Method for imprinting ophthalmic laminates and resist composition therefor

Abstract

The present invention relates to a method for manufacturing an ophthalmic laminate (10) having a first support layer (11, 12) and a resist layer (13) having a microstructure or nanostructure (14) on a surface facing the first support layer, the method comprising: depositing a resist composition (4) on the first support layer to form a resist layer (41); applying a stamp (5) having a negative image (51) of a microstructure or nanostructure onto the resist layer and partially curing the resist layer until it is no longer tacky but acrylate bonds still exist in the resist layer to imprint a microstructure or nanostructure (131) onto the resist layer; and removing the stamp to form a partially cured resist layer (132) having a surface having a microstructure or nanostructure on the first support layer. The present invention also relates to an ophthalmic laminate and a method for manufacturing an ophthalmic lens using an ophthalmic laminate.

Description

Technical Field

[0001] The present invention relates to the technical field of ophthalmic laminates and ophthalmic lens manufacturing. More specifically, the present invention relates to an ophthalmic laminate and an ophthalmic lens produced via imprinting, and a method for manufacturing such wafers and lenses for correcting visual impairment, slowing its progression, and improving the distortion of a specific lens.

Background Art

[0002] An ophthalmic lens having a micro-structure or nano-structure on or embedded in the lens surface can be used to provide improved properties to the ophthalmic lens. For example, the ophthalmic lens may comprise an embedded micro-structure or nano-structure in the shape of a micro-sized or nano-sized lens. Such micro-sized or nano-sized lenses can change the optical function of a part of the lens (e.g., the aberration region) so as to guide more light to the center of the eye compared to an ophthalmic lens not having such features, or redirect a part of the incident light to different regions of the retina, and are configured to treat or slow the progression of a visual condition related to the eye, such as myopia. It is known that in a myopic person, when the focus of light is off at the peripheral part of the retina, this may reduce the progression of myopia over time.

[0003] Nanoimprint lithography (NIL) is a form of UV imprinting (UVI), which is used to create micro-structures or nano-structures on a polymer surface by photocuring a coated resist layer while the coated resist layer is in contact with a patterning template such as a replica stamp. The shape of the micro-structure of the patterning template is the inverse image of the shape of the target micro-structure or nano-structure on the polymer surface. The composition of the resist typically consists of a thermosetting or other energy-curable monomer or oligomer, a curing initiator, a processing aid, a diluent, fine particles, and optionally other reactive molecules.

[0004] The resist may be coated onto a polymer film, flexible foil, rigid metal plate or cylinder, quartz or silicon wafer, or other substrate. A patterning template is then brought into contact with the resist-coated film. The resist is then cured either through the substrate side or the template side. The element undergoing curing must be transparent to the curing energy. Alternatively, the resist may be coated on a patterning template, bringing the film or other substrate into contact with the coated patterning template. The resist is then cured either through the transparent substrate side or the template side. The patterning template may be in the form of a flat plate or shim, a tiled shim, a seamless cylinder or sleeve, a circular drum, a concave or convex curved mold, or other patterned template.

[0005] UV energy exposure induces photopolymerization, including crosslinking, resulting in an increase in the resist's modulus and fixing the shape of microstructures or nanostructures within the resist. The cured resist layer is then demolded from the patterning template. UV light exposure (ion beam, electron beam, or other high-energy means) can be performed via either a transparent template or a clear film or substrate. Transparent templates can be made from quartz glass, polydimethylsiloxane (PDMS) in the form of an incompressible (hard, rigid) or semi-compressible (flexible) working stamp, or other durable materials or blends with particle fillers (e.g., ZrO2).

[0006] Opaque templates can be fabricated by replicating a master template created by diamond cutting, photolithography, or any other micro / nanostructuring means known in the art, and in some cases by creating one or more replica templates. The master or replica template can also be fabricated by using nickel plating on a metal substrate such as stainless steel, brass, or aluminum, or by using other suitable opaque treatments. This technique can be repeated using the master or its replica template to change the image polarity, i.e., to create the opposite micro / nanostructural orientation, or to transfer the design onto a different support substrate.

[0007] Commercially available photoresists suitable for NIL (Natural Ink Resist) are formulated with optimized reliability to ensure consistent physical and mechanical properties, and optimized bonding strength to the support substrate. Such support substrates typically have a hydrophobic silicon or quartz surface in contact with the photoresist. These formulations are usually made from aromatic compounds or compounds with polar pendant groups; therefore, they are colored, inflexible, and incompatible with plastic materials such as polycarbonate (PC). Their colors range from pale yellow to orange or red, and they are not necessarily formulated to be optically clear transparent materials with a specific refractive index. Their lack of flexibility makes them brittle and prone to cracking under tension or compression. Polycarbonate is a common material for making ophthalmic lenses. Therefore, these drawbacks make these commercially available photoresist materials unsuitable for making ophthalmic lenses. They are also very expensive for large-area coatings and defect-free imprinting.

[0008] Furthermore, the imprinted layer may be difficult to bond to other layers for sealing purposes, or the bonding strength may be too weak to withstand abrasion.

[0009] Therefore, there is a need to develop a method and resist composition that are suitable for imprinting microstructures or nanostructures onto a PC support, have sufficient bonding strength to adhere to the PC substrate and adhesive layer, and enable the encapsulation of microstructured patterns as a single-layer film directly bonded to a multilayer film laminate or lens substrate. [Overview of the project] [Problems that the invention aims to solve]

[0010] Therefore, one object of the present invention is to overcome at least one of the drawbacks of the prior art. In particular, one object of the present invention is to provide a resist formulation suitable for imprinting complex nanostructures or microstructures on PC by NIL. [Means for solving the problem]

[0011] Accordingly, the present invention provides a method for manufacturing an ophthalmic laminate having a first support layer and a resist layer having microstructures or nanostructures on a surface facing the first support layer. The method comprises forming a partially cured resist layer having a surface with microstructures or nanostructures on a first support layer, comprising: (i) depositing a resist composition on the first support layer to form the resist layer; (ii) imprinting the microstructures or nanostructures on the resist layer by applying a stamp having a negative image of the microstructures or nanostructures onto the resist layer and partially curing the resist layer until it is no longer tacky but acrylate bonds still exist in the resist layer; and (ii) removing the stamp.

[0012] Depositing the resist composition onto the first support layer can be done via precision coating, such as spin coating, wire-wound Meyer bar coating, knife coating, roll coating, gravure roller coating, or slot die coating.

[0013] The resist composition may be deposited through slot die coating, the stamp may be a stamping drum, and curing may be carried out via a first support layer or stamping drum.

[0014] Before forming a resist layer on the first support layer, the method may include activating the surface of the first support layer.

[0015] The first support layer may be a first thermoplastic layer, and the resist 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 a triacrylate different from urethane triacrylate, and 3-30% by weight of diacrylate. A preferred mixture comprises 50-70% by weight of urethane hexaacrylate, 15-25% by weight of a triacrylate different from urethane triacrylate, and 15-25% by weight of diacrylate. The weight percentages are based on the total weight of polymerizable monomers or oligomers contained in the mixture.

[0016] Instead, the resist composition is one of formulations F1 to F5.

[0017] Formulation F1 comprises a low refractive index urethane acrylate with a value of 20-80 pF, a monofunctional or difunctional acrylate different from the low refractive index urethane acrylate with a value of 10-50 pF, a trifunctional or higher acrylate different from the low refractive index urethane acrylate with a value of 0-50 pF, and a photoinitiator with a value of 1-10 pF.

[0018] Formulation F2 comprises a high refractive index urethane acrylate with a refractive index of 20-80 pH, a monofunctional or difunctional acrylate different from the low refractive index urethane acrylate with a refractive index of 10-50 pH, a trifunctional or higher acrylate different from the low refractive index urethane acrylate with a refractive index of 0-50 pH, an aromatic acrylate with a refractive index of 0-60 pH, and a photoinitiator with a refractive index of 1-10 pH.

[0019] Formulation F3 contains 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene at 20-80 pH, a trifunctional or higher acrylate different from low refractive index urethane acrylate at 0-30 pH, an aromatic acrylate at 0-60 pH, and a photoinitiator at 1-10 pH.

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

[0021] Formulation F5 comprises a low refractive index urethane acrylate with a range of 0 to 50 pH, a monofunctional or difunctional acrylate different from the low refractive index urethane acrylate with a range of 0 to 70 pH, a trifunctional or higher acrylate different from the low refractive index urethane acrylate with a range of 0 to 70 pH, a fluorinated acrylate with a range of 30 to 100 pH, and a photoinitiator with a range of 1 to 10 pH.

[0022] Optionally, the resist composition may contain 20 to 60% by weight of refractive index-increasing nanoparticles, and the total weight of the composition may be 100% by weight.

[0023] In other cases, the first support layer may be a first primer layer prepared by depositing a primer composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers onto the first thermoplastic layer. The mixture may comprise 20-80% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of a triacrylate different from urethane triacrylate, and 3-30% by weight of diacrylate. A preferred mixture comprises 50-70% by weight of urethane hexaacrylate, 15-25% by weight of a triacrylate different from urethane triacrylate, and 15-25% by weight of diacrylate. The weight percentages are based on the total weight of polymerizable monomers or oligomers contained in the mixture.

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

[0025] The method can further include providing a second support layer and a leveling layer between the resist layer and the second support layer.

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

[0027] Providing the leveling layer can include (i) spin-coating, wire-wound Meyer bar coating, knife coating, roll coating, gravure roll coating or slot die coating a leveling composition onto the second support layer to form a leveling film on the second support layer, (ii) depositing the leveling composition onto the partially cured resist layer, (iii) contacting the leveling film with the leveling composition deposited onto the partially cured resist layer, and (iv) fully curing the laminate to obtain an ophthalmic laminate.

