MXPA97009761A - Compositions of resin fotocrom - Google Patents

Abstract

The present invention relates to: A resin characterized in that it comprises a mixture of at least two polymerizable components, at least one torochromic additive, at least one additive and at least one polymerization initiator; minus two polymerizable components are preferably selected from monofunctional, difunctional and multifunctional acrylates and methacrylates, the photochromic additive is preferably selected from spiroxazine and spiropoyran additives, and the additive is preferably selected from antioxidants, radical scavengers and agents ultraviole absorbers

Description

COMPOSITIONS OF PHOTOCROMIC RESIN BACKGROUND OF THE INVENTION Traditionally, len + is for plastic lenses as well as plastic lenses designed for other applications are manufactured in one of two ways: 1) empty the complete len + e between two molds as a monolithic optical finished material and 2) empty a template, then click on the desired prescription. Thermoplastic and thermoset materials can be used as optical materials. Thermoplastic materials are generally formed by injection molding, although compression and transfer molding techniques have also been used. The surface materials, such as resin formulations based on bil to diethylene glycol carbonate (OET BftC) are formed by cast molding techniques. In all cases, what is obtained is an optical material made of a single material. This optical material can subsequently be covered to develop desired surface properties, such as improved scratch resistance, reduced optical reflection, or improved impact strength using mostly conventional coating processes, such as coating or immersion, spin coating. or by vacuum deposition. These coatings rarely exceed 25 microns thick.

Methods of emptying optofac layers of a wide range of thicknesses in lenses have been described, for example, Blurn (U.S. Patent No. 5,21 * 3,497). These methods use a lens jig and a specified bending mold to polish a liquid resin on the surface of the lens substrate. The layer may be uniform in thickness, or it may alter the geornet of the substrate in some specified and controlled manner. Layers of 1000 microns or so may be deposited on the upper end and up to 25 microns in thickness by this method. This method can be applied to thermoplastic substrates and terraznes, and both thermoplastic and terpenoid layers can be deposited through the use of a mold. A mixed optical layer material can be formed by this method. Optical discharge layers of between 25 to 1000 microns or more can perform many optical functions. They can be added to minimize optical aberrations in the lens template, develop an achromatic optic material, or provide bifocal or multi-focal optical materials through the development of refractive index gradients. The layers of the upper layers can also be provided to add a photochromic layer to the lens template. Of course, the quality and range of applicability of plastic lenses is significantly improved by the development of mixed optics, which are formed by the addition of one or more layers to the lens or lens. Although the manufacture of mixed lenses using a mold and a lens jig as described above is well established, the manufacturing method requires a large inventory of molds and a manufacturing facility in addition to the one used to empty the substrates. + blank. It is therefore desirable to develop a manufacturing process in which the evolution of the layers of the upper stratum is matched to the manufacture of the blank substrates of the lenses themselves and does not require their further manipulation after they are formed. . The len + formation methods are photochromic described above (EU patent 4,968,454 by Crano etal, EUft patent 4,286,957 by Le Naour-Sene, EUft patent 4,936,995 by Kwiatkowsl-'iy U.S. Patent No. 4,637,698 by Kakk, et al) have included the application of photochromic layers on lenses or blank substrates of lenses but have not been directed to the integration of the photochromic layer to the substrate, in order to reach a Procedures for continuous and swirlless production at a low cost, or to achieve superior optical quality as well as mechanical and thermal properties by developing an interface between the lens substrate and the upper substrate layer.

