WO2015009349A1 - Lentilles antireflets et procédé de fabrication associés - Google Patents

Lentilles antireflets et procédé de fabrication associés Download PDF

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Publication number
WO2015009349A1
WO2015009349A1 PCT/US2014/038600 US2014038600W WO2015009349A1 WO 2015009349 A1 WO2015009349 A1 WO 2015009349A1 US 2014038600 W US2014038600 W US 2014038600W WO 2015009349 A1 WO2015009349 A1 WO 2015009349A1
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WO
WIPO (PCT)
Prior art keywords
layer
index
refraction
super hydrophobic
hydrophobic material
Prior art date
Application number
PCT/US2014/038600
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English (en)
Inventor
Kai C. Su
Leslie F. STEBBINS
Bill Mantch
Eugene C. LETTER
Original Assignee
Qspex Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/943,570 external-priority patent/US9335443B2/en
Application filed by Qspex Technologies, Inc. filed Critical Qspex Technologies, Inc.
Publication of WO2015009349A1 publication Critical patent/WO2015009349A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00865—Applying coatings; tinting; colouring
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates generally to an optical surface, and more particularly to an anti-reflective lens and methods of manufacturing the same.
  • An anti-reflective lens normally is formed with an anti-reflective coating on a plastic ophthalmic lens.
  • Anti-reflective (AR) coatings are applied to the surfaces of ophthalmic lenses and other optical devices to reduce reflection.
  • AR anti-reflective
  • the reduced reflection makes them not only look better, but more importantly work better because they produce less glare by eliminating multiple reflections, which is particularly noticeable when driving at night or working in front of a computer monitor.
  • the decreased glare means that wearers often find their eyes are less tired, particularly at the end of the day.
  • AR coatings also allow more light to pass through the lens, which increases contrast and therefore increases visual acuity.
  • the art of casting plastic ophthalmic lenses involves introducing a lens-forming material between two molds and then polymerizing the lens-forming material to become a solid.
  • Liquid plastic formulations such as CR39 monomer are injected into a cavity formed by front and rear molds which have been provided with interior polished mold surfaces for the finished surfaces of the lenses.
  • the plastic is cured in the mold, and then the mold is separated to yield a completed ophthalmic lens which meets a selected prescription.
  • the lens is then ground around the edge to fit into the selected frame. Coatings can be applied to the finished lens or to the inside of the front or rear mold, whereupon they will bond to the lens upon curing.
  • Some optometrists offer on-site eyeglass services.
  • Several companies have developed methods by which lenses can be cast on site, in an office.
  • current methods of applying AR coatings to eyeglasses require that they be shipped to a different facility because the AR coatings must be applied via vacuum vapor deposition. This of course means additional time and expense. There is therefore a need for a method for making eyeglasses with an AR coating on-site.
  • One type of AR coating that is used for ophthalmic lenses is an alternating stack of a high index material and a low index material.
  • the most commonly used low index material is silicon dioxide; zirconium dioxide and/or titanium dioxide is often used as the high index material.
  • AR coatings are generally applied via vacuum deposition. It is well known that adhesion of vacuum-deposited coatings to their substrates is in general problematic. The organic, plastic lens material and inorganic AR material do not readily adhere to each other, resulting in peeling or scratching. Accordingly, a new method is needed to apply an AR coating to a plastic lens with greater adhesion.
  • organopolysiloxa e to increase the adhesion of an organosiloxane hard coat to a thermoplastic substrate.
  • US Patent No. 5,025,049 to Takarada et al. also teaches a primer for increasing adhesion of an organopolysiloxane layer to a thermoplastic substrate.
  • the primer is a mixture of an organic copolymer including an aikoxysilylated monomer and other ingredients.
  • US Patent No. 5,096,626 to Takamizawa et al. teaches a plastic lens having an AR coating and/or hard coat.
  • the patent discusses poor adhesion of prior art methods and says they achieve excellent adhesion by forming the lens using a set of molds, wherein the AR coating is first applied to one of the molds and then the lens monomer is poured between the molds and polymerized.
  • a silane coupling agent such as
  • methacryloxypropyltrimethoxysilane can be included in the hard coat/AR coat solution, which may contain colloidal silica, colloidal antimony oxide or colloidal titanium dioxide.
  • US Patent No. 6,986,857 to Klemm et al. teaches a method of assembling a lens with a top coat, AR coat, scratch resistant coat, impact resistant primer, and lens substrate.
  • Klemm's solution to the issue of poor adherence of the top coat to the AR coat is to apply the first layer of the AR coating (which comprises a stack of four layers) as two sublayers of Si0 2 .
  • Another thin layer of Si0 2 is applied between the AR stack and the scratch resistant coating to improve adherence between the two.
  • the present invention relates to a method of applying an anti- reflective (AR) coating to a plastic substrate such as a plastic ophthalmic lens where the AR coating exhibits good adhesion to the substrate, where the method eliminates both an initial Si0 2 or MgF 2 layer and a mold release layer.
  • AR anti- reflective
  • the method includes the steps of providing a lens mold having an optical surface; forming a layer of a super hydrophobic material over the optical surface, by heating a thermal boat that is in contact with one or more crucibles containing the super hydrophobic material to a temperature between about 200 °C and about 500 °C, wherein the super hydrophobic material contains an amount of dipodal silane that is a relative percentage of the super hydrophobic material; forming an AR coating layered structure over the layer of the super hydrophobic material; and forming a layer of a coupling agent deposited with a monolayer thickness to the AR coating layered structure using vapor deposition under aprotic conditions or by dip coating or spin coating using a solution of a coupling agent in an aprotic solvent.
