JPH07508937A - Lenses with high impact resistance and high scratch resistance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Lens with high impact resistance and high scratch resistance The present invention provides a composite lens structure. It is a field of construction and has particularly high impact resistance and scratch resistance. It has a mer-polymer composite lens structure. The present invention also provides a cap for ophthalmic lenses. fast curing polymeric compositions prepared from these compositions suitable for and equipment for manufacturing lenses.

Background of the invention The invention disclosed herein addresses two problems in the field of ophthalmic lens manufacturing. I'm being kicked. The first problem is that both high impact resistance and high scratch resistance It is necessary to provide a lens structure with The second problem is simply plastic Instead of polishing blanks to achieve the desired formulation, we -site) An eyeglass retailer asked us to manufacture plastic lenses. It is a request. Techniques in these areas are considered in the following categories:

, S-1. Eye Len Ophthalmic (prescription) glasses and both prescription and non-prescription sunglasses have traditionally been Lenses have been prepared using inorganic glasses as lens materials. Recently, organic polymers have taken over Introduced as a replacement lens material. Currently, both inorganic glasses and organic polymers , plays a central role in the prescription and non-prescription lens market.

Glass is a material with purely optical properties and is extremely scratch resistant. deer However, glass is heavy and easily broken.

Impact resistance is improved by toughening (either thermal or chemical processes) However, it has the drawbacks of longer manufacturing time and increased manufacturing costs. plastic It has excellent impact resistance and is lightweight. However, plastic scratch resistance The tackiness is inferior to glass. Back poly as a means to obtain the desired quality of both materials. This is in the form of a piano front glass wafer with a layer of These two materials have been used in combination. The outer glass layer is outwardly convex, where typically Most of the scratch "outbreaks" were happening. Therefore, this structure protection against The inner plastic layer makes this composite fracture resistant. enhance The glass-plastic interface can be must be chemically bonded to ensure a strong bond (up to higher temperatures). No. A significant drawback of glass/plastic composites is the rigid attachment of these two materials. Deposition is said to be extremely difficult, especially in a stress-free and defect-free manner. That's true. Additionally, the inherent thermal expansion of glass and most plastic materials Due to the property mismatch, such composites exhibit thermoelastic properties during thermal cycling and thermal shock. Increased susceptibility to stress and potential defects.

Generally, scratch resistance and impact resistance are difficult to obtain with the same polymeric material. former requires a hard material with large internal cohesive energy; Properties include elastomeric behavior (i.e., elastomeric behavior under conditions of rapid impact stress loading). tomeric properties) is required. Two-sided material provides maximum scratch resistance and impact resistance. It is very difficult, if not impossible, to adapt.

No. 4,544,572 to Sandvig et al. Polymer with a wear-resistant polymeric coating (long or thinner) Discloses an ophthalmological lens. This lens contains ethylenically unsaturated functional groups applying a layer of a composition containing a substance to the first side of the lens mold; This mold is filled with a reactable, solidifiable organic material into a dry film, and It is then prepared by curing this organic material. This process Since the first layer must be partially cured before the injection of the surface layer curable material, it takes time. To prepare one lens, as described in this patent: It can take up to 16 hours. Additionally, this method provides contouring (contouring) in the front layer. our shaping).

High scratch resistance, high impact resistance, and thermal cycle and thermal shock resistance There remains a need for lens materials that do not develop thermoelastic stresses and defects during ing. Also, it does not introduce significant stress and/or defects to the material during bonding of the layers. , a method for preparing lens composites with high scratch resistance and high impact resistance There is also a demand for Furthermore, it can be obtained in a relatively short time and the front wafer of the lens High scratch resistance and high impact resistance, providing a means of contouring There is a strong need to provide methods for preparing lenses.

B Booth... The speed of two-lens lenses - an optical display similar to that of an eyeglass retailer. Many of the plastic ophthalmic lenses sold today by The formulation is diethylene glycol bis(allyl carbonate) resin (CR-39). machined on the back of a semi-finished lens blank made from created by These blanks are available elsewhere for CR-39. The starting monomers are supported with flexible gaskets and restraints. It is produced by casting between a set of glass molds. This type The frame assembly is first heated in an oven using a precise curing schedule. It will be done. During the subsequent polymerization process, the liquid resin turns into a glassy solid. 16% of material Shrinkage up to and including shrinkage occurs during polymerization and crosslinking. The formwork is placed on the front side where the lens blank is desired. It must be designed with shrinkage in mind so that it has curvature. semi-finished lens Instead of a blank, the final finished lens has the specified curvature on both the front and back sides. The complexity of the design increases when more specifications are required. Different considerations when preparing CR-39 lenses The disadvantage is that these lenses require a curing schedule of up to 16 hours. be.

Casting lenses in situ from polymerizable compositions involves polymerization during casting. Once the problems associated with possible material shrinkage and long curing times are resolved, optical retailers will This may be preferable to machining lens blanks. Cast on the spot One advantage is that the equipment required for casting is used in lens machining. It is cheaper than lens manufacturing machines and polishing equipment. Second, the casting process The process is cleaner and produces less waste than machining processes.

Additionally, using cast reduces the cost of finished lenses to optical retailers. The lens is perfect due to blank machining! ! Especially when compared to the case where For planar, multifocal and progressive lenses, it can be lower.

CR-39 has a slow reaction rate, so it takes about 1 hour to process the lens in the processing laboratory. Not suitable as a material for strikes. Good abrasion, chemical and impact resistance , of CR-39's desirable properties such as transparency and generally excellent optical properties. It is very difficult to obtain a material that retains most and yet polymerizes in a short time. It is beneficial for Also, equipment that can be used to manufacture lenses on the spot in a short time It is also beneficial to obtain

Urethane has been used in coatings for ophthalmic lenses. Boekeler U.S. Pat. No. 4,800,123 to There are many acryloxy (acryl).

at least one polyfunctional monomer having 1oxy) groups, and at least From a polymerizable composition comprising a monomer containing one type of N-vinylimide group A scratch resistant coating prepared is disclosed. Against Coleman No. 4,435,450 describes the formation of hydroxy-terminated prepolymers ( This is followed by cross lazing or A thin coating of abrasion-resistant polyurethane that includes application to the lens. Discloses the method of granting.

U.S. Pat. No. 4,912,185 to Toh (^) polyoxyalkylene glycol dimethacrylate or diacrylate, (B) at least one a polyfunctional crosslinker, and (C) up to 40% by weight of 2 to 6 terminal acrylates; Ophthalmic lens containing urethane heptamer having lyl group or methacrylic group Discloses a crosslinkable casting composition for. Disclosed in this °185 patent Polymerizable compositions prepared using traditional methods for the preparation of ophthalmic lenses (polymerizable solutions) Pour the liquid into multiple molds, cast with blanket irradiation, heat, and remove. ) was designed to be used. This casting method uses air entrainment (ai Low viscosity polymerization to minimize problems arising from entrapment It is necessary to use possible solutions. The °185 patent states that the viscosity of a polymerizable solution is It states that it should not exceed approximately 200 cps at 25°C. polymerizable Polyoxyalkylene glycol diol present in the solution in the range of 40-60% by weight Acrylates or dimethacrylates are used as viscosity reducing agents for this composition. Function. The polyoxyalkylene moiety is ethylene oxide, as shown below. or based on propylene oxide repeating units, with 6 to 11 alkylene Oxide repeat units are preferred.

In the '185 patent, the methacrylate-terminated polyoxyalkylene glycol is More preferred than acrylic-terminated polyoxyalkylene glycol. Because meta The reactivity of acrylate-terminated polyoxyalkylene glycols lower reactivity than that of oxyalkylene glycols, thereby reducing the reactivity of traditional CAS This is because surface aberrations and internal stresses are reduced by using the hard process. child The composition was heat treated at 100'C for 1 hour after passing under the UV lamp 2-4 times. It is shown in this patent that sufficient curing can be achieved by.

Japanese Patent No. 61064716 (CheII+, Abstract 105 :192198b) is an acrylate or methacrylate, monoepoxide and Adducts with brominated bisphenols, polyisocyanates and styrene or di- prepared by polymerizing other unsaturated compounds such as vinylbenzene An impact resistant optical resin is disclosed.

Advances in the field of polymerization of shrinkable materials are presented by David S., 5oane. No. 5.114.632 and U.S. Pat. No. 5.110.514. There is. Briefly, the polymerizable material is placed between the two hand sections of the formwork (whichever part of them Either or both transmit energy, either heat or UV (constructed with materials that will) be introduced during the installation. Related to stress in polymeric materials The voids cause the partially polymerized material to move along the diffe front. (rential) method to polymerize (material in front of the area of moving polymer) remains liquid and the material passed by the front solidifies) removed. In a typical method, the moving front is a slit through which the U V or thermal energy is transferred. With still liquid in front of the moving polymer region The material is then allowed to flow freely at a velocity equal to the shrinkage rate, and the void A low-stress polymer network is formed. Using this method, the cavity The lens can be mounted while avoiding voids caused by shrinkage or shrinkage during polymerization. I can strike. This method is hereinafter referred to as "continuous polymerization".

It is therefore an object of the present invention to preserve the mechanical and optical properties associated with CR-39. Polymerizable that lasts or exceeds, yet cures faster than CR-39 The objective is to provide a composition that polymerizes to form a lens.

Yet another object of the invention is to continuously The objective is to provide polymeric materials that can be combined into a final product.

Other objects of the invention are U.S. Pat. Suitable for use in conjunction with the apparatus and method for continuous polymerization disclosed in No. 32 by providing polymerizable compositions for the production of high quality ophthalmic lenses. be.

Still another object of the present invention is to provide a lens manufacturing apparatus using a continuous polymerization method. That is.

Another object of the present invention is to provide a lens material having high impact resistance and high scratch resistance. The goal is to provide the following.

Another object of the invention is to prepare the product with short processing time, preferably on the spot at the eyewear retailer. The objective is to develop a compound lens that can be used for various purposes.

Other objects of the invention are high impact resistance and high An object of the present invention is to provide a lens having scratch resistance.

A further object of the invention is to reduce thermoelastic stress or failure during thermal cycling or thermal shock. The object of the present invention is to provide a lens material that does not generate

Another object of the invention is that the front material and the back material can be impregnated with different dyes. We offer pre-tinted or pre-tinted compound lenses. It is to provide.

Another object of the present invention is to achieve a progressive or multifocal prescription while providing a global The objective is to provide a compound lens whose external contour remains smooth.

Summary of the invention In one embodiment, the invention provides a scratch resistant front polymer wafer and a scratch resistant front polymer wafer. It is a composite lens with an impact-resistant back polymer layer. This unique structure allows The flexibility of the meter is maximized and it is easily and relatively quickly manufactured. to this design Therefore, it is possible to simultaneously optimize impact resistance and scratch resistance.

This design can also be used with pre-colored, uniform or controlled gradations. nt), coloring, and built-in anti-reflective properties. It also provides other desirable characteristics.

The lens structure disclosed herein is based on a prefabricated front wafer. by polymerizing or gluing an impact-resistant back layer to the For example, it can be manufactured quickly and easily at an eyeglass retailer. Manufactured with defects The front wafer has an inner concave surface (the surface that joins the convex surface of the back layer). It can be created to have any desired contour.

This compound lens may incorporate progressive or multifocal prescription characteristics, but overall The external outline remains smooth.

Progressive multifocal correction is made possible by sophisticated internal interface contour design.

Whether one or both layers of a polymer-polymer composite lens are the same or or may be precolored with different dyes, in the same or different amounts, as desired. 1 In one embodiment, one layer is pre-stained with the desired dye; Another layer is then used to finely adjust the shading and color.

In another embodiment, a prefabricated front layer with an antireflective coating may be used.

The invention also provides polymerizable compositions and polymers formed thereby. includes. This is impact resistance or resistance for polymer-polymer composite lenses. Useful as a scratchable material or used by commercial eyewear retailers. It can be used alone as a fast-curing material for in-situ plastic lens preparation.

This polymerizable composition contains a) and b): a) 20% by weight; between 90% and preferably at least 50% by weight of acrylate or or methacrylate (or mixture of acrylate and methacrylate) Encapsulated urethane, epoxy, or polyester oligomers; b) between 5% and 50 to 80% by weight, and preferably between 10% and 40% by weight acrylates or methacrylates or mixtures thereof, between % by weight end-capped hydrocarbon diols or crosslinkable tri-, tetra-1 or Any such as poly-acrylate or methacrylate or mixtures thereof diluent; and C) free radical initiator, U absorbent, mold release agent, stabilizer, dye Any conventional diluent.

This polymerizable composition can be cast using U radiation and has impact and resistant properties. Less foggy optical with abrasion properties almost equal to or better than CR-39 A transparent object is manufactured. In one embodiment, the polymerizable composition comprises 2 It has a viscosity higher than 00 cps.

In a preferred embodiment, the polymerizable composition is used as described in detail below. 10 minutes depending on the polymerizable composition used, initiator concentration, and U to I strength. It can be cast using a continuous polymerization method in a time range of 30 minutes. This fluid is air can be introduced into the cavity without entrapping the With the procedure illustrated in Figure 2, a relatively high viscosity polymerizable solution can be produced in a continuous polymerization process. can be cast using By being able to use highly viscous polymerizable solutions , the degree of freedom in selecting the type and concentration of monomers and oligomers increases. higher content oligomers may be used to give the lens superior impact resistance. high official diluent with high viscosity (and therefore high viscosity) to provide excellent wear resistance. It can be used for

In particular, acrylates or methacrylates of urethanes, epoxies, or polyesters. rate oligomers (or mixtures thereof) provide the desired abrasion resistance and It is selected to provide impact resistance and to reduce the amount of shrinkage that occurs during polymerization.

This is because the ratio of non-reactive components to reactive components is high. These ori Sesame has a relatively high viscosity, typically having a viscosity of 1 to 100% at room temperature when diluted. It's Megapoise.

