CN112300686A - Method for surface antifogging treatment - Google Patents
Method for surface antifogging treatment Download PDFInfo
- Publication number
- CN112300686A CN112300686A CN202010744353.8A CN202010744353A CN112300686A CN 112300686 A CN112300686 A CN 112300686A CN 202010744353 A CN202010744353 A CN 202010744353A CN 112300686 A CN112300686 A CN 112300686A
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- China
- Prior art keywords
- composition
- weight
- urethane acrylate
- zwitterionic monomer
- liquid composition
- Prior art date
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Links
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000011282 treatment Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 22
- 230000003287 optical effect Effects 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 4
- 229960003237 betaine Drugs 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- CZRTVSQBVXBRHS-UHFFFAOYSA-N ethyl carbamate prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(N)=O CZRTVSQBVXBRHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 2
- 229940117986 sulfobetaine Drugs 0.000 claims description 2
- 238000012719 thermal polymerization Methods 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- IZWSFJTYBVKZNK-UHFFFAOYSA-O N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonic acid Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCS(O)(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-O 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 11
- 230000000007 visual effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 230000009182 swimming Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000004905 finger nail Anatomy 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000000282 nail Anatomy 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/147—Polyurethanes; Polyureas
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to a method for treating a surface to impart anti-fog properties thereto, said method comprising: -depositing on said surface a liquid composition comprising a reactive component based on a urethane acrylate and a zwitterionic monomer, said composition further comprising a polymerization initiator; -subjecting said surface to a polymerization treatment to form an antifog coating by crosslinking of said composition.
Description
Technical Field
The present invention relates to a method for treating surfaces, in particular optical surfaces, to impart anti-fogging properties thereto, as well as a liquid composition for carrying out such a method and an optical unit comprising a surface having anti-fogging properties by carrying out such a method.
It is particularly suitable for treating optical units intended for use in wet environments, such as lenses for swimming goggles and/or face masks.
Background
Known methods, which comprise the formation of an antifogging coating on the surface to be treated by polymerization and/or crosslinking under ultraviolet radiation (UV), ensure that the antifogging treatment is reliable and relatively durable, while being simple to implement.
These methods generally include:
-depositing on the surface to be treated a liquid composition comprising an active component crosslinkable by ultraviolet radiation and having sufficient hydrophilic properties to be able to impart antifogging properties to said surface, and a photoinitiator for said crosslinking;
-subjecting said surface to ultraviolet radiation to form an antifog coating by crosslinking of said composition.
Document KR-2000/0021399 discloses the use of a liquid composition having an acrylate oligomer-based reactive component curable by ultraviolet radiation, in particular a 4-functional and hydrophilic urethane acrylate.
Documents CN-106380994 and CN-106632830 disclose the use of liquid compositions having active components incorporated into zwitterionic betaine monomers or polymers, the hydrophilic properties of which allow inter alia an antifogging effect by hydration.
However, these solutions are not entirely satisfactory, since the coatings obtained generally have limited durability and/or insufficient wettability for effectively preventing the formation of mist on the treated surface.
Disclosure of Invention
The present invention aims to optimize the prior art by proposing a treatment process designed to ensure good antifogging properties of the surface, in particular in terms of reliability, effectiveness and durability.
To this end, according to a first aspect, the invention proposes a method for treating a surface to impart anti-fogging properties thereto, said method comprising:
-depositing on said surface a liquid composition comprising a reactive component based on a urethane acrylate and a zwitterionic monomer, said composition further comprising a polymerization initiator;
-subjecting said surface to a polymerization treatment to form an antifog coating by crosslinking of said composition.
According to a second aspect, the invention proposes a liquid composition for carrying out such a method, said composition comprising:
-a reactive component based on a urethane acrylate and a zwitterionic monomer;
-a polymerization initiator.
According to a third aspect, the invention proposes an optical unit comprising a surface having anti-fogging properties by implementing such a method.
