JP2018118518A - Addition manufacturing process of transparent ophthalmic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition manufacturing method of a three-dimensional ophthalmic lens which has good uniformity and optical transparency, reduced contractility, and improved geometry precision and thermo-mechanical property.SOLUTION: The manufacturing process contains a step of constituting a voxel of at least one composition, at least one of the compositions being involving one or more kinds of a prepolymer or a polymer; a step of forming one or more incremental elements by inducing connection property between voxels; a step of repeating the step of constituting; and a step of performing the final post treatment.SELECTED DRAWING: None

Description

  The present invention relates to a method of manufacturing a three-dimensional transparent ophthalmic element such as an ophthalmic lens using an additional manufacturing process and apparatus.

  Additive manufacturing techniques (also known as 3D printers) and devices have become well known in various industries for the manufacture of parts and products that were previously manufactured using removal processing techniques such as traditional machining. . The application of such manufacturing techniques has not been systematically applied.

  Additive manufacturing refers to manufacturing techniques defined in the international standard ASTM2792-12, ie, materials that are usually joined in alternating layers based on 3D model data, as opposed to removal processes such as traditional machining. Means the process of manufacturing objects.

  Additional manufacturing methods include stereolithography (SLA), mask (less) stereolithography or mask (less) projection stereolithography, ink jet printing, eg polymer jetting, scanning laser sintering (SLS), scanning laser melting (SLM). Or, but not limited to, melt deposition modeling (FDM).

  Additive manufacturing techniques include the process of forming objects by juxtaposing volume elements according to a predetermined arrangement that can be defined in a CAD (Computer Aided Design) file. Such juxtaposition may build a material layer on top of a previously obtained material layer and / or juxtapose a volume element or voxel of material adjacent to a previously obtained volume element or voxel, etc. It is understood as the result of sequential operation.

  It is well known to those skilled in the art that the determination of voxel geometry and voxel position is the result of an optimized construction strategy that can take into account the order of sequential manufacturing operations in relation to a given additive manufacturing capability.

  Optimization construction strategies typically include determination of voxel geometry and position, determination of the geometry and position of slices made of multiple voxels, and globalization of voxels and / or slices referenced in additive manufacturing equipment. Determining the orientation of the placement and determining the order according to which voxels and / or slices are to be manufactured.

  A 3D printing device that can be used in the present invention is adapted to build an optical element with juxtaposed voxels. Further, the 3D printing device can be adapted to lay down successive layers of liquid material, powder material, or sheet material based on a series of cross-sections. These layers corresponding to the virtual cross section based on the digital model are polymerized, connected together or fused to form at least part of the optical device.

  The main advantage of this technique is the ability to form almost any shape or geometry feature. Advantageously, using such an additive manufacturing method provides more freedom during the shape determination process.

  Additive manufacturing techniques are a group of techniques that are particularly attractive for manufacturing individualized products with high flexibility and responsiveness. Additional manufacturing techniques are considered in the present invention to produce ophthalmic lenses.

  Within the scope of reference terms for the present invention, if image observation is perceived through the ophthalmic lens without significant loss of contrast, i.e. without adversely affecting the quality of the image viewed by the wearer. An ophthalmic lens is understood to be transparent if an image formation is obtained via the ophthalmic lens. This definition of the term “transparent” is applicable to all objects identified as such in the description within the scope of the reference term of the present invention.

  In essence and directly related to the assembly principle of discrete volume elements (voxels), additive manufacturing techniques present difficulties in managing the bulk uniformity of the final product. This is particularly a problem when considering the production of ophthalmic lenses. Due to the typical size of the voxels considered, typically one dimension of the volume element is in the range of 0.1-500 μm, so ophthalmic lenses obtained from additive manufacturing processes are optically There is a tendency to exhibit refractive index variations on a scale that generates scattering (in other words, haze or diffusion) and / or diffraction, with the possibility of a combination with strain. Therefore, reducing or eliminating the visual impact of such voxel processes is a major challenge in the ophthalmic article manufacturing process. In other words, in ophthalmic applications, the final state is sufficient to avoid changing the propagation of light rays and thus to minimize scattering and / or diffraction phenomena that can cause detrimental loss of contrast. There is a need to be able to produce polymer lens bulk with uniformity. This requirement of reducing the detrimental optical effects of the “voxel unit” construction logic inherent in additive manufacturing technology makes it possible to make voxels light-absorbing materials, for example, to produce colored final lenses, such as those for sunware applications. This also applies to the case of manufacturing in (1).

  In addition, the physical configuration of voxels in additive manufacturing techniques routinely uses physical means that cause voxel geometry variations along the fabrication process. Those physical means can be light-induced polymerization and / or thermal management. These typically produce dimensional changes, such as shrinkage, on individual voxel scales, as well as macroscopic stress buildup on the scale of objects produced by additive manufacturing processes, resulting in final products. It is possible to cause a desired geometry change.

  As far as optical applications are concerned, these above mentioned dimensional changes during the manufacturing process that result from dimensional changes at individual voxel scales or from collective effects associated with voxel sets such as stress build-up are transmitted through the optical properties of the final object and the lens. It has a direct impact on its ability to tune optical wavefront propagation in a deterministic manner controlled over the entire cross-section of the beam. In ophthalmic lenses, such dimensional changes change the final prescription associated with the ophthalmic lens and to be individualized depending on the particular wearer.

  The term “prescription” refers to optical power, astigmatism, determined by an ophthalmologist or optometrist, for example, to correct a wearer's visual anomalies using a lens placed in front of the wearer's eye. It should be understood to mean a group of optical properties including prism deflection and, where appropriate, multifocal. For example, a progressive multifocal lens (PAL) prescription includes optical power values and astigmatism values at far vision points and, where appropriate, multifocal values. The prescription data may include data for sighted eyes.

  Thus, with sufficient control of the individual and collective voxel geometry so that the final geometry delivers a product that has a direct relationship with the initially modeled geometry in the CAD file used by the additive manufacturing equipment, The ability to manufacture objects by additive manufacturing is another major challenge for ophthalmic applications.

  More specifically, it is particularly desirable to be able to control the shrinkage of the monomer system during polymerization when the geometric changes of the lens produced by the additive manufacturing considered above are associated with polymerization shrinkage at the voxel level.

  Presented herein is a method of manufacturing a three-dimensional ophthalmic lens, more specifically an ophthalmic lens.

  An “ophthalmic lens” according to the present invention is defined as an adapted lens having the function of eye protection and / or vision correction, ie a lens adapted to be attached to an eyeglass. This lens can be an afocal lens, a single focus lens, a bifocal lens, a trifocal lens, or a progressive lens. The ophthalmic lens can be a corrective lens or a non-corrective lens. The eyeglass to which the ophthalmic lens is attached is a traditional frame that includes two separate ophthalmic lenses for the right and left eyes, or one ophthalmic lens that faces the right and left eyes simultaneously. Or similar masks, visors, helmet sites, or goggles. The ophthalmic lens can be manufactured with a traditional geometry as a circle, or can be manufactured to the intended frame.

  The present invention presents a method for manufacturing a three-dimensional ophthalmic lens that conforms to the geometry of a frame dedicated to ophthalmic lenses. An ophthalmic lens manufactured according to any of the methods according to the present invention can be further functionalized by adding at least a functional coating and / or a functional film, optionally in a further step of post-processing the lens. is there. Functionality can be added to one side of the ophthalmic lens or both sides of the ophthalmic lens, and the functionality of each side can be the same or different. Functionality is anti-wear filter, impact filter, anti-fouling filter, anti-static filter, anti-reflection filter, anti-fog filter, rain filter, self-healing filter, polarizing filter, coloring filter, dimming filter, and absorption filter or The selective wavelength filter can be obtained through a reflection filter, but is not limited thereto. Such selective wavelength filters are particularly useful for blocking, for example, ultraviolet light, blue light, or infrared light. Functionality may be added by at least one process selected from a dip coating process, a spin coating process, a spray coating process, a vacuum deposition process, a transfer process, or a lamination process. A transfer process is understood as that the functionality is first constructed on a support such as a carrier and then transferred from the carrier to the ophthalmic lens via an adhesive layer constructed between the two elements. Is done. Lamination is defined as obtaining permanent contact between a film comprising at least one functionality disclosed herein and the surface of the ophthalmic lens being processed, where permanent contact is defined by two entities. It is obtained by establishing contact between the film and the lens, optionally followed by a polymerization process or a heating process, so that adhesion and adhesion between them is determined. At the end of this lamination process, the assembled film and optical lens form one single entity. During the lamination process, an adhesive is used to laminate the boundary between the film and the ophthalmic lens.

  The ophthalmic lens produced by the method according to the present invention has the following characteristics: 30 or more, preferably 35 in order to avoid high opacity, chromatic aberration, in the absence of light scattering or haze or optionally at very low levels. High Abbe number above, low yellowing index and absence of yellowing over time, good impact strength (specifically according to CEN and FDA standards), various treatments (shock resistant primer construction, antireflection coating) Good suitability for construction, hard coating construction, etc., in particular good suitability for coloration, preferably above 65 ° C., better still glass transition temperature values above 90 ° C.

  Haze is the percentage of transmitted light that deviates from the incident beam due to forward scattering as it passes through the sample. Only luminous fluxes that deviate by more than 2.5 ° on average are considered to be haze. In other words, haze is a measure of the intensity of transmitted light that is scattered over 2.5 °. When viewed through the sample, it can have an emulsion or cloudy appearance. Low values are low “haze” measurements. As haze increases, a loss of contrast occurs until the object becomes invisible. Typically, ophthalmic lenses can exhibit a haze level of less than 1%.

  The present invention describes a method for solving the above-described problems associated with additive manufacturing techniques for manufacturing three-dimensional ophthalmic lenses. The method includes 1) constructing one or more voxels of the composition, wherein at least one of the compositions comprises one or more prepolymers or polymers, and 2) providing connectivity between the voxels. The step of forming one or more incremental elements by guiding, the step of repeating the configuration step, and the final to ensure the final uniformity of the ophthalmic lens produced by the group of juxtaposed voxels And a post-processing step.

  The present invention is based on the use of voxels made of one or more compositions with reduced or no shrinkage, such as dimensional changes between the initial configuration of the voxel and the final state of the ophthalmic lens in an additive manufacturing process. A method of manufacturing a three-dimensional uniform transparent ophthalmic lens is proposed. Described herein are one or more implementations of a method for manufacturing a transparent ophthalmic lens using an additive manufacturing configuration process that provides a transparent ophthalmic lens having particularly improved properties through proper material selection. It is a form.

  More specifically, presented herein comprises constituting a first voxel of a first composition comprising at least one polymer or prepolymer, and at least a polymer or prepolymer. Forming a second voxel of the second composition; forming an incremental intermediate element by inducing connectivity between the configured first and second voxels; and sequentially adding voxels And a step of forming a three-dimensional transparent ophthalmic lens by repeating an arrangement step and a connectivity inducing step to form an incremental intermediate element.

