MXPA01000900A - Photochromic ophthalmic lens - Google Patents

Abstract

A photochromic ophthalmic lens and a process for its preparation are disclosed. The lens comprises a substantially transparent substrate having a lenticular shape and, at least one film adhering to at least one surface of said substrate. The film contains a resinous blend of polycarbonate resin, and polycaprolactone and an effective amount of a photochromic dye selected preferably from a group consisting of spiropyrans, benzopyrans, naphthopyrans, spiroxazines, fulgides and fulgimides. In an additional embodiment the film contains a copoly(carbonate-lactone) block or random copolymer.

Description

PHOTOCROMIC OPHTHALMIC LENSES Field of the Invention The invention relates to a photochromic ophthalmic lens and, more specifically, to a lens made primarily of a polymeric resin. BACKGROUND OF THE INVENTION Current commercial ophthalmic lenses are produced from glass, thermosetting allyl carbonate (thermosetting polycarbonate) or thermoplastic aromatic polycarbonate. Their relatively low molecular weight and durability make these latter materials desirable for the manufacture of ophthalmic lenses. The use of thermoplastic aromatic polycarbonate in this market has been increasing annually, because glass and thermosetting polycarbonate are inferior to thermoplastic aromatic polycarbonate in terms of impact resistance. Thermoplastic aromatic polycarbonate is therefore rapidly replacing these two materials. While thermoplastic aromatic polycarbonate can largely match the performance of glass and thermoplastic polycarbonate in almost every respect, its photochromic behavior is lacking in expectations. The incorporation of photochromic dyes into a thermoplastic aromatic polycarbonate matrix (here, "PC") is problematic. First, the photochromic dyes in an unmodified PC matrix show a slow transition between the light and dark forms. This slow transition speed makes the photochromic material less competitive with glass photochromic and thermohardening allyl carbonate lenses, which can now be purchased commercially. Secondly, the transition temperature of the PC glass is relatively high and the photochromic dyes are thermally sensitive. Therefore, du- during the injection molding process. There is a clear possibility that the dyes will degrade and change the color of the lenses corresponding to a more yellow tint. The resulting color is generally unacceptable for the industry of optical lenses. These defects of thermoplastic aromatic polycarbonate in terms of photochromicity are perceived as an impediment to a wider acceptance of the material in this industry. Therefore, workers in this field have attempted to produce a viable and economical thermoplastic aromatic polycarbonate lens having photochromic properties. Methods for producing plastic lenses are known. U.S. Pat. No. 5,496,641 described a plastic lens, the structure of which included a substrate of a particular refractive index, a first layer consisting of a metallic compound, a hard coating layer and an anti-reflective layer. U.S. Pat. 5,531,940 described a method that involves obtaining (a) a finished or semi-finished plastic lens preform having a first spherical or spherical convex surface in geometry, (b) a mold having a molding surface at least a portion of which has a profile that substantially adapts to the convex surface of the preform and (c) an uncured resin having a low crosslinking density and forming a soft matrix upon curing. These are distributed in such a way that the uncured resin is disposed between the convex surface of the preform and the molding surface of the mold and that the composite plastic lens is impregnated with a photochromic material. In a further embodiment of the '515 patent, the method entails the use as (c) of an uncured resin containing photochromic additive. In still a further embodiment, the 5,531,940 patent described In addition, a second uncured resin having a relatively high cross-linking density, which forms a scratch-resistant matrix upon curing. Also disclosed is the method in which the first uncured resin having a low crosslink density includes a photochromic additive. Polycarbonate is among the preferred materials for making the lens preform. A related method has been described in PCT WO 95/15845. further, the technology currently in practice for the manufacture of ophthalmic lenses of photochromic PC entails first the cleaning of a molded lens and the joining after a polyurethane film to one of the surfaces of the lens. A second film, such as polyester, containing appropriate photochromic dyes, is then applied to the outer surface of the polyurethane film to form a combination through a heat treatment of the combination; the photochromic dye diffuses or migrates from the second film to the polyurethane film. The second film is then removed and a hard coating is given to the polyurethane surface to produce the final product. The resulting combination, now photochromic, is then used to make a lens. The procedure is not attractive from the economic point of view and is characterized by its relatively low performance. Moreover, certain lenses, such as bifocals and progressive lenses, can not currently be produced by this method. On the other hand, it is important to have the dye on the outer surface of the lens more efficient in terms of activation of the photochromic dye and only minimal amounts of dyes are required to produce the photochromic lens. Moreover, contrary to the thermal degradation that occurs frequently as a result of having the photochromic dyes dispersed in the mass of the material, thermal instability does not occur as a consequence, since the dyes are transferred to the lenses at a relatively high temperature. -teM, ^^ A low. The relevant technique also includes US Pat. No. 3,567,605, which describes a series of pyran and chromene derivatives which have been said to undergo color change upon exposure to radiation. US Patents are also relevant. 5,451,344 and 5,552,090, which described the photochromic naphthopyrans, which are useful in the present invention. The document 5,552,090 described the utility of said compounds in the preparation of molded photochromic articles of any polymeric resin, including thermoplastic polycarbonate resins. Also relevant is US Pat. No. 4,064,195, which described a molding composition containing polycarbonate (PC) and polycaprolactone polymer (PCL). A key object of the present invention is to provide a film having photochromic properties suitable for the manufacture of photochromic lenses. A further object is to provide a method for making a photochromic lens using the film of the invention. DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the photochromic reversibility of the PCL / PC composition, which is the subject of patent application, US Pat. Serial Number 08 / 887,075 (Attorney File Number Mo-4683), filed July 2, 1997, in the name of Bayer Corporation. Consequently, it was found that a mixture of PCL and PC was suitable for the incorporation of photochromic dyes and, in its photochromic form, it presents a transition between light and dark forms at a speed that is competitive with current commercial photochromic glass lenses and with lenses based on thermoset carbonate. According to the present invention, a photochromic film is placed, whose resinous components consist of poly- A t ^ &"1 * - > ---..-. thermoplastic aromatic carbonate, PCL and a suitable photochromic dye, in the cavity of an injection molding tool and then a suitable thermoplastic resin is injected over the film to form a lens. The present invention relates to a lens consisting of a film prepared from a composition containing polycarbonate resin, polycaprolactone and a photochromic compound. The film, which is transparent and exhibits desirable photochromic kinetics, is suitable in the preparation of ophthalmic lenses according to the invention. The resistant and transparent film demonstrates a rapid transition between dark and clear when exposed to the radiation source and withdrawn from it. The film suitable for the preparation of a lens according to the present invention consists of (A) at least one resinous component, which may be a homogeneous mixture of polycarbonate resin and polycaprolactone (PCL) or a copolymer of copoly (carbonate-lactone) and (B) at least one compound selected from the group consisting of benzopyrans, naf-topiranes, spirobenzopyrans, spironaphthopyrans, spiroben-zoxazines, spironaphthoxazines, fulgides and fulgimides. In the embodiment in which A is a mixture, the composition contains approximately 1 to 50 mole percent polycaprolactone (the percentages indicated throughout this text refer to percentage in relation to the total weight of resinous components and photochromic compounds) and a positive amount of the photochromic compound, the amount being sufficient to make the composition photochromic. More preferably, the composition contains about 5 to 50% PCL, 95 to 50% polycarbonate and about 0.01 to 1.0 part, preferably 0.03 to 0.5 part, per hundred parts. of resin (ppcr) of the photochromic compound. The polycaprolactone in the context of the invention is a polymeric resin having a molecular weight.

