Method for printing of ophthalmic laminates and photoresist composition for the same

Description

1 / 53 METHOD FOR PRINTING OPHTHALMIC LAMINATES AND COMPOSITION OF PHOTORESIST FOR THE SAME DESCRIPTION Field of Technique

[0001] The present invention pertains to the technical field of manufacturing ophthalmic laminates and ophthalmic lenses. More specifically, the present invention relates to ophthalmic laminates and ophthalmic lenses made through printing and methods for manufacturing such wafers and lenses to correct a visual impairment, retard its progression, and improve specific lens distortions. Previous Technique

[0002] Ophthalmic lenses with micro- or nanostructures on the lens surface or embedded within the lens can be used to provide ophthalmic lenses with enhanced properties. For example, ophthalmic lenses can be equipped with micro- or nanostructures embedded in the form of micro or nanometric lenses. These micro or nanometric lenses can be configured to bring more light to the center of the eye, alter the optical functionality of a portion of a lens (e.g., astigmatic region), or redirect a portion of the incident light to different regions of the retina to treat or slow the progression of eye-related vision conditions such as myopia, compared to ophthalmic lenses without such features. It is known that when light is defocused in the periphery of the retina in myopic individuals, this can slow the progression of myopia over time.

[0003] Nanoprinting lithography (NIL) is a form of UV printing (UVI) used to fabricate micro or nanostructures on polymer surfaces by photocuring a coated photoresist layer while it is in contact with a pattern template, such as a stamp replica, whose microstructure shape is the opposite image of the target micro or nanostructure shape on the surface. Petition 870250093634, dated 10 / 13 / 2025, page 8 / 81 2 / 53 of polymer. The photoresist composition typically comprises thermosetting monomers or oligomers or other energy-curable monomers, curing initiators, processing aids, diluents, particulates and, optionally, other reactive molecules.

[0004] The photoresist can be coated onto a polymer film, flexible sheet, rigid metal plate or cylinder, quartz or silicon wafer, or other substrate. The patterning template is then placed in contact with the photoresist-coated film. Subsequently, the photoresist is cured through the substrate or the template sides. The element through which the curing is performed must be transparent to the curing energy. Alternatively, the photoresist can be coated onto the patterning template and the film or other substrate can be placed in contact with the coated patterning template. Subsequently, the photoresist is cured through the transparent substrate or the template sides. The patterning template can be in the form of a flat plate or shim, tile-welded shims, seamless cylinder or sleeve, circular drum, a concave or convex curved mold, or other patterned template.

[0005] Exposure to UV energy causes photopolymerization, which includes crosslinking, resulting in an increase in the photoresist modulus and causing the shape of micro or nanostructures to be defined in the photoresist. Subsequently, the cured photoresist layer is released from the patterning template. Exposure to UV light (ion beam, electron beam, or other high-energy means) can be carried out using a transparent template or a transparent film or substrate. Transparent templates can be made of quartz glass, polydimethylsiloxane (PDMS), for example, in the form of incompressible (firm, hard) or semi-compressible (soft) working seals, or other durable material or combinations with particle fillers (e.g., ZrO2). Petition 870250093634, dated 10 / 13 / 2025, page 9 / 81 3 / 53

[0006] Non-transparent templates can be made by replicating the master template that was created through diamond turning, photolithography, or any other micro / nanostructuring method known in the art, in some cases by creating one or more replica templates. The master or replica template(s) can also be created using a nickel plating process on a metal substrate, such as stainless steel, brass, aluminum, or another suitable non-transparent process. This technique can be repeated, with the master template or its replicas, to alter the polarity of the image, that is, to create the opposite orientation of the micro / nanostructure, or to transfer the design to a different support substrate.

[0007] Commercially available photoresistes suitable for NIL are optimized for reliability, so that the chemical formulations produce consistent physical and mechanical properties, and for their bond strength to the support substrates. These support substrates typically have a hydrophobic silicon or quartz surface that contacts the photoresistes. These formulations are usually produced from aromatic compounds or compounds that have polar pendant groups; therefore, they are colored, inflexible, and incompatible with plastic materials such as polycarbonate (PC). Their colors range from light yellow to orange or red and they are not necessarily formulated to be optically clear and transparent materials with a specific refractive index. Their lack of flexibility makes them brittle and susceptible to cracking under stress or compression. Polycarbonate is a common material for producing ophthalmic lenses.Therefore, these disadvantages make these commercially available photoresist materials unsuitable for producing ophthalmic lenses. They are also too expensive for covering large areas and producing defect-free prints. Petition 870250093634, dated 10 / 13 / 2025, page 10 / 81 4 / 53

[0008] In addition, it may be difficult to join print layers to another layer for encapsulation purposes, or their bonding strength may be too weak to withstand photoresist wear.

[0009] Therefore, there is a need to develop a method and photoresist compositions that are suitable for printing micro or nanostructures onto PC substrates and have sufficient bond strength to adhere to the PC substrate and adhesive layer to allow encapsulation of microstructured patterns within a multilayer film laminate or as a single-layer film that is directly bonded to the lens substrate. SUMMARY OF THE INVENTION

[0010] Thus, an objective of the present invention is to overcome at least one of the disadvantages of the prior art. In particular, an objective of the present invention is to provide a photoresist formulation that is suitable for printing complex nano or microstructures on PC using NIL.

[0011] Thus, the present invention provides a method for manufacturing an ophthalmic laminate having a first support layer, a photoresist layer having micro or nanostructures on a surface opposite the first support layer. The method comprises forming, on a first support layer, a partially cured photoresist layer with a surface having micro or nanostructures, which includes: (i) depositing a photoresist composition onto the first support layer to form a photoresist layer, (ii) printing the micro or nanostructures onto the photoresist layer by applying a stamp with a negative image of the micro or nanostructures onto the photoresist layer, and partially curing the photoresist layer until it is no longer sticky, while still retaining the acrylate bonds present therein; and (iii) removing the stamp. Petition 870250093634, dated 10 / 13 / 2025, page 11 / 81 5 / 53

[0012] The deposition of the photoresist composition on the first support layer can be carried out through precision coating, such as centrifugal coating, Meyer bar wire-wound coating, knife coating, roller coating, etching roller coating or slit die coating of the photoresist composition onto the first support layer.

[0013] The deposition of the photoresist composition can be done through slit die coating, the stamp can be a stamping drum and the curing can be carried out through the first support layer or the stamping drum.

[0014] Before forming the photoresist layer on the first support layer, the method may involve activating the surface of the first support layer.

[0015] The first support layer may be a thermoplastic first layer, and the photoresist composition may comprise a crosslinking initiator and a mixture of polymerizable monomers or oligomers. The mixture may comprise 20-80% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of triacrylate, which is different from urethane triacrylate, and 3-30% by weight of diacrylate. Preferred mixtures comprise 50-70% by weight of urethane hexaacrylate, 15-25% by weight of triacrylate, which is different from urethane triacrylate, and 15-25% by weight of diacrylate. The percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

[0016] Alternatively, the photoresist composition is any one of the formulations F1 to F5.

[0017] Formulation F1 comprises 20 to 80 phm of urethane acrylate(s) with a lower refractive index, 10 to 50 phm of mono- or difunctional acrylate(s) other than urethane acrylates with a lower refractive index, and 0 to 50 phm of tri- or more functional acrylate(s). Petition 870250093634, dated 10 / 13 / 2025, page 12 / 81 6 / 53 different functional(s) of urethane acrylates with lower refractive index and 1 to 10 phm of photoinitiator.

[0018] Formulation F2 comprises 20 to 80 phm of urethane acrylate(s) with a higher refractive index, 10 to 50 phm of mono- or difunctional acrylate(s) other than urethane acrylates with a lower refractive index, 0 to 50 phm of tri- or more functional acrylate(s) other than urethane acrylates with a lower refractive index, 0 to 60 phm of aromatic acrylate(s) and 1 to 10 phm of photoinitiator.

[0019] Formulation F3 comprises 20 to 80 phm of 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene, 0 to 30 phm of trifunctional acrylate(s) or higher, other than urethane acrylates with a lower refractive index, 0 to 60 phm of aromatic acrylate(s); and 1 to 10 phm of photoinitiator.

[0020] Formulation F4 comprises 0 to 70 pH of 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene, 0 to 70 pH of aromatic acrylate(s), 30 to 100 pH of brominated or chlorinated acrylate(s) and 1 to 10% by weight of photoinitiator.

[0021] Formulation F5 comprises 0 to 50 phm of urethane acrylate(s) with lower refractive index, 0 to 70 phm of mono- or difunctional acrylate(s) other than urethane acrylates with lower refractive index, 0 to 70 phm of tri- or more functional acrylate(s) other than urethane acrylates with lower refractive index, 30 to 100 phm of fluorinated acrylate(s) and 1 to 10 phm of photoinitiator.

[0022] Optionally, the photoresist composition may comprise 20 to 60 % by weight of nanoparticles that increase the refractive index; the total weight of the composition represents 100 % by weight.

[0023] In other cases, the first support layer may be a first primer layer produced from deposition on Petition 870250093634, dated 10 / 13 / 2025, page 13 / 81 7 / 53 A first thermoplastic layer, of an initiator composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers. The mixture may comprise 20-80% by weight of urethane triacrylate or urethane hexaacrylate, 330% by weight of triacrylate, which is other than urethane triacrylate, and 3-30% by weight of diacrylate. Preferred mixtures comprise 50-70% by weight of urethane hexaacrylate, 15-25% by weight of triacrylate, which is other than urethane triacrylate, and 15-25% by weight of diacrylate. The percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

[0024] Alternatively, the initiator composition may be formulation F1 or formulation F2, as defined above.

[0025] The method may further comprise providing a second support layer and a leveling layer between the photoresist layer and the second support layer.

[0026] Before providing the second support layer and the leveling layer, the method may involve activating the surface of the second support layer.

[0027] Providing a leveling layer may comprise (i) coating by centrifugation, coating by Meyer bar wire coiling, coating by knife, coating by rolling, coating by engraving roller or coating by slit die a leveling composition onto the second support layer to form a leveling film thereon, (ii) depositing the leveling composition onto the partially cured photoresist layer, (iii) placing the leveling film in contact with the leveling composition deposited on the partially cured photoresist layer, (iv) fully curing the laminate to obtain the ophthalmic laminate.

[0028] The second support layer can be a thermoplastic layer. Petition 870250093634, dated 10 / 13 / 2025, page 14 / 81 8 / 53

[0029] The second support layer may be a second primer layer produced by depositing, onto a second thermoplastic layer, a composition as defined for the first primer layer.

[0030] The invention also provides a method for manufacturing an ophthalmic lens, comprising providing an ophthalmic laminate with a first support layer and a photoresist layer having micro or nanostructures on a surface opposite the first support layer, using the method described above, and bonding a substrate to the ophthalmic laminate.

[0031] The mold used in this method may comprise a convex matrix and a concave matrix. In this case, the method may comprise placing the ophthalmic laminate against the concave matrix or the convex matrix.

