CN115079317A - Goggles with hydrophilic antifogging film layer and film coating method - Google Patents
Goggles with hydrophilic antifogging film layer and film coating method Download PDFInfo
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- CN115079317A CN115079317A CN202110271894.8A CN202110271894A CN115079317A CN 115079317 A CN115079317 A CN 115079317A CN 202110271894 A CN202110271894 A CN 202110271894A CN 115079317 A CN115079317 A CN 115079317A
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- hydrophilic
- film layer
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- lens
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000007888 film coating Substances 0.000 title claims description 9
- 238000009501 film coating Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 134
- 238000000576 coating method Methods 0.000 claims abstract description 72
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims description 89
- -1 titanium-oxygen organic compound Chemical class 0.000 claims description 69
- 239000011248 coating agent Substances 0.000 claims description 59
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 50
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- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 36
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 11
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- 238000002834 transmittance Methods 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
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- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
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- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 14
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
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- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
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- 239000004744 fabric Substances 0.000 description 5
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 5
- 229960004065 perflutren Drugs 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 125000005023 xylyl group Chemical group 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- 125000004799 bromophenyl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 4
- 125000000068 chlorophenyl group Chemical group 0.000 description 4
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000012994 photoredox catalyst Substances 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
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- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
-
- 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
- C23C16/06—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 deposition of metallic material
- C23C16/18—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 deposition of metallic material from metallo-organic compounds
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- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- 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
-
- 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
- C23C16/513—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 using plasma jets
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
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- Surface Treatment Of Optical Elements (AREA)
Abstract
The invention provides goggles with a hydrophilic anti-fog film layer and a coating method, wherein lenses of the goggles are coated with the hydrophilic anti-fog film layer, and the hydrophilic anti-fog film layer is formed on the surfaces of the lenses by using a hydrophilic raw material as a reaction raw material through a plasma chemical vapor deposition method.
Description
Technical Field
The invention relates to the field of goggles, in particular to goggles with a hydrophilic antifogging film layer and a film coating method.
Background
Fogging is a relatively common problem for eyewear. When the temperature and relative humidity conditions in the space between the lens of the goggle and the wearer's face and eyes have reached the dew point, saturated water vapor can condense on the surface of the goggle, causing the goggle to become blurred by the moisture, thereby affecting the wearer's vision.
Generally, current goggles are generally designed to prevent fogging, but the dew point of the environment in which they are located is affected by a variety of factors, such as varying temperature, humidity, pressure, ventilation conditions, etc., and thus, many times, they still fog. For example, when the movement of the wearer wearing the goggles becomes severe, the difference in temperature between the closed space on the inner surface side and the closed space on the outer surface side of the goggles becomes large, resulting in fogging, or the wearer sweats due to wearing the goggles for a long time, resulting in fogging due to an increase in humidity of the exhaled air.
Currently, the choice of goggles is to prevent fogging by, for example, increasing the airflow into the goggles to remove moisture or higher temperatures to balance the internal and external environment of the goggles, or heating the goggles to remove the water mist, which obviously requires additional mechanical structure and increases the weight of the goggles as well as the manufacturing cost.
Disclosure of Invention
An advantage of the present invention is to provide goggles with a hydrophilic anti-fog film layer and a method for coating the same, wherein the goggles are provided with a hydrophilic film layer, in which water droplets can be spread on the surface of the hydrophilic film layer to form a film, thereby reducing the diffused reflection of light to achieve the anti-fog purpose, which can achieve the anti-fog function without depending on a complicated mechanical structure.
Another advantage of the present invention is to provide eyewear with a hydrophilic anti-fog film layer and a method for coating the same, wherein the hydrophilic film layer has a high transparency without affecting the light transmission properties of the eyewear itself.
Another advantage of the present invention is to provide goggles with a hydrophilic anti-fog film layer and a coating method by which the hydrophilic film layer can be formed on lenses of various types of goggles, such as those made of PP, PET and PC, without affecting the clarity of the goggle lenses themselves.
Another advantage of the present invention is to provide goggles with a hydrophilic anti-fog film layer and a coating method, in which the goggles provided with the hydrophilic film layer have a long-lasting anti-fog function.
According to an aspect of the present invention, there is provided goggles with a hydrophilic anti-fog film layer coated on lenses thereof, wherein the hydrophilic anti-fog film layer is formed on the surfaces of the lenses by a plasma chemical vapor deposition method using a hydrophilic raw material as a reaction raw material.
According to one embodiment of the invention, the lens is made of a material selected from the group consisting of PP, PET and PC.
According to one embodiment of the invention, the contact angle of the lens plated with the hydrophilic anti-fog film layer is not more than 10 °.
According to one embodiment of the invention, the light transmittance of the hydrophilic anti-fog film layer is greater than 90%.
According to one embodiment of the invention, the hydrophilic anti-fog film layer has a thickness of 20nm to 10 μm and a hardness of HB-4H.
According to one embodiment of the invention, the hydrophilic starting material is an olefin monomer and is selected from one or more of the group consisting of olefin monomers containing carboxylic acid groups, olefin monomers containing sulfonic acid groups and olefin monomers containing hydroxyl groups in combination.
According to one embodiment of the invention, the hydrophilic feedstock comprises a titania precursor source and a non-metallic dopant source, wherein the titania precursor source is selected from one or both of a titanium-based source compound plus an oxygen source and a titanium-oxygen organic compound.
According to an embodiment of the invention, the non-metal element in the non-metal doping source is selected from one or more of the combinations C, N, F and S.
According to one embodiment of the invention, the non-metallic dopant source is selected from a combination of nitrogen (N) 2 ) Ammonia (NH) 3 ) Acetylene (C) 2 H 2 ) Octafluoropropane (C) 3 F 8 ) One or more of them.
According to another aspect of the present invention, there is provided a plating method comprising the steps of:
introducing hydrophilic raw materials into a reaction chamber to serve as reaction raw materials; and
and carrying out plasma enhanced chemical vapor deposition on the surface of a lens of goggles in the reaction chamber to form the hydrophilic anti-fog film layer.
According to an embodiment of the invention, in the method, the process of forming the hydrophilic anti-fog film layer includes a pretreatment stage and a coating stage, in the pretreatment stage, the plasma discharge power is 150-600W, the discharge time is 60-450 s, and then the coating stage is entered, the plasma discharge power is adjusted to 10-200W, and the discharge time is 600-7200 s.
According to one embodiment of the invention, the step of introducing hydrophilic raw materials is implemented as:
introducing olefin monomers at a flow rate of 10-1000 mu L/min under a vacuum degree of 30-300 millitorr, wherein the olefin monomers are selected from one or more of olefin monomers containing carboxylic acid groups, olefin monomers containing sulfonic acid groups and olefin monomers containing hydroxyl groups.
According to one embodiment of the invention, the step of introducing hydrophilic raw materials is implemented as:
and introducing a titanium dioxide precursor source and a non-metal doping source under the vacuum degree of 30-300 mTorr, wherein the titanium dioxide precursor source is selected from one or two of a combined titanium-based source compound and an oxygen-based source and a titanium-oxygen organic compound.
According to one embodiment of the invention, the titanyl organic compound has the structural formula TiX, wherein X is an alkoxy group.
According to one embodiment of the invention, the titanium-based source compound has the structural formula TiY, wherein Y is a halogen.
According to an embodiment of the present invention, the titanyl organic compound is one or more selected from tetrabutyl titanate and tetraisopropyl titanate, ethyl titanate.
According to one embodiment of the invention, the temperature of the reaction chamber of the PECVD preparation equipment is controlled to be 30-60 ℃.