  Also presented herein are constituting a first voxel of a first composition comprising at least one polymer or prepolymer, and a second composition comprising at least one monomer. Forming a second voxel of the object, forming an incremental intermediate element by inducing connectivity between the first and second configured voxels, and sequentially configuring and connecting the additional voxels A process for forming a three-dimensional transparent ophthalmic lens by repeating an sex induction process to form an incremental intermediate element.

  More details regarding various embodiments of the present invention are further described in the detailed description.

  The advantages, properties, and various additional features of the present invention will become more fully apparent in view of the exemplary embodiments described in detail below in connection with the accompanying drawings. In the drawings, like reference numbers represent like components throughout the drawings.

  For a more complete understanding of the description provided herein and its advantages, reference is now made to the following brief description in conjunction with the accompanying drawings and detailed description. However, the same reference number represents the same part.

FIG. 1 illustrates a first exemplary process for manufacturing a three-dimensional ophthalmic lens. FIG. 2 illustrates a second exemplary process for manufacturing a three-dimensional ophthalmic lens. FIG. 3 illustrates a third exemplary process for manufacturing a three-dimensional ophthalmic lens. FIG. 4 illustrates a fourth exemplary process for manufacturing a three-dimensional ophthalmic lens.

  Words or terms used herein are expressly defined in the field of this disclosure, unless expressly and explicitly defined in this disclosure, or unless otherwise required by context. Has meaning.

  In case of any conflict in usage of words or terms in one or more patents or other documents that may be incorporated by this disclosure and reference, definitions consistent with this specification should be employed.

  The words “comprising”, “containing”, “including”, “having” and all their grammatical variants are open It is intended to have a non-limiting meaning. For example, a composition that includes an ingredient does not exclude having an additional ingredient, an apparatus that includes a part does not exclude having an additional part, and a method that includes a process requires additional It does not exclude having a process. When such terms are used, the specific components, parts, and processes “consisting essentially of” or “consisting of” compositions, devices, and methods are specifically encompassed and disclosed. As used herein, the term “consisting essentially of” and all grammatical variations thereof are intended to identify the material or process specified and the basics of the claimed invention. It is also intended that the claims be limited to those that do not substantially affect the novel features.

  The indefinite article “a” or “an” means one or more components, parts, or steps introduced by the article.

  Whenever a degree or numerical range of measurement having a lower and upper limit is disclosed, any number and any range falling within the range is also intended to be specifically disclosed. For example, a range of values (“from a to b” or “about a to about b” or “about a to b”, “about all of “a” and “b” in the form of “a to b” (from “a” and “b” representing a range or measurement number) It should be understood to indicate all numbers and ranges that fall within the broader range of values, including the value itself. Terms such as “first”, “second”, “third”, etc. may be arbitrarily assigned and are otherwise two or more components, parts that are similar or corresponding in nature, structure, function, or action Or merely to distinguish the steps. For example, the words “first” and “second” serve no other purpose and are not part of the name or description of the subsequent name word or descriptive word. The mere use of the term “first” does not imply that any “second” similar or corresponding component, part, or step is present. Similarly, the mere use of the word “second” does not imply that any “first” or “third” similar or corresponding component, part, or step is present. Furthermore, the mere use of the term “first” does not mean that the element or step is the very first of any sequence, but merely means that it is at least one of the elements or steps. It should be understood that there is no. Similarly, the mere use of the terms “first” and “second” does not imply any sequence. Accordingly, the mere use of such terms does not exclude an element or step intervening between “first” and “second” elements or steps.

  As used herein, “additional manufacturing” refers to a manufacturing technique defined in International Standard ASTM 2792-12 that describes the process of joining materials to create a 3D solid object from a 3D digital model. The process is called “3D printing” or “material printing” because successive layers are laid down on top of each other. Printing materials include liquids, solids such as powders, or sheet materials from which a series of cross-sectional layers are accumulated. The layers corresponding to the virtual cross section based on the CAD model are connected or automatically fused to form a solid 3D object. Additional manufacturing includes stereolithography, mask (less) stereolithography, mask (less) projection stereolithography, ink jet printing such as polymer jetting, scanning laser sintering (SLS), scanning laser melting (SLM), melt deposition modeling (FDM) ) And the like, but is not limited thereto. Additive manufacturing techniques typically include the process of forming a 3D solid object by juxtaposing volume elements or particles according to a predetermined arrangement defined in a CAD (Computer Aided Design) file. Side-by-side is understood as a sequential operation including accumulating one material layer on a pre-accumulated material layer and / or placing a material volume element adjacent to a preconfigured material volume element. Is done.

  As used herein, “voxel” means a volume element. A voxel is an identifiable geometry shape that is part of a three-dimensional space. The voxel size is typically in the range of one dimension from 0.1 to 500 μm. A “voxel” may refer to an individual element that can define a line or layer or other predetermined shape or pattern in three-dimensional space in combination with other voxels. The constructed voxels can be of any desired shape, depending on the technology used and the conditions of the manufacturing process. Multiple or groups of adjacent voxels, when placed, can form or define a line or layer and can constitute an optical element. A particular voxel can be identified by the x, y, and z coordinates of selected points in the geometry, such as corners, centers, or by other means known in the art. The voxel boundary is defined by the outer surface of the voxel. Such a boundary can be in close proximity, in contact, or not in contact.

  As defined herein, “homogeneity” refers to any variation in the refractive index of a material capable of inducing significant scattering, haze, diffraction, distortion, and / or striations in the visible spectral region. Means absent in the material. Specifically, uniformity means that the bulk lens material includes voxels composed of the same composition, and each voxel exhibits the same final refractive index.

  As used herein, “connectivity” and its derivatives refer to connectivity between at least a portion of a first voxel and at least a portion of a second voxel. At least a portion of each of the first and second voxels is an interaction, for example, but not limited to a chemical bond such as an ionic bond, covalent bond, metal bond, or mechanical bond such as molecular entanglement. Or one or more species that may form any combination thereof. This connectivity is, but is not limited to, at least one species from at least a portion of the first voxel and at least a portion of the second voxel, or from at least a portion of the second voxel. An interaction with or without diffusion between at least one species and at least a portion of the first voxel, or any combination thereof may be included. The species can be at least one molecule, monomer, prepolymer, polymer chain, or any other species known in the art. An advantage of connectivity between two voxels is that the boundary between the voxels is removed to provide improved optical clarity and thermomechanical properties. “Internal connectivity” should be understood to mean connectivity between at least a portion of the first voxel and at least a portion of the same first voxel. An advantage of internal connectivity may be that thermomechanical properties are improved by increasing molecular weight. Connectivity can occur naturally or can be induced by physical, chemical, or mechanical processing, or any combination thereof. As used herein, “physical treatment” may include, but is not limited to, heat treatment by means such as exposure to heat, infrared, microwave, or radiation. Such heat treatment can increase the temperature, thereby increasing the molecular chain mobility of the monomer, prepolymer, or polymer, or any other species in the voxel, improving the connectivity of the voxel. Will. Other examples of physical treatment include plasma discharge or corona discharge to modify the surface. As used herein, “chemical treatment” can be a treatment that uses one or more chemicals that result in chemical modification of one or more compositions. For example, chemical treatment can include exposure to acids, bases, surfactants, halogens, and the like. As used herein, “mechanical processing” includes agitation, for example, agitation by exposure to acoustic or ultrasonic energy, agitation with a high frequency vibration device that can promote mixing of voxels at the voxel surface boundary. Can be mentioned. As a result of any one of the physical, chemical, and / or mechanical treatments described herein, the prepolymer and / or polymer present in the voxel, for example, by a two-pass chemical process or a reversible reaction The molecular weight of can be reduced to promote interdiffusion of voxels.

  As used herein, “inducing connectivity” means that at least a first voxel and at least a second voxel are any one of mechanical, physical, or chemical treatments or their Any combination is meant to cause intimate contact between at least a portion of at least a first voxel and at least a portion of at least a second voxel. Inducing “internal connectivity” means applying any one of mechanical treatment, physical treatment, chemical treatment or any combination thereof to at least a portion of the first voxel. Meaning causing intimate contact between at least a portion of the voxels and at least a portion of the same first voxel.

  As used herein, a “polymer composition” can include a photopolymerizable and / or thermally polymerizable composition. By photopolymerizable composition is meant a composition that undergoes polymerization upon exposure to actinic radiation, including but not limited to UV, visible, IR, microwave, and the like. A thermopolymerizable composition means a composition in which polymerization occurs upon exposure to a temperature change. Broadly interpreted, according to the present invention, the polymerizable composition may comprise a thermoplastic or thermosetting polymer.

  As used herein, a “thermoplastic” polymer is understood to be a thermoplastic resin, preferably optically clear and optical grade, that is meltable when exposed to heat. Examples of thermoplastic materials that can be used include polyolefins such as cycloolefin polymers, polyacrylates such as polymethyl (meth) acrylate, poly (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, and polyisobutyl (meth) acrylate. Polyesters, polyamides, polysiloxanes, polyimides, polyurethanes, polythiourethanes, polycarbonates, polyallyls, polysulfides, polyvinyls, polyarylenes, polyoxides and polysulfones, and blends thereof, but are not limited thereto. At least one of the polymers or prepolymers described herein can include at least one thermoplastic. Thermoplastic materials can be solid particles, including powders, beads, and rods.

  As used herein, “polymerization” refers to a chemical reaction that forms a polymer by forming bonds of one or more monomers and / or prepolymers.

  As used herein, “curing” refers to a chemical process that converts a monomer or prepolymer having a first molecular weight into a polymer and / or network having a second higher molecular weight.

  As used herein, “monomer” and / or “prepolymer” means at least one reaction capable of reacting to exposure to activating light and / or temperature changes in the presence of at least one initiator. It means a chemical compound containing a group. Such monomers and / or prepolymers include at least one reactive group such as, but not limited to, olefins, acrylics, epoxides, organic acids, carboxylic acids, styrene, isocyanates, alcohols, norbornene, thiols, amines. Amides, anhydrides, allyls, silicones, vinyl esters, vinyl ethers, vinyl halides, and episulfides. Other suitable monomer prepolymers are described herein.

  As used herein, “substrate” means the surface on which voxels are deposited to accumulate the desired ophthalmic lens. An example of the substrate is a platen for SLA.

  As used herein, the term “reactive group” means a functional group of a composition that can chemically react with a functional group of the same composition or a different composition to form a covalent bond. The functional groups can be the same or different.