[0028] The second support layer can be a thermoplastic layer.

[0029] The second support layer can be a second primer layer made by depositing the composition defined for the first primer layer onto the second thermoplastic layer.

[0030] The present invention also provides a method for manufacturing an ophthalmic lens, the method including using the above method to provide an ophthalmic laminate having a first support layer and a resist layer having a micro-structure or nano-structure on a surface facing the first support layer, and bonding a substrate to the ophthalmic laminate.

[0031] The mold used in this method can include a convex die and a concave die. In such a case, the method can include that arranging the ophthalmic laminate includes arranging the ophthalmic laminate relative to the concave die or the convex die.

[0032] The present invention also provides an ophthalmic laminate comprising a first thermoplastic layer and a resist layer having a microstructure or nanostructure on its free surface, which are stacked on top of each other in the following order.

[0033] The ophthalmic laminate may further include a leveling layer and a second thermoplastic layer. The resist layer and the leveling layer together form microstructures or nanostructures at their interface.

[0034] The resist layer can be prepared from the resist composition described above.

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

[0036] The ophthalmic laminates provided by the present invention can withstand subsequent processing steps such as thermoforming, pressure molding, blow molding, adhesive lamination, thermoplastic injection molding, thermosetting casting, lens cribbing, surface treatment, edging, frame mounting, and hard multilayer coating. The ophthalmic laminates provided by the present invention are also high-quality ophthalmic lenses free from cosmetic defects. Therefore, the ophthalmic laminates provided by the present invention are substantially free from environmental stress cracking, delamination, low transmittance, haze, color change (yellow index), etc.

[0037] Further objectives, features, and advantages will become clearer in the following detailed description with reference to the drawings below. [Brief explanation of the drawing]

[0038] [Figure 1] This is a schematic diagram of an exemplary ophthalmic laminate according to the present invention, having a first support layer and a resist layer before molding. [Figure 2] This is a schematic diagram of another exemplary ophthalmic laminate according to the present invention, which has a leveling layer in addition to the layers shown in Figure 1 before molding. [Figure 3]This is a schematic diagram of another exemplary ophthalmic laminate according to the present invention, having a first support layer, a resist layer, an adhesive layer, and a second support layer before molding. [Figure 4] This is a schematic diagram of another exemplary ophthalmic laminate according to the present invention, having a first primer layer in addition to the layers shown in Figure 1 before molding. [Figure 5] This is a schematic diagram of another exemplary ophthalmic laminate according to the present invention, having a first primer layer and a second primer layer in addition to the layer shown in Figure 3 before molding. [Figure 6] Figure 1 is a schematic diagram of an exemplary ophthalmic laminate in which a structured wafer has been produced after molding. [Figure 7] Figure 2 is a schematic diagram of an exemplary ophthalmic laminate, showing the sealed structured wafer after molding. [Figure 8] Figure 3 is a schematic diagram of an exemplary ophthalmic laminate, showing the sealed structured wafer after molding. [Figure 9] Figure 7 is a schematic diagram of a light-shielding lens according to the present invention, having a sealed structured wafer. [Figure 10] Figure 8 is a schematic diagram of a light-shielding lens according to the present invention, having a sealed structured wafer. [Figure 11] Figure 8 is a schematic diagram of another light-shielding lens according to the present invention, having a sealed structured wafer. [Figure 12] This is a schematic diagram of another light-shielding lens according to the present invention. [Figure 13] This schematic diagram illustrates an exemplary embodiment of the method of the present invention, in which a microstructure or nanostructure is imprinted onto a partially cured resist layer. [Figure 14] Figure 3 schematically shows the manufacturing process of the unformed ophthalmic laminate. [Figure 15] This diagram schematically illustrates thermoplastic injection overmolding of a substrate onto a structured wafer. [Figure 16] A schematic diagram of thermosetting casting of a substrate onto a structured wafer is shown. [Figure 17]This diagram schematically illustrates continuous roll-to-roll imprinting of resist onto film by curing through a transparent printing drum and a transparent template stamp fixed on a transparent printing drum. [Figure 18] This schematic diagram illustrates continuous roll-to-roll imprinting of resist onto a transparent film by curing through the transparent film, using a template stamp fixed on a printing drum. [Modes for carrying out the invention]

[0039] Unless otherwise specified, all viscosity values ​​were obtained at 25.6°C using a Brookfield viscometer (Brookfield Ametek Small sample adapter SC4-18 spindle, sample volume: 6.7 mL).

[0040] Ophthalmic laminate Here, the ophthalmic laminate according to the present invention will be described with reference to Figures 1 to 4.

[0041] As shown in Figure 1, the ophthalmic laminate 10 includes a first thermoplastic layer 11 and a resist layer 13 having a microstructure or nanostructure 131 on the surface of the ophthalmic laminate 10 facing the first thermoplastic layer 11, which are stacked on top of each other in the following order.

[0042] In another embodiment, the ophthalmic laminate 10 further includes a refractive index leveling layer 15 (hereinafter referred to as the leveling layer) laminated on the resist layer 13, as shown in Figure 2. In such a case, the leveling layer 15 has microstructures or nanostructures that are negative images of the microstructures or nanostructures 131 of the resist layer 13. The leveling layer 15 helps to adjust the overall refractive index of the ophthalmic laminate 10 to a desired overall refractive index according to the refractive index of the resist layer 13.

[0043] In addition to the leveling layer 15, the ophthalmic laminate 10 may further include a second thermoplastic layer 17 on the leveling layer 15, as shown in Figure 3.

[0044] In general, the number of reactive or functional precursors available for use in ophthalmology is limited and includes, for example, epoxy, acrylate, or vinyl monomers having monofunctional or polyfunctional reactive groups containing rings, mixtures of such reactive monomers, diluents, oligomers, prepolymers, or polymers. These compounds are available because they possess all the properties necessary to form optically functional ophthalmic laminates.

[0045] Examples of usable epoxy monomers include, in particular, UV-curable ones such as Delo® Katiobond® 45952, Delo® Katiobond® 4670, Delo® Katiobond® DF698, Delo® Katiobond® EG6133, Delo® Katiobond® GE680, and Delo® Katiobond® KB552.

[0046] The resist layer 13 may be made from a resist 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 a triacrylate different from urethane triacrylate, and 3-30% by weight of diacrylate. These weight percentages are based on the total weight of polymerizable monomers or oligomers contained in the mixture.

[0047] Such a resist composition enables the replication of patterns on a patterning template or work stamp with high replication fidelity and low shrinkage, and in particular, allows for complete demolding from the patterning template or work stamp without leaving any resist material on the patterning template or work stamp. Clean demolding from the template or stamp 5 facilitates cleaning, thus ensuring the durability of the template or stamp 5. The resist composition also has a curing rate from uncured to lightly cured, which is appropriate for the curing process. The resist composition has high bonding strength to the first thermoplastic layer 11 and, if provided, to the leveling layer 15, and has high cohesive strength. In addition, the resist composition is non-brittle and plastic during thermoforming of the eye laminate onto a low or high diopter base curve wafer.

[0048] Furthermore, such resist compositions are inexpensive.

[0049] In one example, the mixture may contain 50-70% by weight of urethane hexaacrylate, 15-25% by weight of a triacrylate different from urethane triacrylate, and 15-25% by weight of diacrylate. These weight percentages are based on the total weight of polymerizable monomers or oligomers contained in the mixture.

[0050] Polymerizable monomers or oligomers are - Bifunctional urethane methacrylate monomers (e.g., CN1969, Sartomer;Visiomer HEMATMDI, Lintech International / Evonik), - 3,3,5-trimethylcyclohexyl methacrylate (e.g., SR421A, Sartomer), - Pentaerythritol tetraacrylate (e.g., SR295, Sartomer), - Monofunctional isolbornyl methacrylate (e.g., Visiomer Terra IBOMA, Lintech International / Evonik), - Aliphatic urethane diacrylate (e.g., Photomer 6024, IGM), - Hexafunctional aliphatic urethane acrylate oligomers (e.g., Photomer 6690, IGM), - Bifunctional aliphatic urethane acrylate (Photomer 6891, IGM), - Trifunctional aliphatic urethane acrylate (Photomer 6892, IGM), - Hexamethylene diacrylate, - Propanediyl diacrylate, - o-phenylphenol ethylene oxide acrylate (e.g., Miramer M1142, Miwon), - Bisful orange acrylate (e.g., Miramer HR6042, Miwon), - Phenol (ethylene oxide) acrylate (e.g., Miramer M140, Miwon), - Trimethylolpropane triacrylate, - Hexanediol diacrylate, - Tripropylene glycol diacrylate, and - Triethylene glycol diacrylate It may be at least three compounds selected from the group consisting of the following.

[0051] Preferably, the polymerizable monomer or oligomer is a photopolymerizable monomer or oligomer, and therefore the resist composition is a photoresist composition, and the resist layer 13 is a photoresist layer.

[0052] The crosslinking initiator may constitute 0.5 to 5% by weight of the resist composition.

[0053] Preferably, the crosslinking initiator is a photoinitiator. In such cases, the crosslinking initiator may be at least one of Omnirad 4265, 2-hydroxy-2-methyl-1-phenylpropanone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 3-hydroxy-3-phenylbutan-2-one, ethyl-phenyl(2,4,6-trimethylbenzoyl)phosphine, 1-hydroxycyclohexylphenyl ketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one.