BRIEF DESCRIPTION OF THE INVENTION According to one embodiment of the invention, a ream is provided comprising: a mixture of at least two polishable components, at least one photochromic additive, at least one additive and at least one polymerization initiator. The mixture of at least two polishable components is preferably selected from acrylate and non-functional, functional, and functional mixtures. The photochromic additive is preferably selected from spiroxane additives and spiropyran additives. The additive is preferably selected from antioxidants, radical scavengers and ultraviolet absorbing agents. The resin preferably comprises: from 0 to 70% by weight of onofunctional component, from 10 to 50% by weight of difunctional component, from 0 to 20% by weight of multifunctional component, from 0.02 to 0.2% by weight of additives of spiroxazine, from 0.05 to 0.3% by weight of spirometry additives, from 0.1 to 2% by weight of additive and from 0.125 to 2.5% by weight of polymerization initiator. The resin preferably forms a material having a glass transition temperature ranging in the range from 20 ° to 90 ° C, preferably from 30 ° to 85 ° C, preferably from 30 to 60 ° C, or an interlacing density from 0.5M / L to 3.0 i / L, preferably from 1 to 2 M / L after polymerization. The resin preferably has a viscosity ranging from 25 to 150 cps at 25 ° C. The di functional component can be selected from hydrophilic acrylates and methacrylates, preferably a polyethylene glycol diacrylate. The rnonofunctional component can be selected from hydrophobic acyl and acrylates, preferably having a long chain rnetylene moiety. The monofunctional component preferably has a glass transition temperature that varies in the range from 50 to 120 ° C after the polymerization. The polymerization initiator may comprise a thermal polymerization initiator or a photochemical polymerization initiator. The photochromic additive is preferably at least one of red-colored chrono ante, a purple spiroxazma dye, a yellow crornene dye and a green sporoxazine dye. The ream can be provided in polimerized form as an optical layer on an almost finished lens or template, with the layer having a thickness ranging in the range from 25 to 1000 microns. The near-finished lens substrate or substrate can comprise a thermophilic material, in which case the resin and the thermophilic material can be formulated with matched polishable components such that the metallic bonds are formed between the matched polyenergy components. as yet, a terpenetran + e layer can be formed on a terf between the resin and a terrnofix material. The lens or the almost finished template can also be a rna + ep l terrnoplastic. The resin may be provided in a layer on a mold, with the layer having a thickness ranging from 25 to 1000 microns, in which case the layer may be non-polyester, partially polyrneized or partially polyrneized and gel-like. In accordance with the embodiment of the invention, there is provided a method comprising: applying a layer of the above resin to a mold to form a mold covered with a pre-coat resin; To make the pre-recess resorvoir come in contact with a casting resin, polish the pre-coat ream and polish the casting resin. The layer can be applied by dipping, spraying, spin coating or by stereo lithography. Any resin can be despolirnepzarse or at least polirnerizar partially before coming into contact with the other.

DESCRIPTION OF THE INVENTION The present invention discloses polymerizable resin formulations which can be raised to form a polymer layer on the molding surface of a mold which is then used to make a plastic lens or a lens template, transferring the preformed layer on the external surface of the lens that is formed by this procedure. The use of pre-coated molds to empty a plastic lens is known in the art. Bandvig, et al (U.S. Patent 4,758,448) discloses the formation of plastic lenses with improved scratch resistance using molds coated with a mixture of acrylates and multifunctional oncorneric and oligomeric inetacrylates. The ream formulations of the present invention are specifically directed towards the development of photochromic layers which vary in thickness in the range from 25 to 1000 microns and can provide uniform or gradient photochromic properties throughout the lens surface. The layers formed from these have glass transition temperatures in the range from 20 ° C to 90 ° C, and preferably in the range from 30 ° C to 85 ° C, and an interlacing density in the range from 0.5 M / L up to 3.0 M / L, all preferred to ensure a desirable change, dye or color dynamics in the activated and deactivated states, as well as the dynamic range (the change in optical transrnitancy between the activated and deactivated states) of photochromic additives as a function of room temperature.

