 4.
Optionally, the monomer of formula (1) is a monomer of formula (4-1), formula (4-2), formula (4-3), formula (4-4), formula (4-5), formula (4-6) or formula (4-7)
Alternatively, the monomer of formula (1) has a structure represented by formula (5),
in formula (5), x3 and x4 are each independently 1, 2, 3 or 4.
Optionally, the monomer of formula (1) is a monomer of formula (5-1) or formula (5-2)
Optionally, the substrate is metal, ceramic, plastic, glass, electronic device or optical instrument.
Optionally, the substrate is a transparent material.
Optionally, the light transmittance of the coating is above 90%.
Optionally, the coating has a measured water contact angle of 10 ° or less.
Alternatively, the coating has a water contact angle of less than 10 ° measured after rubbing 1000 times with a dust-free cloth at a load of 1N.
The preparation method of the hydrophilic coating comprises the following steps:
providing a substrate, and placing the substrate in a plasma reactor; introducing the gaseous monomer of formula (1) into a plasma reactor, discharging plasma, and polymerizing the plasma on the surface of the substrate to form a coating.
Optionally, the plasma is a pulsed plasma.
Optionally, the pulse plasma is generated by applying pulse voltage discharge, wherein the pulse power is 10-300W, the pulse duty ratio is 40-80%, and the plasma discharge time is 100-36000 s.
Alternatively, the monomer of formula (1) is first added to an alcohol solvent to prepare a solution, and then vaporized and introduced into a plasma reactor.
Optionally, the alcohol is one or more of methanol, ethanol or propanol.
A device having a hydrophilic coating as described above on at least part of its surface.
The hydrophilic coating of the specific embodiment of the application is formed by carrying out plasma polymerization on an olefin monomer shown in the formula (1), wherein the olefin monomer consists of a carbon-carbon double bond structure and saturated chain groups which are positioned on the carbon-carbon double bond and are selected from hydrogen atoms, halogen atoms, methyl groups, ethyl groups and hydrophilic end groups with hydroxyl groups, carboxyl groups or amino groups shown in the formula (2), at least two saturated chain groups with hydrophilic end groups shown in the formula (2) are respectively positioned on two carbon atoms of the olefin double bond, and the coating formed by carrying out plasma polymerization on the olefin monomer with the structure has excellent wear resistance, simultaneously has more excellent hydrophilic performance, has small chromatic aberration and excellent light transmittance, and is very suitable for hydrophilic anti-fog coatings.
Detailed Description
Embodiments of the present application provide a hydrophilic coating that is a plasma polymerized coating formed from a substrate contacted with a plasma comprising a monomer of formula (1);
in the formula (1), R 1 、R 2 、R 3 And R is 4 Independently selected from a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a group represented by formula (2), and R 1 And R is 3 At least one of them is a group represented by the formula (2), R 2 And R is 4 At least one of them is a group represented by the formula (2);
*-L-X (2)
in the formula (2), L is C 1 -C 30 Alkylene or C of (2) 1 -C 30 A substituted alkylene group of (a), wherein the substituent of the substituted alkylene group is a hydroxyl group, an amino group or a carboxyl group;
the C is 1 -C 30 Alkylene or C of (2) 1 -C 30 With or without-O-, with or without-O-; -S-or-NH-, and X is hydroxyl, carboxyl or amino.
The hydrophilic coating of the specific embodiment of the application comprises a monomer with a structure shown in a formula (1), a saturated chain group which is positioned on the carbon-carbon double bond and is selected from hydrogen atoms, halogen atoms, methyl groups, ethyl groups and hydrophilic end groups with hydroxyl groups, carboxyl groups or amino groups shown in a formula (2), wherein at least two saturated chain groups with hydrophilic end groups shown in the formula (2) are respectively positioned on two carbon atoms of an olefin double bond, and the monomer with the structure is easy to form a compact and uniform hydrophilic coating in a plasma polymerization process, has excellent wear resistance, simultaneously has more excellent hydrophilic performance, small chromatic aberration and excellent light transmittance, and is very suitable for hydrophilic anti-fog coatings.
The hydrophilic coating of the embodiment of the application, wherein L is C 1 -C 30 Alkylene or C of (2) 1 -C 30 The substituent of the substituted alkylene is hydroxy, amino or carboxyl, meaning that in some embodiments, the L is C 1 -C 30 In some embodiments, L is C with hydroxy, amino or carboxyl substituents 1 -C 30 Alkylene groups of (a).
