Method and system for producing a colored optical coating

Abstract

Methods and systems for producing optical constructions on optical substrates, one such method comprising: (a) microvalving droplets of a dye-containing liquid formulation onto an optical surface of the optical substrate to form a wet continuous layer; and (b) treating the wet layer to produce a continuous, dry, dye-containing layer on the optical surface, wherein the optical surface is a curved surface, and wherein the optical surface is a polymeric 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 optical and ophthalmic devices and articles having colored coatings, and to systems and methods for applying and forming such coatings on these devices and articles.

[0003] The commercialization and high-throughput production of eyeglass coatings typically employs various analog coating processes such as dip coating and spin coating.

[0004] Ultrathin anti-reflective coatings with a thickness of 200 to 300 nanometers can be applied layer by layer by vacuum deposition.

[0005] In various known processes, optical barriers can be significantly aggravated when the target surface is a curved optical surface, such as spectacle lenses, and especially for spectacle lenses with high SAG numbers or base curves.

[0006] The inventors recognize the need to improve optical and ophthalmic devices and articles with colored coatings, as well as the need for systems and methods for producing such devices and articles. Summary of the Invention

[0007] According to some teachings of the present invention, a method for producing an optical structure on an optical substrate is provided, the method comprising: (a) microvacuuming droplets containing an ink formulation of at least one dissolving dye onto an optical surface of the optical substrate to form a wet layer; and (b) treating the wet layer to produce a dry dye-containing layer on the optical surface.

[0008] Other aspects of the invention are disclosed below. Attached Figure Description

[0009] 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.

[0010] 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 colored optical layer or coating according to an aspect of the present invention is provided; Figure 3 for Figure 2 The schematic diagram provides optional steps, wherein pretreatment may include applying a liquid primer formulation to the exposed surface of an ophthalmic substrate, and subsequent drying / curing; Figure 4 It is a schematic cross-sectional view of a multilayer ophthalmic structure, which includes an ophthalmic substrate having a colored ophthalmic structure fixedly attached to a wide surface of the 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

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] Adhesion to optical or ophthalmic substrates, as well as the resistance to peeling or cracking of one or more coatings, can also be crucial for obtaining viable coated lenses, such as coated ophthalmic lenses.

[0017] From a throughput perspective, it is advantageous to apply very large ink droplets (e.g., nanoliters rather than picoliters) to such curved, smooth eyeglass surfaces.

[0018] However, the inventors have discovered that even with precise digital applications, such large ink droplets can adversely reduce image resolution.

[0019] Furthermore, ink droplets tend to slide easily on such curved, smooth eyeglass surfaces, especially with low-viscosity ink droplets. This uncontrolled flow can make the final position of the droplet completely uncertain. This problem is exacerbated for large nanoliter (e.g., 10 nanoliters in volume) droplets: compared to picolinate droplets, which have a volume of about 1 / 1000th that of nanoliter droplets, the volume-to-surface-area ratio of nanoliter ink droplets is significantly higher, as is the volume-to-contact-area ratio of the deposited droplet. Therefore, the inventors have found that various surface-based fixation methods (e.g., adhesive underlayers) can be ineffective, making it possible for the deposition of such nanoliter droplets to adversely produce discontinuous or at least non-uniform wet layers, resulting in bald spots, haze, uneven thickness, uneven optical density, and other optical obstructions in the finished product.

[0020] Although spin coating, rotation, and other methods were considered in an attempt to produce a smooth and uniform wet layer, the inventors found that such methods could not meet various technical challenges and could have their own significant technical drawbacks, especially within the framework of industrial environments.

[0021] Therefore, without employing these methods, it is highly desirable to produce a thin, continuous, and smooth wet layer of ophthalmic quality. For colored layers and coatings, it is further desirable that their optical density be uniform, at least discernible to the naked eye.

[0022] It will be understood that for highly curved lens surfaces (e.g., base curve 4, base curve 6 or higher), uncontrolled flow problems can become even more severe, especially for large-diameter lenses.

[0023] Furthermore, the inventors have discovered that when producing ultrathin optical coatings (e.g., dry film thickness of up to 2 μm, up to 1.6 μm, or up to 1.2 μm), the likelihood of optical obstructions in the finished product may be more pronounced.

[0024] Unwilling to be limited by theory, the inventors believe that by achieving "controlled flow" conditions for ink on optical surfaces, microvacuuming of continuous, relatively smooth, and uniform dye-containing ink layers on optical surfaces (and more specifically, curved optical surfaces such as spectacle lenses) is possible. When ink droplets are microvacuumed on an optical surface without fixation (e.g., when the solvent is primarily a low-evaporation-rate solvent), the applied dye-containing ink may flow unfavorably in a substantially uncontrolled manner, potentially leading to at least one of the following: overflow, bald spots, coffee ring effect, uneven layer thickness, and uneven color intensity within the layer. Furthermore, overflow can be significantly exacerbated by covering the entire surface of the substrate with ink droplets. However, when ink droplets are rapidly and extensively fixed on an optical surface (e.g., when the solvent is primarily a very high-evaporation-rate solvent), the dye-containing layer may be discontinuous, or even if continuous, may lack the necessary smoothness and uniformity required for optical and ophthalmic layers and coatings.

[0025] The inventors have discovered that by balancing a solvent system with a specific mixture of solvents with relatively low evaporation rates and high evaporation rates, a certain degree of controlled flow can be achieved, and surprisingly, this can produce layers with the necessary smoothness and uniformity required for optical and ophthalmic layers or coatings, such as coloring layers or coatings.

[0026] The following sections provide methods and systems for achieving such controlled flows.

[0027] like Figure 1 As illustrated, the method of the present invention includes applying droplets of a dye-containing liquid formulation via a microvalve (i.e., spraying via a microvalve) onto the optical surface of an optical substrate to form a wet layer (step 102).

[0028] Various microvalve technologies (all of which utilize microvalve technology) can be used to microvalve ink formulations onto optical / ophthalmic substrates.

[0029] Microvalves can be components within a microvalves system, and several microvalves can be used (preferably in parallel) to improve throughput.

[0030] Typically, the microvalve of a photochromic agent operates according to a predetermined pattern (such as a predetermined digital pattern).

[0031] 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.

[0032] This type of exemplary microvalve was manufactured by Fritz Gyger AG and the Lee company.

[0033] In some implementations, the microvalve is electro-pneumatically actuated. An exemplary microvalve of this type is the Liquidyn® P-Jet series manufactured by Nordson.

[0034] In some implementations, the optical surface is a curved optical surface, such as a curved lens surface.

[0035] In some implementations, the optical surface is a polymer surface.

[0036] In some implementations, the optical substrate is an ophthalmic substrate, and the optical surface is an ophthalmic surface.

[0037] In some implementations, the ophthalmic substrate is a prescription lens, such as a spectacle lens.

[0038] 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.

[0039] 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 enables the human eye to effectively observe objects through it. While coated lenses are a typical example of ophthalmic devices, those skilled in the art will recognize other applications, including, for example, helmets with transparent goggles.

[0040] An ophthalmic construct may consist of or include ophthalmic components of such ophthalmic devices or systems.

[0041] Regarding the wet ink layer, at least one of the thickness TH, characteristic thickness THc, and average thickness THav (and typically any two or all three of TH, THc, and THav) is at most 100 micrometers (μm) or at most 80 μm, and more typically, at most 70 μm, at most 60 μm, or at most 50 μm.

[0042] Typically, at least one of TH, THc, and THav (and typically any two or all three of TH, THc, and THav) is at least 10 μm, at least 14 μm, at least 18 μm, at least 25 μm, at least 30 μm, at least 40 μm, or at least 45 μm.

[0043] The method may further include treating the wet layer to produce a dried layer containing a colorant or dye on the optical surface (step 104). The treatment includes drying and / or curing the wet layer. The nature of the formulation may largely determine the preferred curing method.

[0044] Therefore, in some embodiments, drying / curing (film formation) is effective essentially or entirely by drying (solvent evaporation), for example, when the polymer is dissolved (e.g., vinyl ester resins or alkyd resins in organic solvents) or dispersed (e.g., aqueous dispersions such as PUDs) or present in emulsion form (e.g., styrene-acrylic emulsion polymers). Such drying is typically carried out at high temperatures (“thermal drying”).

[0045] In some implementations, drying / curing is carried out by chemical drying / curing (e.g., polymerization from prepolymers (monomers and oligomers); polymer crosslinking, oxidative chemical curing, e.g., using ambient oxygen; cationic or free radical curing, e.g., using UV radiation; oxidative chemical curing, e.g., using ambient oxygen; hygroscopic chemical curing, e.g., using ambient humidity).

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] Further methods for producing high-quality optical stacks will be explained in the following description.

[0051] As used herein and in the following claims section, the term "SAGITTA" or "SAG" refers to the convex or concave curvature of an optical substrate, representing the physical distance between the vertex (the highest point of the convex curvature) of the surface of the optical substrate and the center point of a line drawn perpendicular to the 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.

[0052] In some embodiments, the SAG number of the optical substrate is at least 0.5 mm, at least 1 mm, at least 2 mm, at least 3.5 mm, at least 5 mm, or at least 6 mm.

[0053] Typically, the SAG number of optical substrates is at most 15mm, at most 13.5mm, at most 12mm, or at most 10.5mm.

[0054] The base arc of the optical substrate can be at least 2, at least 3, at least 4, at least 5, at least 6, or at least 8.

[0055] The base arc can be up to 14, and more typically, up to 12 or 10. At higher base arcs and SAG numbers, ink flow on the optical surface can be severely restricted, thereby compromising the optical quality of the layer or coating.

[0056] As used in this article, the term "base arc" refers to the theoretical base arc or the "true curve".

[0057] Similarly, uncontrolled flow phenomena may also be related to the peripheral tangential angle α of the lens (discussed in further detail below). The method of the present invention is generally applicable to controlling flow on lenses with peripheral tangential angles of up to 37°, up to 42°, or even up to 50°.

[0058] In some embodiments, the ink formulation (colorant) may include a resin, a dye, and a solvent system, said solvent system including at least one of a very low vapor pressure solvent (LLevap), a low vapor pressure solvent (Levap), a medium vapor pressure solvent (Mevap), a high vapor pressure solvent (Hevap), and a very high vapor pressure solvent (HHevap), wherein the resin and the colorant dye are dissolved in the solvent system.

[0059] In some embodiments, the ink formulation may contain or further contain at least one photochromic dye dissolved in a solvent system.

[0060] These types of ink formulations may contain softeners for softening resins. Typically, the softener forms a single liquid phase with the solvent system, resin, any colorant dyes, and photochromic dyes. These ink formulations are generally solvent-based.

[0061] Softeners include liquid softeners. Typically, liquid softeners are, comprise, or consist essentially of non-volatile liquid softeners.

[0062] In some embodiments, the softener further includes solid softeners such as solid polymer softeners.

[0063] In some implementations, the ink formulation is an ophthalmic formulation.

[0064] In some implementations, the ink formulation is suitable for forming an ophthalmic film on an ophthalmic substrate.

[0065] In some implementations, the resin is an ophthalmic film-forming resin.

[0066] In some implementations, the non-volatile content of the ink formulation is in the range of 2.5% to 15%.

[0067] In some embodiments, the ink formulation may include a soluble dye and a solvent system, said solvent system comprising an extremely low vapor pressure solvent (LLevap) and at least one higher vapor pressure solvent. The dye is typically highly soluble in the solvent system.

[0068] In some embodiments, the ink formulation is an aqueous ink formulation, and the solvent system is an aqueous solvent system.

[0069] In some implementations, the ink formulation is a solvent-based ink formulation, wherein the solvent system is an organic or solvent-based solvent system.

[0070] The aqueous solvent system contains water, which is a low-vapor-pressure (Levap) solvent. In some embodiments, the aqueous solvent system may advantageously additionally contain at least one of low-vapor-pressure (Levap) and / or very low-vapor-pressure (LLevap) solvents, said additional one or more solvents forming a single phase with water in the aqueous solvent system.

[0071] In some embodiments, the aqueous solvent system may include one or more solvents with higher vapor pressures other than water (Mevap and / or Hevap and / or HHevap), wherein the additional solvents form a single phase with water in the aqueous solvent system.

[0072] In some embodiments, the aqueous solvent system may include one or more higher vapor pressure solvents (Mevap and / or Hevap and / or HHevap) other than water and at least one of low (Levap) and / or very low vapor pressure (LLevap) solvents. As described above, one or more higher vapor pressure solvents form a single phase in the aqueous solvent system with water and at least one of low (Levap) solvents and / or very low vapor pressure (LLevap) solvents.

[0073] In some implementations, the first solvent weight ratio of Hevap, HHevap, and LLEvap in the ink formulation to the total solvent Ts is... (Hevap + HHevap + LLevap) / Ts It should be at least 0.6, 0.65, or 0.7.

[0074] In some implementations, LLevap is combined with Hevap and HHevap in a total T H+HH Relative solvent weight ratio (RWSR) LLevap / T H+HH The ratio should be at least 0.15:1.

