Easy To Clean And Anti-Fog Coating With Anti-Reflective Properties
20210325570 · 2021-10-21
Assignee
Inventors
- Tim Reynolds (Ramsey, MN, US)
- Sandy Goebel (Ramsey, MN, US)
- Robin Kezar (Ramsey, MN, US)
- Jeffrey Brown (Ramsey, MN, US)
Cpc classification
C09D183/06
CHEMISTRY; METALLURGY
C08G77/14
CHEMISTRY; METALLURGY
G02B1/18
PHYSICS
C08L83/06
CHEMISTRY; METALLURGY
C08L83/06
CHEMISTRY; METALLURGY
C08L83/00
CHEMISTRY; METALLURGY
Y10T428/31663
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C08L83/00
CHEMISTRY; METALLURGY
C09D7/48
CHEMISTRY; METALLURGY
C09D183/06
CHEMISTRY; METALLURGY
International classification
C09D183/06
CHEMISTRY; METALLURGY
C09D5/00
CHEMISTRY; METALLURGY
C09D7/48
CHEMISTRY; METALLURGY
Abstract
An ophthalmic article having a coating system which provides antireflective, easy clean and anti-fogging properties to the ophthalmic article. The coating system includes alternating layers of low refractive index and high refractive index metal oxides and a sol-gel based hydrophilic top layer formed of one or more silanes, one or more alcohols, DI water and itaconic acid. The coating system provides favorable surface energy and particle size distribution to the ophthalmic article when the sol-gel based top layer is deposited on top surface of the alternating layers of low refractive index and high refractive index metal oxides.
Claims
1. An ophthalmic article having easy-clean and anti-reflective properties comprising: a substrate having a first surface; a plurality of layers of alternating high refractive index and low refractive index materials, a first layer of the plurality of layers deposited directly on said first surface of the substrate and a last layer of the plurality of layers forming a second surface; and a hydrophilic layer distinct from the plurality of layers of alternating high refractive index and low refractive index materials deposited on the second surface, wherein said hydrophilic layer is formed of one or more silanes, one or more alcohols, DI water and an acid; wherein said acid is configured to crosslink with said one or more silanes and said one or more alcohols and control a pH of a solution of said hydrophilic layer.
2. The ophthalmic article of claim 1, wherein said acid comprises trifunctional groups comprising two carboxylic acids and an α,β-unsaturated double bond.
3. The ophthalmic article of claim 2, wherein said acid is itaconic acid.
4. The ophthalmic article of claim 1, wherein said acid maintains said pH of said solution of said hydrophilic layer at 3.2.
5. The ophthalmic article of claim 2, wherein said trifunctional groups comprising said two carboxylic acids and said α,β-unsaturated double bond of said acid are configured to crosslink with said one or more silanes and said one or more alcohols.
6. The ophthalmic article of claim 5, wherein said cross linking among said two carboxylic acids and said α,β-unsaturated double bond of said acid with said one or more silanes and said one or more alcohols provides mechanical robustness to said hydrophilic layer.
7. The ophthalmic article of claim 6, wherein said mechanical robustness of said hydrophilic layer remains unchanged after 12 days of coating pot-life.
8. The ophthalmic article of claim 1, wherein said hydrophilic layer comprises a surface energy in a range of approximately 30 to 90 millijoules per square meter when said acid is configured to control said pH of said solution of said hydrophilic layer at 3.2.
9. The ophthalmic article of claim 1, wherein said hydrophilic layer comprises pores having diameters in a range of approximately 20 to 30 nanometers when said acid is configured to control said pH of said solution of said hydrophilic layer at 3.2.
10. The ophthalmic article of claim 3, wherein curing of said solution of said hydrophilic layer formed of said one or more silanes, said one or more alcohols, DI water and said itaconic acid occurs at a lower temperature than curing of said solution of said hydrophilic layer formed of said one or more silanes, said one or more alcohols, DI water and a combination of acids comprising sulfuric acid and itaconic acid.
11. The ophthalmic article of claim 10, wherein said curing of said solution of said hydrophilic layer formed of said one or more silanes, said one or more alcohols, DI water and said itaconic acid occurs at 50° C.