[0054] The resist composition may contain fluorinated acrylates that allow for a shift in the refractive index of the resist composition. Typically, the addition of fluorinated acrylates lowers the refractive index.

[0055] Other examples of preferred resist compositions are summarized in the table below (amounts are expressed in phm (parts per hundred monomer), i.e., parts per 100 parts by weight of monomer).

[0056] [Table 1]

[0057] Low refractive index urethane acrylates include 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 PU320, Miramer PU340, Miramer PU3450, Miramer PU390, Miramer PU622, Miramer MU9800, Miramer The following can be selected from the list consisting of 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.

[0058] The high refractive index urethane acrylate can be selected from a list consisting of Miramer HR3000, Miramer HR3200, Miramer HR3700, Miramer HR3800, Miramer HR4000, and Miramer PU2900.

[0059] Monofunctional or difunctional acrylates (where acrylate is also methacrylate) may be selected from the list consisting of 1,6-hexanediol diacrylate; 1,10-decanediol diacrylate; tetrahydrofurfuryl acrylate; 1,4-butanediol diacrylate; diethylene glycol diacrylate; tricyclodecanedimethanol diacrylate; 3,3,5-trimethylcyclohexyl acrylate; cyclohexanedimethanol diacrylate; isobornyl acrylate; caprolactone acrylate; cyclic trimethylolpropane formal acrylate; butyl acrylate; and pentyl acrylate.

[0060] Acrylates with three or more functions (acrylates can also be methacrylates) include trimethylolpropane triacrylate; trimethylolpropane (EO) n Triacrylate; trimethylolpropane (PO) n Triacrylate; Tris(2-hydroxyethyl) isocyanurate triacrylate; Pentaerythritol tetraacrylate; Pentaerythritol (EO) n The following may be selected from a list consisting of tetraacrylate; ditrimethylolpropanetetraacrylate; di(pentaerythritol)pentaacrylate; and dipentaerythritol hexaacrylate.

[0061] Aromatic acrylates (acrylates can also be methacrylates) include 2-phenylphenoxyethyl acrylate; 2-phenoxyethyl acrylate; α-naphthyl acrylate; β-naphthyl acrylate; 2-phenylethyl acrylate; diphenylmethyl acrylate; phenyl acrylate; and bisphenol A(EO). n It can be selected from a list consisting of diacrylates.

[0062] Brominated or chlorinated acrylates (where acrylate may also be methacrylate) may be selected from the list consisting of pentabromobenzyl acrylate; pentabromophenyl acrylate; phenyl α-bromoacrylate; p-bromophenyl acrylate; 2,3-dibromopropyl acrylate; methyl α-bromoacrylate; pentachlorophenyl acrylate; and o-chlorodiphenylmethyl acrylate.

[0063] Fluorinated acrylates (acrylates may also be methacrylates) can be selected 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-methylethyl acrylate; 2-trifluoroethoxyethyl acrylate; and trifluoroethyl acrylate.

[0064] The photoinitiator may be Omnirad 4265.

[0065] The resist composition preferably has a viscosity of 430 to 640 cPs, more preferably 480 to 590 cPs, and more preferably 510 to 560 cPs.

[0066] The resist composition preferably has a glass transition temperature (Tg) of 75 to 120°C, preferably 85 to 110°C, and more preferably 90 to 100°C.

[0067] In some cases, the leveling layer 15 is the final layer of the ophthalmic laminate 10, provided to encapsulate the microstructure or nanostructure 131. If the microstructure or nanostructure of this laminate structure faces the outer surface of the lens, the leveling layer 15 may also function as a protective sealing layer.

[0068] In other cases, the leveling layer 15 is an adhesive layer made of an adhesive composition used to bond to a second support layer 17, having the same definition as the resist composition of the resist layer 13 and containing preferred compositions F1 to F5. If the adhesive composition is selected from F1 to F4, it may further contain refractive index shift nanoparticles such as ZrO2 particles. However, the resist composition used for the adhesive layer 15 is different from that used for the resist layer 13.

[0069] The adhesive composition preferably has a curing rate from uncured to partially cured, which is appropriate for the drying or curing process. The adhesive composition also has high bonding strength to the second thermoplastic layer 17 and the resist layer 13. The adhesive composition exhibits high cohesive strength, is non-brittle and plastic during thermoforming of the laminate onto low or high base curve wafers.

[0070] The adhesive composition used in the adhesive layer 15 preferably has sufficient fluidity to fill the created patterns of microstructures or nanostructures in the resist layer, enabling high filling fidelity. For example, the adhesive has a viscosity of 630 to 950 cPs, preferably 710 to 870 cPs, and more preferably 750 to 830 cPs.

[0071] In this viscosity example, the adhesive composition contains refractive index-shifting nanoparticles that result in a higher refractive index and viscosity compared to the resist, allowing the resist composition to easily replicate patterns and focus light during the imprint process.

[0072] In other cases where no refractive index shift nanoparticles are included, the viscosity is preferably 430-640 cPs, preferably 480-590 cPs, and more preferably 505-560 cPs. The adhesive composition preferably has a glass transition temperature (Tg) of 75-120°C, preferably 85-110°C, and more preferably 90-100°C.

[0073] At least one of the resist layer 13 and the leveling layer 15 may contain refractive index shift nanoparticles that allow the refractive index to be adjusted according to the refractive power of the microstructure or nanostructure. Typically, the addition of such nanoparticles increases the refractive index.

[0074] By adding refractive index-shifting nanoparticles, the viscosity of the resist composition or leveling composition can be more precisely adjusted, thereby allowing the resist composition or leveling composition to completely fill the pattern template, partially cure, and completely release from the template during the patterning process. Clean release from the template or stamp 5 facilitates cleaning, thus ensuring the durability of the template or stamp 5.

[0075] These nanoparticles may be selected from the group consisting of oxides, sulfides, selenides, tellurides, halides, carbides, arsenides, antimonides, nitrides, phosphides, carbonates, carboxylates, phosphates, sulfates, silicates, titanates, zirconates, aluminates, tinates, strontium, gallium, titanates, leadates, and combinations thereof. Preferred refractive index shift nanoparticles are zirconium dioxide (ZrO2) particles, titanium dioxide (TiO2) particles, hafnium dioxide (HfO2) particles, and tungsten trioxide (WO3) particles.

[0076] These refractive index shift nanoparticles may be surface-treated with a dispersant before use, or an anti-aggregation agent may be added to the resist composition or leveling composition to ensure that the refractive index shift nanoparticles are uniformly dispersed in the composition and uniformly distributed during the manufacturing process of the ophthalmic laminate 10.

[0077] Refractive index shift nanoparticles may constitute 20 to 75% by weight of the total weight of the resist composition or leveling composition.

[0078] The resist composition and / or leveling composition is preferably made up of mostly non-volatile components, for example, non-volatile components making up at least 90% by weight of the composition. Such characteristics allow a) to prevent the formation of a high-density surface skin layer during solvent evaporation, b) to limit the shrinkage of the layer and the generation of voids (free spaces) during solvent removal (drying) and the subsequent curing process, reducing changes in the shape and dimensions of replicated microstructures or nanostructures, c) to limit or eliminate surface tension-related defects associated with contaminants (mitigated by the addition of wetting agents), and d) to intentionally terminate the propagation of polymer chains to control the degree of curing.

[0079] Each of the microstructures or nanostructures 131 of the resist layer 13 may, individually, be a refractive optical element (such as an aspherical lens, spherical lens, toric lens, or prism lens), a diffractive optical element (such as a Fresnel lens), a diffusive element, a scattering element, or any other element having an optical function. Preferably, all microstructures or nanostructures 131 are of the same type. These optical elements create micro or nanoscale lenslets. Micro or nanoscale lenslets may be either raised (Figures 1, 2, and 4) or recessed (Figures 3 and 5) relative to a reference background plane.

[0080] For example, each microstructure or nanostructure 131 may be a partially spherical projection or a partially spherical recess. If a leveling layer 15 is provided, this leveling layer 15 exhibits a microstructure or nanostructure that is a negative image of the microstructure or nanostructure 131 of the resist layer 13, and therefore each is a partially spherical recess or a partially spherical projection.

[0081] Preferably, the refractive index of the resist layer 13 and the refractive index of the leveling layer 15 are different. For example, the refractive index of the resist layer 13 may be higher than that of the leveling layer 15. In another example, the refractive index of the resist layer 13 may be lower than that of the leveling layer 15. As an example, the focusing or divergence characteristics of incident light passing through a micro or nanoscale structure in the form of a spherical microlens are summarized in the table below.

[0082] [Table 2]

[0083] Preferably, the refractive index difference between the resist layer 13 and the leveling layer 15 is lower than 0.80, for example, 0.05 to 0.15. This is true, for example, when one of the resist layer 13 and the leveling layer 15 contains an aliphatic urethane oligomer such as IGM Photomer 6892 and / or Photomer 6690, and the other layer contains a sulfur-containing aromatic urethane oligomer such as Miwon's Miramer HR3200. For a constant refractive power and microlens chord diameter, the microlens radius and its sagittal height above the lens reference plane (hs, see Figure 1) or sagittal depth below the lens reference plane (ds, see Figure 3) increase with decreasing refractive index difference. This means that when the refractive index difference (ΔRI) has its maximum value, the lowest profile microlens pattern (i.e., the smallest sagittal height or sagittal depth) can be used in the design.

[0084] The microstructures or nanostructures 131 are provided according to a predetermined pattern. The pattern may be regular tiling of regular polygons, where each micro or nanostructure 131 is at the center of a regular polygon. The regular tiling may be triangular tiling, square tiling, hexagonal tiling, or radial tiling. Preferably, for example, in the case of hemispheres, each is tangent to its neighbor.