[0032] The invention also provides an ophthalmic laminate comprising, stacked one on top of the other in the following order, a first thermoplastic layer, a photoresist layer having micro or nanostructures on its free surface.

[0033] The ophthalmic laminate may also comprise a leveling layer and a second thermoplastic layer. The photoresist layer and the leveling layer form micro or nanostructures at their interface.

[0034] The photoresist layer can be produced from a photoresist composition as described above.

[0035] The ophthalmic laminate may further comprise a primer layer between the first thermoplastic layer and the photoresist layer, or between the adhesive layer and the second thermoplastic layer. The primer layer may be produced from a primer composition as described above.

[0036] The ophthalmic laminate provided by the invention survives to Petition 870250093634, dated 10 / 13 / 2025, page 15 / 81 9 / 53 subsequent processing steps, such as: thermoforming, pressure forming, blow forming, adhesive lamination, thermoplastic injection molding, thermoset casting, lens attachment, surfacing, edging, frame assembly, hard multilayer coating, etc. It is also a high-quality ophthalmic lens free from aesthetic defects. Therefore, it is essentially free from environmental stress cracking, delamination, low transmission, opacity, color change (yellowing index), etc. Brief Description of the Drawings

[0037] Objectives, features and additional advantages will become clearer in the following detailed description with reference to the following drawings:

[0038] Figure 1 is a schematic view of an exemplary ophthalmic laminate according to the invention before it is formed and has a first support layer and a photoresist layer.

[0039] Figure 2 is a schematic view of another exemplary ophthalmic laminate according to the invention before molding, which has, in addition to the layers illustrated in Figure 1, a leveling layer.

[0040] Figure 3 is a schematic view of another exemplary ophthalmic laminate according to the invention before it is formed and has a first support layer, a photoresist layer, an adhesive layer and a second support layer.

[0041] Figure 4 is a schematic view of another exemplary ophthalmic laminate according to the invention before molding, which has, in addition to the layers illustrated in Figure 1, a first primer layer.

[0042] Figure 5 is a schematic view of another exemplary ophthalmic laminate according to the invention before it is molded and Petition 870250093634, dated 10 / 13 / 2025, page 16 / 81 10 / 53 which, in addition to the layers illustrated in Figure 3, has a first initiator layer and a second initiator layer.

[0043] Figure 6 is a schematic view of the exemplary ophthalmic laminate of Figure 1 after shaping, producing a structured pellet.

[0044] Figure 7 is a schematic view of the exemplary ophthalmic laminate of Figure 2 after shaping, producing an encapsulated structured pellet.

[0045] Figure 8 is a schematic view of the exemplary ophthalmic laminate of Figure 3 after shaping, producing an encapsulated structured pellet.

[0046] Figure 9 is a schematic view of a sunglass lens according to the invention with an encapsulated structured pellet of Figure 7.

[0047] Figure 10 is a schematic view of a sunglass lens according to the invention with an encapsulated structured pellet of Figure 8.

[0048] Figure 11 is a schematic view of the sunglass lens according to the invention with an encapsulated structured pellet of Figure 8.

[0049] Figure 12 is a schematic view of another sunglass lens according to the invention.

[0050] Figure 13 schematically illustrates the printing of micro or nanostructures on a partially cured photoresist layer according to an exemplary implementation of the invention's method.

[0051] Figure 14 schematically illustrates the manufacturing of the non-conformed ophthalmic laminate of Figure 3.

[0052] Figure 15 schematically illustrates the thermoplastic injection overmolding of a substrate into a structured pellet. Petition 870250093634, dated 10 / 13 / 2025, page 17 / 81 11 / 53

[0053] Figure 16 schematically illustrates the thermoset casting of a substrate into a structured pellet.

[0054] Figure 17 schematically illustrates continuous roll-to-roll printing of a photoresist onto a film using a transparent template seal fixed to a transparent printing drum with curing through the transparent printing drum and the transparent template seal.

[0055] Figure 18 schematically illustrates continuous roll-to-roll printing of a photoresist onto a transparent film using a template stamp fixed to a printing drum with curing through the transparent film. Detailed description of the invention

[0056] Unless otherwise stated, all viscosity values ​​are obtained at 25.6 °C using a Brookfield viscometer (Brookfield Ametek Small Sample Adapter SC4-18 spindle with sample quantity: 6.7 ml). Ophthalmic laminate

[0057] The ophthalmic laminates according to the invention will now be described with reference to Figures 1 to 4.

[0058] This ophthalmic laminate 10 comprises, stacked one on top of the other in the following order, a first thermoplastic layer 11 and a photoresist layer 13 which has micro or nanostructures 131 on its face opposite to the first thermoplastic layer 11 as illustrated in Figure 1.

[0059] In another embodiment, the ophthalmic laminate 10 further comprises, stacked on top of the photoresist layer 13, a refractive index leveling layer 15 (hereinafter leveling layer) as illustrated in Figure 2. In this case, the leveling layer 15 has micro or nanostructures that are the negative image. Petition 870250093634, dated 10 / 13 / 2025, page 18 / 81 12 / 53 of the micro or nanostructures 131 of the photoresist layer 13. The leveling layer 15 helps to adjust the refractive index of the overall ophthalmic laminate 10 to the desired overall refractive index, according to the refractive index of the photoresist layer 13.

[0060] In addition to the leveling layer 15, the ophthalmic laminate 10 may also comprise a second thermoplastic layer 17 over the leveling layer 15 as illustrated in Figure 3.

[0061] In general, the number of reactive or functional precursors that can be used in the ophthalmic field is limited: for example, epoxy, acrylate or vinyl monomers with simple or multifunctional reactive groups, including rings, mixtures of such reactive monomers, diluents, oligomers, prepolymers or polymers. These compounds are available to have all the properties necessary to form an optically functional ophthalmic laminate.

[0062] Examples of usable epoxy monomers are especially UV curable ones, such as Delo® Katiobond® 45952, Delo® Katiobond® 4670, Delo® Katiobond® DF698, Delo® Katiobond® EG6133, Delo® Katiobond® GE680 and Delo® Katiobond® KB552.

[0063] The photoresist layer 13 can be produced from a photoresist composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers. The mixture comprises 20-80% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of triacrylate, which is different from urethane triacrylate, and 3-30% by weight of diacrylate. These weight percentages are based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

[0064] This photoresist composition allows replication of the pattern from the patterning template or work stamp with high replication fidelity, low shrinkage and, in particular, can be completely released from the patterning template or work stamp without leaving Petition 870250093634, dated 10 / 13 / 2025, page 19 / 81 13 / 53 No photoresist material is present in the latter. The clean release of the template or seal 5 ensures the durability of the latter, as cleaning is facilitated. Furthermore, it has a settling rate from uncured to slightly cured, compatible with the curing process. It has high bond strength to the first thermoplastic layer 11 and, when provided, to the leveling layer 15, and has high cohesive strength. Additionally, it is not brittle and is malleable during thermoforming of the ophthalmic laminate into a pad with a low or high diopter base curve.

[0065] In addition, this photoresist composition is less expensive.

[0066] In one example, the mixture may comprise 50-70% by weight of urethane hexaacrylate, 15-25% by weight of triacrylate, which is different from urethane triacrylate, and 15-25% by weight of diacrylate. This percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

[0067] Polymerizable monomers or oligomers may be at least three compounds chosen from the group consisting of: - difunctional urethane methacrylate monomer (e.g., CN 1969, Sartomer; Visiomer HEMATMDI, Lintech International / Evonik), - 3,3,5-trimethylcyclohexyl methacrylate (e.g. SR421A, Sartomer), - pentaerythritol tetraacrylate (e.g., SR295, Sartomer) - Monofunctional isobornyl methacrylate (e.g., Visiomer Terra IBOMA, Lintech International / Evonik), - aliphatic urethane diacrylate (e.g. Photomer 6024, IGM), - hexafunctional aliphatic urethane acrylate oligomer (by Petition 870250093634, dated 10 / 13 / 2025, page. 20 / 81 14 / 53 example, Photomer 6690, IGM), - difunctional aliphatic urethane acrylate (Photomer 6891, IGM), - trifunctional aliphatic urethane acrylate (Photomer 6892, IGM), - hexamethylene diacrylate, - propanedi-yl diacrylate, - ethylene oxide o-phenylphenol acrylate (e.g. Miramer M1142, Miwon), - bisfluorene diacrylate (e.g. Miramer HR6042, Miwon), - phenol acrylate (ethylene oxide) (for example, Miramer M140, Miwon), - trimethylolpropane triacrylate, - hexanediol diacrylate, - tripropylene glycol diacrylate - triethylene glycol diacrylate.

[0068] Preferably, the polymerizable monomers or oligomers are photopolymerizable monomers or oligomers, thus making the resist composition a photoresist composition and the photoresist layer 13 a photoresistant layer.

[0069] The crosslinking initiator may constitute 0.5-5% by weight of the photoresist composition.

[0070] Preferably, the crosslinking initiator is a photoinitiator. In this case, the crosslinking initiator can be at least one of the following: Omnirad 4265, 2-hydroxy-2-methyl-1-phenylpropanone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 3-hydroxy-3-phenylbutan-2-one, ethylphenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxycyclohexylphenyl ketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one.

[0071] The photoresist composition may comprise an acrylate Petition 870250093634, dated 10 / 13 / 2025, page 21 / 81 15 / 53 fluorinated acrylate allows for shifting the refractive index of the photoresist composition. Typically, adding fluorinated acrylate decreases the refractive index.

[0072] Other examples of preferred photoresist compositions are summarized in Table 1 below (quantities are expressed in phm, i.e., parts per 100 parts by weight of monomer): Table 1 - Examples of photoresist compositions F1 F2 F3 F4 F5 Lower refractive index urethane acrylate(s) 20-80 — — — 0-50 Higher refractive index urethane acrylate(s) 20-80 Mono- or difunctional acrylate(s) 10-50 10-50 — — 0-70 Tri- or higher functional acrylate(s) 0-50 0-50 0-30 0-70 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene — — 20-80 0-70 Aromatic acrylate(s) 0-60 0-60 0-70 Brominated or chlorinated acrylate(s) 30-100 Fluorinated acrylate(s) — — 30-100 Photoinitiator 1-10 1-10 1-10 1-10 1-10

[0073] Urethane acrylates with lower refractive indexes may be chosen from the list consisting of: Photomer 6690; Photomer 6892; Photomer 6008; Photomer 6010; Photomer 6019; Photomer 6184; Photomer 6625; Photomer 6720; Ebecryl 1290; Ebecryl 1291; Ebecryl 8301-R; Ebecryl 264; Ebecryl 266; Ebecryl 8405; Ebecryl 8465; Ebecryl 8605; Ebecryl 8606; Ebecyl 8701; Ebecryl 8702; Miramer Petition 870250093634, dated 10 / 13 / 2025, page 22 / 81 16 / 53 PU320; Miramer PU340; Miramer PU3450; Miramer PU390; Miramer PU622; Miramer MU9800; Miramer U3600; Miramer U3304; Sartomer CN929; Sartomer CN968; Sartomer CN989; Sartomer CN9006; Sartomer CN9010; Sartomer CN9013; Sartomer CN9012; Sartomer CN9026; Sartomer CN9029; Sartomer CN9062; Sartomer CN968; and Sartomer CN968.