  • the thermal boat is heated by a low voltage high amperage current. In another embodiment, the thermal boat is heated by an electron beam. In other embodiments, a combination of heating methods is used. In some embodiments, the crucible in contact with the thermal boat contains ceramic or metal pills in which the super hydrophobic material is adsorbed.
  • the amount of the dipodal silane is about 1.7 - 8.3% of the super hydrophobic material by weight.
  • the dipodal silane comprises
  • the layer of the coupling agent is formed of a composition that comprises cyclic azasilanes, wherein the layer of the coupling agent is formed of N- n-butyl-aza-2,2-dimethoxy-silacyclopentane. In another embodiment, the layer of the coupling agent is formed of a composition comprising dipodal silane.
  • the step of forming the AR coating layered structure over the layer further comprises the steps of forming a first layer of a first material with a first index of refraction and a thickness of about 5 to 100 nm, on the layer of the super hydrophobic material; forming a second layer of a second material with a second index of refraction that is higher than the first index of refraction and a thickness of about 40 to 50 nm, on the first layer; forming a third layer of the first material with the first index of refraction and a thickness of about 10 to 20 nm, on the second layer; forming a fourth layer of the second material with the second index of refraction and a thickness of about 50 to 70 nm, on the third layer; forming a fifth layer of the first material with the first index of refraction and a thickness of about 25 to 40 nm, on the fourth layer; forming a sixth layer of the second material with the second index of refraction and a thickness of about 10 to 25 nm, on the fourth
  • the method further includes the step of forming a layer of Si0 2 between the AR coating layered structure and the layer of the super hydrophobic material.
  • the present invention relates to a mold with an optical surface having an AR coating that is transferable to a lens.
  • the mold has a layer of a super hydrophobic material formed over the optical surface, by heating a thermal boat that is in contact with one or more crucibles containing the super hydrophobic material to a temperature between about 200 °C and about 500 °C, wherein the super hydrophobic material contains an amount of dipodal silane that is a relative percentage of the super hydrophobic material; an AR coating layered structure formed over the layer of the super hydrophobic material; and a layer of a coupling agent deposited with a monolayer thickness to the anti-reflective coating layered structure using vapor deposition under aprotic conditions or by dip coating or spin coating using a solution of a coupling agent in an aprotic solvent.
  • the mold further includes a layer of Si0 2 formed between the AR coating layered structure and the layer of the super hydrophobic material.
  • the amount of the dipodal silane is about 1.7 - 8.3% of the super hydrophobic material by weight.
  • the AR coating layered structure comprises a first layer of a first material with a first index of refraction and a thickness of about 5 to 100 nm, formed on the layer of the super hydrophobic material; a second layer of a second material with a second index of refraction that is higher than the first index of refraction and a thickness of about 40 to 50 nm, formed on the first layer; a third layer of the first material with the first index of refraction and a thickness of about 10 to 20 nm, formed on the second layer; a fourth layer of the second material with the second index of refraction and a thickness of about 50 to 70 nm, formed on the third layer; a fifth layer of the first material with the first index of refraction and a thickness of about 25 to 40 nm, formed on the fourth layer; a sixth layer of the second material with the second index of refraction and a thickness of about 10 to 25 nm, formed on the fifth layer; and a seventh layer of the first material with the first index
  • the first material with the first index of refraction is Si0 2
  • the second material with the second index of refraction is Zr0 2
  • each layer of Si0 2 is deposited using ion assist or without using ion assist.
  • the dipodal silane comprises
  • the layer of the coupling agent is formed of a composition that comprises cyclic azasilanes.
  • the layer of the coupling agent is formed of N-n-butyl-aza-2,2-dimethoxy-silacyclopentane.
  • the present invention relates to an optical lens manufactured with a mold having an optical surface.
  • the optical lens has a lens body with an optical surface; a hard coat layer over the optical surface of the lens body; and an AR coating.
  • the AR coating includes a layer of a super hydrophobic material formed over the optical surface of the mold, by heating a thermal boat that is in contact with one or more crucibles containing the super hydrophobic material to a temperature between about 200 °C and about 500 °C, wherein the super hydrophobic material contains an amount of dipodal silane that is a relative percentage of the super hydrophobic material; an anti-reflective coating layered structure formed over the layer of the super hydrophobic material; and a layer of a coupling agent deposited with a monolayer thickness to the anti-reflective coating layered structure.
  • the hard coat layer is substantially in contact with the layer of the coupling agent of the anti-reflective coating.
  • the AR coating layered structure comprises a first layer of a first material with a first index of refraction and a thickness of about 5 to 100 nm, formed on the layer of the super hydrophobic material; a second layer of a second material with a second index of refraction that is higher than the first index of refraction and a thickness of about 40 to 50 nm, formed on the first layer; a third layer of the first material with the first index of refraction and a thickness of about 10 to 20 nm, formed on the second layer; a fourth layer of the second material with the second index of refraction and a thickness of about 50 to 70 nm, formed on the third layer; a fifth layer of the first material with the first index of refraction and a thickness of about 25 to 40 nm, formed on the fourth layer; a sixth layer of the second material with the second index of refraction and a thickness of about 10 to 25 nm, formed on the fifth layer; and a seventh layer of the first material with the first index
  • the first material with the first index of refraction is Si0 2
  • the second material with the second index of refraction is Zr0 2
  • each layer of Si0 2 is deposited using ion assist or without using ion assist.