According to an embodiment of the present invention, in the above method, plasma enhanced chemical vapor deposition is performed on the lens surface of the goggle in the reaction chamber under cyclic coating conditions to form the hydrophilic anti-fog film layer, wherein plasma discharge is turned on for a preset time and then turned off for a preset time, which is primary coating, the cyclic coating is cyclic coating, and the reaction raw material supply is maintained throughout the process.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
The invention provides goggles with a hydrophilic anti-fog film layer and a film coating method. The water drops can be spread on the surface of the hydrophilic anti-fog film layer and form a relatively uniform water film, so that the diffuse reflection of light is reduced, and the anti-fog function is achieved. When the hydrophilic anti-fog film layer is attached to the lens surface of the goggles as a lens, the lens surface can be made to have a better anti-fog performance.
The hydrophilic antifogging film layer has good light transmission performance, so that the hydrophilic antifogging film layer can be applied to transparent lenses and cannot cause excessive influence on the light transmission performance of the transparent lenses. The light transmittance of the hydrophilic antifogging film layer can reach more than 90%. The lens can be made of materials such as but not limited to PC, PET, PP or glass, wherein PC refers to polycarbonate, PET refers to polyethylene terephthalate, and PP refers to polypropylene.
Further, the contact angle of the hydrophilic anti-fog film layer to water may be below 40 °, such as 30 °, 20 °, 10 °, 5 ° or lower, and may be maintained for a long time without ultraviolet light irradiation. For example, the contact angle is kept at the original level after being placed under visible light for 6 months.
The hydrophilic anti-fog film layer has excellent abrasion resistance and can be firmly combined with the lens. The contact angle can still be maintained at the original level after applying a load of 1KG and rubbing 2000 times with a wet dust-free cloth. For example, the contact angle of the hydrophilic anti-fog film layer was 9 °, after 6 months, the contact angle was still 9 °, and after applying a load of 1KG and rubbing 2000 times with a wet dust-free cloth, the contact angle was still 9 °.
The hydrophilic anti-fog film layer can be prepared to have a small thickness, for example, but not limited to, a thickness ranging from 10nm to 20000nm, for example, from 20nm to 10 μm.
According to an embodiment of the invention, the hydrophilic anti-fog film layer is formed on the lens surface by a Plasma Enhanced Chemical Vapor Deposition (PECVD) process. That is, during the preparation process, the lens surface is exposed to a chamber of a plasma enhanced chemical vapor deposition reaction apparatus, plasma is formed in the chamber, and the hydrophilic anti-fog film layer is formed on the surface of the lens through a reactive material deposition reaction.
Plasma Enhanced Chemical Vapor Deposition (PECVD) processes have many advantages over other existing deposition processes: (1) the dry film forming does not need to use organic solvent; (2) the plasma etches the surface of the lens, so that the deposited film has good adhesion with the lens; (3) the coating can be uniformly deposited on the surface of the irregular lens, and the gas phase permeability is extremely strong; (4) the coating has good designability, and compared with the micron-scale control precision of a liquid phase method, the chemical vapor method can control the thickness of the coating at a nanoscale scale; (5) the coating structure is easy to design, the chemical vapor method uses plasma for activation, a specific initiator is not required to be designed for initiating the composite coatings of different materials, and various raw materials can be compounded together by regulating and controlling input energy; (6) the compactness is good, the chemical vapor deposition method usually activates a plurality of active sites in the plasma initiation process, and is similar to the situation that a plurality of functional groups are arranged on one molecule in the solution reaction, and a cross-linking structure is formed among molecular chains through the plurality of functional groups; (7) as a coating treatment technical means, the coating treatment method has excellent universality, and the selection range of coating objects and raw materials used for coating is wide.
The Plasma Enhanced Chemical Vapor Deposition (PECVD) process generates plasma through glow discharge, the discharge method comprises radio frequency discharge, microwave discharge, intermediate frequency discharge, high frequency discharge and electric spark discharge, and the waveforms of the high frequency discharge and the intermediate frequency discharge are sinusoidal or bipolar pulses.
The hydrophilic antifogging film layer is prepared from a hydrophilic material, wherein the hydrophilic material can be various, for example, the hydrophilic material is doped with a nonmetallic photocatalytic substance which has better hydrophilic performance under visible light, and the nonmetallic substance can be C, N, F, S, B, P and halogen elements. It is understood that the photocatalytic material may be doped with a single non-metal, or may be doped with two or more non-metals, such as C, N or C, N, S co-doped. The photocatalytic substance may be a titanium dioxide type photocatalytic substance.
It is to be noted that, in the present invention, the photocatalytic substance is not directly prepared using titanium dioxide, but is prepared using a precursor source of titanium dioxide. The titania precursor source may be a titanium-based source compound and an oxygen-based source, which may generate titania groups in a plasma environment. The titania precursor source may be a titanyl organic compound that can generate a titania group in a plasma environment.
The titanium dioxide type hydrophilic anti-fog film layer is prepared by a titanium dioxide precursor source under the plasma condition, and has better hardness, light transmittance and hydrophilicity. Because the titanium dioxide precursor source and the non-metal doping source are simultaneously introduced into a PECVD reaction chamber for reaction, the doping of the non-metal doping source between titanium atoms and oxygen atoms is facilitated.
According to some embodiments of the present invention, the titanium-based source compound forming the hydrophilic anti-fog film layer has a structural formula of TiY, wherein Ti may be tetravalent and the Y group may be an inorganic group, such as a halogen. The titanium-based source compound may be titanium tetrachloride. The source of oxygen radicals may be oxygen or other oxygen bearing oxides.
The titanium oxide organic compound forming the hydrophilic anti-fog film layer has a structural formula of TiX, and the X group can be an organic group, such as an alkoxy group. According to some embodiments of the invention, the TiX may be one or more of tetrabutyl titanate, tetraisopropyl titanate, ethyl titanate.
It is understood that the titanium based source compound, the oxygen based source, and the titanium oxy-organic compound may be introduced together into the reaction chamber of the PECVD apparatus.
The elements of the non-metal source forming the hydrophilic anti-fog film layer may be C, N, F, S, B, P, a halogen element. The non-metal source can be a single substance or a mixture of substances. According to some embodiments of the invention, the non-metal source may be nitrogen (N) 2 ) Ammonia (NH) 3 ) Acetylene (C) 2 H 2 ) Octafluoropropane (C) 3 F 8 ) One or more of them.
According to some embodiments of the invention, the non-metal source may be C x F 2x+2 Or is C x F 2x Wherein x may be 1 to 6. The non-metal source may be an alkane or an alkene.
The hydrophilic antifogging film layer is prepared by hydrophilic materials, and the hydrophilic materials can be prepared by olefin monomers containing carboxylic acid groups, sulfonic acid groups or hydroxyl groups. The monomer forms active oxygen free radicals on the surface of the lens, can react with holes to generate oxygen holes, and has a hydrophilic surface, and the hydrophilic antifogging film layer provided by the invention does not cause C, O content change on the surface and oxygen-containing group change along with the increase of the standing time, so that the antifogging effect is reduced. In other words, the hydrophilic anti-fog film layer provided by the invention has long-acting anti-fog property.
The carboxylic acid group-containing olefinic monomer may have the following structural formula:
wherein R is 1 、R 2 、R 3 May be a hydrogen radical, an alkyl radical or an aromatic radical. R 1 、R 2 、R 3 May or may not be identical.
The alkenyl and carboxyl groups of the olefin-based monomer containing a carboxylic acid group may be directly linked or may be linked through other groups such as alkyl or aromatic groups.
The carboxylic acid group-containing olefinic monomer may be methacrylic acid, acrylic acid, or phenylacrylic acid.