[0074] Urethane acrylates with higher refractive indexes can be chosen from the list which consists of: Miramer HR3000; Miramer HR3200; Miramer HR3700; Miramer HR3800; Miramer HR4000; and Miramer PU2900.

[0075] Mono- or di-functional acrylate (wherein acrylate may also be methacrylate) may be chosen from the list consisting of: 1,6-hexanediol diacrylate; 1,10-decanediol diacrylate; tetrahydrofurfuryl acrylate; 1,4-butanediol diacrylate; diethylene glycol diacrylate; tricyclodecane dimethanol diacrylate; 3,3,5-trimethylcyclohexyl acrylate; cyclohexane dimethanol diacrylate; isobornyl acrylate; caprolactone acrylate; cyclic trimethylolpropane formal acrylate; butyl acrylate; and pentyl acrylate.

[0076] Tri- or higher functional acrylates (wherein the acrylate may also be methacrylate) may be selected from the list consisting of: trimethylolpropane triacrylate; trimethylolpropane triacrylate (EO)n; trimethylolpropane triacrylate (PO)n; tris(2-hydroxyethyl)isocyanurate triacrylate; pentaerythritol tetraacrylate; pentaerythritol tetraacrylate (EO)n; ditrimethylolpropane tetraacrylate; di(pentaerythritol) pentaacrylate; and dipentaerythritol hexaacrylate.

[0077] Aromatic acrylates (wherein acrylate may also be methacrylate) may be chosen from the list which consists of: 2-phenylphenoxyethyl acrylate; 2-phenoxyethyl acrylate; alpha-naphthyl acrylate; beta-naphthyl acrylate; 2-phenylethyl acrylate; diphenylmethyl acrylate; phenyl acrylate; and bisphenol A (EO)n diacrylate. Petition 870250093634, dated 10 / 13 / 2025, page 23 / 81 17 / 53

[0078] Brominated or chlorinated acrylates (wherein acrylate may also be methacrylate) may be chosen from the list which consists of: pentabromobenzyl acrylate; pentabromophenyl acrylate; phenyl alpha-bromoacrylate; p-bromophenyl acrylate; 2,3-dibromopropyl acrylate; methyl alpha-bromoacrylate; pentachlorophenyl acrylate; and o-chlorodiphenylmethyl acrylate.

[0079] Fluorinated acrylates (wherein the acrylate may also be methacrylate) may be chosen from the list consisting of: pentadecafluorooctyl acrylate; tetrafluoro-3-(heptafluoropropoxy)propyl acrylate; tetrafluoro-3-(pentafluoroethoxy)propyl acrylate; undecafluorohexyl acrylate; nonafluoropentyl acrylate; tetrafluoro-3-(trifluoromethoxy)propyl acrylate; heptafluorobutyl acrylate; octafluoropentyl acrylate; pentafluoropropyl acrylate; 2-heptafluorobutoxy)ethyl acrylate; 2,2,3,4,4,4-hexafluorobutyl acrylate; trifluoroethyl acrylate; 2-(1,1,2,2-tetrafluoroethoxy)ethyl acrylate; trifluoroisopropyl acrylate; 2,2,2-trifluoro-1-methyl acrylate; 2-trifluoroethoxyethyl acrylate; and trifluoroethyl acrylate.

[0080] The photoinitiator can be Omnirad 4265.

[0081] The photoresist composition preferably has a viscosity of 430 to 640 cPs, preferably 480 to 590 cPs, and even more preferably 510 to 560 cPs.

[0082] The photoresist composition preferably has a glass transition temperature (Tg) of 75 to 120 °C, preferably 85 to 110 °C, and even more preferably 90 to 100 °C.

[0083] In some cases, the leveling layer 15 is the last layer of the ophthalmic laminate 10 provided to encapsulate the micro or nanostructures 131. The leveling layer 15 can also act as a protective encapsulation layer when the micro or nanostructures of this laminated structure are facing the outer surface of a lens. Petition 870250093634, dated 10 / 13 / 2025, page 24 / 81 18 / 53

[0084] In other cases, the leveling layer 15 is an adhesive layer made of an adhesive composition that has the same definition as the photoresist composition for the photoresist layer 13 and is used to bond to the second support layer 17, which includes preferred compositions F1 to F5. If the adhesive composition is chosen from F1 to F4, it may further comprise index-shifting nanoparticles, such as ZrO2 particles. The photoresist composition used for the adhesive layer 15 is, however, different from that used for the photoresist layer 13.

[0085] The adhesive composition preferably has a setting rate from uncured to slightly cured, compatible with the drying or curing process. It also has high bond strength to the second thermoplastic layer 17 and to the photoresist layer 13. It exhibits high cohesive strength, is not brittle and is malleable during thermoforming of the laminate into a low or high base curve pad.

[0086] The adhesive composition used for the adhesive layer 15 is preferably sufficiently fluid to fill the created pattern of micro or nanostructures of the photoresist layer, allowing for high fidelity filling. For example, the adhesive has a viscosity of 630 to 950 cPs, preferably 710 to 870 cPs, or even more preferably 750 to 830 cPs.

[0087] In this viscosity example, the adhesive composition comprises refractive index shifting nanoparticles to produce a higher refractive index and viscosity compared to that of photoresist and allow the photoresist composition to easily replicate the pattern during the printing process and converge the light.

[0088] In other cases without any nanoparticles that shift the refractive index, the viscosity is preferably 430 to 640 cPs, preferably 480 to 590 cPs, and still preferably... Petition 870250093634, dated 10 / 13 / 2025, page 25 / 81 19 / 53 505 to 560 cPs. The adhesive composition preferably has a glass transition temperature (Tg) of 75 to 120 °C, preferably 85 to 110 °C, and even more preferably 90 to 100 °C.

[0089] At least one of the photoresist layer 13 and the leveling layer 15 may comprise refractive index shifting nanoparticles, making it possible to adjust the refractive index according to the optical power of the micro or nanostructures. Typically, adding these nanoparticles increases the refractive index.

[0090] Adding index displacement nanoparticles makes it possible to more precisely adjust the viscosity of the photoresist composition or leveling composition, so that they can completely fill the standard template, partially cure, and completely release from the template within the standardization process. Clean release from the template or seal 5 ensures the durability of the latter, as cleaning is facilitated.

[0091] These nanoparticles can be chosen from the group consisting of oxides, sulfides, selenides, tellurides, halides, carbides, arsenides, antimonides, nitrides, phosphides, carbonates, carboxylates, phosphates, sulfates, silicates, titanates, zirconates, aluminates, stannates, strontium, gallium, titanates, plumbates and their combinations. The preferred nanoparticles for refractive index shifting are zirconium dioxide (ZrO2) particles, titanium dioxide (TiO2) particles, hafnium dioxide (HfO2) particles and tungsten trioxide (WO3) particles.

[0092] These refractive index shift nanoparticles may have their surface treated with a dispersing agent before use, or antiflocculants may be added to the photoresist or leveling composition to ensure that the shift nanoparticles Petition 870250093634, dated 10 / 13 / 2025, page 26 / 81 20 / 53 refractive index are homogeneously dispersed in the composition and are homogeneously dispensed during the manufacturing process of the ophthalmic laminate 10.

[0093] Nanoparticles that shift the refractive index can constitute 20-75% by weight of the total weight of the photoresist or leveling composition.

[0094] The photoresist composition and / or the leveling composition are preferably produced primarily from non-volatile components, for example, non-volatile components constitute at least 90% by weight of the composition. This feature a) prevents the formation of a dense surface layer during solvent evaporation, b) limits layer shrinkage and void creation (free space) during solvent removal (drying) and the subsequent curing process, leading to fewer changes in the shape and dimensions of the replicated micro or nanostructures, c) limits or eliminates surface tension-related defects associated with contaminants (mitigated by the addition of wetting agents) and d) deliberately halts polymer chain propagation to control the degree of curing.

[0095] Each of the micro or nanostructures 131 of the photoresist layer 13 can independently be a refractive optical element (such as an aspherical lens, a spherical lens, a toric lens, or a prismatic lens), a diffractive optical element (such as a Fresnel lens), a diffusive element, a dispersing element, or an element with any other optical function. Preferably, all micro or nanostructures 131 are of the same type. These optical elements create small lenses at the micro or nanoscale. The micro or nanoscale lenses can be raised (Figure 1, Figure 2, and Figure 4) or lowered (Figure 3 and Figure 5) relative to the reference background plane. Petition 870250093634, dated 10 / 13 / 2025, p. 27 / 81 21 / 53

[0096] For example, the micro or nanostructures 131 can each be a partially spherical protrusion or a partially spherical recess. When the leveling layer 15 is provided, the latter presents micro or nanostructures that are negative images of the micro or nanostructures 131 of the photoresist layer 13, thus each is respectively a partially spherical recess or a partially spherical protrusion.

[0097] Preferably, the refractive index of the photoresist layer 13 and the refractive index of the leveling layer 15 are different. For example, the refractive index of the photoresist layer 13 may be greater than the refractive index of the leveling layer 15. In another example, the refractive index of the photoresist layer 13 may be less than the refractive index of the leveling layer 15. As an example, the convergent or divergent properties of incident light passing through micro- or nanoscale structures in the form of spherical microlenses are summarized in the following Table 2. Table 2 Spherical microlenses in the elevated / lowered photoresist layer. Refractive index relationships: n_photoresist > leveling, convergent / divergent; n_photoresist < leveling, divergent / convergent.

[0098] Preferably, the difference in refractive indices between the photoresist layer 13 and the leveling layer 15 is less than 0.80, for example between 0.05 and 0.15. This is the case, for example, when one of the photoresist layers 13 and the leveling layer 15 comprises aliphatic urethane oligomers, such as IGM Photomer 6892 and / or Photomer 6690, and the other layer comprises oligomers Petition 870250093634, dated 10 / 13 / 2025, page 28 / 81 22 / 53 aromatic urethane lenses containing sulfur, such as Miwon's Miramer HR3200. For constant optical power and a fixed microlens string diameter, the microlens radius and its sagittal height (hs, cf. Figure 1) above or sagittal depth (ds, cf. Figure 3) below the lens reference plane increase as the difference between the refractive indices decreases. This means that lower profile microlens patterns (i.e., lower height or sagittal depth) can be used in the design when the difference in refractive indices (delta RI) has the highest values.

[0099] The micro or nanostructures 131 are provided according to a predefined pattern. The pattern may be a regular tiling with regular polygons, with each micro or nanostructure 131 in the middle of a regular polygon. The regular tiling may be a triangular tiling, a square tiling, a hexagonal tiling or a radial tiling. Preferably, for example in the case of hemispheres, each one touches its neighbors.