[0075] In some embodiments, the ink formulation is a solvent-based or organic ink formulation, wherein the solvent system is an organic solvent system. The organic solvent system may advantageously contain low vapor pressure (Levap) and / or very low vapor pressure (LLevap) solvents, which together form a single organic phase.

[0076] In some embodiments, the organic solvent system may further include one or more higher vapor pressure solvents (Mevap and / or Hevap and / or HHevap), wherein the additional one or more higher vapor pressure solvents form a single phase with one or more Levap and LLevap solvents within the organic solvent system.

[0077] As used herein and in the following claims section, the term "at most high vapor pressure (Hevap) solvent" means excluding solvents with a faster evaporation rate than Hevap, in this case HHevap.

[0078] Similarly, the term "at most medium vapor pressure (Mevap) solvent" means excluding solvents with a faster evaporation rate than Mevap, in this case HHevap and Hevap.

[0079] Similarly, the term "at least medium vapor pressure (Mevap) solvent" means excluding solvents with a slower evaporation rate than Mevap, in this case, LLEvap and Levap.

[0080] More specifically, volatile liquids are classified into the following five categories: LLevap < 0.1 (e.g., TPM, DPM, EB, NMP, DMSO, ethylene glycol monobutyl ether, DPM acetate).

[0081] 0.1 ≤Levap<0.5 (e.g., EEP, EP, PP, PMA, n-butyl propionate, n-butanol, amyl acetate, water).

[0082] 0.5 ≤Mevap<0.85 (e.g., PM, isobutanol).

[0083] 0.85 ≤ Hevap < 1.8 (e.g., xylene, n-butyl acetate, isobutyl acetate, methyl isobutyl ketone, isopropanol, ethanol).

[0084] 1.8 ≤HHevap (e.g., toluene, methanol, n-propyl acetate, isopropyl acetate, ethyl acetate, methyl propyl ketone, methyl ethyl ketone).

[0085] The vaporization or evaporation rate of the specified standard material n-butyl acetate is assigned as 1.0. Therefore, the terms "relative evaporation rate," etc., are used with reference to n-butyl acetate.

[0086] In some implementations, aqueous or solvent-based ink formulations may further include dissolved resins (polymers).

[0087] In other embodiments, the resin (polymer) may be dispersed within the aqueous ink formulation.

[0088] In other embodiments, the resin (polymer) may be dispersed within the aqueous ink formulation to form an emulsion.

[0089] Now for reference Figure 2 , Figure 2A schematic block diagram is provided of a process for processing the optical surface of an optical substrate (typically a lens blank such as a curved lens blank) according to an aspect of the invention to produce a dry hard coating. The lens blank provided to the process may or may not have a protective hard coating adhered to it.

[0090] Before applying the wet ink layer to the optical surface of the optical substrate, the optical surface may undergo an optional pretreatment stage 205.

[0091] In pretreatment stage 205, the lens blank / optical substrate may undergo surface preparation (optional step 206) prior to the application of the wet ink layer. Such surface preparation may include washing in water or an aqueous cleaning solution, optionally followed by drying (optional step 207).

[0092] In some implementations, the surface preparation of the lens surface includes etching.

[0093] In some implementations, the etching process includes laser etching.

[0094] In some implementations, the etching process includes chemical etching.

[0095] Before applying the photochromic ink formulation, the lens blank may undergo at least one surface treatment (optional step 208), such as energy treatment to increase the surface energy of the optical surface.

[0096] In some implementations, this energy processing includes corona treatment.

[0097] In some implementations, this energy processing includes plasma processing.

[0098] In some implementations, this energy processing includes electron beam processing.

[0099] In some implementations, this energy processing includes electromagnetic (e.g., photochemical) radiation processing.

[0100] In some implementations, this energy processing is a discharge process.

[0101] Figure 3 for Figure 2 The schematic block diagram provides optional steps in which surface treatment or pretreatment (e.g., optional step 208) includes applying a liquid primer formulation to the exposed (lens) surface of an ophthalmic substrate to form a wet primer layer or coating. The wet primer layer or coating is then dried or otherwise cured (e.g., in step 210) to obtain a dried primer layer or coating. Exemplary processes include oven drying, microwave drying, and IR drying.

[0102] The drying / curing of the wet primer layer formulation can be carried out by any conventional curing means used to produce a cured primer layer (as described above regarding step 104). With appropriate modifications The curing of the wet primer layer can proceed advantageously, thus achieving a "fully cured" primer layer.

[0103] Liquid primer formulations can be applied using a variety of conventional techniques (each with its own set of drawbacks), such as spin coating, slot coating, and dip coating.

[0104] In some implementations, and most commonly, a primer microvalves are applied to the exposed surface of an ophthalmic substrate, as will be described in more detail below.

[0105] In some implementations, the primer pretreatment is designed to promote wetting of the subsequently applied ink layer relative to the lens surface.

[0106] In some implementations, the primer pretreatment is designed to promote adhesion of this layer to the lens surface.

[0107] In some implementations, the primer is a polymer primer.

[0108] In some implementations, the polymer primer is in the form of an aqueous emulsion (e.g., an acrylic emulsion).

[0109] In some implementations, the polymer primer is in the form of an aqueous dispersion (e.g., a polyurethane dispersion).

[0110] In some embodiments, the polymer primer is or includes UV-curable materials such as UV-curable oligomers, epoxy acrylates, polyester acrylates, and polyurethane acrylates.

[0111] In some implementations, the polymer primer is in the form of a solution (e.g., a polyurethane resin solution).

[0112] In some of these embodiments, the thickness and / or average thickness of the wet primer layer is at least 0.5 μm, at least 0.8 μm, at least 1 μm, at least 1.5 μm, at least 2 μm, at least 3 μm, at least 5 μm, or at least 7 μm.

[0113] In some of these embodiments, the thickness and / or average thickness of the wet primer layer is at most 80 μm, at most 60 μm, at most 40 μm, and more typically, at most 25 μm, at most 20 μm, or at most 15 μm.

[0114] In some embodiments, the method includes, after step 210 and before the (colorant) dye formulation microvalve, performing such energy treatment (e.g., corona or plasma, or photochemical radiation) on the top / exposed surface of the fully cured primer layer.

[0115] In some implementations of these energy treatments, the energy treatment increases the surface energy of the target surface of the optical substrate by at least 2, 3, 5, 8, or 12 millinewtons per meter (mN / m).

[0116] In some of these implementations, energy treatment increases the surface energy of the target surface by up to 40, up to 30, up to 20, up to 17, or up to 14 mN / m.

[0117] Refer again Figure 2 Following an optional pretreatment stage 205, the method includes applying droplet microvalves (step 222) of a dye-containing ink formulation to an optionally pretreated lens blank / optical substrate. The dye or colorant is dissolved in the liquid phase.

[0118] In some implementations, this ink formulation can be directly microvaped onto the surface of the lens / lens blank / optical substrate.

[0119] In some implementations, this ink formulation can be microvalves placed on top of a primer layer, for example, a primer layer applied in optional surface treatment 208.

[0120] In some embodiments, the ink formulation contains at least one water-soluble dye or colorant.

[0121] In some implementations, the ink formulation does not contain photochromic pigments or colorant pigments.

[0122] In some embodiments, the ink formulation contains at least one polymer resin (e.g., as a film-forming agent and adhesive).

[0123] In some implementations, the polymer resin exists in the ink dispersion in the form of dispersed solid particles.

[0124] In some implementations, the polymer resin is dissolved in the ink formulation.

[0125] In some embodiments, the ink formulation containing dissolved polymer resin is an aqueous ink formulation.

[0126] In some implementations, the ink formulation containing dissolved polymer resin is an organic or "solvent-based" ink formulation.

[0127] The "solvent-based" ink formulations used in this article are the same as those used in the field of ink formulations. Typically, "solvent-based" ink formulations contain up to 2% water (by weight), and more typically, contain no or substantially no water.

[0128] In some implementations, the wet ink layer obtained in step 222 may be dried or cured (step 223) to produce a dried or cured ink layer.

[0129] The drying / curing of the ink layer can be carried out by any conventional curing means used to produce the cured layer (as described above regarding steps 104 and 210). With appropriate modifications The curing of the ink layer can proceed advantageously, thereby achieving a "fully cured" primer layer.

[0130] In some embodiments, the thickness or average thickness of the dye-containing layer after drying and complete curing is in the range of 0.6 to 25 μm or 1 to 20 μm, and more typically, in the range of 1.2 to 20 μm.

[0131] More typically, the thickness or average thickness is at least 1.5 μm, at least 2 μm, at least 2.5 μm, at least 3 μm, at least 4 μm, or at least 4.5 μm.

[0132] In some implementations, the thickness or average thickness is at most 15 μm, at most 12 μm, at most 10 μm, at most 8 μm, or at most 7 μm.

[0133] More typically, the thickness or average thickness is at most 6 μm, at most 5.5 μm, at most 5 μm, at most 4.5 μm, at most 4.0 μm, or at most 3.5 μm.

[0134] In some implementations, an additional ink layer may optionally be applied (step 224) and dried / cured (step 226) (as described above, e.g., regarding step 104, With appropriate modifications The additional ink formulation applied may be the same as the ink formulation applied in step 222.

[0135] In some implementations, the additional ink formulation is a second (i.e., different) water-based ink dispersion.

[0136] In some implementations, the additional ink formulation is a second (i.e., different) aqueous ink solution.

[0137] In some embodiments, the additional ink formulation contains at least one dissolved dye (e.g., a colorant).

[0138] In some implementations, the additional ink formulation is a solvent-based ink formulation (e.g., containing dissolved colorant and dissolved polymer (resin)).

[0139] In some implementations, the additional ink formulation contains at least one dissolved photochromic dye.

[0140] In some implementations, the photochromic ink formulation may include a resin, a photochromic dye, and a solvent system.

[0141] In some embodiments, the photochromic ink formulation may include a softener for softening the resin. Typically, the softener forms a single liquid phase with the solvent system, the resin, and the photochromic dye.

[0142] Softeners include liquid softeners. Typically, liquid softeners are, comprise, or consist essentially of non-volatile liquid softeners.

[0143] In some embodiments, the softener further includes solid softeners such as solid polymer softeners.

[0144] In some embodiments, the additional ink formulation contains at least one dissolved dye (e.g., a colorant).

[0145] In some implementations, the additional ink formulation is a solvent-based formulation.

[0146] The inventors have discovered that various hard coating formulations can dissolve or otherwise erode ink layers containing colorants, and more specifically, the dye-containing layers formed and cured in steps 224 and 226. However, the inventors have further discovered that such erosion can be suppressed or significantly mitigated by applying an outer coating on top of the ink layer containing this colorant (step 228) and drying / curing as needed (step 230).

[0147] Steps 228 and 230 can be repeated in series as needed to produce an additional outer coating.

[0148] In some embodiments, the method includes, after step 226 and before applying the outer coating formulation (step 228), applying an energy treatment (e.g., any of the energy treatments described above) to the top surface / exposed surface of the cured or fully cured coloring ink layer. With appropriate modifications This significantly improves the adhesion between the fully cured coloring ink layer and the outer coating. Typically, this step is not required in the method of this invention.

[0149] In some embodiments, the thickness or average thickness of the first outer coating layer, which serves as the wet layer, is in the range of 6 to 100 μm, 6 to 80 μm, 6 to 60 μm, or 6 to 50 μm.

[0150] In some of these embodiments, the thickness or average thickness of this layer is at least 8 μm, at least 12 μm, at least 20 μm, at least 30 μm, or at least 40 μm.

[0151] In some implementations, the thickness or average thickness of the first outer coating layer, which serves as the dry layer, is in the range of 3 to 15 μm.

[0152] In some of these embodiments, the dry thickness or average thickness is at least 4 μm, at least 5.5 μm, or at least 6.5 μm.

[0153] In some of these implementations, the dry thickness or average thickness is at most 13.5 μm, at most 12 μm, at most 11 μm, at most 10 μm, at most 8 μm, or at most 7 μm.

[0154] In some implementations, the Könighardness of the material used for the dry or fully cured outer coating is at least 80 seconds. More typically, the Könighardness ranges from 80 to 240, 80 to 210, 80 to 180, or 80 to 160.

[0155] In some implementations, the König hardness is at least 90, at least 100, at least 110, at least 120, or at least 130.

[0156] In some implementations, the first outer coating is or contains a thermoplastic polymer.

[0157] In some implementations, the first outer coating is or contains a thermosetting polymer.

[0158] In some implementations, the first outer coating formulation is a polymer emulsion.

[0159] In some implementations, the first outer coating formulation is a polymer dispersion.

[0160] In some implementations, the first outer coating formulation is a polymer solution.

[0161] In some implementations, the first outer coating formulation is an acrylic polymer.

[0162] In some implementations, the first outer coating formulation includes polyurethane.

[0163] In some embodiments, the first outer coating formulation comprises a polyvinyl ester resin such as polyvinyl butyral and polyvinylpyrrolidone vinyl acetate copolymer.

[0164] In some implementations, the first outer coating formulation comprises an epoxy resin.

[0165] In some embodiments, the material of the fully cured outer coating includes, primarily comprises, or consists of any of the polymers described above.

[0166] In some embodiments, the PVB-based outer coating formulation may be an aqueous dispersion containing PVB, for example, as disclosed in EP3587106 (e.g., Example 1A).