Therefore, these oligomers can be prepared using blanket irradiation in larger amounts than in small amounts. Not suitable for use in traditional lens manufacturing. For example, the US patent to Toh No. 4.912.185 states that tetraacrylic urethane monomers are in a polymerizable composition for a surgical lens at a concentration of up to 40% by weight of the composition. states that it can exist. In the polymerizable compositions disclosed herein, the urethane and/or epoxy acrylate or methacrylate oligomers are preferred. Preferably at least 50% by weight of the polymerizable composition.

Diluents such as hydrocarbon diol diacrylates or dimethacrylates The inclusion is necessary to reduce the viscosity so that the liquid can be cast between forms. be done. This diluent also provides desired mechanical properties such as hydrophobicity and abrasion resistance. can impart character to the final product. The diluent participates in the polymerization reaction, so the solvent does not evaporate . This diluent has a molecular weight lower than that of an oligomer (weight average molecular weight 400-9000). is also very low (typically less than 600) and therefore the volume per volume during polymerization is The shrinkage is large. Typical concentrations of diluent in polymerizable compositions range from 50% by weight. The content is low, preferably between 10 and 40% by weight.

Polymerizable compositions are also used in plastic and glass laminates, and special Also used for TGI manufacturing of materials other than ophthalmic lenses, such as optical products or lenses. can be done.

The present invention also finds use in the preparation of ophthalmic lenses in optical retail stores using continuous polymerization methods. It also includes devices that can.

Brief description of the drawing Figure 1 shows a carrier used in the continuous polymerization of polymerizable compositions into ophthalmic lenses. 1 is a schematic side sectional view of a first embodiment of the system; FIG.

FIG. 2 is a schematic side cross-sectional view of a portion of the carriage system embodiment of FIG. This figure shows the procedure for filling a lens mold with a syringe.

3 is a schematic side sectional view of another portion of the carriage system embodiment of FIG. 1; FIG. The model has a lens mold that rotates 180 degrees and is placed in front of a movable UV source. It is.

FIG. 4 is a schematic side sectional view of an apparatus for the preparation of polymer-polymer lens composites.

Detailed description of the invention As used herein, the term "hard monomer" or "hard material" refers to When polymerized, a polymer whose operating temperature (typically room temperature) is below its glass transition temperature Refers to monomers or materials that form remerizable materials.

As used herein, the term "soft monomer" or "soft moiety" A material whose temperature of use (typically room temperature) is above its glass transition temperature during polymerization A monomer or moiety that forms a

As used herein, the term "aryl" refers to phenyl, alkyl or is halogen-substituted phenyl, naphthalene, or alkyl or halo naphthalene substituted with gen, or unsubstituted or alkyl or halo Refers to larger aromatics substituted with gen.

As used herein, the term "alkyl acrylate" refers to H2C=C Say HC02R. Here, R is a straight chain, branched chain, or cyclic alkyl group, and is preferably Preferably C1 to Czo, and especially methyl, ethyl, propyl, iso Propyl, butyl, isobutyl, t-butyl, pentyl, cyclopentyl, iso Pentyl, neopentyl, hexyl, isohexyl, cyclohexyl, 3-methyl lupentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl, and Other longer chain congeners are included.

As used herein, unless indicated otherwise, the term alkyl refers to straight-chain, branched, Refers to a branched or cyclic alkyl group, preferably C1 to Czo, or In particular, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- Butyl, pentyl, cyclopentyl, isopentyl, neopentyl, hexyl, Isohexyl, cyclohexyl, 3-methylpentyl, 2,2-dimethylbutyl , and 2,3-dimethylbutyl, and other longer chain congeners.

As used herein, the terms diacrylate and dimethacrylate Includes mixtures of acrylates and methacrylates.

As used herein, the term (meth)acrylate refers to acrylate, methacrylate, or a mixture thereof.

As used herein, the term [alkyl methacrylate] refers to H,C= C(CH,)CO,R. Here, R is a straight chain, branched chain, or cyclic alkyl group. group, preferably from C1 to Czo, and especially methyl, ethyl, proponent. Pyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, cyclopene Chil, isopentyl, neopentyl, hexyl, isohexyl, cyclohexyl , 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl and other longer chain congeners.

As used herein, the term "aryl" or "aromatic" phenyl, naphthalene or alkyl substituted with naphthalene substituted with kill or /%rogen, or unsubstituted or Refers to larger aromatics substituted with alkyl or halogen.

The term aralkyl refers to an aryl group having an alkyl substituent.

The term alkaryl refers to an alkyl group having an aryl substituent.

As used herein, the term alkenyl refers directly to chain, branched, or cyclic (in the case of Cs-s), having at least one double bond. Refers to hydrocarbons from C2 to Czo.

As used herein, the term oligomer has a weight average molecular weight of 400 or less. repeating units ranging from 800 to 9000, preferably between 800 and 2500. refers to a compound that

As used herein, the term diluent is used to reduce the viscosity of a material. and typically 600. lower viscosity than CPS, and preferably chamber Refers to compounds that have a viscosity of less than 150 cps at elevated temperatures.

As used herein, the term aliphatic refers to C1 to C7 alkyl, aliphatic Refers to lekenyl or alkynyl group.

As used herein, the term "chain polymerization" means that each reaction eliminates a reactive particle. Refers to a polymerization process in which there is a series of reactions that lead to the formation of similar particles.

Reactive particles are radicals, anions, or cations. Polymerization of reactive particles The reaction occurs without elimination of small molecules (as in typical condensation reactions). chain reaction is Typically carried out with ethylenically unsaturated monomers.

As used herein, the term "monomer" refers to , refers to a small reactive molecule.

As used herein, the term "unsaturated hydrocarbon polymer" essentially refers to Consists of carbon and hydrogen atoms and contains alkene (vinyl) groups in the polymer. refers to polymers that

As used herein, the term "oligomer" refers to 20 or fewer refers to a polymer that has no repeating units.

As used herein, the term "high impact resistant material" refers to A rice product that can withstand loads without breaking and has impact resistance for ophthalmic lenses. National food and drug layer requirements (standard dropball test) Refers to a material that satisfies the test).

As used herein, the term "highly scratch resistant" material refers to A material that resists wear without surface deterioration.

A typical abrasion test involves applying a known vertical force to the specimen while It consists of moving the pad laterally with respect to the sample surface. Highly scratch resistant material produces almost no scratches after this process.

■Polymer polymer lens As disclosed, the present invention provides polymers that exhibit excellent impact and scratch resistance. --Includes polymer lens composites.

The front wafer is a very hard, scratch resistant polymeric material and The back wafer is a high impact resistant polymeric material. most plastic Since the thermal expansion properties of are similar, the thermoelastic stress of the polymer-polymer composite lens is This is greatly reduced compared to glass-polymer composites. small due to extreme temperatures Even when stress is induced, the polymer flexes, i.e. deforms elastically (some catastrophic failure is rare. It's not easy. For the polymer composites disclosed herein, the stress associated with the thermoelastic stress field is The strain field (both time and temperature dependent) is Exceeding either ultimate strain (failure limit (failure 11m1t)) There is very little that can be done. Glass-polymer lenses and polymer-polymer lenses This critical difference in is a key aspect of the invention.

Separating refinements into front wafer and back layer cost, optical transparency, hardness of the front wafer, impact resistance of the back layer, and mechanical Individual features including machinability, coloration, polishability, and index-dependent interface design Properties can be optimized.

The front polymer wafer is resin transfer molded or molded using known methods. is produced by casting (thermosetting resin) or injection molding (thermoplastic resin) at low cost. It can be mass-produced to have a uniform thickness.

The back layer of the lens complex is rigid and machinable (versus polishing). but , this layer also has sufficient It must also exhibit elastomeric properties. As disclosed in further detail below , better, 70-Yoko model (+narsha+allow-toothpick model) The supramolecular network is an ideal material for the back layer. originally gills Many other block copolymers that are stomer-like but sufficiently rigid, interpenetrating networks shaped structures, graft copolymers, random copolymers, and even homopolymers , as long as they are sufficiently optically transparent and dimensionally stable. can be selected.

The use of polymer-polymer lens composites depends on the nature of the front and back wafers. It offers many advantages besides individual optimization and ease of fabrication.

It looks like only the front layer or back layer is colored, or both layers are colored. Polymer-polymer composite structures can be created. Dye chemistry for polymers is Well known to those skilled in the art.

By way of example, the front wafer may be made of wafer material, as is generally known to those skilled in the art. After construction (but before incorporation into the composite), whether uniform coloring or gradation coloring is used. It can be colored to give. The front wafer is typically of uniform thickness, so , the resulting lens may appear uniformly colored when viewed from the front. These large quantities The colored front wafer produced can be treated with polymers by any of the methods described below. - Incorporated into polymer composites. The back layer is preserved for curvature formation i.e. can be held. Alternatively, the back layer may be colored and darkened by a different coloration than the front layer. A host can be given.

The polymer-polymer composites described herein can be manufactured in a manner similar to that of standard lenses. , for example, dyed by immersion in a very diverse dye bath or dye baths. It can be done. Dye baths are typically heated at high temperatures, usually at or slightly below the boiling point. maintained at temperature. The finished lens is placed in the selected bath for a certain period of time, e.g. 2 minutes. Dip and get the desired color. For darker colors, take longer.

If a tonal color is desired, periodically lift the lens from the bath to the middle of the bath. Make sure that only one half is dark and the other half is slightly colored.

Thermoset precursors (generally in liquid form) are also used in the resin tranform to form the final wafer. Dyes, UV absorbers (e.g. melamine or synthetic dyes) before sphering , an antioxidant, a mold release agent, etc.

Another advantage of this composite structure is the "thickness" of the back layer.

The preformed front wafer is already thicker than just a coating, to some extent. The thickness of the back layer is particularly high when high-impact materials are used. can be made relatively thin and still achieve formulation and fracture resistance.

Since this back polymer layer is thin, the UV radiation used to initiate polymerization of this layer The dwell time can be relatively short. In addition, Heat removal and temperature control associated with thermal polymerization/curing reactions are less troublesome for thin layers. stomach. This speed of polymerization allows on-site lens manufacturing at an optician.

A front wafer (e.g. epoxy) and a back layer (e.g. as shown in Example 1) The polymers prepared in this manner may have a slight shift in refractive index. front web The thickness of the coating material may be more or less uniform, and therefore contributes little to the formulation. I don't know. Alternatively, curvature can be incorporated into the shape design, as detailed below. It can be rare.

In one embodiment, the front wafer has an anti-reflective coating on its convex surface. has. Reflectance is the percentage of reflected light (intensity) relative to the incident light (intensity). It is measured as follows.

A reflectance value close to 0% is ideal, but a value close to 100% may cause glare ( Provides a bright surface with large glare. Is there an anti-reflection coating on the lens surface? used to reduce the amount of light reflected from This is a specific This is accomplished by depositing a dielectric film with a thickness and index of refraction.

The thickness of the coating determines the wavelength of light affected and It is about 1. Generally, in ophthalmological applications, the wavelengths chosen are those for which the eye is more sensitive. It is also in the high yellow-fringe portion of the visible spectrum. Yellow - wavelength on either side of the edge region Therefore, the amount of reflected light increases. To increase efficiency, more than one film is displayed. deposited on the surface. Multilayer systems include high- and low-index coatings. A combination of tings is used. Zirconium dioxide, titanium dioxide, and Zinc sulfide and cerium fluoride are commonly used high refractive index layers, while cerium fluoride and zinc sulfide Magnesium is often used as the low index layer. Correctly applied multilayer coating In heating, the light transmission can be increased from 92% to 99.5%. these The coating may be applied by a process known as vacuum deposition. anti-reflection Companies that apply coatings to ophthalmic lenses include VM Products and 5ilor (both located in California).

The surface of the front wafer that will later become the interface between the front and back surfaces (the concave surface of the front wafer) surface) or a carefully introduced diffraction pattern (mimicking a moth's eye) may have. This pattern can be in the master formwork and can be injection molded or resin molded. It can be an imprint left on the sample after transfer molding. These patterns (refractive index (after taking into account the deviation of can produce fruit. Moth eyes have naturally produced diffraction patterns and differ Light that is reflected and returned from a place cancels each other out (de 5 truct ively) interfere with each other. Therefore, the net reflectance from any other smooth surface is clearly lower than the reflectance of

Bifocal and multifocal polymer-polymer composite lenses have a curvature-forming back layer and It can be easily manufactured by the use of stacked, Fresnel-like front wafers. back After the layers have been polymerized, they can be honed/polished or formed into certain formwork halves. can be produced with known curvature using

Bifocal, multifocal, progressive, and/or astigmatic lenses may also be made with high refractive index webs. By using a material on the front layer and a low index material on the back layer, or vice versa, the can be prepared from remer-polymer complexes. In this method, the front surface of the complex is The external surfaces of the front layer (convex surface) and the back layer (concave surface) can be spherical. . Progressive, bifocal, cylindrical, aspheric or other complex requirements can be achieved with front and back This can be achieved by elaborate shapes and contours at the interfaces between layers. Those skilled in the art of optical calculations With the help of computer simulation programs, the desired surface container ( surface container) can be easily designed.

Designs in which these refractive indexes interact in a complex manner are required without using thick lenses. It can be used to achieve the desired correction and produce glasses that are comfortable to wear. Ru.

The back and/or front layers are described in U.S. Pat. 10.514 using the continuous polymerization process and equipment disclosed in No. 10.514. in a way that prevents biting, or voids caused by shrinkage of the material during polymerization. Can be polymerized. Simply put, the partially polymerized material is placed between two halves of the formwork. Either or both of them transfer energy, i.e. heat or UV constructed of materials). Stress-related voids in polymeric materials are , polymerizing partially polymerized material in a sequential manner along a moving front. (The material in front of the moving polymer region remains liquid and the front passes through.) The material may be removed by (as it solidifies). Typically, a moving frame is Ronto is a slit through which UV or thermal energy is transmitted.