Other features and advantages of the present invention will appear from the following description of various particular embodiments.
The present invention relates to a method for treating surfaces, in particular optical surfaces, to impart anti-fogging properties thereto, as well as a liquid composition for carrying out such a method and an optical unit comprising a surface having anti-fogging properties by carrying out such a method.
The invention is particularly suitable for treating optical units intended for use in wet environments, such as lenses for swimming goggles and/or face masks, due to the high risk of mist formation under such use conditions.
The invention is also applicable to other types of optical units, such as glasses and/or sunglasses, but also to masks providing protection against projection, which are commonly used in industrial and/or laboratory environments, within the following categories: the proximity of the unit to the user's respiratory tract and/or heat source (e.g., an oven) can result in the formation of a fog, thereby impairing the user's vision.
The method comprises depositing on the surface to be treated a liquid composition comprising a reactive component which can be cross-linked by the action of a suitable polymerization treatment.
Prior to depositing such a composition, the process may comprise degreasing the surface to be treated, in particular removing any residual contaminants that may alter the properties of the antifog coating and/or its adhesion to said surface.
To this end, the method may comprise applying a degreasing solution, in particular based on ethanol, on the surface to be treated, and then drying said surface with compressed air, so as to prepare it for the deposition of the liquid composition.
The method may comprise depositing the composition by soaking the surface in a bath of the composition. This solution advantageously allows to treat both faces of the optical unit in a single operation and to easily produce a coating of uniform thickness.
The method may also comprise depositing the composition by spraying the surface with said composition, for example by means of the so-called "flow coating" technique.
The reactive component is based on a urethane acrylate and a zwitterionic monomer.
The combination of these two types of materials enables antifog coatings of optimal quality to be obtained, in particular in terms of rigidity, transparency, scratch resistance and adhesion to the treated surface. Such a coating additionally has good hydrophilic properties, making it possible to ensure that a uniform film of water is maintained over the entire treated surface and thus effectively limit fogging on said surface.
The zwitterionic monomer may comprise betaine, the hydrophilic nature of which is particularly advantageous in limiting the formation of haze.
In particular, the zwitterionic monomer may comprise sulfobetaine methacrylate (SBMA), which also improves the transparency of the antifog coating. Such monomers may be prepared, for example, from
Products for sale
Obtained in Mer SPE.
The urethane acrylate may comprise an acrylic polyurethane matrix to impart good properties of rigidity, transparency, scratch resistance and adhesion to the treated surface to the antifog coating. In particular, the urethane acrylate may be based on an aliphatic urethane hexaacrylate free of tin, for example from IGM
Photomer for sale
The active component comprises from 15% to 60% by weight of a urethane acrylate and from 40% to 85% by weight of a zwitterionic monomer, which makes it possible to obtain the following coatings: the coating has a good compromise between physical and mechanical properties (resistance, surface adhesion, etc.) on the one hand and functional properties (hydrophilic properties) on the other hand. Advantageously, the reactive component comprises about 20% by weight of urethane acrylate and about 80% by weight of zwitterionic monomer.
In order to obtain coatings with satisfactory properties, the liquid composition advantageously comprises from 10% to 30% by weight of active ingredient.
The liquid composition also contains a polymerization initiator so as to be able to crosslink the active ingredient under the action of a suitable polymerization treatment. In particular, the composition comprises from 0.5% to 2%, and especially about 1% by weight of initiator.
Advantageously, the polymerization treatment may comprise exposing the surface on which the liquid composition has been deposited to ultraviolet radiation.
To this end, the initiator may comprise a photoinitiator and may be based in particular on 1-hydroxycyclohexylphenyl ketone, for example from IGM
Omnirad sold
Or Omnirad
In a variant, the polymerization treatment may comprise a thermal treatment of the surface on which the liquid composition has been deposited.