[0085] In some embodiments, the ophthalmic laminate 10 includes a first primer layer 12 between the first thermoplastic layer 11 and the resist layer 13, as shown in Figure 4.

[0086] In some other embodiments, the ophthalmic laminate 10 further includes a second primer layer 16 between the leveling layer 15 and the second thermoplastic layer 17, as shown in Figure 5.

[0087] However, it should be understood that this specification also includes the case where one of the first primer layer 12 and the second primer layer 16 is absent.

[0088] The first primer layer 12 and the second primer layer 16 are prepared using the above-mentioned resist compositions, particularly preferred resist compositions F1 and F2, respectively. The first primer layer 12 and the second primer layer 16 may be prepared using different resist compositions. The resist compositions used for the first primer layer 12 and the second primer layer 16 are different from those used for the adhesive layer 15. The first primer layer 12 and the second primer layer 16 may be prepared using compositions comprising a reactive diluent and a urethane acrylate.

[0089] In this embodiment, the difference in refractive index between the resist layer 13 and the adhesive leveling 15 may be 0.05 or greater.

[0090] Preferably, the difference in refractive index between the resist layer 13 and the leveling layer 15 is 0.05 to 0.15, and the ophthalmic laminate 10 includes at least one of a first primer layer 12 and a second primer layer 16. This applies, for example, when one of the resist layer 13 and the leveling layer 15 consists of an 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, which has any component to increase its refractive index, such as ZrO2 particles, TiO2 particles, or brominated acrylate.

[0091] Alternatively, the difference in refractive index between the resist layer 13 and the leveling layer 15 is greater than 0.15, and the ophthalmic laminate 10 includes both a first primer layer 12 and a second primer layer 16. This is the case, for example, when one of the resist layer 13 and the leveling layer 15 (the layer with the lower refractive index) is composed of a mixture of aliphatic acrylates having any refractive index-lowering component such as fluorinated acrylate, and the other layer (the layer with the higher refractive index) is mainly composed of bisfluorene acrylate oligomers having any refractive index-uperating component such as ZrO2 particles, TiO2 particles, or brominated acrylate.

[0092] The following table summarizes preferred combinations of the first primer layer, resist layer, adhesive layer, and second primer layer.

[0093] [Table 3]

[0094] In all embodiments, the first thermoplastic layer 11 and the second thermoplastic layer 17 may be made from a material selected from the group consisting of polycarbonate (PC), polyethylene terephthalate (PET), cellulose triacetate (TAC), cyclic olefin copolymer (COC), and poly(methyl methacrylate) (PMMA), other acrylate polymers (AP), and polyamide (PA, nylon). The material of the first thermoplastic layer 11 and the material of the second thermoplastic layer 17 do not have to be the same. For example, the first thermoplastic layer 11 may be made of PC, and the second thermoplastic layer 17 may be made of nylon. Therefore, the combination of materials for the first thermoplastic layer 11 and the second thermoplastic layer 17 is 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), (AP, TAC), (AP, COC), (AP, PMMA), (AP, AP), (AP, PA), (PA, PC), (PA, PET), (PA, TAC), (PA, COC), (PA, PMMA), (PA, AP), (PA, PA)}.

[0095] Structured wafers and eye patches The ophthalmic laminate 10 can be formed to consist of (n sealed) structured wafers 10' including a concave side 102 and a convex side 101 (see Figures 6, 7, and 8). The resist layer 13 may be closer to the concave side than the first support layer 11, and the first support layer 11 may be closer to the convex side than the resist layer 13 (Figures 6 and 7). Alternatively, the resist layer 13 may be further from the concave side than the first support layer 11, and the first support layer 11 may be further from the convex side than the resist layer 13 (Figure 8).

[0096] The ophthalmic laminate 10 or the molded structured wafer 10' may have 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 hot-melt adhesive (HMA), a water-based adhesive, a solvent-based adhesive, or any other adhesive such as a solvent-free adhesive. Thus, the ophthalmic patch can be adhered to the surface of an existing ophthalmic lens.

[0097] Eye lenses The ophthalmic laminate 10 described above can be used to manufacture the ophthalmic lens 1.

[0098] Such an ophthalmic lens 1 typically comprises a substrate 20 and an ophthalmic laminate 10 cut and molded onto a structured wafer 10'. The structured wafer 10' may be overmolded onto the substrate 20, i.e., the structured wafer 10' is located on one side of the ophthalmic lens 1. For example, the ophthalmic lens 1 includes a concave surface and a convex surface. The structured wafer 10' may be on the concave surface or the convex surface. The ophthalmic laminate may be sealed within the substrate 20, or each side of the structured wafer 10' may be overmolded onto the substrate, thereby embedding the structured wafer 10' within the lens substrate 20.

[0099] The base material 20 may be made of a thermoplastic material, a thermosetting material, or a mineral glass material.

[0100] The ophthalmic lens 1 may have different configurations depending on the intended eyewear application.

[0101] One example of such an application lies in the field of sunwear.

[0102] In the first example, a structured wafer 10' having the following structure may be used to fabricate an ophthalmic lens 1 having a polarizing element 30. The structured wafer 10' includes, in the following order, a first polycarbonate layer 11, a resist layer 13 having a microstructure or nanostructure 131, and a leveling layer 15. In the first modified form (Figure 9), the structured wafer 10' is incorporated into the polarizing element 30. The polarizing element 30 includes, 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. Thus, the leveling layer 15 of the structured wafer 10' is incorporated onto the first adhesive layer 33 of the polarizing element 30. In the second variant (Figure 10), the polarizing element 30 has a structured wafer 10' as a first layer, but instead this structured wafer 10' is replaced with a first polycarbonate layer 31. Subsequently, the entire polarizing element 30 can be used as a second support layer 17 for the structured wafer 10' by laminating the polarizing element on a leveling layer 15, which is selected to be, for example, an adhesive layer. In the third variant (Figure 11), a chemical adhesive, pressure-sensitive adhesive, or hot-melt adhesive 21 may be used to directly bond the structured wafer 10' to the surface of the polarizing eye lens 30. In the fourth variant (Figure 11), a chemical adhesive, pressure-sensitive adhesive, or hot-melt adhesive may be used to directly bond the polarizing element 30 to the surface of the eye lens 1 having the structured wafer 10'.

[0103] In a second example in the field of sunwear fittings, a microstructured ophthalmic lens 1 is submerged in a heated tank containing a dye solution (dye bath) to create a colored lens. In one variant, either the film layer 11 or film layer 17 of the ophthalmic laminate 10 is pre-colored or fabricated with a coloring agent before becoming part of the ophthalmic laminate 10. In another variant, at least one of the resist layer, adhesive layer, or leveling layer incorporates a coloring dye or pigment.

[0104] In the third example (Figure 12), the microstructured ophthalmic lens 1 is a photochromic lens comprising a photochromic multilayer coating 23 on the surface of a structured wafer 10' on an ophthalmic substrate. In one variant, the polyvinyl alcohol polarizing layer 35 is replaced with a photochromic plastic layer (e.g., photochromic thermoplastic polyurethane) to create the photochromic lens.

[0105] In the fourth example, the ophthalmic lens 1 is an electrochromic element lens comprising a structured wafer 10' bonded to a lens embedded with mineral glass-based or plastic-based electrochromic elements.

[0106] Another example of such applications is smart eyewear. In such cases, one of the virtual reality lenses, augmented reality lenses, and mixed reality lenses includes a structured wafer 10' for preventing at least one of the following conditions: myopia, eye strain, and other eye-related conditions. In another case, smart eyewear may incorporate sensors on the eyeglass frame or via the lenses to monitor, record, or report health-related information such as blood pressure, diabetes, stroke, heart disease, seizures, and other medical-related conditions.

[0107] Ophthalmic laminate manufacturing method A first method for producing an ophthalmic laminate according to the present invention, in particular an ophthalmic laminate comprising a first thermoplastic layer 11, a resist layer 13, an optionally selected leveling layer 15, and a second thermoplastic layer 17, which are laminated together in the following order, will be described below with reference to Figures 13 and 14.

[0108] This method includes forming a partially cured resist layer 132 having a surface 131 with microstructures or nanostructures on a first thermoplastic layer 11 in order to form a polycarbonate / resist layer assembly. The method may also include providing a leveling layer 15 between the partially cured resist layer 132 and an optional second thermoplastic layer 17 in order to form a laminate.

[0109] Forming a partially cured resist layer involves depositing the resist composition 4 described above onto a first thermoplastic layer 11 to form an uncured resist layer 41; imprinting the microstructure or nanostructure 131 onto the uncured resist layer 41 by applying a stamp 5 having a negative image 51 of a microstructure or nanostructure onto the uncured resist layer and partially curing the uncured resist layer 41 until it is no longer tacky but acrylate bonds still exist in the partially cured resist layer; and removing the stamp 5, thus leaving a partially cured resist layer 132 on the first thermoplastic layer 11.

[0110] When an uncured resist has cured to a state where it is no longer tacky but still contains unreacted acrylate bonds, the resist can be said to be "lightly cured." In relation to this disclosure, this means, for example, that the microstructure or nanostructure 131 has obtained its final shape, and when the stamp 5 is removed, the microstructure or nanostructure 131 retains its shape. In a lightly cured resist layer, this means that the microstructure or nanostructure 131 does not lose its shape when moved or touched. Furthermore, in this state, the microstructure or nanostructure 131 or the lightly cured resist layer can still react with the material of another layer through the remaining acrylate bonds.