The sulfonic acid group-containing olefin-based monomer may have the following structural formula:
wherein R is 4 、R 5 Or R 6 May be a hydrogen radical, an alkyl radical or an aromatic radical. R is 7 May be H or an alkyl or aromatic group. R is 7 Or a metal cation, so that the olefin monomer containing sulfonic acid group becomes sulfonate. R 12 Selected from the group consisting of a bond, an alkyl group, an aromatic group. R 4 、R 5 、R 6 、R 7 May or may not be identical.
The alkenyl group and the sulfonic group of the sulfonic acid group-containing olefin monomer may be directly bonded to each other, or may be bonded to each other through another group such as an alkyl group or an aromatic group.
The olefin monomer containing sulfonic acid group can be sodium vinyl sulfonate, phenyl vinyl sulfonic acid and sodium p-styrene sulfonate.
The hydroxyl group-containing olefinic monomer may have the following structural formula:
wherein R is 8 、R 9 Or R 10 Can be hydrogen radical, alkyl orThese are aromatic groups. R 11 Can be an alkyl group, an aromatic group, or-COO-R 13 Or is-OCO-R 14 Or is-CO-R 15 。R 13 、R 14 Or is R 15 May be an alkyl group or an aromatic group. R 8 、R 9 、R 10 May or may not be identical.
It is understood that the alkenyl and hydroxyl groups of the hydroxyl group-containing olefin monomer may also be directly linked. The hydroxyl-containing olefinic monomer may be hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The hydrophilic antifogging film layer is prepared from a hydrophilic material, wherein the hydrophilic material can be a material with hydrophilic functional groups formed by plasma polymerization. For example, the substrate surface may be provided with hydrophilic groups, which are then regenerated by reaction of the hydrophilic groups with a reactive group-containing reaction material.
In detail, the substrate surface may be provided with-OH groups, -COOH groups, -NH groups 2 group-NO 2 Group, -SO 3 H group and-N + R 3 Y - One of the radicals in which-N + R 3 Y - In which R may represent a lower alkyl group and Y represents a halogen atom. Alternatively, -COOH or-SO 3 The H atom in H can be replaced by alkali metal, alkaline earth metal or other metals, such as alkali metals like lithium, sodium, potassium, ruthenium, etc., alkaline earth metals like magnesium, calcium, strontium, barium, radium, etc., and other metals like cobalt, manganese, iron, etc.
The reactive material containing a reactive group may be a fluorocarbon-based surface active material having chlorosilyl groups at both molecular terminals to cause a reaction between a hydrophilic group on the surface of the substrate and a chlorosilyl group at one molecular terminal of the fluorocarbon. The reactive group-containing starting material may be X p Cl 3-p SiR 1 (CF 2 ) n R 2 S iX q Cl 3-q Wherein n represents an integer, R 1 And R 2 Representing alkylene groups or containing Si or oxygen atomsA substituent, X represents a hydrogen atom, an alkyl group or an alkoxy group substituent, and p and q represent 1 or 2. For example, it may be Cl 3 Si (CH 2 ) 2 (CF 2 ) 6 (CH 2 ) 2 SiCl 3 ，CH 2 ＝CH-(CF 2 ) 6- (CH 2 ) 2 SiCl 3 ，HSi (CH 3 ) 2 (CH 2 ) 2 (CF 2 ) 6 (CH 2 ) 2 SiCl 3 ，
Taking the substrate with-OH as an example, the chlorosilyl group reacts with the-OH group of the substrate in a plasma environment to convert the chlorosilyl bond into a hydrophilic silanol bond, thereby forming a fluorocarbon with a siloxy group to obtain a hydrophilic film layer. In addition, the film containing fluorine atoms is formed on the surface of the substrate through siloxane groups, so that the film has better scratch resistance.
The hydrophilic anti-fog film layer is prepared from a "hydrophilic" material that may be hydrophobic in an initial state and that may be converted to a hydrophilic material under certain conditions, such as visible light conditions or heated conditions. According to one embodiment of the invention, the material may have the following structural formula:
wherein in the above formula, L represents an organic group containing a polyvalent non-metallic atom or atoms necessary for attachment to the polymer backbone; r 1 And R 2 Each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or R 1 And R 2 May be bound together with a secondary carbon atom (CH) and combined with them to form a ring. When R is 1 And R 2 When each represents a substituted or unsubstituted alkyl group, as the alkyl group, a linear, branched or cyclic alkyl group having 1 to 25 carbons, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a cyclohexyl group, is preferably used. When R is 1 And R 2 When it is substituted aryl or unsubstituted aryl, the arylGroups include carbocyclic aryl and heterocyclic aryl. As the carbocyclic aryl group, a carbocyclic aryl group having 6 to 19 carbon atoms, such as phenyl, naphthyl, anthracenyl, can be used. Heterocyclic aryl groups include aryl groups containing 3 to 20 carbons and 1 to 5 heteroatoms, such as pyridyl, furyl, and aryl groups fused to one or more benzene rings, such as quinolyl, benzofuryl, thioxanthone, carbazole, and the like. When R is 1 And R 2 Is a substituted alkyl or substituted aryl group, the substituents including alkoxy of 1 to 10 carbons, such as methoxy or ethoxy; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; haloalkyl, such as trifluoromethyl or trichloromethyl; an alkoxycarbonyl or aryloxycarbonyl group of 2 to 15 carbons such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group or a p-chlorophenoxycarbonyl group; a hydroxyl group; acyloxy groups such as acetoxy, benzoyloxy or p-diphenylaminobenzoyloxy; carbonate groups such as tert-butoxycarbonyloxy; ether groups such as tert-butoxycarbonylmethoxy or 2-pyranoxy; substituted or unsubstituted amino, such as amino, dimethylamino, diphenylamino, morpholino or acetylamino; thioether groups, such as methylthio or phenylthio; alkenyl groups such as vinyl or styryl; nitro, cyano; acyl, such as formyl, acetyl or benzoyl; aryl, such as phenyl or naphthyl; and heteroaryl groups, such as pyridyl. When R is 1 And R 2 Is a substituted aryl group, and as the substituent, an alkyl group such as a methyl group or an ethyl group may be used in addition to the above groups.
The polyvalent linking group of one or more nonmetallic atoms represented by L is composed of 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More specifically, the linking group is composed of a combination of the following structural units:
according to one embodiment of the invention, the material may have the following structural formula:
wherein R is 3 Represents a hydrogen atom; r 4 Represents a hydrogen atom or an alkyl group of up to 18 carbons; r 5 Represents an alkyl group of up to 18 carbons. Alternatively, R 3 ，R 4 And R 5 Two of which may be bonded to each other to form a ring. In particular, R is preferred 4 And R 5 Bonded to each other to form a 5-or 6-membered ring.
According to one embodiment of the invention, the material may have the following structural formula:
wherein in the above formula, L represents an organic group comprising a polyvalent non-metallic atom or atoms necessary for attachment to the polymer backbone; r 1 And R 2 Each independently represents an alkyl group or an aromatic cyclic group. Or, R 1 、 R 2 May be bonded to each other to form a ring. R 1 And R 2 Each independently represents an alkyl group or an aromatic cyclic group. Alternatively, R 1 And R 2 May be bonded to each other to form a ring.
From R 1 And R 2 The alkyl group represented is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl. Or R 1 And R 2 May be represented by- (CH) 2 ) n Units of- (n-1 to 4) are bonded to each other.
Among these groups, R is particularly preferred 1 And R 2 With- (CH) 2 ) n Units of- (n-1 to 4) are bonded to each other to form a ring.
From R 1 And R 2 The alkyl group may be substituted or unsubstituted, and the substituent to be introduced is hydrogenOther monovalent non-metallic radicals. Alternative examples include halogen atoms such as F, Br, Cl and I, hydroxyl, alkoxy, amino, formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, phenyl, biphenyl, naphthyl, tolyl, xylyl, methanesulfonyl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, and the like.