For this purpose, free-radical thermal polymerization initiators can be used, the choice of which depends on the desired implementation temperature. In particular, the initiator may comprise azonitrile, in particular based on Azobisisobutyronitrile (AIBN).
The liquid composition also comprises a solvent designed to ensure its homogeneity, especially with a view to avoiding precipitation of the urethane acrylate and/or zwitterionic monomer in said solvent.
To this end, the liquid composition may comprise:
-40% to 60% by weight of a non-aqueous solvent, in particular based on 2-butoxyethanol; and
-20% to 40% by weight of water, in particular demineralized water.
In particular, antifog coatings with very satisfactory properties are obtained with the aid of a liquid composition comprising:
about 3.9% by weight of a urethane acrylate, in particular based on Photomer
About 15.5% by weight of zwitterionic monomers, especially based on
Mer SPE；
About 0.8% by weight of a photoinitiator, in particular based on Omnirad
-about 47.9% by weight of a non-aqueous solvent, especially based on 2-butoxyethanol;
-about 31.9% by weight of water, in particular demineralized water.
After deposition of the composition on the surface, the method comprises at least one step of removing any excess of said composition from said surface, so as to ensure good uniformity of the coating in terms of thickness and distribution on said surface.
To this end, the method may comprise draining (draining) of the surface, in particular by suspending it in an upright position for about five minutes and/or by sucking up the excess through suitable means.
To carry out this treatment, the method then comprises subjecting the surface coated with the liquid composition to ultraviolet radiation, for example by placing it in an oven at 450W for about five minutes, to form an antifog coating by crosslinking of said composition.
In addition, after forming the coating, the method may comprise removing a possible incompletely crosslinked upper layer from said coating, in particular by rinsing the treated surface with water.
Detailed Description
Examples
During the test carried out in the laboratory, a plurality of samples of liquid compositions were prepared in order to evaluate in a comparative manner several chemical, physical and/or functional properties of said compositions and/or of the coatings obtained from them, in particular:
-the visual appearance of the liquid composition, in particular in terms of transparency and homogeneity;
the visual appearance of the coating, especially in terms of transparency;
-a haze value of the coating;
-a value of the contact angle with water, obtained in particular by depositing a drop of water on the treated surface and observing its retention on said surface;
scratch resistance, which is obtained in particular by visual observation and marking with fingernails;
the thickness of the coating, which is obtained in particular by means of a profilometer.
These liquid composition samples differ from each other by their active components, in particular by:
-the total amount of active ingredients in the liquid composition; and/or
-the weight ratio between the urethane acrylate and the zwitterionic monomer in the reactive component.
With respect to the urethane acrylate/zwitterionic monomer ratio, the samples each comprise a reactive component selected from one of the following:
100% of urethane acrylate and 0% of zwitterionic monomer (component "PU"); or
-75% of urethane acrylate and 25% of zwitterionic monomer (component "75 PU/25 SBMA"); or
-50% of urethane acrylate and 50% of zwitterionic monomer (component "PU/SBMA"); or
25% of urethane acrylate and 75% of zwitterionic monomer (component "25 PU/75 SBMA"); or
0% of urethane acrylate and 100% of zwitterionic monomer (component "SBMA").
In these tests, the following products were used to prepare the active ingredients:
for the urethane acrylate, from IGM
Photomer for sale
For the zwitterionic monomer, from
For sale
Mer SPE。
Furthermore, all samples contained:
-about 0.8% by weight of Omnirad
As a photoinitiator;
-about 47.9% by weight of a blend of
2-butoxyethanol, sold under the reference "801554", as a non-aqueous solvent;
-about 31.9% by weight demineralized water.
All these samples have been used to produce antifog coatings on the surface of transparent polycarbonate sheets, in particular similar to those typically used to produce lenses for swimming goggles or face masks.