  As used herein, “construct voxel” and its derivatives means selectively depositing droplets of a composition on a substrate, for example, via a printhead. In one aspect, voxels can be constructed by depositing molten polymer wire using a heated nozzle printhead. In this case, the additive manufacturing technique is melt deposition modeling (FDM). In other cases, voxels are constructed by depositing droplets of a liquid composition using polymer jetting with additive manufacturing techniques. “Composing voxels” also means selective polymerization of a composition capable of generating voxels. This includes, for example, UV exposure of monomers or prepolymers at specific locations in the bath. In this case, the additive manufacturing technique used is stereolithography, mask (less) stereolithography, or mask (less) projection stereolithography.

  As used herein, “activating light” means light having a wavelength that can cause a chemical change.

  As used herein, “initiator” means a photoinitiator or a thermal initiator.

  As used herein, “photoinitiator” means a molecule that generates at least one reaction-initiating species (ion or radical) upon exposure to light to initiate a chemical reaction or transformation. Photoinitiators can be used alone or in combination with one or more compounds such as coinitiators. The choice of photoinitiator is primarily based on the nature of the reactive groups of the monomer or prepolymer used in the composition, as well as the rate of the polymerization reaction. The photoinitiator can also include a free radical initiator. It is well known that cationic curable compositions cure more slowly than free radical curable compositions. Some examples of photoinitiators include acetophenone, benzyl and benzoin compounds, benzophenone, cationic initiators, and thixanthone. Other exemplary photoinitiators and free radical initiators are described herein.

  As used herein, "thermal initiator" means a species that can efficiently induce or cause polymerization or crosslinking upon exposure to heat. Thermal initiators can include, but are not limited to, organic peroxides, inorganic peroxides, or azo initiators. Organic peroxides can include, but are not limited to, peroxycarbonates, peroxyesters, dialkyl peroxides, diacyl peroxides, diperoxyketals, ketone peroxides, and hydroperoxides. Inorganic peroxide thermal initiators can include, but are not limited to, ammonium persulfate, potassium persulfate, and sodium persulfate.

  As used herein, “co-initiator” means a molecule as part of a chemical system that does not absorb light but is involved in the generation of reactive species. Co-initiators are particularly suitable for combination with certain free radical initiators such as benzophenone that require a second molecule, such as an amine, to generate curable radicals. In that case, under UV radiation, benzophenone reacts with tertiary amines by hydrogen abstraction to generate α-amino radicals that are well known to initiate polymerization of (meth) acrylate monomers or prepolymers.

  Presented herein are four different approaches for forming ophthalmic lenses using polymers and / or prepolymers in compositions used during additive manufacturing processes. These approaches are addressed below and are briefly described in Table 1 below.

  The first technical approach includes 1) constructing a first voxel of a first composition comprising at least one polymer or prepolymer, and 2) second comprising at least one polymer or prepolymer. Forming a second voxel of the composition of 3), 3) inducing connectivity between the first and second voxels to form an intermediate element, and then 4) step 2) with additional voxels. And 3) to form an incremental intermediate element to form a three-dimensional transparent ophthalmic lens. The advantages of this approach include a very low shrinkage incidence, improved geometry accuracy, desired thermomechanical properties, and suitable optical transparency.

  The second approach consists of 1) constructing a first voxel of the first composition comprising at least one polymer or prepolymer and at least one monomer, and 2) at least one polymer or prepolymer. Forming a second voxel of a second composition comprising a polymer and optionally at least one monomer; and 3) inducing connectivity between the first and second voxels to form an intermediate element And then forming the three-dimensional transparent ophthalmic lens by repeating steps 2) and 3) with additional voxels to form an incremental intermediate element. In this approach, the at least one monomer of the first and second compositions can be the same or different. Advantages of this approach include low shrinkage rates, improved geometry accuracy, reduced composition viscosity, and enhanced crosslinking. As a result, it is possible to increase the Tg (glass transition temperature) of the final lens product and ensure improved thermomechanical properties.

  The third approach includes 1) constructing the first voxel of the first composition comprising at least one polymer or prepolymer, and 2) second of the second composition comprising at least one monomer. Repeating the steps 2) and 3) with 2 voxels, 3) inducing connectivity between the first and second voxels to form an intermediate element, and 4) additional voxels. Forming a three-dimensional transparent ophthalmic lens by forming an incremental intermediate element. Advantages of this approach include, but are not limited to, the ability to produce ophthalmic lenses using two or more additional manufacturing processes such as FDM and inkjet printing simultaneously. Another advantage is that additives can be added to the monomer phase. Monomers can facilitate the incorporation of other compounds into the liquid phase that can be used in the manufacture of hybrid ophthalmic lenses, including but not limited to inorganics, organometallics, metal oxides, nanoparticles, etc. is there. A hybrid ophthalmic lens can be defined as an organic lens containing at least one inorganic material. Still other advantages include low shrinkage rates, improved geometry accuracy, and enhanced crosslinking. As a result, it is possible to increase the Tg (glass transition temperature) of the final lens product and ensure improved thermomechanical properties.

  The fourth approach includes 1) constructing the first voxel of the first composition comprising at least one polymer or prepolymer and at least one monomer, and 2) comprising at least one monomer. Forming a second voxel of the second composition; 3) inducing connectivity between the first and second voxels to form an intermediate element; and 4) processing with additional voxels. Forming a three-dimensional transparent ophthalmic lens by repeating 2) and 3) to form an incremental intermediate element. Advantages of this approach include, but are not limited to, the ability to produce ophthalmic lenses using two or more additional manufacturing processes such as FDM and inkjet printing simultaneously. Other advantages include low shrinkage incidence, improved geometry accuracy, reduced composition viscosity, enhanced crosslinking, and increased Tg (glass transition temperature) and improved thermomechanical properties.

  Some advantages are realized from an additive manufacturing process utilizing a composition comprising a prepolymer and / or polymer precursor. The desired three-dimensional element shrinkage during the manufacturing process can be directly related to the internal stress. One advantage is that the presence of prepolymers and / or polymer precursors acting in place of the reaction liquid reduces internal stress and shrinks, resulting in a reliable end product.

  Another advantage of using a composition comprising a prepolymer precursor is that subsequent processing steps can be optimized by filtration, processing, or purification prior to use in an additive manufacturing process. It is possible to use high modulus precursors to improve thermomechanical properties. Also, prepolymers and / or polymer precursors allow safe use of other hazardous chemicals. For example, safe handling of prepolymer cyanoacrylates or isocyanates and use in standard casting processes is possible.

  In addition, the use of polymer and / or prepolymer precursors allows the design of desired precursors containing one or more reactive groups of the same or different types in a single precursor.

  As described above, the present invention includes three main steps incorporating a liquid composition for producing a 3D transparent ophthalmic lens. These steps are as follows: 1) a step of constituting the first voxel of the first composition, and 2) a step of constituting the second voxel of the second composition, wherein the composition is Repeat steps 2) and 3) with the steps described in Table 1, 3) inducing connectivity between the first and second voxels to form an intermediate element, and then with additional voxels Forming a three-dimensional transparent ophthalmic lens by forming an incremental intermediate element. Optionally, a final post-process treatment step can be performed on the final product, and this method is described herein. Ophthalmic lenses formed according to any of these methods are also presented herein.

  In accordance with the present invention and depending on certain additive manufacturing techniques, the three steps described above after voxel units, line units, layer units, and / or after all desired layers or lines have been formed. By completing the above, a three-dimensional transparent ophthalmic lens can be manufactured.

  In one embodiment, the additive manufacturing process described herein can incorporate the use of prepolymers or polymers. In general, for example, a prepolymer or polymer selected in a liquid monomer for use in a 3D printing process can be mixed, dissolved, or dispersed to form an optical element. One or more prepolymers and / or polymers can be used as the prepolymer material. In one aspect, the first and second compositions can be the same or different. The first and second compositions can include the same or different polymers and / or prepolymers.

  The prepolymer or polymer selected can be a solid mixed, dissolved, or dispersed in a liquid having one or more monomers. In one aspect, the monomer of the first or second composition can naturally connect to one or more other monomers of the first or second composition or at least one polymer or prepolymer. In yet another aspect, the monomer is capable of reacting with a second monomer that can be added after the first monomer and configured after the first layer of voxels. As another option, in other embodiments, the first or second composition may include a monomer that can spontaneously react with the monomer itself upon curing.

  A composition having a prepolymer or polymer mixed, dissolved, or dispersed can be configured as a voxel on a substrate using an additive manufacturing process or device. Preferably, as described above, a 3D printer head is used in the composition composition. Additive manufacturing device suppliers provide the specifications and guidelines necessary for the materials used in the device. An example of a commercially available 3D printing device is ZPrinter® (commercially available from 3D Systems). The fluidity of the prepolymer or polymer composition can be achieved by subjecting the composition to a heat treatment. The treatment can be, for example, thermal radiation, convection heating, conduction heating, cooling, chilling, infrared, microwave, UV radiation, visible light, evaporation, or at least to a temperature below that used in at least one component step of the voxel. Includes exposure of one voxel. A plurality of voxels can be formed to form a single layer. In one exemplary embodiment, the layer can be about 0.127 mm or more thick. The neighboring voxels can then be connected to each other using any of the methods described herein to eliminate or initiate a boundary between the voxels.

  The polymer or prepolymer can be present in a solvent, reaction solvent, or monomer. The liquid mixture can be configured as a voxel at a lower temperature after being heated to a high temperature. The temperature range can be about 5 ° C to about 150 ° C, more preferably about 30 ° C to about 150 ° C, and most preferably about 50 ° C to about 100 ° C. At lower temperatures, an increase in mixture viscosity can occur. Increasing the viscosity is sufficient to maintain the voxel geometry and position. The voxels are placed in close proximity to each other so that the monomer can wet the surface of the voxel. The process is repeated until the desired number of voxels is configured in close proximity to each other. In one aspect, the voxels can be placed in close proximity to each other. The wet surfaces of adjacent voxels eliminate the voxel boundaries by interdiffusing.

  Voxel connectivity can be facilitated or triggered by natural connectivity or inductive connectivity, for example, by exposure to radiation (heat, infrared, microwave, etc.). Connectivity is the composition of one or more monomers, prepolymers or polymers present in the composition or between one or more monomers, prepolymers or polymers present in the composition and voxels for that purpose. It can occur between one or more additional monomers, prepolymers, or polymers added later. In other exemplary realizations, they are subjected to mechanical, physical and / or chemical treatment in prepolymers or polymer / monomer mixtures, solutions or suspensions in one voxel. Inducing connectivity in the first voxel, for example, between its prepolymer portion or polymer portion of the voxel and the liquid monomer by forming a uniform intermediate element prior to construction of the second voxel Is possible.