[0100] In some embodiments, the ophthalmic laminate 10 comprises a first primer layer 12 between the first thermoplastic layer 11 and the photoresist layer 13 as illustrated in Figure 4.

[0101] In some other embodiments, the ophthalmic laminate 10 further comprises a second primer layer 16 between the leveling layer 15 and the second thermoplastic layer 17 as illustrated in Figure 5.

[0102] However, it should also be understood that the description covers cases where one of the first initiator layer 12 and the second initiator layer 16 is missing.

[0103] The first primer layer 12 and the second primer layer 16 are each produced from a photoresist composition, as described above, in particular the compositions of Petition 870250093634, dated 10 / 13 / 2025, page 29 / 81 23 / 53 preferred photoresists F1 and F2. The first initiator layer 12 and the second initiator layer 16 can be produced from different photoresist compositions. The photoresist composition used for the first and second initiator layers 12, 16 is different from that of the adhesive layer 15. The first and second initiator layers 12, 16 can be produced from a composition consisting of a reactive diluent and urethane acrylate.

[0104] In this mode, the difference in refractive indices between the photoresist layer 13 and the adhesive leveling 15 can be 0.05 or greater.

[0105] Preferably, the difference in refractive indices between the photoresist layer 13 and the leveling layer 15 is from 0.05 to 0.15 and the ophthalmic laminate 10 comprises at least one of the first and second initiator layers 12, 16. This is the case, for example, when one of the photoresist layer 13 and the leveling layer 15 consists of aliphatic urethane acrylate oligomer as the main reactive component and the other layer consists of a bisfluorene acrylate oligomer, such as Miwon's Miramer HR6042, with an optional component to increase its refractive index, such as ZrO2 particles, TiO2 particles or brominated acrylates.

[0106] Alternatively, the difference in refractive indices between the photoresist layer 13 and the leveling layer 15 is greater than 0.15 and the ophthalmic laminate 10 comprises both the first and second initiator layers 12, 16. This is the case, for example, when one of the photoresist layer 13 and the leveling layer 15 (the layer with the lower refractive index) is composed of a mixture of aliphatic acrylates, with optional refractive index-reducing components such as fluorinated acrylates, and the other layer (the layer with the higher refractive index) is composed mainly of bisfluorene acrylate oligomer, with optional components of Petition 870250093634, dated 10 / 13 / 2025, page 30 / 81 24 / 53 increase in refractive index, such as ZrÜ2 particles, TiO2 particles, or brominated acrylates.

[0107] The following Table 3 summarizes the preferred combinations of first primer layer, photoresist, adhesive and second primer layer. Petition 870250093634, dated 10 / 13 / 2025, page 31 / 81 25 / 53 Table 3 Initiator Layer 12 Photoresist 13 Adhesive / Leveling 15 Initiator 16 Convergent Lowered or Divergent Elevated Option 1 An = +0.07 Not necessary F1 F1 + ZrO2 Not necessary Option 2 An = +0.07 to +0.15 Not necessary F1 F2 + ZrO2 optional Not necessary Option 3 An = +0.07 to +0.15 Not necessary F1 F3 + ZrO2 optional F1 or F2 Option 4 An > +0.15 F1 or F2 F5 F4 + ZrO2 optional F1 or F2 Divergent Lowered or Convergent Elevated Option 5 An = -0.07 Not necessary F1 + ZrO2 F1 Not necessary Option 6 An = -0.07 to -0.15 Not necessary F2 + ZrO2 optional F1 Not necessary Option 7 An = -0.07 to -0.15 F1 or F2 F3 + ZrO2 optional F1 Not Required Option 8 An < -0.15 F1 or F2 F4 + ZrO2 optional F5 F1 or F2 Δη = refractive index of leveling layer - refractive index of photoresist ZrO2 = Solution of zirconium or titanium oxide nanoparticles (20 to 60% of the total composition by weight) Petition 870250093634, dated 10 / 13 / 2025, page 32 / 81 26 / 53

[0108] In all embodiments, the first and second thermoplastic layers 11, 17 may be produced from a material chosen from the group consisting of polycarbonates (PC), polyethylene terephthalates (PET), cellulose triacetates (TAC), cyclic olefin copolymers (COC) and poly(methyl methacrylate) (PMMA) and other acrylate polymers (AP) and polyamides (PA, Nylon). The materials of the first and second thermoplastic layers 11, 17 need not be the same. For example, the first thermoplastic layer 11 may be produced from PC and the second thermoplastic layer 17 may be produced from Nylon.Thus, the combination of materials for the first and second thermoplastic layers 11, 17 can be chosen from the following set (first thermoplastic layer 11; second thermoplastic layer 17): {(PC; PC), (PC, PET), (PC, TAC), (PC, COC), (PC, PMMA), (PC, AP), (PC, PA), (PET, PC), (PET, PET), (PET, TAC), (PET, COC), (PET, PMMA), (PET, AP), (PET, PA), (TAC, PC), (TAC, PET), (TAC, TAC), (TAC, COC), (TAC, PMMA), (TAC, AP), (TAC, PA), (COC, PC), (COC, PET), (COC, TAC), (COC, COC), (COC, PMMA), (COC, AP), (COC, PA), (PMMA, PC), (PMMA, PET), (PMMA, TAC), (PMMA, COC), (PMMA, PMMA), (PMMA, AP), (PMMA, PA), (AP, PC), (AP, PET) Structured lozenge and ophthalmic plaster

[0109] The ophthalmic laminate 10 can be formed to become a structured (encapsulated) pellet 10' comprising a concave side 102 and a convex side 101 (see Figure 6, Figure 7 and Figure 8). The photoresist layer 13 may be closer to the concave side than the first support layer 11, which is closer to the convex side than the photoresist layer 13 (Figure 6 and Figure 7). Alternatively, the photoresist layer 13 is more Petition 870250093634, dated 10 / 13 / 2025, page 33 / 81 27 / 53 further from the concave side than the first support layer 11, which is further from the convex side than the photoresist layer 13 (Figure 8).

[0110] The ophthalmic laminate 10 or the shaped structured pellet 10' may be provided with an adhesive on the free surface of the first thermoplastic layer 11 or the second thermoplastic layer 17 to form an ophthalmic patch. The adhesive may be a pressure-sensitive adhesive (PSA), a heat-melt adhesive (HMA) or other adhesives, such as water-based, solvent-based or even solvent-free. The ophthalmic patch may then be adhered to the surface of an existing ophthalmic lens. Ophthalmic lens

[0111] The ophthalmic laminate 10 described above can be used to manufacture an ophthalmic lens 1.

[0112] This ophthalmic lens 1 typically comprises a substrate 20 and an ophthalmic laminate 10 cut and shaped into a structured pellet 10'. The structured pellet 10' may be overmolded onto the substrate 20, i.e., the structured pellet 10' is situated on one side of the ophthalmic lens 1. For example, the ophthalmic lens 1 comprises a concave face and a convex face. The structured pellet 10' may be on the concave face or on the convex face. The ophthalmic laminate may be encapsulated within the substrate 20 or each face of the structured pellet 10' may be overmolded onto a substrate, thus embedding the structured pellet 10' within the lens substrate 20.

[0113] Substrate 20 can be produced from thermoplastic, thermosetting or mineral glass materials.

[0114] The ophthalmic lens 1 may have different configurations according to the ocular use for which it is intended.

[0115] One example of these applications is in the field of sunglasses. Petition 870250093634, dated 10 / 13 / 2025, p. 34 / 81 28 / 53

[0116] In a first example, a structured wafer 10' with the following structure can be used to make an ophthalmic lens 1 that has a polarizing element 30. The structured wafer 10' comprises in the following order: a first layer of polycarbonate 11, a layer of photoresist 13 having micro or nanostructures 131 and a leveling layer 15. In a first variant (Figure 9), the structured wafer 10' is integrated into the polarizing element 30. The polarizing element 30 comprises in the following order: the structured wafer 10', a first adhesive layer 33, a polyvinyl alcohol polarizing layer 35, a second adhesive layer 37 and a second polycarbonate layer 39. The leveling layer 15 of the structured wafer 10' is then mounted on the first adhesive layer 33 of the polarizing element 30.In a second variant (Figure 10), the polarizing element 30, instead of having the structured pellet 10' as its first layer, has the latter replaced by a first layer of polycarbonate 31. The entire polarizing element 30 can then be used as the second support layer 17 of the structured pellet 10', for example, by laminating the polarizing element onto the leveling layer 15, which is chosen to be an adhesive layer. In a third variant (Figure 11), a chemical adhesive, a pressure-sensitive adhesive, or a hot-melt adhesive 21 can be used to bond the structured pellet 10' directly to the surface of a polarized ophthalmic lens 30. In a fourth variant (Figure 11), a chemical adhesive, a pressure-sensitive adhesive, or a hot-melt adhesive can be used to bond the polarizing element 30 directly to the surface of an ophthalmic lens 1 that has the structured pellet 10'.

[0117] In a second example in the field of sunglasses, the microstructured ophthalmic lens 1 is submerged in a heated tank containing a dye solution (dye bath) to produce colored lenses. In a variant, one of the film layers 11 or 17. Petition 870250093634, dated 10 / 13 / 2025, page 35 / 81 29 / 53 of the ophthalmic laminate 10 was pre-dyed or manufactured with dyes before becoming part of the ophthalmic laminate 10. In another variant, at least one of the photoresist, adhesive or leveling layers incorporates a dye or colored pigment.

[0118] In a third example (Figure 12), the microstructured ophthalmic lens 1 is a photochromic lens comprising multilayer photochromic coatings 23 on the surface of a structured wafer 10' on an ophthalmic substrate. In a variant, the polyvinyl alcohol polarizing layer 35 is replaced by a photochromic plastic layer (e.g., photochromic thermoplastic polyurethane) to produce a photochromic lens.

[0119] In a fourth example, the ophthalmic lens 1 is an electrochromic element lens comprising a structured pellet 10' bonded to an embedded lens with a mineral glass-based or plastic-based electrochromic element.

[0120] Another example of these applications are smart eye devices. In this case, one of the virtual reality lenses, augmented reality lenses, and mixed reality lenses comprises a structured pad 10' to prevent at least one of the following conditions: myopia, eye strain, and other eye-related conditions. In another case, smart eye devices may incorporate sensors in the eyeglass frame or through the lenses to monitor, record, or report health-related information such as blood pressure, diabetes, stroke, heart disease, seizures, and other related medical conditions. Methods for manufacturing ophthalmic laminates

[0121] A first method for manufacturing an ophthalmic laminate, and in particular the ophthalmic laminate comprising, stacked one on top of the other in the following order, a first thermoplastic layer 11, a photoresist layer 13, and optionally a layer of Petition 870250093634, dated 10 / 13 / 2025, page 36 / 81 30 / 53 leveling 15 and a second thermoplastic layer 17, according to the invention, will be described below with reference to Figure 13 and Figure 14.