These coatings are produced according to the method described above, with the aim of:
-preparing a sheet for depositing the liquid composition, in particular by degreasing with ethanol and drying with compressed air to remove any residues;
-depositing a sample of a liquid composition to be tested on the surface of the sheet;
-removing excess liquid composition from the sheet by draining, in particular by hanging said sheet upright for about five minutes, and then by sucking the remaining excess with a micropipette;
-subjecting the sheet to ultraviolet radiation, in particular by placing it in an oven of 450W for about five minutes, to form a coating by crosslinking of the composition; and
removing the possible incompletely crosslinked upper layer from the coating, in particular by rinsing the treated surface with water.
Appearance of liquid composition
For this first testing phase, five samples of the liquid composition were prepared, each of these samples comprising:
-a photoinitiator, a non-aqueous solvent and water in the above mentioned proportions;
-about 19.4% by weight of active ingredient selected from the list mentioned above, i.e.:
o for sample "001": the component "PU";
o for sample "002": the component "75 PU/25 SBMA";
o for sample "003": the component "PU/SBMA";
o for sample "004": the component "25 PU/75 SBMA"; and
o for sample "005": component "SBMA".
Samples containing a mixture of urethane acrylate and zwitterionic monomer (samples "002", "003" and "004") all had a satisfactory visual appearance, especially in terms of homogeneity.
In contrast, the sample containing only urethane acrylate (sample "001") or only zwitterionic monomer (sample "005") had insufficient homogeneity to the extent that the active component precipitated in the solvent/water mixture.
Thus, this first testing phase revealed a synergistic effect of the urethane acrylate/zwitterionic monomer mixture in terms of homogeneity of the liquid composition.
Thickness of antifog coating
During the second testing phase, five new samples of the liquid composition were prepared, each of these samples comprising:
-a photoinitiator, a non-aqueous solvent and water in the above mentioned proportions;
-about 14.55% by weight of active ingredient selected from the list mentioned above, i.e.:
o for sample "011": the component "PU";
o for sample "012": the component "75 PU/25 SBMA";
o for sample "013": the component "PU/SBMA";
o for sample "014": the component "25 PU/75 SBMA"; and
o for sample "015": component "SBMA".
The amounts of active components have been adjusted in comparison with the samples of this first testing stage in order to obtain five samples with satisfactory visual appearance having the same amounts of the other components (water, solvent, photoinitiator) in order not to obtain false results due to the use of samples which are not homogeneous and/or contain variations in the amounts of the components other than the active components.
At the end of these preparations, five polycarbonate sheets have been treated with one of these samples, respectively, according to the method described above.
In particular, the deposition of the liquid composition has been carried out by soaking the sheet in respective sample baths in order to obtain a coating with the best consistency and in a manner that is easy to repeat from one sample to another.
To this end, each sheet was immersed in a respective bath of samples in the following manner:
-lowering it vertically into the bath at a speed of about 200 mm/min;
-immersion in the bath for about 30 seconds; and is
-extracting it vertically from the bath at a speed of about 200 mm/min.
The thickness of each coating was then measured using a profilometer.
These measurements have shown that samples "011" to "014" can achieve very fine thicknesses, especially less than 1 μm. In particular:
samples "012" to "014" (PU/SBMA mixture) produced coatings having a thickness of about:
o for sample "013" (50% PU/50% SBMA): 0.8 μm;
o for samples "012" (75% PU/25% SBMA) and "014" (25% PU/75% SBMA): 0.6 μm; and is
Sample "011" (PU only) produced a coating with a minimum thickness of about 5 μm.
In contrast, for the sample containing only zwitterionic monomer (sample "015"), the coating had insufficient adhesion to the treated surface so that the final step of rinsing with water removed a significant amount of the coating. It has thus proven impossible to measure its thickness.
