Method of producing coated optical substrates

Abstract

Methods and systems for producing optical constructions on a generally curved polymeric optical substrate, one such method comprising: (a) microvalving a droplet of a liquid film-forming formulation onto an optical surface of the optical substrate to form a wet layer; and (b) treating the wet layer to produce a dry transparent layer on the optical surface.

Description

Cross-references with other published sources

[0001] This application claims priority to the following patent applications: U.S. Patent Application No. 63 / 580,003, filed September 1, 2023; U.S. Patent Application No. 63 / 541,293, filed September 28, 2023; U.S. Patent Application No. 63 / 541,279, filed September 28, 2023; U.S. Patent Application No. 63 / 541,292, filed September 28, 2023; and GB Application No. 2409920.2, filed July 8, 2024, and GB Application No. GB2409979.8, filed July 9, 2024; the teachings of all these patent applications are incorporated herein by reference. Technical Field

[0002] The present invention relates to coated optical and ophthalmic devices and articles, such as coated lenses, and to methods and apparatus for applying and forming coatings on such devices and articles.

[0003] Thermosetting coatings for lenses are typically based on siloxanes. They can be made from various siloxane monomers, typically tetraalkoxysilanes and alkyltrialkoxysilanes, which are pre-reacted with water to achieve varying degrees of hydrolysis. Various organic functional moieties can be attached to alkyl groups directly bonded to the central silicon atom. Generally, thermosetting coatings exhibit significantly higher abrasion resistance than radiation-cured coatings. Thermosetting coating technology has been disclosed in numerous patents, including the following U.S. patents: 4,547,397, 5,385,955, and 6,538,092. Radiation-cured coatings are disclosed in U.S. patents 4,478,876 and 5,409,965.

[0004] Various commercial methods for producing eyeglass coatings can utilize such thermosetting coatings. In various known processes, optical obstruction can be significantly amplified when the target surface is a curved optical surface, such as eyeglass lenses, especially for eyeglass lenses with a high SAG number.

[0005] The inventors recognize the need for improvements to optical and ophthalmic devices and articles with hard coatings, as well as the need for systems and methods for producing such devices and articles, especially at high throughput. Summary of the Invention

[0006] According to some teachings of the present invention, a method is provided for producing a dry transparent layer or coating on an ophthalmic substrate, the method comprising: (a) microvacuuming a droplet of a liquid film-forming formulation onto an ophthalmic surface of the substrate to form a wet layer; and (b) treating the wet layer to produce a dry transparent layer on the ophthalmic surface; wherein the ophthalmic surface is a polymer surface.

[0007] According to a further teaching of the present invention, a method for producing an optical or ophthalmic structure on an optical or ophthalmic substrate is provided, the method comprising: (a) microvacuuming a droplet of a liquid film-forming formulation onto an optical or ophthalmic surface of the substrate to form a wet layer; and (b) treating the wet layer to produce a dry transparent layer on the optical or ophthalmic surface, wherein the liquid film-forming formulation is a hard coating formulation. Attached Figure Description

[0008] The invention will be described herein by way of example only with reference to the accompanying drawings. Referring now to the drawings in detail, it should be emphasized that the details shown are by way of example only and for the purpose of illustrative discussion of preferred embodiments of the invention, and are presented to provide a description believed to be the most applicable and readily understood of the principles and concepts of the invention. In this regard, no attempt is made to show the structural details of the invention in more detail than necessary for a basic understanding of the invention; the description, taken in conjunction with the drawings, enables those skilled in the art to understand how several forms of the invention can be practiced. Throughout the drawings, the same reference numerals are used to designate the same elements.

[0009] In the attached diagram: Figure 1 A schematic block diagram of a method for processing an optical surface according to an aspect of the present invention is provided; Figure 2 A schematic block diagram of a method for processing an optical surface to produce a dry hard coating according to an aspect of the present invention is provided; Figure 2A for Figure 2 The schematic block diagram provides optional steps, wherein pretreatment may include applying a liquid primer formulation to the exposed surface of an ophthalmic substrate, and subsequent drying; Figure 3 A schematic general block diagram of a method for processing an optical surface to produce an optical structure according to an aspect of the present invention is provided; Figure 4 It is a schematic cross-sectional view of a multilayer ophthalmic structure, which includes an ophthalmic substrate having an ophthalmic structure having a wide surface fixedly attached to a substrate. Figure 4A and Figure 4B These are schematic diagrams showing how a micro-valve device sprays ink droplets onto the surfaces of a convex and concave lens, respectively. Figure 5 A conceptual representation of a process for coating and finishing optical or ophthalmic substrates using a coating system according to an embodiment of the present invention is shown; Figure 6A , Figure 6B and Figure 6C A corresponding block diagram of an exemplary coating system according to an embodiment of the present invention is shown; Figure 7A and Figure 7B A corresponding conceptual representation of a process for coating optical or ophthalmic substrates using a coating system combined with surface treatment equipment according to an embodiment of the present invention is shown; Figure 8 A block diagram of an exemplary coating system according to an embodiment of the present invention is shown; Figure 9 A block diagram of an exemplary surface treatment apparatus according to an embodiment of the present invention is shown; Figure 10A , Figure 10B , Figure 10C and Figure 11 A corresponding conceptual representation of a process for coating and drying optical or ophthalmic substrates according to an embodiment of the present invention is shown; Figure 12A , Figure 12B , Figure 12C and Figure 12D A corresponding schematic view of an exemplary optical substrate according to an embodiment of the present invention is shown; Figure 13A and Figure 13B A corresponding side view and perspective view of a virtual two-dimensional projection of an optical substrate surface according to an embodiment of the present invention are shown. Figure 14 A schematic side view of droplet deposition on a curved surface of an optical substrate according to an embodiment of the present invention is shown, the side view being a virtual two-dimensional projection of the surface; Figure 15 A schematic top view of an optical substrate according to an embodiment of the present invention is shown, the optical substrate comprising a virtual annular structure including an edge portion; and Figure 16 A schematic side view of an optical substrate with a curved surface according to an embodiment of the present invention is shown, the side view showing certain aspects of the surface geometry. Detailed Implementation

[0010] The principles and operation of the optical construction according to the present invention can be better understood by referring to the accompanying drawings and description.

[0011] Before explaining at least one embodiment of the invention in detail, it should be understood that the application of the invention is not limited to the details of the construction and arrangement of the components set forth in the following description or shown in the drawings. The invention can have other embodiments or can be practiced or implemented in various ways. Similarly, it should be understood that the phrases and terms used herein are for descriptive purposes and should not be considered limiting.

[0012] The inventors have discovered that applying one or more optical coatings to an optical substrate involves various technical hurdles. Some of these hurdles relate to the optical substrate, which is often highly smooth and substantially non-absorbent. The optical substrate is typically transparent, and multiple optical coatings may need to have high transparency. Furthermore, the refractive index of each coating, or all coatings together, may be limited to be similar to the refractive index of the optical substrate.

[0013] The manufactured optical constructs and articles must meet mechanical standards, such as hardness and / or scratch resistance. Each of the coatings must also be relatively inert with respect to other coatings it comes into contact with. Furthermore, since coatings can be applied continuously, at least one of the applied wet or uncured formulations can come into contact with and interact with previously applied coatings.

[0014] The curing time for each coating or layer should be reasonable (at most a few minutes or hours), and the curing temperature should be low enough to avoid damaging the optical substrate and any previously applied coatings.

[0015] Adhesion to optical or ophthalmic substrates, as well as the resistance to peeling or cracking of one or more coatings, can be crucial for obtaining viable coated lenses (such as coated ophthalmic lenses). The inventors have found that such adhesion problems can be significantly exacerbated when the hard coating formulation contains one or more coloring dyes. Not wishing to limit themselves to theory, the inventors believe that the presence of coloring dyes at the interfaces of layers within an optical stack, or at the interface between the bottom layer and the optical substrate, can significantly impair bonding or attachment at such interfaces. Furthermore, the inventors believe that coloring dyes may exhibit an affinity for the interface region, such that the concentration of coloring dye at the interface may be significantly higher than the average concentration of coloring dye in the ink solids.

[0016] Furthermore, and especially in the case of solvent erosion, solvent penetration of subsequently applied layers can impair the adhesion between these layers, as well as between two previously applied layers or between a previously applied layer and the substrate. Therefore, complete curing of the wet layer can be crucial for producing optical stacks or structures with suitable optical and mechanical properties.

[0017] It is worth noting that the inventors have discovered that when solvent permeation cannot be completely avoided, solvent systems containing solvents with high evaporation rates and solvents with low evaporation rates can significantly reduce the degree of such permeation.

[0018] like Figure 1 As illustrated, the method of the present invention includes microvalving droplets of a liquid film-forming formulation (typically a hard coating formulation) onto the optical or ophthalmic surface of an optical or ophthalmic substrate to form a wet layer (step 102). The microvalved droplets can form a continuous and uniform layer on a curved or highly curved optical substrate.

[0019] Under controlled flow conditions, a continuous and uniform layer can be advantageously formed. In uncontrolled flow, droplets slide along the surface, deviating from the digital positioning provided by the microvalve. especially This leads to uneven films, bald spots, and other problems. For low-viscosity formulations, uncontrolled flow can be significantly more severe. While hard-coating formulations may not contain solid binders and are typically low or very low in viscosity, fixation can still be achieved by introducing high concentrations of rapidly evaporating solvents into the formulation.

[0020] However, the inventors have found that this method can encounter problems when attempting to utilize microvalve technology. Large microvalve droplets are bulky relative to their surface and contact areas and are prone to uncontrolled slippage, a tendency exacerbated by their low viscosity. Rapidly evaporating solvents are less effective for small droplets, partly due to their high volume-to-surface-area ratio. The inventors have discovered that by balancing low-evaporation-rate and high-evaporation-rate solvents in the formulation, a thin, continuous, and uniform hard coating can be formed over a narrower droplet diameter range. The calculation of droplet diameter is discussed below. This method has been found to be suitable for lenses within a specific curvature range.

[0021] As used herein, the term "ophthalmic substrate" refers to a substrate through which the human eye views. An ophthalmic substrate is a component of an ophthalmic device or system, or an ophthalmic component of such a device or system. Typically, an ophthalmic substrate is a lens, and an ophthalmic surface is the surface of the lens.

[0022] More generally, as used herein, the term "ophthalmic" is used to modify structures such as "substrate," "surface," "construction," "structure," "device," "arrangement," and "system," referring to the property of the structure that allows the human eye to observe objects through it. While coated lenses are a typical example of ophthalmic devices, those skilled in the art will appreciate other applications, including, for example, helmets with transparent goggles.

[0023] An ophthalmic construct may consist of or include ophthalmic components of such ophthalmic devices or systems.

[0024] The method may further include processing the wet layer to produce a dried / cured transparent layer on the optical surface (step 104).

[0025] For hard coating formulations, drying / curing is chemical curing, i.e., polymerization and / or crosslinking.

[0026] In some implementations, chemical drying / curing is or includes curing by photochemical radiation, i.e., curing by electromagnetic radiation (e.g., UV radiation, electron beams, IR, and microwaves) capable of initiating a chemical reaction.

[0027] The drying / curing of the wet layer can be advantageously carried out, resulting in a "fully cured" layer or coating. The inventors have discovered that partially cured layers can lead to solvent erosion, migration, mixing, etc., from adjacent layers in the stack or subsequently applied layers. These phenomena can significantly degrade optical quality.

[0028] As used herein and in the following claims section, the terms “fully cured” and “fully cured” (e.g., fully cured and fully cured formulation or layer) refer to a polymer material that is at least 85% cured, as determined by a König hardness test according to ASTM D4366 Standard Test Methods for Hardness of Organic Coatings by Pendulum Damping Tests. Therefore, for a 100% fully cured reference polymer sheet (König hardness 80), the König hardness of a “fully cured” or “fully cured” identical material will be in the range of 68 (0.85 • 80) to 80. Thus, the minimum hardness coefficient (C0) of a “fully cured” polymer material is... H The value is at least 0.85.

[0029] Typically, optical surfaces are curved optical surfaces, such as polymer lens surfaces.

[0030] Typically, optical surfaces are polymer surfaces, such as polymer lens surfaces.

[0031] The dried transparent layer has a hardness that can be characterized by pencil hardness. In this specification and claims, all pencil hardness values ​​are measured according to ASTM D3363.

[0032] In some implementations, the pencil hardness of the dried transparent layer is at least H.

[0033] In some implementations, the pencil hardness of the dried transparent layer is at least 2H.

[0034] In a more typical implementation, the pencil hardness of the dried transparent layer is in the range of H to 10H, 2H to 10H, 2H to 9H, 2H to 8H, 2H to 7H, 3H to 10H, 3H to 9H, 3H to 8H, 3H to 7H, 4H to 10H, 4H to 9H, 4H to 8H, 4H to 7H, 5H to 10H, 5H to 9H, or 5H to 8H.

[0035] For dry or fully cured hard coatings, the pencil hardness of the dry or fully cured layer is typically at least 3H, and more often, at least 4H or at least 5H.

[0036] As used herein and in the following claims section, the term "standard pencil hardness unit" refers to one of the following hardnesses in a 19-degree scale for graphite pencils: 14B, 12B, 10B, 8B, 7B, 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, and 6H. For example, a 3H hardness is one standard pencil hardness unit higher than a 2H hardness; a 2H hardness is two standard pencil hardness units higher than an F hardness.

[0037] In some implementations, the ophthalmic substrate or lens may be coated or pre-coated with a hard coating, and microvalves for forming liquid film droplets may be applied to or directly on this "pre-coated" hard coating (i.e., a hard coating that is included with / integrated with the lens blank).

[0038] In some implementations, a primer may be applied to this pre-coated hard coating before any additional layers are applied to enhance the adhesion of the additional layers to the substrate.

[0039] Liquid hard coating formulations can be sprayed onto optical / ophthalmic substrates using digital microvalve technology, according to a predetermined pattern (such as a predetermined digital pattern).

[0040] In some implementations, the microvalve of the liquid film-forming formulation is operated via a microvalve within a microvalve system.

[0041] In some implementations, the microvalve is piezoelectrically actuated (e.g., using Nordson pulse jet valves, Vermes MDS 1560 series, or Techcon 9800 series); In some implementations, the microvalve is electromagnetically actuated (e.g., using a solenoid valve). Fluid or dispersion flows directly through the microvalve. When current is applied through the valve coil, a movable anchor attached to the valve ball is magnetically pulled by the magnetic field of the stationary anchor. The microvalve opens, discharging a portion of the medium. When no current is applied, the microvalve closes because a closing spring acts on the movable anchor associated with the valve ball.

[0042] This type of exemplary microvalve was manufactured by Fritz Gyger AG and the Lee company.

[0043] In some implementations, the microvalve is electro-pneumatically actuated. An exemplary microvalve of this type is the Liquidyn® P-Jet series manufactured by Nordson.

[0044] Now for reference Figure 2 and Figure 3 , Figure 2A schematic block diagram of a process for processing the optical surface of an optical substrate (typically a lens blank) according to an aspect of the invention to produce a dry hard coating is provided. The lens blank provided to the process may or may not have a protective hard coating adhered to it. Figure 3 A schematic general block diagram of a method for processing an optical surface to produce an optical structure according to an aspect of the present invention is provided.

[0045] The lens blank / optical substrate may be surface-prepared prior to the application of the first hard coating (step 206). Such surface preparation may include washing in water or an aqueous cleaning solution, optionally followed by drying (step 207).

[0046] In some implementations, the surface preparation of the lens surface includes etching.

[0047] In some implementations, the etching process includes laser etching.

[0048] In some implementations, the etching process includes chemical etching.

[0049] Before applying the hard coating formulation, the lens blank may undergo surface treatment (step 208), for example, energy treatment to increase the surface energy of the optical surface.

[0050] In some implementations, the pretreatment of the lens surface includes corona treatment.

[0051] In some implementations, the pretreatment of the lens surface includes plasma treatment.

[0052] In some implementations, the pretreatment of the lens surface includes electron beam treatment.

[0053] In some implementations, the pretreatment of the lens surface includes a discharge treatment.

[0054] Following any one of steps 206, 207, 208, 310, 320, and 322, and combinations thereof, the method may optionally include: after curing (steps 210, 310, 318, 322), applying a droplet microvalve of the liquid film-forming hard coating (“first hard coating” or “inner hard coating”) formulation to the optical or ophthalmic surface of the optical or ophthalmic substrate to form a wet layer (step 224). The wet layer may then be treated to produce a dried / cured transparent hard coating on the optical surface (step 226). These steps have been described above with respect to steps 102 and 104.

[0055] exist Figure 2In the provided embodiments, after any one of steps 206, 207, 208, 310, 320, 322, 224, and 226, and combinations thereof, the method includes: after curing (any one of steps 210, 310, 318, 322, and 326), microvalves a droplet of a liquid film-forming hard coating (“second hard coating” or “outer hard coating”) formulation onto the optical or ophthalmic surface of an optical or ophthalmic substrate to form a wet layer (step 228). The wet layer may then be treated to produce a dried, transparent hard coating on the optical surface (step 230). These steps have been described above with respect to steps 102 and 104.

[0056] In some implementations, the hard coating formulation base material includes one or more acrylates, methacrylates, etc., and some of these base materials are provided below (not an exhaustive list): Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxy-poly(alkylene oxide)alkyl acrylate, caprolactone, ethylene glycol diacrylate, butylene glycol diacrylate, hexamethylene diacrylate, hexamethylene diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, hydroxyethyl acrylate Oil ester ethoxylated ester, glyceryl diacrylate propoxylated ester, trimethylolpropane triacrylate, trimethylolpropane ethoxylated triacrylate, trimethylolpropane propoxylated triacrylate, neopentyl glycol diacrylate, neopentyl glycol ethoxylated diacrylate, neopentyl glycol propoxylated diacrylate, monomethoxytrimethylolpropane ethoxylated diacrylate, pentaerythritol ethoxylated tetraacrylate, pentaerythritol propoxylated tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate Tetraol ethoxylated pentaacrylate, dipentaerythritol propoxylated pentaacrylate, di-trimethylolpropane ethoxylated tetraacrylate, bisphenol A ethoxylated diacrylate containing 2 to 30 ethoxy groups, bisphenol A propoxylated diacrylate containing 2 to 30 propoxy groups, bisphenol A alkoxylated diacrylate containing a mixture of 2 to 30 ethoxy and propoxy groups, bisphenol A glycerol ester dimethacrylate, bisphenol A glycerol ester (1 glycerol / 1 phenol) dimethyl Acrylates, glycidyl acrylate, β-methacrylic acid glycidyl acrylate, bisphenol A-monoglycidyl ether acrylate, 4-glycidyloxybutyl methacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 3-(glycidyloxy-1-isopropoxy)-2-hydroxypropyl acrylate, 3-(glycidyloxy-2-hydroxypropoxy)-2-hydroxypropyl acrylate and 3-(trimethoxysilyl)propyl methacrylate.