12. An optical coating composition that imparts an easy-cleaning, an anti-reflecting and an anti-fogging properties on a surface of an article comprising: at least one silane of a formula (1);
R.sub.1Si(OR.sub.2).sub.3(Original)(Original)(Original) (1) wherein R.sub.1 comprises a reactive organic epoxide group and R.sub.2 is a methyl group, an ethyl group, a propyl group or an isopropyl group; an alcohol component, DI water, and a second silane compound having a formula (2),
Si(OR.sub.2).sub.4(Original)(Original)(Original) (2) wherein R.sub.2 is a methyl group, an ethyl group, a propyl group or an isopropyl group; and wherein said optical coating composition further comprising an acid having trifunctional groups comprising two carboxylic acids and an α,β-unsaturated double bond.
13. The optical coating composition of claim 12, wherein a volumetric ratio of said silane of formula (1) and said silane of formula (2) ranges approximately 0.2 to 2.0.
14. The optical coating composition of claim 12, wherein said silane of formula (1) comprises a 3-glycidoxylpropyl group.
15. The optical coating composition of claim 12, wherein said composition further comprises at least one high surface tension reducing surfactant.
16. The optical coating composition of claim 15, wherein said high surface tension reducing surfactant is a silicone-containing surface additive.
17. The optical coating composition of claim 16, wherein said silicone-containing surface additive comprises a polyether modified polydimethylsiloxane.
18. The optical coating composition of claim 12, wherein a pH of said optical coating composition is 3.2.
19. The optical coating composition of claim 18, wherein a hydrophilic layer formed by said composition comprises a surface energy in a range of approximately 30 to 90 millijoules per square meter when said pH of said composition is 3.2.
20. The optical coating composition of claim 18, wherein a hydrophilic layer formed by said composition comprises pores having diameters in a range of approximately 20 to 30 nanometers when said pH of said composition is 3.2.
21. The optical coating composition of claim 12, wherein a curing of said composition occurs at 50° C.
22. The optical coating composition of claim 12, wherein said acid having trifunctional groups comprising said two carboxylic acids and said α,β-unsaturated double bond is itaconic acid.
23. The optical coating composition of claim 22, wherein a molar ratio of said itaconic acid to a total volume of said silane of formula (1) and said silane of formula (2) ranges approximately is 1:8.13.
24. A method of preparing an optical coating composition that imparts an easy-cleaning, an anti-fogging and an anti-reflecting properties on a surface of an article comprising: a) forming a first mixture in a first step by combining: i) at least one silane of a formula (1);
R.sup.1Si(OR.sub.2).sub.3(Original)(Original)(Original) (1) wherein R.sup.1 comprises a reactive organic epoxide group and R.sup.2 is a methyl group, an ethyl group, a propyl group or an isopropyl group; ii) an alcohol component, iii) water, and iv) an acid having trifunctional groups comprising two carboxylic acid groups and an α,β-unsaturated double bond; b) stirring said first mixture in said first step to allow said mixture to cool down to room temperature; c) adding a silane compound having a formula (2) in said first step,
Si(OR.sup.2).sub.4(Original)(Original)(Original) (2) wherein R.sup.2 is a methyl group, an ethyl group, a propyl group or an isopropyl group; d) forming a second mixture in a second step by diluting a portion of said first mixture and adding at least one additional alcohol component from said first mixture; e) curing said second mixture formed at said second step at a range of temperatures and for a period of time.
25. The method of claim 24, wherein said curing of said second mixture formed at said second step occurs at 50° C. for 72 hours.
26. The method of claim 24, wherein forming said first mixture in said first step by combining said silane of formula (1) and said silane of formula (2) comprises a volumetric ratio between said silane of formula (1) and said silane of formula (2) in a range of approximately 0.2 to 2.0.
27. The method of claim 24, wherein forming said first mixture in said first step by combining said silane of formula (1) and said silane of formula (2) with said acid having said two carboxylic acid groups and said α,β-unsaturated double bond comprises a molar ratio between said acid and a total volume of said silane of formula (1) and said silane of formula (2) in a range of approximately 1:8.13.