The ream formulations ("pre-coat resin") can be applied to the surface of the mold by dipping, spraying, spin coating or by stereo lithography. These can be left as a non-polished liquid cover, a pre-gel, a partially polished layer or a partially polimerized gelled layer. The molds can be covered with the ream layer and stored for future use, or they can be covered immediately before they are used to empty lenses. The substrate lens can be emptied from any resin formulated to go through an addition or condensation polymerization process. If the resin used to empty the substrate lens or the lens target ("Rinse Resin") undergoes a chemical reaction with the photochromic additive present in the precursor layer + during the polymerization process, it is necessary to avoid mixing diffusive of the casting resin in the unpolymerized state with the photochromic additive. The photochromic additive can be isolated from the pouring resin by continuing the polymerization and the interlacing of the precoating layer by bringing the photochromic additive to a point such that the diffusion of the additive molecules from the precoat layer to the resin of emptying, or the diffusion of the casting resin into the precoat layer is minimized. It is important to note that while the interdiffusion rate of the components of the previous layer and the recess of emptying may decrease its speed, it is still necessary to maintain good compatability between the two in order to develop a strong adhesive bond between them. It is possible to adopt one or more of the following strategies to integrate the irrespective prerrevest layer or the substrate. 1) During the casting process, the precoat layer deposited on the surface of the mold can retain its integrity and form an adhesive bond to the substrate; in this case, the precoat layer is cured at least partially before filling the mold assembly with the ream formulation to empty the substrate lens. The surface energy of the pre-coated layer is adjusted to be compatible with the substrate. It is also desirable to include polymechanizable paired components in the precoated layer and the substrate lens so that these components can form interfacial bonds, such as hydrogen bonds, -S-? -0-X- bonds when X is Si or C, or other such bonds as amide or ester. 2) The polimerisable components of the ream forming the lens substrate or the precoat layer can undergo diffusion through the third layer-substrate and pass through a polymerization during the process in which the substrate lens is formed. An interpenetrating layer (IPN) is thus formed, constituting a discrete interface between the substrate and the precoat layer. The advantage of forming the t-layer is that the diffusion of light is minimized, the adhesive strength of the interface is enhanced, and in many cases, the impact properties, especially in response to normal forces, are improved. 3) The cover on the mold can be left in a non-polished state before emptying the substrate lens. In this case, it is necessary to use relatively viscous polymerizable components, in order to allow the precoat layer to maintain its integrity and the specified thickness profile through the surface of the mold during the handling and filling steps of the preceding ream. the healing of the substrate lens. The healing procedure may include the application of heat, light or both. For example, it is possible to use high viscosity nitrifunctional oligoes previously mixed with a photoinitiator to form a precoat layer, and a low viscosity polishable formulation that is thermally activated to form the substrate lens. The healing procedure uses heat and light, which starts at a specified temperature. The precoat layer reaches a certain viscosity and diffusion coefficient at the point in time when the photopolymerization starts. In this way, the inter-fusion between the two formulations can be carefully regulated to form the optimum interfacial gradient in the composition and interlacing density of the upper stratum layer. 4) The precoat layer on the mold is partially cut to the mind in order to consume all the initiator molecules and a certain portion of polyenergizable groups available, and its composition is paired to form a strong adhesion towards the substrate lens, following the approximations delineated in (1). The substrate lens is not emptied in situ, but added in the form of a lens template. The resulting lens is a three-layer composite consisting of a substrate covered with two optical layers. This lens can be subsequently coated with a hard shell to provide an external surface that is hard and scratch resistant. In all cases, the polymerization of the precoat layer on the mold as well as the substrate lens itself can be activated by heat, light or a combination of the two. At this point, a combination of thermal and / or photochemical polymerization initiators can be employed in either or both formulations. The use of a combination of thermal and photochromic photoinitiators provides additional control of polymerization initiation rates in the precoat layer and the substrate lens and allows different polymerization initiation rates to be maintained in these two zones at the same time. The molds can be made of glass, metal or plastic materials. Plastic molds can be reusable or disposable, designed for single use or for limited use. The metal olds may be formed from a solid piece of steel or other suitable metal, or it may be made of glass coated with a metallic layer, which may be transparent to active radiation. For example, indium tin oxide (ITO) is metallic but transmits visible radiation which can be used to trigger the polymerization in the substrate lens or in the precursor layer. The pre-coat ream formulation preferably contains a mixture of mono and final functional acrylics and monomers, polymerization initiators, prior antioxies or radical scavengers and photochemical additives. Toh (U.S. Patent 4,912,185) and Gupta, et al (U.S. Patent No. 5,470,892) have described entanglement resin formulations for the manufacture of lenses and blank lens substrates. The ream formulations developed in the present invention are specifically directed to produce reams of a certain range in interlacing density, glass transition temperature and viscosity (25-150 cps at 25 ° C). Chu (U.S. Patent 4,720,356) has described the use of hindered amines and extruders of reaction in the excited state to enhance the weathering characteristics of the photochromic compositions. Photochromic additives can be selected from the family of spiroxazmas, such as spiro - (? Ndol? No) -benzoxazmas, esp? Ro (mdol? No) -n phtoxazmas, espir or (ndolmo) p? Pdobenzoxaz? ñas, etc. ("espi roxazmas"), or a family of spiropyrans ("crómenos"). Photochromic additives have been described in numerous US patents. and from overseas, for example Guglielrnetti, et al, patent of E.U.ft. 5,139,707 and the references of the same. Photochromic additives are available commercially, and were obtained from Darnes Robinson Limited, Huddersfield, UK or Great La es Corporation, Mmneapolis. Table 3 shows a typical combination of photochemical additives obtained from James Robi nson Ltd. The formulation of the recess of emptying includes acplates, rnetacplatos, allyl and vmilo compounds. Generally one or more bi-functional or multi-functional components is used in the formulation in order to constitute a lens body that is highly interlaced. The formulation may include ultraviolet stabilizers, antioxidants, radical scavengers, color neutralizing agents, such as blue staining agents, as well as one or more thermal polymerization initiators or initiators. Alternatively, the main components of this formulation may consist of monomers and reinforcers capable of undergoing polymerization by condensation, for example, functional epoxides, acid anhydrides, which are reacted with amine or hydroxide derivatives.