The still liquid material in front of the moving polymer region then moves at a velocity equal to the contraction rate. Free-flowing, void-free, low-stress polymer network It is formed.

The polymer-polymer lens composite described herein has a periphery of an "insert". This is different from lenses that are prepared by polymerization.

Insert technology uses light or thermoset materials for both the front and back areas. Includes covering. With insert technology, both major exposed surfaces are identical material, separate optimization of desired properties in the front and back layers is not possible. I can't. A hard surface surrounding a soft core is difficult to resist since crack initiation begins at the surface. It's not shocking.

Curable useful for preformed front polymer wafers and back polymer layers These materials are described in detail below. Other suitable materials are listed herein. No. 4,544,572, which is incorporated by reference.

1. Composition of high impact resistant polymer layer The back polymer layer is at least as good as CR-39, a well-known lens blank material. It should exhibit the same impact resistance. This material performance is confirmed by the well-known FDA "Falling Ball" test. It can be tested using This material is as durable as CR-39 of the same size and thickness. It should be able to withstand the impact of a standard steel method dropped from the same height.

This backing layer must be dimensionally stable at the operating temperature, generally room temperature. child Polymers meeting these requirements are known to those skilled in the art and are elastomeric in nature. but sufficiently rigid block copolymers, interpenetrating networks, and graft copolymers -, random copolymers, and even homopolymers. Block also The molecular size is so small that the grafted segments do not scatter light. Should.

Preferred high impact polymeric networks are described below. impact resistant layer Preferred polymeric materials are the polymerizable compositions described in detail in Part 11. Ru. Other examples of polymeric materials that are suitable for this purpose are discussed below.

Suitable materials for the back layer are interconnected by soft, elastomeric, multifunctional cross-linking sites. It is a polymeric network structure containing rigid members (Ine!ber) connected to It was discovered that. In polymerization, these hard monomers first self-polymerize to form a soft crosslinker. Generate members of controlled length that are connected to each other by chemical bonds in bridges. controlled so that The crosslinks (or core) are randomly distributed in space and Shock absorption for optical materials that are generally rigid but impact resistant and optionally transparent. Gives yield. The machinability (polishing and honing) of hard plastics is maintained. On the other hand, rebound resilience is introduced into the polymer network structure.

The polymeric network structure combines the soft joint material (crosslinked material) with hard monomers or hard material, and a free radical initiator, or other suitable polymerization initiator. It can be prepared by Hard monomer or hard material and soft joint The materials must be thoroughly mixable to form a homogeneous solution. this mixture partially polymerized to a honey- or molasses-like consistency (typical The viscosity can range from 100 centipoise to 1000 poise, and its At this point, the material can be poured into a mold or cast on a sheet and stirred. Polymerization is completed without any problems.

A key aspect of this method is the true dispersion (dispersion at the molecular level) of the hard and soft reactants. is a pre-cast polymerization or “prepolymerization” step used to ensure that . Since the soft element is polyfunctional, it can be efficiently made into a soft reaction through the prepolymerization process. Most of the reactive components are tied up and the hard and soft reactive components are then tied up. Separation of is impossible.

Polymeric rigid components (struts) are made of soft polymeric It is bonded to a polyfunctional crosslinking site (soft joint) at both ends. I'll disclose In addition, the present invention also provides that the rigid skeleton may be knotted, branched, or randomly coiled. It includes a polymeric network that gives it a rigid plastic structure.

Liquid crystal (rigid rod) polymers can be used as rigid segments. artificial molecules The liquid crystal strut with the bent portion has a joint shape. High glass transition amorphous po Reamers are generally random coil structures. These geometrically linear rigid structures In addition to the structural members, the rigid "strants" themselves are It can further be crosslinked.

Generally, heterogeneous materials with sizes comparable to or larger than the wavelength of visible light are introduced. If so, the light transmission of the transparent material will be affected. Polymer networks described herein In eye-like structures, the cross-linking sites are molecular size, so light scattering is not detected, and The transparency of the material is thereby not adversely affected. Cross-linked molecules have dimensions comparable to the wavelength of light As long as there is no self-agglomeration, the transparency of the sample is guaranteed.

The hard and soft segments are placed in a sea fence distribution or spatial arrangement, Can be random, alternating, block, or grafted. Random or alternating Polymers are generally single-phased and In the pure form (pure for + n), there can be an optical absorption band. The outside is light transparent. Block and graft copolymers are generally polyphasic and the size of the phase-separated domains is determined to maintain optical transparency in the material. It has to be made smaller.

In either case, the final mechanical properties are intermediate. In this specification The described polymeric supernetwork combines the best mechanical and optical properties. It will be done.

a) Description of rigid skeleton Once polymerized, the hard monomer or hard material can be used at the operating temperature (typically room temperature). A rigid, light-transmitting plastic with a higher glass transition temperature and better optical properties. It is chosen because of the rigid backbone of the polymer network that it provides. This monomer is Generally, it is a monomer that polymerizes by a chain mechanism, such as an alkene derivative. good A preferred salt is methyl methacrylate. Other alkene derivatives are Alkyl methacrylate, alkyl acrylate, allyl or aryl acrylate esters and methacrylates, cyanoacrylates, styrene, α-methylstyrene vinyl esters, including vinyl acetate, vinyl chloride, methyl vinyl ketone , vinylidene chloride, acrylamide, methacrylamide, acrylonitrile, metal Includes tacrylate, acrylic acid and methacrylic acid. These monomers Mixtures of - may also be used in the polymerization process.

Partially halogenated or fully halogenated, including these fluorine-containing monomers (perhalogenated) hard monomers (e.g. 2.2.2-) refluorinated Ethyl methacrylate, trifluoromethyl methacrylate, 2.2.2.3. 4.4.4-heptafluorobutyl methacrylate, and 2.2.2.2°, Partially or completely, such as 2', 2-hexafluoroisobutyl methacrylate fluorinated C1 to C fluorine-containing methacrylic acid or acrylic acid (including but not limited to stells) may also be used in rigid skeletons.

Acrylate-terminated or other unsaturated urethanes, carbonates, and epoxy Oxygen may also be used for rigid skeletons. An example of an unsaturated carbonate is allyl diglyco carbonate (CR-39). Unsaturated epoxy is glycidyl acrylic ester, glycidyl methacrylate, allyl glycidyl ether and 1,2- Including, but not limited to, epoxy-3-allylpropane.

Bisphenol-A-bis-2-hydroxypropyl methacrylate and bis Phenol-A-bis-2-hydroxypropyl acrylate is also a hard monomer. Can be used as a marker. In addition, allyl terephthalate, allyl isophthalate , aryl terephthalate or isophthalate, or acrylic isophthalate Rates or terephthalates may also be used.

Preformed polymers with ethylenically unsaturated functional groups are also mentioned herein. This method improves impact resistance. The acrylate-terminated novolac is It can be used as or in a rigid backbone of a remerizable polymeric network. Aku Derivatized to contain rylate, methacrylate or other unsaturated functional groups Polyurethanes, polymeric epoxies, and polycarbonates are well known. , is commercially available.

Examples of commercially available photocurable materials include Cray valley Product 5ynocure product line (e.g. bisphenol) sold by 5ynocure 3101, a diacrylate derivative for 5ynocure 3134), which is a group urethane diacrylate, and 5he EpOn products sold by ll Corporation (e.g. both are diacrylates of the diglycidyl ether of bisphenol-A, Epon 1001 and Epon 828). vinyl terminated liquid crystal polymer may also be used.

Poly(carbonyldioxy-1,4-phenyleneisopropylidene-1,4-7 Nielen) sells products called Lexan, Makrolon and Merlon. It is sold under the product name. This polycarbonate has good mechanical properties over a wide temperature range quality, good impact and creep resistance, high light transmission, and good dimensional stability It has a sexual nature.

Poly(carbonyldioxy-1,4-phenyleneisopropylidene-1,4-ph) unsaturation of this polymer, such as allyl or acrylate derivatives of The derivative is reacted with a polymer having a soft portion, as described herein. By doing so, the impact resistance can be further improved.

Optical grade, terminally unsaturated epoxy is l,2-propylene oxy Sid, ■, 2-butylene oxide, ■, 2-epoxydecane, 1,2-epoxy Octane, 2,3-epoxynorbornane, 1,2-epoxy-3-ethoxyp Ropane, 1,2-epoxy-3-phenoxypropane, oxetane, 1,2-ethyl Poxy-5-hexene-1,2-epoxyethylbenzene, 1,2-epoxy- 1-methoxy-2-methylpropane, perfluorohexylethoxypropylene oxide, benzyloxypropylene oxide, and mixtures thereof. epoxies with terminal unsaturation.

Mixtures of hard monomers can be used to prepare polymeric networks. For example, methi methacrylate, such as methyl acrylate or ethyl acrylate, Can be polymerized in combination with alkyl acrylates or aryl acrylates .

Hard monomers can be used in any proportion as long as the components are compatible and miscible. Can be mixed. Acrylates are compatible with their esters, typically in length A whole range of compositions can be mixed with methacrylates as long as they are equivalent. Acrylate is Generally, using either photochemical or thermal initiation, methacrylate Polymerizes quickly.

In addition, preformed polymers with terminal or internal unsaturation are ethylenic In the presence of soft parts with unsaturation, can be copolymerized with hard monomers, high impact resistance It is possible to form a material with properties.

Other embodiments may thicken the mixture, make it easier to handle, or reduce the total reaction time. Inert polymers are added to the starting mixture for shrinkage or for other reasons. Can be added. This inert polymeric material adversely affects the desired properties of the final material. Any polymer that does not have a negative impact may be used in any amount. inert polymer is generally a polymer that does not react with other components in the reaction solution. One embodiment In, a hard monomer or an inert polymer of hard material is added to the polymerization solution. . For example, methyl methacrylate acts as a hard monomer in a polymer network structure. If used, polymethyl methacrylate may be added to the polymerization solution.

Additives such as UV absorbers, colorants, and antioxidants may also improve the desired final product. It can be added to the polymerization mixture to obtain properties. For example, R, B, Seymour [,”5tate of the Art; ＾dditives for Pl astics”, AcadeIIIic Press, New York, 1 See 978.

b) Description of soft joint It has a low glass transition temperature (lower than room temperature to as low as possible) and is not homopolymerizable. When combined, it provides a soft and flexible material, is stable at high and low temperatures, and is copolymerized. A polymer or oligomer that is compatible and soluble with the polymeric soft polymer selected for use as an int. This polymer is used for soft joints. - or oligomers must be of a size that does not scatter light and that less than about 100 nanometers, and optimally about 10 nanometers. smaller than the data.

Examples of polymers suitable for flexible joints are vinyl-substituted siloxanes, allyl-substituted siloxanes, Loxane, acrylic terminated or substituted siloxane, and vinyl substituted siloxane , allyl-substituted siloxane, acrylic-terminated or partially or completely substituted siloxane. perfluorinated derivatives. For example, polydimethylsiloxane The transition temperature is 1123°C, the lowest known polymeric glass transition temperature. Ke When one of the two methyl groups bonded to an ionic atom is replaced with a vinyl group, it becomes reactive. Polyvinylmethylsiloxane (PvMS), a multifunctional polymer, is produced. Ru. This polymer is soft and seeded using well-established free radical chemistry. It can be copolymerized with various monomers.

The 5i-0 bond is highly flexible and provides a cushioning effect against impact. Ru. Polyvinyl perfluoromethylsiloxane is also used as a soft joint material. Can be used.

Hydrocarbon polyunsaturated (polyfunctional) compounds (both homopolymers and copolymers, and especially oligomers) can also be used as soft joints in polymeric networks. Ru. Hydrocarbon unsaturated compounds are produced by butadiene, isoprene, among other methods. and can be produced by polymerization of conjugated dienes such as chloroprene. 1.3- Two different types of polymerization reactions occur with dienes. One type is typical In a chain polymerization, one or the other of the double bonds is polymerized. second route In this case, these two double bonds act in concert, and either the carbon at the 2nd position or the carbon at the 4th position Either produces an allyl radical that can react with subsequent monomers (respectively, 1,2 polymerization and 1.4 polymerization).

1.2-Polymer has pendant unsaturation while 1.4-Polymer has -Has unsaturation in the skeleton. The various types of polymerization products of these conjugated dienes are It can be used to prepare the polymeric networks described herein.

To guarantee optical transparency while using a limited amount of soft segments, Child compatibility is essential. Compatibility is often determined by the use of low molecular weight soft parts. Optimized by

C) tether of terminal chains The polymeric networks prepared as described above can further be characterized by small difunctional or polyfunctional a functional reactive molecule or a mixture of small di- or polyfunctional reactive molecules can be crosslinked by containing.

Crosslinking agents for hard monomers polymerized by chain reactions are known to those skilled in the art. and tri- or tetrafunctional acrylate or methacrylate, divinyl base. (DVD), alkylene glycol, and polyalkylene glycol Diacrylates and methacrylates (ethylene glycol dimethacrylate and and ethylene glycol diacrylate), vinyl or allyl acrylate rylate or methacrylate, divinylbenzene, diallyl diglycol dica carbonate, diallyl maleate, diallyl fumarate, diallyl itaconate , vinyl esters (divinyl oxalate, divinyl malonate, etc.), diary Rusuccinate, triallylisocyanurate, bisphenol-Δ or etho Dimethacrylate or diacrylate of oxygenated bisphenol-A, methylene or polymethylene bisacrylamide or bismethacrylamide (hexame Including tyrene bisacrylamide or hexamethylene bismethacrylamide ), di(alkene) tertiary amine, trimethylolpropane triacrylate, Pentaerythritol tetraacrylate, divinyl ether, divinyl sulfonate Diaryl phthalate, triallylmelamine, 2-isocyanatoethylmethac rylate, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate acrylate, ■-methyl-2-isocyanatoethyl methacrylate, and 1. Includes 1-dimethyl-2-isocyanatoethyl acrylate. especially useful is tetraethylene glycol diacrylate, tetraethylene glycol Dimethac 1 root, triethylene glycol diacrylate, triethylene glycol Cold diacrylate, hexanethiol dimethacrylate, hexanediol diacrylates, and other higher alkanes (including C4 to C+o), [This is not specified L)) It is a diol diacrylate or dimethacrylate. . These bifunctional molecules have a relatively long length between acrylates or Deep bridging maintains distance and provides flexibility.