[0057] UV catalysts for photopolymerization initiation may include, for example, any of the following materials: benzoin, benzoin, benzoin methyl ether, benzoin isobutyl ether, phenol, acetophenone, benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(N,N'-dimethylamino)benzophenone, diethoxyacetophenone, fluorenones (e.g., available from Spectra Group) Limited's H-Nu series initiators), 2-hydroxy-2-methyl-1-phenylprop-1-one, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthone, α-aminoalkylphenyl ketone (e.g., 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone), acylphosphine oxides such as 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,6-dichlorobenzoyl diphenylphosphine oxide, and 2,6-dimethoxybenzoyl diphenylphosphine oxide; diacylphosphine oxides Such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,6-dichlorobenzoyl)-2,4,4-trimethylpentylphosphine oxide; phenyl-4-octyloxyphenyliodonium hexafluoroantimonate, dodecyl diphenyliodonium hexafluoroantimonate, (4-(2-tetradecanoyl)oxyphenyl)-iodonium hexafluoroantimonate and mixtures thereof.

[0058] In some implementations, ophthalmic hard coating formulations are based on sol-gel monomers and oligomers. While the underlying chemistry is well known to those skilled in the art, background information is provided below: Silane monomers Silanes may include hydrolyzable organoalkoxysilanes of the following general formula: Wherein R is an organic free radical, R' is preferably a low molecular weight alkyl group, and X is preferably at least 1 and less than 4.

[0059] R is preferably selected from the group consisting of alkyl, vinyl, methoxyethyl, phenyl, γ-glycidoxypropyl, or γ-methacryloyloxypropyl, and preferably has a low molecular weight moiety having 1 to 6 carbon atoms. R' is preferably a two- to four-carbon alkyl group. Particularly preferred organoalkoxysilanes are those in which R is methyl and R is ethyl, such as methyltriethoxysilane.

[0060] The sol can be prepared from at least one alkoxysilane (such as epoxysilane, preferably trifunctional) and / or its hydrolysate, for example by hydrolysis with hydrochloric acid solution. Following the hydrolysis step, the duration is typically about 2 to 24 hours, and typically, 2 to 6 hours, one or more catalysts can be added. Surfactant compounds can be added to improve the optical quality of the deposit.

[0061] Preferred epoxyalkoxysilanes comprise one epoxy group and three alkoxy groups, the latter being directly attached to a silicon atom. Preferred epoxyalkoxysilanes may be alkoxysilanes with a β-(3,4-epoxycyclohexyl) group, such as β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane.

[0062] Preferred epoxyalkoxysilanes can be represented by the following formula: Where: R 1 An alkyl group having 1 to 6 carbon atoms, preferably a methyl or ethyl group, R 2 is a methyl group or a hydrogen atom, a is an integer from 1 to 6, and b represents 0, 1 or 2.

[0063] Examples of such epoxysilanes include γ-glycidoxypropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl-dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxyethoxypropylmethyldimethoxysilane. Epioxide dialkoxysilanes are preferably used at a smaller ratio than that of epioxide trimekoxysilanes.

[0064] Other preferred alkoxysilanes can be represented by the following formula: R 3 c R 4 d SiZ 4-(c+d) Where R 3 and R 4Selected from alkyl, methacryloxyalkyl, alkenyl and aryl groups, substituted or unsubstituted (examples of substituted alkyl groups are haloalkyl, especially chlorinated or fluorinated alkyl); Z is alkoxy, alkoxyalkoxy or alkoxy group; c and d are equal to 0, 1 or 2 respectively; and c+d is equal to 0, 1 or 2. This formula includes the following compounds: (1) tetraalkoxysilanes, such as methyl silicates, ethyl silicates, n-propyl silicates, isopropyl silicates, n-butyl silicates, sec-butyl silicates and tert-butyl silicates; and / or (2) trialkoxysilanes, trialkoxyalkoxysilanes or triacyloxysilanes, such as methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, vinyltriketoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-trifluoropropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane; and / or (3) dialkoxysilanes, such as dimethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane and methylphenyldimethoxysilane.

[0065] In some embodiments, the coating composition used in conjunction with the present invention comprises an aqueous organic solvent mixture containing about 10 to about 99.9% by weight (based on the total solids of the composition) of a mixture of hydrolysis products and partial condensates of epoxy-functional silanes and tetrafunctional silanes, and about 0.1 to about 30% by weight (based on the total solids of the composition) of a crosslinked polyfunctional compound selected from the group consisting of crosslinked polyfunctional carboxylic acids, crosslinked polyfunctional anhydrides, and combinations thereof.

[0066] Epoxy-functionalized silanes and tetrafunctionalized silanes may be present in an aqueous organic solvent mixture in a molar ratio of about 0.1:1 to about 5:1. The coating composition of the present invention may further comprise a mixture of hydrolysis products and partial condensates of one or more silane additives, about 0.1 to about 50% by weight (based on the total solids of the composition), and / or colloidal silica or metal oxides or combinations thereof, equivalent to a solids content of about 0.1 to about 50% by weight (based on the total solids of the composition).

[0067] Those skilled in the art will understand that: (a) the description herein of coating formulations containing epoxy-functionalized silanes, tetrafunctional silanes, epoxy-free silane additives, and crosslinked multifunctional components refers to the initial silanes and crosslinked multifunctional components that form the coating system; (b) when epoxy-functionalized silanes, tetrafunctional silanes, and epoxy-free silane additives are combined with aqueous solvent mixtures, partially or completely hydrolyzed substances will be produced; (c) the resulting fully or partially hydrolyzed substances will combine to form mixtures of crosslinked multifunctional oligomeric siloxane substances; (d) these oligomers may contain or not contain side-chain hydroxyl and side-chain alkoxy moieties, and are composed of siloxane-containing materials with siloxane-oxygen-crosslinked multifunctional component bonds; and (e) oligomer suspensions are dynamic and may undergo structural changes depending on various factors, including temperature, pH, water content, and catalyst concentration.

[0068] However, generally, the desired results are obtained when epoxy-functionalized silanes and tetrafunctionalized silanes are present in an aqueous solvent mixture in a molar ratio of about 0.1:1 to about 5:1 or about 0.1:1 to about 3:1.

[0069] Formulation components water: While the presence of water in an aqueous organic solvent mixture is necessary for the formation of hydrolysis products of the silane component in the mixture, the actual amount can vary considerably. Essentially, sufficient water is required to provide a substantially homogeneous coating mixture of hydrolysis products and partial condensates of epoxy-functionalized and tetrafunctionalized silanes, providing a substantially clear coating with a Bayer number of at least 5 or 6 when applied and cured onto an article, using ASTM F735-21. Those skilled in the art will recognize that this amount of water can be determined empirically.

[0070] Solvent: The solvent component of the aqueous organic solvent mixture of the coating composition of the present invention can be any solvent or combination of solvents compatible with epoxy functional silanes, tetrafunctional silanes, and crosslinked multifunctional components. For example, the solvent component of the aqueous organic solvent mixture can be alcohols, ethers, ethylene glycol or ethylene glycol ethers, ketones, esters, ethylene glycol ether acetates, and mixtures thereof.

[0071] The alcohol family: Suitable alcohols can be represented by the formula ROH, where R is an alkyl group containing one to about ten carbon atoms. Specific examples of useful alcohols include at least one of the following: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, cyclohexanol, pentanol, octanol, and decanol.

[0072] The ethylene glycol family: Suitable ethylene glycol, ether, and ethylene glycol ether can be derived from formula R 1-(OR 2 ) x -OR 1 Represents, where x is 0, 1, 2, 3, or 4, R 1 It is hydrogen or an alkyl group containing one to about 10 carbon atoms, and R 2 This refers to alkylene groups containing one to about ten carbon atoms, and combinations thereof. Examples of ethylene glycol, ethers, and ethylene glycol ethers having the molecular formula defined above and usable as solvent components in aqueous organic solvent mixtures of coating compositions of the present invention include at least one of the following: di-n-butyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, dibutyl glycol, and tributylene glycol.

[0073] family of cyclic ethers Cyclic ethers such as tetrahydrofuran and dioxane may be suitable ethers for mixtures of aqueous organic solvents.

[0074] The family of ketones Examples of ketones suitable for use in aqueous organic solvent mixtures include at least one of the following: acetone, diacetone alcohol, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone.

[0075] The family of esters Examples of esters suitable for use in aqueous organic solvent mixtures include at least one of the following: ethyl acetate, n-propyl acetate, and n-butyl acetate.

[0076] The family of glycol ether acetates: Examples of glycol ether acetates suitable for use in aqueous organic solvent mixtures include at least one of the following: propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, and glycol ethyl ether acetate.

[0077] 1. Silane • Epoxy-functionalized silanes: Representative structures of epoxy silanes: These epoxy-functionalized silanes are typically composed of formula R 3 x Si(OR 4 ) 4-x This represents the expression, where X is typically an integer of 1, 2, or 3, and R... 3 The group is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, or a combination thereof, wherein the group contains one to about ten carbon atoms and has at least one epoxy functional group; and R 4H, alkyl groups containing 1 to about 5 carbon atoms, acetyl groups, -Si(OR) 5 ) 3-y R 6 y Groups (where y is an integer of 0, 1, 2, or 3) and combinations thereof; where R 5 H, an alkyl group containing one to about five carbon atoms, an acetyl group, or another Si (OR) group. 5 ) 3-y R 6 y Groups and their combinations; and R 6 The group can be H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, or a combination thereof, wherein the group contains one to about ten carbon atoms and may also contain an epoxy functional group.

[0078] Examples of epoxy-functionalized silanes (suppliers: Gelest or Merck): glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrihydrosilane, 3-glycidoxypropyldimethylhydroxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldimethoxymethoxysilane, 3-glycidoxypropyltriethoxysilane, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, 1,3- Bis(glycidoxypropyl)tetramethoxydisiloxane, 1,3-bis(glycidoxypropyl)-1,3-dimethyl-1,3-dimethoxydisiloxane, 2,3-epoxypropyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 6,7-epoxyheptyltrimethoxysilane, 9,10-epoxydecyltrimethoxysilane, 1,3-bis(2,3-epoxypropyl)tetramethoxydisiloxane, 1,3-bis(6,7-epoxyheptyl)tetramethoxydisiloxane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0079] • Tetrafunctional silanes: Representative structures of tetrafunctional silanes: Tetrafunctional silanes can be derived from the formula Si(OR) 7 )4 indicates that R 7 H, alkyl groups containing one to about five carbon atoms and their ethers, (OR) 7 ) carboxylic acid esters, -Si(OR) 8 ) groups, wherein R is H, alkyl groups containing 1 to about 5 carbon atoms and their ethers, OR 3 Carboxylic acid esters or another -Si(OR) 8 )3 groups and their combinations.

[0080] From Si(OR)7 Examples of tetrafunctional silanes (suppliers Gelest or Merck) include at least one of the following: tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate, tetraisobutyl orthosilicate, tetra(methoxyethoxy)silane, tetra(methoxypropoxy)silane, tetra(ethoxyethoxy)silane, tetra(methoxyethoxyethoxy)silane, trimethoxyethoxysilane, dimethoxydiethoxysilane, triethoxymethoxysilane, poly(dimethoxysiloxane), poly(diethoxysiloxane), poly(dimethoxydiethoxysiloxane), tetra(trimethoxysiloxane), tetra(triethoxysiloxane).

[0081] Examples of tetrafunctional silanes with carboxylic acid ester functional groups (supplier Gelest): In addition to the above-mentioned tetrafunctional silanes with R... 7 and R 8 In addition to substituents, R 7 and R 8 With oxygen (OR) 7 ) and (OR 8 The combination can be a carboxylic acid ester group, including: tetraacetic acid silicon, tetrapropionic acid silicon, and tetrabutyric acid silicon.

[0082] Additives (silane-free): Crosslinked polyfunctional compounds: any crosslinked polyfunctional carboxylic acids, crosslinked polyfunctional anhydrides, and combinations thereof, which are compatible with and able to interact with the hydrolysis products and partial condensates of epoxy-functional silanes and tetrafunctional silanes, thereby providing a coating composition that, upon curing, produces a substantially transparent, abrasion-resistant coating with a Bayer number of at least 5. The nature of the interactions between epoxy-functional silanes, tetrafunctional silanes, and crosslinked polyfunctional compounds, and the effect of such interactions on the abrasion resistance of the cured coating, is not fully understood. However, it is believed that the role of crosslinked polyfunctional compounds is not limited to acting as hydrolysis catalysts for silanes. In this regard, it has been proposed that crosslinked polyfunctional compounds possess specific activity towards the epoxy functional groups on silanes. The reaction of epoxy groups with carboxylic acids is well known and can occur under acidic or basic conditions. The carboxylate groups on crosslinked polyfunctional compounds are also likely to be reactive with silicon atoms in the matrix; and such interactions may occur through normal exchange reactions with residual alkoxide and hydroxide groups, or through some hypervalence state on the silicon atoms. The actual interactions involving crosslinked polyfunctional compounds can be a combination of all the above possibilities, resulting in a highly crosslinked matrix. Therefore, the matrix is ​​enhanced by extended bonding involving crosslinked polyfunctional compounds. As a significant example of these potential interactions, coatings prepared with non-crosslinked polyfunctional compounds, such as acetic acid, fail to exhibit the same level of high stability and abrasion resistance as those obtained using crosslinked polyfunctional compounds.

[0083] Examples of cross-linked polyfunctional carboxylic acids (supplier Merck): at least one of the following: malic acid, aconitic acid (cis, trans), itaconic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, cyclohexylsuccinic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,1-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,3,5-cyclohexanetricarboxylic acid, unsaturated dicarboxylic acids such as fumaric acid and maleic acid.

[0084] Examples of cross-linked multifunctional anhydrides (supplier Merck): at least one cyclic anhydride of the above-mentioned dicarboxylic acids, including succinic anhydride, itaconic anhydride, glutaric anhydride, pyromellitic anhydride, pyromellitic tetracarboxylic anhydride, phthalic anhydride and maleic anhydride.

[0085] 2. Additives for silane hydrolysis and partial condensation products Silane Additive Structure: The selection of silane additives and the amount of such silane additives incorporated into the coating composition depend on the specific properties to be enhanced or imparted to the coating composition or the cured coating composition. For example, when a bifunctional silane, dimethyldimethoxysilane, is used as a silane additive and incorporated into the coating composition at about 10% or less (based on the total solids content of the composition), the viscosity increase during aging of the coating composition is significantly reduced without having a significant impact on the resulting abrasion resistance of the cured coating. The coating composition may further comprise about 0.1 to about 50% by weight (based on the total solids weight of the coating composition) of a mixture of hydrolysis products and partial condensates of one or more silane additives (i.e., trifunctional silanes, difunctional silanes, monofunctional silanes, and mixtures thereof). Silane additives that can be incorporated into the coating compositions of the present invention have the formula R. 9 x Si(OR 10 ) 4-x Where x is a number of 1, 2, or 3; R 9 H or an alkyl group, functionalized alkyl group, alkylene group, aryl group, alkyl ether group, and combinations thereof containing one to about 10 carbon atoms; R 10 H, alkyl groups containing 1 to about 10 carbon atoms, acetyl groups; and combinations thereof.

[0086] Examples of silane additives (suppliers: Gelest or Merck): Methyltrimethoxysilane, Ethyltrimethoxysilane, Propyltrimethoxysilane, Butyltrimethoxysilane, Isobutyltrimethoxysilane, Hexyltrimethoxysilane, Octyltrimethoxysilane, Decyltrimethoxysilane, Cyclohexyltrimethoxysilane, Cyclohexylmethyltrimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, Vinyltrimethoxysilane, Allyltrimethoxysilane, Dimethyldimethoxysilane, 2-(3-cyclohexenyl)ethyl 3-Cyanopropyltrimethoxysilane, 3-Chloropropyltrimethoxysilane, 2-Chloroethyltrimethoxysilane, Phenylethyltrimethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Aminopropyltrimethoxysilane, Phenyltrimethoxysilane, 3-Isocyanopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 4-(2-aminoethylaminomethyl)phenylethyltrimethoxysilane, Chloromethyltriethoxysilane, 2-Chloroethyltriethoxysilane, 3-Chloropropyltriethoxysilane phenyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, 2-(3-cyclohexenyl)ethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 3-methacrylamidopropyltriethoxysilane, 3-Methoxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, 3-propoxypropyltrimethoxysilane, 3-methoxyethyltrimethoxysilane, 3-ethoxyethyltrimethoxysilane, 3-propoxyethyltrimethoxysilane, 2-methoxy(polyoxyvinyl)propylheptamethyltrisiloxane, methoxy(polyoxyvinyl)propyltrimethoxysilane, methoxy(polyoxyvinyl)ethyltrimethoxysilane, methoxy(polyoxyvinyl)propyltriethoxysilane, and methoxy(polyoxyvinyl)ethyltriethoxysilane.