Other Properties of the antifogging coating
During the third testing phase, five new samples, similar to the one used during the second phase, were prepared to evaluate the other properties of the antifog coating obtained, namely:
its visual appearance, especially in terms of transparency;
-a haze value;
-a value of the contact angle with water, obtained in particular by depositing a drop of water on the treated surface and observing its retention on said surface;
scratch resistance, which is obtained in particular by visual observation and marking with fingernails.
Then, five polycarbonate sheets were each treated with one of these samples according to the method described above. Thus:
-sheet "016" has been treated with sample "011";
-sheet "017" treated with sample "012";
-sheet "018" was treated with sample "013";
-sheet "019" was treated with sample "014";
sheet "020" was treated with sample "015".
During these treatments, the deposition of the liquid composition is carried out after spraying the respective samples onto the sheet using the "flow coating" technique. For this purpose, 1ml of each sample was deposited on the corresponding sheet using a pasteur pipette.
At the end of these treatments, the various treated sheets as well as the control sheet without coating were examined to evaluate the properties as described above.
Regarding the visual appearance of the coating after rinsing:
satisfactory transparency was observed on the control sheets and on sheets "016", "018", "019" and "020";
white fogging was observed on sheet "017" treated with a sample containing 75% urethane acrylate and 25% zwitterionic monomer.
With respect to haze, all treated sheets had a value greater than that obtained with the control sheet, i.e., 0.49.
Sheets "016" and "020" having coatings comprising only urethane acrylate and only zwitterionic monomer, respectively, have rather low values, in particular 0.94 (for sheet "016") and 1.04 (for sheet "020").
With respect to sheets having coatings incorporating urethane acrylate/zwitterionic monomer mixtures, sheets "018" and "019" have higher values, but less than 3, especially 2.66 for sheet "018" (50/50 mixture with two components) and even 1.51 for sheet "019" (25% PU/75% SBMA).
In contrast, sheet "017" had a very large value of about 32.5 due to the presence of the white haze described above.
Regarding the contact angle with water, the sheets "016" and "020" treated with the sample whose active component is "single component" showed slightly lower results than those obtained with the control sheet. Thus, the control sheet had an angle of 72.80 °, while sheets "016" and "020" had angles of 69.02 and 67.75, respectively.
Further, the sheet "017" treated with sample "012" (75% PU/25% SBMA) gave a result of 77.64 °, which was thus slightly greater than the result for the control sheet.
In contrast, sheets "018" and "019" treated with samples comprising a greater proportion of zwitterionic monomer had contact angles with water values much lower than those of the control sheet, i.e., 27.49 ° (for sheet "018") and 33.31 ° (for sheet "019").
Finally, all treated sheets have satisfactory results as regards the resistance of the coating to the passage of the nails.
Thus, this third test stage shows that coatings comprising "one-component" active components do not provide an anti-fog effect on the treated surface. In fact:
although a coating comprising only urethane acrylate has good properties in terms of protection of the treated surface (rigidity, transparency, adhesion, scratch resistance), it has low wettability in comparison;
coatings comprising only zwitterionic monomers do not have satisfactory adhesion to the treated surface to the extent that rinsing with water after their formation removes a substantial part thereof.
Furthermore, this third test stage shows a synergy between the urethane acrylate and the zwitterionic monomer, but in a defined ratio.
Indeed, the results obtained with the sheet "017" show that, in addition to insufficient transparency not ensuring good vision for the user, an insufficient amount of zwitterionic monomer contributes to the hydrophobic nature of the treated surface to the extent that the contact angle with water is greater than that observed on the untreated surface.
In contrast, the results obtained with sheets "018" and "019" show that an active component having a zwitterionic monomer content equal to at least 50% but less than 99% can provide such a coating as follows: the coating has good antifogging properties while being satisfactory in particular in terms of transparency, resistance and adhesion to the treated surface.
In particular, when using a reactive component comprising at least 75% by weight of a zwitterionic monomer, a very satisfactory compromise is obtained between thickness (0.6 μm), transparency (haze 1.51) and antifogging properties (contact angle with water 33.31 °).