[0167] In some embodiments, the method further includes applying a second or additional outer coating on top of the dried first outer coating after the outer coating has dried / cured (step 230).

[0168] In some embodiments, the method further includes drying / curing a second outer coating or an additional outer coating.

[0169] In some implementations, the dried second or additional outer coating may exhibit increased hardness relative to the dried first outer coating.

[0170] In some implementations, the dried second outer coating or additional outer coating may exhibit a lower coefficient of linear thermal expansion (CTE) relative to the dried first outer coating.

[0171] In some embodiments, the method further includes, after curing (steps 223, 226, or 228), applying a liquid (film-forming) hard coating (“first hard coating” or “inner hard coating”) formulation to an exposed optical or ophthalmic surface of an optical or ophthalmic substrate to form a wet hard coating (step 232). The wet layer may then be treated to produce a dry, generally transparent hard coating on the optical surface (step 234).

[0172] In some embodiments, the method includes, after step 226 or 230 and before applying the hard coating formulation (step 232), applying an energy treatment (e.g., any of the energy treatments described above) to the top / exposed surface of the cured or fully cured ink layer or outer coating, respectively. With appropriate modifications This can significantly improve the adhesion between the fully cured substrate and the hard coating.

[0173] In some embodiments, the application of the (first) liquid hard coating formulation is performed by applying droplet microvalves of the formulation to the exposed surface of the ophthalmic substrate.

[0174] In some embodiments, the method further includes, after curing the first hard coating, applying a second liquid (film-forming) hard coating (“second hard coating” or “outer hard coating”) formulation to the exposed optical or ophthalmic surface of the optical or ophthalmic substrate to form a wet second hard coating. This optional step may be followed by treating the wet layer to produce a dry, generally transparent second hard coating on the optical surface.

[0175] In some embodiments, the application of the (second) liquid hard coating formulation is performed by applying droplet microvalves of the formulation to the exposed surface of the ophthalmic substrate.

[0176] In some embodiments, the hard coating formulation base material includes one or more acrylates, methacrylates, etc., some of which are provided below in a non-exhaustive manner: hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxy-poly(alkylene oxide)alkyl acrylate, caprolactone acrylate, ethylene glycol diacrylate, butylene glycol diacrylate, hexamethylene diacrylate, hexamethylene diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate.

[0177] UV catalysts used for photopolymerization initiation may include, for example, any of the following materials: benzoyl, benzoin, benzoin methyl ether, benzoin isobutyl ether, phenol, acetophenone, benzophenone, and mixtures thereof. Those skilled in the art will readily appreciate that other suitable UV catalysts may also be used.

[0178] In some implementations, ophthalmic hard coating formulations are based on sol-gel monomers and oligomers.

[0179] In some embodiments, the hard 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.

[0180] Hard coating compositions are well known to those skilled in the art. For example, thermosetting coating techniques have been disclosed in numerous patents, including U.S. Patents 4,547,397, 5,385,955 and 6,538,092, and radiation-cured coatings have been disclosed in U.S. Patents 4,478,876 and 5,409,965.

[0181] 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 comprises one or more relatively soft layers. It must be emphasized that when a single hard coating is applied, this layer is the “outer hard coating” of step 228.

[0182] In some embodiments, the thickness or average thickness of the outermost hard coating or coating layer that serves as the wet layer is in the range of 1.5 to 40 μm, 2.5 to 40 μm, 4 to 40 μm, 6 to 40 μm, 4 to 25 μm, 6 to 25 μm, 4 to 15 μm, or 6 to 15 μm.

[0183] In some embodiments, the thickness or average thickness of at least one optional 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.

[0184] 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.

[0185] In some implementations, only a single layer of hard coating is applied to the substrate.

[0186] 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 alpha alumina (sapphire); alumina, silicon dioxide, tin oxide, zirconium oxide, and titanium oxide.

[0187] Following drying / curing step 230 or drying / curing step 232, the method may include applying a liquid (film-forming) post-hard coating formulation to the optical or ophthalmic surface of an optical or ophthalmic substrate to form a wet layer. The wet layer may then be treated to produce a dried (fully cured) transparent post-hard coating on the optical surface. These steps have been described in general terms above.

[0188] 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.

[0189] Those skilled in the art will understand that these post-hardening coating formulations can be applied via microvalves or inkjet printing, or via conventional coating processes such as spin coating and dip coating, or via PVD or CVD (for extremely thin layers).

[0190] In some embodiments, the microvalve coating system includes an ink formulation application station, the photochromic ink formulation application station including a microvalve device configured to microvalve droplets of formulation onto a target surface of an optical substrate to form a wet layer of colored or photochromic ink formulation on the target surface; a drying and / or curing station configured to dry and / or cure the wet layer of ink formulation on the target surface to form its dry coating; and optionally, but typically, an optical substrate transfer device configured to transfer the optical substrate and the wet layer on its target surface from the ink formulation application station to the drying and / or curing station.

[0191] In some embodiments, 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.

[0192] In some embodiments, the microvalve coating system further includes a controller for adjusting 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 layer has been formed on the target surface of the optical substrate.

[0193] In some implementations, the drying and / or curing station includes at least one of a heating lamp and / or an oven.

[0194] In some embodiments, the drying and / or curing station includes an oven: (i) the oven is open when an optical substrate with a wet layer on a target surface is transferred into a housing of the optical substrate with a wet layer on a target surface; and (ii) the oven is closed after the optical substrate has been transferred into the oven and remains closed during drying and / or curing.

[0195] In some embodiments, the system further includes a primer application station for applying droplet microvalve of primer formulation to a target surface of the optical substrate before transferring the optical substrate to an ink formulation application station.

[0196] In some implementations, the microvalve device of the ink formulation application station is configured to deliver droplets of colored ink to the target surface of the optical substrate via microvalve.

[0197] In some embodiments, the microvalve coating system further includes a surface treatment station for increasing the surface energy of the target surface before applying a primer or ink formulation microvalve to the target surface of the optical substrate.

[0198] In some embodiments, the microvalve coating system further includes a cleaning station for cleaning the target surface before applying the primer or ink formulation microvalve to the target surface of the optical substrate.

[0199] In some implementations, the surface treatment station includes at least one of a corona treatment device and a plasma treatment device.

[0200] In some embodiments, the hard coating formulation application station includes a tank of hard coating formulation and is configured to deliver the hard coating formulation stored in the tank to a target surface of the optical substrate via a microvalve.

[0201] In some implementations, the system does not contain any dip coating equipment.

[0202] In some implementations, the system does not contain any spin coating equipment.

[0203] 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 configuration 403 fixedly attached to a wide surface 401 of the substrate 402. Configuration 403 further includes an optional primer layer 440 disposed between the wide surface 401 and an ink layer 404. The thickness of the ink layer 404 (containing an aqueous dye or colorant in some embodiments, and a photochromic dye in other embodiments) is specified as T. PC The thickness of the primer layer 440 is specified as Tp. One or more additional ink layers (not shown), a photochromic ink layer, and an outer coating 406 may be provided above the ink layer 404, substantially as described above. The thickness of the outer coating 406 is specified as Tov. According to a further feature of the invention, one or more hard coatings 420 may be provided above the outer coating 406. One or more post-hard coatings 430 may be provided above the one or more hard coatings 420 with a thickness specified as Th. The overall thickness of the optical structure 403 is specified as Toc.

[0204] In some implementations, Tp is in the range of 0.2 to 3 μm.

[0205] In some implementations, Tp is at least 0.4, at least 0.6, or at least 0.8 μm.

[0206] In some implementations, Tp is up to 2.5 μm, up to 2 μm, up to 1.6 μm, up to 1.3 μm, or up to 1.0 μm.

[0207] In some implementations, T PC Within the range of 1 to 10 μm.

[0208] In some implementations, T PC Within the range of 1.2 to 8 μm.

[0209] In some implementations, T PC The thickness is at least 1.5, at least 1.8, at least 2.0, at least 2.5, or at least 3 μm.

[0210] In some implementations, T PC The maximum size is 7μm, 6μm, 5μm, 4.5μm, or 4μm.

[0211] In some implementations, Tov is at least 4, at least 6, at least 7, or at least 7.5 μm.

[0212] In some implementations, Tov is up to 18 μm, up to 15 μm, up to 13 μm, up to 12 μm, or up to 11 μm.

[0213] In some embodiments, at least one of the local thickness Th-l and the average thickness Th-a of the fully cured hard coating is at least 1.2 μm, at least 1.5 μm, at least 1.8 μm, at least 2 μm, at least 2.5 μm, and more generally, at least 3 μm or at least 3.5 μm.

[0214] In some implementations, at least one of Th-l and Th-a is at most 8 μm, at most 6 μm, or at most 4.5 μm, at most 3.5 μm. When applied directly to an outer coating, the thickness or average thickness of the fully cured hard coating can range from 1.2 to 3.5 μm, 1.5 to 3.5 μm, or 1.8 to 3 μm. More typically, the thickness or average thickness is at most 2.7 μm, 2.4 μm, 2.2 μm, or 2 μm.

[0215] In some implementations, at least one of Th-l and Th-a is at most 8 μm, at most 6 μm, at most 4.5 μm, at most 3.5 μm, at most 3 μm, at most 2.7 μm, at most 2.4 μm, or at most 2.2 μm.

[0216] 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, 3 to 50 μm, or 4 to 50 μm.

[0217] In some implementations, Toc is at least 5 μm, at least 7 μm, at least 8 μm, at least 10 μm, or at least 12 μm.

[0218] In some implementations, Toc is up to 40 μm, up to 30 μm, up to 25 μm, up to 20 μm, up to 15 μm, or up to 12 μm.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] 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 device 1200.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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'.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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.

[0250] 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).

[0251] 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.

[0252] 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.

[0253] 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.

[0254] 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.

[0255] 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.

[0256] 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).

[0257] 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 2 Step 310 of A and / or Figure 3 Step 324 and / or Figure 3 Step 228.

[0258] 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.

[0259] 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.

[0260] 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 .

[0261] 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.

[0262] 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.

[0263] 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.

[0264] 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.

[0265] 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 dried layer disclosed herein is formed primarily of droplets in the range of [0.1 mm, 3 mm].

[0266] 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].

[0267] 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.

[0268] (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.

[0269] In various embodiments, the drying and / or curing equipment 1910 may be configured for performing... 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 2 Step 320 of A 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.

[0270] (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 2 Step 310 of A.

[0271] (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.

[0272] 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.

[0273] (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.

[0274] (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).

[0275] 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.

[0276] 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 a microvalve after a wet coating of the formulation has been applied to the surface of the first oven 1630 to increase its wet coating capacity; and (iv) Provide a second oven 1650 for drying and / or curing the wet coating of the second formulation.

[0277] 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.

[0278] 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.

[0279] 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.

[0280] 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.

[0281] 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.

[0282] 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.

[0283] 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.

[0284] 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.

[0285] 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.

[0286] 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.

[0287] 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.

[0288] 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.

[0289] 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.

[0290] 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 proportionally 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.

[0291] 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.

[0292] 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.

[0293] 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.

[0294] Example The invention is now described in a non-limiting manner with reference to the following embodiments, which together with the above description.

[0295] Material Lens material • Polycarbonate, a thermoplastic polymer • Trivex® (PPG), a thermosetting polymer based on polyurethane • CR-39® (PPG), a thermosetting polymer made from allyl diethylene glycol carbonate. Dyes for use in water-based formulations:

[0296] Photochromic dyes (powder, James Robinson Specialty Ingredients Ltd.): • Reversacol Amazon Green • Reversacol Midnight Grey • Reversacol Leather Brown • Reversacol Corn Yellow • Reversacol Ocean Blue Liquid softener • Emoltene™ 3GO (Perstorp) – Triethylene glycol mono-2-ethylhexanoate • Pevalen (Perstorp) – Pentaerythritol Tetravalerate (PETV) • Jayflex™ DIDP – Diisodecyl Phthalate – (Exxon Mobile) • Jayflex™ L9TM – Trinonyl trimellitate (Exxon Mobile) • Jayflex™ MB 10 – Isodecyl Benzoate (Exxon Mobile) • DEHP - Di-2-ethylhexyl phthalate (Arkema) • DEHTP - Di-2-ethylhexyl terephthalate (Arkema) • Palatinol N-diisononyl phthalate (BASF) • Palatinol 10-P – Di-2-propylheptyl phthalate (BASF) • Paraplex® A-8000 – Low molecular weight polyester adipate (Hallstar) • Paraplex® A-8200 – Medium molecular weight polyester adipate (Hallstar) Thermoplastic resin (solvent-soluble) ○ Pearlcoat™ DIPP 119 – A thermoplastic polyurethane (TPU) (Lubrizol) based on aromatic polycaprolactone copolyester ○ Mowital ®BA20S polyvinyl acetal (Kuraray) 14%-18% polyvinyl alcohol, 1%-4% polyvinyl acetate, dynamic viscosity 24-30 cP; glass transition temperature 84–93℃ (DIN EN ISO 11357-1:2017-02).