  To successfully achieve natural connectivity, the voxel composition can be manufactured at a constant ratio at manufacturing conditions so that sufficient connectivity is achieved between the juxtaposed voxels to achieve the desired thermomechanical and optical properties. It is expected to be less than the viscosity. The connected voxels can then be subjected to various treatments, such as exposure to radiation (eg, infrared, microwave, UV, visible light, or any combination thereof) to obtain an intermediate element. It is possible to react this with additional voxel compositions by reactions such as crosslinking (cations, free radicals, condensation-heat). Curing can also be achieved, for example, by annealing, drying, and / or solvent evaporation. Optionally, when configuring the second voxel of the second composition to induce connectivity between the voxel and successive additional voxels, the method evaporates at least one voxel and at least one intermediate element. Or it may further include subjecting to cooling. If desired, further treatments such as UV or IR radiation can be performed for solvent evaporation or reaction solvent curing. The process can be repeated to form an ophthalmic lens of the desired shape.

  Connectivity can occur naturally or can be induced by the introduction of an energy source. Connectivity is defined between one or more monomers present in the composition or one or more monomers present in the composition and one or more additional monomers added for that purpose after the composition of the composition. Can occur between. The connected voxels can then be subjected to various treatments to cure the layer as a monolithic optical element. Curing can be accomplished by exposure to UV, IR, heat, microwave, or other radiation, and any combination thereof. Curing can also be achieved by crosslinking (cations, free radicals, condensation-heat), annealing, drying, and / or solvent evaporation.

  In one aspect, a first prepolymer composition (having one or more prepolymers) and a different second composition (having one or more prepolymers) are used as the first and second voxel compositions. Two or more prepolymer compositions can be prepared and used alternately in an additive manufacturing process so that they can be configured sequentially and alternately. As another option, a single composition may include multiple monomers that each react or cure in response to different curing methods. For example, the composition may have a first monomer curable in response to UV radiation and a second monomer curable in response to thermal radiation.

  In an exemplary embodiment, the voxels can be configured with a predetermined order, a predetermined sequence or pattern of first and second compositions, or a pre-programmed time / temperature profile of a predetermined composition. . For example, the order of voxel configuration in which two or more compositions A and B are used may be any order, eg, ABAB. . . , AABB. . . , AABAAB. . . And so on. Furthermore, the voxels can be configured as a single composition of voxels in a layer. For example, a voxel group of the first composition A can constitute a first layer, and then a voxel group of the second composition B can constitute a second layer. This same approach uses three or more compositions A, B, C,... Where voxels of different compositions can be configured in any order. . . It is applicable to a method using n.

  Voxels (regardless of their composition) can be configured in rows, full or partial layers, lines, clusters, or based on manufacturing process requirements such as when non-adjacent configurations are obtained by temperature control . The pattern can also depend on practical concerns such as the preferred shape of the final optical element.

  Materials that can be used as polymers or prepolymers particularly recommended for optical elements such as ophthalmic lenses are polycarbonates, for example those made from bisphenol-A polycarbonate, such as LEXAN® (Sabic Innovation Plastics) or Diethylene glycol sold under the trade name MAKROLON® (Bayer AG) or di-ethylene glycol sold under the trade name CR-39® (PPG Industries) (ORMA® Essilor lens) Obtained by polymerization or copolymerization of bis (allyl carbonate), acrylic having a refractive index of 1.56, for example ORMUS® (Essilor), thiourethane Rimmer, and polyepisulfide polymer. Other suitable are synthetic organic polymer materials such as polyester, polyamide, polyimide, acrylonitrile-styrene copolymer, styrene-acrylonitrile-butadiene copolymer, polyvinyl chloride, butyrate, polyethylene, polyolefin, epoxy resin, epoxy-fiber glass composite. Other recommended materials include those obtained by polymerization of thio (meth) acrylic monomers as disclosed in French Patent 2734827. These materials can be obtained by polymerizing a mixture of monomers described herein. Thus, the voxels described herein can include any of these materials desirable for the manufacture of optical elements based on optimal quality of transparency and transparency. More specifically, any of the polymers or prepolymers used in the processes described herein can include one or more of these materials. In some methods, additional components may also be included in one or more monomer compositions, prepolymer compositions, or polymer compositions described herein. For example, a pre-monomer composition, a pre-polymer composition, or a polymer composition may vary depending on the manufacturing process, the characteristics of the composition, and the mechanical, chemical, and / or physical processes that are applied. One or more additives, solvents, initiators, catalysts, surfactants, and / or other components as described herein may be included. That is, additional additives include light inhibitors (HALS), diluents, stabilizers, tackifiers, thickeners, diluents, fillers, antiozonants, dyes, UV or IR absorbers, fragrances Agents, deodorizers, antioxidants, yellowing inhibitors, binders, plasticizers, light control materials, pigments, nucleating agents, thixotropic agents.

  Examples of acceptable solvents suitable for the compositions described herein comprising monomers and / or prepolymers or polymers are organic solvents, preferably methanol, ethanol, propanol, butanol, glycol, and glycol monoethers. Such a polar solvent. These solvents can be used alone or in combination. Solvents suitable for liquid polymerizable compositions containing polymers such as thermoplastic polymers include toluene, benzene, cyclohexene, hexane, tetrahydrofuran, pentane, ketones such as acetone and methyl ethyl ketone, and acetates to name a few. An organic solvent such as, preferably a polar solvent.

  Examples of acceptable surfactants that can be used in accordance with the disclosed methods are ionic (cationic, anionic, or amphoteric) or nonionic surfactants, preferably nonionic or anionic interfaces It can be an active agent. However, mixtures of surfactants belonging to these various categories can be envisaged. Most of these surfactants are commercially available. In one exemplary embodiment, a surfactant comprising a poly (oxyalkylene) group can be used. Examples of nonionic surfactants suitable for use in the present invention include poly (alkyleneoxy) alkyl ethers, specifically poly (ethyleneoxy) alkyl ethers, such as the trade name BRIJ®. Commercially available by ICI, poly (alkyleneoxy) alkylamines, poly (alkyleneoxy) alkylamides, polyethoxylated fatty alcohols, polypropoxylated fatty alcohols, or polyglycerolated fatty alcohols, polyethoxylated α Fatty diol, polypropoxylated α-fatty diol, or polyglycerolated α-fatty diol, polyethoxylated fatty alkylphenol, polypropoxylated fatty alkylphenol, or polyglycerolated fatty alkylphenol, and polyethoxy Fatty acids, polypropoxylated fatty acids, or polyglycerolated fatty acids, all having, for example, fatty chains containing 8 to 18 carbon atoms, especially if the number of ethylene oxide units or propylene oxide units is Those that can be in the range of 2-50, or those in which the number of glycerol moieties can specifically be in the range of 2-30, ethoxylated acetylenic diols, hydrophilic blocks and hydrophobic blocks (eg, poly Examples thereof include a block copolymer type compound containing an oxyethylene block and a polyoxypropylene block at the same time, a copolymer of poly (oxyethylene) and poly (dimethylsiloxane), and a surfactant having a sorbitan group incorporated therein.

  In other embodiments, anionic surfactants containing sulfonic acid groups can be used, including alkyl sulfosuccinate, alkyl ether sulfosuccinate, alkylamido sulfosuccinate, alkyl sulfosuccinate, among others. Cinnamate, polyoxyethylene alkylsulfosuccinic acid dibasic salt, alkylsulfosuccinic acid dibasic salt, alkyl sulfoacetate, sulfosuccinic acid hemiester salt, alkyl sulfate and aryl sulfate, such as sodium dodecylbenzene sulfonate and sodium dodecyl Sulfate, ethoxylated fatty alcohol sulfate, alkyl ether sulfate, alkyl amide ether sulfate, alkylaryl polyether sulfate, alkyl sulfonate, alcohol Kill phosphate, alkyl ether phosphate, alkyl amide sulfonate, alkyl aryl sulfonate, α-olefin sulfonate, secondary alcohol ethoxy sulfate, polyoxyalkylated carboxylic acid ether, monoglyceride sulfate, polyoxyethylene alkyl ether sulfate, sulfate ester Salts, N-acyl taurates, such as N-acylmethyl taurate, monosulfonic acid hydroxyalkane salts, or alkene monosulfonates, and the alkyl or acyl groups of all these compounds are preferably 12 to The optional oxyalkylene groups containing 20 carbon atoms and these compounds preferably contain 2 to 50 monomer units. These anionic surfactants and many others that are preferably used in this application are described in EP 1418211 and US Pat. No. 5,997,621.

  Examples of suitable cationic surfactants for use in the present invention include primary, secondary, or tertiary fatty amine salts, optionally polyoxyalkylenated quaternary ammonium salts, Examples include tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium, or alkylpyridinium chlorides or bromides, cationic imidazoline derivatives or amine oxides.

  In one embodiment, the surfactant used may comprise a fluorinated surfactant. In this case, preferably those containing at least one fluoroalkyl group or polyfluoroalkyl group will be used, more preferably those containing at least one perfluoroalkyl group.

  In general, the photoinitiator for initiating polymerization of the lens-forming composition preferably exhibits an absorption spectrum ranging from 200 to 400 nm, more preferably from 300 to 400 nm. The following: methylbenzoyl formate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-di-sec-butoxyacetophenone, 2,2- Diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-dimethoxy-2-phenyl-acetophenone, benzoin methyl ether, benzoin isobutyl ether, benzoin, benzyl, benzyl disulfide, 2,4-dihydroxy Benzophenone, benzylidene acetophenone, benzophenone, and acetophenone are examples of exemplary photoinitiator compounds that are within the scope of the present invention. Still other exemplary photoinitiator compounds are 1-hydroxycyclohexyl phenyl ketone (commercially available from Ciba-Geigy as Irgacure® 184), methyl benzoylformate (commercially available from Polysciences, Inc.). ), Or a mixture thereof.

  Methyl benzoyl formate is an exemplary one-photoinitiator because it tends to provide a slower polymerization rate. Slower polymerization rates tend to prevent excessive heat build-up during polymerization (and consequent lens cracking). In addition, it is relatively easy to mix liquid methyl benzoyl formate (which is liquid at ambient temperature) with many acrylate, diacrylate, and allyl carbonate compounds to form a lens-forming composition. Lenses made with methyl benzoyl formate photoinitiator tend to exhibit more advantageous stress patterns and uniformity as described in US Pat. No. 6,022,498.