28. The method of claim 24, wherein a pH of said second mixture by diluting said portion of said first mixture and adding said at least one additional alcohol component from said first mixture remains at 3.2.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] These and other aspects, features and advantages of which embodiments of the invention are capable will be apparent and elucidated from the following description of embodiments of the present invention, reference being made to the accompanying drawings, in which:
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
DESCRIPTION OF EMBODIMENTS
[0027] Specific embodiments of the invention will now be described with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. The terminology used in the detailed description of the embodiments illustrated in the accompanying drawings is not intended to be limiting of the invention. In the drawings, like numbers refer to like elements. While different embodiments are described, features of each embodiment can be used interchangeably with other described embodiments. In other words, any of the features of each of the embodiments can be mixed and matched with each other, and embodiments should not necessarily be rigidly interpreted to only include the features shown or described.
[0028] In a preferred embodiment, the present invention provides a hydrophilic coating system of an ophthalmic article which uses an organic acid, for example, itaconic acid, as a stabilizer to improve the shelf-life or the stability of the resulting easy-cleaning coating solution. In some embodiments, the coating solution comprises a sol-gel layer formed by one or more silanes, alcohols, water and itaconic acid. Itaconic acid comprises two carboxylic acid functionalities and an α,β-unsaturated double bond. The trifunctional structure of the Itaconic acid allows cross-linking with the available reactants in the reaction medium, and, therefore, makes it a desirable precursor into coating formulations to improve coating hardness. The use of itaconic acid as a stabilizer reduces the surface tension of the easy clean coating and controls the particle size distribution towards relatively smaller particles, which are important aspects of the mechanical integrity of the coating.
[0029] In some embodiments of the present invention, an ophthalmic article comprises a substrate having a first surface; a first of a plurality of refractive layers deposited directly on said first surface and a last of the plurality of refractive layers forming a second surface. A top layer of hydrophilic easy clean coating is deposited on the second surface. The hydrophilic easy clean coating comprises a surface energy in a range of approximately 30 to 90 millijoules per square meter. The ophthalmic article comprises refractive index in a range of approximately 1.40 to 1.49 at a wavelength of 589 nanometers. The ophthalmic article shows improved easy clean and antireflective properties after the top hydrophilic coating is deposited on the second surface. In some embodiments, the surfaces of ophthalmic articles which the coating of the present invention can be applied includes, but is not limited to, glass, plastics, metals, painted or colored surfaces, and other materials where cleanability is desirable.
[0030] In certain embodiments of the present invention, a surface of an article with a durable anti-reflective and easy-cleaning properties are obtained. With reference to
[0031] The pre-tuned anti-reflective stack 20 will not have anti-reflective properties until the easy-cleaning layer or coating 30 is applied as a final layer on the top surface (20e in
[0032] In one embodiment, a refractive index of the resulting easy-clean layer or coating, i.e. the refractive index of an optical article having a tuned anti-reflective stack as defined above, is in a range of approximately 1.40 to 1.49 measured at 589 nanometers.
[0033] An adhesive or adhesives may be employed in, among, on, and/or under any of the other functional coatings or layer present on the substrate.
[0034] In one embodiment, the top layer of the easy clean coating is hydrophilic in nature and it is synthesized in a two-step process.
[0035] In a first step, an alcohol, a silane and DI water are mixed together until the mixture becomes homogenous and allowed to react for a period, for example, 4 hours. Next, a combination of acids, for example, a mixture of sulfuric acid and itaconic acid, is added to the reaction mixture and the mixture is stirred for extended period until the temperature of the mixture returns to room temperature. In some embodiments, the silane employed is, for example, a glycidoxypropyltrimethoxysilane (GPTMS).
[0036] Next, a second silane, for example, a tetramethyl orthosilicate (TMOS) is added to the reaction mixture and the reaction mixture is stirred for a period, for example, 2-4 hours. In one preferred embodiment, these silanes (TMOS:GPTMS) are combined at a molar ratio ranging from approximately 19:1 to 1:1 or from approximately 4:1 to 3:2. In one preferred embodiment, a molar ratio of DI water to the total moles of silanes is in a range 11.13:1. The combination of acids, for example, a mixture of sulfuric acid and itaconic acid are added by saturating the DI water during the hydrolysis and condensation reactions of the GPTMS and TMOS mixture. In one preferred embodiment, a molar ratio of the sulfuric acid to the total moles of silanes are in a range of 1:30.1. One preferred embodiment, a molar ratio of the itaconic acid to the total moles of silanes are in a range of 1:8.13.