[0297] ○ Pearlbond™ 360 – A polyether-based thermoplastic polyurethane (TPU) (Lubrizol) ○ Pearlstick TM 47-60 Linear thermoplastic polyurethane elastomer (Lubrizol) SETALUX ® 2127 XX-60 – A thermoplastic acrylic resin (Allnex) with good adhesion to plastics. ○ Polyvinyl butyral (or PVB) [Also used in primers and topcoats] ○ Laropal A-81 — Thermoplastic aldehyde resin (BASF).

[0298] 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, styrene-acrylate copolymer (BASF); primer ○ Joncryl ® 9530-A—Waterborne acrylic emulsion self-crosslinking polymer, designed for topcoat and primer; topcoat ○ 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 resin solution that provides an excellent balance of hardness, adhesion, film toughness, clarity, and transparency; outer coating • PU polymer emulsions and dispersions: ○ 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 – Water-based emulsion (SDC); primer ○ ALBERDINGK ® U9800 – Solvent-free aliphatic polyester polyurethane dispersion (Alberdingk Boley); outer coating • Resin solvent-based solutions: ○ Versamid ® PUR 1010 - Primer ○ Laroflex ® HS-9000 - Primer.

[0299] Exemplary solvents: Solvent: Extremely low evaporation rate / extremely low vapor pressure at 25°C • 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 (Dipropylene glycol propyl ether, Pr-O-[CH2-CHMe-O]2-H, CAS 29911-27-1) • Acetone-glycerol (ALDRICH, 2,2-dimethyl-1,3-dioxolane-4-methanol, CAS 100-79-8) • Butylcarbidol (CAS 112-34-5) • EGBE (ethylene glycol monobutyl ether, CAS 111-76-2) Solvent: High evaporation rate / high vapor pressure at 25°C • n-Butyl acetate • Isobutyl acetate • Methyl isobutyl ketone • Isopropanol • Ethanol Solvent: Extremely high evaporation rate / high vapor pressure at 25°C • Ethyl acetate • Methylpropyl ketone • Propyl acetate • Isopropyl acetate • Methyl ethyl ketone 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).

[0300] • 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.

[0301] 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.

[0302] 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.

[0303] Example 3: Procedure for 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.

[0304] Example 4: Optimization of Inkjet Parameters In the various ink application steps, inkjet printing can optionally be used, utilizing inkjet ink formulations. A Ricoh printhead is used, typically preheated to 40°C. The droplet characteristics of 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). The waveform is optimized for each inkjet ink, jetting at a frequency of 0.5–3 kHz. The distance between the printhead and the substrate is 0.6–1.0 mm. The resolution is set to 300 dots per inch (dpi).

[0305] Example 5: Applying film-forming ink microvalves to lens substrates By using electromagnetically actuated microvalves (Fritz Gyger AG) with a nozzle diameter of 0.1 mm, film-forming inks are microvalvesed onto a lens substrate to create optical structures with at least one of various functions (primer, coloring ink, photochromic ink, top coating, hard coating, post-hard coating, etc.). 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.

[0306] Example 6A: Drying Unless otherwise instructed, the drying of primers, topcoats, coloring inks and photochromic inks is generally carried out at 60°C for 30 minutes.

[0307] Example 6B: Thermosetting The curing of the hard coating (inner layer, if used, and outer layer) is typically carried out at 120°C for 3 hours.

[0308] Example 6C: UV Curing UV curing uses a UV LED curing system: FJ100 Gen 2, 395nm, 12W / cm². 2 (Phoseon Technology) for 10 seconds.

[0309] Example 6D: Concentrated Aqueous Dye Solution One or more water-soluble dyes are slowly introduced into a stirred container containing water. After adding the last drop of dye, the container is stirred for 60 minutes to produce a concentrated aqueous dye solution in which the dye is completely dissolved.

[0310] Example 6E: Water-based ink formulation A water-based formulation containing a film-forming polymer is added to a stirred vessel containing an aqueous dye concentrate solution (e.g., prepared according to Example 6D), the film-forming polymer being selected to exhibit low MFFT in the final aqueous ink formulation. Typically, after stirring for several minutes at room temperature, a surfactant may be added while stirring, and stirring continues for an additional 20 minutes.

[0311] Example 6F: Water-based ink formulation A water-based formulation containing fine film-forming polymer particles, selected to exhibit low MFFT in the final aqueous ink formulation, is added to a stirred vessel containing an aqueous dye concentrate solution (e.g., prepared according to Example 6D). Typically, after stirring for several minutes at room temperature, one or more solvents and surfactants may be added while stirring, and stirring continues for an additional 20 minutes to produce an aqueous dispersion.

[0312] Example 6G: Water-based ink formulation Add the water-soluble dye and the water-soluble or dispersible resin (binder) to a stirred container containing water, and stir until completely dissolved (or a dispersion of the resin). Stirring is typically done at room temperature, and one or more solvents and surfactants may be added, and stirring continues for another 60 minutes.

[0313] 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. 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).

[0314] Example 8 22 g of DBA solvent and 72.3 g of DPP solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes, 0.15 g of surfactant BYK®-346 and 1.45 g of Emoltene™ 3GO were added to the solvent mixture while mixing. Then, 2 g of Reversacol Amazon Green dye and 2.1 g of Mowital were added while mixing. ® B 30 HH resin. Continue mixing at 60°C for another 20 minutes to produce photochromic ink, then filter it using a syringe filter (0.45 microns).

[0315] Example 9 An aqueous dye concentrate containing 10% yellow dye dissolved in water (90%) was prepared according to Example 6D. Then, according to Example 6F, this dye concentrate was used in a CrystalCoat-based... TM Aqueous dispersions of PR-670 water are prepared, wherein the formulation contains 64%-74% water, 2%-7% ethylene glycol monobutyl ether, 10%-20% N-methyl-2-pyrrolidone, and approximately 12% polymer (polyurethane) solids. The aqueous dispersion contains 20 g of an aqueous dye concentrate solution and 79.5 g of CrystalCoat. TM PR-670 and 0.5g BYK®-346.

[0316] Example 9A An aqueous dye concentrate solution containing 5.7% black (Direct Black 168) dye dissolved in water (94.3%) was prepared according to Example 6D. Then, according to Example 6F, an aqueous dispersion (emulsion) was prepared using this dye concentrate solution and a Carboset® 3119 acrylic dispersion. The aqueous dispersion contained 52.5 g of the aqueous dye concentrate solution, 20 g of Carboset® 3119, 11.5 g of 2-butoxyethanol solvent, 15 g of TPM solvent, and 1 g of Surfynol 465 surfactant.

[0317] Example 9B An aqueous dye concentrate solution containing 4.8% blue (Basic Blue 9) dye dissolved in water (95.2%) was prepared according to Example 6D. Then, according to Example 6F, an aqueous dispersion (emulsion) was prepared using this dye concentrate solution and a Joncryl LMV 7034 acrylic dispersion. The aqueous dispersion contained 53 g of the aqueous dye concentrate solution, 25 g of Joncryl LMV 7034, 6 g of 2-butoxyethanol solvent, 15 g of TPM solvent, and 1 g of Surfynol 465 surfactant.

[0318] Example 9C An aqueous dye concentrate solution containing 5.7% black (Direct Black 168) dye dissolved in water (94.3%) was prepared according to Example 6D. Then, according to Example 6F, an aqueous dispersion (emulsion) was prepared using this dye concentrate solution and a Carboset® 3119 acrylic dispersion. The aqueous dispersion contained 52.5 g of the aqueous dye concentrate solution, 20 g of Carboset® 3119, 12 g of 2-butoxyethanol solvent, and 15.5 g of TPM solvent.

[0319] Example 9D An aqueous dye concentrate solution containing 4.8% blue (Basic Blue 9) dye dissolved in water (95.2%) was prepared according to Example 6D. Then, according to Example 6F, an aqueous dispersion (emulsion) was prepared using this dye concentrate solution and a Joncryl LMV 7034 acrylic dispersion. The aqueous dispersion contained 53 g of the aqueous dye concentrate solution, 25 g of Joncryl LMV 7034, 6.3 g of 2-butoxyethanol solvent, and 15.7 g of TPM solvent.

[0320] Example 10 An aqueous dye concentrate solution was prepared according to Example 6D, containing 10% Basic Yellow 2 dye, 10% Basic Blue 9 dye, 10% Acid Red 33 dye, and 10% Direct Black 168 dye dissolved in water (90%). Then, according to Example 6F, these dye concentrate solutions were used with CrystalCoat... TM PR-670 was used to prepare an aqueous dispersion. The aqueous dispersion contained 5.3 g of yellow concentrate, 1 g of blue concentrate, 2.5 g of red concentrate, 5 g of black concentrate, and 85.7 g of CrystalCoat. TM PR-670 and 0.5g BYK®-3481.

[0321] Example 11 An aqueous dye concentrate solution was prepared according to Example 6D, containing 10% Basic Yellow 2 dye dissolved in water (90%) and 10% Acid Red 33 dye dissolved in water (90%). Then, according to Example 6F, these dye concentrate solutions were used with CrystalCoat... TM PR-670 was used to prepare an aqueous dispersion. The aqueous dispersion contained 8.7 g of a yellow concentrate, 5.2 g of a red concentrate, and 85.7 g of CrystalCoat. TM PR-670 and 0.4g BYK®-3481.

[0322] Examples 11A-11E

[0323] According to Example 6G, a series of water-based inks containing dissolved resin were prepared using the amounts described in Examples 11A-11E of the tables provided above.

[0324] Example 12 39.54 g of TPM solvent was heated to 80°C and mixed in a 150 ml glass beaker equipped with a magnetic stirrer. While stirring, 6.98 g of BA20S polymer was gradually added to the heated solvent. The beaker was covered with aluminum foil and mixed under heat for 8 hours. After 8 hours, the mixture became clear and homogeneous. The temperature was lowered to 70°C, and the following components were added while stirring: TPM solvent (4.8 g); PMA solvent (44.34 g); and a dye mixture consisting of the following premixed substances: Solvent Red 122 (0.35 g), Solvent Yellow 82 (0.23 g), and Solvent Black 27 (0.66 g).

[0325] After mixing the components for 1 hour, remove the ink, cool it to room temperature, and filter it through a syringe filter (0.45 microns).

[0326] Example 13 45.0 g of TPM solvent was heated to 80°C and mixed in a 150 ml glass beaker equipped with a magnetic stirrer. While stirring, 5.0 g of BA20S polymer was gradually added to the heated solvent. After mixing for 8 hours according to Example 12, the temperature was lowered to 70°C, and the following components were added while stirring: TPM solvent (2.0 g); PMA solvent (46.95 g); and the dye mixture of Example 12 (1.05 g). Processing was then carried out according to Example 12.

[0327] Example 14 45.0 g of TPM solvent was heated to 80°C and mixed in a 150 ml glass beaker equipped with a magnetic stirrer. While stirring, 5.0 g of BA20S polymer was gradually added to the heated solvent. After mixing for 8 hours according to Example 12, the temperature was lowered to 70°C, and the following components were added while stirring: ethyl acetate solvent (24.5 g); PMA solvent (24.5 g); and the dye mixture of Example 12 (1.05 g). Processing was then carried out according to Example 12.

[0328] Example 15 44.97 g of TPM solvent was heated to 80°C and mixed in a 150 ml glass beaker equipped with a magnetic stirrer. While stirring, 5.0 g of BA20S polymer was gradually added to the heated solvent. After mixing for 8 hours according to Example 12, the temperature was lowered to 70°C, and the following components were added while stirring: ethyl acetate solvent (34.6 g); PMA solvent (14.53 g); and the dye mixture of Example 12 (0.9 g). Processing was then carried out according to Example 12.

[0329] Example 16 45.0 g of TPM solvent was heated to 80°C and mixed in a 150 ml glass beaker equipped with a magnetic stirrer. While stirring, 5.0 g of BA20S polymer was gradually added to the heated solvent. After mixing for 8 hours according to Example 12, the temperature was lowered to 70°C, and the following components were added while stirring: TPM solvent (8.10 g); ethyl acetate solvent (40.85 g); and the dye mixture of Example 12 (1.05 g). Processing was then carried out according to Example 12.

[0330] Example 17 45.0 g of TPM solvent was heated to 80°C and mixed in a 150 ml glass beaker equipped with a magnetic stirrer. While stirring, 5.0 g of BA20S polymer was gradually added to the heated solvent. After mixing for 8 hours according to Example 12, the temperature was lowered to 70°C, and the following components were added while stirring: TPM solvent (1.98 g); ethyl acetate solvent (46.98 g); and the dye mixture of Example 12 (1.05 g). Processing was then carried out according to Example 12.

[0331] Example 18 22 g of DBA solvent and 72.3 g of DPP solvent were mixed in a 200 ml glass beaker equipped with a magnetic stirrer. After mixing the components for 5 minutes, 0.15 g of surfactant BYK®-346 and 1.45 g of Emoltene™ 3GO were added to the solvent mixture while mixing. Then, 2 g of Reversacol Amazon Green dye and 2.1 g of Mowital were added while mixing. ® B 30 HH resin. Continue mixing at 60°C for another 20 minutes to produce photochromic ink, then filter it using a syringe filter (0.45 microns).