[0087] 3. Nanoparticle additives: Applications of Nanoparticles: Colloidal silica is considered a reactive material when added to coating compositions. The surface of silica is coated with silicon-bonded hydroxyl groups, some of which are deprotonated and can react with materials in the coating composition. The extent of these interactions depends on various factors, including the solvent system, pH, concentration, and ionic strength. It has been observed that the addition of colloidal silica to the coating compositions of the present invention further enhances the abrasion resistance of the cured coating composition and further promotes the overall stability of the coating composition. The manufacturing process further influences these interactions. Colloidal silica can be added to the coating formulation in different ways, producing different results. In the coating compositions of the present invention, colloidal silica can be added to the coating composition in a variety of different ways. In some cases, it is desirable to add colloidal silica in the final step of the reaction sequence. In other cases, colloidal silica is added in the first step of the reaction sequence. In still other cases, colloidal silica can be added in the middle step of the sequence. The most significant results were achieved using an alkaline aqueous solution of colloidal silica (i.e., an aqueous solution of colloidal silica with a pH greater than 7). In such cases, high pH is accompanied by higher concentrations of stable counterions, such as sodium ions. Cured coatings formulated from coating compositions containing alkaline colloidal silica have shown abrasion resistance comparable to that of the catalytic coating compositions of the present invention (i.e., compositions of hydrolysis products and partial condensates of epoxy-functionalized silanes, tetrafunctional silanes, polyfunctional compounds, and catalysts such as sodium hydroxide), but the coating compositions containing colloidal silica exhibit enhanced stability relative to catalytic compositions without colloidal silica. Similarly, other metal oxides may be added to the coating composition. Such additions may be made in place of any colloidal silica or in addition to any colloidal silica addition. Metal oxides may be added to the coating to provide or enhance specific properties of the cured coating, such as abrasion resistance, refractive index, antistatic properties, antireflective properties, weather resistance, etc. Examples of metal oxides that can be used in the coating compositions of the present invention include silica, zirconium oxide, titanium dioxide, cerium dioxide, tin oxide, and mixtures thereof. When colloidal silica and / or metal oxides are added, it is desirable to add about 0.1 to about 50% by weight of solids (based on the total solids of the composition) of colloidal silica and / or metal oxides to the coating composition of the present invention. The particle size of the colloidal silica and / or metal oxides is typically in the range of 2 to 150 nanometers, and more preferably in the range of about 2 to 50 nanometers.

[0088] Examples of silica particle types: Colloidal silica is commercially available under various trade names, including Nalcoage (Nalco Chemical Co., Naperville, Ill.); Nyacol(R) (Nyacol Products, Inc., Ashland, Md.); Snowtex(R) (Nissan Chemical Industries, LTD., Tokyo, Japan); Ludox(R) (DuPont Company, Wilmington, Del.); and Highlink OG(R) (Hoechst Celanese, Charlotte, NC). Colloidal silica is an aqueous or organic solvent dispersion of particulate silica, and the main differences between various products lie in particle size, silica concentration, pH, presence of stable ions, solvent composition, etc.

[0089] 4. Additives - Catalysts: Uses of catalysts: While not an essential component, the addition of catalysts can affect the abrasion resistance and other properties of the coating, including stability, colorability, porosity, appearance, corrosion resistance, and water resistance. The amount of catalyst used can vary considerably, but when present, it is typically sufficient to provide approximately 0.1 to approximately 10% by weight (based on the total solids content of the composition).

[0090] Examples of catalysts: metal acetylacetone salts, diamides, imidazoles, amine and ammonium salts, organic sulfonic acids and their amine salts, alkali metal salts of carboxylic acids, alkali metal hydroxides, fluoride salts, aluminum, zinc, iron and cobalt acetylacetone salts, dicyandiamide, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-propylimidazolium, benzyl dimethylamine, 1,2-diaminocyclohexane, trifluoromethanesulfonic acid, sodium acetate, sodium hydroxide and potassium hydroxide, tetra-n-butylammonium fluoride.

[0091] 5. Additives - Surfactants (Suppliers: Altana, BASF, 3M): Uses of wetting agents and leveling agents: Effective amounts of leveling agents or flow control agents can be incorporated into the composition to allow the composition to spread or level more evenly on the substrate surface and provide substantially uniform contact with the substrate. The amount of leveling agent or flow control agent can vary considerably, but it is generally sufficient to provide a coating composition having about 10 to about 5,000 ppm of leveling agent or flow control agent. Any conventionally available leveling agent or flow control agent that is compatible with the coating composition and the substrate, enables the coating composition to level on the substrate, and enhances the wetting properties between the coating composition and the substrate can be used.

[0092] Examples of such leveling or flow control agents include: Byk and Efka surfactants, as well as organic polyethers such as Rohm and Haas' TRITON X-100, X-405, N-57, OSi Specialties' SILWET L-77 and SILWETL-7600, and fluorosurfactants such as 3M's FLUORAD FC-171, FLUORAD FC-430, and FLUORADFC-431.

[0093] 6. Additives - Functionality: Functional additives can be added to enhance the usefulness of the coating composition or the coating produced by curing the coating composition.

[0094] Examples of functional additives: UV absorbers, antioxidants, etc.

[0095] Refer again Figure 2 When two or more layers of a hard coating are applied to a substrate, the outermost layer is typically the hardest. One or more inner layers of the hard coating may be slightly softer and can be tuned to allow for gradual changes in their physical properties (e.g., hardness, coefficient of thermal expansion, etc.), thereby imparting improved mechanical properties to the layered stack. This can be particularly important if the stack includes one or more relatively soft photochromic layers, as will be explained in further detail below. It must be emphasized that when a single hard coating is applied, this layer is the “outer hard coating” of step 228.

[0096] In some embodiments, the thickness or average thickness of the outermost hard coating or coating that serves as the wet layer is in the range of 1.5 to 40 μm or in the range of 2.5 to 40 μm, and more typically, in the range of 3 to 30 μm, 3 to 25 μm, 4 to 25 μm, 3 to 20 μm, 3 to 15 μm, 4 to 15 μm or 6 to 12 μm.

[0097] In some embodiments, the thickness or average thickness of the outermost hard coating or coating after complete drying is in the range of 0.6 micrometers (μm) to 10 μm or 1 μm to 8 μm, and more typically, in the range of 1.5 to 8 μm, 1.5 to 7.5 μm, 1.5 to 7 μm, 1.5 to 6 μm, 1.5 to 5 μm, 1.5 to 4.5 μm, 2 to 8 μm, 2 to 7 μm, 2 to 6 μm, 2 to 5 μm, 2 to 4.5 μm, 2 to 4 μm, 2 to 3.5 μm, 2.5 to 8 μm, 2.5 to 7 μm, 2.5 to 6 μm, 2.5 to 5 μm, 2.5 to 4 μm, 3 to 8 μm, 3 to 7 μm, 4 to 8 μm, 4 to 7 μm, 5 to 8 μm, 5 to 7.5 μm or 5 to 7 μm.

[0098] In some embodiments, the thickness or average thickness of at least one inner hard coating or coating as a wet layer is in the range of 1 to 25 μm or in the range of 1.5 to 20 μm, and more typically, in the range of 1.5 to 15 μm, 1.5 to 10 μm, 1.5 to 7 μm, 1.5 to 5 μm, 2 to 10 μm, 2 to 7 μm or 3 to 7 μm.

[0099] Once the inner coating or coating is completely dry, its thickness is typically in the range of 0.6 to 5 μm or 0.6 to 4 μm, and more commonly, in the range of 0.6 to 3.5 μm, 0.6 to 3 μm, 0.6 to 2.5 μm, 0.8 to 2.2 μm, 0.8 to 2.0 μm, 0.8 to 1.8 μm, 0.8 to 1.6 μm or 1.0 to 1.5 μm.

[0100] In some embodiments, the hard coating formulation comprises one or more types of nanoparticles, for example, to increase hardness or strength. Such nanoparticles may include boron nitride, B4C, cubic BC2N, silicon carbide, crystalline α-alumina (sapphire); alumina Al2O3, silicon dioxide SiO2, zirconium oxide ZrO2, titanium oxide TiO2, antimony oxide Sb2O5, tantalum oxide Ta2O5, zinc oxide, tin oxide SnO2, indium oxide, cerium oxide, Si3N4, and mixtures thereof; mixed oxides or composite particles, particularly particles with a core / shell structure, and their heterostructured nanoparticle layers.

[0101] Preferably, the nanoparticles are particles of alumina, tin oxide, zirconium oxide, or silicon dioxide (SiO2), more preferably SiO2 nanoparticles. The mineral filler is preferably used in colloidal form, i.e., in the form of fine particles dispersed in a dispersion medium.

[0102] Following the drying / curing step 230, the method may include microvaping a droplet of the liquid post-film-forming hard coating formulation onto the optical or ophthalmic surface of an optical or ophthalmic substrate to form a wet layer (step 232). The wet layer may then be treated to produce a dried, transparent post-hard coating on the optical surface (step 234). These steps have been described above in a generalized manner with respect to steps 102 and 104.

[0103] Such post-hardening coatings may include at least one of the following functions: • Anti-wetting layer • Anti-reflective layer • Superhydrophobic / antifog layer • Super hydrophilic / anti-fog layer • Anti-glare layer • Blue light.

[0104] Those skilled in the art will understand that these post-hard coating formulations can also be applied by inkjet printing or by conventional coating processes such as spin coating and dip coating.

[0105] Figure 2A for Figure 2 The schematic diagram provides optional steps in which pretreatment includes applying a liquid primer formulation to the exposed (lens) surface of an ophthalmic substrate. The wet primer layer or coating is then dried or allowed to dry to obtain a dried (cured) primer layer or coating.

[0106] Liquid primer formulations can be applied using a variety of conventional techniques, such as spin coating, slot coating, and dip coating.

[0107] In some implementations, a primer microvalves are applied to the exposed surface of the ophthalmic substrate, as will be described in more detail below.

[0108] In some implementations, primer pretreatment is designed to promote wetting of the hard coating or subsequently applied layer relative to the lens surface.

[0109] In some implementations, the primer pretreatment is designed to promote the adhesion of the hard coating to the lens surface.

[0110] In some implementations, the primer is a polymer primer.

[0111] In some implementations, the polymer primer is in the form of an aqueous emulsion (e.g., an acrylic emulsion).

[0112] In some implementations, the polymer primer is in the form of a solution (e.g., a polyurethane resin solution).

[0113] In some embodiments, at least one of the thickness and average thickness of the wet primer layer is in the range of 0.2 to 5 μm or in the range of 0.2 to 3 μm, and more typically, in the range of 0.2 to 2.5 μm, 0.3 to 2 μm, 0.4 to 2 μm, 0.4 to 1.5 μm, 0.5 to 2 μm, 0.5 to 1.8 μm, 0.5 to 1.5 μm or 0.5 to 1.2 μm.

[0114] In some embodiments, at least one of the thickness and average thickness of the dried or dry primer layer is in the range of 0.2 to 4 μm or in the range of 0.2 to 2.5 μm, and more typically in the range of 0.2 to 2 μm, 0.2 to 1.5 μm, 0.3 to 2 μm, 0.3 to 1.5 μm, 0.4 to 2 μm, 0.4 to 1.8 μm, 0.4 to 1.5 μm or 0.4 to 1 μm.

[0115] Refer again Figure 3 , Figure 3A schematic general block diagram of a method for processing an optical surface to produce an optical structure according to an aspect of the invention is provided. Steps 306, 307, 308, and 310 are substantially the same as steps 206, 207, 208, and 210 described above.

[0116] In optional step 316, an ink formulation, such as an ink formulation containing a colorant, may be applied directly to the surface of the optical substrate, or applied on top of the primer layer applied in optional surface treatment 308.

[0117] In some embodiments, the ink formulation is a photochromic ink formulation containing at least one photochromic dye and a polymer binder.

[0118] In some implementations, the ink formulation or photochromic ink formulation may be applied to the surface of the optical substrate by a microvalve or micro-valve.

[0119] In some implementations, the ink formulation or photochromic ink formulation may be inkjet-printed onto the surface of the optical substrate.

[0120] In some embodiments, the ink formulation or photochromic ink formulation may be applied by at least one of dip coating, spin coating, and slot coating.

[0121] If necessary, the obtained layer can be dried and cured to produce a cured ink layer or a cured photochromic ink layer (step 318).

[0122] In some embodiments, the thickness or average thickness of the layer containing the photochromic dye after complete drying and curing is in the range of 0.6 to 40 μm or 1 to 40 μm, and more typically, in the ranges of 1.5 to 40 μm, 1.5 to 30 μm, 1.5 to 15 μm, 1.5 to 10 μm, 1.5 to 8 μm, 1.5 to 6 μm, 1.5 to 4 μm, 2 to 40 μm, 2 to 30 μm, The range is 2 to 15 μm, 2 to 10 μm, 2 to 8 μm, 2 to 6 μm, 2.5 to 30 μm, 2.5 to 20 μm, 2.5 to 12 μm, 2.5 to 8 μm, 2.5 to 6 μm, 3 to 40 μm, 3 to 15 μm, 3.5 to 40 μm, 3.5 to 25 μm, 3.5 to 15 μm, 3.5 to 12 μm, 3.5 to 8 μm, or 3.5 to 6 μm.

[0123] The inventors have discovered that various hard coating formulations can dissolve or otherwise erode ink layers containing colorants, and more specifically, layers containing photochromic dyes formed and cured in steps 316 and 318. However, the inventors have further discovered that such erosion can be suppressed or significantly mitigated by applying an outer coating (step 320) on top of the ink layer containing this colorant and then drying / curing it (step 322).

[0124] In some embodiments, the thickness or average thickness of the first outer coating layer as a wet layer is in the range of 1.5 to 40 μm or in the range of 2.5 to 40 μm, and more typically, in the range of 3 to 30 μm, 3 to 25 μm, 4 to 25 μm, 3 to 20 μm, 3 to 15 μm, 4 to 15 μm or 6 to 12 μm.

[0125] In some embodiments, the thickness or average thickness of the first outer coating layer as a dry layer is in the range of 1 to 20 μm or in the range of 1 to 15 μm, and more typically, in the range of 1 to 12 μm, 1 to 10 μm, 1 to 7 μm, 1 to 6 μm, 1.5 to 7 μm, 1.5 to 6 μm, 1.5 to 5 μm, 1.5 to 4 μm, 2 to 7 μm, 2 to 5 μm or 2 to 4 μm.

[0126] In some implementations, the first outer coating is a thermoplastic polymer.

[0127] In some implementations, the first outer coating is a thermosetting polymer.

[0128] In some implementations, the first outer coating formulation is a polymer emulsion.

[0129] In some implementations, the first outer coating formulation is a polymer dispersion.

[0130] In some implementations, the first outer coating formulation is an acrylic polymer.

[0131] In some implementations, the first outer coating formulation includes polyurethane.

[0132] In some implementations, the material of the dry or fully cured outer coating has a König hardness of at least 80 (seconds). More typically, this König hardness is in the range of 80 to 180, 80 to 160, 90 to 180, 100 to 160, 100 to 150, 100 to 140, 110 to 180, 110 to 160, or 110 to 150.

[0133] Figure 3 Steps 324, 326, 328, 330, 332, and 234 may essentially correspond to Figure 2 Steps 224, 226, 228, 230, 232, and 234, and have been described above.

[0134] In some embodiments, the thickness or average thickness of the hard coating after complete drying is in the range of 0.6 micrometers (μm) to 10 μm or 1 μm to 8 μm, and more typically, in the range of 1.5 to 8 μm, 1.5 to 7.5 μm, 1.5 to 7 μm, 1.5 to 6 μm, 1.5 to 5 μm, 1.5 to 4.5 μm, 2 to 8 μm, 2 to 7 μm, 2 to 6 μm, 2 to 5 μm, 2 to 4.5 μm, 2 to 4 μm, 2 to 3.5 μm, 2.5 to 8 μm, 2.5 to 7 μm, 2.5 to 6 μm, 2.5 to 5 μm, 2.5 to 4 μm, 3 to 8 μm, 3 to 7 μm, 4 to 8 μm, 4 to 7 μm, 5 to 8 μm, 5 to 7.5 μm or 5 to 7 μm.

[0135] Figure 4 This is a schematic cross-sectional view of a multilayer optical or ophthalmic device, component, or structure 400, including an optical or ophthalmic substrate 402 having an optical or ophthalmic construction 403 fixedly attached to a wide surface 401 of the substrate 402. Construction 403 further includes a primer layer 440 disposed between the wide surface 401 and a colorant layer 404. The thickness of the primer layer 440 is specified as Tp. An outer coating layer 406 may be disposed over the colorant layer 404, substantially as described above. The thickness of the outer coating layer 406 is specified as Tov. According to a further feature of the invention, one or more hard coating layers 420 may be disposed over the outer coating layer 406. One or more post-hard coating layers 430 may be disposed over the one or more hard coating layers 420, the thickness of which is specified as Th. The total thickness of the optical construction 403 is specified as Toc.

[0136] In some embodiments, at least one of the wet thickness and average wet thickness of the hard coating is in the range of 1 to 50 μm, 1 to 40 μm or 1 to 30 μm, and more typically, in the range of 1 to 25 μm, 1 to 20 μm, 1.2 to 15 μm, 1.2 to 12 μm, 1.2 to 10 μm or 1.5 to 8 μm.

[0137] In some embodiments, at least one of the thickness Th and the average thickness Th-a of the dried or cured hard coating is in the range of 0.6 to 7.5 μm or 0.8 to 5.5 μm or in the range of 0.8 to 5 μm, and more generally, in the range of 0.8 to 4.5 μm, 0.8 to 4 μm, 0.8 to 3.5 μm, 1 to 3.5 μm, 0.8 to 3 μm, 1 to 3 μm, 1.2 to 4.5 μm, 1.2 to 4 μm, 1.2 to 3.5 μm or 1.2 to 3 μm.

[0138] Regarding the overall thickness Toc of the optical structure 403, in some embodiments, the average thickness of the dried (cured) optical structure is in the range of 1 to 50 μm, 1 to 40 μm, 1.5 to 30 μm, 1.5 to 20 μm, 1.5 to 15 μm, 2 to 40 μm, 2 to 30 μm, 2 to 25 μm, 2 to 20 μm, 2 to 15 μm, 2.5 to 15 μm, 3 to 30 μm, 3 to 20 μm, 3 to 15 μm, 3 to 12 μm, 4 to 30 μm, 4 to 15 μm, 5 to 25 μm, 5 to 20 μm, 5 to 15 μm, 5 to 12 μm, 7 to 35 μm, 7 to 25 μm, 7 to 20 μm, or 7 to 15 μm.

[0139] like Figure 4A and Figure 4B Provided illustratively, the microvalve device can be used to eject ink droplets onto surfaces of varying profiles, including convex lens surfaces. Figure 4A ) and concave lens surface ( Figure 4B ).

[0140] Figure 5 Selected steps of a process for coating an optical or ophthalmic substrate (OS) 1100 (e.g., a lens blank) using a coating system 1300 are illustrated.

[0141] Examples of OS1100 (e.g., applying one or more coatings thereon using any of the teachings or combinations of teachings disclosed herein) include, but are not limited to: (i) spectacle lenses; (ii) single-vision lenses; (iii) multifocal lenses; (iv) anti-fatigue lenses (e.g., including single-vision prescriptions and magnification at the base of the lens); (v) progressive lenses (e.g., designed to correct multiple vision distances in a single lens, including hyperopia, intermediate vision, and myopia); (vi) prism lenses; (vii) spherical lenses; and (viii) cylindrical lenses. Other examples of OS1110 include lenses for virtual reality (VR) devices, including but not limited to VR glasses or VR goggles.