In addition, samples similar to the first stage samples "002", "003", "004" (in other words, samples incorporating about 19.4% by weight of an active component incorporating a mixture of a urethane acrylate and a zwitterionic monomer) have been subjected to tests similar to the second and third stage tests, and results similar to those of samples "012", "013" and "014" incorporating about 14.55% by weight of the corresponding active component have been observed.
Claims (19)
1. A method for treating a surface to impart anti-fog properties thereto, the method comprising:
-depositing on said surface a liquid composition comprising a reactive component based on a urethane acrylate and a zwitterionic monomer, said composition further comprising a polymerization initiator;
-subjecting said surface to a polymerization treatment to form an antifog coating by crosslinking of said composition.
2. The method according to claim 1, characterized in that the zwitterionic monomer comprises betaine, in particular sulfobetaine methacrylate (SBMA).
3. The method according to claim 1 or 2, characterized in that the urethane acrylate comprises an acrylic polyurethane matrix, in particular based on an aliphatic urethane hexaacrylate free of tin.
4. A method according to any one of claims 1 to 3, characterized in that the reactive component comprises from 15% to 60% by weight of urethane acrylate and from 40% to 85% by weight of zwitterionic monomer.
5. The method of claim 4, wherein the reactive component comprises about 20% by weight of a urethane acrylate and about 80% by weight of a zwitterionic monomer.
6. The method according to any one of claims 1 to 5, characterized in that the composition comprises 10% to 30% by weight of active ingredient.
7. The method according to any one of claims 1 to 6, characterized in that the composition comprises from 0.5% to 2% by weight, and in particular about 1% by weight, of the polymerization initiator.
8. The method according to any one of claims 1 to 7, characterized in that the polymerization treatment comprises exposing the surface on which the liquid composition is deposited to ultraviolet radiation.
9. The process according to claim 8, characterized in that the polymerization initiator comprises a photoinitiator, in particular based on 1-hydroxycyclohexylphenyl ketone.
10. The method according to any one of claims 1 to 7, characterized in that the polymerization treatment comprises a thermal treatment of the surface on which the liquid composition is deposited.
11. The process according to claim 10, characterized in that the polymerization initiator comprises a free-radical thermal polymerization initiator, in particular based on azonitrile.
12. The method according to any one of claims 1 to 11, characterized in that the composition comprises 40% to 60% by weight of a non-aqueous solvent, in particular based on 2-butoxyethanol.
13. The method according to any one of claims 1 to 12, characterized in that the composition comprises 20% to 40% water.
14. A method according to any one of claims 1 to 13, characterized in that the method comprises depositing the composition by soaking the surface in a bath of said composition.
15. A method according to any one of claims 1 to 13, characterized in that the method comprises depositing the composition by spraying the surface with said composition.
16. A liquid composition for carrying out the surface treatment method according to any one of claims 1 to 15, the composition comprising:
-a reactive component based on a urethane acrylate and a zwitterionic monomer;
-a polymerization initiator.
17. The liquid composition of claim 16, wherein:
-the zwitterionic monomer comprises a betaine, especially sulphobetaine methacrylate (SBMA);
the urethane acrylate comprises an acrylic polyurethane matrix, in particular based on an aliphatic urethane hexaacrylate free of tin; and is
The initiator is based on 1-hydroxycyclohexyl phenyl ketone or azonitrile.
18. Liquid composition according to one of claims 16 or 17, characterized in that the composition comprises:
-10% to 30% by weight of a reactive component comprising about 20% by weight of a urethane acrylate and about 80% by weight of a zwitterionic monomer; and
from 0.5% to 2% by weight and in particular about 1% by weight of a polymerization initiator.