[0332] Example 19 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 is added to the mixture, and mixing continues for another 10 minutes at 30°C to produce the primer formulation.

[0333] Example 20 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.

[0334] Example 21 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 the primer formulation.

[0335] Example 22 2.0 g of Mowital PVB 16H and 97.7 g of ethyl acetate were mixed in a 200 ml glass flask equipped with a magnetic stirrer. After mixing the components for 30 minutes, 0.3 g of surfactant BYK was added. ® -307 is added to the mixture, and mixing continues for another 10 minutes at 30°C to produce the primer formulation.

[0336] Example 23 1.77 g of Mowital PVB 30H and 98.2 g of ethyl acetate were mixed in a 200 ml glass flask equipped with a magnetic stirrer. After mixing the components for 30 minutes, 0.3 g of surfactant BYK was added. ® -307 is added to the mixture, and mixing continues for another 10 minutes at 30°C to produce the primer formulation.

[0337] Example 24 2.0 g Pearlcoat at 40℃ TM DIPP 119 and 98 g of ethyl acetate were mixed in a 200 ml glass flask equipped with a magnetic stirrer for 1 hour. After mixing the components for 60 minutes, 0.3 g of surfactant BYK was added. ® -307 is added to the mixture, and mixing continues for another 20 minutes to produce the primer formulation.

[0338] Example 25 2.0 grams of Pearlstick were placed at 40°C. TM 47-60 g of ethyl acetate and 98 g of ethyl acetate were mixed in a 200 ml glass flask equipped with a magnetic stirrer for 1 hour. After mixing the components for 60 minutes, 0.3 g of surfactant BYK was added. ® -307 is added to the mixture, and mixing continues for another 20 minutes to produce the primer formulation.

[0339] Example 26 Mix 80 g of U9800 with 19.5 g of water and 0.5 g of BYK 346 in a 200 ml glass flask equipped with a magnetic stirrer for 1 hour to produce an outer coating formulation.

[0340] Example 27 According to Example 1, Trivex ® (PPG) lenses undergo a corona treatment process.

[0341] Example 28 A corona treatment process was performed on a polycarbonate lens according to Example 1.

[0342] Example 29 The corona surface treatment procedure of Example 1 was performed on the polycarbonate lens pre-coated with a hard coating.

[0343] Example 30 Trivex with pre-coated hard coating ® (PPG) lenses undergo the corona surface treatment procedure of Example 1.

[0344] Example 31 CR-39 with a pre-coated hard coating ® (PPG) lenses undergo the corona surface treatment procedure of Example 1.

[0345] Example 32 Versamid ® PUR 1010 was applied as a primer to the polycarbonate lens. 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 to produce a primer layer.

[0346] Example 33 Laroflex ® HS-9000 was applied as a primer to the polycarbonate lens. 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 to produce a primer layer with a thickness of approximately 1.5 μm.

[0347] Example 34 Joncryl from Example 20 ® Formulation 1534 was applied as a primer to the polycarbonate lens. Spin coating was performed according to Example 2, and a calculated wet thickness of 1.9 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.

[0348] Example 35 Joncryl from Example 20 ®Formulation 1534 was applied as a primer to a corona-treated polycarbonate lens. Spin coating was performed according to Example 2. 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.

[0349] Examples 36-37: Microvalves are used to apply photochromic ink to the surface of the lens. The photochromic dye formulation of Example 8 (which also contains a polymer binder and a non-volatile liquid softener) was brought to the Trivex microvalves at a pressure below 1 bar, according to Example 5. ® Lens (Example 30) and CR-39 ® On the lens (Example 31).

[0350] Example 38 The formulation microvalves produced in Example 9 were applied to the lenses treated in Example 37 to create a wet layer with a calculated average thickness (based on the amount of ink applied divided by the total area covered) of 45 μm. The wet layer was then heat-dried in a Venticell ECO forced-ventilation oven at 60°C for 30 minutes. The dried (calculated average) thickness was approximately 5.4 μm.

[0351] Example 39 The formulation microvalves produced in Example 10 were applied to the lenses treated in Example 37 to create a wet layer with a calculated average thickness (based on the amount of ink applied divided by the total area covered) of 38 μm. The wet layer was then heat-dried in a Venticell ECO forced-ventilation oven at 60°C for 30 minutes. The dried (calculated average) thickness was approximately 4.6 μm.

[0352] Example 40 The formulation microvalves produced in Example 11 were applied to the lenses treated in Example 36 to create a wet layer with a calculated average thickness (based on the amount of ink applied divided by the total area covered) of 53 μm. The wet layer was then heat-dried in a Venticell ECO forced-ventilation oven at 60°C for 30 minutes. The dried (calculated average) thickness was approximately 6.4 μm.

[0353] Example 41 The outer coating formulation of Example 26 was microvalves applied to the coated CR-39® lens produced in Example 37. The wet layer was then heat-dried in a Venticell ECO forced-ventilation oven at 60°C for 30 minutes. The dry (average calculated) thickness was approximately 3.1 μm.

[0354] Example 42 The outer coating formulation of Example 26 was microvalves applied to the coated CR-39® lens produced in Example 38. The wet layer was then heat-dried in a Venticell ECO forced-air oven at 60°C for 30 minutes.

[0355] Examples 43-46: Hard Coating Varnish Formulation Example 43: 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.

[0356] Example 44: 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.

[0357] Example 45: 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.

[0358] Example 46: 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 37 and mixed for 15 hours.

[0359] Example 47 The formulations of Examples 35-38 were applied as hard coating microvalves to the coated polycarbonate lenses produced in Example 42. The samples were then cured according to the procedure of Example 6B.

[0360] Example 48 Measuring 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.

[0361] Unless otherwise expressly indicated, as used herein in this specification and the following claims section, the term "percentage" or "%" means weight percentage.

[0362] 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.

[0363] 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.

[0364] 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.

[0365] Unless otherwise expressly indicated, as used herein in this specification and the following claims section, the term "ratio" refers to a weight ratio.

[0366] 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 drying a lens / optical substrate coated with the formulation in an oven at 120°C for 3 hours, and then removing some or all of the solvent and carrier liquid from the lens / optical surface. The residue includes solid particles within the formulation, as well as dissolved solids remaining after solvent removal.

[0367] As used herein in this specification and the following claims section, the term "drying / curing" (e.g., drying / curing of a formulation or layer) refers to the drying or otherwise curing of a formulation or layer. It will be understood that for many types of formulations, thermal drying is the mechanism for complete curing.

[0368] As used herein in this specification and the following claims section, the term "completely dry and cured" means the complete removal of the liquid solvent / carrier and the 100% curing of the layer or coating.

[0369] As used herein and in the following claims section, the terms “fully cured” and “fully cured” (e.g., fully cured and fully cured of a formulation or layer) refer to a polymer material that is at least 85% cured, as determined by Koenig hardness testing 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 (Koenig hardness 80), the Koenig hardness of “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.

[0370] 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.

[0371] 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.

[0372] In addition, these techniques can be used to map the surface of thin films and calculate the average thickness of such films.

[0373] 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.

[0374] The "average thickness" of a dried film can be calculated as follows: when a certain volume of material... vol (It is calculated 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 specific gravity. As mentioned above, specific gravity is typically assumed to be 1.

[0375] 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 .

[0376] 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.

[0377] 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.

[0378] 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.

[0379] 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%.

[0380] 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.

[0381] The term "ophthalmic preparation" is intended to be understood as being used in the field of ophthalmic substrate coatings.

[0382] For example, regarding liquid softeners, the term "non-volatile" is intended to be understood as something typically used in solvent-based formulations.

[0383] Similarly, the term "non-volatile content" is generally used in the context of formulations such as ink formulations and is intended to be understood as commonly used in solvent-based formulations. Specifically, it refers to high-boiling-point liquids such as glycerol (290°C).

[0384] As used herein, the term "film formation" generally refers to resins, polymers, or formulations and is intended to be understood as commonly used in the field of coatings for ophthalmic substrates. Typically, the average or characteristic thickness of the dry film of a film-forming material ranges from 0.2 to 5 micrometers.

[0385] As used herein and in the following claims section, the terms "softener" and the like are used substantially as understood in the art.

[0386] As used herein and in the following claims section, the term "liquid" refers to the state of the material at 25°C.

[0387] As used herein and in the following claims section, the terms “LLevap,” “Levap,” “Mevap,” “Hevap,” and “HHevap” refer to volatile liquids that, according to ASTM D3539, have a characteristic relative evaporation rate range relative to n-butyl acetate at 25°C and atmospheric pressure. More specifically, volatile liquids are classified into the following five categories: LLevap < 0.1 (e.g., TPM, DPM, EB, NMP, DMSO, ethylene glycol monobutyl ether, DPM acetate) 0.1 ≤Levap<0.5 (e.g., EEP, EP, PP, PMA, n-butyl propionate, n-butanol, amyl acetate, water) 0.5 ≤Mevap<0.85 (e.g., PM, isobutanol) 0.85 ≤ Hevap < 1.8 (e.g., xylene, n-butyl acetate, isobutyl acetate, methyl isobutyl ketone, isopropanol, ethanol) 1.8 ≤HHevap (e.g., toluene, methanol, n-propyl acetate, isopropyl acetate, ethyl acetate, methyl propyl ketone, methyl ethyl ketone).

[0388] The vaporization or evaporation rate of the specified standard material n-butyl acetate is assigned as 1.0. Therefore, the terms "relative evaporation rate," etc., are used with reference to n-butyl acetate.

[0389] 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".

[0390] 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.

[0391] Additional implementation plan : This document discloses various formulations, methods, optical structures, and systems. Additional implementation methods are provided below.

[0392] Method Implementation Plan 1. A method for producing an optical structure on an optical substrate, the method comprising: (a) Applying an ink droplet microvalve containing at least one dissolving dye to the optical surface of an optical substrate to form a wet layer; and (b) Processing the wet layer to produce a dry or cured dye-containing layer on the optical surface; Optionally, the optical surface is a curved surface, and optionally, the optical surface is a polymer surface.

[0393] 2. The method of embodiment 1, wherein the ink formulation is an aqueous ink formulation containing an aqueous solvent system.

[0394] 3. The method of embodiment 1, wherein the ink formulation is an organic or solvent-based ink formulation containing an organic or solvent-based solvent system.

[0395] 4. The method of embodiment 2, wherein the water-based ink formulation further comprises a polymer resin.

[0396] 5. The method as described in embodiment 4, wherein the polymer resin is dissolved in the aqueous ink formulation.

[0397] 6. The method as described in embodiment 5, wherein the aqueous solvent system contains a single liquid phase.

[0398] 7. The method of embodiment 4, wherein the polymer resin is dispersed as particles in the aqueous ink formulation.

[0399] 8. The method of embodiment 7, wherein the polymer resin particles form an emulsion within the aqueous ink formulation.

[0400] 9. The method of embodiment 3, wherein the organic or solvent-based ink formulation further comprises a polymer resin dissolved in an organic or solvent-based solvent system.

[0401] 10. The method of embodiment 9, wherein the organic or solvent-based solvent system contains a single liquid phase.

[0402] 11. The method as described in any of the foregoing embodiments, wherein the optical surface is the polymer surface.

[0403] 12. The method as described in any of the foregoing embodiments, wherein the optical surface is the curved surface.

[0404] 13. The method of embodiment 12, wherein the SAG number of the optical substrate is defined by any feature of system embodiments 25 to 36.

[0405] 14. The method as described in any of the foregoing embodiments, wherein the base arc of the optical substrate is at least 2.

[0406] 15. The method as described in embodiment 14, wherein the base arc is at least 3.

[0407] 16. The method as described in embodiment 14, wherein the base arc is at least 4.

[0408] 17. The method as described in embodiment 14, wherein the base arc is at least 5.

[0409] 18. The method as described in embodiment 14, wherein the base arc is at least 6.

[0410] 19. The method as described in embodiment 14, wherein the base arc is at least 8.

[0411] 20. The method as described in any of the foregoing embodiments, wherein the base arc of the optical substrate is at most 14.

[0412] 21. The method as described in embodiment 20, wherein the base arc is at most 12.

[0413] 22. The method as described in embodiment 20, wherein the base arc is at most 10.

[0414] 23. 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°.

[0415] 24. The method as described in implementation scheme 23, wherein α max The temperature should be at least 7°.

[0416] 25. The method as described in implementation scheme 23, wherein α max It should be at least 10°.

[0417] 26. The method as described in implementation scheme 23, wherein α max The angle should be at least 13°.

[0418] 27. The method as described in implementation scheme 23, wherein α max It should be at least 16°.

[0419] 28. The method as described in implementation scheme 23, wherein α max It should be at least 19°.

[0420] 29. The method as described in implementation scheme 23, wherein α max It should be at least 23°.

[0421] 30. The method as described in implementation scheme 23, wherein α max It should be at least 26°.

[0422] 31. The method as described in implementation scheme 23, wherein α max It is at least 31°, at least 34°, or at least 40°.

[0423] 32. The method as described in any one of embodiments 23 to 31, wherein α max The maximum angle is 50°.

[0424] 33. The method as described in implementation scheme 32, wherein α max The maximum is 42°.

[0425] 34. The method as described in implementation scheme 32, wherein α max The maximum is 37°.