[0142] Element 1110 schematically represents a target surface of an optical substrate 1100, the target surface to be coated with at least one dried layer, such as multiple dried layers stacked directly or indirectly on top of each other. For example, the optical substrate (OS) 1110 may correspond to an optical or ophthalmic device, component, or structure 400 (e.g., its uncoated or partially uncoated version). For example, the target surface 1110 may correspond to surface 401, or to... Figure 4 Any other surface of any other layer.

[0143] For example, target surface 1110 may correspond to 'outward-facing surface', that is, the surface on the eyeglass lens that faces away from the wearer.

[0144] The target surface 1110 may be uncoated or pre-coated before being altered by the coating system 1300, for example, before 'delivery'. In contrast, the coated substrate OS1100' has a version of the coated target surface 1110, i.e., after the coating is applied by the coating system 1300.

[0145] In some embodiments, the optical coating system 1300 can be used to provide 'customization' of optical manufactured articles (e.g., eyeglasses). For example, the optical coating system 1300 can be deployed in a factory or store, such as an optometrist's factory or store. For example, the optical coating system 1300 may include, or be connected to, a digital computer (not shown), which stores and / or includes instructions for producing custom optical manufactured articles.

[0146] In a non-limiting use case, a customer with a certain optical prescription may require one or more of the following, such as any combination thereof: (i) a specific tinting or target color, i.e., customizing one or more lenses for a specific color; and / or (ii) a specific physical characteristic, such as, for example, abrasion resistance; and / or (iii) the presence or absence of a photochromic feature; and / or (iv) the desired gloss level; and / or (v) the presence or absence of a desired varnish.

[0147] The manufacturing of the lens geometry, for example to meet a certain optical prescription and / or shape, may optionally be carried out 'off-site' at a location different from the deployment location of the coating system 1300.

[0148] Because there can be a great many possible combinations of manufactured articles, such as many types of lens geometry, various types of coated lens 'color characteristics' or target colors of coated lenses, target digital pixel patterns of lenses, etc., maintaining an inventory of 'every possibility' may not be practical.

[0149] Conversely, it may be necessary to maintain a supply 1120 of multiple types of 'raw material' substrates 1100 based on lens geometry. Therefore, a specific workpiece such as OS1100 can be selected from multiple candidates based on specified geometric characteristics (such as, for example, characteristics expressed in optical prescriptions), which may optionally be stored in a digital computer. The 'input' OS1100 can be selected by rejecting some candidates and supporting the 'preferred candidate' OS1100 whose geometric characteristics best match the desired lens geometry and / or refractive index and / or multifocal direction and / or astigmatic direction and / or optical prescription data.

[0150] The coated OS1100', such as eyeglass blanks or eyeglass lenses, can be cut and / or mounted into eyeglass frames in the lens cutting and / or eyeglass frame mounting equipment 1200.

[0151] In some embodiments, OS1100 is rigid, for example, having an average thickness (or, in addition, the thickness at at least one location of OS1100) of at least 0.5 mm, at least 1 mm, at least 2 mm, or at least 3 mm.

[0152] As will be discussed below, in various embodiments, the coating system 1300 applies one or more layers of material, optionally transparent material dry layers, to or over the surface 1110 of OS1100.

[0153] The following combination of elements employed in any embodiment or implementation of the coating system 1300: (A) one or more operating parameters of the coating system 1300 and / or (B) physical and / or chemical properties of the materials (e.g., viscosity and / or solids fraction and / or surface energy) may cause the layer, i.e. the dried and / or transparent layer produced on or above the surface 1110 of OS1100, to have one or more specific properties.

[0154] Such properties include, but are not limited to, (i) the thickness of a particular dried clear layer or the ratio between different clear layer ratios; (ii) the continuous area of ​​a clear layer or its convex sub-parts over the entire area of ​​its convex sub-parts; (iii) the color and / or optical density of any dried layer; and (iv) the mechanical properties of any dried layer or a combination of one or more layers. Therefore, system 1300 can be configured to produce on surface 1110 of OS1100 any of the properties or combinations of properties of the wet or dried layers disclosed herein.

[0155] As will be discussed below, the coating system 1300 or any one or more of its components (including, for example, those capable of being controlled by the controller 1250) Figure 5 Operating parameters of the controlled components (not shown) may include, but are not limited to: (i) parameters of the microvalve or inkjet drop (or equivalent, as used herein: droplet), such as, for example, droplet velocity, droplet deposition frequency, droplet size and / or volume, droplet spacing, or any other operating parameters for droplet deposition, droplet ejection velocity, and the gap distance between the nozzle of the microvalve or inkjet device and the target surface 1110; (ii) drying time or drying temperature or drying intensity or power, or any other parameters related to drying the wet layer, such as, for example, oven temperature, parameters for convection and / or radiation drying, such as, for example, UV intensity; (iii) the relative motion between any nozzle used to deliver the droplets and the target surface 1110; (iv) characteristics related to the surface 1110 of OS1100 being processed, such as obtaining the required surface energy or energy within a certain range; (v) the selection of formulations or containers, cartridges or tanks of formulations and / or mixtures of formulations from a plurality of candidates; and aeration operating parameters.

[0156] In different embodiments, the term 'equipment' may refer to a specific station (e.g., a drying station and / or a wet layer application station for any wet layer). Therefore, any reference to 'equipment' may also be understood as (i.e., in embodiments of the invention) 'station'.

[0157] In various embodiments, the components of the optical coating system 1300 are configured and / or arranged for carrying out any of the methods described herein (e.g., references...). Figures 1 to 3 (All steps or any combination of one or more steps) to provide any feature or combination of one or more features, not all steps are required.

[0158] The resulting coated OS1100' may include a reference Figure 4 Any dry layer or combination of layers taught, or one or more of their characteristics or combinations thereof (not all layers are required), produces a layer and its properties (e.g., in...). Figure 4 Within the framework of the coating system 1300, there are specific elements (and one or more operating parameters and one or more formulations) according to a specific implementation of the coating system 1300. We note that various versions of the system 1300 are described herein.

[0159] Figures 6A to 6C , Figures 7A to 7B , Figure 8 , Figure 9 , Figures 10A to 10C and Figure 11 Various examples and / or embodiments of the coating system 1300 and / or processes associated with the coating system are schematically presented in the form of block diagrams and / or flowcharts, which illustrate various systems and methods according to various embodiments of this disclosure.

[0160] Figure 6A A block diagram of an exemplary coating system 1300A is shown. The coating system 1300A may include any one or more (or all) of the following: (i) a hard coating formulation application device 1350 for applying a coating or layer of hard coating formulation, for example, via a microvalve; (ii) a hard coating drying and / or curing device 1370 for drying and / or curing a wet layer of hard coating formulation; (iii) a selection and / or transfer device 1330; and (iv) a controller 1250. In some embodiments, the hard coating formulation includes inks, such as inks for coloring and / or photochromic coloring, and / or electrochromic inks. The wet layer can be very 'thin', characterized by a thickness of at most 100 or 90 or 75 or 50 or 25 or 20 or 15 or 10 micrometers.

[0161] Figure 6BA block diagram of another exemplary coating system 1300B is shown. The coating system 1300B may include any one or more (or all) of the following: (i) a microvalve-based coating apparatus 1900 for coating the surface of an optical substrate 1100, configured, for example, to coat one or more thin layers of a formulation onto the surface 1110 of the optical substrate 1100 via microvalve droplets. Such thin layers may be characterized by a thickness of up to 100, 90, 75, 50, 25, 20, 15, or 10 micrometers. (ii) a drying and / or curing apparatus 1910, (iii) a selection and / or transfer apparatus 1330, and (iv) a controller 1250. In this example, one or more wet layers are applied by the microvalve-based coating apparatus 1900, and a drying and / or curing process is performed by the drying and / or curing apparatus 1910. Examples of 'formulations' that can be applied by the microvalve-based coating device 1900 include: (i) hard coating formulations, which can be microvalved to produce a layer of hard coating formulation; (ii) ink formulations, for example, for coloring or photochromic and / or electrochromic inks to produce a layer of ink formulation; and (iii) surface energy increasing formulations, which can be microvalved to produce a layer of surface energy increasing formulation, thereby increasing the surface energy of the target surface 1110 of the optical substrate 1100.

[0162] In Figure 6B In related embodiments, the coating system 1300B (or its components) may provide one or more of the following features: (i) a microvalve-based coating device 1900 forming one or more continuous wet layers by microvalving droplets onto a target surface 1110, the wet layers being stacked by drying the previous layer; (ii) a microvalve-based coating device 1900 for forming a continuous thin wet layer by microvalving droplets onto the target surface 1110, characterized in that the thickness is at most 100 or 90 or 75 or 50 or 25 or 20 or 15 or 10 micrometers; and (iii) a drying and / or curing device 1910 that converts the continuous wet layer into a continuous dry layer, whether it is a single layer or multiple stacked layers.

[0163] Those skilled in the art will appreciate that the microvalve-based coating apparatus 1900 may provide only one such layer or may provide multiple such layers, such that the layers are stacked on top of each other. For example, the first layer may be dried first by the drying and / or curing apparatus 1910, and then the second layer may be applied directly or indirectly on top of the first layer.

[0164] Figure 6C An exemplary coating system 1300C is Figure 6BA specific example of the coating system 1300B is wherein multiple layers are stacked on top of each other on the upper target surface 1110 of the optical substrate 1100. At least one of such layers is generated by microvalve droplets, for example by microvalve-based coating devices 1900 or 1920.

[0165] Now for reference Figure 7A .exist Figure 7A In one example, the optical substrate 1100 is first treated with a surface energy increasing device 1310 to increase the surface energy of the target surface 1110, and then coated with a coating system 1300A or any other coating system 1300 disclosed herein to apply one or more layers, for example, with a hard coating formulation.

[0166] Figure 7B This is another example of an encoding system in which an optical substrate 1100 is first treated by a surface energy increasing device, and then coated with a wet layer and / or coating of a hard coating agent by a hard coating agent application device 1350. Subsequently, this wet layer and / or coating of the hard coating agent is dried and / or cured by a hard coating drying and / or curing device 1370 to produce a coated optical substrate 1100'. Figure 7B The system may also include (i) a selection and / or transfer device 1330 and / or (ii) a controller 1250.

[0167] According to the implementation scheme, the coating system 1300 may include any one or more of the following components: One or more controllers 1250: For simplicity, only a single controller 1250 is shown in the various figures. The controller 1250 can adjust the operating parameters of any other element of the coating system 1300, including but not limited to: microvalve devices, drying devices, inkjet devices, transfer devices, or any other device or combination thereof (if present). The controller 1250 may be part of the coating system 1300 and / or located within the coating system or any component, and / or may be individually and / or remotely located. The controller 1250 may include any electrical and / or electronic components necessary to perform its function of controlling any component or combination of components.

[0168] In some embodiments of the invention, any coating system 1300 disclosed herein may include data acquisition and / or monitoring devices 1430, such as, for example, imaging and / or detection components. The controller 1250 may receive data directly or indirectly from such data acquisition and / or monitoring devices 1430.

[0169] The hard coating formulation application device 1350 applies droplet microvalve of the hard coating formulation to the target surface 1110 of OS 1100 to create a wet layer of hard coating formulation of microvalve droplets from the hard coating formulation on surface 1110. The hard coating device 1350 may be in communication with and / or loaded with the hard coating formulation. In any embodiment of the coating system, the formulation (including, but not limited to, the hard coating formulation) may be disposed in a cartridge or any other container or tank.

[0170] The hard coating formulation used in hard coating device 1350 may be any hard coating formulation taught herein or any combination thereof. As disclosed above, the hard coating formulation used in microvalve-based devices (e.g., microvalve device 1900) may optionally be an ink.

[0171] In various embodiments, the hard coating apparatus 1350 may be configured and / or adjusted by the controller 1250 to produce a wet layer of a hard coating formulation with specific properties. For example, the wet layer may comprise a wet layer of a hard coating formulation with a thickness of less than 100 μm. For example, the thickness of the wet layer may be at most 90 μm, at most 75 μm, at most 50 μm, at most 25 μm, at most 20 μm, at most 15 μm, or at most 10 μm. For example, the wet layer may be continuous at least in a certain area (e.g., at least in a convex region with a specific area, such as at least 1 cm², at least 2 cm², at least 4 cm², or at least 8 cm²).

[0172] In various embodiments, device 1350 is configured, for example, via controller 1250 and / or via formulation characteristics, to perform... Figure 1 Step 102 and / or Figure 2 Step 224.

[0173] A hard coating drying and / or curing apparatus 1370 may be provided and configured to apply heat energy to a wet layer of the hard coating formulation, such as a wet layer produced by the hard coating apparatus 1350 and having a thickness or any other properties taught herein, to convert this wet layer in the hard coating formulation into a dried hard coating having any of the properties disclosed herein. In various embodiments, the hard coating apparatus 1350 is configured, for example, by a controller 1250 and / or by formulation characteristics to perform... Figure 1 Step 102 and / or Figure 2 Step 224.

[0174] Selection and / or transfer device 1330 is used to select and / or provide relative movement of OS1110 relative to any device and / or unit and / or station or component thereof of 1300. Such 'relative movement' may, for example, be by translational and / or rotational movement, transporting OS1100 or a portion thereof and / or any device and / or component and / or station of coating system 1300 relative to OS1100.

[0175] In different implementations, the selection and / or transfer device 1330 may be at least partially controlled by the controller 1250, for example, to achieve instructions stored in a digital computer, such as, for example, the target characteristics of a hard coating.

[0176] In various embodiments, the selection and / or transfer device 1330 may include one or more of the following: a robotic arm, grippers, a conveyor belt, and a lift, for raising or lowering the height of the wet layer on the optical substrate and its target surface.

[0177] The selection and / or transfer device 1330 may be configured to perform such relative movement between components of the coating system 1300, and / or to select OS1110 from a plurality of candidates according to instructions stored in a computer and / or instructions read by a digital computer (such as, for example, an optical prescription).

[0178] Microvalve-based coating apparatus 1900 or 1920: Any wet layer disclosed herein can be applied via microvalve apparatus 1900, which in embodiments may be controlled by controller 1250, for example, Figure 1 Step 102 is shown. The operating parameters of device 1900 may depend on the specific layer to be formed or the formulation used to produce this layer. Therefore, device 1900 can be implemented in different embodiments. Figure 2 Step 224 and / or Figure 2 Step 228 and / or Figure 2A Step 310 and / or Figure 3 Step 324 and / or Figure 3 Step 228.

[0179] The coating system may include a single instance of a microvalve device 1900 or 1920, which is configured to operate based on a wet layer to be dried / converted into a dry layer, according to multiple sets of operating parameters.

[0180] Any drying layer disclosed or claimed herein, such as a drying layer produced by any method or system disclosed herein, such as by... Figure 1 Step 104 or Figure 2 / 3 Step 210 / 310 or Figure 2 / 3 Step 226 / 326 or Figure 2 / 3 Step 230 / 330 or Figure 2 Steps 234 / 334 of / 4, and / or the dried layer produced by element 1370 or 1910 or 1420 or 1530 or element 1630 or element 1650 or element 1670, may be considered as continuous and / or thin in the terms defined herein.

[0181] A 'continuous' drying layer is a drying layer that is continuous throughout the entire virtual convex region, such as, for example... Figure 12D The illustration schematically shows that regions 1962, 1966, and 1968 are examples of convex regions, while region 1964 is a counterexample. In this example, in different embodiments, the area of ​​the convex region on the target surface 1110 can be at least 0.5 cm². 2 or at least 1 cm 2 or at least 2 cm 2 Or at least 4 cm 2 or at least 8 cm 2 Or at least 10 cm 2 Or at least 20 cm 2 .

[0182] The boundaries of the regions are 'virtual' rather than any physical boundaries; therefore, the term 'convex region' refers to the shape of these 'virtual' boundaries rather than any geometrical characteristic of the physical morphology of the target surface 1110 of the optical substrate 1100.

[0183] Therefore, as Figure 12B and Figure 12C As shown, even if the morphological surface 1100 is completely concave (e.g. Figure 12C As shown), it is also possible to define convex portions or convex regions within the concave topographic surface 1100 by defining / virtual boundaries.

[0184] The thickness of the 'thin' drying layer is at most 20 micrometers, or at most 15 micrometers, or at most 10 micrometers, or at most 5 micrometers, or at most 3 micrometers, or at most 1 micrometer.

[0185] In any of the embodiments disclosed herein, at least 75% by weight, at least 80% by weight, or at least 90% by weight of any 'dry layer' formed from the 'wet layer formed by the microvalve droplets' originates from the microvalve droplets.

[0186] In any of the embodiments disclosed herein, by 'primarily in [ r mm, s Any "dry layer" produced by a wet layer formed by droplets within the range of [mm] (where r and s are both positive numbers, and mm is millimeters) is a dry layer that is at least 75% by weight, at least 80% by weight, or at least 90% by weight derived from droplets (i.e., a precursor wet layer is formed and then dried), the width of which is at leastr mm and at most s mm. In different embodiments, any drying layer disclosed herein is formed primarily of droplets in the range of [0.1 mm, 3 mm].

[0187] In various embodiments, any drying layer disclosed herein is primarily formed from droplets in the range of [0.1 mm, 2 mm]. In different embodiments, any drying layer disclosed herein is primarily formed from droplets in the range of [0.1 mm, 1.5 mm]. In different embodiments, any drying layer disclosed herein is primarily formed from droplets in the range of [0.1 mm, 1 mm]. In different embodiments, any drying layer disclosed herein is primarily formed from droplets in the range of [0.01 mm, 1 mm]. In different embodiments, any drying layer disclosed herein is primarily formed from droplets in the range of [0.15 mm, 3 mm]. In different embodiments, any drying layer disclosed herein is primarily formed from droplets in the range of [0.2 mm, 1 mm].

[0188] Alternatively, multiple instances of 1900 or 1920 may be provided, each instance for drying different wet layers of the formulation, and each instance is operated according to different operating parameters.