[0122] This method comprises forming a partially cured photoresist layer 132 on a first thermoplastic layer 11 with a surface having micro or nanostructures 131 to form a polycarbonate / photoresist layer assembly. The method may also comprise providing a leveling layer 15 between the partially cured photoresist layer 132 and, optionally, a second thermoplastic layer 17 to form a laminate.

[0123] Forming the partially cured photoresist layer comprises depositing the photoresist composition 4 as described above, onto the first thermoplastic layer 11 to form an uncured photoresist layer 41, printing the micro or nanostructures 131 onto the uncured photoresist layer 41 by applying a stamp 5 with a negative image 51 of the micro or nanostructures onto the uncured photoresist layer and partially curing the uncured photoresist layer 41 until it is no longer sticky, while still retaining acrylate bonds present in the partially cured photoresist layer, and removing the stamp 5, thus leaving a partially cured photoresist layer 132 on the first thermoplastic layer 11.

[0124] When an uncured photoresist is cured until it is no longer sticky, while still retaining unreacted acrylate bonds, it can be said that the photoresist has been softly cured. In the context of the present disclosure, this means, for example, that the micro or nanostructures 131 have acquired their final shape; when the seal 5 is removed, they retain their shape. For a softly cured photoresist layer, it means that it does not Petition 870250093634, dated 10 / 13 / 2025, page 37 / 81 31 / 53 will lose its shape when moved or touched. However, in this state, the micro or nanostructures 131 or the gently cured photoresist layer can still react with the material of another layer due to the remaining acrylate bonds.

[0125] The degree of cure can be in the range of 80 to 99% of the theoretically fully cured photoresist, preferably 95 to 99%. This is determined by measuring an infrared spectrum of the partially cured photoresist and using the polymer and monomer peaks corresponding to the skeletal stretching vibrations of the C=C bonds in their aromatic rings. Insufficient cure can lead to deformation of the micro or nanostructure during the release of the photoresist layer 13 from the seal 5, while excessive cure can prevent the bond strength between the photoresist layer 13 and the leveling layer 15. Clean release from the template or seal 5 ensures the durability of the latter, as cleaning is facilitated.

[0126] The cure depends on the nature of the photoresist composition 4. When the photoresist composition 4 is a photoresist composition, curing is performed by radiation, for example, with UV light energy. When the photoresist composition 4 is a thermosetting photoresist composition, curing is performed by thermal energy, optionally with the use of a curing initiator, such as a peroxide initiator.

[0127] Depositing the photoresist composition 4 onto the first thermoplastic layer 11 can be carried out by centrifugation coating, Meyer bar wire-wound coating, knife coating, rolling coating, etching roll coating, slit die coating, in a sheet-size batch process or in a continuous roll-to-roll film blanket process. Petition 870250093634, dated 10 / 13 / 2025, page 38 / 81 32 / 53

[0128] Because the properties of the 5 seal may require the use of flexible material, which generally has low durability, the 5 seal can be manufactured from a master template. The master template acts as a mold to shape the 5 seal and is produced from a more durable material, such as metal, glass, silicon, or delicate photolithographic layers deposited on quartz or silicon material. The same master template can be used for a 5 seal with elevated macro or nanostructures and a seal with recessed macro or nanostructures through the use of an intermediate template; in particular, because manufacturing a master template is expensive. The intermediate template can, in fact, be a so-called first-generation seal, and the seal obtained from this intermediate template can be a so-called second-generation seal. In general, it is possible to use an nth generation seal, i.e., with n-1 intermediate templates between the master template and the 5 seal.The integer n has no limit and can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0129] For example, a single master stamp is made using a precision tooling method (e.g., diamond turning, photolithography, etc.) to capture the finest details of the micro or nanostructured pattern using a material best suited to the tooling method. Several first-generation stamp replicas of the master stamp would be made to invert the structural pattern and / or use more process-friendly stamp materials (e.g., from a brittle stamp material to a more durable one). Several second-generation working stamps would be produced from the first-generation stamp at a lower cost, using the same stamp materials or different materials from the first-generation stamp, so that these working stamps could be replaced more frequently in a high-volume production environment, by Petition 870250093634, dated 10 / 13 / 2025, page 39 / 81 33 / 53 For example, less expensive job stamps could be replaced once a day, week or month, depending on the production process, stamp material, photoresist chemistry, contamination level, wear from handling, etc.

[0130] The table below summarizes the types of macro or nanostructures in stamp 5 for: - cases with no intermediate templates or an even number of intermediate templates (marked as 2k); and - the case with an odd number of intermediate templates (marked as 2k+1)

[0131] The photoresist layer 13 always has macro or nanostructures 131 which are the negative images of the macro or nanostructures of the seal 5. Table 4 Master template Seal 2k 2k+1 raised lowered raised lowered raised lowered

[0132] The material used to produce seal 5 may be a silicone-based elastomer, resulting, for example, in a polydimethylsiloxane (PDMS), such as a PDMS with a tensile strength of 4 to 6 MPa, preferably 4.5 to 5.5 MPa, even more preferably 5.0 to 5.4 MPa, and a Shore hardness of 35 to 55 at 20 °C, preferably 40 to 50, even more preferably 42 to 46. An example of such a PDMS is Sylgard® 184.

[0133] Manufacturing seal 5 may therefore comprise pouring the silicone-based elastomer into the master die, curing the silicone-based elastomer until it is fully solidified, and releasing seal 5 from the master die. Alternatively, manufacturing seal 5 may comprise depositing nickel onto the master die to form the 2k seal. Petition 870250093634, dated 10 / 13 / 2025, pp. 40 / 81 34 / 53 intermediate and / or a second nickel deposition on the 2k intermediate stamp to form the 2k+1 replicated stamp with greater durability.

[0134] The master template can be prepared by a variety of methods including subtractive methods and additive methods related to the base support material. Among the subtractive methods, we can mention: diamond turning, laser ablation and electrodeposition of metal, glass or other suitable support material. Among the additive methods, we can mention the following: 3D printing, photolithography or jetting on a quartz support material or silicon wafer.

[0135] The choice of method for manufacturing the master jig usually depends on the micro or nanostructures to be formed in it. But all methods generally start by using an initial jig with a highly polished surface with very low macro-contour and micro-roughness values ​​before any additional processes.

[0136] In principle, subtractive methods would be more suitable for creating recessed micro or nanostructures, while additive methods would be more suitable for creating elevated micro or nanostructures. This is because removing all background material and leaving behind elevated microstructures generally takes more time than sculpting only the recessed areas. Furthermore, the sculpted background (non-elevated areas) is no longer in a highly polished state because subtractive tool marks are left on the surface. Conversely, the effort and precision required by additive methods to build and / or overlay only the material necessary to create the elevated micro or nanostructures are expected to be faster and easier than building and / or overlaying the entire non-recessed background and leaving behind the recessed micro or nanostructures. In addition Petition 870250093634, dated 10 / 13 / 2025, pp. 41 / 81 35 / 53 of this, the background (non-recessed areas) is no longer in a highly polished state because additive tool marks are left on the surface. In grayscale photoligography, positive or negative photoresists can be used to build up multilayers of raised structures while removing unwanted areas after each masking step.

[0137] Providing a leveling layer 15 may comprise centrifugally coating an adhesive composition 6 onto the second thermoplastic layer 17 to form an adhesive film 61 thereon, depositing the adhesive composition 6 onto the partially cured photoresist layer 132, placing the adhesive film 61 in contact with the adhesive 62 deposited on the partially cured photoresist layer 132 to form an uncured laminate, and curing the uncured laminate to obtain the laminate.

[0138] Alternatively, providing a leveling layer may comprise wet coating of an adhesive composition 6 onto the second thermoplastic layer 17 to form an adhesive film 61, for example by Meyer bar wire coating, knife coating, roller coating, engraving roller coating, slit die coating, curtain coating or drip coating in a squeeze cylinder lamination process; wherein the adhesive film 61 thus forms a continuous wet bonding sphere. Alternatively still, providing a leveling layer 15 may comprise applying an adhesive composition 6 onto the second thermoplastic layer 17 by any adhesive application process, such as a measured drip distribution, to form a continuous wet bonding sphere in a squeeze cylinder lamination process. In both cases, providing a leveling layer. Petition 870250093634, dated 10 / 13 / 2025, page 42 / 81 36 / 53 further comprises placing the adhesive sphere in contact with the partially cured photoresist layer 132 in a continuous roll-to-roll process using a wet bonding squeeze cylinder, to form an uncured laminate, and curing the uncured laminate to obtain the ophthalmic laminate 10. Alternatively, the optically transparent adhesive solution may be coated onto a carrier film material using any of the precision coating methods described above, partially or fully dried to form an adhesive layer (2 microns to 50 microns) which is then transferred to the second thermoplastic layer 17, before coming into contact with the partially cured microstructures 131 in the first thermoplastic layer 11, in a squeeze cylinder lamination process.

[0139] The method may further comprise, before forming the photoresist layer 41 on the first thermoplastic layer 11, activating the surface of the first thermoplastic layer 11. Activating the surface of the first thermoplastic layer 11 may be carried out by plasma treatment, corona treatment or chemical treatment of the surface of the first thermoplastic layer 11 or by treating the surface of the first thermoplastic layer 11 with a silane coupling agent.

[0140] The method may further comprise, prior to providing the leveling layer 15, activating the surface of the second thermoplastic layer 17. Activating the surface of the second thermoplastic layer 17 may be accomplished by plasma treatment, corona treatment or chemical treatment of the surface of the second thermoplastic layer 17 or by treating the surface of the second thermoplastic layer 17 with a silane coupling agent.

[0141] Another method for manufacturing an ophthalmic laminate aims to improve the adhesion of the photoresist layer and the adhesive layer. Petition 870250093634, dated 10 / 13 / 2025, page 43 / 81 37 / 53 siva with a specific refractive index that would not bond directly to the thermoplastic layer. This method uses a thin initiator layer between the photoresist layer and the thermoplastic layer or between the leveling layer and the thermoplastic layer. This is generally necessary when using materials where the difference in refractive index between the photoresist layer and the leveling layer is greater than 0.07.

[0142] The following description will be made with reference to an ophthalmic laminate comprising, stacked one on top of the other in the following order, a first thermoplastic layer 11, a first primer layer 12, a photoresist layer 13, a leveling layer 15, a second primer layer 16, and a second thermoplastic layer 17, which will be described below. However, it is also necessary to understand that the description covers the following cases: - where the first initiator layer 12 is absent (therefore all steps relating to the formation of this layer 12 should be disregarded and the description of the remaining steps should be read replacing the first initiator layer 12 with the first thermoplastic layer 11); and - where the second initiator layer 16 is absent (therefore all steps relating to the formation of this layer 16 should be disregarded and the description of the remaining steps should be read replacing the second initiator layer 16 with the second thermoplastic layer 17).

[0143] The method comprises forming a first layer of initiator 12 on a first thermoplastic layer 11, forming on the first layer of initiator 12 a layer of photoresist 13 with a surface having micro or nanostructures to form a laminate. The method may further comprise forming a second layer of initiator 16 on a second thermoplastic layer 17, and providing Petition 870250093634, dated 10 / 13 / 2025, page 44 / 81 38 / 53 a leveling layer 15 between the photoresist layer 13 and the second primer layer 16.