[0111] The degree of curing can theoretically range from 80 to 99%, preferably 95 to 99%, of a fully cured resist. This is determined by measuring the infrared spectrum of the partially cured resist and using the polymer and monomer peaks corresponding to the skeletal stretching vibrations of the C=C bonds in its aromatic rings. Insufficient curing risks causing deformation of micro- or nanostructures during demolding of the resist layer 13 from the stamp 5, while over-curing can impair the bond strength between the resist layer 13 and the leveling layer 15. Clean demolding from the template or stamp 5 ensures the durability of the template or stamp 5 by facilitating cleaning.

[0112] The curing process depends on the properties of the resist composition 4. If the resist composition 4 is a photoresist composition, curing is performed, for example, by radiation using UV light energy. If the resist composition 4 is a thermosetting resist composition, curing is performed by thermal energy, optionally using a curing initiator such as a peroxide initiator.

[0113] The deposition of the resist composition 4 on the first thermoplastic layer 11 can be carried out by spin coating, wire-wound Meyer bar coating, knife coating, roll coating, gravure roller coating, or slot die coating, either in a sheet-size batch process or a roll-to-roll film web continuous process.

[0114] Due to the characteristics of stamp 5, it is usually necessary to use a flexible material with low durability; therefore, stamp 5 can be manufactured from a master template. The master template functions as a mold for shaping stamp 5 and is made from a more durable material such as metal, glass, silicon, or a delicate photolithographic layer deposited on a quartz or silicon material. In particular, since the manufacture of master stamps is expensive, the same master template can be used for stamps 5 with raised macrostructures or nanostructures and stamps with concave macrostructures or nanostructures by using an intermediate template. The intermediate template can actually be a so-called first-generation stamp, and the stamp obtained from this intermediate template can be a so-called second-generation stamp. Generally, it is possible to use n-1 intermediate templates between the master template and stamp 5, i.e., an n-th generation stamp. There is no restriction on the integer n and it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0115] For example, a single master stamp is fabricated using precision tooling methods (e.g., diamond cutting, photolithography, etc.) and materials best suited to the tooling method to capture finer details of the micro or nanostructured pattern. Several first-generation stamp replicas of the master stamp are fabricated either to reverse the structural pattern and / or to use more easily processable stamping materials (e.g., from brittle stamping materials to more durable stamping materials). Numerous second-generation working stamps are fabricated at a lower cost from the first-generation stamps using the same or different stamping materials. These working stamps can then be replaced more frequently in a mass production environment; for example, inexpensive working stamps may be replaced once a day, once a week, or once a month, depending on the production process, stamping material, chemical properties of the resist, contamination levels, handling wear, etc.

[0116] The following table summarizes the types of macrostructures or nanostructures on stamp 5 in the following cases. - If there are no intermediate templates or if the number of intermediate templates is even (indicated as "2k"), and - When the number of intermediate templates is odd (displayed as "2k+1").

[0117] The resist layer 13 always has a macrostructure or nanostructure 131 which is a negative image of the macrostructure or nanostructure of the stamp 5.

[0118] [Table 4]

[0119] The material used to produce stamp 5 may be a silicone elastomer that yields polydimethylsiloxane (PDMS), such as PDMS, which has a tensile strength of 4 to 6 MPa, preferably 4.5 to 5.5 MPa, more preferably 5.0 to 5.4 MPa, and a Shore hardness of 35 to 55, preferably 40 to 50, more preferably 42 to 46 at 20°C. An example of such PDMS is Sylgard® 184.

[0120] Therefore, manufacturing stamp 5 may include pouring a silicone elastomer into a master template, curing the silicone elastomer until it is completely solidified, and demolding stamp 5 from the master template. Alternatively, manufacturing stamp 5 may include performing nickel deposition on the master template to form a 2k-th intermediate stamp and / or performing a second nickel deposition on the 2k intermediate stamp to form a more durable 2k+1-th replica stamp.

[0121] Master templates can be prepared by various methods, including subtractive and additive methods on the base support material. Subtractive methods include diamond cutting, laser ablation, and electrolytic etching of metal, glass, or other suitable support materials. Additive methods include 3D printing, photolithography, or jetting onto quartz or silicon wafer support materials.

[0122] The choice of method for manufacturing a master template typically depends on the microstructures or nanostructures formed on the master template. However, all methods generally begin with using a starting template that has a highly polished surface with very low macro-contour and micro-roughness values ​​before any further processing.

[0123] In principle, subtractive methods are more suitable for creating concave microstructures or nanostructures, while additive methods are more suitable for creating both raised microstructures and nanostructures. This is because removing all background material and leaving raised microstructures generally takes more time than carving only the concave areas. In addition, the carved background (non-raised areas) is no longer highly polished because subtractive tool marks remain on the surface. In contrast, the effort and precision required by additive methods to construct and / or layer only the material necessary to create raised microstructures or nanostructures is expected to be faster and easier than constructing and / or layering the entire non-concave background and leaving the concave microstructures or nanostructures. In addition, the background (non-concave areas) is no longer highly polished because additive tool marks remain on the surface. In grayscale photolithography, multiple layers of raised structures can be stacked using positive or negative photoresists, washing away unwanted areas after each masking step.

[0124] Providing a leveling layer 15 may include spin-coating an adhesive composition 6 onto a second thermoplastic layer 17 to form an adhesive film 61 on the second thermoplastic layer 17, depositing the adhesive composition 6 onto a partially cured resist layer 132, contacting the adhesive film 61 with the adhesive 62 deposited on the partially cured resist layer 132 to form an uncured laminate, and curing the uncured laminate to obtain a laminate.

[0125] Alternatively, providing the leveling layer 15 may include wet coating the adhesive composition 6 onto the second thermoplastic layer 17 to form an adhesive film 61, for example by wire-wound Meyer bar coating, knife coating, roll coating, gravure roller coating, slot die coating, curtain coating, or drip coating into a nip-roll lamination process, so that the adhesive film 61 forms a continuous wet bonding bead. Further alternatively, providing the leveling layer 15 may include applying the adhesive composition 6 onto the second thermoplastic layer 17 by any adhesive application process, such as quantitative drop-feed, to form a continuous wet bonding adhesive bead in a nip-roll lamination process. In both cases, providing the leveling layer 15 further includes contacting the adhesive bead with a partially cured resist layer 132 in a wet bonding nip-roll continuous roll-to-roll web process to form an uncured laminate, and curing the uncured laminate to obtain an eye laminate 10. Alternatively, an optically transparent adhesive solution may be coated onto a carrier film material using one of the precision coating methods described above, partially or completely dried to form an adhesive layer (2 to 50 microns), which is then transferred to a second thermoplastic layer 17 before being brought into contact with a partially cured microstructure 131 on a first thermoplastic layer 11 in a nip-roller lamination process.

[0126] The method may further include activating the surface of the first thermoplastic layer 11 before forming the resist layer 41 on the first thermoplastic layer 11. Activating the surface of the first thermoplastic layer 11 can be done by plasma treatment, corona treatment, or chemical treatment of the surface of the first thermoplastic layer 11, or by still treating the surface of the first thermoplastic layer 11 with a silane coupling agent.

[0127] The method may further include activating the surface of the second thermoplastic layer 17 before providing the leveling layer 15. Activating the surface of the second thermoplastic layer 17 can be done by plasma treatment, corona treatment, or chemical treatment of the surface of the second thermoplastic layer 17, or by still treating the surface of the second thermoplastic layer 17 with a silane coupling agent.

[0128] Another method for manufacturing ophthalmic laminates aims to improve adhesion between a resist layer and an adhesive layer having a specific refractive index that does not directly bond to the thermoplastic layer. This method uses a thin primer layer between the resist layer and the thermoplastic layer, or between the leveling layer and the thermoplastic layer. This is usually necessary when using materials where the refractive index difference between the resist and the leveling layer is greater than 0.07.

[0129] The following description will refer to an ophthalmic laminate comprising a first thermoplastic layer 11, a first primer layer 12, a resist layer 13, a leveling layer 15, a second primer layer 16, and a second thermoplastic layer 17, which are laminated together in the following order. However, it should be understood that this specification also includes the following cases. - In the absence of the first primer layer 12 (and therefore all steps related to the formation of this layer 12 must be ignored, and in the description of the other steps, the first primer layer 12 must be read by substituting the first thermoplastic layer 11) and - In the absence of the second primer layer 16 (and therefore all steps related to the formation of this layer 16 must be ignored, and in the description of the other steps, the second primer layer 16 must be read as being replaced by the second thermoplastic layer 17).

[0130] This method includes forming a first primer layer 12 on a first thermoplastic layer 11, and forming a resist layer 13 having a surface with microstructures or nanostructures on the first primer layer 12 in order to form a laminate. This method may further include forming a second primer layer 16 on a second thermoplastic layer 17, and providing a leveling layer 15 between the resist layer 13 and the second primer layer 16.

[0131] In this method, forming the first primer layer 12 includes depositing the primer composition on the first thermoplastic layer 11 to form an uncured primer layer, and partially curing the uncured primer layer until it is no longer tacky, but acrylate bonds still exist in the partially cured resist layer.

[0132] The deposition of the resist composition on the first primer layer can be carried out by spin coating, wire-wound Meyer bar coating, knife coating, roll coating, gravure roller coating, or slot die coating, either in a sheet-size batch process or a roll-to-roll film web continuous process.

[0133] Forming the resist layer 13 may include depositing a resist composition on a first primer layer 12 to form an uncured resist layer, imprinting the microstructure or nanostructure onto the uncured resist layer by applying a stamp having a negative image of a microstructure or nanostructure onto the uncured resist layer and partially curing the uncured resist layer until it is no longer tacky but acrylate bonds still exist in the partially cured resist layer, and removing the stamp.