From R 1 And R 2 The aromatic cyclic group represented may preferably be a group having 6 to 14 carbon atoms, for example, phenyl, biphenyl, naphthyl and mesityl, preferably phenyl and naphthyl.
From R 1 And R 2 The aromatic ring group represented may be substituted or unsubstituted, and the substituent to be introduced is a monovalent non-metallic atomic group other than hydrogen. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl groups, alkoxy groups, amino groups, formyl groups, acyl groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups and the like.
As R 1 And R 2 Particularly preferably, the group whose terminal structure is represented by the following formula includes a bonded carbonyl group and a nitrogen atom bonded to the carbonyl group.
According to one embodiment of the invention, the material may have the following structural formula:
in the above formula, L represents an organic group containing a polyvalent non-metallic atom or atoms necessary for attachment to the polymer backbone; r 3 And R 4 Each independently represents a monovalent substituent. Or, R 3 And R 4 Possibly combined with each other to form a ring. R 3 And R 4 Each independently represents a monovalent substituent, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, a formyl group, an acyl group, a carboxyl group, a cyano group or an aromatic cyclic group. When R is 3 And R 4 When alkyl, they preferably contain 1 to 8 carbonsAnd are exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl. Or R 3 And R 4 May be represented by- (CH) 2 ) n Units of- (n ═ 1 to 4) are bonded to each other. Among these groups, R is particularly preferred 3 And R 4 Is methyl, or is- (CH) 2 ) n - (n ═ 1 to 4) are units bonded to each other to form a ring, or a cyano group.
From R 3 And R 4 The alkyl group, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group or cyano group represented may be substituted or unsubstituted, and the substituent to be introduced is a group other than hydrogen which is a monovalent non-metal atom. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl, alkoxy, amino, formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, phenyl, biphenyl, naphthyl, tolyl, xylyl, methanesulfonyl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl and the like.
From R 3 And R 4 The aromatic ring group represented may be preferably an aromatic ring group having 6 to 14 carbon atoms, for example, a phenyl group, a biphenyl group, a naphthyl group and a mesityl group, preferably a phenyl group and a naphthyl group.
From R 3 And R 4 The aromatic ring group represented may be substituted or unsubstituted, and the substituent to be introduced is a monovalent non-metallic atomic group other than hydrogen. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl groups, alkoxy groups, amino groups, formyl groups, acyl groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups and the like.
In particular, R 3 And R 4 Preferably a substituted or unsubstituted aromatic cyclic group of 6 to 14 carbon atoms having at least one nitro group.
According to one embodiment of the invention, the material may have the following structural formula:
-L-SO 2 -NR 6 -SO 2 -R 5
in the above formula, L represents an organic group containing a polyvalent non-metallic atom or atoms necessary for bonding to the polymer skeleton; r 5 And R 6 Each independently represents an alkyl group or an aromatic cyclic group. Alternatively, R 5 And R 6 Each represents an organic group containing a polyvalent non-metallic atom or atoms necessary for attachment to the polymer backbone.
From R 5 And R 6 Preferred alkyl groups represented include, for example, a straight chain alkyl group having 1 to 25 carbon atoms, such as methyl, ethyl, propyl, butyl or pentyl, or a branched alkyl group having 1 to 8 carbon atoms, such as isopropyl, tert-butyl, sec-butyl, isopentyl or neopentyl. Among them, methyl, ethyl, isopropyl and tert-butyl are particularly preferable.
From R 5 And R 6 The alkyl group represented may be substituted or unsubstituted, and the substituent to be introduced is a monovalent non-metallic radical other than hydrogen. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl, alkoxy, amino, formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, phenyl, biphenyl, naphthyl, tolyl, xylyl, methanesulfonyl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl and the like.
From R 5 And R 6 The aromatic cyclic groups represented include carbocyclic aromatic groups and heterocyclic aromatic groups. As the carbocyclic aromatic group, preferred are those having 6 to 19 carbon atoms, more preferably formed of 1 to 4 benzene rings, such as phenyl, naphthyl, anthryl, biphenyl, xylyl or trimethyl. The heterocyclic aromatic group preferably includes a group having 3 to 20 carbon atoms and 1 to 5 hetero atoms, more preferably a pyridyl group, a furyl group, and a group condensed with one or more benzene rings, such as a quinolyl group, a benzofuryl group, a thioxanthone, a carbazole and the like.
From R 5 And R 6 The aromatic ring radical may be represented bySubstituted or unsubstituted, and the substituent to be introduced is a monovalent non-metallic radical other than hydrogen. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl groups, alkoxy groups, amino groups, formyl groups, acyl groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups and the like.
According to one embodiment of the invention, the material may have the following structural formula:
-L-SO 2 -R 7
in the above formula, L has the same structural formula as described above, wherein R 7 Represents an alkyl or aromatic cyclic group).
From R 7 The alkyl group represented is preferably an alkyl group having 1 to 8 carbon atoms, and is exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl.
From R 7 The alkyl groups represented may be substituted or unsubstituted, and the substituents to be introduced are monovalent non-metallic radicals other than hydrogen. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl, alkoxy, amino, formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, phenyl, biphenyl, naphthyl, tolyl, xylyl, methanesulfonyl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl and the like.
From R 7 The aromatic ring groups represented may preferably be those having 6 to 14 carbon atoms, for example, phenyl, biphenyl, naphthyl and mesityl, with phenyl and naphthyl being preferred.
From R 7 The aromatic ring group represented may be substituted or unsubstituted, and the substituent to be introduced is a monovalent non-metallic atomic group other than hydrogen. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl groups, alkoxy groups, amino groups, formyl groups, acyl groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups and the like.
According to one embodiment of the invention, the material may have the following structural formula:
wherein L has the same structure as described above, wherein R 8 And R 9 Each independently represents a carbon atom number of
Alkyl group of (1).
Further, according to an embodiment of the present invention, the preparation process of the hydrophilic anti-fog film layer may be:
(1) pretreatment: placing the lens in a reaction chamber of the PECVD device, vacuumizing, introducing plasma source gas, and starting a movement mechanism to enable the lens to move in the reaction chamber;
(2) deposition: introducing the hydrophilic raw material into the reaction chamber, and starting plasma discharge to perform chemical vapor deposition; and
(3) and (3) post-treatment: stopping plasma discharge, introducing air to one atmosphere after vacuumizing, stopping the movement of the lens, and then taking out the lens with the hydrophilic anti-fog film layer.
It is understood that the plasma source gas may be an inert gas or a non-metallic dopant source gas, for example, when the plasma source gas is nitrogen, the plasma source gas may also serve as the non-metallic dopant source.
It is noted that in the above steps, the reaction temperature can be maintained at a low level to keep the lens itself working properly after coating, while the lens surface can be effectively formed with the hydrophilic anti-fog film layer.
It is noted that both the inner and outer surfaces of the lens may be formed with the hydrophilic anti-fog film layer. The whole goggles can be placed in the reaction chamber for coating, the part where the hydrophilic anti-fog film layer is not required to be formed can be shielded, and the whole goggles can also be coated.
According to an embodiment of the present invention, the overall preparation method of the hydrophilic anti-fog film layer may include the steps of:
(1) pretreatment:
placing the lens in a reaction chamber of PECVD (plasma enhanced chemical vapor deposition) preparation equipment, continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 10-200 mTorr, introducing the plasma source gas, and starting a movement mechanism to enable the lens to move in the reaction chamber;
(2) preparing a hydrophilic antifogging film layer:
the following steps are carried out, and a hydrophilic antifogging film layer is prepared on the surface of the lens:
introducing hydrophilic materials into the reaction chamber until the vacuum degree is 30-300 mTorr, starting plasma discharge and carrying out chemical vapor deposition.