In the hydrophilic coating according to the embodiment of the present application, R in the monomer having the structure represented by formula (1) 1 、R 2 、R 3 And R is 4 In the case of the group of formula (2), are independent of each other, for example, when R 1 And R is 3 R is a group of the formula (2) 1 And R is 3 The L chains in the two groups may be identical or not, R 1 And R is 3 X in (a) may be the same as, for example, hydroxyl, carboxyl or amino, or may be different from, for example, R 1 Wherein X is hydroxy, R 3 X in (2) is carboxyl.
In some embodiments, the hydrophilic coating of embodiments of the present application, in formula (2), L is C 1 -C 30 Alkylene or C of (2) 1 -C 30 Substituted alkylene of (C) 1 -C 30 Alkylene or C of (2) 1 -C 30 With or without-NH-between carbon-carbon linkages of the substituted alkylene group.
Hydrophilic coatings according to embodiments of the application, the C 1 -C 30 Alkylene or C of (2) 1 -C 30 The substituted alkylene group of (a) may be a linear or branched alkylene group, but the C is given better abrasion resistance and hydrophilicity 1 -C 30 Alkylene or C of (2) 1 -C 30 Is a linear alkylene group.
The hydrophilic coatings of embodiments of the present application, in some embodiments, in formula (1), R, in view of higher hydrophilic anti-fog properties 1 、R 2 、R 3 And R is 4 Independently selected from hydrogen atoms or groups of formula (2), e.g.The R is 1 And R is 2 Is a hydrogen atom, R 3 And R is 4 Is a group represented by formula (2).
The hydrophilic coatings of embodiments of the present application, in view of better hydrophilic anti-fog properties, in some embodiments, the L is C 1 -C 4 Further, in some embodiments, the L is methylene or ethylene.
In some embodiments, the hydrophilic coating of embodiments of the present application, the group of formula (2) is of the structure of formula (3),
in the formula (3), n is 1, 2, 3 or 4.
In some embodiments, the hydrophilic coating of embodiments of the present application, the monomer of formula (1) has a structure represented by formula (4),
in formula (4), x1 and x2 are each independently 1, 2, 3 or 4.
In some embodiments, the hydrophilic coating of embodiments of the present application, the monomer of the structure represented by formula (4) is a monomer of the structure represented by the following formula (4-1), formula (4-2), formula (4-3), formula (4-4), formula (4-5), formula (4-6), or formula (4-7).
In some embodiments, the hydrophilic coating of embodiments of the present application, the monomer of formula (1) has a structure represented by formula (5),
in formula (5), x3 and x4 are each independently 1, 2, 3 or 4.
In some embodiments, the hydrophilic coating of embodiments of the present application is a monomer of the structure represented by formula (5) is a monomer of the structure represented by the following formula (5-1) or formula (5-2).
In some embodiments, the substrate is made of metal, ceramic, plastic, glass, polymer, electronic device, optical instrument, or the like.
The hydrophilic coating of embodiments of the present application, in some embodiments, has a water contact angle of less than 10 ° as measured according to GB/T30047-2013, and water drops can spread on the surface of the coating and form a relatively uniform water film, thereby reducing diffuse reflection of light to perform an anti-fog function, and thus, in some embodiments, is particularly suitable for use as an anti-fog coating of transparent materials, such as, for example, lenses for glasses, goggles, laser goggles, telescopes and lenses for various imaging devices, various mechanical viewing windows, moving goggles, bathroom glasses, chemical or biological respirators, vehicle windshields and rear-view mirrors, explosion-proof treatment protection devices, helmets, solar panels, viewing windows for measuring instruments, glass covers, glass walls for greenhouses, and the like. Further, in some embodiments, the coating has super-hydrophilic properties, with a water contact angle of less than 5 ° as measured according to GB/T30047-2013.
In some embodiments, the hydrophilic coatings of embodiments of the present application have a light transmittance of greater than 90% so as not to unduly affect the light transmittance properties of the transparent substrate.
In some embodiments, the hydrophilic coatings of embodiments of the present application have excellent abrasion resistance and hydrophilicity, and the coatings have a water contact angle of 10 ° or less as measured according to GB/T30047-2013 after being rubbed 1000 times with a dust-free cloth under a load of 1N.