[0037] In some embodiments, exchanging a strong acid, such as, hydrochloric acid with another strong acid, such as sulfuric acid, does not impact the outcome of the reaction. In some embodiments, the first step of the two-step synthesis may be exothermic in nature. Therefore, it may be desirable to allow the reaction mixture to return to room temperature before proceeding to the second step of the synthesis.
[0038] In some embodiments, a molar ratio of sulfuric acid and itaconic acid in the first mixture is in a range of about 1:3.7. In some embodiments, the first mixture after adding the combination of sulfuric acid and itaconic acid may have a pH of 1.7.
[0039] Ina second step of the two-step synthesis process, a second mixture is formed by combining a portion of the first mixture with additional alcohol or alcohols. The second step of the reaction aids in regulating evaporation and surface tension gradient behavior during subsequent drying of the coating solution. The alcohol employed in the second mixture is optionally the same as the alcohol employed in the first mixture and is selected from alcohols having the general formula R—OH, where R is a methyl, ethyl, propyl, or isopropyl group, but is preferably a methyl group.
[0040] Next, the reaction mixture from the second step is thermally cured to remove any residual solvent that may be present. Curing is achieved in a range of temperatures and for certain time periods, for example, at 125 to 130 degrees Celsius for approximately 3 hours. In a preferred embodiment curing is achieved at 50 degrees Celsius for approximately 3 days.
[0041] In some embodiments, a sample of the compound generated from the second step is diluted for use. A control of the coating thickness and uniformity of the resulting easy-cleaning coating solution is achieved by dilution of the second mixture, by the addition of high surface tension reducing agents or surfactants.
[0042] In a preferred embodiment, at least one high surface tension reducing surfactant/agent is added for the dilution. A high surface tension reducing surfactant/agent may, for example, be a silicone-containing surface additive, such as, a polyether modified polydimethylsiloxane, for example, BYK333 or other silicone-containing surface additives appropriate for solvent-borne coating systems. In addition to BYK333, some alcohols, for example but not limited to methanol, ethanol and 1-methoxy-2-propanol, and DI water may be added for the dilution.
[0043] After dilution, a sample of the diluted solution is placed in a coater for number of days with constant recirculation. On each day, the coating solution is measured for particle size distribution and surface tension. The measurements of the surface tension over several days, for example, up to 25 days are shown in
[0044] As can be seen in
[0045]
[0046]
[0047] It has been concluded that the presence of the strong acid, such as, sulfuric acid in combination with itaconic acid in the first step of the two-step synthesis renders the final hydrophilic easy clean coating solution highly acidic with a low pH of 1.7. This low pH is likely detrimental to the stability of the surfactant of a polyether modified polydimethylsiloxane, for example, BYK333 used to reduce the high surface tension of the hydrophilic easy clean coating during dilution. At pH 1.7, the BYK333 may get decomposed, and the resulting fragments then become integrated into the coating resulting in degraded performance. The removal of the surfactant reduces the coating uniformity and further degrades the coating.
[0048] To overcome the problem of degradation of the high surface tension reducing surfactant under highly acidic reaction condition, the two-step synthesis of the hydrophilic easy clean coating is performed with only one acid, namely, the itaconic acid and without the addition of the sulfuric acid. Performing the two-step synthesis with the addition of itaconic acid only in the first step renders the final hydrophilic easy clean coating solution less acidic with a higher pH of 3.2 compared to the lower pH of 1.7 when sulfuric acid and itaconic acids are combined in the first step of the synthesis. In some embodiments, the stability of the high surface tension reducing surfactant, for example, BYK333, remained intact at pH 3.2.
Synthesis of Easy Clean Coating Using Itaconic Acid:
[0049] One embodiment of the synthesis of the easy clean coating by using one acid, namely itaconic acid, in the first step is described herein.