The hydrophilic antifogging film layer: the total thickness of the coating is 20nm-10 mu m; the hardness of the coating is HB-4H.
The hydrophilic material can be the titanium-based source compound, the oxygen-based source compound and the non-metal doping source, or the titanium-oxygen organic compound and the non-metal doping source, or the mixture of the titanium-based source compound, the oxygen-based source compound and the titanium-oxygen organic compound and the non-metal doping source steam, or the olefin monomer.
(3) And (3) post-treatment:
stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of a reaction chamber at 10-200 mTorr, introducing atmosphere to one atmosphere after 1-5 min, stopping the movement of the lens, and then taking out the lens; or stopping plasma discharge, filling air or inert gas into the reaction chamber to the pressure of 2000-5000 mTorr, then vacuumizing to 10-200 mTorr, carrying out the steps of filling air and vacuumizing at least once, filling air to an atmospheric pressure, stopping the movement of the lens, and then taking out the lens.
In the step (2), the flow rate of the titanium-based source compound, the titanium organic compound or the olefin monomer may be 10 to 1000. mu.L/min. In the step (2), the flow rate of the oxygen-based source may be 2 to 200sccm, and the flow rate of the non-metal doping source may be 2 to 200 sccm.
In step (2), the titanium-based source compound has the formula TiY, where Ti may be tetravalent and the Y group may be an inorganic group, such as a halogen.
In the step (2), the titanium-based source compound is titanium tetrachloride.
In the step (2), the titanyl organic compound has a structural formula of TiX, and the X group may be an organic oxygen-carrying group, such as an alkoxy group.
In the step (2), the titanyl organic compound may be one or more selected from tetrabutyl titanate, tetraisopropyl titanate, ethyl titanate, and methyl titanate.
In the step (2), the nonmetal of the nonmetal doping source can be C, N, F, S, B, P or one or more of halogen elements.
In the step (2), the non-metal doping source may be C x F 2x+2 Or is C x F 2x Wherein x may be 1 to 6. The non-metal source may be an alkane or an alkene.
In the step (2), the non-metal doping source may be selected from a combination of nitrogen (N) 2 ) Ammonia (NH) 3 ) Acetylene (C) 2 H 2 ) Octafluoropropane (C) 3 F 8 ) One or more of them.
In the step (2), the olefin monomer is selected from one or more of olefin monomers containing carboxylic acid groups, olefin monomers containing sulfonic acid groups and olefin monomers containing hydroxyl groups.
In the step (2), when the olefin monomer is an olefin monomer containing a carboxylic acid group, the olefin monomer containing a carboxylic acid group may have the following structural formula:
wherein R is 1 、R 2 、R 3 May be a hydrogen radical, an alkyl radical or an aromatic radical. R 1 、R 2 、R 3 May or may not be identical.
The alkenyl and carboxyl groups of the olefin-based monomer containing a carboxylic acid group may be directly linked or may be linked through other groups such as alkyl or aromatic groups.
In the step (2), the carboxylic acid group-containing olefin monomer may be methacrylic acid, acrylic acid, or phenylacrylic acid.
In the step (2), when the olefin monomer is a sulfonic acid group-containing olefin monomer, the sulfonic acid group-containing olefin monomer may have the following structural formula:
wherein R is 4 、R 5 Or R 6 May be a hydrogen radical, an alkyl radical or an aromatic radical. R 7 May be H or an alkyl or aromatic group. R 7 Or a metal cation, so that the olefin-based monomer containing sulfonic acid group becomes sulfonate. R 12 Selected from the group consisting of a bond, an alkyl group, an aromatic group. R 4 、R 5 、R 6 、R 7 May or may not be identical.
The alkenyl group and the sulfonic acid group of the sulfonic acid group-containing olefin-based monomer may be directly connected to each other, or may be connected to each other through another group such as an alkyl group or an aromatic group.
In the step (2), the olefin monomer containing sulfonic acid group can be sodium vinyl sulfonate, phenyl vinyl sulfonic acid, sodium p-styrene sulfonate.
In the step (2), when the olefin monomer is a hydroxyl group-containing olefin monomer, the hydroxyl group-containing olefin monomer may have the following structural formula:
wherein R is 8 、R 9 Or R 10 May be a hydrogen radical, an alkyl radical or an aromatic radical. R is 11 Can be an alkyl group, an aromatic group, or-COO-R 13 Or is-OCO-R 14 Or is-CO-R 15 。R 13 、R 14 Or is R 15 May be an alkyl group or an aromatic group. R 8 、R 9 、R 10 May or may not be identical.
The alkenyl and hydroxyl groups of the hydroxyl group-containing olefin monomer may also be directly linked.
In the step (2), the hydroxyl group-containing olefin monomer may be hydroxyethyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
In the step (1), the plasma source gas may be an inert gas, such as He and/or Ar, or may be a non-metal doping source capable of serving as a plasma source, such as nitrogen or a fluorocarbon.
In the step (2), the inert gas, such as He, can still be introduced, and the flow rate is 2-200 sccm.
In the step (1), the lens moves in the reaction chamber, the lens moves in a form of linear reciprocating motion or curvilinear motion relative to the reaction chamber, and the curvilinear motion comprises circular motion, elliptical circular motion, planetary motion, spherical motion or other curvilinear motion with irregular routes.
The reaction chamber in the step (1) is a rotating body-shaped chamber or a cube-shaped chamber, the volume of the reaction chamber is 50-1000L, the temperature of the reaction chamber is controlled at 30-60 ℃, and the flow of the inert gas is 5-300 sccm.
In the step (2): plasma discharge, namely performing chemical vapor deposition, wherein the plasma discharge process in the deposition process is continuous discharge or pulse discharge, and the method specifically comprises the following deposition processes at least once: the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 150-600W, the continuous discharge time is 60-450 s, then the coating stage is started, the plasma discharge power is adjusted to 10-200W, and the discharge time is 600-7200 s.
In the step (2), the plasma discharge mode is radio frequency discharge, microwave discharge, medium frequency discharge, high frequency discharge and electric spark discharge, and the waveforms of the high frequency discharge and the medium frequency discharge are sinusoidal or bipolar pulses.
Compared with an undoped titanium dioxide coating, the hydrophilic antifogging film layer does not need ultraviolet illumination, has long-acting hydrophilicity under visible light, has contact angles with water lower than 10 degrees, still maintains super-hydrophilicity after being placed for 6 months, has contact angles lower than 10 degrees after being rubbed by wet dust-free cloth for 2000 times by applying a load of 1KG, has excellent antifogging performance, has light transmittance of more than 90 percent, and can be used for antifogging occasions of transparent lenses.
The hydrophilic antifogging film layer has long-acting hydrophilicity under visible light, the contact angle to water is lower than 10 degrees, the super-hydrophilicity is still maintained after the hydrophilic antifogging film layer is placed for 6 months, the contact angle is still lower than 10 degrees after 1KG load is applied and the hydrophilic antifogging film layer is rubbed by wet dust-free cloth for 2000 times, the antifogging performance is excellent, the light transmittance can reach more than 90 percent, and the hydrophilic antifogging film layer can be used for antifogging occasions of transparent lenses.
The hydrophilic anti-fog film layer can improve the anti-fog performance of the lens surface, and the anti-fog method of the lens surface can be as follows: exposing the lens in the environment with the titanium dioxide precursor source and the non-metal doping source or the olefin monomer as reaction raw materials, and depositing on at least part of the surface of the lens by a plasma chemical vapor deposition method to form the hydrophilic anti-fog film layer.