In some embodiments, the hydrophilic coating of embodiments of the present application is a plasma polymerized coating formed from a plasma of a monomer of the structure of formula (1), and in other embodiments, the coating is a plasma polymerized coating formed from a plasma of a monomer of the structure of formula (1) and other monomers, as is particularly practical.
In some embodiments, the hydrophilic coating of embodiments of the present application, in some embodiments, the coating has a thickness of from 1 to 1000nm, specifically, for example, 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.
The specific embodiment of the application also provides a preparation method of the hydrophilic coating, which comprises the following steps:
providing a substrate, and placing the substrate in a plasma reactor; introducing the gaseous monomer of formula (1) into a plasma reactor, discharging plasma, and polymerizing the plasma on the surface of the substrate to form a coating.
According to the preparation method of the hydrophilic coating, the gaseous monomer raw material can be a chemical substance which is gaseous at normal temperature and pressure, or can be monomer steam formed by decompressing, heating and the like of a liquid substance at normal temperature and pressure.
The preparation method of the hydrophilic coating according to the embodiment of the present application is as described above for the monomer and the substrate.
In order to further enhance the bonding force between the plasma coating and the substrate, in some embodiments, the substrate is pretreated by continuous plasma before the coating, for example, the plasma discharge power is 20-500W in inert gas, oxygen or hydrogen atmosphere, the discharge mode is continuous, and the continuous discharge time is 1-60 min.
In some embodiments, the plasma of the monomer is plasma excited in a pulse mode, the flow rate of the monomer is 10 to 500 mu L/min, and specifically, for example, 10 mu L/min, 50 mu L/min, 100 mu L/min, 150 mu L/min, 200 mu L/min, 300 mu L/min, 400 mu L/min, or the like, and in some embodiments, the flow rate of the monomer is 100 mu L/min or more in consideration of the influence of the amount of the monomer on hydrophilicity; the temperature in the cavity is controlled at 20-80 ℃, 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 monomer vaporization temperature is 50-180 ℃, specifically, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, etc., and vaporization occurs under vacuum conditions, the pulsed plasma is generated by applying a pulsed voltage discharge, wherein the pulsed power is 10W to 300W, specifically, for example, 10W, 20W, 30W, 50W, 70W, 80W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W, 300W, etc., and in some embodiments, 40W to 100W; 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., and in some embodiments, the pulse duty cycle is 40% to 80% in view of better hydrophilicity, and further the pulse duty cycle is 45% to 75%; the plasma discharge time is 100s-36000s, and specifically, for example, 100s, 500s, 1000s, 1800s, 2000s, 1000s, 2000s, 3000s, 4000s, 5000s, 6000s, 7000s, 7200s, 10800s, 14400s, 18000s, 21600s, 25200s, 28800s, 32400s, 36000s, or the like may be used.
In some embodiments, the plasma discharge mode may be any of various existing discharge modes, for example, electrodeless discharge (such as rf inductively coupled discharge, microwave discharge), single electrode discharge (such as corona discharge, plasma jet formed by unipolar discharge), double electrode discharge (such as dielectric barrier discharge, bare electrode rf glow discharge), and multi-electrode discharge (such as discharge using a floating electrode as a third electrode).
In some embodiments, the monomer of formula (1) is added into an alcohol solvent to prepare a solution, and then the solution is vaporized into a plasma reactor, so that the vaporization temperature of the monomer can be reduced, and the vaporization of the monomer is more beneficial, for example, when X is amino or carboxyl in the monomer of the structure shown in formula (4) or formula (5), the boiling point is relatively high, the monomer can be firstly added into the alcohol solvent to prepare the solution, and then the solution is vaporized into the plasma reactor at relatively low temperature, so that the prepared coating also has excellent wear resistance, hydrophilicity and the like, and in some embodiments, the alcohol is one or more of methanol, ethanol or propanol.
Embodiments of the present application also provide a device having at least a portion of its surface provided with any of the hydrophilic coatings described above, in some embodiments, a portion or all of its surface is deposited with a hydrophilic coating as described above.
The application is further illustrated by the following examples.
Examples
Description of the test methods
Coating thickness test: detection was performed using a Filmetrics F20-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: calculation is carried out according to the GB11186.3-1989 standard, a spectrocolorimeter is used for detection, 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.
Friction performance test: the water contact angle change before and after rubbing was measured by rubbing 1000 times with a dust-free cloth under a load of 1N using a reciprocating type abrader.