  • the amount of the dipodal silane is about 1.7 - 8.3% of the super hydrophobic material by weight. In one embodiment, the dipodal silane comprises
  • the layer of the coupling agent is formed of a composition that comprises cyclic azasilanes. In one embodiment, the layer of the coupling agent is formed of N-n-butyl-aza-2,2-dimethoxy-silacyclopentane.
  • the optical lens further comprises a layer of Si0 2 formed between the AR coating layered structure and the layer of the super hydrophobic material.
  • the present invention relates to a method for applying an AR coating to an optical surface of a mold.
  • the method includes the steps of providing a lens mold having an optical surface; forming a layer of a super hydrophobic material over the optical surface, wherein the super hydrophobic material contains an amount of dipodal silane that is a relative percentage of the super
  • the amount of the dipodal silane is about 1.7 - 8.3% of the super hydrophobic material by weight.
  • the step of forming an AR coating layered structure over the layer further comprises the steps of forming a first layer of a first material with a first index of refraction on the layer of the super hydrophobic material; forming a second layer of a second material with a second index of refraction on the first layer; forming a third layer of the first material with the first index of refraction on the second layer; forming a fourth layer of the second material with the second index of refraction on the third layer; forming a fifth layer of the first material with the first index of refraction on the fourth layer; forming a sixth layer of the second material with the second index of refraction on the fifth layer; and forming a seventh layer of the first material with the first index of refraction on the sixth layer.
  • the first index of refraction and the second index of refraction satisfy a ratio of H/L > 1, where L and H are values of the first and second index of refraction, respectively.
  • the first material with the first index of refraction is Si0 2
  • the second material with the second index of refraction is Zr0 2 .
  • the layer of coupling agent is formed of a composition that comprises cyclic azasilanes.
  • the step of forming the layer of super hydrophobic material over the optical surface comprises heating a thermal boat that is in contact with one or more crucibles containing the super hydrophobic material. In one embodiment, the heating step comprises heating the thermal boat to a temperature between about 200 °C and about 500 °C.
  • the present invention relates to a mold with an optical surface having an AR coating that is transferable to a lens.
  • the mold has a layer of a super hydrophobic material formed over the optical surface, wherein the super hydrophobic material contains an amount of dipodal silane that is a relative percentage of the super hydrophobic material; an AR coating layered structure formed over the layer of the super hydrophobic material; and a layer of a coupling agent deposited with a monolayer thickness to the AR coating layered structure using vapor deposition under aprotic conditions or by dip coating or spin coating using a solution of a coupling agent in an aprotic solvent.
  • the amount of the dipodal silane is about 1.7 - 8.3% of the super hydrophobic material by weight.
  • the layer of super hydrophobic material is formed over the optical surface by heating a thermal boat that is in contact with one or more crucibles containing the super hydrophobic material, at a temperature, wherein the temperature is between about 200 °C and about 500 °C.
  • the AR coating layered structure comprises a first layer of a first material with a first index of refraction formed on the layer of the super hydrophobic material; a second layer of a second material with a second index of refraction formed on the first layer; a third layer of the first material with the first index of refraction formed on the second layer; a fourth layer of the second material with the second index of refraction formed on the third layer; a fifth layer of the first material with the first index of refraction formed on the fourth layer; a sixth layer of the second material with the second index of refraction formed on the fifth layer; and a seventh layer of the first material with the first index of refraction formed on the sixth layer.
  • the first index of refraction and the second index of refraction satisfy a ratio of H/L > 1, where L and H are values of the first and second index of refraction, respectively.
  • the first material with the first index of refraction is Si0 2
  • the second material with the second index of refraction is Zr0 2 .
  • the layer of coupling agent is formed of a composition that comprises cyclic azasilanes.
  • the present invention relates to an optical lens manufactured with a mold having an optical surface.
  • the optical lens has a lens body with an optical surface; a hard coat layer over the optical surface of the lens body; and an AR coating.
  • the AR coating includes a layer of a super hydrophobic material formed over the optical surface of the mold, wherein the super hydrophobic material contains an amount of dipodal silane that is a relative percentage of the super hydrophobic material; an anti-reflective coating layered structure formed over the layer of the super
  • hydrophobic material hydrophobic material; and a layer of a coupling agent deposited with a monolayer thickness to the anti-reflective coating layered structure.
  • the hard coat layer is substantially in contact with the layer of the coupling agent of the anti-reflective coating.
  • the layer of the super hydrophobic material is formed over the optical surface of the lens mold by heating a thermal boat that is in contact with one or more crucibles containing the super hydrophobic material, at a temperature. In one embodiment, the temperature is between about 200 °C and about 500 °C.
  • the amount of the dipodal silane is about 1.7 - 8.3% of the super hydrophobic material by weight.
  • the AR coating layered structure comprises a first layer of a first material with a first index of refraction formed on the layer of the super hydrophobic material; a second layer of a second material with a second index of refraction formed on the first layer; a third layer of the first material with the first index of refraction formed on the second layer; a fourth layer of the second material with the second index of refraction formed on the third layer; a fifth layer of the first material with the first index of refraction formed on the fourth layer; a sixth layer of the second material with the second index of refraction formed on the fifth layer; and a seventh layer of the first material with the first index of refraction formed on the sixth layer.