The hydrophilic anti-fog film layer can be formed on the surface of the lens of the goggle to improve the anti-fog performance of the lens, for example, a lens having the hydrophilic anti-fog film layer is prepared by forming the hydrophilic anti-fog film layer on at least a part of the surface of the lens by plasma chemical vapor deposition exposed to an environment of hydrophilic raw materials.
The present invention is further illustrated by the following specific examples, which are intended to facilitate the understanding of the invention and are not intended to be limiting in any way.
Example 1
The hydrophilic antifogging coating can be prepared according to the following steps:
(1) pretreatment:
placing the lens made of PP in a reaction chamber of a PECVD device, closing the reaction chamber, continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 10 mTorr, introducing inert gas Ar, and starting a movement mechanism to enable the lens to move in the reaction chamber;
in the step (1), the reaction chamber is a rotating body-shaped chamber, the volume of the reaction chamber is 500L, the temperature of the reaction chamber is controlled at 40 ℃, and the flow rate of the introduced inert gas is 50 sccm.
In the step (1), the lens moves in the reaction chamber, the lens moves in a circular motion mode relative to the reaction chamber, and the rotating speed is 10 revolutions per minute.
(2) Preparing a hydrophilic antifogging coating:
introducing olefin monomer steam into the reaction chamber, starting plasma discharge when the vacuum degree is 20 mTorr, carrying out chemical vapor deposition, and preparing a hydrophilic antifogging coating on the surface of the lens by chemical vapor deposition;
the monomer steam component is: introducing monomer steam into the reaction chamber by atomizing and volatilizing the monomer through a feed pump and introducing the monomer into the reaction chamber at low pressure of 10 mTorr, wherein the flow of the introduced monomer steam is 120 mu L/min;
and (3) performing chemical vapor deposition by plasma discharge in the step (2), wherein the plasma discharge mode in the deposition process is radio frequency discharge, and the method specifically comprises the following steps of once deposition process:
the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 400W, the discharge duration is 400s, then the coating stage is started, the plasma discharge power is adjusted to be 30W, the energy output mode of the plasma radio frequency discharge of the coating stage is pulse output, the pulse width is 200 mus during discharge, and the repetition frequency is 500 Hz. It is worth noting that in the plasma discharge process of the coating stage, a cyclic coating process is adopted, the discharge can be firstly carried out for 20 seconds, then the discharge is continuously closed for 30 seconds, and the process is repeated for 100 times;
(3) and (3) post-treatment:
stopping introducing the monomer steam, simultaneously stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 10 mTorr, introducing air to atmospheric pressure after 5min, and then taking out the lens.
Example 2
The hydrophilic antifogging coating can be prepared according to the following steps:
(1) pretreatment:
placing the lens manufactured by PC in a reaction chamber of a PECVD device, closing the reaction chamber and continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 15 mTorr, introducing inert gas He, and starting a movement mechanism to enable the lens to be coated to move in the reaction chamber;
in the step (1), the reaction chamber is a rotating body-shaped chamber, the volume of the reaction chamber is 80L, the temperature of the reaction chamber is controlled at 35 ℃, and the flow rate of the introduced inert gas is 70 sccm.
In the step (1), the base material moves in the reaction chamber, the lens moves in a mode that the lens carries out circular motion relative to the reaction chamber, and the rotating speed is 10 revolutions per minute.
(2) Preparing a hydrophilic antifogging coating:
introducing monomer steam into the reaction chamber, starting plasma discharge when the vacuum degree is 50 mTorr, carrying out chemical vapor deposition, and preparing a hydrophilic antifogging coating on the surface of the lens by chemical vapor deposition;
the olefin monomer vapor component is: introducing monomer steam into the sodium vinylsulfonate, wherein the monomer is atomized and volatilized by a feeding pump and is introduced into the reaction chamber from a low pressure of 10 millitorr, and the flow of the introduced monomer steam is 100 mu L/min;
and (3) performing plasma discharge in the step (2) to perform chemical vapor deposition, wherein the plasma discharge mode in the deposition process is radio frequency discharge, and the method specifically comprises the following steps of once deposition process:
the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 500W, the discharge duration is 400s, then the coating stage is started, the plasma discharge power is adjusted to be 20W, the energy output mode of plasma radio frequency is controlled to be pulse output in the plasma radio frequency discharge process of the coating stage, the pulse width is 200 mus during discharge, the repetition frequency is 500Hz, the coating stage adopts a cyclic coating process, the discharge can be firstly carried out for 60s, then the discharge is continuously closed for 20 s, and the process is repeated for 30 times;
(3) and (3) post-treatment:
stopping introducing the monomer steam, simultaneously stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 20 mTorr, introducing air to atmospheric pressure after 2min, and then taking out the lens.
Example 3
The hydrophilic antifogging coating can be prepared according to the following steps:
(1) pretreatment:
placing the lens made of PET in a reaction chamber of a PECVD device, closing the reaction chamber, continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 15 mTorr, introducing inert gases He and Ar, and starting a movement mechanism to enable the lens to move in the reaction chamber;
in the step (1), the reaction chamber is a rotating body-shaped chamber, the volume of the reaction chamber is 900L, the temperature of the reaction chamber is controlled at 45 ℃, and the flow of the introduced inert gas is 550 sccm.
In the step (1), the lens moves in the reaction chamber, the lens moves in a mode that the lens carries out circular motion relative to the reaction chamber, and the rotating speed is 15 revolutions per minute.
(2) Preparing a hydrophilic antifogging coating:
introducing olefin monomer steam into the reaction chamber, starting plasma discharge when the vacuum degree is 60 mTorr, carrying out chemical vapor deposition, and preparing a hydrophilic antifogging coating on the surface of the lens by chemical vapor deposition;
the monomer steam component is: introducing monomer steam into hydroxyethyl acrylate, wherein the monomer is atomized and volatilized by a feeding pump and is introduced into a reaction chamber from a low pressure of 10 millitorr, and the flow of the introduced monomer steam is 120 mu L/min;
and (3) performing chemical vapor deposition by plasma discharge in the step (2), wherein the plasma discharge mode in the deposition process is medium-frequency discharge, and the method specifically comprises the following steps of once deposition process:
the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 600W, the continuous discharge time is 400s, then the coating stage is started, and the plasma discharge power is adjusted to be 20W. The coating stage adopts a cyclic coating process, and the process can be repeated for 70 times by first discharging for 30 seconds and then continuously closing the discharge for 20 seconds.
(3) And (3) post-treatment:
stopping introducing the monomer steam, simultaneously stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 20 mTorr, introducing air to atmospheric pressure after 2min, and then taking out the lens.
Example 4:
the hydrophilic anti-fog film layer can be prepared according to the following steps:
(1) pretreatment:
placing the lens made of the PP material in a reaction chamber of PECVD (plasma enhanced chemical vapor deposition) preparation equipment, closing the reaction chamber, continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 10 mTorr, introducing plasma source gas-inert gas Ar, and opening a movement mechanism to enable the lens to move in the reaction chamber;
in the step (1), the reaction chamber is a rotating body-shaped chamber, the volume of the reaction chamber is 600L, the temperature of the reaction chamber is controlled at 60 ℃, and the flow of the introduced inert gas is 60 sccm.
In the step (1), the lens moves in the reaction chamber, the lens moves in a mode that the lens carries out circular motion relative to the reaction chamber, and the rotating speed is 16 revolutions per minute.