[0189] (A) The drying and / or curing apparatus 1910 may, in various embodiments, include an oven and / or UV equipment or other elements for converting a wet layer of the formulation into a dry layer, optionally including a clear layer. The operating parameters of the drying and / or curing apparatus 1910 depend on the specific formulation and its characteristics. For example, for a hard coating formulation, the required / used drying temperature and / or energy and / or duration may exceed the required / used drying temperature and / or energy and / or duration for a 'primer formulation'. Any coating system 1300 may include a single 1910 or multiple drying and / or curing apparatuses 1910, and one or more of its operating parameters depend on the formulation and / or structure of the specific wet layer to be converted into a dry layer.

[0190] In various embodiments, the drying and / or curing equipment 1910 can be configured to perform... Figure 1 Step 104 and / or Figure 2 Step 207 and / or Figure 2 Step 210 and / or Figure 2 Step 226 and / or Figure 2 Step 230 and / or Figure 2 Steps 234 and / or Figure 2A Step 320 and / or Figure 3 Step 307 and / or Figure 3 Step 310 and / or Figure 3Step 326 and / or Figure 3 Step 330 and / or Figure 3 Step 334.

[0191] (B) such as Figure 9 As further detailed, a surface energy increasing device 1310 can be provided for increasing the surface energy of a target surface 1110 of an optical substrate 1100. In various embodiments, the surface energy increasing device 1310 operates to increase the surface energy of the target surface 1110 of the OS 1100 by at least 2 mN / m, at least 3 mN / m, at least 5 mN / m, at least 8 mN / m, or at least 12 mN / m. Alternatively, the surface energy increasing device 1310 operates to increase the surface energy of the target surface 1110 of the OS 1100 by at most 40 mN / m, at most 30 mN / m, at most 20 mN / m, at most 17 mN / m, or at most 14 mN / m. Figures 7C to 7E illustrate a non-limiting example of a coating system 1300 including the surface energy increasing device 1310. In various examples, such as Figure 9 As shown in the block diagram, the surface energy increasing device 1310 includes a plasma treatment device 1501A and / or a corona treatment device 1510B and / or an electron beam device 1510C and / or a discharge device 1510D. Alternatively or additionally, the device 1310 includes: (i) a droplet deposition device 1520 (e.g., a microvalve or inkjet printer loaded or in fluid communication with a suitable surface energy increasing formulation, as taught herein) and (ii) a drying and / or curing device 1530, which operates at a lower power and / or temperature and / or duration than drying a wet-hardened coating, for example, due to a wet layer of surface energy increasing formulation. In various embodiments, the device 1310 is configured to perform... Figure 2 Step 208 and / or Figure 3 Step 308. Or, alternatively, device 1520 (i.e., any instance thereof, if present) is configured to perform... Figure 2A Step 310.

[0192] (C) For Figure 8 The microvalve application device 1490 and additional drying and / or curing device 1420 may exist, and there may be more than one microvalve-based layer application device. Similarly, as discussed elsewhere, there may be more than one drying device.

[0193] Still referencing Figure 8 Any coating system 1300 disclosed herein may include any combination of any of the following components: (i) A cleaning apparatus 1440 may be provided to treat a target surface 1110 of the optical substrate 1100, for example, for surface cleaning. For example, the cleaning apparatus 1440 may be configured to apply a washing solution and / or soap and / or surfactant to the target surface 1110 of the optical substrate 1100. For example, the cleaning apparatus 1440 may be configured to dry the applied cleaning solution and / or perform a dust removal process on the target surface 1110. For example, the cleaning apparatus 1440 may treat the target surface 1110 before the target surface 1110 is subsequently subjected to a surface energy increasing process (e.g., via apparatus 1310) or before the target surface 1110 is coated by any coating apparatus disclosed herein.

[0194] (ii) One or more additional drying and / or curing devices 1420, for example, in addition to 1370 or 1910. For example, multiple wet coatings may be applied to the target surface 1110 of the optical substrate 1100. For example, a first wet coating or layer may be dried and / or cured by a first drying and / or curing device (e.g., 1370 or 1910), and a second wet coating or layer may be dried by element 1420.

[0195] (iii) Ventilation equipment 1450; (iv) Shell 1442; (v) One or more microvalve-based additional layer application devices 1490, as described above, and there may be more than one microvalve-based layer application; and (vi) Select and / or transfer device 1330 (e.g. for substrate and / or solvent and / or cartridge and / or other device).

[0196] Figures 10A to 10C and Figure 11 The illustration depicts a non-limiting example of operating a corresponding exemplary coating system 1300, which includes one or more ovens for drying and / or curing a wet coating on an optical substrate 1100.

[0197] Figure 10A An exemplary operating procedure is described below: (i) A first microvalve device 1610 is provided in communication with and / or loaded with the surface energy increasing agent for increasing the surface energy of a target surface 1110 of an optical substrate 1100, such that droplets from the microvalve to the surface 1110 co-form a wet coating of the surface energy increasing agent on the target surface 1110. (ii) A first oven 1630 is provided to operate the drying process at a 'low' temperature and / or a short duration (i.e. a relatively 'short' duration drying process) to dry the wet coating delivered by the microvalve device 1610; (iii) Providing a second microvalve device 1640 for applying a second wet coating to the target surface 1110 via droplets of a second formulation (e.g., a hard coating) through the microvalve after the surface of the first oven 1630 has been dried to form a wet coating capable of increasing the formulation; and (iv) Provide a second oven 1650 for drying and / or curing the wet coating of the second formulation.

[0198] Figure 10B The example illustrates a setup comprising a single oven 1670 instead of multiple ovens. An optical substrate 1100 is first transferred to the single oven 1670 for drying / curing a wet coating from a microvalve device 1610. After the first drying / curing process, the optical substrate is first transferred out of the single oven 1670. The optical substrate is then transferred a second time to the single oven 1670 to dry or cure a wet coating from a second microvalve device 1640. The necessary movement of the substrate 1100 can be performed at least partially by the optical substrate transfer device 1602, and at least partially by automation or robotic operation.

[0199] Figure 10C A third setup is shown, in which the coating is performed by an inkjet printer 1690 instead of a microvalve device. Apart from this, the setup and process are the same as... Figure 10A The setup and process shown are the same.

[0200] Figure 11 It shows the relationship with Figure 7B A similar fourth configuration adds ink preparation equipment 1646 and one or more ink layer drying and / or curing equipment 1420.

[0201] Now for reference Figure 13A , Figure 13B , Figure 14 , Figure 15 and Figure 16 , Figure 13A A cross-sectional side view of a virtual two-dimensional projection 1800 of the curved surface 1110 of an exemplary optical substrate 1100 is shown, and Figure 13BA top perspective view is shown. In embodiments, a coating system (such as any of the coating systems 1300 disclosed herein, including a controller 1250) can be configured to dispense microvalve droplets at a constant density (expressed as volume of formulation per unit area of ​​a two-dimensional projection 1800). As used herein, the term 'constant density' may mean completely constant, or it may mean within ±10%, ±5%, ±2%, or ±1% of the average density (i.e., volume of formulation per unit area of ​​a two-dimensional projection), the ratios applicable across the entire two-dimensional projection. A constant density, or, alternatively, a density within one of a given range of average values, can be measured over a small area of ​​the two-dimensional projection, such as, for example, any subdivided region of the two-dimensional projection 1800, having an area of ​​5% or more of the area of ​​the projection 1800.

[0202] The applied formulation may include any one or more of the ink and / or coating formulations disclosed herein. In some embodiments, especially Formulations are selected based on the physical characteristics that make them suitable for deposition on curved surfaces in the manner described herein.

[0203] The aforementioned term 'configuration' should be understood to include 'programmed' and / or 'programmable,' meaning that the controller 1250 is programmed or programmable to control the microvalve device accordingly.

[0204] In some implementations, the controller 1250 may be programmed or be programmable to generate a two-dimensional projection 1800 and / or calculate or select a target value and / or average value of the formulation volume ratio per unit area of ​​the two-dimensional projection 1800.

[0205] Figure 14 The illustration schematically depicts droplets 175 of a formulation applied at a constant density relative to a two-dimensional projection via a microvalve device 1610; however, for clarity, it should be noted again that the two-dimensional projection is virtual. Droplets 175 are actually applied to a curved surface 1100, although the applied density or equivalent frequency is determined by the area of ​​the two-dimensional projection 1800. As can be understood from the schematically illustrated geometry, the surface area of ​​the curved surface 1110 is larger than that of the two-dimensional projection. Furthermore, for Figures 13A to 14In the non-limiting example shown, the deviation between the area of ​​the curved surface 1110 and the area of ​​the two-dimensional projection 1800 of the single-beam convex lens surface is greater in the peripheral region of the optical substrate 1100 than in the central region. It is known that the degree of deviation between the area of ​​the curved surface 1110 and the area of ​​the two-dimensional projection 1800 can be determined by the curvilinear geometry of the surface, for example, by curvilinear geometry parameters such as the sag 180 of the surface 1110 and the radius of the spherical curve. Furthermore, the actual density, i.e., the volume of formulation actually applied to the actual curved surface 1110 per unit area of ​​the surface 1110, is generally inversely proportional to the ratio of the area of ​​the curved surface 1110 to the area of ​​the two-dimensional projection, and this also applies to any subdivision of the surface 1110.

[0206] Therefore, in some embodiments, the application process can achieve a deposition of the formulation in a manner or distribution suitable for a specific formulation and curve geometry without taking into account the curve geometry when selecting or calculating the application density. Furthermore, in some embodiments, the application of the formulation can cover an area larger than the surface of the optical substrate without considering the application process of other geometric parameters, such as the diameter or shape of the optical substrate.

[0207] Figure 15 An annular cross-section 1150 of the periphery of an exemplary optical substrate 1100 is schematically shown. This annular cross-section can be used to characterize the deviation between the area of ​​the curved surface 1110 of the optical substrate 1100 and the corresponding area of ​​the two-dimensional projection 1800, as well as to characterize the decrease in actual density on the actual curved surface 1110 with distance from the center. In this non-limiting example, the annular cross-section 1150 describes a region characterized by being located between 90% and 100% of the distance from the centroid of the optical substrate 1100 to the edge 1151. In an exemplary embodiment, the droplet 175 of the microvalve formulation is controlled by the controller 1250 such that the average formulation volume ratio applied per unit area of ​​the outer ring 1150, located between 90% and 100% of the distance from the centroid of the surface 1110 to the circumference 1151, is typically between 0.6 and 0.97 times, or between 0.6 and 0.96 times, or between 0.6 and 0.94 times the maximum formulation volume ratio applied per unit area of ​​the surface 1100.

[0208] Now for reference Figure 16 Points on the curved surface 1110 of the optical substrate 1110 ( x,yA virtual tangent 1111 (or plane) is drawn at the location. The tangent can be used to characterize the surface 1110, for example, at an angle α relative to the horizontal plane, and to describe the local deviation of the area of ​​the actual surface 1110 from the corresponding local portion of the virtual two-dimensional projection 1800. In an embodiment, the angle α can be between 5° and 50°, or between 10° and 40°, or between 5° and 20°, or between 20° and 50°, or any intermediate range between 5° and 50°. In an embodiment, the droplet 175 of the microvalve formulation is such that the average formulation volume ratio applied per unit area of ​​the surface 1110 at a given point on the surface 1110 is equal to a reduction factor multiplied by the maximum formulation volume ratio applied per unit area at any point on the surface 1100, said reduction factor being equal to the cosine of the acute angle α formed between (i) the plane or line 1111 tangent to the surface 1110 at the given point and (ii) the horizontal plane.

[0209] All horizontal planes mentioned in this article refer to planes that are level with the ground, and tangent planes or tangent angles refer to planes or angles when the optical substrate is stationary on a horizontal surface.

[0210] In the first example, the front surface of the optical substrate 1100 (such as a lens blank) is characterized by a base curve of 6.00 diopters. The lens blank has a diameter of 60 mm and a SAG number of 5.25 mm. A virtual tangent 1111 (or plane) drawn at a point on the edge of the curved surface 1110 forms an angle α of 19.9° with respect to the horizontal plane. The deviation between the area of ​​the curved surface 1110 and the area of ​​the two-dimensional projection 1800 results in that at a point on the perimeter 1151 of the curved surface 1110, the area of ​​the curved surface 1110 is 6.3% larger than the area at the corresponding point on the two-dimensional projection 1800. The outer ring 1150, located between 90% and 100% of the distance from the centroid of the surface 1110 to the perimeter 1151, is proportionally 5.6% to 5.7% larger than the corresponding outer ring area on the two-dimensional projection 1800. In contrast, the area of ​​the inner region located between 0% and 10% of the distance from the centroid of the surface 1110 to the perimeter 1151 increases less relative to the corresponding inner region area on the two-dimensional projection 1800.

[0211] In the second example, the front surface of the optical substrate 1100 (such as a lens blank) is characterized by a base curve of 4.00 diopters. The lens blank has a diameter of 80 mm and a SAG number of 6.2 mm. A virtual tangent 1111 (or plane) drawn at a point on the edge of the curved surface 1110 forms an angle α of 17.6° with respect to the horizontal plane. The deviation between the area of ​​the curved surface 1110 and the area of ​​the two-dimensional projection 1800 results in that at a point on the perimeter 1151 of the curved surface 1110, the area of ​​the curved surface 1110 is 4.9% larger than the area at the corresponding point on the two-dimensional projection 1800. The outer ring 1150, located between 90% and 100% of the distance from the centroid of the surface 1110 to the perimeter 1151, is 4.4% larger than the corresponding outer ring area on the two-dimensional projection 1800. In contrast, the area of ​​the inner region located between 0% and 10% of the distance from the centroid of the surface 1110 to the perimeter 1151 increases less relative to the corresponding inner region area on the two-dimensional projection 1800.

[0212] In the third example, the front surface of the optical substrate 1100 (such as a lens blank) is characterized by a base curve of 10.00 diopters. The lens blank has a diameter of 70 mm and a SAG number of 13.2 mm. A virtual tangent 1111 (or plane) drawn at a point on the edge of the curved surface 1110 forms an angle α of 41.3° with respect to the horizontal plane. The deviation between the area of ​​the curved surface 1110 and the area of ​​the two-dimensional projection 1800 results in that at a point on the perimeter 1151 of the curved surface 1110, the area of ​​the curved surface 1110 is 33.2% larger than the area at the corresponding point on the two-dimensional projection 1800. The outer ring 1150, located between 90% and 100% of the distance from the centroid of the surface 1110 to the perimeter 1151, is proportionally larger by 28.5% to 28.6% than the corresponding outer ring area on the two-dimensional projection 1800. In contrast, the area of ​​the inner region located between 0% and 10% of the distance from the centroid of the surface 1110 to the perimeter 1151 increases less relative to the corresponding inner region area on the two-dimensional projection 1800.

[0213] In the fourth example, the front surface of the optical substrate 1100 (such as a lens blank) is characterized by a base curve of 6.00 diopters. The lens blank has a diameter of 80 mm and a SAG number of 9.6 mm. A virtual tangent 1111 (or plane) drawn at a point on the edge of the curved surface 1110 forms an angle α of 26.9° with respect to the horizontal plane. The deviation between the area of ​​the curved surface 1110 and the area of ​​the two-dimensional projection 1800 results in that at a point on the perimeter 1151 of the curved surface 1110, the area of ​​the curved surface 1110 is 12.2% larger than the area at the corresponding point on the two-dimensional projection 1800. The outer ring 1150, located between 90% and 100% of the distance from the centroid of the surface 1110 to the perimeter 1151, is proportionally 10.8% larger than the corresponding outer ring area on the two-dimensional projection 1800. In contrast, the area of ​​the inner region located between 0% and 10% of the distance from the centroid of the surface 1110 to the perimeter 1151 increases less relative to the corresponding inner region area on the two-dimensional projection 1800.

[0214] In the fifth example, the front surface of the optical substrate 1100 (such as a lens blank) is characterized by a base curve of 8.00 diopters. The lens blank has a diameter of 80 mm and a SAG number of 13.4 mm. A virtual tangent 1111 (or plane) drawn at a point on the edge of the curved surface 1110 forms an angle α of 37.1° with respect to the horizontal plane. The deviation between the area of ​​the curved surface 1110 and the area of ​​the two-dimensional projection 1800 results in that at a point on the perimeter 1151 of the curved surface 1110, the area of ​​the curved surface 1110 is 25.4% larger than the area at the corresponding point on the two-dimensional projection 1800. The outer ring 1150, located between 90% and 100% of the distance from the centroid of the surface 1110 to the perimeter 1151, is proportionally 22.1% to 22.2% larger than the corresponding outer ring area on the two-dimensional projection 1800. In contrast, the area of ​​the inner region located between 0% and 10% of the distance from the centroid of the surface 1110 to the perimeter 1151 increases less relative to the corresponding inner region area on the two-dimensional projection 1800.

[0215] Example The invention is now described in a non-limiting manner with reference to the following embodiments, which together with the above description.

[0216] Material Photochromic dyes: • Reversacol Amazon Green (James Robinson Specialty Ingredients Ltd.): A photochromic dye in powder form; • Reversacol Midnight Grey (James Robinson Specialty Ingredients Ltd.): A photochromic dye in powder form; • Reversacol Leather Brown (James Robinson Specialty Ingredients Ltd.): A photochromic dye in powder form; • Reversacol (James Robinson Specialty Ingredients Ltd.): A photochromic dye in powder form; • Reversacol Ocean Blue (James Robinson Specialty Ingredients Ltd.): A photochromic dye in powder form; thermoplastic resin ○ Pearlcoat™ DIPP 119 – A thermoplastic polyurethane (TPU) (Lubrizol) based on aromatic polycaprolactone copolyester ○ Pearlbond™ 360 – A polyether-based thermoplastic polyurethane (TPU) (Lubrizol) SETALUX ® 2127 XX-60 – A thermoplastic acrylic resin (Allnex) with good adhesion to plastics. ○ Laropal A-81 — Thermoplastic aldehyde resin (BASF).