EXAMPLE 1 Beginning with a typical formulation of isobornyl nitrate (40%), neopentyl glycol diaconlate (41%), polymethylene glycol diacrylate (400) (15%), 1-hydroxyl-cyclohexyl-phenyl ketone, of b? s-2,6-d? rnetox? benzoyl-2, 4, 4-tnrnet? lpent? phosphine (2%), and a hindered amine oxide (b? s ~ 2, 2, 6,6-tetrarnet? l-4-p? per? d? l sebacate) (L%) as a scavenging agent of radicals, a combination of four photochromic additives is added to develop a blue-gray color after activation 8Table 3). This formulation is placed on the concave surface of a glass mold incorporating an area of accumulated power of 2.00D, and a second mold of curvature that matches (base curve) is placed on the resin lagoon, spraying it in the form of a layer thin. The space of the liquid layer is maintained at 200 microns to the portion of the distance, being thicker in the area of accumulated power. The liquid ream layer is partially polimerized by exposing it to radiation in the wavelength range of 350-700 nrn for 20 minutes. The second mold is removed, and the first mold with the pre-coating layer is used to fabricate a nearly finished progressive addition lens template as follows: The previously covered mold is used to form a filling assembly using a back mold and a filling suitable to form an almost finished lens template. Casting resin is injected into the filler assembly consisting of ethyl allyl diethylene glycol carbonate (96.2%), dusopropyl percarbonate, a thermal polymerization catalyst, (3.5%) and 5-rnet? L-2-h? Drox? Phen ? l-2H-benzotnazol, an ultraviolet radiation absorbing agent (0.3%). The glass transition temperature of the pre-lapped layer on the final semi-finished lens template is measured to be 85 ° C. Table 1 shows the experimental results.

Table 1. Experimental details for the coating layer.

Trirnetylololpropane ethoxylatedg triacrilate (TMPTflg) Trirnetylolpropane ethoxylatedis triaprylate (TrlPTftlS) 2-phenoxetane metatheate (PErlfi) Polyethylene glycol diaccolate (400) (PGDfi) Neopentii giicol diaccolate (MGDR) isobormyl rletacnlate ( IBMfi) laccharide plate (Lfi) Ethoxylated bisphenol ft (BRDft) l-h? Drox? -c? Clohex? L-feml ketone diamine (184) b? S-2,6-d? Rnetox? Benzo oxide ? l-2,4,4-tr? rnetHpent? l phosphine Oxide of hindered amine (B? S-2,2,6,6-tetramet? I-4-p? Pend? L-sebacate) (765) EXAMPLE 2 The composition of the precoat resin is L7 as in example 1, except that the proportion of the hydrophilic diacrylate of polyphenylene glycol is raised to 15%. The precoat resin is filtered by passing it through a 0.2 micron stainless steel filter, then the gas is removed by passing argon through the filtered ream for 30 minutes. The resin is applied to the concave surface of a single view glass by mounting the mold on a mandrel, then rotating it at the speed of 200 rprn as the ream is added to the surface of the mold. The mold is irradiated with a pulse of 10 seconds of UV light while it is rotated after the addition of the ream is stopped. Additional liquid ream can be added to the surface of the mold and gelled by a pulse of UV light, thus shaping the thickness of the prerequisite layer to its specification. In this case, five beef applications produce a total thickness of 200 microns. The pre-coating step is carried out in a nitrogen atmosphere in order to decrease * the duration of the UV pulse that is needed to bring it to gelation. The glass transition temperature of the precoat layer is decreased, increasing the rate of change and the interlacing density decreases from 0.75 M / L to 0.35 fl / L. Table 2 provides the experimental results. The previously covered mold is used to form a filling assembly, necessary to empty a finished lens of a single vision (-2.00D sph, -2.00D astig.). A casting resin consisting of 840% alpha-methylsulienamine, 84U% ethoxylated bisphenol H, diallyl carbonate of diethylene glycol (L9%) and azo-isobutyronitrile, a thermal polymerization initiator (1.0 %). The lens is cured by placing the filling assembly in a convection oven and subjecting it to a thermal ramp + L point from a temperature of 82.22 ° C for a period of twenty hours. The deactivated color of the finished lens is somewhat obscure, indicative of the interaction of certain photochromic additives of the spiromereolysis type with an increasingly polar medium to form a polished population richer in the open ring shape which is colored.