  Still other examples of suitable photoinitiators include 1-hydroxycyclohexyl phenyl ketone (commercially available from Ciba Additives under the trade name Irgacure® 184), bis (2,6-dimethoxybenzoyl) (2 , 4,4-trimethylphenyl) phosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (commercially available from Ciba Additives under the trade name Irgacure® 1700), A mixture of bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylphenyl) phosphine oxide and 1-hydroxycyclohexyl phenyl ketone (trade names Irgacure® 1800 and Irgacure® 1850) (Commercially available from Ciba Additives under the trade name), 2,2-dimethoxy-2-phenylacetophenone (commercially available from Ciba Additives under the trade name Irgacure® 651), 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one (commercially available from Ciba Additives under the trade name Darocur® 1173), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-2-methyl- Mixture with 1-phenyl-propan-1-one (commercially available from Ciba Additives under the trade name Darocur® 4265), 2,2-diethoxyacetophenone REAP) (First Chemical C rportation of Pascagoula, Miss.), benzyl dimethyl ketal (commercially available from Sartomer Company under the name KB-1), alpha hydroxyketone initiator (Esacure® KIP100F) Commercially available under the name Sartomer), 2-methylthioxanthone (MTX), 2-chloro-thioxanthone (CTX), thioxanthone (TX), and xanthone (all commercially available from Aldrich Chemical), 2-isopropyl- Thioxanthone (ITX) (commercially available from Aceto Chemical in Flushing, NY), triarylsulfonium hexafluoroantimonate And propylene carbonate (commercially available from Sartomer Company under the trade names SarCat CD-1010, SarCat 1011 and SarCat KI85), diaryl iodonium hexafluoroantimonate (commercially available from Sartomer Company under the trade name SarCat CD-1012) A mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone (commercially available from Ciba Additives under the trade name Irgacure® 500), 2-benzyl-2-N, N-dimethylamino-1 -(4-morpholinophenyl) -1-butanone (commercially available from Ciba Additives under the trade name Irgacure (R) 369) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (commercially available from Ciba Additives under the trade name Irgacure® 907), bis ( η5-2,4-cyclopentadien-1-yl) bis- [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium (available from Ciba Additives under the trade name Irgacure® 784DC) ), A mixture of 2,4,6-trimethyl-benzophenone and 4-methyl-benzophenone (commercially available from Sartomer Company under the trade name Esacure® TZT), and US Pat. No. 6,786. , 598B2 specification Kishido and methylbenzoyl formate (both Aldrich Chemical in Milwaukee, Wis. Commercially available).

  Examples of free radical initiators suitable for the present invention include benzophenone, methylbenzophenone, xanthone, acyl phosphine oxide types such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxydiphenyl. Examples include, but are not limited to, phosphine oxide, bisacylphosphine oxide (BAPO), benzoin, and benzoin alkyl ethers such as benzoin methyl ether and benzoin isopropyl ether. Free radical photoinitiators are also, for example, haloalkylated aromatic ketones such as chloromethyl benzophenone, some benzoin ethers such as ethyl benzoin ether and isopropyl benzoin ether, dialkoxyacetophenones such as diethoxyacetophenone and α, α-dimethoxy-α-phenylacetophenone, hydroxy ketones such as (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one) (manufactured by CIBA) Irgacure® 2959), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure® 184 from CIBA), and 2-hydroxy-2-methyl-1-phenylpropan-1-one For example, Darocur® 1173 sold by CIBA), α-amino ketones, particularly those containing a benzoyl moiety, also referred to as α-aminoacetophenone, such as 2-methyl 1- [4-phenyl] -2 -Morpholinopropan-1-one (Irgacure® 907 from CIBA), (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure (registered trademark) from CIBA) 369), oxides and sulfides of monoacyl and bisacyl phosphines, such as phenylbis (2,4,6-trimethylbenzoyl))-phosphine oxide (Irgacure® 819 sold by CIBA), triacyl Phosphineoxy And mixtures thereof, can be selected.

  Suitable cationic photoinitiators for the methods described herein can include compounds capable of forming aprotic or Bronsted acids upon exposure to activating light such as UV or visible light. Examples of suitable cationic photoinitiators include, but are not limited to, aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, or triaryl selenium salts.

  Additional coinitiators that can be used in any of the methods described herein include acrylylamine coinitiators (Sartomer under the trade names CN-381, CN-383, CN-384, and CN-386). These co-initiators are monoacrylylamine, diacrylylamine, or mixtures thereof. Other coinitiators include ethanolamine. Examples of ethanolamine include, but are not limited to, N-methyldiethanolamine (NMDEA) and triethanolamine (TEA), both commercially available from Aldrich Chemicals. Aromatic amines (eg, aniline derivatives) can also be used as coinitiators. Examples of aromatic amines include ethyl-4-dimethylaminobenzoate (E-4-DMAB), ethyl-2-dimethylaminobenzoate (E) as described in US Pat. No. 6,451,226 B1. -2-DMAB), n-butoxyethyl-4-dimethylaminobenzoate, p-dimethylaminobenzaldehyde, N, N-dimethyl-p-toluidine, and octyl-p- (dimethylamino) benzoate (Aldrich Chemicals or The First Chemical Group of Pascagoula, Miss.), But is not limited thereto.

  Examples of catalysts that can be used in certain methods according to the invention described herein include dibutyltin dilaurate, dibutyltin dichloride, butylchlorotin dihydroxide, butyltin tris (2-ethylhexoate), dibutyltin diacetate, Dibutyltin oxide, dimethyltin dichloride, dibutyltin distearate, butylstannic acid, dioctyltin dilaurate and dioctyltin maleate, potassium thiocyanate (in the presence of crown ether), sodium thiocyanate (in the presence of crown ether), Or lithium thiocyanate (in the presence of crown ether), phosphine, for example triphenylphosphine. Cocatalysts or promoters such as N, N-dimethylcyclohexylamine and 1,4-diazabicyclo- [2,2,2] -octane (DABCO) are also used with catalysts that enhance their activity or any combination thereof Can be used.

  Several examples are presented herein with respect to four different embodiments according to the present invention.

Method 1 Use of polymer or prepolymer 1 + polymer or prepolymer 2 Example 1
As an example, in an additive manufacturing process such as a melt deposition method known in the art, as a first configuration of a first composition having a thermoplastic polymer, such as, but not limited to, at least one voxel. Polycarbonate (PC) material that is extruded onto a substrate can be used. In other embodiments, the polymer or prepolymer can comprise thermoplastic polystyrene, polysulfone, or polyamide. Multiple or series of voxels of the first composition can be configured on the substrate. In one exemplary embodiment, as described above, the first composition can be melt extruded onto a substrate in conjunction with a printhead. The PC material of this first composition can be selected from relatively high molecular weight PCs with Mn> about 14,000.

  A second configuration of the same polymer PC composition as the first PC composition or a different polymer composition is constructed and then applied to the substrate. As an example, a second series of voxels of a second composition can be configured on the first series of voxels. As described below, a second series of voxels of the second composition can be heated. Desirably, the second configuration polymer or prepolymer is some other composition, in which case the polymer or prepolymer has a relatively low molecular weight of Mn <14,000 and Mn> 14, Having a lower melting temperature than the first composition of 000. For example, the material can be a liquid or a powder. The at least one polymer or prepolymer of the second composition can have a refractive index in the range of about 0.02 to about 0.001 based on the first composition. The connectivity between at least one voxel and at least a second voxel can then be induced by processing. Furthermore, it is possible to subject at least one of the voxels and at least one incremental intermediate element to at least one mechanical, physical or chemical treatment. For example, in one embodiment using a heated printhead and a heated confinement / delivery system, the voxel temperature can be lowered after dispensing to stabilize the voxel and fix its shape.

  As another example, by applying a heat source, such as microwave, UV, infrared, etc., to melt the second composition containing the powder, the second melted second composition containing the powder It is possible to connect the voxel with the voxel of the first configured PC composition, to remove the voxel boundary and to determine the polymerization. Also during this process, the thermoplastic particles can be subjected to fusing, sintering or bonding. In this case, optionally, the particles are treated, for example using thermal radiation, and fused together. These steps are repeated to achieve the final geometric design of the ophthalmic lens. Additional processing can be performed on the intermediate element or at least a portion of the ophthalmic lens to improve ophthalmic lens uniformity. Such treatments can include, but are not limited to, UV radiation, IR radiation, microwave radiation, thermal annealing, solvent evaporation, drying, and combinations thereof.

  Optionally, further final processing can be applied. This treatment includes thermal radiation, convection heating, conduction heating, cooling, chilling, infrared, microwave, UV, visible light, cross-linking, evaporation, or thermal radiation or UV radiation used in at least one component step of voxel or Exposure of at least one voxel to a temperature below the annealing temperature can be included, but is not limited to.

Method 2 Polymer or Prepolymer 1 + Monomer 1 and Polymer or Prepolymer 2 + Optional Monomer 2 Use Example 2
Isocyanate (NCO) end-capped thiourethane prepolymer (A) is obtained using a molar excess of isocyanate groups, MR-7B (2,3-bis ((2-mercaptoethyl) thio) -1-propanethiol), etc. The thiol monomer is reacted with an isocyanate monomer such as MR-7A (m-xylylene diisocyanate) to produce a first composition (both MR-7A and MR-7B are Commercially available from Mitsui Chemicals, Inc.). The thiol monomer can be an SH-terminated polysulfide.

  The thiol (SH) end-capped thiourethane prepolymer (B) is obtained by using a molar excess of thiol groups, MR-7B (2,3-bis ((2-mercaptoethyl) thio) -1-propanethiol), etc. The thiol monomer is reacted with an isocyanate monomer such as MR-7A (m-xylylene diisocyanate) to produce a second composition.

  Any prepolymer preparation may contain any of the metal catalysts such as those known in the art such as dibutyltin dichloride and dibutyltin dilaurate, or the catalysts disclosed herein. To assist in final curing, a second catalyst, such as a UV-activated anionic photocatalyst, such as that described in WO 03/089478 A1, or a heat-activated catalyst, such as potassium thiocyanate, For example, those described in US Pat. No. 6,844,415 can be added to the prepolymer.

  The first composition of voxel A of prepolymer A (NCO) is constructed on a substrate using additive manufacturing techniques. For example, a printhead can be used to construct the first and / or second composition of voxels. The second composition of voxel B of prepolymer B (SH) can be configured in close proximity to voxel (A).

  A treatment such as thermal radiation or UV radiation can be applied to the first and second voxels to induce connectivity between the voxels. During the connectivity induction process, at least a portion of the first voxel isocyanate monomer diffuses into the second voxel and at least a portion of the second voxel thiol monomer diffuses into the first voxel. .

  The construction process is repeated until the desired geometry is obtained. Final curing or annealing of the monolithic ophthalmic lens is achieved by exposure to UV or thermal radiation.

Technique 3 Use Example 3 of Polymer or Prepolymer 1 and Monomer 2
In this example, a first composition comprising a polymer and a second composition comprising a monomer can be used in an additive manufacturing process to produce an ophthalmic lens. For example, styrene and allyl methacrylate are polymerized in solution using an organic peroxide (US Pat. No. 4,217,433) to provide a low molecular weight copolymer having allyl functionality in the first composition. Can be generated. The copolymer can be isolated and dried. At least a first voxel of the first composition is configured on the substrate. A second composition comprising a thiol monomer (eg, MR-7B as described above) can be configured as a second voxel on the substrate. An intermediate element is formed by applying heat and / or UV to the constructed voxels. Additional voxels of the compositions described herein can be constructed and this procedure can be repeated until the final ophthalmic element design is achieved. Final curing or annealing of the monolithic optical element is accomplished by additional heat or UV radiation, IR radiation, thermal annealing, solvent evaporation, drying, and combinations thereof.