Is the crosslinking agent used as a hard monomer before the initial prepolymerization step? = it polymer, and and soft joints. The final network structure depends on the amount of crosslinking agent added. One strong force strongly determines whether or not it will be crosslinked. The crosslinking agent can be added in any amount that gives the desired result. Used and humiliated. Typically added in the range of 0.1% to 30% by weight. be done.

In one embodiment, an acrylate-terminated monophytadiene (PB) is used as a soft resin. Used as an int material. PB+ of any molecular weight that gives the desired result. However, typical songs include ζma, 100 to too, ooo. with hard monomer Certain methyl methacrylates and benzyl acrylates (or common acrylates) 1 route or mixtures of aromatic esters of methacrylates (polymerization with PB) It is useful for Because aromatic acrylate or methacrylate is , the refractive index of the base polymer material to be equal or nearly equal to the refractive index of the PH. This is because it increases the As a non-limiting example, 38% benzyl methacrylate A high impact resistant material can be prepared by mixing the powder with 62% MMA.

Next, this mixture was mixed with PB (13, OOOMIII) at a weight ratio of 73%, respectively. Mix at 27%. This solution is homogeneous. Adding a small amount of photoinitiator , this solution can be prepolymerized so that the PB does not phase separate in the later casting step. . Very thin (l mm) discs of this material are free from cracks (even cracks). , up to eight times the FDA-required height of 50 inches (i.e., up to 400 inches) Withstands FDA falling ball test. In contrast, a CR-39 sheet of comparable thickness has FD often cracked before reaching the height required by A (50 inches). This base This formulation contains tetraethylene glycol diacrylate or dimethacrylate. , or triethylene glycol acrylate or methacrylate, or Xanediol diacrylate may be added to improve scratch resistance . Even after adding 20% of this crosslinker, the sample is still light transparent.

d) Preparation of network structure Preparing polymer networks in which soft joints are uniformly distributed throughout the polymer. In order to It is important that it is well stirred. The soft and rigid components are simply mixed; in a static, quiet cavity. If left to polymerize, the two components tend to phase separate during polymerization. Before polymerization Phase separation causes a cloudy, opaque product. Furthermore, these two components are typical have different densities. If left alone in a stationary cavity for a long time, , the heavier components move to the bottom, and when they polymerize, they form a group with a gradient in the direction of the gravitational field. A product with the following properties is produced. Polyvinylmethylsiloxane and methylmethacrylate When combining rates, the PVMS collects near the bottom of the container. This layer consists of Polymerization of the mixture results in a product having a rigid upper part and a soft lower part. generate.

In a preferred embodiment, in the first stage of polymerization, the two components are present in any proportion. , stirring constantly while initiating the polymerization. Thickening of reaction mixture, shortening of reaction time If desired, for polymerization or other reasons, an inert polymer may be added to the polymerization mixture. can be added. This prepolymerization step is carried out in an open container such as a beaker with air or Preferably, this can be achieved by exposure to an inert gas such as N2. Initial copolymer and The polymerization is allowed to proceed with constant stirring until a partial network is formed. Department The viscosity of a partially polymerized reaction solution is determined by injecting this solution and leaving it undisturbed for a long time. The temperature rises to the point where phase separation and layer formation do not occur when the temperature increases. To the final formwork Partial polymerization involving stirring during the early stages of polymerization, prior to filling and completion of polymerization. , either due to slow reaction rates or for thermodynamic reasons, the phase separation It is ensured that separation or settling is completely suppressed. Because the initial copolymer This is because the structure is similar and uniform in all parts of the sample.

The second stage of polymerization involves transferring the partially polymerized material to a final, stationary formwork key. cavity, for example poured into a lens mold, is transparent, light-transmissive, and has a composition Forms a final product without material gradients. Requires precise dimensions, shape, and curvature Therefore, injection molding, transfer molding, or compression molding are excluded. can get The material depends on whether you want a laminate or pure plastic product. may or may not adhere firmly to one or both sides of the formwork. Sometimes it's bad.

As an example, under strong UV irradiation, approximately 90% of methyl methacrylate and 1 0% polyvinylmethylsiloxane (weight average molecular weight 300 to upper limit (optical light) It has trace amounts of PVMS (low enough to ensure permeability) and virtually 1 Blends up to 00% methyl methacrylate provide improved light transmission with break resistance Give plastic. 90% methyl meth prepared as described in Example 1 A plastic network of rylate and 10% polyvinylmethylsiloxane When projected at high velocity onto a hard concrete surface, this material shatters. er), chipping, or cracking (frBcture), Recoil over long distances. 90% methyl methacrylate and 10% polyvinyl methacrylate Even 2ffIffl sheets prepared from luciloxane are not suitable for ophthalmic lenses. Meets the US Food and Drug Administration's requirements for impact resistance (standard falling ball test).

The copolymerization of hard and soft monomers, depending on their composition, produces the best Give the final material. When the product polymer is neither extremely rigid nor unnecessarily soft, Generally balanced.

Any component proportions that give the desired results can be used in the polymeric network. spare The polymerization step and final polymerization can be accomplished at any temperature that gives the desired product and Typically, the range is from room temperature to the boiling point of the lowest boiling component. The preliminary polymerization process is , which typically takes on the order of minutes to hours. Ensures vigorous stirring and eliminates air during stirring By minimizing the entrapment of the soft joint and preventing partial polymerization of the Allow the prepolymerization process to proceed to the extent that the polymer is uniformly and permanently distributed throughout the network. Thereby, the optical transparency can be optimized.

Completion of polymerization is carried out in an open mold and free radical reactions are occurring. If so, it is preferably carried out under an inert atmosphere. Oxygen inhibits free radical polymerization It is known to do so and to prolong the polymerization time. Closed type for forming articles If a frame is used, the formwork may be made of poly(tetrafluoroethylene), silicone Non-stick, such as rubber, polyethylene, polypropylene, and polyester should be made from inert materials. Glass and metal formwork are suitable If a mold release agent is used, it may be used. High impact resistant material used as laminate If desired, the formwork may actually consist of the material to which the laminate will adhere, or may contain the material.

The final step of this polymerization is carried out using a continuous polymerization method and the apparatus shown in Figure 4. How to prevent cavitation, or voids, caused by shrinkage of the material inside This is done by

In FIG. 4, the form body 310 is shown in cross-section. This formwork body is particularly suitable for convex and concave Designed for ophthalmic lenses with shaped surfaces. Device 31 shown in FIG. 0 is composed of at least two parts 312 and 314, which are joined together. is bent to form a cavity 316. The cavity 316 is about to be molded. It is formed to have a precise lens shape. The cavity contains the final product lens. The convex surface of the layer contacts the convex surface of the back polymer layer 318 and the concave surface of the back polymer layer 318. A preformed lens 317 having a concave surface is optionally inserted. As shown in Figure 4. The device described above uses a preformed wafer that ultimately forms the back layer of the lens. may be applied such that the front layer is polymerized in situ (in 5 itu). It should be understood that The first part and When the second part is assembled, the gate 320 provides continuity to the formwork body 310. Ru. used to supply raw material to cavity 316 through gate 320. The reservoir 324 connected to the gate 320 is electrically connected to the gate 320 . The reservoir 324 is shown in FIG. 4 shows a device with a uniform hopper. The vent 322 also connects the cavity 31 6 may be included to facilitate filling. cavity 316 through gate 318 It should be understood that other methods of supplying raw materials to the Ru.

For example, it may be appropriate to supply the raw material to the cavity 316 under pressure. .

As can be seen in FIG. 4, the formwork body 310 is one that is transparent to the energy source. (shown here as portion 314). Energy source 3 26 is movable relative to the formwork body 310 and provides a focal point such as a gate 330. Includes focusing tneans. Energy #326 is two The second portion 314 may be driven by a directional motor 334 . energy Source 326 is selected according to the material to be molded. For example, reservoir 320 monomer (reaction mixture or pre-polymer) supplied to mold cavity 316 from If the precursor is thermally polymerized, the energy source 326 is clearly a focal point. A heat source is focused through the opening 328 in the gate 330. opening The portion 328 is preferably configured to align the energy plane onto the second portion 314. It is measured. The energy plane is substantially perpendicular to the movement of focus gate 330. Ru. The monomer used in cavity 316 is an ultraviolet light source or other light source. If so, the energy source 326 can be light at a suitable wavelength. Turn on the light source again When polymerization is carried out with the second portion 314 attached, the second portion 314 is It needs to be transparent to the wavelength of the light used. With the result of applying heat In the case of polymerization occurring as or made of a material with no insulation properties at all. It may also include a cooling path 338. . These routes can be used selectively so that time-dependent temperature gradients are maintained. Ru.

Movement of the focal gate 330 relative to the formwork body 310 causes the energy source 326 to The formwork starts at the closed end 336 of the tee 316 and moves to the gate 32o. 3], is controlled to scan across O.

The reaction mixture contained in reservoir 324 passes through gate 320 into cavity 3. 16 is constantly resupplied. Therefore, the polymerization may occur at the lower end of the formwork 310 or at the closed end. As it occurs at the chain end 336, the contraction that occurs and appears as a void is Immediately supplemented by the reaction mixture or polymer mixture contained in reservoir 324. It will be completed. The reaction mixture is highly fluid and flows easily, indicating that the reaction is already in progress. It will of course be understood that the loss of volume due to shrinkage of the mixture portion carried out is compensated for.

Immediate replacement of the space formed by the contraction with unreacted material results in a free of scratches and distortions. ensuring a high-quality final product. Movement of the energy source 326 relative to the formwork body 310 is necessary. Naturally, the closure is made such that polymerization occurs at a steady rate from the closed end to the gate end. With opening 328 in focal gate 330 moving from end 336 to gate 320. must be started.

When the energy source 326 based on the properties of the monomer is a heat source, the energy source 326 is a heat source. movement of the focal gate through the second portion 314 at a faster rate than polymerization occurs. The speed must be such that heat cannot be transferred. That is, the thermal energy source 326 When moving upward, the second portion 314 absorbs heat and to the bottom of cavity 316 where the coupling occurs. a second portion above the opening 328; The cooling that can be achieved by the cooling fluid circulating through the passages 338 is maintained. must be Therefore, it is possible to sequentially supply heat to the formwork cavity 316. As a result, the top of the portion 314 is colder than the bottom of the portion 314.

The formwork 310, together with the reservoir 324, is secured in the indicated position by conventional methods. (clafflp). Reservoir 324 contains the reaction mixture, in this case, Initiator and/or other materials that readily flow into cavity 316 monomers, monomer mixtures, or monomers/crosslinkers loaded with a catalyst of filled with a mixture of. Cavity 316 is thoroughly reactively mixed before polymerization occurs. It is important to ensure that you are filled with things.

Therefore, it may be appropriate to provide a vent 322 in the formwork cavity 316.

If a vent is used, it must be closed or plugged before polymerization occurs. Must be. Closing the vents is more important than allowing air to flow into the formwork. Rather, it supplements the introduction of additional reaction mixture into the cavity 316 during polymerization. .

Once the formwork cavity 316 is filled, the energy source 322 is activated. and the focal gate 324 is moved relative to the form body 310, thereby removing heat. or applying light (whichever is appropriate) to the formwork body in a sequential manner. Heat is the energy source If so, before the focal gate 324 moves over the entire surface of the formwork, the heat conduction to the formwork body is completed. Cooling of the upper end of the formwork body to ensure that polymerization does not start in the upper part of the formwork. It may be appropriate to activate the recovery path 338.

Once the movement of the focus gate 330 is finished and the polymerization in the formwork body 310 is finished, If so, the molded structure is removed and the molded precision part is removed. .

Any UV or thermal free radical release method known to those skilled in the art of free radical polymerization may be used. Initiators may be used to initiate the process of the invention. Examples of UV and thermal polymerization initiators include: Benzoyl peroxide, acetyl peroxide, lauryl peroxide, azo Bisisobutyronitrile, t-butyl peracetate, cumyl peroxide, t -Butyl peroxide, t-butyl hydroperoxide, bis(isopropyl) Peroxydicarbonate, benzoin methyl ether, 2.2゛-azobis (2゜4-dimethylvaleronitrile), tert-butyl peroctoate, Phthalate peroxide, jetoxyacetophenone, and tert-butyl Peroxyvivalate, Jetoxyacetophenone, 1-Hydroxycyclohexyl Silphenylketone, 2,2-dimethoxy-2-phenyl-acetophenone, and phenothiazine, diisoprobyl xanthogen disulfide.

An example of a commercially available product that provides a non-yellowing product is Irgacure 184 (Cib a.Sold by Geigy Corporation, 1-hydroxycycloheki Any amount of initiator can be used to produce the desired product (sil phenyl ketone). Can be used. Typically, the amount of initiator is 0.00000000000000000000 per weight hard monomer.　1% to 5%, preferably 0. It is 5% to 3%.

Example 1 Polymer network of methyl methacrylate and polyvinylmethylsiloxane Preparation of shaped structures Methyl methacrylate (94% by weight), polyvinylmethylsiloxane (5% by weight) , Mw 300-500), and 1% UV photoinitiator (I rgacu re ) under ay light (300-400nlI'l) until the mixture is honey or sugar. Stir vigorously until it reaches a consistency similar to honey. Pour the solution into a closed lens mold followed by polymerization with UV light as shown above and in Figure 4. Shatter resistant, transparent and light transmitting material provided.