EXAMPLE 3 As in Example 1, except that the hydrotyl diaclate is replaced by Lsoctyl acnlate, a hydrophobic monomer with a low glass transition temperature in the pre-coat ream formulation. A single-vision lens mold is previously covered, in order to form at the end a sernitepnmada template of a single vision with a photochromic layer on the convex surface. The pre-coat layer is formed using a second glass mold, the pre-coat ream being used to fill the space between the two molds. The previously covered mold is used to form a filling assembly necessary to form a finished serm template of a single vi ion. The interior color of the sernterminal template is subsequently reduced relative to Example 2, although the rate of change remains unchanged, indicating that the reduction of the polarity of the photochromic medium serves to reduce the color of the lens in the deactivated state. A second cured ream may be added to the semi-blank template of a single vision to form a serpentine template FT-28, following the method described in Bl urn (U.S. Patent No. 5,219,497). Table 2 shows the properties of change and other optical properties of photochromic lenses made using the formulations listed in Table 1. The precoat resin is formulated with a mixture of photochromic dyes such that the dye in the activated state which unfolds after exposure to the outside is gray blue. The following dyes are used in vain formulations: Mora Reversacol Red, Palatmado Reversacol Purple, Ornan lio Reversacol Corn and Reversacol Water Green. Table 3 shows the composition of the dye mixture used in Examples 1-3 and its chemical nature.

Table 2. Interior color, optical clarity and darkening characteristics of photochromic lenses.

Temperature Percentage of Experiment Color of Transmission Transmission Inner number optical glass interior solar optics 1 Ve / flrn 84 84 42 2 View / flm 81 84 42 3 View / Rrn 73 85 44 4 Green 5 View- / ftrn 6 ftmapllo L. Activation measures performed using a Solar Simulator equipment placed in flMl.O at 29, 4 ° C at 20 minutes.

Table 3. Composition of the photochromic tmtes used in the pre-coating resins.

COLORING CHEMICAL FTHMILIft PERCENTFACE WEIGHT (PREFERRED INTERVAL) RED MORFT REVERSACOL CHROME 0.090% (0.05-0.1) PURPLE PALATINATE OF ESPTOXAZINA 0.15% (0.10-0.20) REVERSACOL YELLOW CHROME MOLD 0.085% (0.075% -0.150) REVERSACOL GREEN WATER FROM REVERSftCOI. ESPROXAZINft 0.060% (0.40-0.10)

Claims (31)

NOVELTY OF THE INVENTION CLAIMS

1. - A resin characterized in that it comprises: a mixture of at least two polymerizable components selected from monotonic, di functional and multifunctional acrylates and methacrylates, such that the monofunctional component comprises from 0 to 70% by weight of the resin, functional component comprises from 10 to 50% by weight of the ream and the functional component includes from 0 to 20% by weight of the resin; at least one photochromic additive selected from spiroxazm additives, said spiroxazm additives being further characterized in that they comprise from 0.02 to 0.2% by weight of the resin and said spiropyran additives characterized furthermore because they comprise from 0.05 to 0.3% by weight of the ream; about 0.1 to 2% by weight of at least one additive selected from antioxidants, radical scavengers and ultraviolet absorbing agents; and approximately from 0.125 to 2.5% by weight of at least one polymerization initiator said ream forming a material further characterized in that it has a glass transition temperature that ranges in the range from 20 ° C to 90 ° C or an interlacing density which varies in the range from 0.5 M / L to 3.0 M / L after polymerization.