[0426] 35. The method as described in any of the preceding embodiments, wherein the ink formulation is a film-forming formulation.

[0427] 36. The method of claim 35, wherein the minimum film-forming temperature (MFFT) of the polymer is at most 60°C.

[0428] 37. The method of embodiment 36, wherein the MFFT of the polymer is at most 50°C.

[0429] 38. The method of embodiment 37, wherein the MFFT of the polymer is at most 45°C.

[0430] 39. The method of embodiment 37, wherein the MFFT of the polymer is at most 40°C.

[0431] 40. The method of embodiment 37, wherein the MFFT of the polymer is at most 35°C.

[0432] 41. The method of embodiment 37, wherein the MFFT of the polymer is at most 30°C.

[0433] 42. The method of embodiment 37, wherein the MFFT of the polymer is at most 25°C.

[0434] 43. The method of embodiment 37, wherein the MFFT of the polymer is at most 20°C.

[0435] 44. The method of embodiment 37, wherein the MFFT of the polymer is at most 15°C.

[0436] 45. The method of any one of embodiments 36 to 44, wherein the MFFT of the polymer is at least -50°C.

[0437] 46. ​​The method of embodiment 45, wherein the MFFT of the polymer is at least -35°C.

[0438] 47. The method of embodiment 45, wherein the MFFT of the polymer is at least -20°C.

[0439] 48. The method of embodiment 45, wherein the MFFT of the polymer is at least -10°C.

[0440] 49. The method as described in any of the foregoing embodiments, wherein at least one of the thickness TH of the wet layer, the characteristic thickness THc, and the average thickness THav is at most 100 micrometers (μm).

[0441] 50. The method as described in embodiment 49, wherein at least one of TH, THc and THav is at most 80 μm.

[0442] 51. The method as described in embodiment 49, wherein at least one of TH, THc and THav is at most 70 μm.

[0443] 52. The method as described in embodiment 49, wherein at least one of TH, THc and THav is at most 60 μm.

[0444] 53. The method as described in embodiment 49, wherein at least one of TH, THc and THav is at most 50 μm.

[0445] 54. The method as described in any one of embodiments 49 to 53, wherein at least one of TH, THc and THav is at least 10 μm.

[0446] 55. The method as described in embodiment 54, wherein at least one of TH, THc and THav is at least 18 μm.

[0447] 56. The method as described in embodiment 54, wherein at least one of TH, THc and THav is at least 25 μm.

[0448] 57. The method as described in embodiment 54, wherein at least one of TH, THc and THav is at least 30 μm.

[0449] 58. The method as described in embodiment 54, wherein at least one of TH, THc and THav is at least 35 μm.

[0450] 59. The method as described in embodiment 54, wherein at least one of TH, THc and THav is at least 40 μm.

[0451] 60. The method as described in embodiment 54, wherein at least one of TH, THc and THav is at least 45 μm.

[0452] 61. The method as described in any one of embodiments 49 to 60, wherein at least one of TH, THc and THav includes TH.

[0453] 62. The method as described in any one of embodiments 49 to 60, wherein at least one of TH, THc and THav includes THav.

[0454] 63. The method as described in any one of embodiments 49 to 60, wherein at least one of TH, THc and THav includes TH and THav.

[0455] 64. The method as described in any one of embodiments 49 to 60, wherein at least one of TH, THc and THav includes TH, THc and THav.

[0456] 65. The method as described in any one of embodiments 49 to 58 and 61 to 64, wherein at least one of TH, THc and THav is at most 40 μm.

[0457] 66. The method as described in any one of embodiments 49 to 56 and 61 to 64, wherein at least one of TH, THc and THav is at most 30 μm.

[0458] 67. The method as described in any one of embodiments 49 to 66, wherein at least one of TH, THc and THav is at least 4 μm.

[0459] 68. The method of embodiment 47, wherein at least one of TH, THc and THav is at least 5.5 μm.

[0460] 69. The method as described in embodiment 47, wherein at least one of TH, THc and THav is at least 7 μm.

[0461] 70. The method as described in any of the preceding embodiments, wherein for an ink droplet, at least one of the droplet volume Vd, the characteristic droplet volume Vd-c, and the average droplet volume Vd-av is in the range of 4 to 400 nanoliters (nL).

[0462] 71. The method as described in embodiment 70, wherein at least one of Vd, Vd-c and Vd-av is at least 5nl.

[0463] 72. The method as described in embodiment 70, wherein at least one of Vd, Vd-c and Vd-av is at least 6nl.

[0464] 73. The method as described in embodiment 70, wherein at least one of Vd, Vd-c and Vd-av is at least 8nl.

[0465] 74. The method as described in embodiment 70, wherein at least one of Vd, Vd-c and Vd-av is at least 10 nml.

[0466] 75. The method as described in embodiment 70, wherein at least one of Vd, Vd-c and Vd-av is at least 12nl.

[0467] 76. The method of embodiment 70, wherein at least one of Vd, Vd-c and Vd-av is at least 15 nml.

[0468] 77. The method as described in any one of embodiments 70 to 76, wherein at least one of Vd, Vd-c and Vd-av is at most 250 nml.

[0469] 78. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 100nl.

[0470] 79. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 70nl.

[0471] 80. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 50 nml.

[0472] 81. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 45nl.

[0473] 82. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 40nl.

[0474] 83. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 35nl.

[0475] 84. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 30nl.

[0476] 85. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 25nl.

[0477] 86. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 22nl.

[0478] 87. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 20nl.

[0479] 88. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 18nl.

[0480] 89. The method as described in embodiment 77, wherein at least one of Vd, Vd-c and Vd-av is at most 16nl.

[0481] 90. The method as described in any one of embodiments 70 to 89, wherein at least one of Vd, Vd-c, and Vd-av includes Vd.

[0482] 91. The method as described in any one of embodiments 70 to 90, wherein at least one of Vd, Vd-c and Vd-av includes Vd-c.

[0483] 92. The method as described in any one of embodiments 70 to 91, wherein at least one of Vd, Vd-c and Vd-av includes Vd-av.

[0484] 93. The method of any one of the foregoing embodiments, wherein the dispersed polymer particles form a polyurethane dispersion in the dye-containing aqueous solution.

[0485] 94. The method of any one of embodiments 1 to 92, wherein the dispersed polymer particles form a polyurethane-acrylic dispersion in the dye-containing aqueous solution.

[0486] 95. The method of any one of embodiments 1 to 92, wherein the dispersed polymer particles form a polycarbonate dispersion in the dye-containing aqueous solution.

[0487] 96. The method of any one of embodiments 1 to 92, wherein the dispersed polymer particles form a polycarbonate-polyurethane dispersion in the dye-containing aqueous solution.

[0488] 97. The method of any one of the foregoing embodiments, wherein the viscosity of the ink formulation at 25°C is at most 65 cP.

[0489] 98. The method as described in embodiment 97, wherein the viscosity at 25°C is at most 50 cP.

[0490] 99. The method as described in embodiment 97, wherein the viscosity at 25°C is at most 35 cP.

[0491] 100. The method as described in embodiment 97, wherein the viscosity at 25°C is at most 25 cP.

[0492] 101. The method as described in embodiment 97, wherein the viscosity at 25°C is at most 20 cP.

[0493] 102. The method as described in embodiment 97, wherein the viscosity at 25°C is at most 15 cP.

[0494] 103. The method of embodiment 97, wherein the viscosity at 25°C is at most 12 cP.

[0495] 104. The method of any one of embodiments 97 to 103, wherein the 25°C viscosity of the liquid film-forming formulation is at least 1.5 cP.

[0496] 105. The method as described in embodiment 104, wherein the viscosity at 25°C is at least 2.5 cP.

[0497] 106. The method of embodiment 104, wherein the viscosity at 25°C is at least 4 cP.

[0498] 107. The method as described in embodiment 104, wherein the viscosity at 25°C is at least 6 cP.

[0499] 108. The method of any of the foregoing embodiments, wherein the polymer surface is or includes a thermosetting polymer, and the polymer surface is optionally coated with a hard coating.

[0500] 109. The method of embodiment 108, wherein the polymer surface is coated with the hard coating.

[0501] 110. The method as described in embodiment 108 or 109, wherein the thermosetting polymer is a polyurethane-based thermosetting polymer such as Trivex. ® .

[0502] 111. The method as described in embodiment 108 or 109, wherein the thermosetting polymer is composed of allyl diethylene glycol carbonate such as CR-39. ® Made.

[0503] 112. The method of any of the foregoing embodiments, wherein the polymer surface is or comprises a thermoplastic polymer, and the polymer surface is optionally coated with a hard coating.

[0504] 113. The method of embodiment 112, wherein the polymer surface is coated with the hard coating.

[0505] 114. The method as described in embodiment 112 or 113, wherein the thermoplastic polymer is polycarbonate.

[0506] 115. The method as described in any of the foregoing embodiments, wherein the non-volatile content of the ink formulation is at least 5%.

[0507] 116. The method of embodiment 115, wherein the non-volatile content of the ink formulation is at least 7%.

[0508] 117. The method of embodiment 115, wherein the non-volatile content of the ink formulation is at least 9%.

[0509] 118. The method of embodiment 115, wherein the non-volatile content of the ink formulation is at least 10%.

[0510] 119. The method of embodiment 115, wherein the non-volatile content of the ink formulation is at least 11%.

[0511] 120. The method of embodiment 115, wherein the non-volatile content of the ink formulation is at least 12%.

[0512] 121. The method as described in any of the foregoing embodiments, wherein the non-volatile content of the ink formulation is at most 20%.

[0513] 122. The method of embodiment 121, wherein the non-volatile content of the ink formulation is at most 18%.

[0514] 123. The method of embodiment 121, wherein the non-volatile content of the ink formulation is at most 16.5%.

[0515] 124. The method of embodiment 121, wherein the non-volatile content of the ink formulation is at most 15.5%.

[0516] 125. The method of embodiment 121, wherein the non-volatile content of the ink formulation is at most 15%.

[0517] 126. The method of embodiment 121, wherein the non-volatile content of the ink formulation is at most 14.5%.

[0518] 127. The method of embodiment 121, wherein the non-volatile content of the ink formulation is at most 14%.

[0519] 128. The method as described in any of the foregoing embodiments, wherein the liquid in the ink formulation reacts with the polymer R P-L The weight ratio is at most 0.24.

[0520] 129. The method as described in embodiment 128, wherein R P-L It is at most 0.22.

[0521] 130. The method as described in embodiment 128, wherein R P-L It is at most 0.20.

[0522] 131. The method as described in embodiment 128, wherein R P-L It is at most 0.18.

[0523] 132. The method as described in embodiment 128, wherein R P-LIt is at most 0.16.

[0524] 133. The method as described in embodiment 128, wherein R P-L It is at most 0.14.

[0525] 134. The method as described in any one of embodiments 128 to 133, wherein R P-L It is at least 0.06.

[0526] 135. The method as described in embodiment 134, wherein R P-L It should be at least 0.08.

[0527] 136. The method as described in embodiment 134, wherein R P-L It is at least 0.09.

[0528] 137. The method as described in embodiment 134, wherein R P-L It is at least 0.095.

[0529] 138. The method as described in embodiment 134, wherein R P-L It should be at least 0.1.

[0530] 139. The method as described in embodiment 134, wherein R P-L It is in the range of 0.075 to 0.15.

[0531] 140. The method as described in embodiment 134, wherein R P-L It is in the range of 0.085 to 0.135.

[0532] 141. The method as described in embodiment 134, wherein R P-L It is in the range of 0.09 to 0.13.

[0533] 142. The method as described in any of the preceding embodiments, wherein the surface tension σ of the ink formulation at 25°C is at most 35 dynes / cm.

[0534] 143. The method as described in embodiment 142, wherein σ is at most 32 dynes / cm.

[0535] 144. The method as described in embodiment 142, wherein σ is at most 30 dynes / cm.

[0536] 145. The method as described in embodiment 142, wherein σ is at most 29 dynes / cm.

[0537] 146. The method of any one of embodiments 142 to 145, wherein the σ of the ink formulation is at least 24 dynes / cm.

[0538] 147. The method as described in embodiment 146, wherein σ is at least 25 dynes / cm.

[0539] 148. The method as described in embodiment 146, wherein σ is at least 26 dynes / cm.

[0540] 149. The method as described in any of the preceding embodiments, wherein at least 85% by weight of the total polymer content in the ink formulation is a film-forming polymer.

[0541] 150. The method of any one of the preceding embodiments, wherein at least 90% by weight of the total polymer content in the ink formulation is a film-forming polymer.

[0542] 151. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 50% by weight of the total solvent in the ink formulation is at most a high vapor pressure (Hevap) solvent.

[0543] 152. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 60% by weight of the total solvent in the ink formulation is at most a high vapor pressure (Hevap) solvent.

[0544] 153. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 70% by weight of the total solvent in the ink formulation is at most a high vapor pressure (Hevap) solvent.

[0545] 154. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 80% by weight of the total solvent in the ink formulation is at most a high vapor pressure (Hevap) solvent.

[0546] 155. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 90% by weight of the total solvent in the ink formulation is at most Hevap solvent.