Procedure 4 Use Example 4 of Prepolymer or Polymer 1 + Monomer 1 and Monomer 2
As yet another example, a first prepolymer composition comprising a polymer and a monomer is mixed with a second composition comprising a monomer during an additive manufacturing process. More specifically, the first prepolymer composition comprises a molar such as 4,4′-methylenebis (cyclohexyl isocyanate)) (Desmodur® W (commercially available from Bayer AG)) with polycaprolactone diol. It can be prepared by methods known in the art using excess isocyanate.

  First, the isocyanate is mixed with the OH-containing polycaprolactone in an equivalent ratio of about 3.0 NCO / 1.0 OH and then reacted. The isocyanate reactant and polycaprolactone diol (having a molecular weight of about 400 to about 1,000) (commercially available from Perstorp) are heated to 135 ° C. to 143 C under dry nitrogen and at that temperature for 3-5 minutes It can be held and reacted to form a prepolymer. The prepolymer can be cooled to 104-121 [deg.] C. and optionally UV stabilizers, antioxidants, color screening agents, and / or optical brighteners can be added. The prepolymer is further cooled to 77-93 ° F., then depressurized and stored at 71 ° C. for 24 hours.

  As described above, the first and second compositions can be constituted by a print head using, for example, a prepolymer composition. As an example, the second composition can be configured proximate to the first voxel of the first composition. After constructing the voxel of this first composition on the substrate, a void space is intentionally left between the voxels. To fill the void space between the voxels, the second composition of at least one monomer comprises voxels of at least one aromatic amine, such as diethyltoluenediamine or Ethacure® 100-LC, One prepolymer composition can be placed or deposited in the void space between the first configured voxels to form an intermediate element. The amine is used in a ratio of 0.92 to 0.96 NH2 / 1.0 NCO. For applications requiring optical clarity, Ethacure® 100-LC (low color hardener) is used. . Ethacure® 100-LC is commercially available from Albemarle (US Pat. Nos. 5,962,617, 6,127,505, and 7,767,779). Description (incorporated herein by reference)).

  Additional voxels of the compositions described herein can be constructed and this procedure can be repeated until the final ophthalmic element design is achieved. Final curing or annealing of the monolithic ophthalmic lens is accomplished by an additional thermal curing method. As an example, the constructed voxels are cured to a desired amount with a controlled amount of thermal energy. Finally, the polymer can be cured at 110-135 ° C. for 4-24 hours.

  Additional examples of acceptable monomers or prepolymers that can be used in accordance with the disclosed methods of the present invention described above are classified as either aromatic (eg, bisphenol A and F epoxies) or aliphatic. Mention may be made of epoxy monomers or thioepoxy monomers. Aliphatic epoxies have a lower viscosity. Any of the aliphatic epoxies can be fully saturated hydrocarbons (alkanes) or contain double or triple bonds (alkenes or alkynes). They can also contain non-aromatic rings. Epoxy can also be monofunctional or multifunctional and such epoxies can be derived from the alkoxysilane epoxy family.

  Non-alkoxysilane polyfunctional epoxy monomers include pentaerythritol poly, such as diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol tetraglycidyl ether trimethylolethane triglycidyl ether. Glycidyl ether, trimethylol methane triglycidyl ether, trimethylol propane triglycidyl ether, triphenylol methane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylol ethane triglycidyl ether, tetraglycidyl ether of tetraphenylol ethane, p- Aminophenol triglycidyl ether, , 2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerin triglycidyl ether, ethylene glycol diglycidyl ether 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether, (3,4-epoxycyclohexane) methyl It may be selected 4-epoxy white-hexyl carboxylate, and mixtures thereof.

  Monoepoxysilanes are commercially available, and examples include β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, (γ-glycidoxypropyltrimethoxysilane), and (3-glycidoxypropyl). -Methyl-diethoxysilane and γ-glycidoxy-propylmethyldimethoxysilane. These commercially available monoepoxysilanes are listed merely as examples and are not meant to limit the broad scope of the invention. Specific examples of the alkyltrialkoxysilane or tetraalkoxysilane suitable for the present invention include methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane. It is done.

  Other monomers that can be used include meth (acrylates) that can be monofunctional, difunctional, trifunctional, tetrafunctional, pentafunctional, or even hexafunctional. Typically, the higher the functionality, the greater the crosslink density. Methacrylate has a slower cure than acrylate. 2, 3, 4, or 6 (meth) acrylic functional groups are pentaerythritol triacrylate, pentaerythritol tetraacrylate, tetraethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol Di (meth) acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylol ethane triacrylate, trimethylol methane triacrylate, trimethylol propane triacrylate, trimethylol propane triacrylate, 1, 2 , 4-Butanetriol trimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate , Di-trimetholpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, triphenylol methane triacrylate, trisphenol triacrylate, tetraphenylol ethane triacrylate, 1,2,6-hexanetriol triacrylate, glycerol triacrylate, Diglycerol triacrylate, glycerol ethoxylate triacrylate, ethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,4 butanediol dimethacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, dipropylene glycol diacrylate , Polypropylene glycol diacrylate dipentaerythritol hexaa Relate, polyester hexaacrylate, sorbitol hexaacrylate, and fatty acid modified polyester hexaacrylate, it is selected from the group consisting of, most preferably, dipentaerythritol hexaacrylate.

Other monomers or prepolymers as disclosed in U.S. Patent Application Publication No. 2002/0107350 (incorporated herein by reference), for example, but not limited to, Monomers can be selected.

  In the formula, R1, R2, R ′, and R ″ each independently represent a hydrogen atom or a methyl group, and Ra and Rb are the same or different and each have 1 to 10 carbon atoms. And m and n represent an integer, and m + n is contained in 2 to 20 including both ends.

  Other monomers that can be used include 2,2-di (C2-C10) alkyl 1,3-propanediol 2x-propoxylate di (meth) acrylate and 2,2-di (C2-C10) alkyl-1. , 3-propanediol 2 × -ethoxylate di (meth) acrylate, such as, but not limited to, 2-ethyl-2-n-butyl-1,3-propanediol 2 × -propoxylate dimethacrylate. It is not something. The (meth) acrylic monomers described above and the process for preparing them are disclosed in WO95 / 11219. This type of monomer can be polymerized by photopolymerization techniques or a mixture of photopolymerization techniques and thermal polymerization techniques. The polymerizable composition containing the (meth) acrylic monomer includes other monomers that are polymerizable by a radical route and present one or more (meth) acrylate functional groups and / or one or more allyl groups. Among these monomers, poly (methylene glycol) mono and di (meth) acrylates, poly (ethylene glycol) mono and di (meth) acrylates, poly (propylene glycol) mono- and di (meth) acrylates, alkoxy poly ( Methylene glycol) mono and di (meth) acrylate [sic], alkoxy poly (ethylene glycol) mono and di (meth) acrylate [sic], and poly (ethylene glycol) -poly (propylene glycol) mono and di (meth) acrylate Can be mentioned. These monomers are disclosed in particular in US Pat. No. 5,583,191.

  Other classes of monomers that can be used in combination with (meth) acrylic monomers include allyl monomers, such as poly (alkylene glycol) di (allyl carbonate) [sic], and (meth) acrylate functional groups and allyl groups. Monomers, particularly those containing methacrylate functional groups and allyl groups. Among poly (alkylene glycol) di (allyl carbonate) [sic] suitable for the present invention, ethylene glycol di (2-chloroallyl carbonate), di (ethylene glycol) di (allyl carbonate), tri (ethylene glycol) di (Allyl carbonate), propylene glycol di (2-ethylallyl carbonate), di (propylene glycol) di (allyl carbonate), tri (methylene glycol) di (2-ethylallyl carbonate), and penta (methylene glycol) di (allyl) Carbonate). A well-known monomer is di (allyl carbonate) di (ethylene glycol) di (allyl carbonate) sold under the trade name CR39-allyl diglycol carbonate (commercially available from PPG Industries Inc.).

  Other monomers such as tri (propylene glycol) di (meth) acrylate, poly (ethylene glycol) dimethacrylate [sic] (eg poly (ethylene glycol-600) dimethacrylate, poly (propylene glycol) dimethacrylate [sic] (Eg poly (propylene glycol-400) dimethacrylate), bisphenol A alkoxylate dimethacrylate [sic], in particular bisphenol A ethoxylate and propoxylate dimethacrylate [sic] (eg bisphenol A5-ethoxylate di). Methacrylate, bisphenol A4,8-ethoxylate dimethacrylate, and bisphenol A30-ethoxylate dimethacrylate). It can be used those containing a functional group and an allyl group.

  Other monofunctional monomers such as, but not limited to, aromatic mono (meth) acrylate prepolymers, and among trifunctional monomers, tri (2-hydroxyethyl) iso-cyanurate triacrylate, Trimethylolpropane ethoxylate acrylate [sic] and trimethylolpropane propoxylate acrylate [sic] can be used as well.

  The polymerizable composition according to the present invention comprising such a (meth) acrylic monomer or prepolymer also includes a system for initiating polymerization. The polymerization initiator system includes one or more thermal polymerization initiators or photochemical polymerization initiators, or alternatively, preferably a mixture of thermal polymerization initiators and photochemical polymerization initiators. Among the thermal polymerization initiators that can be used in the present invention, mention may be made of peroxides such as benzoyl peroxide, cyclohexyl peroxydicarbonate, and isopropyl peroxydicarbonate. Among the photoinitiators, especially 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one [sic], and alkyl Mention may be made of benzoyl ether. Generally, the initiator is used in a proportion of 0.01 to 5% by weight, based on the total weight of polymerizable monomers present in the composition. As described above, the composition more preferably includes a thermal polymerization initiator and a photoinitiator at the same time.

  Other monomers or prepolymers that can be used in the present invention include thio (meth) acrylates, especially 5-8 membered consisting of hydrogen atoms, carbon atoms, and sulfur atoms and having at least two endocyclic sulfur atoms. It may be a mono (thio) (meth) acrylate type or mono and di (meth) acrylate type functional monomer having a heterocycle. Preferably, the heterocycle is 6-membered or 7-membered, better 6-membered. Preferably, the number of sulfur atoms in the ring is 2 or 3. The heterocycle is optionally condensable with a substituted or unsubstituted C5-C8 aromatic or polycyclane ring, preferably a C6-C7 ring. When the heterocycle of the functional monomer contains two endocyclic sulfur atoms, these endocyclic sulfur atoms are preferably positions 1-3 or 1-4 of the heterocycle. According to the invention, the monomer is also preferably a thio (meth) acrylate monomer. Finally, the monomers according to the invention preferably have a molar mass of 150-400, preferably 150-350, better 200-300. Examples of such monomers are described in US Pat. No. 6,307,062 (incorporated by reference).