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 helium gas at the temperature of 45 ℃ in the cavity, and enabling the flow to be 40sccm;
maintaining the air pressure of the cavity at 80 millitorr, maintaining the helium flow at 40sccm, starting the radio frequency plasma discharge, and continuously discharging the energy output mode of the radio frequency for 30s and the discharge power at 300w;
then, introducing the monomer according to the monomer and the monomer flow rate with the structures shown in the following table 1, wherein the monomer gasification temperature is 110 ℃, the cavity air pressure is kept at 80 millitorr, the helium flow rate is kept at 40sccm, the radio frequency plasma discharge is started, the radio frequency energy output mode is pulse, the discharge power and the pulse duty ratio are as shown in the following table 1, the pulse frequency is 50Hz, the discharge time is 1800s, and a 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.
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 helium gas at the temperature of 45 ℃ in the cavity, and enabling the flow to be 40sccm;
maintaining the air pressure of the cavity at 80 millitorr, maintaining the helium flow at 40sccm, starting the radio frequency plasma discharge, and continuously discharging the energy output mode of the radio frequency for 30s and the discharge power at 300w;
then, monomers with the structures shown in the table 1 and the monomer flow are introduced, the monomer gasification temperature is 110 ℃, the cavity air pressure is 80 millitorr, the helium flow is 40sccm, the radio frequency plasma discharge is started, the radio frequency energy output mode is pulse, the discharge power and the pulse duty ratio are as shown in the table 1 below, the pulse frequency is 50Hz, the discharge time is 1800s, and a coating is formed on the 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 example 1, monomer of comparative examples 1-2, plasma coating conditions and test results
From the results in table 1 above, it is clear that under the same conditions, the monomers of the structure shown in example 1, having a double bond and two hydroxyl groups distributed on both sides of the double bond and located at the ends of the saturated carbon chain, produced a coating having a water contact angle far smaller than that of the coating produced from the monomers of the structure shown in comparative example 1 having a double bond and two hydroxyl groups and the monomers of the structure shown in comparative example 2 having a double bond and a single hydroxyl group under the same production conditions, showed that the coating produced from the monomers of the structure shown in example 1, plasma had better hydrophilic properties. As can be seen from comparison of the plasma coating conditions in example 1, the influence of the pulse duty cycle on the water contact angle is relatively large, and when the pulse duty cycle is 45%, 60% and 75%, the water contact angle is the smallest by 5 degrees, which shows that the monomer has better hydrophilicity in the coating prepared by the monomer with the pulse duty cycle of 40-80% or further 45-75%, and in addition, when the monomer flow rate is too small, the hydrophilicity of the formed coating is not as good as that of the coating formed under the monomer flow rate of 100 mu L/min.
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 helium gas at the temperature of 45 ℃ in the cavity, and enabling the flow to be 40sccm;
maintaining the air pressure of the cavity at 80 millitorr, maintaining the helium flow at 40sccm, starting the radio frequency plasma discharge, and continuously discharging the energy output mode of the radio frequency for 30s and the discharge power at 300w;
then introducing a monomer with the structure shown in the following formula (4-1), wherein the monomer flow is 100 mu L/min, the monomer gasification temperature is 110 ℃, the cavity air pressure is 80 millitorr, the helium flow is 40sccm, the radio frequency plasma discharge is started, the radio frequency energy output mode is pulse, the discharge time is 1800s, the discharge power is 80w, the pulse frequency is 50Hz, the pulse duty ratio is 45%, and a coating is formed on a transparent glass plate;
after the coating preparation was completed, air was introduced to restore the reaction chamber to normal pressure, the chamber was opened, and the transparent glass plate was taken out to perform coating thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance test, and the test results are shown in table 2 below.
Example 3
The thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in the same manner as in example 2 except that the monomer of the structure of formula (4-1) in example 2 was replaced with the monomer of the structure of formula (4-3), and the test results are shown in Table 2 below.