[0134] Stamps can be manufactured as described above.

[0135] The curing process depends on the properties of the resist composition 4 described above.

[0136] Providing a leveling layer 15 may include depositing an adhesive composition on a second primer layer 16 to form an adhesive film on the second primer layer 16, depositing an adhesive composition on a partially cured resist layer, contacting the adhesive film with the adhesive deposited on the partially cured resist layer to form an uncured laminate, and completely curing the uncured laminate to obtain a laminate.

[0137] The deposition of the adhesive composition on the second primer layer 16 can be carried out in either a sheet-size batch process or a roll-to-roll film web continuous process by any precision coating technique such as spin coating, wire-wound Meyer bar coating, knife coating, roll coating, gravure roller coating, or slot die coating.

[0138] This method may further include activating the surface of the first thermoplastic layer 11 before forming the first primer layer 12 on the first thermoplastic layer 11. Activating the surface of the first thermoplastic layer 11 can be done by plasma treatment, corona treatment, or chemical treatment of the surface of the first thermoplastic layer 11, or by still treating the surface of the first thermoplastic layer 11 with a silane coupling agent.

[0139] This method may further include activating the surface of the second thermoplastic layer 17 before providing the second primer layer 16. Activating the surface of the second thermoplastic layer 17 may be done by plasma treatment, corona treatment, or chemical treatment of the surface of the second thermoplastic layer 17, or by still treating the surface of the second thermoplastic layer 17 with a silane coupling agent.

[0140] In both methods, imprinting can be performed using a continuous method such as the roll-to-roll method, as shown in Figures 17 and 18.

[0141] In the roll-to-roll method, the stamp 5 may be in the form of a drum, a cylindrical roller, a shim mounted on the drum or roller, or a sleeve mounted on the drum or roller (hereinafter referred to as the drum, but encompassing all these options). The surface of the drum has a negative image of a microstructure or nanostructure formed on a thermoplastic layer, such as the first thermoplastic layer 11, as the stamping template 51. In the following description, the first thermoplastic layer 11 and the resist layer 13 will be referred to. However, the same description may be given for the second thermoplastic layer 17 and the leveling layer 15.

[0142] The first thermoplastic layer 11 is supplied so as to contact the drum by the action of two conveyor rollers 81, 82. Both conveyor rollers rotate in the opposite direction to the rotation direction of the drum, contacting the opposing surface of the first thermoplastic layer 11. The first thermoplastic layer 11 has a coated uncured resist layer 41 facing the drum, opposite to the conveyor rollers 81, 82, and both are supplied in the form of a continuous web. Optionally, a first primer layer 12 is placed between the first thermoplastic layer 11 and the uncured resist layer 41.

[0143] When the uncured resist layer 41 comes into contact with the stamping template 51, microstructures or nanostructures are formed within the uncured resist layer 41. The pressure of the stamping template 51 is maintained by a drum on the uncured resist layer 41 for a predetermined time, during which time the uncured resist layer 41 is lightly cured by the curing energy 7. The curing properties depend on the resist composition 4 described above.

[0144] The stamping template 51 may be transparent. In such cases, light curing can be performed via the stamping template 51 (Figure 17).

[0145] The first thermoplastic layer 11 may be transparent. In such cases, mild curing can be performed via the first thermoplastic layer 11 (Figure 18).

[0146] After partial curing, the assembly of the first thermoplastic layer 11 and the partially cured resist layer 132, optionally having a first primer layer 12 in between, is removed from the drum and carried away by transport rollers 81 and 82.

[0147] Both methods may further include forming the laminate. For example, forming the laminate may include die-cutting the laminate and thermoforming the ophthalmic laminate to obtain a 3D-shaped structured wafer 10'.

[0148] Method for manufacturing ophthalmic lenses A method for manufacturing an ophthalmic lens according to the present invention will be described below with reference to Figures 15 and 16.

[0149] This method includes manufacturing a structured wafer 10' using one of the methods described herein, placing the structured wafer 10' in an ophthalmic lens mold M, and forming a substrate 20 in the lens mold to obtain an ophthalmic lens.

[0150] The mold may include a concave side M1 and a convex side M2. In such a case, positioning the structured wafer 10' may include positioning the convex side 101 of the structured wafer 10' relative to the concave side M1 of the mold (see Figure 15).

[0151] Alternatively, the mold includes a concave side M1 and a convex side M2. In such a case, positioning the structured wafer 10' involves positioning the concave side 102 of the structured wafer 10' relative to the convex side M2 ​​of the mold.

[0152] Alternatively, positioning the structured wafer 10' may involve positioning it between the two sides M1, M2 of the mold such that neither the convex side 101 nor the concave side 102 of the structured wafer 10' touches the concave side M1 or convex side M2 ​​of the mold. In such a case, the structured wafer 10' can be brought close to the concave side M1 (see Figure 16) or convex side M2 ​​of the mold. Preferably, the distance between the side of the structured wafer 10' closest to one side of the mold M and that side of the mold M is 1 mm or less.

[0153] The substrate 20 can be made from a thermoplastic composition. In such cases, the substrate 20 is preferably formed by injection overmolding, during which the thermoplastic composition used fills the void M3 between the structured wafer 10' and the mold M. By injection molding, the positioning of the structured wafer 10' is preferably done relative to side M1 or side M2 ​​of the mold M.

[0154] The thermoplastic substrate 20 can be made from polycarbonate (PC), cyclic olefin copolymer (COC), poly(methyl methacrylate) (PMMA) and other acrylate polymers, polyamide (PA, nylon), or other thermoplastic injection molding materials used in the ophthalmic industry.

[0155] In some cases, it may be necessary to promote the adhesion of the structured wafer 10' to the injected thermoplastic plastic. This may be the case when the structured wafer 10' does not have any adhesive layer 15 or any second support layer 17 (see Figure 6). Therefore, prior to injection overmolding with the thermoplastic substrate 20, the method may include, for example, promoting the adhesion of the structured wafer 10' to the partially cured resist layer 13 and / or first support layer 11 of the ophthalmic laminate 10 before it is formed on the structured wafer 10' by corona treatment, plasma treatment or chemical treatment.

[0156] Other methods may be used to manufacture such ophthalmic lenses. For example, the structured wafer 10' may be incorporated into the surface (Figure 15) or bulk (Figure 16) of a thermosetting cast ophthalmic lens. Thus, the substrate 20 may be made from thermosetting materials such as poly(allyl diglycol carbonate (e.g., CR-39™ of PPR)) and urethane-based prepolymers (e.g., Trivex™ of PPG). Other suitable materials are Mitsui Chemicals, Inc.'s MR™ Series or other thermosetting casting materials used in the ophthalmic industry. Thus, forming the substrate 20 may involve casting a thermosetting composition within a mold M. Because thermosetting compositions are more fluid than thermoplastics, they can easily flow through all the free space of the mold M, even if the structured wafer 10' is not positioned against either side M1 or side M2 ​​of the mold. Therefore, the embodiment shown in Figure 16 is more suitable for forming the substrate 20 by casting a thermosetting composition.

[0157] Another example is to provide a structured wafer 10' having 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 hot-melt adhesive (HMA), a water-based adhesive, a solvent-based adhesive, or even a solvent-free adhesive. Thus, the ophthalmic laminate 10 can be bonded to the surface of an existing ophthalmic lens. Alternatively, a UV-curable and / or heat-curable fluid optical adhesive may be used to bond the structured wafer 10' to the surface of an existing thermoplastic or thermosetting ophthalmic lens. [Examples]

[0158] Example 1 Example 1 shows an example of a method for producing an ophthalmic laminate 10 without a primer layer.

[0159] First, a stamp 5 is manufactured by pouring a Sylgard® 184 mixture onto a micro or nanostructured master template having a positive image of the desired microstructure or nanostructure 131 of the resist layer 13. Then, the Sylgard® 184 mixture is cured until it is completely solid, and the stamp 5 having a negative image of the desired microstructure or nanostructure 131 is released from it.

[0160] Subsequently, the acrylate resist layer 41 was spin-coated onto the surface of the first polycarbonate layer 11, which was made from the first composition. This surface had been pre-plasma treated. Then, the stamp 5 was applied onto the resist layer 41, and the resist layer 41 was lightly cured. In this lightly cured state, the resist layer 41 still has unreacted and unbonded functional acrylate (C=C) groups at its interface, which improves its bonding strength with the adhesive layer that will be applied later. At this point, the patterned resist layer 41 was demolded from the stamp 5.

[0161] Subsequently, a layer 61 of acrylate adhesive was spin-coated onto the surface of a second polycarbonate layer 17 made from the second composition. This surface had been pre-plasma treated. The acrylate adhesive 6 was also added to the surface of a lightly cured micro or nanostructured resist layer 132. Then, the layer 61 of acrylate adhesive was applied to the resist layer 13 having the acrylate adhesive between a steel roller and a hard rubber nip-pinch roller lamination tool. The resulting laminate was then exposed to ultraviolet light to completely cure the resist layer 13 and the acrylate adhesive, forming an acrylate adhesive layer 15. After the completely cured laminate 10 was die-cut and molded, a structured wafer 10' was obtained.

[0162] Subsequently, in order to obtain the ophthalmic lens 1, an ophthalmic lens mold M having a concave side M1 and a convex side M2 ​​is used in the injection molding method. To do this, a structured wafer 10' is inserted into the concave side M1, and both sides M1 and M2 of the mold are brought together to form a mold cavity M3. Molten polycarbonate is injected into the mold cavity M3, and an ophthalmic substrate 20 is overmolded onto the structured wafer 10', thus forming the ophthalmic lens 1.