The refractive index of the material prepared in Example 1 is relatively high (approximately 1°51) and The refractive index was between that of hydrogen polymers and inorganic glasses.

Example 2 Methyl methacrylate, styrene, divinylbenzene, and polyvinylbenzene Preparation of polymer networks from nylmethylsiloxane Methyl methacrylate (90% by weight), styrene (5% by weight), divinylbenze (0.5%) and polyvinylmethylsiloxane (3% by weight), and 1. 5% UV photoinitiator (cyclohexylbenzoin) was treated with UV light (300-400n m) mix under and stir vigorously until the mixture reaches a consistency similar to honey or molasses do. The solution is poured into a closed lens mold, followed by By polymerizing with UV light, we offer highly shatter-resistant transparent and light-transparent materials. provide

Alternatively, mix everything except divinylbenzene first and reach the desired consistency. Polymerize with UV until. Then add divinylbenzene to the mixture and Pour into the formwork.

Example 3 Preparation of high impact polycarbonate Liquid monomer was placed on an absorbent bed (basic Allyl diglycol carbonate (CR- 39) is stripped from the inhibitor. Next, this was coated with 98 weight carbonate. % by weight to 2% by weight of PVMS. Next, the materials were prepared in Example 1. Polymerize as described.

Example 4 Preparation of high impact optical grade epoxy 5ynocure 3101 (95% by weight) mixed with 4.5% by weight polybutadiene and 0.5% initiator. and polymerized as described in Example 1.

Example 5 Methyl methacrylate, methyl acrylate, and polyvinyl methyl Preparation of polymer networks with siloxanes Methyl methacrylate (42,5% by weight) and methyl acrylate (42,5% by weight) % by weight), and polyvinylmethylsiloxane (4% by weight, My 3 00-500) and 1% UV photoinitiator (Irgacure) under UV light (30 0-400 na+) until the mixture reaches a consistency similar to honey or molasses. Stir vigorously. The solution is poured into a closed lens mold, followed by the above and As described in Example 4, highly shatter-resistant transparent materials can be obtained by polymerization with UV light. provided a light-transparent material.

Example 6 Methyl using ethylene glycol dimethacrylate as a crosslinking agent Preparation of polymer network structure of methacrylate and polyvinylmethylsiloxane methacrylate (92% by weight), polyvinylmethylsiloxane (5% by weight), Ethylene glycol dimethacrylate (1% by weight), and 2% UV photoinitiator (Irgacure) and then mix until the mixture has a consistency equivalent to honey or molasses. Stir vigorously and allow the reaction to proceed under direct light until reaching . lens with closed solution It is poured into a mold and subsequently polymerized with UV light as described above. Provides a shatter resistant, transparent and light transmitting material.

Alternatively, ethylene glycol dimethacrylate is added after the prepolymerization step. obtain.

Example 7 Comparison of physical properties between conventional polymer and high impact polymer Density, refractive index, and temperature of the polymer network structure (denoted as S-5) prepared in Example 1 number, flexural modulus, CTE (coefficient of thermal expansion), glass transition temperature, and visible light transmittance , thermoplastic polycarbonate (Lexan), and PPG Industry Prepared from allyl diglycol carbonate (CR39) obtained from I.E.S. Compared with thermosetting polycarbonate. The results are provided in Table 1.

(Margin below) 2. Composition of the front wafer with high scratch resistance The front wafer is at least bare Scratch resistance equivalent to CR-39 itself (uncoated or untreated) can be prepared from any polymer shown. Hard construction with high impact resistant polymer network structure Any material listed above that exhibits the desired scratch resistance (soft portion and with or without end tethers) are shown on the plano front wafer. It can be used in fur. Alternatively, the polymer compositions described in Section II can be used.

Typically, the front wafer is preformed to at least 100 microns. wafer, and more typically typically 0.5a+m to 1 ．． It is 5 nm.

Conventional scratch-resistant polymers include CR-39 and polymethyl methacrylate. and polycarbonate.

CR-39 has long been the material of choice. It is PPG [ndust ries and essentially allyl diglycol carbonate polymer (which also contains mold release agents, dye components, and/or antioxidants). ). It is the current market leader as a lens material. Po (PMMA) has poor scratch resistance, but It has been widely used as a medical material.

Poly(carbonyldioxy-1,4-phenyleneisopropylidene-1,4-ph) Polycarbonates like CR39 have a higher refractive index and impact resistance than CR39. scratch resistance, but typically exhibits poorer scratch resistance than CR39.

The scratch-resistant front plastic is also compatible with many other transparent high-performance engineering Alling thermoplastics (polyetherimide, polyimide, polyether rusulfone, polysulfone, polyethylene terephthalate, and other amorphous (random copolymers) include polyamides, polyesters, and urethanes However, these are not absolutely required). non-limiting fruit Examples include the polymers shown below.

Alternatively, clear, high-performance engineering thermosets (epoxies or bis including but not limited to maleimides) may be used. thermosetting wood Transfer molding of the resin to form a plano wafer Requires. In contrast, thermoplastics are injection molded. heat Many curing agents (crosslinking agents) exist and are known for curable resins, including aliphatic and aromatic amines and anhydrides. Homopolymerized epoxy can also be used. I can stay. Front wafer - A hard, transparent epoxy coating that is useful as a material. Puccell materials have long been formulated for integrated circuit protection and for coating LEDs. It has been.

IIl, Preparation of Polymer-Polymer Composites Polymer-polymer conjugates described herein Rimmer lens complexes are prepared by a variety of methods that are ideal for a wide range of applications. It can be done. The present invention provides a wide variety of highly durable products by eyewear manufacturers and retailers. Includes a rapid, in-situ preparation method for impact-resistant, highly scratch-resistant lenses. Ru.

Typically, the lens mold has a metal or glass front surface, as shown in Figure 4. Examples include molds with a UV-transparent or thermally conductive back surface. these conventional molds can be used to manufacture polymer-polymer composites. Current Given the disclosure herein, one skilled in the art will be able to use a conventional lens mold. This duplication can be done by using one of the methods listed below or by other known methods. Consolidations can be prepared. The composite is prepared by polymerizing the back layer on a preformed front wafer. By polymerizing the front wafer on the preformed back layer by Alternatively, bond a preformed front wafer onto a preformed back wafer. It can be prepared by:

Surface hydrophobicity can be achieved by modifying the surface of either layer of the composite with a glow discharge. properties or hydrophilicity to provide good anti-condensation properties or other desirable properties. obtain.

A combination of a pre-prepared front wafer and a pre-prepared sea urchin In some embodiments, the polymer-polymer lens composite is pre-prepared. a scratch-resistant front polymer wafer and a pre-prepared impact-resistant polymer wafer. It can be prepared by bonding the back side wafer with an adhesive. preferred practice In embodiments, the front surface is a scratch resistant polymer and the back surface is an impact resistant polymer. - is. This bilayer consists of a polymer-polymer or polymer-glass composite. It may be adhered with any adhesive material known to those skilled in the art for adhesion. favorable fruit In embodiments, the bilayer is a partially polymerized impact resistant material as detailed above. adhesive (polymerized in situ by following the above polymerization method) .

The front and back layers can have different curvatures, thus positive or negative Any lens can be made.

Example 8: Combination of a pre-prepared front lens and a pre-prepared back lens join The front wafer is a CR-39 bifocal flat top 1■ wafer. . The material described in Example 1 was partially polymerized (honey-like consistency) in situ. The back layer (also CR-39) was bonded to the front layer by successive polymerization in Glue it to the buffer.

In another embodiment, the polymer polymer The Rimmerlens composite is placed on a pre-prepared front polymer wafer and then It can be prepared by polymerizing the polymer layer in situ. Perform this step Shown in Examples 9-11.

Example 9 CR-39 front wafer and PVMS/MM^ back wafer Preparation of lenses with CR-39r flat top” (bifocal) thin front wafer (thickness approx. ．． 21, and a diameter of about 7511 IIn) is used as the front wafer. web A cavity having a space of about 1 inch inside is formed on the back side of the core. cavite A partially polymerized mixture of 7% PVMS and 93% MMA was inserted into the chamber. Enter. The material is then polymerized as described above and shown in FIG. back formwork is transparent and UV-transparent quartz glass, and is a piece of precisely curved surface, so it cannot be viewed with a lens. The mold has a precise formulation when it is finally molded.

Example 10 Layer with epoxy front wafer and PVMS\■A back layer Preparation of lenses Thin front wafer of epoxy (dianhydride cured novolac) (Plano 6 curvature, thickness IIIrn, diameter 7bn) is used as the front wafer. We In addition to the fur, a cavity having about 111 spaces inside is formed. Kya 3% PVMS, 96% MMA and 1% EGDMA (Ethiele a partially polymerized mixture of diglycol dimethacrylate). Next The material is then polymerized as described above and in FIG. The back formwork is transparent The lens is made of UV-transparent quartz glass and is a precisely curved piece, so the final It has a precise formulation when molded.

Example 11 PET (polyethylene terephthalate) front wafer and PV Preparation of lenses with back layer of MS/M^methyl acrylate PET thin front wafer (plano 6 curvature, thickness 1+nIo, diameter 71 mm) ) is used as the front wafer. Wafer (in addition, about 1fflff1 form a cavity having a space inside.

Partially polymerized 5% pnts and 95% MMA into the cavity. Insert the mixture. The material is then polymerized as shown above and in Figure 41. . The back formwork is a transparent, UV-transparent quartz glass piece with a precision curved surface. Therefore, lens 1 has an accurate prescription when it is finally molded.

II+, Ophthalmology Lens No.17-1 and Lens-1 Ruta No. High quality, impact resistant material that can be cured in 30 minutes or less using continuous polymerization methods Polymerizable composition for the preparation of ophthalmic lenses resulting in impact- and abrasion-resistant materials is disclosed L).

This polymerizable composition disclosed herein may also be prepared by conventional methods and methods. The composition can also be polymerized using equipment for polymerization known to those skilled in the art. At least 50% by weight of acrylate or methacrylate (or acrylate) urethane, epoxy, or polyester oligomers (or mixtures thereof), optional diluents, e.g. For example, hydrocarbon diols end-capped with acrylates or methacrylates, or low molecular weight crosslinkable tri-, tetra-1 or poly-acrylates. Contains methacrylate.

1. Oligomer Proper selection of oligomers to obtain the desired physical properties of the resulting lens is an important It is essential. This is because this oligomer is the main component of the polymerizable composition (polymerizable composition). (in quantity). End-capping with acrylates and methacrylates The remarkable optical and mechanical properties of polymers prepared from synthesized oligomers are known. It is. Desired mechanical properties can be achieved by blending diverse materials Coatings, adhesives, medical plastics, lenses, etc. It is a candidate for numerous applications, including fiber optic lenses, optical fibers, and glazing materials.

Three types of oligomeric acrylates or methacrylates (or urethane end-capped with a mixture of Epoxy or polyester end-capped with polyester (or mixtures thereof) is preferred for preparing ophthalmic lenses using continuous polymerization methods. Found. Generally, urethane oligomers are used to provide a sturdy structure to the final lens. epoxy and polyester Ligomers provide hardness and chemical resistance. In a preferred embodiment, the recorder This oligomer used in the manufacture of lenses has a molecular weight ranging from 400 to 9000. molecular weight, preferably between 800 and 2500. High molecular weight oligos oligomers produce lenses that are too flexible, while low molecular weight oligomers Producing lenses that are too rigid and have low impact resistance. The sensuality of this oligomer (acrylic (methacrylate or methacrylate) can range from 2 to 6. This oligomer is between 2ON% and 90% by weight of the final formulation, preferably 50% of the composition. %, more typically between 50% and 75% by weight of the composition. can be contained in

a) Urethane acrylate Polyurethanes contain at least two -NHCOO- bonds within the backbone of the polymer. A general class of polymers having, optionally, esters, ethers, Contains both urea and other functional groups such as amide. Urethane oligomer? The polymer prepared from the above has good abrasion resistance, toughness, flexibility for impact resistance, Demonstrates transparency and stain resistance. Making urethane useful for the coating industry These properties are also important for the properties of ophthalmic products.

There is a wide range of methods known to those skilled in the art for preparing urethane polymers. cormorant Rethane prepolymers are typically aliphatic or aromatic polyols of various compositions. polyester, polyester, or polyether with a stoichiometric excess of diisocyanene. It is a reaction product with Typically, the polyols, polyesters, or The number of terminal hydroxyl groups in the polyether is 2 or more. The above terminal hydroxyl group is Reacts with diisocyanate to form a urethane bond, and the terminal ends with isocyanate. A prepolymer end-capped with ate groups is obtained. Conversion of NCO group to 10H group Depending on the stoichiometry, urea may also be present within the backbone of the isocyanate-terminated oligomer. Tan bonds may be incorporated.

(1) diisocyanate, (2) polyol, polyester, or polyether or (3) by changing the stoichiometric ratio of NCO groups and 10H groups, Different urethanes can be obtained. Description of urethane oligomers and polymers is F r1sch, K, C,, ^pplied Polymer 5science (J, in, Craver & R, W, Te5sW), chapter 54, page 828.

See AC3,0RPL, Washington, 1975.