  • the first index of refraction and the second index of refraction satisfy a ratio of H/L > 1, where L and H are values of the first and second index of refraction, respectively.
  • the first material with the first index of refraction is Si0 2
  • the second material with the second index of refraction is Zr0 2 .
  • the layer of the coupling agent is formed of a composition that comprises cyclic azasilanes.
  • FIG. 1 shows chemical reactions related to coupling agents utilized in prior art for manufacturing an anti-reflective coated lens.
  • FIG. 2 shows chemical reactions related to coupling agents utilized for manufacturing an anti-reflective coated lens according to one embodiment of the present invention.
  • FIG. 3 shows the dependency of the AR coating and the resulting lens on the temperature at which the super hydrophobic layer is applied according to embodiments of the present invention.
  • FIG. 4 shows preparation of an anti-reflective coated lens mold according to one embodiment of the present invention.
  • FIG. 5 shows preparation of an anti-reflective coated lens mold according to one embodiment of the present invention.
  • first, second, third etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the disclosure.
  • relative terms such as “lower” or “bottom”, “upper” or “top”, and “left” and “right”, may be used herein to describe one element's relationship to another element as illustrated in the Figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures. For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower”, can therefore, encompasses both an orientation of “lower” and “upper”, depending of the particular orientation of the figure.
  • this invention relates to AR-coated spectacle lenses, molds, compositions and methods of making AR lenses.
  • both the initial Si0 2 or MgF 2 layer and the mold release layer can be eliminated.
  • the super hydrophobic material can be applied directly to the mold surface.
  • the super hydrophobic material used in the examples of the specification was, but not limited to, Daikin Optool DSX. It should be appreciated that other super hydrophobic materials can also be utilized to practice the invention.
  • the super hydrophobic material is applied at less than 540 degrees C (as measured on the thermal boat).
  • the preferred temperature range is about 250-500 degrees C.
  • the super hydrophobic layer may be anywhere from 20 nm to 100 nm thick, with a preferred thickness of 40 nm.
  • dipodal is still required to stabilize the super hydrophobic layer.
  • the dipodal is placed into the pill along with the super hydrophobic, and they are applied together.
  • the amount of dipodal mixed with the super hydrophobic must be between 0.01 g and 0.1 g per pill. Two pills are used in a single run.
  • the preferred weight of the dipodal (for a 40 nm super hydrophobic layer) is 0.04 g per pill.
  • Dipodal silanes are available from Gelest, Inc.
  • a preferred dipodal silane can be bis(trimethoxysilylpropyl)amine having the formula:
  • the super hydrophobic material contains about 1.7-8.3% of dipodal silane by weight relative to the super hydrophobic material.
  • the super hydrophobic layer on the mold is not a mold release layer.
  • the super hydrophobic layer transfers to, and becomes part of, the lens during lens casting and curing.
  • an anti-reflective (AR) coating is applied.
  • the AR coating is a layered structure with multiple layers of dielectric materials (4 to 7 layers or even more) that are applied by vacuum deposition such that the last layer is ion-assisted Si0 2 .
  • the AR coating is a layered structure with multiple layers of three or more dielectric materials having alternating high and low refractive indexes.
  • a layer of silane coupling agent is applied to the AR-coated mold to promote adhesion of the hard coating.
  • the coupling agent layer must be applied under aprotic conditions. This can be done using methods commonly practiced in the lens industry today (such as spin, spray, dip, vacuum coating).
  • the coupling agent layer is applied at room temperature.
  • the silane coupling agent may be a dipodal silane.
  • the silane coupling agent is a cyclic azasilane. The silane from the cyclic azasilane will bond to the AR coating and the functional group will bond with the organic hard coat, respectively.
  • the next coating layer applied to the mold is the scratch-resistant (hard) coating.
  • the hard coat can be applied by conventional methods used in the lens industry, including spin, spray, or dip coating followed by curing.
  • the exemplary process illustrated above can be repeatedly applied to different optical surfaces of an optical mold assembly containing a front mold and a back mold. Following the applications of the coating to both of the front and back molds, the molds are assembled with a spacer ring to form the optical mold assembly. The cavity of the assembly is then filled with lens material formulation and cured. After the cure is complete, the lens is removed from the assembly. All coatings are transferred to the lens so that the lens has super hydrophobic, anti-reflective, and scratch resistance coatings applied. This process may also be used to make polarized and photochromic lenses.
  • the invention relates to a method for making an AR-coated plastic substrate having good adhesion of the AR coating.
  • the plastic substrate in one embodiment is a plastic ophthalmic spectacle lens.
  • the invention relates to a method of making AR coated plastic ophthalmic spectacle lenses on-site.
  • an AR coating is commonly applied to the surface of lenses to reduce reflection. Often, the AR coating is made of multiple layers of high index and low index materials such as Zr0 2 and Si0 2 .
  • One problem with inorganic silica AR coatings is that they do not readily adhere to plastic organic lenses.
  • the present invention successfully solves the problem by, among other things, using a coupling layer between the inorganic silica AR coating and the lens.
  • the coupling layer is formed by utilizing cyclic azasilane.
  • the coupling layer is formed by utilizing a dipodal silane.
  • the method for forming an ophthalmic lens having an AR coating thereon is comprised of the steps of preparing first and second molds having optical surfaces facing each other.