19. An optical unit comprising a surface having anti-fogging properties by carrying out the treatment method according to any one of claims 1 to 15.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1908597A FR3099480B1 (en) | 2019-07-29 | 2019-07-29 | Process for anti-fog treatment of a surface |
| FR1908597 | 2019-07-29 |
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| CN112300686A true CN112300686A (en) | 2021-02-02 |
| CN112300686B CN112300686B (en) | 2024-04-16 |
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| EP (1) | EP4004123A1 (en) |
| CN (1) | CN112300686B (en) |
| FR (1) | FR3099480B1 (en) |
| TW (1) | TW202110897A (en) |
| WO (1) | WO2021018912A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292541A (en) * | 2021-12-23 | 2022-04-08 | 南通纳尔材料科技有限公司 | Optically transparent anti-fouling scratch-resistant protective film composition |
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| FR3139341A1 (en) | 2022-09-02 | 2024-03-08 | Decathlon | Process for functionalizing a surface of an optical substrate in order to give it anti-fogging properties |
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|---|---|---|---|---|
| EP1845141A1 (en) * | 2006-03-13 | 2007-10-17 | Mitsubishi Gas Chemical Company, Inc. | Antifogging coating composition |
| US20150259570A1 (en) * | 2012-11-29 | 2015-09-17 | Osaka Organic Chemical Industry Ltd. | Hydrophilic coating agent |
| CN106632830A (en) * | 2016-10-10 | 2017-05-10 | 天津大学 | Betaine type zwitterionic polymer antifogging coating and preparation method thereof |
| JP2018001087A (en) * | 2016-06-30 | 2018-01-11 | 関西ペイント株式会社 | Hydrophilic coating film forming method |
| CN109401657A (en) * | 2018-10-11 | 2019-03-01 | 斯迪克新型材料（江苏）有限公司 | For camber display screen can heavy industry rupture pressure disc |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000021399A (en) | 1998-09-29 | 2000-04-25 | 장용균 | Antifogging composition and antifogging film formed from the composition |
| CN106380994B (en) | 2016-09-10 | 2018-08-21 | 天津大学 | Amphipathic nature block polymer containing polyhedral oligomeric silsesquioxane and antifog/anti-fog coatings and preparation method |
-
2019
- 2019-07-29 FR FR1908597A patent/FR3099480B1/en active Active
-
2020
- 2020-07-28 WO PCT/EP2020/071305 patent/WO2021018912A1/en unknown
- 2020-07-28 EP EP20744059.5A patent/EP4004123A1/en active Pending
- 2020-07-29 TW TW109125614A patent/TW202110897A/en unknown
- 2020-07-29 CN CN202010744353.8A patent/CN112300686B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1845141A1 (en) * | 2006-03-13 | 2007-10-17 | Mitsubishi Gas Chemical Company, Inc. | Antifogging coating composition |
| US20150259570A1 (en) * | 2012-11-29 | 2015-09-17 | Osaka Organic Chemical Industry Ltd. | Hydrophilic coating agent |
| JP2018001087A (en) * | 2016-06-30 | 2018-01-11 | 関西ペイント株式会社 | Hydrophilic coating film forming method |
| CN106632830A (en) * | 2016-10-10 | 2017-05-10 | 天津大学 | Betaine type zwitterionic polymer antifogging coating and preparation method thereof |
| CN109401657A (en) * | 2018-10-11 | 2019-03-01 | 斯迪克新型材料（江苏）有限公司 | For camber display screen can heavy industry rupture pressure disc |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114292541A (en) * | 2021-12-23 | 2022-04-08 | 南通纳尔材料科技有限公司 | Optically transparent anti-fouling scratch-resistant protective film composition |
Also Published As
| Publication number | Publication date |
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| FR3099480B1 (en) | 2022-02-11 |
| EP4004123A1 (en) | 2022-06-01 |
| WO2021018912A1 (en) | 2021-02-04 |
| CN112300686B (en) | 2024-04-16 |
| TW202110897A (en) | 2021-03-16 |
| FR3099480A1 (en) | 2021-02-05 |
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