[0144] In this method, forming the first primer layer 12 comprises depositing a primer composition, as described above, onto the first thermoplastic layer 11 to form an uncured primer layer, which partially cures the uncured primer layer until it is no longer tacky, while still retaining acrylate bonds present in the partially cured photoresist layer.

[0145] Depositing the photoresist composition onto the first primer layer can be carried out by means of centrifugation coating, Meyer bar wire-wound coating, knife coating, rolling coating, etching roll coating, slit die coating, in a sheet-size batch process or in a continuous roll-to-roll film blanket process.

[0146] Forming the photoresist layer 13 may involve depositing a photoresist composition onto the first initiator layer 12 to form an uncured photoresist layer, printing the micro or nanostructures onto the uncured photoresist layer, applying a stamp with a negative image of the micro or nanostructures onto the uncured photoresist layer, and partially curing the uncured photoresist layer until it is no longer sticky, while still retaining acrylate bonds present in the partially cured photoresist layer, and removing the stamp.

[0147] The seal can be manufactured as described above.

[0148] The cure depends on the nature of the photoresist composition 4, as described above.

[0149] Providing the leveling layer 15 may involve depositing an adhesive composition over the second primer layer 16 to form an adhesive film over it, depositing the Petition 870250093634, dated 10 / 13 / 2025, page 45 / 81 39 / 53 adhesive composition on the partially cured photoresist layer, place the adhesive film in contact with the adhesive deposited on the partially cured photoresist layer to form an uncured laminate, and fully cure the uncured laminate to obtain the laminate.

[0150] Depositing an adhesive composition on the second primer layer 16 can be performed by any precision coating technique, such as centrifugal coating, Meyer bar wire-wound coating, knife coating, rolling coating, etching roll coating, slit die coating, in a sheet-size batch process or in a continuous roll-to-roll film blanket process.

[0151] This method may further comprise, before forming the first initiator layer 12 on the first thermoplastic layer 11, activating the surface of the first thermoplastic layer 11. Activating the surface of the first thermoplastic layer 11 may be carried out by plasma treatment, corona treatment or chemical treatment of the surface of the first thermoplastic layer 11 or by treating the surface of the first thermoplastic layer 11 with a silane coupling agent.

[0152] This method may further comprise, before providing the second initiator layer 16, activating the surface of the second thermoplastic layer 17. Activating the surface of the second thermoplastic layer 17 may be accomplished by plasma treatment, corona treatment or chemical treatment of the surface of the second thermoplastic layer 17 or by treating the surface of the second thermoplastic layer 17 with a silane coupling agent.

[0153] In both methods, printing can be carried out using a continuous method, such as the roll-to-roll method, as illustrated in Figures 17 and 18. Petition 870250093634, dated 10 / 13 / 2025, p. 46 / 81 40 / 53

[0154] In the roll-to-roll method, the stamp 5 can be in the form of a drum, a cylindrical roller, a shim mounted on a drum or roller, or a sleeve mounted on a drum or roller (hereinafter referred to as drum, but it encompasses all these options). The surface of the drum is provided, as a stamping template 51, with the negative image of the micro or nanostructures to be formed in the thermoplastic layer, such as the first thermoplastic layer 11. The following description will refer to the first thermoplastic layer 11 and the photoresist layer 13. However, the same description can be made for the second thermoplastic layer 17 and the leveling layer 15.

[0155] The first thermoplastic layer 11 is fed into contact with the drum by the action of two conveyor rollers 81,82. Both conveyor rollers rotate in a direction opposite to the direction of rotation of the drum that is in contact with the opposite surface of the first thermoplastic layer 11. The first thermoplastic layer 11 contains an uncured coated photoresist layer 41 facing the opposite direction to the conveyor rollers 81, 82 and towards the drum, and both are provided in the form of a continuous sheet. Optionally, a first primer layer 12 is placed between the first thermoplastic layer 11 and the uncured photoresist layer 41.

[0156] When the uncured photoresist layer 41 comes into contact with the stamping jig 51, micro or nanostructures are formed in the uncured photoresist layer 41. The pressure of the stamping jig 51 is maintained by the drum on the uncured photoresist layer 41 for a predetermined period of time during which the uncured photoresist layer 41 is gently cured by curing energy 7. The nature of the cure depends on the photoresist composition 4, as described above.

[0157] Stamping template 51 can be transparent. In this Petition 870250093634, dated 10 / 13 / 2025, page 47 / 81 41 / 53 case, gentle curing can be performed using stamping template 51 (Figure 17).

[0158] The first thermoplastic layer 11 can be transparent. In this case, gentle curing can be achieved through the first thermoplastic layer 11 (Figure 18).

[0159] After gentle curing, the assembly of the first thermoplastic layer 11 and the gently cured photoresist layer 132, with optionally a first primer layer 12 between them, leaves the drum and is driven by the transport rollers 81, 82.

[0160] Both methods may also include forming the laminate. For example, forming the laminate may include at least one of die-cutting the laminate and thermoforming the ophthalmic laminate to obtain the 3D structured pellet 10'. Method for manufacturing ophthalmic lenses

[0161] A method for manufacturing an ophthalmic lens according to the invention will be described below with reference to Figures 15 and 16.

[0162] This method involves manufacturing a structured pellet. 10' using one of the methods described above, place the structured pellet 10' in an ophthalmic lens mold M, and form a substrate 20 within the lens mold to obtain the ophthalmic lens.

[0163] The mold may comprise a concave side M1 and a convex side M2. In this case, placing the structured insert 10' may involve placing its convex side 101 against the concave side M1 of the mold (see Figure 15).

[0164] Alternatively, the mold comprises a concave side M1 and a convex side M2. In this case, placing the structured insert 10' involves placing its convex side 102 against the convex side M2 ​​of the mold.

[0165] Alternatively, placing the 10' structured insert may involve placing it between both sides M1, M2 of the mold, Petition 870250093634, dated 10 / 13 / 2025, pp. 48 / 81 42 / 53 so that neither the convex side 101 nor the concave side 102 of the structured insert 10' touches the concave side M1 or the convex side M2 ​​of the mold. In this case, the structured insert 10' may be closer to the concave side M1 (see Figure 16) or the convex side M2 ​​of the mold. Preferably, the distance from the side of the structured insert 10' closest to one of the sides of the mold M to that side of the mold M is 1 mm or less.

[0166] Substrate 20 can be produced from a thermoplastic composition. In this case, forming substrate 20 is preferably done through injection overmolding, during which the thermoplastic composition used fills the void M3 between the structured pellet 10' and the mold M. In injection molding, the placement of the structured pellet 10' is preferably against side M1 or M2 of the mold M.

[0167] The thermoplastic substrate 20 can be made of polycarbonate (PC), cyclic olefin copolymer (COC), poly(methyl methacrylate) (PMMA) and other acrylate polymers, polyamides (PA, nylon) or other thermoplastic injection molding materials used in the ophthalmic industry.

[0168] In some cases, it may be necessary to promote adhesion of the structured pellet 10' to the injected thermoplastic. This may be the case when the structured pellet 10' has no adhesion layer 15 nor any second support layer 17 (see Figure 6). Thus, before injection overmolding with the thermoplastic substrate 20, the method may comprise promoting adhesion to the partially cured photoresist layer 13 and / or to the first support layer 11 of the structured pellet 10' (or of the ophthalmic laminate 10 before transforming it into the structured pellet 10'), for example, by corona treatment, plasma treatment or chemical treatment. Petition 870250093634, dated 10 / 13 / 2025, p. 49 / 81 43 / 53

[0169] Other methods can be used to manufacture such an ophthalmic lens. For example, the structured 10' pellet can be incorporated into the surface (Figure 15) or into the volume (Figure 16) of a thermoset casting ophthalmic lens. Thus, substrate 20 can be made of thermoset materials such as poly(allyl diglycol carbonate) (e.g., PPR's CR39™) and urethane-based prepolymer (e.g., PPG's Trivex™). Other suitable materials are Mitsui Chemicals' MR™ series or other thermoset casting materials used in the ophthalmic industry. Consequently, forming substrate 20 may involve melting a thermoset composition in mold M. Since thermoset compositions are more fluid than thermoplastics, they can flow more easily throughout the free space of mold M even if the structured pellet 10' is not positioned against one of the sides M1 or M2 of the mold.Therefore, the method shown in Figure 16 is more suitable for forming substrate 20 by melting a thermoset composition.

[0170] Another example is providing the structured wafer 10' with an adhesive on the free surface of the first thermoplastic layer 11 or the second thermoplastic layer 17. The adhesive may be a pressure-sensitive adhesive (PSA), a heat-melt adhesive (HMA), or other adhesives, such as water-based, solvent-based, or even solvent-free. The ophthalmic laminate 10 can then be bonded to the surface of an existing ophthalmic lens. Alternatively, a UV and / or heat-curable fluid optical adhesive may be used to bond the structured wafer 10' to the surface of an existing thermoplastic or thermoset ophthalmic lens. Examples Example 1

[0171] Example 1 illustrates an example of a method for manufacturing ophthalmic laminate 10 without primer layers. Petition 870250093634, dated 10 / 13 / 2025, pp. 50 / 81 44 / 53

[0172] Firstly, a seal 5 is manufactured by pouring a mixture of Sylgard® 184 into a micro or nanostructured master template, which has a positive image of the desired micro or nanostructures 131 for the photoresist layer 13. The Sylgard® 184 mixture is then cured until it solidifies completely and the seal 5, which has a negative image of the desired micro or nanostructures 131, is released from it.

[0173] Next, a layer of acrylate photoresist 41 was centrifugally applied to the surface of a first layer of polycarbonate 11, produced from a first composition, the surface having been previously plasma-treated. The seal 5 is then applied over the photoresist layer 41 and gently cured. In this gently cured state, the photoresist layer 41 still has unreacted and unbonded functional acrylate groups (C=C) at the interface, which will improve its bond strength with the subsequently applied adhesive layer. At this point, the standardized photoresist layer 41 was released from the seal 5.

[0174] A layer of acrylate adhesive 61 was then applied by centrifugation onto the surface of a second polycarbonate layer 17 produced from a second composition, the surface having been previously treated with plasma. Acrylate adhesive 6 was also added to the surface of the softly cured micro or nanostructured photoresist layer 132. The acrylate adhesive layer 61 was then applied against the photoresist layer 13 with the acrylate adhesive between a steel cylinder and a hard rubber squeezer pressure cylinder laminating tool. The resulting laminate was then exposed to UV radiation to fully cure the photoresist layer 13 and the acrylate adhesive to form an acrylate adhesive layer 15. After die cutting and shaping the fully cured laminate 10, a structured pellet 10' was obtained. Petition 870250093634, dated 10 / 13 / 2025, pp. 51 / 81 45 / 53

[0175] Subsequently, an ophthalmic lens mold M having a concave side M1 and a convex side M2 ​​is used in an injection molding method to obtain an ophthalmic lens 1. For this, the structured pellet 10' was inserted against the concave side M1 and both sides M1, M2 of the mold were joined forming a mold cavity M3. A molten polycarbonate was injected into the mold cavity M3 to overmold an ophthalmic substrate 20 onto the structured pellet 10', thus forming the ophthalmic lens 1. Example 2

[0176] Example 2 illustrates another example of a method for manufacturing ophthalmic laminate 10 without primer layers.