  • molds and a gasket such as described in U.S. Patent No. 7,114,696, which is incorporated herein by reference in its entirety, are used.
  • Various desired coatings are applied to the interior of one or both molds.
  • the molds with the coatings thereon are placed in a gasket assembly which provides a space between the molds.
  • a liquid monomer is placed in the space and is cured to provide a lens.
  • the molds can be formed of any suitable material which is capable of
  • an AR coating is applied by electron beam deposition directly onto the plastic mold optical surface. Subsequent to the first coating, a second coating may be applied before a multilayer AR coating is applied in reverse order.
  • an AR coating is a multilayer structure with alternating layers formed with two different materials, a high index material and a low index material.
  • an AR coating is a multilayer structure with 7 alternating layers formed with two different materials, a high index material and a low index material with a ratio H/L > 1 , wherein L and H are values of the first and second index of refraction, respectively.
  • Materials found to be suitable for practicing the present invention are zirconium dioxide (referred as "Zr0 2 ") as a high index material and silicon dioxide as a low index material, having an index of refraction of approximately 1.46.
  • the layers are applied by vacuum deposition such that the first and last layers are silicon dioxide (Si0 2 ).
  • a layer or film of the coupling agent is applied by vapor phase deposition.
  • the coupling agent is cyclic azasilane, it will bond to surface hydroxyls on the silicon dioxide layer, opening the ring and resulting in an organic molecule on the surface. This can be done under vacuum, at room
  • the hard coat can be applied as either an extension of the AR coating process by vacuum deposition or by the more conventional methods of spin, spray, or dip coating, with the coating application followed by curing.
  • a front and back mold are assembled.
  • the cavity of the assembly is then filled with lens material formulation which is then cured and bonds to the hard coat.
  • the lens is removed from the assembly. All coatings are transferred to the lens so that the lens has super hydrophobic, anti-reflective, and scratch resistance coatings applied.
  • Cyclic azasilanes are available from Gelest, Inc. Generic formulas include azasilacyclopentanes having the formula:
  • R 1 and R 2 are independently selected from the group consisting of branched and linear, substituted and unsubstituted alkyl, alkenyl and alkoxy groups, and where R 3 is selected from the group consisting of substituted and unsubstituted, saturated and unsaturated, branched and linear aliphatic hydrocarbon groups; substituted and unsubstituted, branched and linear aralkyl groups; substituted and unsubstituted aryl groups; and hydrogen.
  • Cyclic azasilanes also include diazasilacyclic compounds having the formula:
  • R 3 is selected from the group consisting of substituted and unsubstituted, saturated and unsaturated, branched and linear aliphatic hydrocarbon groups; substituted and unsubstituted, branched and linear aralkyl groups; substituted and unsubstituted aryl groups; and hydrogen; and wherein R4 and R 5 are independently selected from the group consisting of substituted and unsubstituted, branched and linear alkyl and alkoxy groups.
  • a preferred super hydrophobic compound is Optool DSX available from Daikin. This hydrophobic compound does not contain additives that are typically included in commercial super hydrophobic preparations to increase sticking of the super
  • cyclic azasilanes can be used to practice the present invention, including:
  • This example shows various tests utilized for the bonding of coatings produced according to various embodiments of the present invention.
  • Cross-Hatch Test In the cross-hatch test, a series of 10 lines spaced 1 mm apart is cut into the coating with a razor blade. A second series of 10 lines spaced 1mm apart at right angles to and overlaying the first is cut into the coating. A piece of cellophane tape is then applied over the Crosshatch pattern and pulled quickly away from the coating.
  • crazing test In the crazing test, a lens is de-molded then annealed at 80 °C for 20 minutes. The lens is quickly transferred to room temperature water and it is checked for crazing. If no crazing is apparent, then the AR/coupling agent system is acceptable.
  • Boiling Salt Water Test In the boiling salt water test, the lens is first immersed for two minutes in a boiling salt solution containing 4.5% NaCl and 0.8%
  • the lens is quickly transferred to room temperature (18-24°C) deionized water. If no crazing or delamination in the coating is noted, then the
  • AR/coupling agent system is acceptable.
  • a layer of a super hydrophobic material with a thickness of about 40 nm was deposited onto the molds.
  • the super hydrophobic material was evaporated from two copper crucibles, also called copper "liners", containing steel wool, each of which contained 0.04 g dipodal silane and excess super hydrophobic.
  • the quality of the AR coating and the resulting lens are substantially dependent on the temperature of the steel thermal boat at which the super hydrophobic layer was applied. All temperature measurements were taken by recording the temperature of the steel thermal boat during deposition.
  • Example (F) The temperature of the steel boat was raised to 500 degrees Fahrenheit (approximately 260 degrees Celsius). The contact angle was acceptable but not as good as the results in Example 5. It also became more difficult to separate the mold from the lens after casting. No crazing occurred.
  • FIG. 3 shows the dependency of the AR coating and the resulting lens on the temperature of the steel thermal boat at which the super hydrophobic layer was applied.
  • the preferred temperature range is about 200-500 degrees Celsius.
  • a process of preparation of applying an AR coating to a disposable mold is provided according to yet another embodiment of the present invention. It is noted that in this Example, Si0 2 layers are formed or deposited with or without ion assist.