Example 4
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 helium gas at the temperature of 45 ℃ in the cavity, and enabling the flow to be 40sccm;
maintaining the air pressure of the cavity at 80 millitorr, maintaining the helium flow at 40sccm, starting the radio frequency plasma discharge, and continuously discharging the energy output mode of the radio frequency for 30s and the discharge power at 300w;
then preparing a mixed solution of a monomer with a structure shown in the following formula (4-5) and ethanol according to the proportion of 70 wt%, gasifying the mixed solution at 110 ℃, introducing the gasified mixed solution into a reaction cavity at the flow rate of 150 mu L/min, keeping the air pressure of the cavity at 80 millitorr, keeping the flow rate of helium at 40sccm, starting radio-frequency plasma discharge, and forming a coating on a transparent glass plate, wherein the energy output mode of the radio-frequency is pulse, the discharge time is 1800s, the discharge power is 100w, the pulse frequency is 50Hz, and the pulse duty ratio is 45%;
after the coating preparation was completed, air was introduced to restore the reaction chamber to normal pressure, the chamber was opened, and the transparent glass plate was taken out to perform coating thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance test, and the test results are shown in table 2 below.
Example 5
The thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in the same manner as in example 4 except that the monomer of the structure of the formula (4-5) in example 4 was replaced with the monomer of the structure of the following formula (5-1), and the test results are shown in Table 2 below.
Example 6
The thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in the same manner as in example 2 except that the monomer of the structure of the formula (4-1) in example 2 was replaced with the monomer of the structure of the following formula (4-7), and the test results are shown in Table 2 below.
Example 7
The transparent glass plate in example 2 was replaced with a transparent PC (polycarbonate) sheet, and the thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in accordance with example 2, and the test results are shown in table 2 below.
Example 8
The transparent glass plate in example 3 was replaced with a transparent PC (polycarbonate) sheet, and the thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in accordance with example 3, and the test results are shown in table 2 below.
Example 9
The transparent glass plate in example 4 was replaced with a transparent PC (polycarbonate) sheet, and the thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in accordance with example 4, and the test results are shown in table 2 below.
Example 10
The transparent glass plate in example 5 was replaced with a transparent PC (polycarbonate) sheet, and the thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in accordance with example 5, and the test results are shown in table 2 below.
Example 11
The transparent glass plate in example 6 was replaced with a transparent PC (polycarbonate) sheet, and the thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in accordance with example 6, and the test results are shown in table 2 below.
Comparative example 3
The thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in the same manner as in example 2 except that the monomer of the structure of formula (4-1) in example 2 was replaced with the monomer of the structure of formula (6), and the test results are shown in table 2 below.
Comparative example 4
The thickness, light transmittance, chromaticity value, water contact angle and abrasion resistance of the obtained coating were tested in the same manner as in example 2 except that the monomer of the structure of formula (4-1) in example 2 was replaced with the monomer of the structure of formula (7) below, and the test results are shown in table 2 below.
TABLE 2 results of Performance test of examples 2-11 and comparative examples 3-4
From the results of table 2, it is clear that the coatings of examples 2 to 11 all have a water contact angle of 5 ° before rubbing, which is much lower than the water contact angles of 62 ° and 76 ° of the coatings of comparative examples 2 and 3, thereby further indicating that the coatings prepared have a double bond and two hydrophilic groups selected from hydroxyl groups, carboxyl groups or amino groups, which are distributed on both sides of the double bond and are located at the chain ends, which are the type of monomer having more excellent hydrophilic properties. Meanwhile, as is apparent from the results of table 2, the coatings prepared in examples 2 to 11 have excellent abrasion resistance, and after abrasion with a dust-free cloth 1000 times under a load of 1N using a reciprocating type abrasion machine, the change of the water contact angle is quite small, not more than 2 °, and the color difference of the coating is very small, only about 0.5, and the light transmittance is very good, and on the contrary, the coating has an anti-reflection effect to some extent. In addition, as is clear from examples 4, 5, 9 and 10, for monomers having a higher boiling point, the boiling point of the monomers can be reduced by adding ethanol, and the finally obtained coating also has excellent hydrophilicity, abrasion resistance, small color difference and excellent light transmittance.
Although the present application is disclosed above, the present application 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 application, and the scope of the application should be assessed accordingly to that of the appended claims.
Claims (20)
1. A hydrophilic coating, characterized in that the hydrophilic coating is a plasma polymerized coating formed by contacting a substrate with a plasma comprising a monomer of formula (1);
in the formula (1), R 1 、R 2 、R 3 And R is 4 Independently selected from a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a group represented by formula (2), and R 1 And R is 3 At least one of them is a group represented by the formula (2), R 2 And R is 4 At least one of them is a group represented by the formula (2);
*-L-X
(2)
in the formula (2), L is C 1 -C 30 Alkylene or C of (2) 1 -C 30 A substituted alkylene group of (a), wherein the substituent of the substituted alkylene group is a hydroxyl group, an amino group or a carboxyl group;
the C is 1 -C 30 Alkylene or C of (2) 1 -C 30 With or without-O-, with or without-O-; -S-or-NH-, and X is hydroxyl, carboxyl or amino.