  Advantageously, the prepolymer or polymer composition that may comprise such a thio (meth) acrylate monomer may comprise a comonomer. Among the comonomers that can be used in combination with the (thio) (meth) acrylate type monomer in the polymerizable composition according to the present invention, monofunctional or polyfunctional vinyl monomers, acrylic monomers, and methacrylic monomers may be mentioned.

  Among the vinyl comonomers useful in the composition according to the present invention, mention may be made of vinyl alcohol and vinyl esters such as vinyl acetate and vinyl butyrate. The acrylic and methacrylic comonomers can be monofunctional or polyfunctional alkyl (meth) acrylate comonomers and polycyclene or aromatic mono (meth) acrylate comonomers.

  Among the alkyl (meth) acrylates, styrene, α-alkylstyrene, such as α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, or bifunctional Mention may be made of functional derivatives such as butanediol dimethacrylate, or trifunctional derivatives such as trimethylolpropane triacrylate.

  Among the polycyclene mono (meth) acrylate comonomers, mention may be made of cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.

  Comonomers that may also be mentioned are aromatic mono (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, fluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate , Bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, cyanophenyl (meth) acrylate, biphenyl (meth) acrylate, bromobenzyl (meth) acrylate, tribromobenzyl (meth) acrylate , Bromobenzylethoxy (meth) acrylate, tribromobenzylethoxy (meth) acrylate, and phenoxyethyl (meth) acrylate.

  Among the comonomers that can be used in the composition according to the present invention, linear or branched aliphatic or aromatic liquid polyols of allyl carbonate, such as aliphatic glycol bis (allyl carbonate) or alkylene bis (allyl) Carbonate). Among the polyols (allyl carbonates) that can be used to prepare transparent polymers that can be used according to the present invention, ethylene glycol bis (allyl carbonate), diethylene glycol bis (2-methallyl carbonate), diethylene glycol bis (allyl carbonate), Ethylene glycol bis (2-chloroallyl carbonate), triethylene glycol bis (allyl carbonate), 1,3-propanediol bis (allyl carbonate), propylene glycol bis (2-ethylallyl carbonate), 1,3-butanediol bis (Allyl carbonate), 1,4-butanediol bis (2-bromoallyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethyl) Lil carbonate), pentamethylene glycol bis (allyl carbonate), and isopropylene bisphenol bis (allyl carbonate) may can be mentioned.

  A particularly suitable polymerization process for the present invention is photochemical polymerization. The recommended polymerization process is photochemical polymerization via ultraviolet light, preferably UV-A radiation. Accordingly, the polymerizable composition may also contain a polymerization initiator, preferably a photoinitiator, in a proportion of 0.001 to 5% by weight, even more preferably 0.01 to 1%, based on the total weight of the composition. May contain. Photoinitiators that can be used in the polymerizable composition according to the present invention are specifically 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2 -Diphenyl-1-ethanone and alkylbenzoin ethers.

  Also presented herein are monomers or prepolymers that contain vinyl ether groups as reactive groups. Examples of such compounds containing this functionality are ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, butyl vinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, hexanediol. Divinyl ether and cyclohexanedimethanol monovinyl ether.

  In addition, other possible monomers include a wide variety of compounds that can be used as polyethylene functional monomers containing two or three ethylenically unsaturated groups. One exemplary polyethylene functional compound containing 2 or 3 ethylenically unsaturated groups is generally an acrylate and methacrylate ester of an aliphatic polyhydric alcohol, such as ethylene glycol, Triethylene glycol, tetraethylene glycol, tetramethylene glycol, glycerol, diethylene glycol, butylene glycol, pylene glycol, pentanediol, hexanediol, trimethylolpropane, and tripropylene glycol as di and triacrylates and di and trimethacrylates Can be described. Examples of certain suitable polyethylene functional monomers containing 2 or 3 ethylenically unsaturated groups include trimethylolpropane triacrylate (TMPTA), tetraethylene glycol diacrylate (TTEGDA), tripropylene glycol diacrylate (TRPGDA), 1,6 hexanediol dimetaclear (HDDMA), and hexanediol diacrylate (HDDA).

  Other examples of monomers include aromatic-containing bis (allyl carbonate) functional monomers, including dihydroxy aromatic-containing materials bis (allyl carbonate). The dihydroxy aromatic-containing material from which the monomer is derived can be one or more dihydroxy aromatic-containing compounds. Preferably, the hydroxyl group is directly bonded to the core aromatic carbon atom of the dihydroxy aromatic-containing compound. Preferably, the hydroxyl group is directly bonded to the core aromatic carbon atom of the dihydroxy aromatic-containing compound. Monomers are known per se and can be prepared by procedures well known in the art.

  Among exemplary polyisocyanate or isothiocyanate monomers, tolylene diisocyanate or diisothiocyanate, phenylene diisocyanate or diisothiocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate or diisothiocyanate, dimethylphenylene diisocyanate or diisothiocyanate, Diethylphenylene diisocyanate or diisothiocyanate, diethylphenylene diisocyanate or diisothiocyanate, diisopropylphenylene diisocyanate or diisothiocyanate, trimethylbenzyl triisocyanate or triisothiocyanate, xylylene diisocyanate or diisothiocyanate, benzyltriiso (thio) cyanate, , 4′diphenylmethane diisocyanate or diisothiocyanate, naphthalene diisocyanate or diisothiocyanate, isophorone diisocyanate or diisothiocyanate, bis (isocyanate or diisothiocyanate methyl) cyclohexane, hexamethylene diisocyanate or diisothiocyanate, and dicyclohexylmethane diisocyanate or diiso Thiocyanates may be mentioned.

  Among exemplary polythiol monomers, aliphatic polythiols such as pentaerythritol tetrakismercaptoproprionate, 1- (1 ′ mercaptoethylthio) -2,3-dimercaptopropane, 1- (2′-mercaptopropylthio) ) -2,3-dimercaptopropane, 1-(-3′mercaptopropylthio) -2,3 dimercaptopropane, 1-(-4′mercaptobutylthio) -2,3 dimercaptopropane, 1- (5 'Mercaptopentylthio) -2,3 dimercaptopropane, 1- (6'-mercaptohexylthio) -2,3-dimercaptopropane, 1,2-bis (-4'-mercaptobutylthio) -3-mercapto Propane, 1,2-bis (-5′-mercaptopentylthio) -3-mercaptopropane, 2, -Bis (-5'mercaptopentylthio) -3-mercaptopropane, 1,2-bis (6'-mercaptohexyl), 3-mercaptopropane, 1,2,3-tris (mercaptomethylthio) propane, 1,2 , 3-tris (-3'-mercaptopropylthio) propane, 1,2,3-tris (-2'-mercaptoethylthio) propane, 1,2,3-tris (-4'-mercaptobutylthio) propane 1,2,3-tris ('6'-mercaptohexylthio) propane, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol and 1,6-hexanethiol 1,2,3-propanetrithiol, and 1,2-bis (-2 - mercaptoethylthio) -3-mercapto propane may be mentioned.

CONCLUSION The specific embodiments disclosed above are merely exemplary, as the present invention may be modified and implemented in different but equivalent ways that will be apparent to those of ordinary skill in the art having the benefit of the teachings herein. . It is therefore evident that the particular exemplary embodiments disclosed above may be modified or altered and all such variations are considered within the scope of the invention. To increase the efficiency and benefits obtainable from the present invention, various combinations or subcombinations of elements or process sequences may be made to advantageously combine various elements or processes in accordance with the disclosed elements or processes. Or it can be performed together.

  It will be appreciated that one or more of the above embodiments may be combined with one or more of the other embodiments, unless otherwise specified. The invention disclosed by way of example herein may suitably be practiced in the absence of any element or process not specifically disclosed or claimed. Furthermore, except as set forth in the claims, the details of construction, compositions, designs, or steps set forth herein are not intended to be limiting.

Claims (74)