Examples of suitable diisocyanates include 4,4'-diphenylmethane diisocyanate. (MD[, ICI Po1yurethanes Group, test D eptford, New Jersey), PB^2259 (A more stable water-dispersible version of MDI, also ICI Po1yureth available from anes Group): 3'-isocyanatomethyl-3,5, 5-) Limethylcyclohexyl isocyanate (IPDI or isophoronediyl) Socyanate, available from Huls Aa+erica, Inc.); 2, 4- and 2,6-toluene diisocyanate (TDI); ethylene diisocyanate Anate, trimethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate, octamethylene diisocyanate, decamethyl diisocyanate, cyclohexyl diisocyanate, methylene bis(4 -cyclohexyl isocyanate), phenylene diisocyanate, diphenyl Ether-4,4'-diisocyanate, 2. 2. 4-trimethyl hexa Methylene diisocyanate, xylene diisocyanate, tetramethylxylene Diisocyanate, polyether diisocyanate, polyester diisocyanate Polyamide diisocyanate, dianisidine diisocyanate, 4,4° -diphenylmethane diisocyanate, toluidine diisocyanate, and dimer acid diisocyanate (prepared from the reaction product of two unsaturated carboxylic acids) diisocyanates).

Urethane prepolymers contain acrylate or methacrylate groups in the prepolymer. It is formed to be radiation curable by adding . This is typically is an isocyanate-terminated oligomer and a hydroxy-substituted acrylate or It is carried out by reaction with methacrylate. Examples include 2-hydroxyethyl ( meth)acrylate, 2-hydroxypropyl(meth)acrylate, dodecyl Oxyhydroxypropyl (meth)acrylate and glycerin (meth)acrylate Includes, but is not limited to, related. High (meth)acrylate functionality diisocyanate-terminated oligomer and pentaerythritol tri(meth) ) can be obtained by reacting with compounds such as acrylates. This page Taerythritol tri(meth)acrylate is approximately Contains one equivalent of hydroxyl group and three (meth)acrylate groups. Or Acrylates or methacrylates containing other functional groups that can react with isocyanates Ester, e.g. epoxy such as glycidyl acrylate or methacrylate or aminoalkyl or aminoaryl acrylates or Amino-containing esters such as methacrylates may also be used.

Non-limiting examples of di- or tri-functional urethane prepolymers are shown below. : Here, P is an aliphatic or aromatic polyether, polyester, or polyol. R is an isocyanate residue (to which the isocyanate moiety is bonded). ), n is 2 or 3, and A is the end cap of the oligomer. aliphatic ( typically an alkyl) or aromatic ester moiety. Acrylic between 2 and 6 Urethane (meth)acrylates containing ester or methacrylate functional groups are It is commercially readily available.

The characteristics of the above acrylate or methacrylate-terminated oligomers depend on the structure of the backbone. Dependent. Alkyl esters and ethers are aromatic esters and ethers. It has less yellowing and is more stable against light. However, aromatic esters and The alkyl esters and ethers impart hardness to the composition, and their corresponding alkyl esters and It has a higher refractive index than ether.

This is preferred to reduce lens thickness for a given prescription. Po Polyester-based urethane acrylates or methacrylates are Compared to ether-based urethane acrylates or methacrylates, Usually hard. Because polyester has stronger dipolar interactions and hydrogen bonds More polar bond structures and This is because it provides more basic oxygen.

Hydroxy-terminated polyester starting materials are often dicarboxylic acids or anhydrides and a monomeric glycol or triol. This dicarboxylic acid or anhydrides include adipic acid, phthalic anhydride, and dimerized linoleic acid. Including, but not limited to. Examples of glycols include ethylene glycol, Propylene glycol, 1. 2-butylene glycol, 1,4-butylene glycol Cole, 1,6-hexylene glycol, trimethylolpropane, glycerol le, and 1. 2. Includes 6-hexandriol.

The widely used polyether diol to produce urethane oligomers Polyols and polyols include poly(oxypropylene) glycol, poly(1,4 -oxybutylene) glycol, random copolymer of alkylene oxide, and copolymers of tetrahydrofuran and alkylene oxide. Ji Depending on the isocyanate monomer, polyol group, and stoichiometry, different Urethane oligomers with mechanical and chemical properties are obtained.

Branched oligos based on branched polyols, polyesters, or polyethers Polymers are also useful as polymerizable compositions.

Urethane methacrylates or acrylates have more than one functional group. The material obtained after polymerization is a thermoset rather than a thermoplastic material.

Although this material cannot be reworked once cast, it has remarkable chemical resistance It is advantageous in terms of properties and thermal-mechanical stability. Affects mechanical thermoset properties An important factor is the crosslink density in the network structure. This density increases (this This is due to a decrease in the molecular weight between the acrylate groups or an increase in the functionality of the oligomer. ) typically results in higher Tg and better wear-resistant systems. . However, flexibility is compromised (this results in lower impact resistance and higher (causing high shrinkage) is also a result of high crosslinking density.

Stable commercially available acrylic resins that can be used in the polymerizable compositions disclosed herein For base- or methacrylate-terminated urethanes, the UCB Radcure Urethane acrylate 2264.284.488L 4866.8301, and 8804.5artoffler Ureta commercially available from Coff1pany Acrylate CN955, CN960, CN961. CN963, and C N970, a urethane commercially available from Imperial Chemical Ind. Includes, but is not limited to, acrylate NR2075.

b) Epoxy and polyester acrylate epoxy and polyester acrylate Rylates and methacrylates are also fast-curing polymers for ophthalmic lenses. It is useful as an oligomer for inclusion in possible solutions. Because these Polymers prepared from materials have properties such as hardness, chemical resistance, and high refractive index. This is because it exhibits desired characteristics. Polymers prepared from these monomers are Compared to rethane-based materials, they may be less flexible and therefore less impact resistant.

Aromatic epoxies and polyester acrylates and methacrylates Poor photostability compared to killurethane acrylates or methacrylates. good In a preferred embodiment), instead of the urethane acrylate or methacrylate Although epoxies and polyester acrylates cannot be used in Instead, epoxies and polyester acrylates are replaced by urethane acrylates or are used in any suitable combination with methacrylate oligomers. one In embodiments of epoxy and/or polyester acrylate or Methacrylates may be present from 0% to 50% by weight of the total oligomer content. It will be done.

Epoxy acrylates typically contain epoxide functional groups and acrylic acid, meth Acrylic acid obtained by reaction with acrylic acid or mixtures thereof and esterified Forms rylate or methacrylate resins. For difunctional epoxy-terminated resins The above reaction is shown below: where P is an aliphatic or aromatic chain, optionally including oxygen, silica, and sulfur. Tero atoms, as well as amides, esters, epoxies, ethers, and atoms in the backbone. R is H (in the case of acrylate) and CH 3 (in the case of methacrylate). Acrylate or methacrylate groups are It is then subjected to conventional free radical polymerization. Typical epoxies used include , aliphatic or aromatic glycidyl ethers, epoxyphenol novolaks, Poxycresol novolac, epoxy modified with polyamine or polyamide , cycloaliphatic epoxy resins, and others. Part of the epoxy part can be left unsaturated. Final epoxy acrylate or methacrylate Oligomeric compositions include (meth)acrylates, epoxies, esters, and can be included.

Epoxy acrylate is Kir k-Othmer, Encyclopedia of Chemical T technology, 2nd edition, 3rd edition, volume 8, pages 294-312 (John 1ily & S.

Polyester acrylates are prepared in excess using acrylic or methacrylic acid. It is prepared by esterification of a polyester having hydroxyl groups. Hydroxyl group-terminated poly Preparations of esters are usually adipic acid, phthalic anhydride, isophthalic acid, azela Acids such as inic acid or dimeric linoleic acid and monomeric glycols, It is obtained by reacting lyol and ε-caprolactone. Al Kill glycols and triols include, by way of non-limiting example, ethylene glycol. alcohol, propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol glycol, and 1,6 hexylene glycol. used Triols include, for example, trimethylolpropane, glycerol, and , 2°6 hexanetriol. More highly branched systems also can be used to provide higher crosslink density.

Polyester acrylates provide both elastic and rigid properties to the final product. I can do it. For example, polyesters containing aromatic acids such as phthalic anhydride or isophthalic anhydride. Tel imparts rigidity and heat resistance to the final product. Highly branched systems are also rigid Gives the final product straightness, high chemical and heat resistance, hardness, and low elongation. Ru.

2. Diluent In order to improve the processability of the final resin, a low viscosity reactive diluent is added. Contained in a polymerizable composition. This diluent is incorporated into the lens, so as appropriate to give the desired properties (e.g. hydrophobicity, abrasion resistance and impact resistance) should be selected. Diluents can be monofunctional, difunctional, or polyfunctional. obtain. The term "functionality" here refers to groups that are reactive in radiation curing (e.g. For example, acrylates and methacrylates).

Generally used in both the oligomeric and diluent components of polymerizable compositions. Acrylates are preferred over methacrylates even when Because a Acrylate cures more quickly than methacrylate, so manufacturing time This is because it can shorten.

The diluent is the urethane acrylate or methacrylate used in the polymerizable composition. chemically compatible with acrylates or epoxy acrylates or methacrylates There should be.

A diluent is said to be compatible if no phase separation occurs during the polymerization of the composition. be considered.

In one embodiment, the polymerizable composition has the following CH-=CRCO( X) OCR=CH is a hydrocarbon diol series where R is each independently H or methyl, and X is C2 to CI4 linear or branched alkanes. Hydrocarbon diols and branched hydrocarbons Diol-based diacrylates and dimethacrylates are more effective against polio Preferred over xyalkylene glycol diacrylate or dimethacrylate stomach. Hydrocarbon diol acrylate series diluent (ethylene glycol diacrylate) ester and dimethacrylate, 1,4-butanediol diacrylate and Dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate ester, decamethylene diol diacrylate and dimethacrylate, and including but limited to neopentyl diacrylate and dimethacrylate ) than the series based on polyoxyalkylene glycols. , which is more hydrophobic. These also include alcohols, which are often used as cleaning agents. It is also more resistant to chemical attack by polar solvents such as solvents. difference In addition, butanediol diacrylate and dimethacrylate and hexane Diol diacrylates and dimethacrylates at the expense of impact resistance gives good hardness and wear resistance. They also have good photostability and low viscosity. Typical diacrylate or dimethacrylate diluents The concentration is between 0% and 50% by weight, and preferably between 2% and 2% by weight. 0% by weight.

In other embodiments, polyfunctional acrylics are used to provide a strong thermoset network. esters and methacrylates are included in the composition. These highly sensual systems gives good abrasion resistance to the final lens product. Examples include tree, tetra, Penta- and hexa-acrylated and methacrylated aliphatic or aromatic Aromatic monomers are included. It may be ethoxylated; Limethylolpropane tri(meth)acrylate, propoxylated trimethylol Lupropane tri(meth)acrylate, ethoxylated pentaerythritol tetra (meth)acrylate, pentaerythritol tri(meth)acrylate, glycol Seryl propoxytri(meth)acrylate, dipentaerythritol penta (meth)acrylate, dipentaerythritol (meth)acrylate, trimester Tyrolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate t) Includes, but is limited to, acrylate and di-trimethylolpropane. Not done. The ethoxylated and propoxylated additives can be added in any desired amount. typically 3 to 9 moles of ethoxylation, T Although it has the disadvantages of lower g and higher viscosity, it offers improved flexibility, reduced shrinkage, and Low toxicity is provided.

3. Initiator Any UV free radical initiator known to those skilled in the art of free radical polymerization or a thermal free radical initiator or a mixture of these initiators to initiate the polymerization. It can be used to Mixtures of photoinitiators can be more efficient in certain cases is sometimes preferred because it can provide the generation of radical radicals.

The initiator should be non-yellowing, if UV initiator should have a broad absorption spectrum and good curing efficiency.

The initiator should also be non-toxic and have low odor. in a polymerizable composition. Any concentration of initiator can be used as long as it provides the desired product. typically ranges from 0.1 to 5% by weight. Relatively low concentration (from 0,1 0.8% by weight) is preferred because it reduces yellowing.

There are a number of commercially available UV initiators that are non-yellowing. For example, lrgacure 184 (1-hydroxycyclohexylphenyl ketone), and C1ba Darocur 2959 sold by Geigy Corporation is 1173, and Fratelli Laff1berti Esacure Includes KIP 100F (2-hydroxyalkylphenol) sold by but not limited to. KIP 100F and Darocur 2 959 and 1173 are liquids and they are combined with other components of the polymerizable composition. Mixes easily. Irgacure 184 is a white powder with very good absorption. Has luminous intensity and non-yellowing properties.

Other UV and thermal initiators include benzophenone, trimethylbenzophenone, isopropylthioxanthone, and ethyl 4-(dimethylamino)benzo ate, benzoyl peroxide, acetyl peroxide, lauryl peroxide azobisisobutyronitrile, t-butyl peracetate, cumyl peroxide acid, t-butyl peroxide, t-butyl hydroperoxide, bis(isopropylene) peroxycarbonate, benzoin methyl ether, 2,2゛　-a Zobis(2,4-dimethylvaleronitrile), tert-butyl peroctoate phthalic peroxide, jetoxyacetophenone, and tertiary -butylperoxypivalate, jetoxyacetophenone, 1-hydroxysiloxane chlorhexyl phenyl ketone, 2,2-dimethoxy-2-phenyl-acetophene Includes non-, phenothiazine, and diisopropylxanthogen disulfides be done.

4. Inhibitor Inhibitors act as radical scavengers and inhibit polymerization under normal storage conditions. It is added to the polymerizable composition to inhibit it. Any inhibitor known to those skilled in the art may be used at any effective concentration. The most common inhibitor is hydroquinone (HQ) and hydroquinone monomethyl ether (ME HQ). HQ is It has been found that high concentrations can intensify yellowing; It has not been. Inhibitor levels should be minimized. Because inhibitors are This is because it slows down the initiation of mating and the growth process.

Typical concentration in the final formulation is optimized to 0.002-0.2% by weight .