[0217] Primer and topcoat • Acrylic polymer emulsion: ○ Joncryl ® 1532—A water-based acrylic emulsion that provides excellent adhesion to a variety of substrates, including plastics (BASF); primer ○ Joncryl ® 1534—A water-based acrylic emulsion that provides excellent adhesion to a variety of substrates, including plastics (BASF); primer ○ Joncryl ® 2110—Waterborne acrylic emulsion primer, styrene-acrylate copolymer (BASF); primer ○ Joncryl ® 9530-A—Waterborne acrylic emulsion self-crosslinking polymer, designed for topcoat and primer coatings; topcoat coatings ○ Joncryl ®617-A—Waterborne acrylic polymer emulsion film-forming overprinting varnish formulation (BASF); outer coating SETALUX ® 17-7202—with ketimine resin (SETALUX) ® 10-1440) combination of acetoacetate functionalized acrylic resins used as primers; topcoat ○ SETALUX® 17-1246—a fast-drying thermoplastic acrylic solution that provides an excellent balance of hardness, adhesion, film toughness, clarity, and transparency; outer coating. • PU polymer emulsion: ○ ALBERDINGK ® APU 10600 self-crosslinking acrylic, PES / PC-polyurethane mixed dispersion (Alberdingk Boley); outer coating Bondthane™ UD-620 – A self-crosslinking polyurethane ideal for rigid, clear, or colored coatings on rigid plastics (BPI); outer coatings ○ CrystalCoat ® PR 670 – Waterborne emulsion (SDC); primer ○ Hi-Gard HP 1500 – A thermosetting coating for hard coatings (PPG); primer • Resin solvent-based solutions: ○ Versamid ® PUR 1010 - Primer ○ Laroflex ® HS-9000 - Primer.

[0218] Solvent: Low evaporation rate / low vapor pressure • TPM (tripropylene glycol methyl ether, CAS 25498-49-1) • PPH (Ph-O-CH2-CHMe-OH, CAS 770-35-4) • DBA (2-(2-Butoxyethoxy)ethyl acetate, CAS 124-17-4) • TPnB (Tripropylene glycol n-butyl ether, 55934-93-5) • DPnP (Pr-O-[CH2-CHMe-O]2-H, CAS 29911-27-1) • Augeo ® (HO-CH2-Me2Acetal, CAS 100-79-8) • DPnP (Pr-O-[CH2-CHMe-O]2-H, CAS 29911-27-1) • Butylcarbidol (CAS 112-34-5) equipment • Coating equipment ○ Inkjet Printer: The Dimatix DMP-2831 material printer is equipped with 10 pL Dimatix material cartridges (Fujifilm Dimatix™ Inc.); Ricoh gen4I mh2620, driven by GIS PMB C8 and hib-rh-384 (ink supply system: MegnaJet LabJet). ○ Miniature: Electromagnetically actuated (Fritz Gyger AG); Nozzle diameter 0.1mm, pressure 0.5-2.0 bar ○ Spin Coator: MUTECH μCoater (Mutech Microsystems SAS) ○ UV LED curing system: FJ100 Gen 2, 395nm, 12W / cm² 2 (Phoseon Technology) ○ Thermosetting system: Venticell ECO forced ventilation oven (MMM) ○ Surface activation: Corona treatment device for electrosurface treatment of HF SpotTEC Single (Tantec).

[0219] • Testing equipment ○ Spectrophotometer: Cary 4000 UV-Vis dual-beam spectrophotometer, ISO / EN 8980-3:2013 (Agilent) ○ Transmittance and haze measuring instrument: TH-100, ASTM D1003 / D1044 (Hangzhou CHN SpecTechnology Co., Ltd.) ○ Thickness measurement: ThetaMetrisis layer thickness analyzer.

[0220] Example 1: Corona Surface Treatment Procedure The head of the corona treatment device (Tantec) is positioned 1 cm from the surface of the ophthalmic lens, and then activated for 10 seconds. This process is performed twice before applying various coating materials to the ophthalmic lens.

[0221] Example 2: Procedure for applying primer using spin coating The ophthalmic lens is attached to the vacuum chuck of the spin coating device. The ophthalmic lens is rotated at a speed of 3000 rpm and an acceleration of 1000 rpm / second for 10 seconds.

[0222] Example 3: The procedure of applying a post-hardened coating using spin coating. The ophthalmic lens is attached to the vacuum suction cup of the spin coating device. The ophthalmic device is rotated at a speed of 1500 rpm and an acceleration of 500 rpm / second for 10 seconds.

[0223] Example 4: Optimization of Inkjet Parameters Inkjet printing is optionally employed in all ink application steps. A Ricoh printhead is used, typically preheated to 40°C. The droplet characteristics for each ink are then optimized using a Jet Expert stroboscope (Image Expert) mounted on the printing press (a camera and light source synchronized with the jetting frequency). Waveforms are optimized for each ink, jetting at a frequency of 0.5–3 kHz. The distance between the printhead and the substrate is 0.6–1.0 mm. Jetting produces droplets of approximately 50 micrometers in size (on the test substrate). The resolution is set to 300 dots per inch (dpi).

[0224] Example 5: Applying film-forming ink microvalves to lens substrates Optical structures with at least one of various functions (hard coating, primer, top coating, photochromic coating, thermochromic coating, tinted hard coating, post-hard coating, etc.) are fabricated by microvaping film-forming ink onto a lens substrate. The microvalves are mounted on a controllable XYZ stage, where a PLC synchronizes the actuation of the microvalves with the positioning of the lens. The frequency and relative speed between the stage and the microvalves are maintained at fixed values. The microvalves operate according to any of a variety of predetermined digital patterns.

[0225] Example 6A: Drying Unless otherwise instructed, the drying of primers, topcoats and photochromic inks is generally carried out at 60°C for 30 minutes.

[0226] Example 6B: Thermosetting Thermosetting of hard coatings (inner and outer layers) or colored hard coatings typically takes place at 120°C for 3 hours.

[0227] Example 6C: UV Curing UV curing uses a UV LED curing system: FJ100 Gen 2, 395nm, 12W / cm². 2 (Phoseon Technology) for 10 seconds.

[0228] Example 7 29 g of DBA (2-(2-butoxyethoxy)ethyl acetate) solvent and 66.6 g of propylene glycol methyl ether solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes at room temperature, 0.2 g of surfactant BYK was added simultaneously with the mixture. ® -333 was added to the solvent mixture. Then, while mixing, 2 g of Reversacol Midnight Grey dye and 2.2 g of Pearlbond™ 360 were added as a binder. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0229] Example 8 28 g of TPM solvent and 67.8 g of ethyl acetate solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes at room temperature, 0.2 g of surfactant BYK was added simultaneously. ® -358 was added to the solvent mixture. Then, while mixing, 2 g of Reversacol leather brown dye and 2 g of Laropal A-81 were added as a binder. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0230] Example 9 29.4 g of TPM solvent and 62.5 g of methyl isobutyl ketone solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes at room temperature, 0.2 g of surfactant BYK was added simultaneously. ® -358 was added to the solvent mixture. Then, while mixing, 2 g of Reversacol Midnight Grey dye, 2 g of Reversacol Amazon Green dye, and 3.8 g of Laropal A-81 were added as a binder. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0231] Example 10 28.6 g of TPM solvent and 66.8 g of methyl propyl ketone solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes at room temperature, 0.2 g of surfactant BYK was added during mixing. ® -358 was added to the solvent mixture, followed by 2 g of Reversacol Midnight Grey dye and 1 g of Emoltene. TM3GO plasticizer and 1.4g SETALUX ® 2127 XX-60. Continue mixing at 60°C for another 20 minutes to produce the photochromic ink, then filter it through a syringe filter (0.45 microns).

[0232] Example 11 27.6 g of TPM solvent and 66.8 g of ethyl acetate solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes at room temperature, 0.2 g of surfactant BYK was added simultaneously. ® -358 was added to the solvent mixture, followed by 2 g of Reversacol Amazon Green dye, 2.4 g of Pearlbond™ 360, and 1 g of Pevalen plasticizer. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0233] Example 12 Mix 44 g of TPM solvent with 51.8 g of ethyl acetate solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 1 g of Pearlcoat DIPP 119 and mix at 60°C for 2 hours. While mixing, add 0.2 g of surfactant BYK®-358, followed by 2 g of Reversacol Amazon Green dye and 2 g of Pearlbond™ 360. Continue mixing at 60°C for another 20 minutes to produce the photochromic ink, which is then filtered through a syringe filter (0.45 microns).

[0234] Example 13 28.5 grams of Auugeo ® (HO-CH2-Me2Acetal) solvent and 62.8 g of isopropyl acetate solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing for 5 minutes, 0.2 g of surfactant BYK was added simultaneously. ® -358 was added to the solvent mixture. 2 g of Reversacol Midnight Grey dye, 2 g of Reversacol Amazon Green dye, and 3.5 g of Pearlcoat DIPP 119 were added, and the mixture was incubated at 60°C for 2 hours. Then, 1 g of Emotene was added during mixing. TM 3GO plasticizer. Continue mixing at 60°C for another 20 minutes to produce photochromic ink, then filter it through a syringe filter (0.45 microns).

[0235] Example 14 Mix 30 g of TPM solvent and 65.8 g of MEK solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2 g of Laropal. ® A-81 was mixed at 60°C for 2 hours. Simultaneously, 0.2 g of surfactant BYK was added. ® -358 was added to the mixture, followed by 2 grams of Reversacol Amazon Green dye. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0236] Example 15 Mix 29 g of TPM solvent and 66.3 g of n-propyl acetate solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2.5 g of Pearlbond 360 and mix at 60°C for 2 hours. Simultaneously, add 0.2 g of surfactant BYK. ® -358 was added to the mixture, followed by 2 grams of Reversacol Amazon Green dye. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0237] Example 16 Mix 28.2 g of butyl carbitol solvent and 66.8 g of n-propyl acetate solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2.8 g of SETALUX. ® 2127 XX-60, and mixed at 60°C for 2 hours. Simultaneously, 0.2 g of surfactant BYK was added. ® -358 was added to the mixture, followed by 2 grams of Reversacol Amazon Green dye. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0238] Example 17 Mix 30 g of TPM solvent and 65.8 g of isobutyl acetate solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2 g of Laropal. ® The A-81 dispersion was prepared and mixed at 60°C for 2 hours. Simultaneously, 0.2 g of surfactant BYK was added. ® -358 was added to the mixture, followed by 2 g of Reversacol corn yellow dye. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0239] Example 18 Mix 28.8 g of TPM solvent and 66.8 g of MEK solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2.2 g of SETALUX. ® 2127 XX-60, and mixed at 60°C for 2 hours. Simultaneously, 0.2 g of surfactant BYK was added. ® -358 was added to the mixture, followed by 2 grams of Reversacol Midnight Grey dye. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0240] Example 19 Mix 30 g of TPM solvent with 65.3 g of ethyl acetate solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2.2 g of SETALUX. ® 2127 XX-60, and mixed at 60°C for 2 hours. Simultaneously, 0.2 g of surfactant BYK was added. ® -358 was added to the mixture. Then, 2.3 g of Reversacol Amazon Green dye was added while mixing. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0241] Example 20 Mix 32 g of TPM solvent and 63.4 g of isobutyl acetate solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2.4 g of SETALUX. ® 2127 XX-60, and mixed at 60°C for 2 hours. Simultaneously, 0.2 g of surfactant BYK was added. ® -358 was added to the mixture. Then, 2 grams of Reversacol Amazon Green dye were added while mixing. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0242] Example 21 Mix 29 g of TPM solvent and 66.5 g of methyl propyl ketone solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 2.3 g of Pearlbond 360 and mix at 60°C for 2 hours. Simultaneously, add 0.2 g of surfactant BYK. ®-358 was added to the mixture. Then, 2 grams of Reversacol Amazonian Ocean Blue dye were added while mixing. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0243] Example 22 Mix 30 g of butyl carbitol solvent and 65.8 g of MEK solvent in a 200 ml glass beaker equipped with a magnetic stirrer. Add 1.8 g of SETALUX. ® 2127 XX-60, and mixed at 60°C for 2 hours. Simultaneously, 0.2 g of surfactant BYK was added. ® -358 was added to the mixture. Then, 2.2 g of Reversacol Amazonian Ocean Blue dye was added while mixing. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0244] Example 23 Mix 30 g of butylcarbitol solvent and 67.9 g of MEK solvent in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes, add 0.1 g of surfactant BYK while mixing. ® -346 was added to the solvent mixture, and 1 gram of Reversacol Midnight Grey dye and 1 gram of Reversacol Amazon Green dye were added simultaneously. Mixing was continued at 60°C for another 20 minutes to produce the photochromic ink, which was then filtered through a syringe filter (0.45 microns).

[0245] Example 24 65 grams of Joncryl ® Mix 1532 with 20g of water in a 200ml glass beaker equipped with a magnetic stirrer. Then, while mixing, add 9.5g of EB solvent, 4.8g of DPM solvent, and 0.2g of BYK. ® 024. After mixing the components for 5 minutes, add 0.5 g of surfactant BYK. ® -346 was added to the mixture and mixed for another 10 minutes at 30°C to produce the primer formulation.

[0246] Example 25 70 grams of Joncryl ® Mix 1534 with 15g of water in a 200ml glass beaker equipped with a magnetic stirrer. Then, while mixing, add 9.5g of EB solvent, 4.8g of DPM solvent, and 0.2g of BYK. ®024. After mixing the components for 5 minutes, add 0.5 g of surfactant EFKA. ® Add 3200 to the mixture and continue mixing at 30°C for another 10 minutes to produce the primer formulation.

[0247] Example 26 75 grams of Joncryl ® Mix 2110 with 10 grams of water in a 200 ml glass beaker equipped with a magnetic stirrer. Then, while mixing, add 10 grams of EB solvent, 4.5 grams of DPM solvent, and 0.25 grams of BYK. ® 044. After mixing the components for 5 minutes, add 0.25 g of surfactant BYK. ® Add 346 to the mixture and continue mixing at 30°C for another 10 minutes to produce a primer formulation.

[0248] Example 27 According to Example 1, Trivex made from a polyurethane-based prepolymer... ® (PPG) lenses undergo a corona treatment process.

[0249] Example 28 A corona treatment process was performed on a polycarbonate lens according to Example 1.

[0250] Example 29 The corona surface treatment procedure of Example 1 was performed on the polycarbonate lens pre-coated with a hard coating.

[0251] Example 30 Trivex with pre-coated hard coating ® (PPG) lenses undergo the corona surface treatment procedure of Example 1.

[0252] Example 31 CR-39, made of poly(allyl diethylene glycol carbonate) (PADC) and pre-coated with a hard coating ® (PPG) lenses undergo the corona surface treatment procedure of Example 1.

[0253] Example 32 Versamid ®PUR 1010 was applied as a primer to the polycarbonate lens. Microvaping was performed according to Example 5, and a calculated (average) wet thickness of 1.8 μm was obtained. The wet layer was then heat-dried and cured in a Venticell ECO forced-air oven at 60°C for 10 minutes, followed by curing at 100°C for 10 minutes to produce a primer layer.

[0254] Example 33 Laroflex ® HS-9000 was applied as a primer to the polycarbonate lens. Microvaping was performed according to Example 5, and a calculated wet thickness of 2.1 μm was obtained. The wet layer was then heat-dried and cured in a Venticell ECO forced-air oven at 60°C for 10 minutes, followed by curing at 100°C for 10 minutes to produce a primer layer with a thickness of approximately 1.5 μm.

[0255] Example 34 Joncryl from Example 25 ® Formulation 1534 was applied as a primer to the polycarbonate lens. Microvaping was performed according to Example 5, and a calculated wet thickness of 0.9 μm was obtained. The wet layer was then heat-dried and cured in a Venticell ECO forced-ventilation oven at 60°C for 10 minutes, followed by curing at 100°C for 10 minutes.

[0256] Example 35 Joncryl from Example 25 ® Formulation 1534 was applied as a primer to a polycarbonate lens that had undergone corona treatment according to Example 29. Microvaping was performed according to Example 5. The wet layer was then heat-dried and cured in a Venticell ECO forced-air oven at 60°C for 10 minutes, followed by curing at 100°C for 10 minutes.

[0257] Example 36 Joncryl from Example 38 ® Formulation 1534 was applied as a primer to CR-39 that had undergone corona treatment according to Example 31. ® On the lens. Microvalves were applied according to Example 5. The wet layer was then heat-dried and cured in a Venticell ECO forced-air oven at 60°C for 10 minutes, followed by curing at 100°C for 10 minutes.

[0258] Examples 37-42: Applying photochromic ink microvalves to the lens surface The photochromic dye formulations (containing photochromic dyes and polymer binders) of Examples 14, 15, 17, 20, 21 and 23 were applied to various lens substrates by microvalves at a pressure maintained below 1 bar, according to Example 5.

[0259] Example 43 Setalux ® 17-7202 was applied as an outer coating formulation microvalves onto the coated polycarbonate lens produced in Example 39. The wet layer (calculated average thickness of 13 μm) was then heat-dried in a Venticell ECO forced-ventilation oven at 60°C for 30 minutes. The dried (calculated average) thickness was approximately 6.5 μm.

[0260] Examples 44-48: Hard Coating Varnish Formulation Example 44: Non-colored hard coating varnish 15.0 g of 3-glycidyl etherpropyltrimethoxysilane, 33.6 g of tetraethyl orthosilicate, 22.5 g of itaconic acid, and 24.8 g of ethyl acetate were combined and stirred for 10 minutes until a homogeneous mixture was obtained. 24.8 g of water was added dropwise to the premixed silane solution using a peristaltic pump to obtain the resulting mixture. The mixture was then stirred for 12 hours to produce the coating composition.

[0261] Example 45: Non-coloring HC varnish + catalyst 0.2 g of benzyldimethylamine was added dropwise to the 99.8 g mixture of Example 44 and mixed for 10 hours.

[0262] Example 46: Non-coloring HC varnish + nanoparticles A mixture of 15.5 g of 3-glycidyl ether propyltrimethoxysilane, 25.5 g of tetraethyl orthosilicate, 2.3 g of itaconic acid, and 23.2 g of ethyl acetate was stirred for 20 minutes until a homogeneous mixture was obtained. 19.1 g of water was added to 16.3 g of Ludox HS-30 (Grace) nano-silica dispersion and mixed for 15 minutes. This mixture was then added dropwise to the premixed silane solution using a peristaltic pump to obtain the desired mixture. The mixture was then stirred for 24 hours to produce the coating composition.

[0263] Example 47: Non-coloring HC varnish + silane additive 12.0 g of methyltrimethoxysilane (Gelest), 8.0 g of 3-glycidyl ether propyltrimethoxysilane (Gelest), 29.1 g of tetraethyl orthosilicate (Merck), 22.5 g of succinic anhydride (Merck), and 24.8 g of isopropyl acetate (Dow) were combined and stirred for 10 minutes until a homogeneous mixture was obtained. 24.8 g of water was added dropwise to the premixed silane solution using a peristaltic pump to obtain the resulting mixture. The mixture was then stirred for 7 hours to produce the coating composition.