An additional manufacturing method for a three-dimensional transparent ophthalmic lens comprising the following steps:
(1) constituting a first voxel of a first composition comprising at least one polymer or prepolymer;
(2) constituting a second voxel of a second composition comprising at least a polymer or a prepolymer;
(3) forming an incremental intermediate element (p) by inducing connectivity between the configured first and second voxels;
(4) Repeating steps (2) and (3) with sequentially added voxels (n + 1, n + 2,... N) to form incremental intermediate elements (p + 1, p + 2,. Forming an original transparent ophthalmic lens;
Including methods.   The method of claim 1, wherein the first and second compositions are different.   The method of claim 1, wherein the first and second compositions are the same.   4. The method according to any one of claims 1 to 3, wherein the first and second compositions comprise different polymers or prepolymers.   The method of any one of claims 1-3, wherein the first and second compositions comprise the same polymer or prepolymer.   The at least one polymer is polyacryl, polyol, polyamine, polyamide, polyanhydride, polycarboxylic acid, polyepoxide, polyisocyanate, polynorbornene, polysiloxane, polysilazane, polystyrene, polyolefin, polyester, polyimide, polyurethane, polythiourethane. Selected from the group consisting of polycarbonate, polyallyl, polysulfide, polyvinyl ester, polyvinyl ether, polyarylene, polyoxide, polysulfone, polycycloolefin, polyacrylonitrile, polyethylene terephthalate, polyetherimide, and polypentene. The method according to any one of the above.   The prepolymer is polyacrylic, polyol, polyamine, polyamide, polyanhydride, polycarboxylic acid, polyepoxide, polyisocyanate, polynorbornene, polysiloxane, polysilazane, polystyrene, polyolefin, polyester, polyimide, polyurethane, polythiourethane, polycarbonate, 7. Any one of claims 1-6 selected from the group consisting of polyallyl, polysulfide, polyvinyl ester, polyvinyl ether, polyarylene, polyoxide, and polysulfone, polycycloolefin, polyacrylonitrile, polyethylene terephthalate, polyetherimide, polypentene. The method according to item.   8. A method according to any one of the preceding claims, wherein at least one of the polymer or prepolymer comprises at least one thermoplastic.   9. The method of claim 8, wherein the at least one thermoplastic material is a solid particle, including powders, beads, and rods.   The at least one thermoplastic material is a polyolefin such as a cycloolefin polymer, a polyacrylate such as polymethyl (meth) acrylate, poly (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, polyisobutyl ( 9. A compound selected from the group consisting of (meth) acrylates, polyesters, polyamides, polysiloxanes, polyimides, polyurethanes, polythiourethanes, polycarbonates, polyallyls, polysulfides, polyvinyls, polyarylenes, polyoxides, and polysulfones, and blends thereof. Or the method according to 9;   11. A method according to any one of claims 8 to 10, further comprising melting, fusing, sintering or bonding the particles of the at least one thermoplastic material during step (3).   12. A method according to any one of claims 8 to 11, further comprising melting, fusing, sintering or bonding the particles of the at least one thermoplastic material during step (4).   13. The additive manufacturing process according to any one of claims 1 to 12, wherein the additive manufacturing process is selected from the group consisting of scanning laser sintering (SLS), scanning laser melting (SLM), melt deposition modeling (FDM), and ink jet printing. the method of.   14. Step (4) further comprises subjecting at least one voxel and at least one incremental intermediate element to at least one mechanical, physical or chemical treatment. The method described in 1.   The treatment is thermal radiation, convection heating, conduction heating, cooling, chilling, infrared, microwave, UV radiation, visible light, evaporation, or to a temperature below that used in at least one component step of the voxel. The method of claim 14, further comprising exposing the at least one voxel.   16. A method according to any one of the preceding claims, wherein step (4) comprises subjecting at least one voxel and at least one intermediate element to evaporation or cooling.   The method further comprises an additional step (5) of performing additional processing on the intermediate element or at least a portion of the ophthalmic lens after step (4) to improve homogenization of the ophthalmic lens. The method as described in any one of -16.   The method of claim 17, wherein the additional treatment comprises at least one of UV radiation, IR radiation, microwave radiation, thermal annealing, solvent evaporation, drying, and combinations thereof.   19. A method according to any one of the preceding claims, wherein the first composition and the second composition are different and the voxels are alternately composed of the first and second compositions.   20. A method according to any one of the preceding claims, wherein the voxels are composed of a predetermined pattern of the first and second compositions.   21. The method of any one of claims 1 to 20, further comprising: configuring a first layer of voxels of the first composition and a second layer of voxels of the second composition. the method of.   The method of claim 1, wherein the at least one polymer or prepolymer of the first composition comprises a thermoplastic polycarbonate (PC) material.   23. The method of claim 22, wherein step (1) further comprises melt extruding a first group of voxels of the first composition onto a substrate using a print head.   24. The method of any one of claims 22-23, wherein the PC material has a relatively high molecular weight, Mn> greater than about 14,000.   Step (2) further comprises constructing a second series of voxels of the second composition on the first series of voxels, wherein the second composition is a powder or a liquid. Item 25. The method according to any one of Items 22 to 24.   The at least one polymer or prepolymer of the second composition has a relatively low molecular weight less than Mn <about 14,000 and a lower melting temperature than the first composition. Item 26. The method according to any one of Items 22 to 25.   27. The at least one polymer or prepolymer of the second composition has a refractive index in the range of about 0.02 to about 0.001 based on the first composition. The method described.   26. The method of claim 25, further comprising heating at least the second series of voxels of the second composition.   Step (5) comprising at least one treatment is further included after step (4), said treatment comprising thermal radiation, convection heating, conduction heating, cooling, chilling, infrared, microwave, UV, visible light, crosslinking, evaporation Or exposure of the at least one voxel to a temperature below that of thermal radiation or UV radiation or annealing used in at least one construction step of the voxel. The method described.   The method of claim 1, wherein the at least one polymer or prepolymer comprises thermoplastic polystyrene, polysulfone, or polyamide.   31. The method of any one of claims 1-30, wherein the first composition further comprises at least one monomer.   32. The method of any one of claims 1-31, wherein the second composition further comprises at least one monomer.   33. The method of claim 32, wherein the at least one monomer of the first and second compositions is different.   34. The method of claim 33, wherein the at least one monomer of the first and second compositions is the same.   The group wherein at least one voxel is composed of olefin, acrylic, epoxide, organic acid, carboxylic acid, styrene, isocyanate, alcohol, norbornene, thiol, amine, amide, anhydride, allyl, silicone, vinyl ester, vinyl ether, vinyl halide, and episulfide 35. A method according to any one of claims 31 to 34 comprising at least one monomer comprising a reactive group selected from:   32. The method further comprises naturally providing connectivity between a monomer of the first or second composition and at least one polymer or prepolymer of the first or second composition. 36. The method according to any one of -35.   32. The method of claim 31, further comprising preparing a thiourethane prepolymer with a molar excess of isocyanate prior to step (1).   38. The method of claim 37, further comprising preparing a thiourethane prepolymer with a molar excess of thiol prior to step (1). Step (3) includes the following steps:
Diffusing at least a portion of the isocyanate monomer of the first voxel into the second voxel;
Diffusing at least a portion of the thiol monomer of the second voxel into the first voxel;
40. The method of claim 37 or 38, further comprising:   40. The method according to any one of claims 31 to 39, wherein at least one of steps (1) and (2) further comprises printing the composition using a printhead.   41. The method according to any one of claims 31 to 40, further comprising a step (5) of final curing or annealing of the ophthalmic lens by exposure to UV or thermal radiation.   The method of claim 1, further comprising, prior to step (1), preparing a thiourethane prepolymer made from the reaction of a thiol monomer with an isocyanate monomer using a molar excess of isocyanate groups.   The method of claim 1, further comprising, prior to step (1), preparing a thiourethane prepolymer made from a reaction of a thiol monomer with an isocyanate monomer using a molar excess of thiol groups.   44. The method of claim 42 or 43, wherein the thiol monomer is 2,3-bis ((2-mercaptoethyl) thio) -1-propanethiol) and the isocyanate monomer is m-xylylene diisocyanate. Step (3) includes the following steps:
Diffusing at least a portion of the isocyanate monomer of the first voxel into the second voxel;
Diffusing at least a portion of the thiol monomer of the second voxel into the first voxel;
45. The method of any one of claims 42 to 44, further comprising:   46. A method according to any one of claims 42 to 45, wherein at least one of steps (1) and (2) further comprises constructing voxels using a printhead.   47. A method according to any one of claims 42 to 46, wherein step (3) further comprises applying thermal radiation or UV radiation to the first and second voxels.   43. The method of claim 42, further comprising prior to step (1), preparing a thiourethane prepolymer made from the reaction of an SH-terminated polysulfide with an isocyanate monomer using a molar excess of isocyanate groups.   49. The method of claim 48, wherein step (1) further comprises configuring a first voxel of the prepolymer composition using a print head.   50. An ophthalmic lens formed according to any one of the methods according to any one of claims 1-49. An additional manufacturing method for a three-dimensional transparent ophthalmic lens comprising the following steps:
(1) constituting a first voxel of a first composition comprising at least one polymer or prepolymer;
(2) configuring a second voxel of a second composition comprising at least one monomer;
(3) forming an incremental intermediate element by inducing connectivity between the first and second configured voxels;
(4) Repeat steps (1) and (3) with sequentially added voxels (n + 1, n + 2,... N) to form incremental intermediate elements (p + 1, p + 2,. Forming a three-dimensional transparent ophthalmic lens;
Including methods.   The at least one polymer is polyacryl, polyol, polyamine, polyamide, polyanhydride, polycarboxylic acid, polyepoxide, polyisocyanate, polynorbornene, polysiloxane, polysilazane, polystyrene, polyolefin, polyester, polyimide, polyurethane, polythiourethane. 52, selected from the group consisting of: polycarbonate, polyallyl, polysulfide, polyvinyl ester, polyvinyl ether, polyarylene, polyoxide, and polysulfone, polycycloolefin, polyacrylonitrile, polyethylene terephthalate, polyetherimide, polypentene. Method.   The at least one prepolymer is a polyacryl, polyol, polyamine, polyamide, polyanhydride, polycarboxylic acid, polyepoxide, polyisocyanate, polynorbornene, polysiloxane, polysilazane, polystyrene, polyolefin, polyester, polyimide, polyurethane, polythiol. 53. Selected from the group consisting of urethane, polycarbonate, polyallyl, polysulfide, polyvinyl ester, polyvinyl ether, polyarylene, polyoxide, and polysulfone, polycycloolefin, polyacrylonitrile, polyethylene terephthalate, polyetherimide, polypentene. The method described in 1.   The at least one monomer is from olefin, acrylic, epoxide, organic acid, carboxylic acid, styrene, isocyanate, alcohol, norbornene, thiol, amine, amide, anhydride, allyl, silicone, vinyl ester, vinyl ether, vinyl halide, and episulfide. 54. The method according to any one of claims 51 to 53, wherein the method is selected from the group consisting of:   The additive manufacturing process is selected from the group consisting of inkjet printing, stereolithography (SLA), scanning laser sintering (SLS), scanning laser melting (SLM), and melt deposition modeling (FDM). The method according to any one of the above.   56. A method according to any one of claims 51 to 55, wherein step (4) comprises subjecting the at least one voxel and the incremental intermediate element to at least one treatment.   The treatment is thermal radiation, convection heating, conduction heating, cooling, chilling, infrared, microwave, UV, visible light, crosslinking, evaporation, or to a temperature below that used in at least one component step of the voxel. 57. The method of claim 56, comprising exposing the at least one voxel.   58. The method of any one of claims 51 to 57, further comprising naturally generating connectivity between a monomer of the second composition and a polymer or prepolymer of the first composition. Method.   59. A method according to any one of claims 51 to 58, wherein step (4) comprises subjecting at least one voxel and intermediate element to evaporation or cooling.   60. The method further comprises a step (5) of performing additional processing on the intermediate element or at least part of the ophthalmic lens after step (4) to improve the homogenization of the ophthalmic lens. The method as described in any one of.   61. The method of claim 60, wherein the treatment comprises at least one of UV radiation, IR radiation, microwave radiation, thermal annealing, solvent evaporation, drying, and combinations thereof.   62. A method according to any one of claims 51 to 61, wherein the voxels are alternately composed of the first and second compositions.   63. A method according to any one of claims 51 to 62, wherein the voxels are configured in a predetermined pattern.   64. The method of any one of claims 51-63, further comprising the step of configuring a first layer of voxels of the first composition and a second layer of voxels of the second composition. .   52. The method of claim 51, further comprising preparing a prepolymer composition using a molar excess of isocyanate with polycaprolactone diol prior to step (1).   66. The method of claim 65, wherein the isocyanate is 4,4'-methylenebis (cyclohexyl isocyanate).   67. The method according to any one of claims 51 to 66, wherein step (1) further comprises constructing a first voxel of the prepolymer composition using a print head.   68. A method according to any one of claims 51 to 67, wherein the at least one monomer of the second composition comprises at least one aromatic amine.   69. The method of claim 68, further comprising diethyltoluenediamine.   70. The method according to any one of claims 51 to 69, wherein step (2) comprises disposing the second composition in a void space between the first voxels of the first composition. .   71. A method according to any one of claims 52 to 70, wherein step (3) comprises applying a controlled amount of thermal energy to cure the constructed voxels to a desired amount.   72. The method of any one of claims 51-71, wherein step (2) comprises configuring the second composition proximate to the first voxel of the first composition.   73. A method according to any one of claims 51 to 72, wherein step (3) further comprises applying a controlled amount of thermal energy to cure the constructed voxels to a desired amount.   74. An ophthalmic lens formed according to any one of the methods according to any one of claims 51 to 73.