[0163] Example 2 Example 2 shows an example of a method for producing an ophthalmic laminate 10 without a primer layer.

[0164] First, a stamping template in the form of a thin sheet is manufactured by pouring a Sylgard® 184 mixture onto a micro or nanostructured master template having a positive image of the desired microstructure or nanostructure in the resist layer. Then, the Sylgard® 184 mixture is cured until completely solidified, the stamping template having a negative image of the desired microstructure or nanostructure is released from it, and applied to the side of a drum with the microstructure or nanostructure facing outwards, thus forming a stamp (or stamping drum).

[0165] This method uses a first polycarbonate layer and a second polycarbonate layer, each in the form of a continuous sheet. The first and second polycarbonate layers are unwound from their respective polycarbonate film rolls. This makes it possible to continuously manufacture multiple ophthalmic laminates. The continuous sheets of the first and second polycarbonate layers are transported through subsequent stations.

[0166] First polycarbonate layer: In the first station, its surface is pre-treated with plasma or chemically treated with a silane coupling agent. In the second station, an acrylate resist layer is slot-die coated onto the treated surface. In the third station, the acrylate resist layer comes into contact with the surface of the stamping drum. During this contact, while the stamping drum makes a large winding angle of approximately 180° full rotation, the stamping template is applied to and maintained on the acrylate resist layer, and a portion of the laminated acrylate resist layer and stamping template are transported to the radiation curing station. In the radiation curing station, ultraviolet light is irradiated onto the acrylate resist layer through the first polycarbonate layer to lightly cure the acrylate resist layer. In this lightly cured state, the resist layer still has unreacted and unbonded functional acrylate (C=C) groups at the interface, which improves its bonding strength with the adhesive layer applied later. Subsequently, the patterned resist layer is released from the stamping drum when a continuous sheet having a lightly cured micro or nanostructured resist layer on top thereof is transported to a station where acrylate adhesive is deposited as a quantitative dropper bead coating on the surface of the lightly cured micro or nanostructured resist layer, and then transported to a wet bonding nip pinch roller lamination station.

[0167] Second polycarbonate layer: In the first station, its surface is pre-treated with plasma or chemically treated with a silane coupling agent. In the second station, a layer of acrylate adhesive may be slot-die coated onto the treated surface. The continuous sheet having the acrylate adhesive layer is then transported to a wet bonding nip-pinch roller lamination station.

[0168] In the lamination station, a continuous sheet having an acrylate adhesive layer is applied onto a continuous sheet having a lightly cured micro or nanostructured resist layer, such that the acrylate adhesive layer is in contact with the lightly cured micro or nanostructured resist layer. The laminated assembly is then fully cured in a subsequent station.

[0169] After curing, the ophthalmic laminate was cut from the laminated assembly, molded, and incorporated into the ophthalmic lens using the same method as in Example 1.

[0170] Example 3 Example 3 illustrates a method for producing an ophthalmic laminate having a primer layer.

[0171] First, a stamp 5 is manufactured by pouring a Sylgard® 184 mixture onto a micro or nanostructured master template having a positive image of the desired microstructure or nanostructure 131 of the resist layer 13. Then, the Sylgard® 184 mixture is cured until it is completely solid, and the stamp 5 having a negative image of the desired microstructure or nanostructure 131 is released from it.

[0172] Subsequently, a first thin primer layer 12 was spin-coated onto the first polycarbonate layer 11 of the first polycarbonate composition, and a second thin primer layer 16 was spin-coated onto the second polycarbonate layer 17 of the second polycarbonate composition. The primer layers 12 and 16 were lightly UV-cured.

[0173] Subsequently, the acrylate resist layer 41 was spin-coated onto the lightly cured first primer layer 12. A macrostructure or microstructure was imprinted onto the resist layer 41 using a flexible, adaptable work stamp 5, the resist was lightly cured, and the stamp 5 was removed.

[0174] An acrylate adhesive layer 61 was spin-coated onto the plasma-treated surface of the second primer layer 16. Additional acrylate adhesive 6 was added as a quantitative dropper bead coating between the lightly cured resist layer and the acrylate adhesive layer 61 between a steel roller and a hard rubber nip-pinch roller lamination tool. The resulting laminate was exposed to ultraviolet light to completely cure all lightly cured layers 12, 13, 16 and the uncured layer 15. The fully cured laminate was then die-cut to form (molde) it, thus obtaining a structured wafer 10'.

[0175] Subsequently, in order to obtain the ophthalmic lens 1, an ophthalmic lens mold M having a concave side M1 and a convex side M2 ​​is used in the injection molding method. To do this, a structured wafer 10' is inserted into the concave side M1, and both sides M1 and M2 of the mold are brought together to form a mold cavity M3. Molten polycarbonate is injected into the mold cavity M3, and an ophthalmic substrate 20 is overmolded onto the structured wafer 10', thus forming the ophthalmic lens 1.

[0176] Example 4 In this embodiment, a composition comprising 55% by weight of aliphatic urethane hexaacrylate, 20% by weight of trimethylolpropane triacrylate, 20% by weight of hexanediol diacrylate, and 5% by weight of Omnirad 4265 as a crosslinking initiator was used for the resist layer 13. Its glass transition temperature was 98°C.

[0177] The composition used in the adhesive layer 15 contains 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% by 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.

[0178] After complete curing, the refractive index is 1.52 for the resist layer 13 and 1.59 for the adhesive layer 15. The viscosity is 535.1 cPs for the resist layer 13 and 791.8 cPs for the adhesive layer 15.

[0179] The first thermoplastic layer 11 and the second thermoplastic layer 17 were made of polycarbonate.

[0180] An ophthalmic lens was manufactured according to the method of Example 1. This demonstrates that manual delamination of the structured wafer is impossible and that there are no cracks or delaminations after the injection overmolding process.

[0181] Example 5 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.

[0182] Example 6 The ophthalmic laminate 10 was manufactured using the same composition as in Example 4 and the same method as in Example 1. The only difference was that the resist layer 13 was fully cured before forming the adhesive layer 15.

[0183] Manual peeling of the ophthalmic laminate in Example 6 is possible, and when the resist layer 13 is lightly cured, the interlayer adhesion of the ophthalmic laminate in Example 4 is significantly higher.

[0184] Example 7 In this example, a composition comprising 65% by weight of Miwon Miramer HR6042 (containing 60% by weight of bisflorene 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 resist layer 13.

[0185] The composition used for the resist layer in Example 3 was used as the first primer layer 12 and the adhesive layer 15. There was no second primer layer. The first thermoplastic layer 11 and the second thermoplastic layer 17 were made of polycarbonate.

[0186] The refractive index after the resist layer had completely hardened was 1.60.

[0187] Eye lenses were manufactured according to Example 3. Manual delamination of the sealed structured wafer was impossible, and no cracking or delamination was observed during the injection overmolding process.

[0188] Example 8 A structured wafer 10' having a first support layer 11 and a resist layer 13 is manufactured using the same stamping process as described in Example 1.

[0189] In this example, the first support layer 11 is made of polycarbonate, poly(methyl methacrylate), nylon, or other optically good film material. Optionally, the adhesion of the partially cured resist layer 13 is facilitated by corona treatment, plasma treatment, or chemical treatment.

[0190] Subsequently, the resulting ophthalmic laminate 10 is formed into a structured wafer 10' (for example, by thermoforming, hydroforming, or blow forming) so as to take the 3D curved shape of the concave side (previous mold M1) of the mold M.

[0191] A structured wafer 10' was inserted into the concave side M1, and both sides M1 and M2 of the mold were joined to form a mold cavity M3. A molten thermoplastic polymer such as poly(methyl methacrylate) was injected into the mold cavity M3, and an ophthalmic substrate 20 was overmolded onto the structured wafer 10', thus forming an ophthalmic lens 1.

[0192] Example 9 A structured wafer 10' having a first support layer 11 and a resist layer 13 is manufactured using the same stamping process as described in Example 1.

[0193] In this example, the adhesion of the partially cured resist layer 13 is facilitated by corona treatment, plasma treatment, or chemical treatment. Optionally, the adhesion of the first support layer 11 to the opposing side is also facilitated by the same or different methods.

[0194] Subsequently, the resulting ophthalmic laminate 10 is formed into a structured wafer 10' (for example, by thermoforming, hydroforming, or blow forming) so as to take the 3D curved shape of the concave side (previous mold M1) of the mold M.

[0195] A structured wafer 10' was inserted between the recessed side M1 and the convex side M2 ​​of the mold, and these were joined to form a mold cavity M3. When the mold M is assembled, the convex side of the structured wafer 10' is less than 1 mm away from the inner surface of the recessed side of the mold (or the previous mold M1). Therefore, the mold cavity M3 is divided into a front cavity between the recessed side M1 and the structured wafer 10' and a back cavity between the structured wafer 10' and the convex side M2 ​​of the mold.

[0196] A thermosetting curing material was injected into the mold cavity M3, and an ophthalmic substrate 20 was molded onto the structured wafer 10', thus forming the ophthalmic lens 1.

[0197] Example 10 This example utilizes a structured wafer 10' having a first support layer 11, a resist layer 13, and a flat leveling layer 15. The resist layer 13 is formed on the first support layer 11 using the same method as described in Example 1. Subsequently, the flat leveling layer 15 is coated onto the resist layer 13. Optionally, the leveling layer 15 contains refractive index shift nanoparticles. Optionally, adhesion of the leveling layer 15 is facilitated by corona treatment, plasma treatment, or chemical treatment.