  • the super hydrophobic material is contained within one or more crucibles in contact with a metal plate or boat. In certain embodiments, the super hydrophobic material is evaporated in vacuo from the one or more crucibles while heating the metal boat to a temperature between about 200 °C and about 500 °C. In some embodiments, the crucible is a copper material and the boat is a stainless steel material.
  • the layer 406 of the super hydrophobic material contains about 1.7-8.3% of dipodal silane by weight relative to the super hydrophobic material so that the AR coating can be stable.
  • concentration of dipodal silane in the super hydrophobic is that every 0.6g of super hydrophobic material contains about 0.0 lg to 0.05g of dipodal silane. If no or too little dipodal silane is used in the super hydrophobic material, the AR coating crazes and separates from the mold.
  • layer 410 of Si0 2 functions as a protective seal to the AR layered structure 511 and also as natural bonding surface or a "link" between the AR layered structure 511 and the layer 406 of a super hydrophobic material.
  • layer 424 of Si0 2 provides a natural bonding surface or "link" between the AR layered structure 511 and the layer 426 of the coupling agent. It is noted that although layer 410 and layer 412 both are formed of Si0 2 , they are formed with different processes such that they adhere to each other but function differently.
  • a process of applying an AR coating to a disposable mold is provided according to a further embodiment of the present invention. It is noted that in this Example, Si0 2 layers are formed or deposited with or without ion assist.
  • the super hydrophobic material is contained within one or more crucibles in contact with a metal plate or boat. In certain embodiments, the super hydrophobic material is evaporated in vacuo from the one or more crucibles while heating the metal boat to a temperature between about 200 °C and about 500 °C. In some embodiments, the crucible is a copper material containing steel wool, and the boat is a stainless steel material.
  • the present invention is practiced with a layer of a coupling agent that is applied to the AR-coated mold to promote adhesion of the hard coating.
  • the coupling agents are functional silanes in which the silane bonds to the AR coating and the functional group bonds with the organic hard coat.
  • cyclic azasilanes are particularly well suited for the application, as they will form silane bonds at room temperature via a ring-opening reaction. This results in a monolayer with functional groups that readily attach to the hard coat, forming a strong AR to hard-coat bond. It is believed that it is the first time in the industry and only by the inventive discovery of the present invention, that cyclic azasilanes are utilized in an optical lens forming process as coupling agents.
  • the functional silane is a dipodal silane. For embodiments as shown in FIGS.
  • the coupling agent must be applied under aprotic conditions and can be done using many of the methods commonly practiced in the lens industry today, such as spin, spray, dip, and vacuum coating. Three specific examples of coupling agent application are provided below.
  • a pair of optical molds comprising a front mold and a back mold, where corresponding optical surfaces of the molds are AR-coated molds according to one of various embodiments of the present invention as illustrated in Examples 4 and 5, is placed in a vacuum chamber, which is evacuated to create an aprotic environment with a predetermined pressure, in which a coupling agent will vaporize when introduced into the chamber.
  • the coupling agent is introduced into the sealed chamber and allowed to coat and react with each AR coating for a minimum of 10 minutes.
  • the chamber is evacuated to the original (pre-coupling agent),
  • the vacuum is released and the optical mold assembly is removed from the chamber. Afterwards, a hard coat can be applied.
  • a solution of coupling agent in an aprotic solvent is prepared (0.05% minimum).
  • aprotic solvents include toluene, benzene, petroleum ether, or other hydrocarbon solvents.
  • An AR-coated mold prepared according to one of various embodiments of the present invention as illustrated in Examples 4 and 5, is exposed to (or treated with) the solution for a minimum of 5 minutes at room temperature.
  • the treated mold is removed from the solution and rinsed with ethanol or a similar solvent.
  • the mold is then air-dried and afterwards a hard coat can be applied.
  • a solution of coupling agent in an aprotic solvent is prepared (0.05% minimum).
  • aprotic solvents include toluene, benzene, petroleum ether, Isopar L, or other hydrocarbon solvents.
  • the solution is placed into a spin-coating system, wherein a pump or pressure chamber is used to spray the solution onto a rapidly rotating spindle.
  • An AR-coated mold prepared according to one of various embodiments of the present invention as illustrated in Examples 4 and 5, is placed on the spindle.
  • the coupling agent solution is applied while the mold is rotating, creating an even coating.
  • Hard coat can then be applied.
  • This example shows a method or procedure of making an AR-coated lens according to one embodiment of the present invention.
  • a layer (426, 526) of a coupling agent consisting of or having N-n-butyl-aza-2,2-dimethoxy-silacyclopentane was then formed onto the AR surfaces (424, 524) using a dip coating method as set forth above in
  • Example 6 A solution was prepared of 0.05% coupling agent in petroleum ether. The optical surfaces were submerged in the solution for 5 minutes at room temperature. They were then rinsed with ethanol, allowed to air-dry, and immediately hard-coated using a spin-coating process. Upon casting, the hard coat, AR, and super hydrophobic coatings transferred from the mold onto the lens.
  • the present invention relates to a method for applying an anti- reflective coating to an optical surface of a mold.
  • a method for applying an anti- reflective coating to an optical surface of a mold has the steps of:
  • a layer 406 or506 of a super hydrophobic material with a thickness of about 20 to 100 nm over the optical surface 404 or 504, where the super hydrophobic material contains about 1.7-8.3% of dipodal silane by weight relative to the super hydrophobic material;
  • the super hydrophobic material is contained within one or more crucibles in contact with a metal plate or boat. In certain embodiments, the super hydrophobic material is evaporated in vacuo from the one or more crucibles while heating the metal boat to a temperature between about 200 °C and about 500 °C. In some embodiments, the crucible is a copper material and the boat is a stainless steel material.