[0177] First, a stamping template in the form of a thin sheet is manufactured by pouring a mixture of Sylgard® 184 into a micro- or nanostructured master template, which has a positive image of the desired micro- or nanostructures for the photoresist layer. The Sylgard® 184 mixture is then cured until completely solidified, and the stamping template, which has a negative image of the desired micro- or nanostructures, is released and applied to the side surface of a drum with the micro- or nanostructures facing outwards, thus forming a stamp (or stamping drum).

[0178] In this method, a first and a second layer of polycarbonate are used, each in the form of a continuous sheet. The first and second layers of polycarbonate are unwound from their respective rolls of polycarbonate film. This allows for the continuous manufacture of a plurality of ophthalmic laminates. The continuous sheets of the first and second layers of polycarbonate are transported through subsequent stations.

[0179] First layer of polycarbonate: in a first stage, a surface of the same is plasma treated or chemically pre-treated with a silane coupling agent. In a Petition 870250093634, dated 10 / 13 / 2025, pp. 52 / 81 46 / 53 Second station, a layer of acrylate photoresist is applied by a slit die on top of the treated surface. In a third station, the acrylate photoresist layer meets the surface of the stamping drum. During this contact, the stamping jig is applied over the acrylate photoresist layer and held while the stamping drum makes a large wrap angle, approximately a full 180° rotation, taking the stacked acrylate photoresist layer and portion of the stamping jig to a radiation curing station, where UV radiation is emitted through the first polycarbonate layer to the acrylate photoresist layer to gently cure it. In this gently cured state, the photoresist layer still has unreacted and unbonded functional acrylate (C=C) groups at the interface, which will improve its bond strength with the subsequently applied adhesive layer.The standardized photoresist layer was then released from the stamping drum while the continuous sheet with the softly cured micro or nanostructured photoresist layer was conveyed to a station where the acrylate adhesive was deposited as a metered drip coating onto the surface of the softly cured micro or nanostructured photoresist layer and then conveyed to the wet bonding squeeze cylinder lamination station.

[0180] Second layer of polycarbonate: in a first station, a surface of the same is plasma treated or chemically pre-treated with a silane coupling agent. In a second station, an acrylate adhesive layer can be applied by slit die on top of the treated surface. Then, the continuous sheet with the acrylate adhesive layer is conveyed to the wet bonding squeeze cylinder lamination station.

[0181] At the lamination stacking station, the continuous sheet with the acrylate adhesive layer is applied over the continuous sheet with Petition 870250093634, dated 10 / 13 / 2025, pp. 53 / 81 47 / 53 The gently cured micro- or nano-structured photoresist layer is applied so that the acrylate adhesive layer comes into contact with the gently cured micro- or nano-structured photoresist layer. The stacked assembly is then fully cured in a subsequent station.

[0182] After curing, the ophthalmic laminates are cut from the stacked assembly, shaped, and incorporated into an ophthalmic lens in the same manner as in Example 1. Example 3

[0183] Example 3 illustrates the method for manufacturing the ophthalmic laminate with primer layers.

[0184] Firstly, a seal 5 is manufactured by pouring a mixture of Sylgard® 184 into a micro or nanostructured master template, which has a positive image of the desired micro or nanostructures 131 for the photoresist layer 13. The Sylgard® 184 mixture is then cured until it solidifies completely and the seal 5, which has a negative image of the desired micro or nanostructures 131, is released from it.

[0185] Next, a first thin layer of initiator 12 was centrifugally applied over a first layer of polycarbonate 11 of a first polycarbonate composition, and a second thin layer of initiator 16 was centrifugally applied over a second layer of polycarbonate 17 of a second polycarbonate composition. The layers of initiator 12, 16 were gently UV cured.

[0186] A layer of acrylate photoresist 41 was subsequently centrifugally coated onto the first gently cured primer layer 12. Macro or microstructures are imprinted onto the photoresist layer 41 by means of a flexible and adaptable work stamp 5 and the photoresist is gently cured and the stamp 5 is removed. Petition 870250093634, dated 10 / 13 / 2025, pp. 54 / 81 48 / 53

[0187] An adhesive layer of acrylate 61 was centrifugally coated onto the plasma-treated surface of the second initiator layer 16. Additional acrylate adhesive 6 was added as a metered drip coating between the softly cured photoresist layer and the acrylate adhesive layer 61 between a steel cylinder and a hard rubber squeezer pressure cylinder laminating tool. The resulting laminate was exposed to UV radiation to fully cure all softly cured layers 12, 13, 16 and the uncured layer 15. The fully cured laminate is then die-cut and shaped (formed), thus producing a structured wafer 10'.

[0188] Subsequently, an ophthalmic lens mold M having a concave side M1 and a convex side M2 ​​is used in an injection molding method to obtain an ophthalmic lens 1. For this, the structured pellet 10' was inserted against the concave side M1 and both sides M1, M2 of the mold were joined forming a mold cavity M3. A molten polycarbonate was injected into the mold cavity M3 to overmold an ophthalmic substrate 20 onto the structured pellet 10', thus forming the ophthalmic lens 1. Example 4

[0189] In this example, a composition comprising 55 wt% aliphatic urethane hexaacrylate, 20 wt% trimethylolpropane triacrylate, 20 wt% hexanediol diacrylate and 5 wt% Omnirad 4265 as a crosslinking initiator was used for the photoresist layer. 13. Its glass transition temperature is 98 °C.

[0190] The composition used for the adhesive layer 15 comprises 26.9% by weight of aliphatic urethane hexaacrylate, 9.3% of trimethylolpropane triacrylate, 14.3% by weight of hexanediol diacrylate, 2.4% by weight of Omnirad 4265 as a crosslinking initiator, and 47.1% of Petition 870250093634, dated 10 / 13 / 2025, pp. 55 / 81 49 / 53 weight of ZrO2 dispersed in ethanolamine (50% by weight of ZrO2 particles in 50% by weight of ETA). Its glass transition temperature is 94 °C.

[0191] The refractive index after complete curing is 1.52 for the photoresist layer 13 and 1.59 for the adhesive layer 15. The viscosity is 535.1 cPs for the photoresist layer 13 and 791.8 cPs for the adhesive layer 15.

[0192] The first and second thermoplastic layers 11, 17 were produced from polycarbonate.

[0193] An ophthalmic lens was manufactured according to the method of example 1. It shows that it is impossible to manually detach the structured pellet and there are no cracks or delamination after the injection overmolding process. Example 5

[0194] Another composition usable for the adhesive layer 15 comprises 55% by weight of aliphatic urethane triacrylate, 20% of trimethylolpropane triacrylate, 20% by weight of hexanediol diacrylate and 5% by weight of Omnirad 4265 as a crosslinking initiator. Its viscosity is 720.5 cPs. Example 6

[0195] An ophthalmic laminate 10 was manufactured with the same compositions as example 4 and using a method similar to that of example 1. The only difference is that the photoresist layer 13 was fully cured before forming the adhesive layer 15.

[0196] Manual detachment of the ophthalmic laminate from example 4 was possible, showing that the adhesion between the layers of the ophthalmic laminate from example 4 was significantly greater when the photoresist layer 13 was gently cured. Example 7

[0197] In this example, a composition comprising 65% in Petition 870250093634, dated 10 / 13 / 2025, pp. 56 / 81 50 / 53 weight of Miwon Miramer HR6042 (comprising 60% by weight of bisfluorene difunctional acrylate diluted in 40% by weight of 2-phenylphenoxyethyl acrylate), 15% by weight of Miwon Miramer M140 (2-phenoxyethyl acrylate), 15% by weight of Sartomer SR295 (pentaerythritol tetraacrylate) and 5% by weight of Omnirad 4265 as a crosslinking initiator, was used for the photoresist layer 13.

[0198] The composition used in example 3 for the photoresist layer was used as the first initiator layer 12 and the adhesive layer 15. There was no second initiator layer. The first and second thermoplastic layers 11, 17 were produced from polycarbonate.

[0199] The refractive index after complete curing of the photoresist layer was 1.60.

[0200] An ophthalmic lens was manufactured according to the example 3. Manual detachment of the encapsulated structured pellet was impossible and showed no cracks or delamination during the injection molding process. Example 8

[0201] A structured wafer 10' with a first support layer 11 and a photoresist layer 13 is manufactured using the same stamping process described in example 1.

[0202] In this example, the first support layer 11 is produced from polycarbonate, poly(methyl methacrylate), nylon or other optical quality film material. In some cases, the adhesion of the partially cured photoresist layer 13 is promoted through corona treatment, plasma treatment or chemical treatment.

[0203] The resulting ophthalmic laminate 10 is then shaped (e.g., by thermoforming, hydroforming or blow molding) onto the structured pellet 10' to obtain the 3D curved shape of a concave side of a mold M (frontal mold M1). Petition 870250093634, dated 10 / 13 / 2025, pp. 57 / 81 51 / 53

[0204] The 10' structured tile is inserted against the concave side M1 and both sides M1, M2 of the mold were joined together forming a mold cavity M3. A molten thermoplastic polymer, such as poly(methyl methacrylate), was injected into the mold cavity M3 to overmold an ophthalmic substrate 20 onto the structured pellet 10', thus forming the ophthalmic lens 1. Example 9

[0205] A structured wafer 10' with a first support layer 11 and a photoresist layer 13 is manufactured using the same stamping process described in example 1.

[0206] In this example, adhesion of the partially cured photoresist layer 13 is promoted through corona treatment, plasma treatment, or chemical treatment. In some cases, adhesion of the first support layer 11 on the opposite side is also promoted through the same method or by a different method.

[0207] The resulting ophthalmic laminate 10 is then shaped (e.g., by thermoforming, hydroforming or blow molding) onto the structured pellet 10' to obtain the 3D curved shape of a concave side of a mold M (frontal mold M1).

[0208] The structured insert 10' is inserted between the concave side M1 and the convex side M2 ​​of the mold, which have been joined together to form a mold cavity M3. Once the mold M is assembled, the convex side of the structured insert 10' is less than 1 mm away from the inner surface of the concave side of the mold (or front mold M1). The mold cavity M3 is thus divided into a front cavity between the concave side M1 and the structured insert 10' and a rear cavity between the latter and the convex side M2 ​​of the mold.