2. The hydrophilic coating of claim 1 wherein L is C 1 -C 4 Alkylene groups of (a).
3. The hydrophilic coating of claim 2 wherein L is methylene or ethylene.
4. The hydrophilic coating according to claim 1, wherein the group of formula (2) has a structure represented by formula (3),
in the formula (3), n is 1, 2, 3 or 4.
5. The hydrophilic coating of claim 1 wherein R is 1 And R is 2 Is a hydrogen atom, R 3 And R is 4 Is a group represented by formula (2).
6. The hydrophilic coating according to claim 1, wherein the monomer of formula (1) has a structure represented by formula (4),
in formula (4), x1 and x2 are each independently 1, 2, 3 or 4.
7. The hydrophilic coating according to claim 6, wherein the monomer of formula (1) is a monomer of the structure represented by formula (4-1), formula (4-2), formula (4-3), formula (4-4), formula (4-5), formula (4-6) or formula (4-7)
8. The hydrophilic coating according to claim 1, wherein the monomer of formula (1) has a structure represented by formula (5),
in formula (5), x3 and x4 are each independently 1, 2, 3 or 4.
9. The hydrophilic coating according to claim 8, wherein the monomer of formula (1) is a monomer of the structure represented by formula (5-1) or formula (5-2)
10. The hydrophilic coating of claim 1, wherein the substrate is a metal, ceramic, plastic, glass, electronic device, or optical device.
11. The hydrophilic coating of claim 10 wherein the substrate is a transparent material.
12. The hydrophilic coating of claim 1 wherein the coating has a light transmittance of greater than 90%.
13. The hydrophilic coating of claim 1 wherein the coating has a measured water contact angle of 10 ° or less.
14. The hydrophilic coating of claim 13 wherein the coating has a measured water contact angle of 10 ° or less after rubbing 1000 times with a dust-free cloth at a load of 1N.
15. A method for producing a hydrophilic coating according to any one of claims 1 to 14, comprising the steps of:
providing a substrate, and placing the substrate in a plasma reactor; introducing the gaseous monomer of formula (1) into a plasma reactor, discharging plasma, and polymerizing the plasma on the surface of the substrate to form a coating.
16. The method of claim 15, wherein the plasma is a pulsed plasma.
17. The method of claim 16, wherein the pulsed plasma is generated by applying a pulsed voltage discharge, wherein the pulsed power is 10W to 300W, the pulsed duty cycle is 40% to 80%, and the plasma discharge time is 100s to 36000s.
18. The preparation method according to claim 15, wherein the monomer of formula (1) is first added to an alcohol solvent to prepare a solution, and then vaporized and introduced into a plasma reactor.
19. The method of claim 18, wherein the alcohol is one or more of methanol, ethanol, or propanol.
20. A device, characterized in that at least part of the surface of the device is provided with a hydrophilic coating according to any one of claims 1-14.
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| CN202210320685.2A CN116925606A (en) | 2022-03-29 | 2022-03-29 | Hydrophilic coating, preparation method and device |
| PCT/CN2023/081534 WO2023185465A1 (en) | 2022-03-29 | 2023-03-15 | Hydrophilic coating, preparation method, and device |
| TW112110302A TW202348578A (en) | 2022-03-29 | 2023-03-20 | Hydrophilic coating, preparation method, and device |
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| US5723219A (en) * | 1995-12-19 | 1998-03-03 | Talison Research | Plasma deposited film networks |
| EP1643005A3 (en) * | 2004-09-01 | 2008-03-19 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Depositing organic and/or inorganic nanolayers by plasma discharge |
| CN101935821B (en) * | 2010-10-25 | 2013-03-06 | 上海理工大学 | Preparation method of polymaleic anhydride film |
| CN110144569A (en) * | 2019-07-03 | 2019-08-20 | 东莞市和域战士纳米科技有限公司 | The preparation method of long-acting hydrophilic film |
| CN111501023A (en) * | 2020-04-30 | 2020-08-07 | 江苏菲沃泰纳米科技有限公司 | Hydrophilic antifogging film layer, preparation method, application and product thereof |
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