  • the step of forming an anti-reflective coating layered structure 411 or 51 lover the layer 408 or 508 can be performed with the steps of:
  • the first index of refraction and the second index of refraction satisfy a ratio of H/L > 1, wher L and H are values of the first and second index of refraction, respectively.
  • the value of the second index of refraction is greater than the value of the first index of refraction.
  • the first material with first index of refraction comprises Si0 2
  • the second material with second index of refraction comprises Zr0 2 .
  • each layer of Si0 2 is deposited using ion assist or without using ion assist.
  • a step of forming a layer 410, 510 of Si0 2 that is deposited without ion assist and with a thickness of 5 to 40 nm over the super hydrophobic layer 406, 506 is performed such that the Si0 2 layer 410, 510 is formed between the super hydrophobic layer 506, 606 and the first layer 412, 512.
  • the dipodal silane can be bis(trimethoxysilylpropyl)amine.
  • the layer of the coupling agent is formed of a composition that comprises cyclic azasilanes.
  • the layer of the coupling agent is formed of N-n-butyl-aza-2,2-dimethoxy-silacyclopentane.
  • the layer of the coupling agent is formed of a composition that comprises dipodal silane.
  • the present invention relates to a mold with an optical surface having an anti-reflective coating that is transferable to an optical surface of a lens.
  • a mold has a layer 406 or 506 of a super hydrophobic material with a thickness of about 20 to 100 nm deposited over an optical surface 404 or 504 of the mold 402 or 502, where the super hydrophobic material contains about 1.7-8.3% of dipodal silane by weight relative to the super hydrophobic material.
  • the super hydrophobic material is contained within one or more crucibles in contact with a metal plate or boat.
  • the super hydrophobic material is evaporated in vacuo from the one or more crucibles while heating the metal boat to a temperature between about 200 °C and about 500 °C.
  • the crucible is a copper material and the boat is a stainless steel material.
  • the mold also has an anti-reflective coating layered structure 411 or 511 deposited over the super hydrophobic layer 406 or 506; and a layer 426 or 526 of a coupling agent that is deposited using dip coating or vapor deposition and with a monolayer thickness deposited over the anti-reflective coating layered structure 411 or 511.
  • the anti-reflective coating layered structure 411 or 511 has:
  • the first index of refraction and the second index of refraction satisfy a ratio of H/L > 1 , wherein L and H are values of the first and second index of refraction, respectively.
  • L and H are values of the first and second index of refraction, respectively.
  • the value of the second index of refraction is greater than the value of the first index of refraction.
  • the first material with first index of refraction comprises Si0 2
  • the second material with second index of refraction comprises Zr0 2 .
  • Each layer of Si0 2 in the anti-reflective coating layered structure is deposited using ion assist or without using ion assist.
  • a layer 410, 510 of Si0 2 is deposited without ion assist and with a thickness of 5 to 40 nm over the layer 406, 506 such that the layer 410, 510 is formed between the layer 406, 506 and the layer 412, 512.
  • the dipodal silane can be bis(trimethoxysilylpropyl)amine.
  • the layer of coupling agent is formed of a composition that comprises a functional silane.
  • the functional silane comprises dipodal silanes in some embodiments. In other embodiments the functional silane comprises cyclic azasilanes. In various embodiments as shown in FIGS. 4 and 5, the layer of coupling agent is formed of N-n- butyl-aza-2,2-dimethoxy-silacyclopentane.
  • the present invention relates to an optical lens.
  • the optical lens has a lens body with an optical surface and an anti-reflective coating formed on the optical surface, where in various embodiments as shown in FIGS. 4 and 5, the anti- reflective coating has a layer 406 or 506 of a super hydrophobic material with a thickness of about 20 to 100 nm deposited over an optical surface 404 or 504 of the mold 402 or 502, where the super hydrophobic material contains about 1.7-8.3% of dipodal silane by weight relative to the super hydrophobic material.
  • the super hydrophobic material is contained within one or more crucibles in contact with a metal plate or boat.
  • the super hydrophobic material is evaporated in vacuo from the one or more crucibles while heating the metal boat to a temperature between about 200 °C and about 500 °C.
  • the crucible is a copper material and the boat is a stainless steel material.
  • the anti-reflective coating also has an anti-reflective coating layered structure 411 or 511 deposited over the super hydrophobic layer 406 or 506; and a layer 426 or 526 of a coupling agent that is deposited using vapor deposition and with a monolayer thickness deposited over the anti-reflective coating layered structure 411 or 511 and coupled to the optical surface of the lens body.
  • the anti-reflective coating layered structure 411 or 511 is formed with:
  • the first index of refraction and the second index of refraction satisfy a ratio of H/L > 1 , where L and H are values of the first and second index of refraction, respectively. In other words, the value of the second index of refraction is greater than the value of the first index of refraction.
  • the first material with first index of refraction comprises Si0 2
  • the second material with second index of refraction comprises Zr0 2 .
  • Each layer of Si0 2 in the anti-reflective coating layered structure is deposited using ion assist or without using ion assist.
  • a layer 410, 510 of Si0 2 is deposited without ion assist and with a thickness of 5 to 40 nm over the layer 406, 506 such that the layer 410, 510 is formed between the layer 406, 506 and the first layer 412, 512.