[0209] A thermoset curing material was injected into the mold cavity M3 to mold an ophthalmic substrate 20 onto the structured pellet 10', thus forming the ophthalmic lens 1. Petition 870250093634, dated 10 / 13 / 2025, pp. 58 / 81 52 / 53 Example 10

[0210] This example makes use of a structured wafer 10' with a first support layer 11, a photoresist layer 13 and a flat leveling layer 15. The photoresist layer 13 is formed on the first support layer 11 in the same manner described in example 1. The flat leveling layer 15 is then coated onto the photoresist layer 13. In some cases, the leveling layer 15 comprises refractive index shift nanoparticles. In some cases, adhesion of the leveling layer 15 is promoted through corona treatment, plasma treatment or chemical treatment.

[0211] The resulting ophthalmic laminate 10 is then shaped (e.g., by thermoforming, hydroforming or blow molding) onto the structured pellet 10' to obtain the 3D curved shape of a concave side of a mold M (frontal mold M1).

[0212] In one variant, the manufacture of an ophthalmic lens is carried out in the same manner as described in Example 9. Here, the leveling layer 15 increases the difference in refractive index between the cured thermoset casting material and the photoresist layer 13. It also improves adhesion with the cured thermoset casting material.

[0213] In another variant, the fabrication of an ophthalmic lens is carried out in the same manner described in Example 9. The leveling layer 15 and the micro or nanostructures 131 are on the convex surface of the laminate 10 and are facing the concave mold M1. Here, the leveling layer alters the difference in refractive index between the photoresist layer 13 and air, protects the micro or nanostructure 131 from abrasion and forms a leveled outer surface for hard coating, anti-reflective coating, photochromic coating, etc. without the surface coating altering the contours and functionality of the micro or nanostructures 131. Petition 870250093634, dated 10 / 13 / 2025, pp. 59 / 81 53 / 53

[0214] In another variant, the manufacture of an ophthalmic lens is carried out in the same manner described in Example 8. Here, the leveling layer 15 increases the difference in refractive index between the thermoplastic injection molding material and the photoresist layer 13. It also improves adhesion with the thermoplastic material and protection of micro or nanostructures 131.

[0215] In another variant, the fabrication of an ophthalmic lens is carried out in the same manner described in Example 8. The leveling layer 15 and the micro or nanostructures 131 are on the convex surface of the laminate 10' and are facing the concave mold M1. Here, the leveling layer alters the difference in refractive index between the photoresist layer 13 and air, protects the micro or nanostructure 131 from abrasion and forms a leveled outer surface for hard coating, anti-reflective coating, photochromic coating, etc. without the surface coatings altering the contours and functionality of the micro or nanostructures 131. Petition 870250093634, dated 10 / 13 / 2025, pp. 60 / 81

Claims

1 / 8 CLAIMS 1. Method for manufacturing an ophthalmic laminate (10), characterized in that it has: - a first support layer (11,12); - a photoresist layer (13) having micro or nanostructures (14) on a surface opposite to the first support layer; the method comprising: - forming on a first support layer (11, 12), a partially cured photoresist layer (132) with a surface having micro or nanostructures; wherein forming a partially cured photoresist layer comprises: - depositing a photoresist composition (4) on the first support layer to form a photoresist layer (41);- printing the micro or nanostructures (131) onto the photoresist layer, applying a stamp (5) with a negative image (51) of the micro or nanostructures onto the photoresist layer, and partially curing the photoresist layer until it is no longer sticky, while still retaining the acrylate bonds present in it; and - removing the stamp.

2. A method according to claim 1, characterized in that the deposition of the photoresist composition onto the first support layer is carried out by means of a precision coating technique, such as centrifugal coating, Meyer bar wire-wound coating, knife coating, rolling coating, etching roller coating or slit matrix coating of the photoresist composition onto the first support layer.

3. Method, according to claim 2, characterized Petition 870250093634, of 10 / 13 / 2025, p. 61 / 81 2 / 8 by the fact that depositing the photoresist composition is done through slit die coating, and wherein the stamp is a stamping drum (5, 51); and wherein the curing is carried out through the first support layer or the stamping drum.

4. A method according to any one of claims 1 to 3, characterized in that it further comprises, before forming the photoresist layer on the first support layer, activating the surface of the first support layer.

5. Method, according to any one of claims 1 to 4, characterized in that the first support layer is a thermoplastic first layer (11), and wherein the photoresist composition comprises a crosslinking initiator and a mixture of polymerizable monomers or oligomers; wherein the mixture comprises: 20-80 % by weight of urethane triacrylate or urethane hexaacrylate, 3-30 % by weight of triacrylate, which is different from a urethane triacrylate and 3-30 % by weight of diacrylate; wherein the percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

6. Method, according to any one of claims 1 to 4, characterized in that the first support layer is a thermoplastic first layer (11), and wherein the photoresist composition is chosen from: - formulation F1 comprising: 20 to 80 phm of urethane acrylate(s) with lower refractive index; 10 to 50 phm of mono- or difunctional acrylate(s), other than urethane acrylates with lower refractive index; Petition 870250093634, dated 10 / 13 / 2025, page 62 / 81 3 / 8 0 to 50 phm of trifunctional acrylate(s) or higher, other than urethane acrylates with lower refractive index; and 1 to 10 phm of photoinitiator; - Formulation F2 comprising: urethane acrylate(s) with a refractive index 20 to 80 phm higher; 10 to 50 phm of mono- or difunctional acrylate(s), other than the urethane acrylates with a lower refractive index;- Formulation F3 comprising: 20 to 80 pH of 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene; 0 to 30 pH of trifunctional acrylate(s) or higher, other than urethane acrylates with lower refractive index; 0 to 60 pH of aromatic acrylate(s); and 1 to 10 pH of photoinitiator; - Formulation F4 comprising: 0 to 70 pH of 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene; 0 to 70 pH of aromatic acrylate(s); 30 to 100 pH of brominated or chlorinated acrylate(s); and 1 to 10% by weight of photoinitiator; - formulation F5 comprising: 0 to 50 pH of urethane acrylate(s) with lower refractive index; 0 to 70 pH of mono- or difunctional acrylate(s), other than urethane acrylates with lower refractive index;0 to 70 phm of trifunctional acrylate(s) or higher, different from urethane acrylates with lower refractive index; Petition 870250093634, dated 10 / 13 / 2025, page 63 / 81 4 / 8 30 to 100 phm of fluorinated acrylate(s); and 1 to 10 phm of photoinitiator; with optionally 20 to 60% by weight of nanoparticles increasing the refractive index.

7. Method, according to any one of claims 1 to 4, characterized in that the first support layer is a first initiator layer (12) produced from the deposition onto a first thermoplastic layer (11) of a composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers; wherein the mixture comprises: 20-80 % by weight of urethane triacrylate or urethane hexaacrylate, 3-30 % by weight of triacrylate, which is different from a urethane triacrylate and 3-30 % by weight of diacrylate; wherein the percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

8. Method, according to any one of claims 1 to 4, characterized in that the first support layer is a first initiator layer (12) produced from the deposition onto a first thermoplastic layer (11), of formulation F1 or formulation F2, as defined in claim 6.

9. Method according to claim 5 or 7, characterized in that the mixture comprises: 50-70% by weight of urethane hexaacrylate, 15-25% by weight of triacrylate, which is different from a urethane triacrylate, and 15-25% by weight of diacrylate; wherein the percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

10. A method according to any one of claims 1 to 9, characterized in that it further comprises providing a second support layer and a leveling layer between the photoresist layer and the second support layer.

11. Method according to claim 10, characterized in that it comprises, before providing the second support layer and the leveling layer, activating the surface of the second support layer.

12. Method according to claim 10 or 11, characterized in that providing a leveling layer comprises: - coating by centrifugation, coating by Meyer bar wire coil, coating by knife, coating by rolling, coating by engraving roller or coating by slit die a leveling composition onto the second support layer to form a leveling film thereon; - depositing the leveling composition onto the partially cured photoresist layer; - placing the leveling film in contact with the leveling composition deposited on the partially cured photoresist layer; - fully curing the laminate to obtain the ophthalmic laminate.

13. Method, according to any one of claims 10 to 12, characterized in that the second support layer is a thermoplastic layer (17).

14. Method, according to any one of claims 10 to 12, characterized in that the second support layer Petition 870250093634, of 10 / 13 / 2025, page 65 / 81 6 / 8 is a second initiator layer (16) produced from the deposition onto a second thermoplastic layer (17) of a composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers; wherein the mixture comprises: 5-60 % by weight of urethane triacrylate or urethane hexaacrylate, 3-30 % by weight of triacrylate, which is different from a urethane triacrylate and 3-30 % by weight of diacrylate; wherein the percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture.

15. Method, according to any one of claims 10 to 12, characterized in that the second support layer is a second initiator layer (16) produced from the deposition onto a second thermoplastic layer (17), of formulation F1 or formulation F2, as defined in claim 6.

16. Method for manufacturing an ophthalmic lens, characterized in that it comprises: - providing an ophthalmic laminate with a first support layer (11, 12) and a photoresist layer (13) having micro or nanostructures (14) on a surface opposite to the first support layer; and - attaching a substrate to the ophthalmic laminate; wherein providing the ophthalmic laminate is, according to the method for manufacturing an ophthalmic laminate, as defined in any one of claims 1 to 12.

17. Method according to claim 16, characterized in that: - the mold comprises a convex die and a concave die; and - placing the ophthalmic laminate comprises placing the ophthalmic laminate against the concave die or the convex die.

18. Ophthalmic laminate (10), characterized in that it comprises, stacked one on top of the other in the following order: - a first thermoplastic layer (11), - a photoresist layer (13), - an adhesive layer (15) and - a second thermoplastic layer (17), wherein the photoresist layer and the adhesive layer form micro or nanostructured joints (14) at their interface, wherein the photoresist layer is produced from a photoresist composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers; wherein the mixture comprises: 5-60 % by weight of urethane triacrylate or urethane hexaacrylate, 3-30 % by weight of triacrylate, which is different from urethane triacrylate and 3-30 % by weight of diacrylate; wherein the percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture; or the mixture is chosen from formulations F1 to F5, as defined in claim 6.

19. Ophthalmic laminate (10), characterized in that it comprises, stacked one on top of the other in the following order: - a first thermoplastic layer (11), - a photoresist layer (13), - an adhesive layer (15), and - a second thermoplastic layer (17), Petition 870250093634, dated 10 / 13 / 2025, page.67 / 81 8 / 8 wherein the ophthalmic laminate further comprises an initiator layer (12, 16) between the first thermoplastic layer and the photoresist layer, or between the adhesive layer and the second thermoplastic layer; wherein the initiator layer is produced from an initiator composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers; wherein the mixture comprises: 5-60 % by weight of urethane triacrylate or urethane hexaacrylate, 3-30 % by weight of triacrylate, which is different from a urethane triacrylate and 3-30 % by weight of diacrylate; wherein the percentage by weight is based on the total weight of the polymerizable monomers or oligomers contained in the mixture; or the mixture is chosen from formulation F1 and formulation F2, as defined in claim 6. Petition 870250093634, dated 10 / 13 / 2025, pp. 68 / 81.

Images