5. UV stabilizer Stabilizers may be used to prevent the properties of the lens from changing over time. For stabilizers , U■ absorber (UVA), hindered amine light stabilizer (hindered li ght affline 5 tabilizer) (HALS), and oxidation Included are inhibitors (AO). UVA preferentially absorbs incoming UV radiation. , thereby preventing UV radiation from reaching the cast polymer. do. As an example, C1ba Geigy's Tinuvin 328, Tinuv In 900 and Tinuvin 1130 are included. HALS is Although it does not absorb UV radiation, the cast polymer absorbs free radicals. This prevents it from bonding with and decomposing. As an example, (iba Geigy's Ti nuvin 292, and Tinuvin 144.

AO also destroys free radicals, especially those related to peroxide radicals. Extinguish. These are generally not used as light stabilizers. As an example , C1ba Geigy I rganox 1010, Irganox 10 76 are included.

Even after the lens material is cast, it can be protected by applying an anti-UV coating. Protect against UV radiation by immersing the lens in a suitable solution. can be done.

6. Other additives Internal mold release agents are added to polymerizable compositions to improve mold release from the mold. can be done, but is not necessary, and should be avoided if possible . This is because it reduces transparency. An example of a mold release agent is butylsteel. Alate, dioctyl phthalate, E, 1. DuPont NeMoursa Zelec IJV and Zelec NE sold by nd Company Included.

Other additives may also be included, such as dyes and wetting agents.

7. Polymerization method Shrinkage and long curing times associated with traditional ophthalmic lens casting methods The polymerizable compositions disclosed herein can be synthesized in a continuous manner as previously described in detail. The problem is solved by casting using a polymerization method. Using continuous polymerization , the formwork design becomes easy. Necessary for designing formwork that takes resin shrinkage into consideration Expensive testing is avoided. Continuous methods are compatible with either light curing or heat curing. easily applied.

Light curing is preferred because it is more convenient and generally has shorter curing times. light Curing at a moderately high temperature may further reduce the polymerization time.

Apparatus for manufacturing lenses from polymerizable compositions preferably comprises: : Carriage frame; Energy source attached to the carriage frame and capable of starting polymerization. a concave (or convex) formwork that can pass through the carriage frame; obtaining, moving stage: for moving the stage across the carriage frame; means; convex (or concave) formwork, where the convex (or concave) formwork is attached to a moving stage, and the convex (or concave) formwork is a transparent concave (or convex) formwork, and move it to the vicinity of the convex formwork and the concave formwork. This internal cavity can accommodate the exact dimensions of the lens. means for introducing the polymerizable composition into said internal cavity: in a continuous manner; energy source for transmission through the concave (or convex) formwork; and polymerization The polymerizable composition is introduced starting from a position opposite to the position where the polymerizable composition is introduced. The polymerizable material is continuously exposed to an energy source as it advances to the point where it is inserted. A means of

One embodiment of the method and apparatus for the preparation of lenses by continuous polymerization is shown in FIG. Shown in 1 to 3. Figure 1 shows a concave formwork I that forms the convex surface of the final product lens. O1 and a carrier comprising a convex formwork 20 forming the concave surface of the final product lens. Showing ridge system. In a preferred embodiment, the convex formwork 20 is While attached to the moving stage 30, the concave formwork 10 is attached to one of the carriage frames 40. The pieces are snapped into holders. The side closest to the lamp source (i.e. front type) The wear resistance of the frame) can be made greater than that of surfaces further away, but . Most ophthalmic retail outlefts have a coating on the concave surface of the lens. This embodiment is preferred because it has the ability to Reverse arrangement (i.e. convex The formwork is attached to the stage and the concave formwork is attached to the holder) is also It is possible. The formwork attached to the holder is made of UV transparent material such as BK-7 glass. It must be made of a permeable material.

It should be noted that the back formwork 20 does not need to be UV transparent.

Therefore, metal, non-UV transparent glass or plastic.

Even molded formwork can be used. If not handled with care, the glass or Although metal formwork offers a long service life, they are very expensive. , can be easily damaged.

Plastic formwork, especially plastic formwork that can be injection molded, is expensive to manufacture. is cheap. Polystyrene, polyester (PET or PBT), polyaceter polyfluorinated alcohol, Teflon, polyamide, polysulfone, polyimide such as hardness, thermal stability, and ease of removing (formed) parts of the final product. Materials with low surface energy can be formwork candidates in the method of the invention.

This formwork lO attached to the carriage frame has a gonier that displays the degree of rotation around the axis. It can be sealed by an outer ring that acts as an ohmometer. This feature is a non-spherical It is necessary for shaped formwork. Especially when making aspherical, multifocal, or progressive lenses. In this case, this rotation involves the rotation of the desired cylinder with respect to the formwork attached to the stage 20. – Requires adjustment of orientation.

The lead screw 50 moves the stage 30 back and forth along the guide bar 60. distance indicator The position 70 indicates the position of the stage to the user.

The carriage consists of two formworks LO120 filled with a flowable polymerizable composition. form a cavity between. FIG. 2 shows one embodiment of the carriage system of FIG. Figure 3 is a schematic side cross-sectional view of a section showing a procedure for filling a lens mold; Assemble the formwork Inert material such as flexible PvC, silicone, or rubber before bonding. A flexible gasket 100 made of , is tightly attached to the periphery of the formwork ■0. then A rigid lamp 110 is mounted around the gasket for support. Next Then, the stage 30 is arranged so that the molds are separated by a desired distance.

The brake or locking system is then operated under high pressure (30 psi and 50 psi). so that the stage is fixed in its locked position even during used in sea urchins. Any suitable mechanism, such as a backstop or brake A lock system may be used. In a preferred embodiment, the UV-transparent formwork IO The interior of the cavity is black or black to prevent light scattering. Lined with anti-reflective coating.

The polymerizable resin is placed in a reservoir 80 and molded into a mold by a number of methods. can be introduced into the cavity. Mechanical methods such as motor-driven pistons are used It can be done. However, a simpler and preferred system uses gas pressure to direct the fluid. (See Figure 2). piston to separate gas from fluid may be granted. However, if the gas is in contact with a fluid, oxygen into the composition The gas is inert (e.g. nitrogen or helium) to minimize dissolution of It is preferable. The reservoir has a valve 85 and a tapered tip 90 at the end. connected to the formwork cavity by a flexible plastic hose. tapered Push the chip through the small hole in the bottom of the gasket and introduce the resin . Fluid enters from the bottom of the cavity to fill it without creating bubbles. Sky Air can be released through small vents 120 on the top of the gasket. Fill the cavity After filling, screw the cap 130 and plug the vent to seal the cavity. Ru.

The carriage is transferred to a curing station for continuous polymerization. Figure 3 shows 18 Figure 1, with a mold for a lens that rotates 0 degrees and is placed in front of a movable UV fi. 1 is a schematic side view of another portion of one embodiment of the carriage system; FIG. hardened stay The option is long wavelength UV light source (from 250nlr+ to 400nffl) 150 or Preferably, before emitting the parallel light attached to the moving stage 160, Consists of a light source. U, V, transmits light but prevents the transmission of visible light and IR radiation. The colored glass filter 165 minimizes irradiation and heating of the resin by the light source. added to do. Attached to motor 180 and drive system 190 The stage is driven by a lead screw 170. This motor is preferably Computer-like controls to set and vary desired scan speed connected to the system. 11 adjustable vertically between 0.25 inch and 2.0 inch The slit 200, which is a directly located opening, is attached to the frame 210, and Provides a planeband of UV light. This frame has a light source and and the slit are mounted on a translation stage 160 so that they can move as a single unit. can be attached. In a preferred embodiment, during continuous polymerization, the carriage assembly Movement of the light source/slit assembly to the cavity 2 causes a flat band of UV light to 30 and move toward the bottom surface 220 where the resin boundary is located. controlled to scan across the carriage.

Carriage 140 is arranged in such a way that the resin source is repositioned on the top surface of the carriage. When rotating at Skip across the carriage starting at surface 220 and moving toward top surface 230. The reverse arrangement for scanning is also possible. However, this method requires an additional rotation process. Also, the air in the cavity is completely removed during the filling process. If not removed, rotation of the cavity after filling will be trapped during curing. This induces air bubbles to rise through the cavity, producing a defective lens. times Other arrangements that do not involve moving the carriage and moving the light source and slit This is a fixed arrangement.

Other similar schemes can be used to provide continuous effects. slit Instead, the curtain connects the first U to the area opposite the supply port. V-light exposure can be reduced (or increased). This curtain has all lenses. Move until you are forced to move. For this arrangement, the U exposure time is It should be noted that it is not constant, but depends on its position. other possible A typical arrangement is to open the slits continuously starting from the center of the lens. be. Here, the central part of the lens is the longest (exposed to UV light).

The main disadvantage of this scheme is that there are two slits at the opposite end of the opening. supply port.

If you want to use a widening hole instead of a gradually widening slit, It only requires one port. This uses a diaphragm. achieved. With the aperture, the initial Uv@ outcrop area is inside the lens assembly. It is a small circular hole in the heart. This exposed area is gradually increased by the aperture of the aperture. Add. Continuous aperture aperture ensures sufficient exposure of all lens assemblies be done. Since the edges will be the last area exposed to UV light, this method requires only one One port is required.

Expansion rate depends on sample reactivity, UV intensity, and thickness of irradiated area It requires a lot of adjustment. The lens assembly may be held vertically or horizontally during the curing process. can be held.

The fluid polymerizable composition placed in the reservoir 240 is continuously placed in the cavity. It will be resupplied immediately. A known positive pressure typically between 20 psi and 50 psi or A force is applied to the syringe during the polymerization process. The optimum pressure is determined by the planned flow rate and system Specified by viscosity and curing rate. Therefore, polymerization occurs in areas exposed to light. occurs, so that the shrinkage that occurs is immediately supplemented by additional polymerizable composition. It will be done. Polymerizable compositions are highly fluid and easily flowable, already polymerized. Fill the volume lost during contraction of the mixture portion. formed by contraction Almost instant replacement of the created space ensures a final destination virtually free of defects and distortions. keep

In an optional embodiment, after the continuous polymerization is completed, the entire mold cavity is covered. A curing step may be performed after exposure to concentrated Uv radiation. To ensure that defects do not appear In order to Post-curing must be carried out only if Post-curing is preferably a curing process. This is done while the part is still in the formwork to prevent oxygen inhibition during the process. be exposed. Upon completion of the curing process, the formwork structure is removed and the precision cast The part can be removed.

The above device can be used for manufacturing spherical, progressive and aspheric lenses. Polymerization method After completion of the process, the final product lenses can optionally be colored with dyes or UV inhibitors. .

The polymerizable compositions described herein using the continuous polymerization method illustrated in FIGS. Using various embodiments of the article, a diopter value of -2,0 A final product spherical lens with a diameter of 74ffIffl was prepared.

Initiator and other additives were added to the diluent and stirred vigorously. Next, this mixture Add the compound to the oligomer and carefully immerse the sample in a water bath. Heat to 50°C and stir vigorously for 2 and 3 hours, stirring for 30 minutes. to 3 hours) to ensure that the oligomers are completely dissolved in solution. I was careful to secure it. It is then heated in a vacuum oven to remove dissolved gases. The resin was degassed. Inject the resulting polymerizable fluid into the reservoir and It was introduced between two glass molds with a center spacing of 211 Iffl (Fig. 2 checking). This glass formwork is made of BK-7, which transmits long-wavelength V radiation. Constructed of glass.

The mold was coated with an external mold release agent. Flexible PvC gasket and clamp assembly A bridge was used to hold the fluid between the molds. 25 psi during the entire curing process A pressure between and 35 psi was maintained on the fluid. Above as well as U.S. Patent No. 5. Mercury vapor lamps between 160 W and 300 W and water as described in No. 114.632 The composition was polymerized continuously using a flat slit assembly. the opening of the slit It was varied from 0.5 inch to 1.0 inch. Continuous polymerization time from 8 minutes to 27 minutes It changed down to the minute. Initiator concentration was varied from 0.2 wt% to 0.5 wt% .

Example 12 Preparation of ophthalmic plastic lens 50% by weight Radcure 2 84 urethane diacrylate, 20% by weight Radcure 8301 urethane Hexaacrylate, 29.6% by weight ethoxylated trimethylolpropanetri Prepare a mixture of acrylate and 0.4 wt% IP 100F initiator. , and cast as above using a 374 inch slit size.

The sample was continuously irradiated for 22 minutes.

Example 13 Preparation of ophthalmic plastic lens 75% by weight Radcure 2 84 urethane diacrylate, 24.6% by weight hexanediol diacrylate and 0.4% by weight of Darocur 1173 initiator, Cast as above. Irradiated for 22 minutes using a slit size of 374 inches. I shot it.

Example 14 Preparation of ophthalmic plastic lens 75% by weight Sartomer 963E75 urethane diacrylate, 24°6% by weight pentaerythritol triacrylate, and 0°3% by weight of [rgacure 184 initiator] A mixture was prepared and cast as described above. 1 inch slit size was used for 18 minutes.

Example 15 Preparation of ophthalmic plastic lens 37.5% by weight Radcure 264 urethane triacrylate, 37° 5% by weight 5artoffler 963E75 urethane diacrylate, 24.7% by weight hexanediol, and 0.3% by weight of Darocure 1173 initiator, and and cast as above.

A 1 inch slit size was used and the run was for 18 minutes.

Example 16 Preparation of ophthalmic plastic lens 40% by weight Radcure 2 84 urethane diacrylate, 40% by weight Radcure 264 urethane trimethylolpropane triacrylate, 19.7% by weight and 0.3% by weight of Irgacure 184 initiator, and and cast as above. Irradiation for 18 minutes using 1 inch slit size did.

Example 17 Preparation of ophthalmic plastic lens 37.5% by weight Radcure 284 urethane diacrylate, 37.5% by weight Radcure 264 u Lethane triacrylate, 24.7ffi% ethoxylated trimethylolpropylene Pantriacrylate and 0.3% by weight Darocure 1173 start A mixture of agents was prepared and cast as described above. 1 inch slit was used and irradiated for 18 minutes.