(2) Preparing an N-doped titanium dioxide type hydrophilic antifogging film layer:
tetrabutyl titanate (the titanium oxide organic compound of the titanium dioxide precursor source) and nitrogen (a non-metal doping source) are introduced into the reaction chamber, when the vacuum degree is 30 millitorr, plasma discharge is started, chemical vapor deposition is carried out, and a hydrophilic anti-fog film layer is prepared on the surface of the lens through chemical vapor deposition;
the tetrabutyl titanate is monomer steam, the monomer is atomized and volatilized through a feeding pump and is introduced into a reaction chamber at low pressure of 10 millitorr, and the flow of the introduced monomer steam is 120 mu L/min; the nitrogen flow rate was 60 sccm.
And (3) performing plasma discharge in the step (2) and performing chemical vapor deposition, wherein the plasma discharge mode in the deposition process is radio frequency continuous discharge, and the method specifically comprises the following deposition process at least once: the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 300W, the continuous discharge time is 450s, then the coating stage is started, the plasma discharge power is adjusted to 200W, the coating stage adopts a cyclic coating process, the discharge can be firstly carried out for 40 seconds, then the discharge is stopped for 20 seconds, and the process is repeated for 20 times.
(3) And (3) post-treatment:
stopping introducing the monomer steam, simultaneously stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 10 mTorr, introducing air to atmospheric pressure after 1min, and then taking out the lens.
Example 5:
the hydrophilic anti-fog film layer can be prepared according to the following steps:
(1) pretreatment:
placing the lens made of the PC material in a reaction chamber of PECVD (plasma enhanced chemical vapor deposition) preparation equipment, closing the reaction chamber, continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 10 mTorr, introducing inert gas He, and starting a movement mechanism to enable the lens to move in the reaction chamber;
in the step (1), the reaction chamber is a rotating body-shaped chamber, the volume of the reaction chamber is 200L, the temperature of the reaction chamber is controlled at 70 ℃, and the flow rate of the introduced inert gas is 60 sccm.
In the step (1), the lens moves in the reaction chamber, the lens moves in a mode of circular motion relative to the reaction chamber, and the rotating speed is 20 revolutions per minute.
(2) Preparing a C-doped titanium dioxide type hydrophilic antifogging film layer:
introducing tetraisopropyl titanate (the titanium oxide organic compound of a titanium dioxide precursor source) and acetylene (a non-metal doping source) into a reaction chamber, starting plasma discharge when the vacuum degree is 30 mTorr, carrying out chemical vapor deposition, and preparing a hydrophilic anti-fog film layer on the surface of the lens through chemical vapor deposition;
tetraisopropyl titanate is monomer steam which is formed by atomizing and volatilizing the monomer through a charging pump and introducing the monomer into a reaction chamber at low pressure of 10 millitorr, wherein the flow of the introduced monomer steam is 110 mu L/min;
the acetylene flow is 40 sccm;
and (3) performing chemical vapor deposition by plasma discharge in the step (2), wherein the plasma discharge process in the deposition process is radio frequency continuous discharge, and the method specifically comprises the following deposition process once:
the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 300W, the continuous discharge time is 450s, then the coating stage is started, the plasma discharge power is adjusted to 200W, the coating stage adopts a cyclic coating process, the discharge can be carried out for 60 seconds, then the shutdown is carried out for 20 seconds, and the above process is repeated for 15 times.
(3) And (3) post-treatment:
stopping introducing the monomer steam, simultaneously stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 10 mTorr, introducing air to atmospheric pressure after 1min, and then taking out the lens.
Example 6:
the hydrophilic anti-fog film layer can be prepared according to the following steps:
(1) pretreatment:
placing the lens made of the PET material in a reaction chamber of PECVD (plasma enhanced chemical vapor deposition) preparation equipment, closing the reaction chamber, continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 10 mTorr, introducing inert gases Ar and He, and starting a movement mechanism to enable the lens to move in the reaction chamber;
in the step (1), the reaction chamber is a rotating body-shaped chamber, the volume of the reaction chamber is 50L, the temperature of the reaction chamber is controlled at 40 ℃, and the flow rate of the introduced inert gas is 60 sccm.
In the step (1), the lens moves in the reaction chamber, the lens moves in a circular mode relative to the reaction chamber, and the rotating speed is 6 revolutions per minute.
(2) Preparing an F-doped titanium dioxide type hydrophilic antifogging film layer:
introducing ethyl titanate (the titanium oxide organic compound of the titanium dioxide precursor source) and octafluoropropane (a non-metal doping source) into the reaction chamber, starting plasma discharge when the vacuum degree is 30 mTorr, carrying out chemical vapor deposition, and preparing a hydrophilic anti-fog film layer on the surface of the lens by chemical vapor deposition;
the ethyl titanate is monomer steam, and is formed by atomizing and volatilizing the monomer through a charging pump and introducing the monomer into a reaction chamber at low pressure of 10 millitorr, wherein the flow of the introduced monomer steam is 130 mu L/min;
the flow rate of the octafluoropropane is 60 sccm;
and (3) performing chemical vapor deposition by plasma discharge in the step (2), wherein the plasma discharge mode in the deposition process is microwave discharge, and the method specifically comprises the following steps of once deposition process:
the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 500W, the continuous discharge time is 450s, then the coating stage is started, the plasma discharge power is adjusted to be 200W, the coating stage adopts a cyclic coating process, the discharge can be carried out for 60 seconds, then the shutdown is carried out for 20 seconds, and the above process is repeated for 13 times.
(3) And (3) post-treatment:
stopping introducing the monomer steam, simultaneously stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 10 mTorr, introducing air to atmospheric pressure after 1min, and then taking out the lens.
Comparative example 6A is different from example 6 in that the plasma discharge is turned on 780s and then turned off 260s as one discharge.
Comparative example 6B is different from example 6 in that the plasma discharge was continuously turned on until the end, and the discharge duration was 1040s, which was a sustain discharge.
Example 7:
the hydrophilic anti-fog film layer can be prepared according to the following steps:
(1) pretreatment:
placing the lens with-OH groups on the surface in a reaction chamber of PECVD (plasma enhanced chemical vapor deposition) preparation equipment, closing the reaction chamber, continuously vacuumizing the reaction chamber, vacuumizing the reaction chamber to 10 mTorr, introducing inert gas He, and starting a movement mechanism to enable the lens to move in the reaction chamber;
in the step (1), the reaction chamber is a rotating body-shaped chamber, the volume of the reaction chamber is 50L, the temperature of the reaction chamber is controlled at 40 ℃, and the flow rate of the introduced inert gas is 60 sccm.
In the step (1), the lens moves in the reaction chamber, the lens moves in a circular mode relative to the reaction chamber, and the rotating speed is 6 revolutions per minute.
(2) Preparing a hydrophilic antifogging film layer:
introduction of Cl 3 Si(CH 2 ) 2 (CF 2 ) 6 (CH 2 ) 2 SiCl 3 Starting plasma discharge in a reaction chamber until the vacuum degree is 50 mTorr, carrying out chemical vapor deposition, and preparing a hydrophilic antifogging film layer on the surface of the lens by chemical vapor deposition;
Cl 3 Si(CH 2 ) 2 (CF 2 ) 6 (CH 2 ) 2 SiCl 3 is monomer steam which is generated by atomizing the monomer through a charging pump,Volatilizing and introducing the mixture into a reaction chamber at low pressure of 10 mTorr, wherein the flow of the introduced monomer steam is 120 mu L/min;
and (3) performing chemical vapor deposition by plasma discharge in the step (2), wherein the plasma discharge process in the deposition process is radio frequency continuous discharge, and the method specifically comprises the following deposition process once:
the deposition process comprises a pretreatment stage and a coating stage, wherein the plasma discharge power of the pretreatment stage is 400W, the continuous discharge time is 400s, then the coating stage is started, the plasma discharge power is adjusted to be 100W, the coating stage adopts a cyclic coating process, the discharge can be carried out for 80 seconds firstly, then the shutdown is carried out for 20 seconds, and the above process is repeated for 13 times.