[0547] 156. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 95% by weight of the total solvent in the ink formulation is at most Hevap solvent.

[0548] 157. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 70% by weight of the total solvent in the ink formulation is at most a medium vapor pressure (Mevap) solvent.

[0549] 158. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 75% by weight of the total solvent in the ink formulation is at most Mevap solvent.

[0550] 159. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 80% by weight of the total solvent in the ink formulation is at most Mevap solvent.

[0551] 160. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 85% by weight of the total solvent in the ink formulation is at most Mevap solvent.

[0552] 161. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 90% by weight of the total solvent in the ink formulation is at most Mevap solvent.

[0553] 162. The method as described in any of the preceding embodiments, wherein, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate, at least 55% by weight of the total solvent in the ink formulation is at most a low vapor pressure (Levap) solvent.

[0554] 163. The method of embodiment 162, wherein at least 60% by weight of the total solvent in the ink formulation is at most Levap solvent.

[0555] 164. The method of embodiment 162, wherein at least 65% by weight of the total solvent in the ink formulation is at most Levap solvent.

[0556] 165. The method of embodiment 162, wherein at least 70% by weight of the total solvent in the ink formulation is at most Levap solvent.

[0557] 166. The method of embodiment 162, wherein at least 80% by weight of the total solvent in the ink formulation is at most Levap solvent.

[0558] 167. The method of embodiment 162, wherein at least 90% by weight of the total solvent in the ink formulation is at most Levap solvent.

[0559] 168. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 30% by weight of the total solvent in the ink formulation is at most 0.35, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0560] 169. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 40% by weight of the total solvent in the ink formulation is at most 0.35, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0561] 170. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 50% by weight of the total solvent in the ink formulation is at most 0.35, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0562] 171. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 60% by weight of the total solvent in the ink formulation is at most 0.35, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0563] 172. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 70% by weight of the total solvent in the ink formulation is at most 0.35, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0564] 173. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 75% by weight of the total solvent in the ink formulation is at most 0.35, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0565] 174. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 80% by weight of the total solvent in the ink formulation is at most 0.4, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0566] 175. The method as described in any of the preceding embodiments, wherein the normalized evaporation rate of at least 90% by weight of the total solvent in the ink formulation is at most 0.4, expressed on a 25°C evaporation rate scale normalized to n-butyl acetate.

[0567] 176. The method as described in any of the preceding embodiments, wherein the concentration of the extremely low vapor pressure (LLevap) solvent in the total solvent of the ink formulation is at least 20% by weight.

[0568] 177. The method as described in embodiment 176, wherein the concentration of the LLevap solvent is at least 30 by weight.

[0569] 178. The method of embodiment 176, wherein the concentration of the LLevap solvent is at least 35% by weight.

[0570] 179. The method of embodiment 176, wherein the concentration of the LLevap solvent is at least 40 by weight.

[0571] 180. The method of embodiment 176, wherein the concentration of the LLevap solvent is at least 45% by weight.

[0572] 181. The method as described in embodiment 176, wherein the concentration of the LLevap solvent is at least 50 by weight.

[0573] 182. The method as described in embodiment 176, wherein the concentration of the LLevap solvent is at least 55% by weight.

[0574] 183. The method as described in embodiment 176, wherein the concentration of the LLevap solvent is at least 60 by weight.

[0575] 184. The method of embodiment 176, wherein the concentration of the LLevap solvent is at least 65% by weight.

[0576] 185. The method as described in embodiment 176, wherein the concentration of the LLevap solvent is at least 70% by weight.

[0577] 186. The method of embodiment 176, wherein the concentration of the LLevap solvent is at least 75% by weight.

[0578] 187. The method of any one of embodiments 176 to 186, wherein the normalized evaporation rate of the LLEVAP solvent is at most 0.05.

[0579] 188. The method of embodiment 187, wherein the normalized evaporation rate of the LLevap solvent is at most 0.025.

[0580] 189. The method of embodiment 187, wherein the normalized evaporation rate of the LLevap solvent is at most 0.015.

[0581] 190. The method of embodiment 187, wherein the normalized evaporation rate of the LLevap solvent is at most 0.012.

[0582] 191. The method as described in any one of embodiments 187 to 190, wherein the normalized evaporation rate of the LLEVAP solvent is at least 0.0015.

[0583] 192. The method of embodiment 191, wherein the normalized evaporation rate of the LLEVAP solvent is at least 0.004.

[0584] 193. The method as described in any of the foregoing embodiments, the method further comprising performing at least one surface treatment on the optical surface of the optical substrate prior to the ink droplet of the ink formulation in the microvalve.

[0585] 194. The method of embodiment 193, wherein the at least one surface treatment includes an energy treatment that increases the surface energy of the optical surface.

[0586] 195. The method of embodiment 194, wherein the energy processing comprises at least one energy processing selected from the group consisting of corona, plasma, electron beam and discharge processing.

[0587] 196. The method of any one of embodiments 193 to 195, wherein the surface treatment increases the surface energy of the optical substrate by at least 2 mN / m.

[0588] 197. The method of embodiment 196, wherein the surface treatment increases the surface energy of the optical substrate by at least 3 mN / m.

[0589] 198. The method of embodiment 196, wherein the surface treatment increases the surface energy of the optical substrate by at least 5 mN / m.

[0590] 199. The method of embodiment 196, wherein the surface treatment increases the surface energy of the optical substrate by at least 8 mN / m.

[0591] 200. The method of embodiment 196, wherein the surface treatment increases the surface energy of the optical substrate by at least 12 mN / m.

[0592] 201. The method of any one of embodiments 193 to 200, wherein the surface treatment increases the surface energy of the optical substrate by up to 40 mN / m.

[0593] 202. The method of embodiment 201, wherein the surface treatment increases the surface energy of the optical substrate by up to 30 mN / m.

[0594] 203. The method of embodiment 201, wherein the surface treatment increases the surface energy of the optical substrate by up to 20 mN / m.

[0595] 204. The method of embodiment 201, wherein the surface treatment increases the surface energy of the optical substrate by up to 14 mN / m.

[0596] 205. The method of any one of embodiments 193 to 204, wherein the surface treatment comprises applying a primer to a first surface of an optical substrate to form a wet primer coating, and drying and curing the wet primer coating to form the optical surface of the optical substrate.

[0597] 205A. The method of embodiment 205, wherein curing the wet primer coating produces a fully cured primer coating before applying the dye-containing ink formulation.

[0598] 205B. The method as described in embodiment 205A, wherein the hardness coefficient (C) of the fully cured primer coating H The value is at least 0.9 or at least 0.95.

[0599] 205C. The method as described in embodiment 205A or 205B, wherein the thickness (Tp) of the cured primer coating is at least 0.4 μm.

[0600] 205D. The method as described in embodiment 205C, wherein Tp is at least 0.6 μm.

[0601] 205E. The method as described in embodiment 205C, wherein Tp is at least 0.8 μm.

[0602] 205F. The method as described in embodiment 205C, wherein Tp is at least 1.0 μm.

[0603] 205G. The method as described in any one of embodiments 205C to 205F, wherein Tp is at most 3 μm.

[0604] 205H. The method as described in embodiment 205G, wherein Tp is at most 2.5 μm.

[0605] 205I. The method as described in embodiment 205G, wherein Tp is at most 2.0 μm.

[0606] 205J. The method as described in embodiment 205G, wherein Tp is at most 1.7 μm.

[0607] 205K. The method as described in embodiment 205G, wherein Tp is at most 1.4 μm.

[0608] 205L. The method as described in any one of embodiments 205C to 205K, wherein Tp is at least one of local thickness and average thickness.

[0609] 205M. The method as described in any one of embodiments 205 to 205L, wherein the cured primer coating has a non-stick upper surface.

[0610] 206. The method as described in any of the foregoing embodiments, the method further comprising, after processing the wet layer to produce a dry dye-containing layer on the optical surface, applying a wet outer coating onto the outer surface or top of the exposed surface of the dry dye-containing layer.

[0611] 207. The method of embodiment 206, the method further comprising drying and curing the wet outer coating to produce a dry or cured outer coating.

[0612] 208. The method of embodiment 207, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at least 4 μm.

[0613] 209. The method of embodiment 208, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at least 5 μm.

[0614] 210. The method of embodiment 208, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at least 6 μm.

[0615] 211. The method of embodiment 208, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at least 7 μm.

[0616] 212. The method of any one of embodiments 208 to 211, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at most 18 μm.

[0617] 213. The method of embodiment 212, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at most 15 μm.

[0618] 214. The method of embodiment 212, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at most 12 μm.

[0619] 215. The method of embodiment 212, wherein at least one of the local thickness and average thickness of the dried or cured outer coating is at most 10 μm.

[0620] 216. The method as described in any of the preceding embodiments, wherein a first liquid hard coating formulation is applied to the currently exposed optical surface of an optical substrate to form a first wet hard coating.

[0621] 217. The method of embodiment 216, the method further comprising curing the first wet hard coating to form a first fully cured hard coating.

[0622] 218. The method of embodiment 216, wherein at least one of the local thickness and average thickness of the first cured hard coating is at least 2 μm.

[0623] 219. The method of embodiment 216, wherein at least one of the local thickness and average thickness of the first cured hard coating is at least 2.5 μm.

[0624] 220. The method of embodiment 216, wherein at least one of the local thickness and average thickness of the first cured hard coating is at least 3 μm.

[0625] 221. The method of embodiment 216, wherein at least one of the local thickness and average thickness of the first cured hard coating is at least 3.5 μm.

[0626] 222. The method of any one of embodiments 218 to 221, wherein at least one of the local thickness and average thickness of the first cured hard coating is at most 7 μm.

[0627] 223. The method of any one of embodiments 218 to 221, wherein at least one of the local thickness and average thickness of the first cured hard coating is at most 6 μm.

[0628] 224. The method of any one of embodiments 218 to 221, wherein at least one of the local thickness and average thickness of the first cured hard coating is at most 5 μm.

[0629] 225. The method of any one of embodiments 218 to 224, the method further comprising applying a second liquid hard coating formulation to the currently exposed optical surface of the optical substrate to form a second wet hard coating.

[0630] 226. The method of embodiment 225, the method further comprising curing the second wet hard coating to form a second cured hard coating.

[0631] 227. The method as described in any of the preceding embodiments, wherein the optical surface is an ophthalmic surface.

[0632] 228. The method as described in any of the foregoing embodiments, wherein the optical substrate is an ophthalmic substrate.

[0633] 229. The method as described in embodiment 227 or 228, wherein the optical surface or ophthalmic surface is the front surface of the substrate.

[0634] 230. The method as described in embodiment 227 or 228, wherein the optical surface or ophthalmic surface is the back surface of the substrate.

[0635] 231. The method as described in any one of embodiments 227 or 230, wherein the optical surface or ophthalmic surface is convex.

[0636] 232. The method as described in any one of embodiments 227 or 230, wherein the optical surface or ophthalmic surface is concave.

[0637] 233. The method as described in any of the preceding embodiments, wherein the relative motion direction between the nozzle of the microvalve device and the optical substrate is in the XY plane of the optical substrate.

[0638] 234. The method as described in any of the preceding embodiments, wherein the relative motion direction between the nozzle of the microvalve device and the optical substrate is restricted within the XY plane of the optical substrate.

[0639] 235. The method as described in any of the preceding embodiments, wherein during microvalving, the distance between the nozzle of the microvalving device and the optical substrate varies by at least 0.5 mm due to the curvature of the optical substrate.

[0640] 236. The method as described in any of the preceding embodiments, wherein during microvalving, the distance between the nozzle of the microvalving device and the optical substrate varies by at least 1.0 mm due to the curvature of the optical substrate.

[0641] 237. The method as described in any of the preceding embodiments, wherein during microvalving, the distance between the nozzle of the microvalving device and the optical substrate varies by at least 2 mm due to the curvature of the optical substrate.

[0642] 238. The method as described in any of the preceding embodiments, wherein during microvalving, the distance between the nozzle of the microvalving device and the optical substrate varies by at least 3.5 mm due to the curvature of the optical substrate.

[0643] 239. The method as described in any of the preceding embodiments, wherein during microvalving, the distance between the nozzle of the microvalving device and the optical substrate varies in the range of 3.5 to 5 mm due to the curvature of the optical substrate.

[0644] 240. The method as described in any of the preceding embodiments, wherein during the microvalving process, the distance between the nozzle of the microvalving device and the optical substrate is uncontrolled.

[0645] 241. The method as described in any of the preceding embodiments, wherein the average (mean) thickness of the dye on the optical substrate in the printing area is at least 0.2 μm.

[0646] 242. The method of embodiment 241, wherein the average calculated thickness of the dye on the optical substrate is at least 0.3 μm.

[0647] 243. The method of embodiment 241, wherein the average calculated thickness of the dye on the optical substrate is at least 0.4 μm.

[0648] 244. The method of embodiment 241, wherein the average calculated thickness of the dye on the optical substrate is at least 0.5 μm.

[0649] 245. The method of any one of embodiments 241 to 244, wherein the average calculated thickness of the dye on the optical substrate is at most 2 μm.