[0198] Subsequently, the resulting ophthalmic laminate 10 is formed into a structured wafer 10' (for example, by thermoforming, hydroforming, or blow forming) so as to take the 3D curved shape of the concave side (previous mold M1) of the mold M.

[0199] In one modified form, the manufacturing of the ophthalmic lens is carried out using the same method as described in Example 9. Here, the leveling layer 15 increases the inherent difference in refractive index between the cured thermosetting casting material and the resist layer 13. The leveling layer 15 also improves adhesion with the cured thermosetting casting material.

[0200] In another variant, the manufacturing of the ophthalmic lens is carried out using the same method as described in Example 9. The leveling layer 15 and the microstructure or nanostructure 131 are located on the convex surface of the laminate 10 and face the concave mold M1. Here, the leveling layer alters the inherent difference in refractive index between the resist layer 13 and air, protecting the microstructure or nanostructure 131 from wear and forming a flat outer surface for hard coatings, anti-reflective coatings, photochromic coatings, etc., so that the surface coating does not alter the contour and functionality of the microstructure or nanostructure 131.

[0201] In another variant, the manufacturing of the ophthalmic lens is carried out using the same method as described in Example 8. Here, the leveling layer 15 increases the inherent difference in refractive index between the thermoplastic injection molding material and the resist layer 13. The leveling layer 15 also improves adhesion to the thermoplastic material and protection of the microstructure or nanostructure 131.

[0202] In another variant, the manufacturing of the ophthalmic lens is carried out using the same method as described in Example 8. The leveling layer 15 and the microstructure or nanostructure 131 are located on the convex surface of the laminate 10' and face the concave mold M1. Here, the leveling layer alters the inherent difference in refractive index between the resist layer 13 and air, protecting the microstructure or nanostructure 131 from wear and forming a flat outer surface for hard coatings, anti-reflective coatings, photochromic coatings, etc., so that the surface coating does not alter the contour and functionality of the microstructure or nanostructure 131.

Claims

1. A method for manufacturing an ophthalmic laminate (10) having a first support layer (11, 12) and a resist layer (13) having a microstructure or nanostructure (14) on the surface facing the first support layer, The method involves forming a partially cured resist layer (132) having a surface with microstructures or nanostructures on a first support layer (11, 12), In order to form a resist layer (41), the resist composition (4) is deposited on the first support layer, The microstructure or nanostructure (131) is imprinted on the resist layer by applying a stamp (5) having a negative image (51) of the microstructure or nanostructure onto the resist layer, and partially curing the resist layer until it is no longer tacky but acrylate bonds still exist in the resist layer. A method comprising removing the aforementioned stamp and forming.

2. The method according to claim 1, wherein the resist composition is deposited on the first support layer by precision coating techniques such as spin coating, wire-wound Meyer bar coating, knife coating, roll coating, gravure roller coating, or slot die coating.

3. The method according to claim 2, wherein the deposition of the resist composition is performed by slot die coating, the stamp is a stamping drum (5, 51), and curing is performed via the first support layer or the stamping drum.

4. The method according to any one of claims 1 to 3, further comprising activating the surface of the first support layer before forming the resist layer on the first support layer.

5. The first support layer is a first thermoplastic layer (11), and the resist composition comprises a crosslinking initiator and a mixture of polymerizable monomers or oligomers. The mixture is determined based on the total weight of the polymerizable monomer or oligomer contained in the mixture. 20 to 80% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of urethane triacrylate and a different triacrylate, The method according to any one of claims 1 to 4, comprising 3 to 30% by weight of diacrylate.

6. The first support layer is a first thermoplastic layer (11), and the resist composition is Formulation F1, Low refractive index urethane acrylate with a pH of 20-80, A monofunctional or difunctional acrylate different from a low refractive index urethane acrylate with a pH of 10 to 50, Low refractive index urethane acrylate with a pH of 0-50 pH and other trifunctional or higher acrylates, Formulation F1 containing a photoinitiator at 1-10 pH, Formulation F2, High refractive index urethane acrylate with a pH of 20-80, A monofunctional or difunctional acrylate different from a low refractive index urethane acrylate with a pH of 10 to 50, Low refractive index urethane acrylate with a pH of 0-50 pH and other trifunctional or higher acrylates, Aromatic acrylates in the range of 0-60 pH, Formulation F2 containing a photoinitiator at 1-10 pH, Formulation F3, 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene at 20-80 pH, Low refractive index urethane acrylate with a pH of 0-30, and acrylates with three or more functions different from other acrylates, Aromatic acrylates in the range of 0-60 pH, Formulation F3 containing a photoinitiator at 1-10 pH, Formulation F4, 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene at 0-70 pH, Aromatic acrylates in the range of 0-70 pH, Brominated or chlorinated acrylate at 30-100 pH, Formulation F4 containing 1 to 10% by weight of a photoinitiator, Formulation F5, Low refractive index urethane acrylate with a pH of 0-50, A monofunctional or difunctional acrylate different from a low refractive index urethane acrylate with a pH of 0 to 70, Low refractive index urethane acrylate with a pH of 0-70, and acrylates with three or more functions different from other acrylates, Fluorinated acrylates at 30-100 pH, Formulation F5 containing a photoinitiator at 1-10 pH The method according to any one of claims 1 to 4, wherein the nanoparticles are selected from and optionally comprise 20 to 60% by weight of refractive index increasing nanoparticles.

7. The first support layer is a first primer layer (12) prepared by depositing a composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers onto a first thermoplastic layer (11). The mixture is determined based on the total weight of the polymerizable monomer or oligomer contained in the mixture. 20 to 80% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of urethane triacrylate and a different triacrylate, The method according to any one of claims 1 to 4, comprising 3 to 30% by weight of diacrylate.

8. The method according to any one of claims 1 to 4, wherein the first support layer is a first primer layer (12) prepared by depositing the formulation F1 or formulation F2 specified in claim 6 onto a first thermoplastic layer (11).

9. The mixture is determined based on the total weight of the polymerizable monomer or oligomer contained in the mixture. 50-70% by weight of urethane hexaacrylate, 15-25% by weight of urethane triacrylate and a different triacrylate, The method according to claim 5 or 7, comprising 15 to 25% by weight of diacrylate.

10. The method according to any one of claims 1 to 9, further comprising providing a second support layer and a leveling layer between the resist layer and the second support layer.

11. The method according to claim 10, further comprising activating the surface of the second support layer before providing the second support layer and the leveling layer.

12. Providing the leveling layer means A leveling composition is applied to the second support layer by spin coating, wire-wound Meyer bar coating, knife coating, roll coating, gravure roller coating, or slot die coating to form a leveling film on the second support layer. Depositing the leveling composition onto the partially cured resist layer, The leveling film is brought into contact with the leveling composition deposited on the partially cured resist layer, The method according to claim 10 or 11, comprising completely curing the laminate in order to obtain the aforementioned ophthalmic laminate.

13. The method according to any one of claims 10 to 12, wherein the second support layer is a thermoplastic layer (17).

14. The second support layer is a second primer layer (16) prepared by depositing a composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers onto the second thermoplastic layer (17). The mixture is determined based on the total weight of the polymerizable monomer or oligomer contained in the mixture. 5 to 60% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of urethane triacrylate and a different triacrylate, The method according to any one of claims 10 to 12, comprising 3 to 30% by weight of diacrylate.

15. The method according to any one of claims 10 to 12, wherein the second support layer is a second primer layer (16) prepared by depositing the formulation F1 or formulation F2 specified in claim 6 onto the second thermoplastic layer (17).

16. A method for manufacturing ophthalmic lenses, To provide an ophthalmic laminate having a first support layer (11, 12) and a resist layer (13) having a microstructure or nanostructure (14) on the surface facing the first support layer, This includes bonding a substrate to the aforementioned ophthalmic laminate, A method for providing the ophthalmic laminate, wherein the method is described in any one of claims 1 to 12.

17. Using a mold that includes a convex die and a concave die, The method according to claim 16, wherein providing the ophthalmic laminate comprises arranging the ophthalmic laminate relative to the concave die or the convex die.

18. They are stacked on top of each other in the following order: A first thermoplastic layer (11) and The resist layer (13) and Adhesive layer (15) and A second thermoplastic layer (17), An ophthalmic laminate (10) containing, The resist layer and the adhesive layer together form a microstructure or nanostructure (14) at their interface. The resist layer is made of a resist composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers. The aforementioned mixture is determined based on the total weight of the polymerizable monomer or oligomer contained in the mixture. 5 to 60% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of urethane triacrylate and a different triacrylate, It contains 3 to 30% by weight of diacrylate, or The mixture is an ophthalmic laminate (10) selected from formulations F1, F2, F3, F4, and F5 as defined in claim 6.

19. They are stacked on top of each other in the following order: A first thermoplastic layer (11) and The resist layer (13) and Adhesive layer (15) and A second thermoplastic layer (17), An ophthalmic laminate (10) containing, The material further includes a primer layer (12, 16) between the first thermoplastic layer and the resist layer or between the adhesive layer and the second thermoplastic layer. The primer layer is made of a primer composition comprising a crosslinking initiator and a mixture of polymerizable monomers or oligomers. The aforementioned mixture is determined based on the total weight of the polymerizable monomer or oligomer contained in the mixture. 5 to 60% by weight of urethane triacrylate or urethane hexaacrylate, 3-30% by weight of urethane triacrylate and a different triacrylate, It contains 3 to 30% by weight of diacrylate, or The mixture is an ophthalmic laminate (10) selected from the formulation F1 and orientation F2 specified in claim 6.

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