(3) And (3) post-treatment:
stopping introducing the monomer steam, simultaneously stopping plasma discharge, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 10 mTorr, introducing air to atmospheric pressure after 1min, and then taking out the lens.
Comparative example 7A, which is different from example 7, is that the plasma discharge 1040s is turned on and then the discharge 260s is turned off as one discharge.
Comparative example 7B is different from example 7 in that the plasma discharge was continuously turned on until the end, the sustain discharge time was 1300s, and the discharge was sustained.
It is understood that the lens may be subjected to a PECVD coating in which a material having-OH groups is disposed on the surface of the substrate, and then Cl is introduced 3 Si(CH 2 ) 2 (CF 2 ) 6 (CH 2 ) 2 SiCl 3 And carrying out secondary coating to obtain the expected hydrophilic antifogging film layer.
The lens coated with the film in each embodiment is subjected to film thickness, water contact angle and light transmittance test.
The film thickness was measured using a film thickness measuring apparatus, filmetrics f 20-UV-film thickness gauge.
And (4) testing the water contact angle of the film layer according to the GB/T30447-2013 standard.
The light transmittance of the film was measured using a UV-Vis spectrophotometer model Perkin-Elmer-Lambda950, USA.
And (4) carrying out a salt spray resistance test according to the GB/T2423.18-2000 environmental test method for electrical and electronic products.
And (4) testing the scratch resistance, and no scratch is generated when the glass is rubbed by dustless cloth for 10000 times.
Attached table 1: examples 1 to 6 respective Performance parameters
| Examples | Film thickness/nm | Water contact angle/° c | Light transmittance (%) |
| Example 1 | 101 | 9 | 90 |
| Example 2 | 98 | 8 | 91 |
| Example 3 | 110 | 10 | 92 |
| Example 4 | 60 | 10 | 90 |
| Example 5 | 65 | 9 | 95 |
| Example 6 | 55 | 10 | 94 |
| Example 7 | 60 | 9 | 92 |
Regarding the influence of the discharge mode in the plating process on the final plating result, taking example 6 and example 7 as examples to illustrate, the data of the test on the film layers obtained in example 6, example 7, comparative example 6A and comparative example 6B, and comparative example 7A and comparative example 7B are as follows:
the film is coated in a circulating film coating mode in the film coating process, and the performance of the hydrophilic antifogging film layer formed on the surface of the lens of the goggles is superior to that of a film layer obtained by primary film coating or continuous film coating.
It will be appreciated by persons skilled in the art that the embodiments of the invention described above are given by way of example only and are not limiting of the invention. The objects of the invention have been fully and effectively accomplished. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles.
Claims (20)
1. Goggles with a hydrophilic anti-fog film layer, characterized in that the lenses of the goggles are coated with the hydrophilic anti-fog film layer, wherein the hydrophilic anti-fog film layer is formed on the surfaces of the lenses by a plasma chemical vapor deposition method using a hydrophilic raw material as a reaction raw material.
2. The goggle of claim 1, wherein the lens is fabricated from a material selected from one of the group consisting of PP, PET, and PC.
3. The goggle of claim 1, wherein the contact angle of the lens plated with the hydrophilic anti-fog film layer is no greater than 10 °.
4. The goggle of claim 1, wherein the light transmittance of the hydrophilic anti-fog film layer is greater than 90%.
5. The goggle of claim 1, wherein the hydrophilic anti-fog film layer has a thickness of 20nm to 10 μ ι η and a hardness of HB to 4H.
6. Goggles as claimed in any one of claims 1 to 5, wherein the reactive material is a hydrophilic material selected from the group consisting of olefinic monomers containing carboxylic acid groups, olefinic monomers containing sulphonic acid groups and olefinic monomers containing hydroxyl groups in combination.
7. The goggle of any of claims 1 through 5 wherein the reactive material comprises a titania precursor source and a non-metallic dopant source, wherein the titania precursor source is selected from one or both of a titanium-based source compound plus an oxo source and a titanium-based organic compound.
8. Goggles as claimed in any one of claims 1 to 5, wherein the surface of the lens carries-OH groups-, -COOH groups, -NH groups 2 A group,-NO 2 Group, -SO 3 H group and-N + R 3 Y - One of the radicals in which-N + R 3 Y - Wherein R is selected from lower alkyl, and Y represents a halogen atom; wherein the reaction raw material is X p Cl 3-p SiR 1 (CF 2 ) n R 2 SiX q Cl 3-q Wherein n represents an integer, R 1 And R 2 One selected from the group consisting of alkylene groups, substituents containing Si, and substituents containing oxygen atoms, X is one selected from the group consisting of hydrogen atoms, alkyl groups, and alkoxy substituents, and p and q are one selected from the group consisting of 1 and 2.
9. The goggle of any of claims 1-5, wherein the reaction feedstock has the structural formula:
wherein R is 3 Represents a hydrogen atom; r 4 One selected from a hydrogen atom and an alkyl group of up to 18 carbons; r 5 Represents an alkyl group of up to 18 carbons.
10. The film coating method is characterized by comprising the following steps:
introducing hydrophilic raw materials into a reaction chamber to serve as reaction raw materials; and
and carrying out plasma enhanced chemical vapor deposition on the surface of a lens of goggles in the reaction chamber to form the hydrophilic anti-fog film layer.
11. The coating method according to claim 10, wherein the process of forming the hydrophilic anti-fog film comprises a pretreatment stage and a coating stage, the pretreatment stage comprises a plasma discharge power of 150-600W and a discharge time of 60-450 s, and then the coating stage comprises a plasma discharge power of 10-200W and a discharge time of 600-7200 s.
12. The plating method according to claim 10, wherein the step of introducing a hydrophilic raw material is performed as follows:
introducing olefin monomers at a flow rate of 10-1000 mu L/min under a vacuum degree of 30-300 mTorr, wherein the olefin monomers are selected from one or more of olefin monomers containing carboxylic acid groups, olefin monomers containing sulfonic acid groups and olefin monomers containing hydroxyl groups.
13. The plating method according to claim 10, wherein the step of introducing a hydrophilic raw material is performed as follows:
and introducing a titanium dioxide precursor source and a non-metal doping source under the vacuum degree of 30-300 mTorr, wherein the titanium dioxide precursor source is selected from one or two of a combined titanium-based source compound and an oxygen-based source and a titanium-oxygen organic compound.
14. The coating method according to claim 13, wherein the titanyl organic compound has the formula TiX, wherein X is an alkoxy group.
15. The plating method according to claim 13, wherein the titanium-based source compound has a structural formula TiY, wherein Y is a halogen.
16. The plating method according to claim 13, wherein the titanium oxygen organic compound is one or more selected from tetrabutyl titanate, tetraisopropyl titanate and ethyl titanate.
17. The method according to any one of claims 10 to 16, wherein the temperature of the reaction chamber is controlled to be 30 to 60 ℃.
18. The plating method according to any one of claims 10 to 16, wherein the lens is made of a material selected from the group consisting of PP, PET and PC.
19. The plating method according to any one of claims 10 to 16, wherein in the above method, the contact angle of the lens plated with the hydrophilic anti-fog film layer is not more than 10 °.
20. The plating method according to any one of claims 10 to 16, wherein in the above method, the light transmittance of the hydrophilic anti-fog film layer is greater than 90%.
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| CN202110271894.8A CN115079317A (en) | 2021-03-12 | 2021-03-12 | Goggles with hydrophilic antifogging film layer and film coating method |
| PCT/CN2022/077893 WO2022188639A1 (en) | 2021-03-12 | 2022-02-25 | Goggles with a hydrophilic anti-fog film layer, and film-coating method |
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