[0650] 246. The method of embodiment 245, wherein the average calculated thickness of the dye on the optical substrate is at most 1.5 μm.

[0651] 247. The method of embodiment 245, wherein the average calculated thickness of the dye on the optical substrate is at most 1.2 μm.

[0652] 248. The method of embodiment 245, wherein the average calculated thickness of the dye on the optical substrate is at most 1.0 μm.

[0653] 249. The method of embodiment 245, wherein the average calculated thickness of the dye on the optical substrate is at most 0.9 μm.

[0654] 250. The method of embodiment 245, wherein the average calculated thickness of the dye on the optical substrate is at most 0.8 μm.

[0655] 251. The method of embodiment 245, wherein the average calculated thickness of the dye on the optical substrate is at most 0.7 μm.

[0656] 252. The method of embodiment 245, wherein the average calculated thickness of the dye on the optical substrate is at most 0.6 μm.

[0657] 253. The method as described in any of the preceding embodiments, wherein the treatment of the wet layer to produce a dry dye-containing layer is performed after at most three of the wet layers have been micro-valved.

[0658] 254. The method as described in any of the preceding embodiments, wherein the treatment of the wet layer to produce a dry dye-containing layer is performed after at most two of the wet layers have been micro-valved.

[0659] 255. The method as described in any of the preceding embodiments, wherein the treatment of the wet layer to produce a dried dye-containing layer is performed after a single wet layer of the wet layer is micro-valved.

[0660] 256. The method of any one of embodiments 1 to 252, wherein the optical structure has a single dye layer containing a dye.

[0661] 257. The method as described in any of the foregoing embodiments, wherein the first total concentration of the group consisting of tetrahydrofuran (THF), methyl ethyl ketone (MEK) and acetone in the ink formulation is at most 12% by weight.

[0662] 258. The method as described in embodiment 257, wherein the first total concentration is at most 8%.

[0663] 259. The method as described in embodiment 257, wherein the first total concentration is at most 4%.

[0664] 260. The method as described in embodiment 257, wherein the first total concentration is at most 1%.

[0665] 261. The method as described in any of the foregoing embodiments, wherein the second total concentration (TC2) of the group consisting of glycerol, triacetin, propylene glycol, ethylene glycol and polyethylene glycol is at most 3% by weight.

[0666] 262. The method as described in implementation scheme 261, wherein TC2 is at most 2%.

[0667] 263. The method as described in implementation scheme 261, wherein TC2 is at most 1%.

[0668] 264. The method as described in implementation scheme 261, wherein TC2 is at most 0.5%.

[0669] 265. The method of any one of embodiments 77 to 81, wherein the surface treatment includes applying a primer to a first surface of an optical substrate to form a wet primer coating, and drying the wet primer coating to form an optical surface of the optical substrate.

[0670] 266. The method as described in any of the foregoing embodiments, wherein during microvalving, the distance between the nozzle of the microvalving device and the optical substrate is uncontrolled.

[0671] 267. The method as described in any of the foregoing embodiments, wherein the diameter of the optical substrate is at least 40 mm.

[0672] 268. The method as described in any of the foregoing embodiments, wherein the diameter of the optical substrate is at least 50 mm.

[0673] 269. The method as described in any of the foregoing embodiments, wherein the diameter of the optical substrate is at least 60 mm.

[0674] 270. The method as described in any of the foregoing embodiments, wherein the diameter of the optical substrate is at least 70 mm.

[0675] 271. The method as described in any of the foregoing embodiments, wherein the diameter of the optical substrate is at least 80 mm.

[0676] 272. The method as described in any of the foregoing embodiments, wherein the diameter of the optical substrate is at most 90 mm.

[0677] 273. The method as described in any of the foregoing embodiments, wherein the diameter of the optical substrate is in the range of 50 mm to 80 mm.

[0678] 274. The method as described in any of the foregoing embodiments, wherein the optical substrate is a lens blank.

[0679] 275. The method as described in embodiment 274, wherein the lens blank is a semi-finished product.

[0680] 276. The method as described in embodiment 274, wherein the lens blank is a finished product.

[0681] 277. The method as described in any of the foregoing embodiments, wherein the optical substrate is a lens (e.g., an edge lens).

[0682] 278. The method as described in any of the foregoing embodiments, the method further comprising mounting an optical substrate having a dried dye-containing layer to an eyeglass frame (e.g., as its lens).

[0683] 279. The method as described in any of the foregoing embodiments, wherein the method utilizes any one or more features of any ink formulation and property disclosed herein.

[0684] 280. The method as described in any of the foregoing embodiments, wherein the method utilizes any one or more features provided in the system embodiments below.

[0685] 281. The method as described in any of the foregoing embodiments, wherein the method utilizes any one or more features as described herein.

[0686] Optical construction implementation scheme 1. An optical construction as described herein.

[0687] 2. An optical structure comprising any structural feature disclosed in method embodiments 1 to 281.

[0688] 3. An optical configuration comprising any structural feature disclosed in system embodiments 1 to 72.

[0689] 4. The optical structure as described in any one of embodiments 1 to 3, wherein the optical structure is or includes spectacle lenses.

[0690] 5. Eyeglasses, the eyeglasses comprising an eyeglass frame and at least one eyeglass lens according to embodiment 4.

[0691] 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 layer to produce a cured coating on a target surface.

[0692] 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.

[0693] 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.

[0694] 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 photochromic ink formulation application station that a wet layer has been formed on the target surface of the optical substrate.

[0695] 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.

[0696] 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 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.

[0697] 7. The system as described in any of the foregoing embodiments, the system 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.

[0698] 8. The system as described in embodiment 7, wherein the primer application station includes a microvalve device for applying droplets of primer formulation.

[0699] 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 a primer or ink formulation microvalve to the target surface.

[0700] 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.

[0701] 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.

[0702] 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.

[0703] 13. The system as described in any of the foregoing embodiments, wherein the system does not include dip coating equipment.

[0704] 14. The system as described in any of the foregoing embodiments, wherein the system does not contain a spin coating device.

[0705] 15. The system as described in any of the foregoing embodiments, the system comprising a controller configured or programmed to control droplets of the formulation onto a microvalve on a target surface.

[0706] 16. The system as described in any of the foregoing embodiments, wherein the target surface is curved.

[0707] 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.

[0708] 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.

[0709] 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.

[0710] 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.

[0711] 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.

[0712] 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.

[0713] 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.

[0714] 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.

[0715] 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.

[0716] 26. The system as described in embodiment 25, wherein the SAG number is at least 2 mm.

[0717] 27. The system as described in embodiment 25, wherein the SAG number is at least 3.5 mm.

[0718] 28. The system as described in embodiment 25, wherein the SAG number is at least 4.5 mm.

[0719] 29. The system as described in embodiment 25, wherein the SAG number is at least 5 mm.

[0720] 30. The system as described in embodiment 25, wherein the SAG number is at least 6 mm.

[0721] 31. The system as described in embodiment 25, wherein the SAG number is at least 7 mm.

[0722] 32. The system as described in embodiment 25, wherein the SAG number is at least 9 mm.

[0723] 33. The system as described in any one of embodiments 25 to 32, wherein the SAG number is at most 13.5 mm.

[0724] 34. The system as described in embodiment 33, wherein the number of SAGs is at most 12 mm.

[0725] 35. The system as described in embodiment 33, wherein the number of SAGs is at most 10.5 mm.

[0726] 36. The system as described in any one of embodiments 25 to 31, wherein the SAG number is at most 8 mm.

[0727] 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.

[0728] 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.

[0729] 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.

[0730] 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.

[0731] 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.

[0732] 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.

[0733] 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.

[0734] 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.

[0735] 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.

[0736] 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°.

[0737] 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°.

[0738] 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°.

[0739] 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°.

[0740] 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.

[0741] 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.

[0742] 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.

[0743] 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.

[0744] 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.

[0745] 55. The system of embodiment 54, wherein the ink formulation application station includes a non-rotating optical substrate support.

[0746] 56. The system as described in any of the preceding embodiments, wherein the microvalve device is piezoelectrically actuated.

[0747] 57. The system as described in any one of embodiments 1 to 55, wherein the microvalve device is electromagnetically actuated.

[0748] 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°.

[0749] 59. The system as described in embodiment 58, wherein αmax It should be at least 10°.

[0750] 60. The system as described in embodiment 58, wherein α max The angle should be at least 15°.

[0751] 61. The system as described in embodiment 58, wherein α max It should be at least 20°.

[0752] 62. The system as described in embodiment 58, wherein α max The angle should be at least 25°.

[0753] 63. The system as described in embodiment 58, wherein α max The angle should be at least 30°.

[0754] 64. The system as claimed in any one of claims 2 to 4, wherein α max The maximum angle is 50°.

[0755] 65. The system as described in any one of embodiments 58 to 64, wherein α max 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.

[0756] 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.

[0757] 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.

[0758] 68. The system as described in any of the foregoing embodiments, wherein the liquid ink formulation is the ink formulation of any one of formulation embodiments 1 to 231.

[0759] 69. The system as described in any of the foregoing embodiments, wherein the system comprises any one or more features of the ink formulation described in any one of embodiments 1 to 231.

[0760] 70. The system as described in any of the foregoing embodiments, wherein the system includes any one or more features provided in the formulation embodiments.

[0761] 71. 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.

[0762] 72. The system as described in any of the foregoing embodiments, wherein the system includes any one or more features as described herein.

[0763] 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.

[0764] 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 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 prior art to the invention.

Claims

1. A coating system, the coating system comprising: (a) An ink formulation application station, the ink formulation application station including 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; (b) A drying and / or curing station configured to dry and / or cure the wet layer on the target surface to produce its cured coating; (c) An optical substrate transfer apparatus configured to transfer an optical substrate having the wet layer on the target surface from the ink formulation application station to the drying and / or curing station; as well as (d) A processing station for increasing the surface energy of the target surface before applying a wet layer to the target surface; as well as (e) A controller configured or programmed to control the droplets of the formulation onto the microvalve on the target surface; The microvalve described therein enables a dimensionless ink coverage (R) defined by the average formulation volume ratio applied per unit area of ​​the target surface in the edge portion characterized by being located between 90% and 100% of the distance from the centroid of the target surface to its circumference. D1 The characteristic is that the average formulation volume ratio applied per unit area is between 0.60 and 0.96 times in the central region located between 0% and 10% of the distance from the centroid of the target surface to the perimeter.

2. The system of claim 1, 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), wherein the maximum α on the target surface is α0. max And where α max The angle should be at least 5°.

3. The system of claim 2, wherein α max It should be at least 10°.

4. The system of claim 2, wherein α max The angle should be at least 15°.

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

6. The system as claimed in any one of claims 2 to 4, wherein α max 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.

7. The system as claimed in any one of claims 2 to 4, 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.

8. The system as claimed in any one of claims 2 to 4, 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.

9. The system of any one of claims 1 to 8, 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% of the calculated or selected ratio.

10. The system of any one of claims 1 to 9, wherein the processing station is further configured to increase the surface energy of the top surface of the fully cured coating.

11. The system of any one of claims 2 to 10, wherein the system does not include dip coating and spin coating equipment.

12. The system of any one of claims 1 to 11, wherein during the formation of the wet layer, the system is not configured to perform the microvalve while causing relative rotational movement between the microvalve device and the target surface in a horizontal xy plane.

13. The system of claim 12, wherein the ink formulation application station comprises a non-rotating optical substrate support.

14. A method for producing an optical structure on an optical substrate, the method comprising: (a) Providing the system according to any one of claims 1 to 13; (b) Applying an ink droplet microvalves containing at least one dissolving dye to the optical surface of the optical substrate to form a wet layer; as well as (c) Process the wet layer to produce a dry or cured dye-containing layer on the optical surface.

15. The method of claim 14, further comprising, prior to the microvalve, applying a primer to a first surface of the optical substrate to form a wet primer coating, and fully curing the wet primer coating to form the optical surface of the optical substrate.

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

17. The method of claim 15 or 16, the method further comprising applying a surface energy treatment to the top surface of the fully cured primer coating prior to the microvalve.

18. The method of any one of claims 14 to 17, further comprising, after processing the wet layer to produce a dry dye-containing layer on the optical surface, applying a wet outer coating onto the outer surface or top of the exposed surface of the dry dye-containing layer.

19. The method of any one of claims 14 to 18, wherein the liquid ink formulation comprises (a) Resin; (b) Dyes; (c) A solvent system comprising at least one of an extremely low vapor pressure solvent (LLevap), a high vapor pressure solvent (Hevap), and an extremely high vapor pressure solvent (HHevap); The resin, the photochromic dye, and the non-volatile liquid softener are dissolved in the solvent system to form a single liquid phase. The first weight ratio of the resin to the dye is at least 0.5:1; The non-volatile content of the ink formulation is in the range of 2.5% to 15%; The first solvent weight ratio of Hevap, HHevap, and LLEvap in the ink formulation to the total solvent Ts (Hevap + HHevap + LLevap) / Ts It should be at least 0.7; Furthermore, the solvent weight ratio of LLevap to the total amount of Hevap and HHevap is in the range of 0.15:1 to 2.2:

1.

20. The method of claim 19, wherein the relative evaporation rate of LLEvap is at most 0.04.

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