[0050] In the first step of the synthesis, 465 mL of methanol, 205 mL of 3-glycidoxypropyltrimethoxysilane and 622 mL of DI water were mixed together in a container until homogeneity was achieved and the mixture was allowed to react for 4 hours. Then 49.4 gm of itaconic acid was added to the mixture and the mixture was stirred. This step was exothermic and the reaction mixture was allowed to return to room temperature before adding 322.8 mL of TMOS. The container was sealed and shook to ensure homogeneity of the mixture. The reaction mixture was cooled down to room temperature typically within 2-4 hours.
[0051] In the second step of the synthesis, 6.4 L of methanol was added to the reaction mixture. The container was sealed again and placed in an oven at 50 degrees Celsius for 72 hours to complete the reaction.
[0052] After 72 hours of curing at 50 degrees Celsius, the coating solution obtained after the second step of the synthesis was diluted with one or more alcohols, for example but not limited to methanol, ethanol, 1-methoxy-2 propanol, DI water and a surfactant, for example, BYK333. A 7.06% by volume of undiluted reaction mixture was diluted with 30.11% by volume of methanol and 33.15% by volume of ethanol, 17.82% by volume of DI water, 11.69% by volume of 1-methoxy-2 propanol and 0.2% by volume of BYK333, as can be seen in
[0053] After dilution, a sample of the diluted solution is placed in a coater for number of days with constant recirculation. On each day, the coating solution was measured for surface tension and particle size distribution.
[0054]
[0055]
[0056] The reason for obtaining the desired range of surface tension may be attributed to the fact that the stability of the high surface tension reducing surfactant, BYK333, remains intact at pH 3.2 and efficiently reduces the surface tension of the easy clean coating to a favorable range. The same solution stability test was repeated and each time the test results showed the clear benefits of the process with regards to the solution stability.
[0057] Next,
[0058]
[0059] Durability testing of the easy clean coating was performed when the first step of the two-step synthesis of the easy clean coating includes only itaconic acid and maintains the pH of the coating solution at 3.2.
[0060] These test results indicate that the easy cleaning coating obtains extra mechanical stability when itaconic acid is used as the primary stabilizer. This extra stability of the easy clean coating may be attributed to the trifunctional structure (two carboxylic acid functionalities and an α,β-unsaturated double bond) of the Itaconic acid which provides cross-linking with the available reactants in the reaction medium to generate extra mechanical robustness of the coating which provides favorable surface energy (30-90 milli Joules per square meter) and particle size distribution (20-30 nm).
[0061] Based on the foregoing, it is contemplated that any organic acid that has 2 carboxyl groups and one unsaturated C═C bond and has similar properties as itaconic acid is compatible and within the scope of the invention.
[0062]
[0063] In optical-based industries, it is often also desirable to combine the properties or characteristics of ease of cleaning and antireflective with functional properties or characteristics such as the property of anti-fogging. However, the inherent hydrophobicity of current easy-cleaning coatings renders them undesirable for fogging resistance since water droplets are capable of adhering to them in a partially non-wetted state, creating the appearance of fogging by way of light scattering.
[0064] The present invention demonstrates that by adjusting the ratios of the silanes, for example, tetramethyl orthosilicate (TMOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS), the speed of clearing the condensed moisture, in other words, the anti-fogging advantage, can be achieved in an ophthalmic article in addition to the easy clean and antireflective properties. A volumetric ratio of GPTMS to TMOS may range from 0.2 to 2.0 to impart an anti-fogging property to the ophthalmic article. Such a volumetric ratio between GPTMS and TMOS provides the ophthalmic article characteristics such as ease of cleaning, surface energy, resistance to fogging, and speed of recovery after fogging.
[0065] Although the invention has been described in terms of particular embodiments and applications, one of ordinary skill in the art, in light of this teaching, can generate additional embodiments and modifications without departing from the spirit of or exceeding the scope of the claimed invention. Accordingly, it is to be understood that the drawings and descriptions herein are proffered by way of example to facilitate comprehension of the invention and should not be construed to limit the scope thereof.