[0264] Example 48: Non-coloring HC varnish + catalyst 1.5 g of a 10% by weight potassium hydroxide aqueous solution was added dropwise to the 98.5 g mixture of Example 47 and mixed for 15 hours.

[0265] Examples 49A-49N: Hard coating formulations for microvalves The hard coating formulation suitable for microvalves was formulated according to the table provided below.

[0266] Examples 50A-50N: Hard coating formulations for microvalves The colored hard coating formulation suitable for microvalves was formulated according to the table provided below:

[0267] Example 51 The formulations of Examples 49A-49N were applied as hard-coating microvalves to the coated polycarbonate lenses produced in Example 39.

[0268] Example 52 The formulations of Examples 50A-50N were used as colored hard coating microvalves on the coated polycarbonate lenses produced in Example 39.

[0269] Example 53: Measurement of Haze and Transmittance % After calibrating the T-100 instrument, the target lens (uncoated reference lens) is measured. Then, the coated lens is tested in sample mode. The instrument then displays the following results for both coated and uncoated lenses: % transmittance, Δ% transmittance, haze, and Δhaze. A lower Δ value between coated and uncoated lenses indicates good optical sharpness / transparency.

[0270] Example 54: Measuring Coloring Properties Spectrophotometric studies were performed using a Cary 4000 UV-Vis two-beam spectrophotometer. The light source was a UV-LED lamp (395 nm). In the spectrophotometric studies, the coated samples were characterized relative to uncoated reference slides or lenses. Spectral data were typically collected at a resolution of 1 nm in the 350–700 nm range. Transmittance was measured at the maximum absorption wavelength for each coloring dye.

[0271] Unless otherwise expressly indicated, as used herein in this specification and the following claims section, the term "percentage" or "%" means weight percentage.

[0272] As used herein and in the following claims section, the terms “anti-glare,” “anti-reflective,” “anti-fog,” “hard coating,” “ultraviolet absorber,” “photochromic,” “coloring,” “blue light absorber,” etc., unless otherwise stated, are intended to be used in the field of optical substrate coatings.

[0273] As used herein in this specification and the following claims section, the term "scratch resistant" in relation to materials such as formulations or coatings means that the dried and cured coating exhibits a haze value of less than 6%, using the following Taber abrasion characteristics, according to ASTM D1004-08: CS 10 F wheel, 500g load, 500 cycles.

[0274] Alternatively, the term "scratch resistant" in relation to materials such as formulations or coatings refers to materials with a Bayer number of at least 5 or at least 6 when using ASTM F735-21.

[0275] Unless otherwise expressly indicated, as used herein in this specification and the following claims section, the term "ratio" refers to a weight ratio.

[0276] As used herein and in the following claims section, the term "SAGITTA" or "SAG" refers to the convex curvature of an optical substrate, representing the physical distance between the vertex (the highest point of the convex curvature) of the curved surface of the optical substrate and the center point of a line drawn perpendicular to the curved surface from one edge of the optical substrate to the other. SAG can be measured or determined according to the following established equation: Where R is the radius of curvature of the optical surface, and D is the diameter of the optical surface.

[0277] As used herein and in the following claims section, the term "non-volatile component" in relation to a formulation or a lens / optical substrate refers to the residue remaining after some or all of the solvent and carrier liquid have been removed from the lens / optical surface following drying of a lens / optical substrate coated with the formulation in an oven at 120°C for 3 hours. The residue includes solid particles within the formulation, as well as dissolved solids remaining after solvent removal.

[0278] The “thickness” of one or more layers at a specific location is measured along the normal direction (N) of the lens substrate at that location.

[0279] Those skilled in the art are familiar with various types of thin film thickness measurements. For example, single-point thickness measurements can be performed using spectral reflectance or spectral elliptic polarization.

[0280] In addition, these techniques can be used to map thin film surfaces and calculate the average thickness of such films.

[0281] The "average thickness" of the wet layer can be determined as follows: when a certain volume of material... vol Based on the area covered by the wet layer SA When the surface area of ​​the surface is , the thickness of the wet layer is assumed to be . vol / SA. If the weight of the material is known, it can be calculated by dividing it by the material's specific gravity. vol Generally, the specific gravity of various coating materials can be safely approximated as 1.00.

[0282] The "average thickness" of a dried film can be calculated as follows: when a certain volume of material... vol (It is measured by weight) x% (liquid), the surface area that wets or covers the surface. SA And when all the liquid has evaporated to convert the wet layer into a dry film, the thickness of the dry film is calculated as follows: vol / ρ 湿层 (100-x) / (SA•ρ) 干层 ) Where ρ 湿层 It is the specific gravity of the wetted layer, and ρ 干层 This is the specific gravity of the dry layer. This calculation requires knowledge of various properties of the wet coating material, such as its specific gravity. As mentioned above, the specific gravity can usually be assumed to be 1.

[0283] Similarly, the average diameter of droplets, such as jet droplets or microvalve droplets (D-droplets), can be calculated by weighing a large number of jet droplets, converting the total weight to volume using specific gravity, dividing by the number of droplets, and using the equation between the diameter of a spherical droplet and the volume of a sphere: D = (6*V / π ) 1 / 3 .

[0284] Those skilled in the art will understand that the individual layers disposed on the optical or ophthalmic surface (e.g., lens surface) of the present invention generally have a substantially uniform thickness, and therefore the “average thickness” can be determined by evaluating the thickness at one or more points on the film or layer.

[0285] As used herein and in the following claims section, the term "characteristic" refers to the maximum value of a dot size (such as height, length, or diameter). For example, for a square dot with a side length of 30 micrometers, the characteristic diameter would be the diagonal, i.e., 30√2 = 42.4 micrometers. For a dot with some peaks on its top surface and far from the optical substrate, the dot height would be the maximum height measured perpendicular to the top surface of the substrate. For multiple dots, the characteristic size is the average of the characteristic sizes of the individual dots.

[0286] As used herein and in the following claims section, the term "average value" refers to the arithmetic mean of the dimensions of a plurality of points (such as their height, length, or diameter), and is calculated using the characteristic dimensions of each of the plurality of points.

[0287] As used herein and in the following claims section, the term "transparent" generally refers to a material (e.g., a material used for coating or as a substrate) that can be determined according to ASTM D1003. Using ASTM D1003, a haze measurement of less than 2% and a total transmittance ( Tt Materials with at least 85% transparency are considered "transparent." More typically, haze is a maximum of 1.5% or 1.0%. More typically, Tt It must be at least 90% or at least 95%. More typically, the haze is at most 1.0% and... Tt It should be at least 95%.

[0288] As used herein and in the following claims section, the term "liquid medium" refers to a medium that is liquid at its operating temperature. For example, the liquid medium in inkjet ink that is jetted at 38°C is liquid at 38°C. "Liquid medium" is generally liquid at 25°C.

[0289] In the context of this application and the claims, the phrase "at least one of A and B" is equivalent to an inclusive "or" and includes any one of "only A", "only B", or "A and B". Similarly, the phrase "at least one of A, B, and C" is equivalent to an inclusive "or" and includes any one of "only A", "only B", "only C", "A and B", "A and C", "B and C", or "A and B and C".

[0290] As used herein in this specification and the following claims section, the terms “top,” “bottom,” “above,” “below,” “upper,” “lower,” “height,” and “side,” etc., are for convenience of description or for relative orientation and are not necessarily intended to indicate absolute orientation in space.

[0291] Additional implementation plan : This document discloses various formulations, methods, optical structures, and systems. Additional implementation methods are provided below.

[0292] Method Implementation Plan 1. A method for producing an optical structure on an optical substrate, the method comprising: (a) A droplet microvalve of a liquid film-forming formulation is applied to the optical surface of an optical substrate to form a wet layer; (b) Process the wet layer to produce a dry transparent layer on the optical surface; Optionally, the optical surface is a curved surface, and optionally, the optical surface is a polymer surface.

[0293] 2. The method of claim 1, wherein the optical surface has the curved surface.

[0294] 3. The method of claim 1 or claim 2, wherein the optical surface has the polymer surface.

[0295] 4. A method for producing an optical structure on an optical substrate, the method comprising: (a) A droplet microvalve of a liquid film-forming formulation is applied to the optical surface of an optical substrate to form a wet layer; (b) Process the wet layer to produce a dry transparent layer on the optical surface; The optical surface is a curved surface, and optionally the optical surface is a polymer surface.

[0296] 5. The method of claim 4, wherein the optical surface has the polymer surface.

[0297] 6. The method of any of the preceding claims, wherein the liquid film-forming formulation is a hard coating formulation.

[0298] 6A. The method of any of the preceding claims, wherein the liquid film-forming formulation is an external coating formulation.

[0299] 7. A method for producing an optical structure on an optical substrate, the method comprising: (a) A droplet microvalve of a liquid film-forming formulation is applied to the optical surface of an optical substrate to form a wet layer; (b) Process the wet layer to produce a dry transparent layer on the optical surface; The liquid film-forming formulation is a hard coating formulation; and the optical surface is optionally curved.

[0300] 8. The method of claim 7, wherein the optical surface has the curved surface.

[0301] 9. The method of any of the preceding claims, wherein the non-volatile component of the liquid film-forming formulation accounts for at least 10% by weight.

[0302] 10. The method of claim 9, wherein the non-volatile component of the liquid film-forming formulation comprises at least 15%.

[0303] 11. The method of claim 9, wherein the non-volatile component comprises at least 20%.

[0304] 12. The method of claim 9, wherein the non-volatile component comprises at least 25%.

[0305] 13. The method of claim 9, wherein the non-volatile component comprises at least 30%.

[0306] 14. The method of claim 9, wherein the non-volatile component comprises at least 35%.

[0307] 15. The method of claim 9, wherein the non-volatile component comprises at least 40%.

[0308] 16. The method of claim 9, wherein the non-volatile component comprises at least 45%.

[0309] 17. The method of claim 9, wherein the non-volatile component comprises at least 50%.

[0310] 18. The method of any one of claims 9 to 17, wherein the non-volatile component comprises up to 75%.

[0311] 19. The method of claim 18, wherein the non-volatile component comprises up to 70%.

[0312] 20. The method of claim 18, wherein the non-volatile component comprises up to 65%.

[0313] 21. The method of claim 18, wherein the non-volatile component comprises up to 60%.

[0314] 22. The method of claim 18, wherein the non-volatile component comprises up to 55%.

[0315] 23. The method as described in any of the preceding claims, wherein the SAG number of the optical substrate is at least 0.5 mm.

[0316] 24. The method of claim 23, wherein the SAG number of the optical substrate is at least 1 mm.

[0317] 25. The method of claim 23, wherein the SAG number of the optical substrate is at least 2 mm.

[0318] 26. The method of claim 23, wherein the SAG number of the optical substrate is at least 3.5 mm.

[0319] 27. The method of claim 23, wherein the SAG number of the optical substrate is at least 5 mm.

[0320] 28. The method of claim 23, wherein the SAG number of the optical substrate is at most 12 mm.

[0321] 29. The method of any one of claims 1 to 28, wherein the total solvent content of the liquid film-forming formulation is St in weight percent, and wherein the liquid film-forming hard coating formulation contains a high vapor pressure solvent Hvp and a low vapor pressure solvent Lvp.

[0322] 30. The method of claim 29, wherein the concentration of Lvp is at least 2% St.

[0323] 31. The method of claim 30, wherein the concentration of Lvp is at least 5% St.

[0324] 32. The method of claim 30, wherein the concentration of Lvp is at least 10% St.

[0325] 33. The method of claim 30, wherein the concentration of Lvp is at least 15% St.

[0326] 34. The method of claim 30, wherein the concentration of Lvp is at least 20% St.

[0327] 35. The method of claim 30, wherein the concentration of Lvp is at least 25% St.

[0328] 36. The method of claim 30, wherein the concentration of Lvp is at least 30% of St.

[0329] 37. The method of claim 30, wherein the concentration of Lvp is at least 35% St.

[0330] 38. The method of claim 30, wherein the concentration of Lvp is at least 40% of St.

[0331] 39. The method of claim 30, wherein the concentration of Lvp is at least 45% St.

[0332] 40. The method of claim 30, wherein the concentration of Lvp is at least 50% of St.

[0333] 41. The method of claim 30, wherein the concentration of Lvp is at least 55% St.

[0334] 42. The method of any one of claims 29 to 41, wherein the concentration of Lvp is at most 80% of St.

[0335] 43. The method of claim 42, wherein the concentration of Lvp is at most 75% of St.

[0336] 44. The method of claim 42, wherein the concentration of Lvp is at most 70% of St.

[0337] 45. The method of claim 42, wherein the concentration of Lvp is at most 65% of St.

[0338] 46. ​​The method of claim 42, wherein the concentration of Lvp is at most 60% of St.

[0339] 47. The method of any one of claims 30 to 40, wherein the concentration of Lvp is at most 55% of St.

[0340] 48. The method of any one of claims 30 to 39, wherein the concentration of Lvp is at most 50% of St.

[0341] 49. The method of any one of claims 30 to 38, wherein the concentration of Lvp is at most 45% of St.

[0342] 50. The method of any one of claims 30 to 37, wherein the concentration of Lvp is at most 40% of St.

[0343] 51. The method of any one of claims 30 to 36, wherein the concentration of Lvp is at most 35% of St.

[0344] 52. The method of any one of claims 29 to 31, wherein the concentration of Hvp is at most 90% of St.

[0345] 53. The method of any one of claims 29 to 32, wherein the concentration of Hvp is at most 85% of St.

[0346] 54. The method of any one of claims 29 to 33, wherein the concentration of Hvp is at most 80% of St.

[0347] 55. The method of any one of claims 29 to 34, wherein the concentration of Hvp is at most 70% of St.

[0348] 56. The method of any one of claims 29 to 37, wherein the concentration of Hvp is at most 60% of St.

[0349] 57. The method of any one of claims 29 to 39, wherein the concentration of Hvp is at most 50% of St.

[0350] 58. The method of any one of claims 29 to 40, wherein the concentration of Hvp is at most 40% of St.

[0351] 59. The method of any one of claims 29 to 41, wherein the concentration of Hvp is at most 30% of St.

[0352] 60. The method of any one of claims 29 to 59, wherein the normalized evaporation rate of Lvp, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, is at most 0.4.

[0353] 61. The method of claim 60, wherein the normalized evaporation rate of Lvp is at most 0.3.

[0354] 62. The method of claim 60, wherein the normalized evaporation rate of Lvp is at most 0.2.

[0355] 63. The method of claim 60, wherein the normalized evaporation rate of Lvp is at most 0.1.

[0356] 64. The method of claim 60, wherein the normalized evaporation rate of Lvp is at most 0.05.

[0357] 65. The method of claim 60, wherein the normalized evaporation rate of Lvp is at most 0.02.

[0358] 66. The method of any one of claims 60 to 65, wherein the normalized evaporation rate of Lvp is at least 0.001.

[0359] 67. The method of claim 66, wherein the normalized evaporation rate of Lvp is at least 0.002.

[0360] 68. The method of claim 66, wherein the normalized evaporation rate of Lvp is at least 0.004.

[0361] 69. The method of claim 66, wherein the normalized evaporation rate of Lvp is at least 0.007.

[0362] 70. The method of any one of claims 29 to 69, wherein the normalized evaporation rate of Hvp, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, is at least 0.7.

[0363] 71. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 0.8.

[0364] 72. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 1.0.

[0365] 73. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 1.2.

[0366] 74. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 1.5.

[0367] 75. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 2.0.

[0368] 76. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 2.6.

[0369] 77. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 3.2.

[0370] 78. The method of claim 70, wherein the normalized evaporation rate of Hvp is at least 3.8.

[0371] 79. The method of any one of claims 70 to 78, wherein the normalized evaporation rate of Hvp is at most 11.

[0372] 80. The method of claim 79, wherein the normalized evaporation rate of Hvp is at most 9.5.

[0373] 81. The method of claim 79, wherein the normalized evaporation rate of Hvp is at most 8.

[0374] 82. The method of claim 79, wherein the normalized evaporation rate of Hvp is at most 7.

[0375] 83. The method of claim 79, wherein the normalized evaporation rate of Hvp is at most 6.5.

[0376] 84. The method of any of the preceding claims, wherein the dried transparent layer is a dried hard coating layer.

[0377] 85. The method of any of the preceding claims, wherein at least one of the thickness Twl of the wet layer and the average thickness Ta-wl is at most 90 micrometers (μm).

[0378] 86. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 70 μm.

[0379] 87. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 60 μm.

[0380] 88. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 50 μm.

[0381] 89. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 40 μm.

[0382] 90. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 30 μ.

[0383] 91. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 20 μm.

[0384] 92. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 15 μm.

[0385] 93. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 12 μm.

[0386] 94. The method of claim 85, wherein at least one of Twl and Ta-wl is at most 10 μm.

[0387] 95. The method of any one of claims 85 to 94, wherein the viscosity of the liquid film-forming formulation at 25°C is at most 55 cP.

[0388] 96. The method of claim 95, wherein the viscosity at 25°C is at most 45 cP.

[0389] 97. The method of claim 95, wherein the viscosity at 25°C is at most 35 cP.

[0390] 98. The method of claim 95, wherein the viscosity at 25°C is at most 25 cP.

[0391] 99. The method of claim 95, wherein the viscosity at 25°C is at most 20 cP.

[0392] 100. The method of claim 95, wherein the viscosity at 25°C is at most 15 cP.

[0393] 101. The method of claim 95, wherein the viscosity at 25°C is at most 12 cP.

[0394] 102. The method of claim 95, wherein the viscosity at 25°C is at most 10 cP.

[0395] 103. The method of claim 95, wherein the viscosity at 25°C is at most 8 cP.

[0396] 104. The method of any one of claims 95 to 103, wherein the viscosity of the liquid film-forming formulation at 25°C is at least 1.5 cP.

[0397] 105. The method of claim 104, wherein the viscosity at 25°C is at least 2.5 cP.

[0398] 106. The method of claim 104, wherein the viscosity at 25°C is at least 4 cP.

[0399] 107. The method of claim 104, wherein the viscosity at 25°C is at least 6 cP.

[0400] 108. The method as described in any of the foregoing embodiments, wherein the base arc of the optical substrate is at least 2.

[0401] 109. The method as described in embodiment 108, wherein the base arc is at least 3.

[0402] 110. The method as described in embodiment 108, wherein the base arc is at least 4.

[0403] 111. The method as described in embodiment 108, wherein the base arc is at least 5.