  • the dipodal silane can be bis(trimethoxysilylpropyl)amine.
  • the layer of coupling agent is formed of a composition that comprises cyclic azasilanes.
  • the layer of coupling agent is formed of N-n-butyl-aza-2,2-dimethoxy-silacyclopentane.
  • the present invention relates to a coupling agent usable in lens making.
  • the coupling agent comprises dipodal silanes.
  • the coupling agent comprises cyclic azasilanes.
  • cyclic azasilanes comprise N-n-butyl-aza-2,2-dimethoxy-silacyclopentane. It is noted that in use, cyclic azasilanes and dipodal silanes are applied in a solvent.
  • a solvent for embodiments as shown in FIGS. 4 and 5, where Si0 2 is used as the first material with the first index of refraction, utilizing N-n-butyl-aza-2,2-dimethoxy-silacyclopentane as a coupling agent allows a surface bonding ring opening reaction without requiring water or heat, as shown in FIG. 2, resulting in much better bonding and making on-site AR lens formation a reality. This is much better than the process shown in FIG. 1, which requires high heat, among other things.
  • the present invention relates to an optical lens.
  • the optical lens has a lens body with an optical surface, a hard coat layer over the optical surface, and an anti-reflective coating over the optical surface.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

La présente invention concerne un procédé permettant d'appliquer un revêtement antireflet sur une surface optique d'un moule. Dans un mode de réalisation, le procédé comprend les étapes consistant à proposer un moule de lentille présentant une surface optique ; former une couche fabriquée dans un matériau super hydrophobe sur la surface optique, le matériau super hydrophobe contenant une quantité de silane bipode qui est un pourcentage relatif du matériau super hydrophobe ; former une structure à revêtement antireflet sur la couche en matériau super hydrophobe ; et former une couche d'agent d'accouplement déposée avec une épaisseur monocouche sur la structure à revêtement antireflet en utilisant un dépôt par évaporation sous vide dans des conditions aprotiques ou par dépôt par trempage ou à la tournette en utilisant une solution d'un agent d'accouplement dans un solvant aprotique.
PCT/US2014/038600 2013-07-16 2014-05-19 Lentilles antireflets et procédé de fabrication associés WO2015009349A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020101944A1 (fr) * 2018-11-13 2020-05-22 Quantum Innovations, Inc. Lentille antireflet et procédé de traitement d'une lentille pour réduire les réflexions pour des mammifères placentaires à vision dichromatique
US11021607B2 (en) 2016-03-23 2021-06-01 Dow Silicones Corporation Metal-polyorganosiloxanes
US11353630B2 (en) 2019-03-18 2022-06-07 Quantum Innovations, Inc. Method for treating a lens to reduce light reflections for animals and devices that view through the ultra violet light spectrum
US11448797B1 (en) 2018-11-29 2022-09-20 Quantum Innovations, Inc. Viewing lens and method for treating lenses to minimize glare and reflections for birds with tetra-chromatic vision

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190033491A1 (en) * 2017-07-28 2019-01-31 Ppg Industries Ohio, Inc. Multi-layer antireflective coated articles

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040065968A1 (en) * 2001-05-29 2004-04-08 Essilor International Compagnie Generale D'optique Method for preparing a mold part useful for transferring a coating onto an optical substrate
JP2007504500A (ja) * 2003-09-04 2007-03-01 エシロール アンテルナショナル コムパニー ジェネラル ドプテイク 光学基板上の反射防止被膜処理法と被膜処理された光学基板および被膜処理実施装置
US20080113188A1 (en) * 2006-11-09 2008-05-15 Shah Pratik B Hydrophobic organic-inorganic hybrid silane coatings
US20090075092A1 (en) * 2007-09-18 2009-03-19 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
CN101724342A (zh) * 2009-12-17 2010-06-09 复旦大学 一种超双亲自清洁涂层材料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040065968A1 (en) * 2001-05-29 2004-04-08 Essilor International Compagnie Generale D'optique Method for preparing a mold part useful for transferring a coating onto an optical substrate
JP2007504500A (ja) * 2003-09-04 2007-03-01 エシロール アンテルナショナル コムパニー ジェネラル ドプテイク 光学基板上の反射防止被膜処理法と被膜処理された光学基板および被膜処理実施装置
US20080113188A1 (en) * 2006-11-09 2008-05-15 Shah Pratik B Hydrophobic organic-inorganic hybrid silane coatings
US20090075092A1 (en) * 2007-09-18 2009-03-19 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
CN101724342A (zh) * 2009-12-17 2010-06-09 复旦大学 一种超双亲自清洁涂层材料及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11021607B2 (en) 2016-03-23 2021-06-01 Dow Silicones Corporation Metal-polyorganosiloxanes
WO2020101944A1 (fr) * 2018-11-13 2020-05-22 Quantum Innovations, Inc. Lentille antireflet et procédé de traitement d'une lentille pour réduire les réflexions pour des mammifères placentaires à vision dichromatique
US11448797B1 (en) 2018-11-29 2022-09-20 Quantum Innovations, Inc. Viewing lens and method for treating lenses to minimize glare and reflections for birds with tetra-chromatic vision
US11353630B2 (en) 2019-03-18 2022-06-07 Quantum Innovations, Inc. Method for treating a lens to reduce light reflections for animals and devices that view through the ultra violet light spectrum

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