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The resin according to claim 1 further characterized in that the functional component is selected from acrylics and hydrophilic receptors. 3. The resin according to claim 2, further characterized in that the di functional component is a polyethylene glycol diaclet.

4. The ream according to claim 1 characterized furthermore because the constituent + onofncional is selected from hydrophobic acnlatos and rnetacnlatos.

5. The resin according to claim 4 further characterized in that the non-functional component is an acrylate or methane having a long-chain methylene portion.

6. The ream according to claim 1 further characterized in that the monofunctional component has a glass transition temperature that varies in the range from 50 ° C to 120 ° C after the polymerization.

7. The ream according to claim 1 further characterized in that the polymerization initiator comprises a thermal polymerization initiator.

8. The resin according to claim 1 further characterized in that the polymerization initiator comprises a photochemical polymerization initiator.

9. The ream according to claim 1 further characterized in that said glass transition temperature varies in the range from 30 ° C to 85 ° C.

10. - The ream according to claim 1 further characterized in that it has a viscosity that ranges from 25 to 50 cps at 25 ° C.

11. The resin according to claim 1 further characterized in that it is provided in polish-like form as an optical layer on a serrated lens or insole, said layer having a thickness that varies in the range of 25 to 1000 micras.

12. The resin according to claim 11 further characterized in that said lens or stencil will be terminated comprising a fixed material. 13.- The resin in accordance with the claim 11 further characterized in that said serniternmed lens or template comprises a thermoplastic material. 14.- The resin in accordance with the claim 12 further characterized in that said ream and said terrnofix material are formulated with matched polishable components and interfacial bonds are formed in said polishable components. 15. The resin according to the claim 12 further characterized in that an interpenetrating layer is formed in the inter-phase between said ream and said thermo-fixed material. 16. The resin according to claim 1 further characterized in that a mold is provided in a layer, said layer having a thickness that varies in the range from 25 to 1000 microns. 17. The resin according to claim 16 further characterized in that said layer is non-polymerized. 18.- The ream in accordance with the claim 16 further characterized in that said layer is partially polished. 19. The resin according to claim 16 further characterized in that said layer is partially polished and gelled. 20. A method characterized in that it comprises: providing the resin according to claim 1; applying a layer of said ream according to claim 1 to a mold; causing said ream according to claim 1 to come into contact with a casting resin; polishing said resin according to claim 1; and polishing said recess of emptying. 21. The method according to claim 20 further characterized in that said layer is applied to said mold by immersion. 22. The method in accordance with the claim 20 further characterized in that said layer is applied to said mold by spray. 23. The method in accordance with the claim 20 further characterized in that said layer is applied to said mold by lining by twist. 24. The method according to claim 20 further characterized in that said layer is applied to said mold by stereo lithography. 25.- The method in accordance with the claim Further characterized in that said resin according to claim 1 is at least partially poly-curled and said drainage ream is not polished before coming into contact with each other. 26.- The method in accordance with the claim Further characterized in that said ream according to claim 1 is not polymeated and said casting resin is at least partially polished before coming into contact with each other. 27.- The method of compliance with the claim Further characterized in that said head according to claim 1 and said recess of recess are at least partially polished before coming into contact with each other. 28.- The method of compliance with the claim Further characterized in that none of said resin in accordance with the rei indication 1 or said recess of recess is polished before coming into contact with each other. 29.- The resin in accordance with the claim 1, characterized furthermore because it comprises at least one color-ante ro or chromene, a purple dye of spiroxazma, a dye love! chromene and a green spiroxazine dye. 30. The resin according to claim 1, further characterized in that said glass transition temperature varies in the range from 30 ° C to 60 ° C. 31. The resin according to claim 1, further characterized in that said interlacing density varies in the range from 1 to 2 M / L.