Example 18 Preparation of ophthalmic plastic lens 43% by weight Radcure 2 84 urethane diacrylate, 37% by weight Radcure 264 urethane Reacrylate, 10% by weight ethoxylated trimethylolpropane triacrylate 9.7 wt% trimethylolpropane triacrylate, and 0.3 wt. Prepare a mixture of wt% KIP 100F initiator and cast as described. I did it. Irradiation was performed for 18 minutes using a 1 inch slit.

Example 19 Preparation of ophthalmic plastic lens 40% by weight Radcure 2 84 urethane diacrylate, 40% by weight Radcure 264 urethane Reacrylate, 19.8% by weight ethoxylated pentaerythritol tetraac A mixture of rylate and 0.2% by weight Irgacure 184 initiator was prepared. and cast as described above. Use a slit size of 0.75 inch. It was irradiated for 15 minutes.

Example 20 Preparation of ophthalmic plastic lens 37% by weight Radcure 2 84 urethane diacrylate, 33% by weight Radcure 264 urethane Reacrylate, 29.8% by weight ethoxylated pentaerythritol tetraac A mixture of lylate and 0.2% by weight lrgacure 184 initiator was prepared. and cast as described above. Use a slit size of 0.75 inch. It was irradiated for 15 minutes.

Example 21 Preparation of ophthalmic plastic lens 60% by weight Radcure 2 84 urethane diacrylate, 10% by weight polyester acrylate, 29. 6% by weight of ethoxylated trimethylolpropane triacrylate, and 0.4% A mixture of wt% Irgacure 184 initiator was prepared and as described above. was cast. Irradiation was performed for 18 minutes using a slit size of 0-75.

Example 22 Evaluation of lenses prepared in Examples 12 to 21 Prepared in Examples 12 to 21 The lenses were evaluated for impact resistance and abrasion resistance. optical magnification of the lens In order to evaluate this, an N1kon lens meter was used. Optics of all lenses The target magnification is less than 1/8 diopter of the specified magnification (-2,0 diopters). No cylinder was found anywhere on the lens.

Based on reading the haze of worn lenses (Bayer test method (ASTM F)) -735), a lens abrasion test was conducted. The results of the wear test are shown in Table 2. . This shows the difference in abrasion resistance between the test lens and CR-39 .

Impact resistance was evaluated using the FDA falling ball test. According to FDA regulations, 5/8” When a stainless steel ball is dropped from a height of 50 inches and subjected to an impact, the lens It is necessary that it does not break. All lenses prepared as described herein pass this test easily. When dropped from a height of 50 inches, Tests were also conducted in which the ball was gradually made heavier until the lens broke. Table 2 is 5/8” Indicates the increased weight of the ball required to break the lens when compared to the FDA ball. are doing. The heaviest weight used was eight times the weight of a 5/8” ball. The preparation did not crack even at this weight.

(Margin below) E3 284 75 ETMPTA 25 1.3 >814 963E75 75 PETA 25 0. ci 3.4 The present invention with respect to its preferred embodiments I have written it down.

Changes and modifications of the invention described herein may be apparent from the foregoing detailed description of the invention. It will be clear to those skilled in the art. All such changes and modifications may fall within the scope of the appended claims. is intended to be encompassed within the scope.

FIGURE2 Continuation of front page (51) Int, C1,' Identification code Office serial number G O2B 1/11 (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), AU, CA, JPI (72) Inventor Pei, Young C.

United States California 94588゜Pleasanton, Apartment H205, Stoneridge Mall Road (72) Inventor Thorne, De IPID varnish.

United States California 94610° Piedmont, King Ave. 109

Claims (44)

[Claims] 1. Polymer-polymer composite lenses comprising (i) and (ii): (i) a scratch-resistant front polymer wafer with at least a bare CR; -39 has a hardness equivalent to itself and is at least 100 microns thick. a wafer: where the wafer has a convex surface forming the front side of the lens; , having a concave surface; and (ii) a back polymer layer with impact resistance at least equivalent to CR-39; the back polymer layer has a concave surface and a convex surface; and the front polymer layer has a concave surface and a convex surface; The concave surface of the fur joins the convex surface of the back layer. 2. The scratch-resistant front wafer has an anti-reflective coating on its convex surface. 2. The polymer-polymer composite lens of claim 1, wherein the polymer-polymer composite lens has a ring. 3. The concave surface of the front wafer provides a composite thickness profile that corrects astigmatism. The polymer-polymer composite lens according to claim 1, comprising: 4. The concave surface of the front wafer has a compound thickness profile providing bifocal correction. 2. The polymer-polymer composite lens of claim 1, wherein the polymer-polymer composite lens has a 5. The concave surface of the front wafer has a composite thickness profile that provides progressive correction. 2. The polymer-polymer composite lens of claim 1, wherein the polymer-polymer composite lens has a 6. The concave surface of the front wafer forms a diffractive pattern that gives the lens anti-reflection properties. 2. The polymer-polymer composite lens of claim 1, having a lens. 7. The convex surface of the front polymer wafer provides bifocal or multifocal correction. The polymer-polymer composite lens according to claim 1, which provides a polymer-polymer composite lens according to claim 1. 8. the impact-resistant back lens comprises a block copolymer, an interpenetrating network; From the group consisting of graft copolymers, random copolymers, and homopolymers Polymer-polymer composite lens according to claim 1, containing selected polymers. Z. 9. 22, wherein the backside polymer wafer contains the composition of claim 21. The polymer-polymer composite lens according to claim 1. 10. Claim 1, wherein the back polymer layer contains the composition of claim 21. The polymer-polymer composite lens described in . 11. The scratch-resistant front wafer is made of allyl diglycol carbonate. Polymer, polymethyl methacrylate, and polycarbonate The compound lens according to claim 1, containing a material selected from the group consisting of: 12. The scratch-resistant front wafer is made of polyetherimide, polyimide polyether sulfone, polysulfone, polyethylene terephthalate, and other amorphous (random copolymers) polyamides, polyesters and urethanes 2. A compound lens according to claim 1, containing a material selected from the group consisting of: 13. The scratch-resistant front wafer is made of alkyl methacrylate, alkyl methacrylate, Kill acrylates, allyl or aryl acrylates and methacrylates, Styrene, α-methylstyrene, vinyl ester, vinyl chloride, methylvinyl chloride ton, vinylidene chloride, acrylamide, methacrylamide, acrylonitrile , methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and 1,2-epoxy-3-allyl propane, and polymers or copolymers of monomers selected from the group consisting of and mixtures thereof; The composite lens according to claim 1, comprising: -. 14. 14. The composite according to claim 13, wherein the monomer is methyl methacrylate. lens. 15. The front wafer is made of unsaturated urethane, carbonate, or epoxy. The compound lens according to claim 1, which is. 16. Claim 1, wherein the front wafer is attached to the back layer with an adhesive. Composite lens described in. 17. 2. The method of claim 1, wherein the back layer is polymerized onto the front wafer. compound lens. 18. 1. A method of preparing a polymer-polymer lens composite comprising: It has at least the same scratch resistance as CR-39, and the thickness is Preformed scratch resistant front surface that is at least 100 microns The polymer wafer has an impact resistance at least equivalent to CR-39. A method comprising adhesively attaching to a preformed back wafer. . 19. 29. The method of claim 28, wherein the adhesive is continuously polymerized. 20. A method for forming a polymer-polymer lens composite, the method comprising the following steps: How to include: a. providing a form body having a first portion and a second portion; and the second part delimit an internal cavity between them, and the second part defines an internal cavity between them; The tee corresponds to the exact dimensions of the final product and has a closed end and an open end. An open end is located opposite the closed end and a minor portion of the first portion and the second portion. At least one of the steps includes: discharging the polymerizable material in the internal cavity in a sequential manner and A continuous method allows exposure to an energy source, and here the convex It has a shaped surface and a concave surface, and has a scratch resistance at least equivalent to that of CR-39. a prefabricated material having latching properties and having a thickness of at least 100 microns; a shaped wafer, the polymerizable material curing on the concave surface of the wafer; positioned in the formwork so as to; b. by sequential and sequential methods. providing an energy source for imparting to the surface of the polymerizable material; c. providing a source of polymerizable material at the open end of the formwork; d. The polymerizable material contacts the preformed concave surface of the front wafer. filling the interior cavity with the polymerizable material so as to e. The polymerization is possible starting from the closed end and proceeding towards the open end. intermittently exposing the polymerizable material to the energy source; The process of continuously feeding the open end. 21. A free-radically polymerizable composition for producing ophthalmic lenses. A composition containing the following a) and b): a) between 20% and 90% by weight of acrylates or methacrylates, or is a urethane, epoxy resin end-capped with a mixture of acrylates and methacrylates. or polyester oligomer, or a mixture thereof; b) 5% by weight and 80% by weight of acrylate or methacrylate end-capped carbon Hydrogen diols, and tri-, tetra-, or poly-acrylates or A diluent selected from the group consisting of tacrylate, or mixtures thereof. 22. In addition, free radical initiators, UV absorbers, templating agents, stabilizers, dyes, acids Claim 2, further comprising an additive selected from the group consisting of anti-fouling agents and wetting agents. 1. The composition according to 1. 23. the diluent is present in the composition in an amount between 10% and 40% by weight; 22. The composition of claim 21. 24. The urethane oligomer is polyol, polyester, and polyether. 22. The composition according to claim 21, prepared from a material selected from the group consisting of . 25. The urethane is a difunctional or polyfunctional prepolymer having the following structure. The composition according to claim 21: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ where P is an aliphatic or aromatic polyether, polyester or polyol and R is a diisocyanate residue (an isocyanate moiety is bonded to the residue). ), and n is 2 or 3. and A is hydroxylated atalaryl or methacrylate aliphatic or aromatic ester moiety. 26. The urethane, epoxy, or polyester oligomers are two and 22. A set according to claim 21, comprising between 6 acrylate or methacrylate groups. A product. 27. 5. The oligomer has a molecular weight between 400 and 7000. 22. The composition according to 21. 28. 6. The oligomer has a molecular weight between 800 and 2500. 22. The composition according to 21. 29. The oligomers used are difunctional urethane acrylates and trifunctional urethane acrylates. 22. The composition of claim 21, wherein the composition is a combination of polyurethane acrylates. 30. Claim wherein the oligomer is contained between 50% and 70% by weight. The composition according to item 21. 31. The diluent is 1,6-hexanediol diacrylate and ethoxy A mixture of pentaerythritol tri- or tetraacrylates. 22. The composition according to claim 21. 32. The diluent is 1,6-hexanediol diacrylate and ethoxy 22. A mixture of trimethylolpropane triacrylates according to claim 21. Composition of. 33. The diluent is tri-, tetra-, or polyacrylic with higher functionality. 22. Consisting of esters and methacrylates or mixtures thereof. Composition of. 34. A lens prepared from the composition of claim 21. 35. An apparatus for manufacturing lenses from a polymerizable composition, comprising the following i) to vi: ii) a device comprising: i) a carriage frame; ii) a concave formwork attached to the carriage frame, which is capable of initiating polymerization; a concave formwork capable of transmitting energy; iii) capable of being driven across the carriage frame; , a moving stage iv) for moving the stage across the carriage frame; means; v) a convex formwork attached to the moving stage, the convex formwork being attached to the concave mold; moving near the frame to form an internal cavity between the convex formwork and the concave formwork; vi) a convex mold, in which the cavity corresponds to the exact dimensions of the lens; vi) polymerizable; vii) in a continuous manner, introducing a composition into the cavity; energy source for transmission through; viii) adding the polymerizable composition starting from a position opposite to the position where the polymerizable composition is introduced; The polymerizable material is advanced to the point where the polymerizable composition is introduced. A means of continuous exposure to a source of energy. 36. An apparatus for manufacturing lenses from a polymerizable composition, comprising the following i) to vi: ii) a device comprising: i) a carriage frame; ii) a convex formwork attached to the carriage frame, which is capable of initiating polymerization; a convex formwork capable of transmitting energy; iii) capable of being driven across the carriage frame; , a moving stage iv) for moving the stage across the carriage frame; means; v) a concave formwork attached to the moving stage, the convex formwork being attached to the concave mold; moving near the frame to form an internal cavity between the convex formwork and the concave formwork; vi) a concave mold, in which the cavity corresponds to the exact dimensions of the lens; vi) polymerizable; vii) in a continuous manner, introducing a composition into the cavity; energy source for transmission through; viii) adding the polymerizable composition starting from a position opposite to the position where the polymerizable composition is introduced; The polymerizable material is advanced to the point where the polymerizable composition is introduced. A means of continuous exposure to a source of energy. 37. 37. The device according to claim 35 or 36, wherein the energy source is ultraviolet radiation. Place. 38. The claim further comprises a distance indicating device attached to the moving stage. 37. The device according to item 35 or 36, wherein the distance indicating device is connected to the key of the stage. A device that indicates the user's position relative to the carriage. 39. The means for introducing the polymerizable composition is a syringe or a reservoir. 37. The apparatus according to claim 35 or 36. 40. Said means for moving the stage across the carriage includes a leadscrew. 37. The device according to claim 35 or 36, comprising: 41. 5. The stage of claim 1, wherein the stage moves on a guide bar along the carriage. 36. The device according to 35 or 36. 42. Claim 35 or 36, further comprising a flexible gasket. In the apparatus, when the concave formwork and the convex formwork are adjacent to each other, the gasket The gasket fits tightly around the concave formwork and the convex formwork, and passes through the gasket. A device into which said polymerizable composition is introduced. 43. further comprising a rigid clamp attached to said gasket; 43. The device according to item 42. 44. The stage further includes means for fixing the stage to the carriage at a desired position. 37. The apparatus according to claim 35 or 36.