[0404] 112. The method as described in embodiment 108, wherein the base arc is at least 6.

[0405] 113. The method as described in embodiment 108, wherein the base arc is at least 8.

[0406] 114. The method as described in any of the foregoing embodiments, wherein the base arc of the optical substrate is at most 14.

[0407] 115. The method as described in embodiment 114, wherein the base arc is at most 12.

[0408] 116. The method as described in embodiment 114, wherein the base arc is at most 10.

[0409] 117. The method as described in any of the preceding embodiments, wherein for any point on the target surface, (i) the acute angle formed between the plane tangent to the target surface at the given point and (ii) the horizontal plane is angle (α), and wherein the maximum α on the target surface is α0. max And where α max The angle should be at least 5°.

[0410] 118. The method as described in embodiment 117, wherein α max The temperature should be at least 7°.

[0411] 119. The method as described in embodiment 117, wherein α max It should be at least 10°.

[0412] 120. The method as described in embodiment 117, wherein α max It should be at least 13°.

[0413] 121. The method as described in embodiment 117, wherein α max It should be at least 16°.

[0414] 122. The method as described in embodiment 117, wherein α max It should be at least 19°.

[0415] 123. The method as described in embodiment 117, wherein α max It should be at least 23°.

[0416] 124. The method as described in embodiment 117, wherein α max It should be at least 26°.

[0417] 125. The method as described in embodiment 117, wherein α max It is at least 31°, at least 34°, or at least 40°.

[0418] 126. The method as described in any one of embodiments 117 to 125, wherein α maxThe maximum angle is 50°.

[0419] 127. The method as described in embodiment 126, wherein α max The maximum is 42°.

[0420] 128. The method as described in embodiment 126, wherein α max The maximum is 37°.

[0421] Optical construction implementation scheme 1. An optical construction as described herein.

[0422] 2. An optical construct comprising any structural features disclosed in the method embodiments provided above.

[0423] 3. An optical configuration comprising any structural feature disclosed in system embodiments 1 to 70.

[0424] 4. The optical structure as described in any one of embodiments 1 to 3, wherein the optical structure is or includes spectacle lenses.

[0425] 5. Eyeglasses, the eyeglasses comprising an eyeglass frame and at least one eyeglass lens according to embodiment 4.

[0426] System Implementation Plan 1. A coating system, the coating system comprising: (a) An ink formulation application station, the ink formulation application station comprising a microvalve device configured to apply droplets of ink formulation to a target surface of an optical substrate to form a wet layer on the target surface; and (b) A drying and / or curing station configured to dry and / or cure a wet ink layer to produce a cured coating on a target surface.

[0427] 2. The system as described in embodiment 1, wherein the system further comprises: (c) An optical substrate transfer apparatus configured to transfer an optical substrate having a wet layer on a target surface from an ink formulation application station to a drying and / or curing station.

[0428] 3. The system as described in embodiment 1 or 2, wherein the optical substrate transfer device includes at least one of the following: a robotic arm, grippers, a conveyor belt, and a lift for raising or lowering the height of the wet layer on the optical substrate and its target surface.

[0429] 4. The system as described in any of the foregoing embodiments, the system further comprising a controller programmed or programmable to adjust the optical substrate transfer device such that the transfer of the optical substrate depends on the detection at the ink formulation application station that a wet ink layer has been formed on the target surface of the optical substrate.

[0430] 5. The system as described in any of the foregoing embodiments, wherein the drying and / or curing station includes at least one of a heating lamp, an oven, and a UV curing mechanism.

[0431] 6. The system as described in any of the foregoing embodiments, wherein the drying and / or curing station comprises an oven: (i) the oven is open when an optical substrate having a wet ink layer on a target surface is transferred therein, and (ii) the oven is closed after the optical substrate has been transferred therein, and remains closed during drying and / or curing.

[0432] 7. The system as described in any of the foregoing embodiments, the system further comprising a primer application station configured to apply droplets of primer formulation to the target surface prior to applying ink formulation microvalves to the target surface.

[0433] 8. The system as described in embodiment 7, wherein the primer application station includes a microvalve device for applying droplets of primer formulation.

[0434] 9. The system as described in any of the foregoing embodiments, the system further comprising at least one of: (i) a processing station for increasing the surface energy of the target surface before applying a primer or ink formulation to the target surface; and (ii) a cleaning station for subjecting the target surface to a cleaning process before applying the primer or ink formulation to the target surface.

[0435] 10. The system of embodiment 9, further comprising a surface energy treatment station, the surface energy treatment station comprising at least one of a corona treatment device and a plasma treatment device.

[0436] 11. The system as described in any of the foregoing embodiments, wherein the ink formulation application station includes a reservoir of ink formulation and is configured to apply the ink formulation stored in the reservoir to a target surface of the optical substrate via a microvalve.

[0437] 12. The system as described in any of the foregoing embodiments, wherein the system is further configured to apply at least one of the coloring agent and the photochromic agent optionally via a microvalve to the target surface of the optical substrate prior to applying a wet layer of the ink formulation to the target surface.

[0438] 13. The system as described in any of the foregoing embodiments, wherein the system does not include dip coating equipment.

[0439] 14. The system as described in any of the foregoing embodiments, wherein the system does not contain a spin coating device.

[0440] 15. The system as described in any of the foregoing embodiments, the system comprising a controller configured or programmed to control droplets of ink formulation onto a target surface via microvalves.

[0441] 16. The system as described in any of the foregoing embodiments, wherein the target surface is curved.

[0442] 17. The system as described in any of the preceding embodiments, wherein the SAG number of the target surface is at least 0.5 mm.

[0443] 18. The system of any one of embodiments 15 to 17, wherein the controller is configured or programmed to control the microvalve such that the volume ratio of the formulation applied per unit area of ​​the two-dimensional projection of each target surface is constant.

[0444] 19. The system of any one of embodiments 15 to 17, wherein the controller is configured or programmed to control the microvalve such that, in any subdivision region of the projection having an area of ​​5% or more of the area of ​​the two-dimensional projection, the volume of formulation applied per unit area of ​​the two-dimensional projection of the target surface is within ±10%, ±5%, ±2%, or ±1% of the average of the ratios of all the two-dimensional projections.

[0445] 20. The system of any one of embodiments 15 to 19, wherein the controller is configured or programmed to generate a two-dimensional projection of the target surface in front of the microvalve.

[0446] 21. The system of any one of embodiments 15 to 20, wherein the controller is configured or programmed to calculate or select the formulation volume ratio per unit area of ​​a two-dimensional projected surface for each target surface prior to the microvalve.

[0447] 22. The system of embodiment 21, wherein the controller is configured or programmed to control the microvalve such that, in any subdivision region of the projection which is 5% or more of the area of ​​the two-dimensional projection, the volume of the formulation applied per unit area of ​​the two-dimensional projection of the target surface is within ±10%, ±5%, ±2%, or ±1% of the calculated or selected ratio.

[0448] 23. The system as described in any of the foregoing embodiments, wherein the microvalve is characterized in that the average formulation volume ratio applied per unit area of ​​the target surface in the edge portion located between 90% and 100% of the distance from the centroid of the target surface to its perimeter is between 0.60 and 0.96 times the maximum formulation volume ratio applied per unit area of ​​the target surface.

[0449] 24. The system of any one of embodiments 1 to 22, wherein the microvalve is characterized in that the average formulation volume ratio applied per unit area of ​​the target surface in the edge portion located between 90% and 100% of the distance from the centroid of the target surface to its perimeter is between 0.60 and 0.96 times the average formulation volume ratio applied per unit area in the central region located between 0% and 10% of the distance from the centroid of the target surface to its perimeter.

[0450] 25. The system as described in any one of embodiments 23 or 24, wherein the SAG number of the target surface is at least 1 mm and at most 15 mm.

[0451] 26. The system as described in embodiment 25, wherein the SAG number is at least 2 mm.

[0452] 27. The system as described in embodiment 25, wherein the SAG number is at least 3.5 mm.

[0453] 28. The system as described in embodiment 25, wherein the SAG number is at least 4.5 mm.

[0454] 29. The system as described in embodiment 25, wherein the SAG number is at least 5 mm.

[0455] 30. The system as described in embodiment 25, wherein the SAG number is at least 6 mm.

[0456] 31. The system as described in embodiment 25, wherein the SAG number is at least 7 mm.

[0457] 32. The system as described in embodiment 25, wherein the SAG number is at least 9 mm.

[0458] 33. The system as described in any one of embodiments 25 to 32, wherein the SAG number is at most 13.5 mm.

[0459] 34. The system as described in embodiment 33, wherein the number of SAGs is at most 12 mm.

[0460] 35. The system as described in embodiment 33, wherein the number of SAGs is at most 10.5 mm.

[0461] 36. The system as described in any one of embodiments 25 to 31, wherein the SAG number is at most 8 mm.

[0462] 37. The system as described in any one of embodiments 23 to 36, wherein the ratio of the edge portion is between 0.6 and 0.9 times the maximum ratio.

[0463] 38. The system as described in any one of embodiments 23 to 36, wherein the ratio of the edge portion is between 0.6 times and 0.85 times the maximum ratio.

[0464] 39. The system as described in any one of embodiments 23 to 36, wherein the ratio of the edge portion is between 0.8 and 0.96 times that of the central region.

[0465] 40. The system as described in any one of embodiments 23 to 36, wherein the ratio of the edge portion is between 0.9 and 0.96 times the ratio of the central region.

[0466] 41. The system of any one of embodiments 13 to 22, wherein the SAG number of the target surface is between 9 mm and 13 mm, and the microvalve is characterized in that the volume ratio of the formulation applied per unit area of ​​the target surface near the edge located between 90% and 100% of the distance from the centroid of the target surface to its perimeter is between 0.62 and 0.85 times the maximum volume ratio of the formulation applied per unit area of ​​the target surface.

[0467] 42. The system of any one of embodiments 13 to 22, wherein the SAG number of the target surface is between 7 mm and 9 mm, and the microvalve is characterized in that the volume ratio of the formulation applied per unit area of ​​the target surface near the edge located between 90% and 100% of the distance from the centroid of the target surface to its perimeter is between 0.72 and 0.92 times the maximum volume ratio of the formulation applied per unit area of ​​the target surface.

[0468] 43. The system of any one of embodiments 13 to 22, wherein the SAG number of the target surface is between 5 mm and 7 mm, and the microvalve is characterized in that the volume ratio of the formulation applied per unit area of ​​the target surface near the edge located between 90% and 100% of the distance from the centroid of the target surface to its perimeter is between 0.82 and 0.96 times the maximum volume ratio of the formulation applied per unit area of ​​the target surface.

[0469] 44. The system of any one of embodiments 13 to 22, wherein the microvalve causes the average formulation volume ratio applied per unit area of ​​the target surface at a given point on the target surface to be equal to a reduction factor multiplied by the maximum formulation volume ratio applied per unit area at any point on the target surface, the reduction factor being equal to the cosine of the acute angle formed between (i) the plane tangent to the target surface at the given point and (ii) the horizontal plane.

[0470] 45. The system as described in embodiment 44, wherein the reduction factor at any point on the perimeter of the surface is between 0.63 and 0.96.

[0471] 46. ​​The system of any one of embodiments 13 to 45, wherein for any point on the target surface, (i) the maximum acute angle formed between the plane tangent to the target surface at the given point and (ii) the horizontal plane is between 10° and 40°.

[0472] 47. The system of any one of embodiments 13 to 45, wherein for any point on the target surface, (i) the maximum acute angle formed between the plane tangent to the target surface at the given point and (ii) the horizontal plane is between 5° and 50°.

[0473] 48. The system of any one of embodiments 13 to 45, wherein for any point on the target surface, (i) the maximum acute angle formed between the plane tangent to the target surface at the given point and (ii) the horizontal plane is between 15° and 40°.

[0474] 49. The system of any one of embodiments 13 to 45, wherein for any point on the target surface, (i) the maximum acute angle formed between the plane tangent to the target surface at the given point and (ii) the horizontal plane is between 5° and 20°.

[0475] 50. The system as described in any of the foregoing embodiments, wherein the system is configured to be in any relative perpendicularity between the microvalve device and the target surface. z Microvalves are operated while the shaft is in motion.

[0476] 51. The system as described in any of the foregoing embodiments, wherein the system is not configured to cause a relative perpendicularity between the microvalve device and the target surface. z The micro-valve operates simultaneously with the shaft movement.

[0477] 52. The system as described in any of the foregoing embodiments, wherein the system is not configured to cause a relative perpendicularity between the microvalve device and the target surface. z-axis The micro-valve operates simultaneously with the movement.

[0478] 53. The system as described in any of the foregoing embodiments, wherein during the formation of the wet layer, the system is configured to maintain a horizontal distance between the non-microvalve device and the target surface. xy Microvalves are operated under relative rotational motion on a plane.

[0479] 54. The system as described in any of the foregoing embodiments, wherein during the formation of the wet layer, the system is not configured to cause horizontal [conditioning] between the microvalve device and the target surface. xy The micro-valve operates simultaneously with relative rotational motion on a plane.

[0480] 55. The system of embodiment 54, wherein the ink formulation application station includes a non-rotating optical substrate support.

[0481] 56. The system as described in any of the preceding embodiments, wherein the microvalve device is piezoelectrically actuated.

[0482] 57. The system as described in any one of embodiments 1 to 55, wherein the microvalve device is electromagnetically actuated.

[0483] 58. The method as described in any of the preceding embodiments, wherein for any point on the target surface, (i) the acute angle formed between the plane tangent to the given point and the target surface and (ii) the horizontal plane is angle (α), wherein the maximum α on the target surface is α0. max And where α max The angle should be at least 5°.

[0484] 59. The system as described in embodiment 58, wherein α max It should be at least 10°.

[0485] 60. The system as described in embodiment 58, wherein α max The angle should be at least 15°.

[0486] 61. The system as described in embodiment 58, wherein α max It should be at least 20°.

[0487] 62. The system as described in embodiment 58, wherein α max The angle should be at least 25°.

[0488] 63. The system as described in embodiment 58, wherein α max It should be at least 30°.

[0489] 64. The system as claimed in any one of claims 2 to 4, wherein α max The maximum angle is 50°.

[0490] 65. The system as described in any one of embodiments 58 to 64, wherein αmax Within the range of 30-40°, and where R D1 It is at most 0.90, or in the range of 0.62 to 0.90.

[0491] 66. The system as described in any one of embodiments 58 to 64, wherein α max Within the range of 19-27°, and where R D1 It is at most 0.93, or in the range of 0.85 to 0.93.

[0492] 67. The system as described in any one of embodiments 58 to 64, wherein α max Within the range of 15-20°, and where R D1 It is at most 0.97, or in the range of 0.90 to 0.97.

[0493] 68. The system as described in any of the foregoing embodiments, wherein the system includes any one or more features provided in the formulation embodiments.

[0494] 69. The system as described in any of the foregoing embodiments, wherein the system includes any one or more features provided in the above method embodiments.

[0495] 70. The system as described in any of the foregoing embodiments, wherein the system includes any one or more features as described herein.

[0496] It will be understood that certain features of the invention described in the context of individual embodiments for clarity may also be provided in combination in a single embodiment. Conversely, various features of the invention described in the context of individual embodiments for brevity may also be provided separately or in any suitable sub-combination.

[0497] Although the invention has been described in conjunction with specific embodiments thereof, it will be apparent to those skilled in the art that many alternatives, modifications, and variations will be readily apparent. Therefore, it is intended to cover all such alternatives, modifications, and variations falling within the spirit and broad scope of the appended claims. All publications, patents, and patent applications referenced in this specification, including U.S. Patent Nos. 4,547,397, 5,385,955, 6,538,092, 10,310,151, 4,478,876, and 5,409,965, are incorporated herein by reference in their entirety, as if each individual publication, patent, or patent application were specifically and individually indicated to be incorporated herein by reference. Furthermore, any reference or designation of any reference in this application should not be construed as an admission that such reference is available as prior art to the invention.

Claims

1. A method for producing an optical structure on an optical substrate, the method comprising: (a) A droplet microvalve of a hard coating formulation is applied to a curved polymer optical surface of the optical substrate to form a wet hard coating; (b) Curing the wet-hardened coating to produce a dry transparent layer on the optical surface; The SAG number of the surface is at least 2 mm and at most 12 mm; The viscosity of the hard coating formulation at 25°C is at most 15 cP; Furthermore, at least one of the average diameter and characteristic diameter (D-droplet) of the microvalve droplet is in the range of 0.2 to 0.55 mm.

2. The method of claim 1, wherein the D droplet is at most 0.45 mm.

3. The method of claim 1, wherein the D droplet is at most 0.4 mm.

4. The method of claim 1, wherein the D droplet is at most 0.38 mm.

5. The method of claim 1, wherein the D droplet is at most 0.36 mm.

6. The method of any one of claims 1 to 5, wherein the D droplet is at least 0.22 mm.

7. The method of claim 6, wherein the D droplet is at least 0.24 mm.

8. The method of any one of claims 2 to 7, wherein the SAG number is at least 5 mm.

9. The method according to any one of claims 2 to 8, wherein the viscosity at 25°C is in the range of 4 to 12 cP.

10. The method of any one of claims 2 to 9, wherein the total solvent content of the liquid film-forming formulation is St in weight percent, wherein the liquid film-forming hard coating formulation contains a high vapor pressure solvent Hvp and a low vapor pressure solvent Lvp, wherein the normalized evaporation rate (EVn) of Lvp is at least 0.001 and at most 0.1, expressed on a normalized 25°C evaporation rate scale of n-butyl acetate, and the EVn of Hvp is at least 0.7 and at most 6.

5.

11. The method of claim 10, wherein the concentration of Lvp is at least 20% of St, and the concentration of Hvp is at most 60% of St.

12. The method of claim 10, wherein the EVn of Hvp is at least 1.

5.

13. The method of any one of claims 2 to 12, wherein the hard coating formulation is a colored hard coating formulation.

14. The method of any one of claims 2 to 13, wherein the hard coating formulation is applied directly to the surface of the optical substrate.

15. The method of any one of claims 2 to 13, wherein a primer is applied to and cured on the surface of the optical substrate prior to step (a).

16. The method of claim 15, wherein the primer is fully cured prior to step (a).

17. The method of claim 15 or claim 16, wherein the cured or fully cured primer has a non-sticky upper surface.

18. The method of any one of claims 2 to 17, wherein the wet hard coating is formed as a continuous layer on the surface of the optical substrate.

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