Weighted average cell of up to about 250,000, preferably 25,000 to 150,000, more preferably 30,000 to 100,000, whose molecular structure contains units that conform to Suitable PCLs are partially crystalline, commercially available resins, such as those of Union Carbide under the designation Tone Polymers P-767 and P-787. The PCL preferably has a reduced viscosity (measured with 0.2 g of polymer in 100 milliliters of benzene at 30 ° C) of about 0.1 to 1.5, more preferably about 0.5 to 0.9. PCL is a linear polyester formed throthe ring-opening reaction of e-caprolactone. Aromatic polycarbonates within the scope of the present invention are homopolycarbonates, copolycarbonates, branched polycarbonate and mixtures thereof. The polycarbonates have, in general, a weight average molecular weight of 10,000 to 200,000, preferably 20,000 to 80,000, and their melt flow rate, according to ASTM D-1238 at 300 ° C, is from about 1 to about 85 g / 10 min, preferably from about 2 to 15 g / 10 min. They can be prepared, for example, by the known diphasic interface process from a carbonic acid derivative, such as phosgene, and dihydroxy compounds by polycondensation (see German Patent Application Publications 2,063,050, 2-063). -052, 1,570,703, 2,211,956, 2,211,957 and 2,248,817, French Patent 1,561,518, and monograph by H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York, New York , 1964, - -TO. »**.,. ^^ «All these are incorporated here by way of reference). In the present context, suitable dihydroxy compounds for the preparation of the polycarbonates of the invention conform to structural formulas (1) or (2). (1) (2) where A represents an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a cycloalkylidene group with 5 to 15 carbon atoms, carbonyl group, an oxygen atom, a sulfur atom, -SO- or -S02-, or a radical that conforms to - ^ - ük .. _ _? ~ g _? - É --- e and g both represent the number 0 to 1; Z represents F, Cl, Br or C? -C alkyl and, if several Z radicals are substituents on an aryl radical, they can be identical or different from each other; d represents an integer from 0 to 4, and f represents an integer from 0 to 3. Among the dihydroxy compounds useful in the practice of the invention are hydroquinone, resorcinoi, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) ethers, bis- (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfoxides, bis- (hydroxyphenyl) sulphides, bis (hydroxyphenyl) sulfones, 2,2,4-trimethylcyclohexyl-1,1-diphenol and, a-bis (hydroxyphenyl) -diisopropylbenzenes, as well as its alkylated compounds in the nucleus. These and other suitable aromatic dihydroxy compounds are described, for example, in U.S. Pat. 3,028,356, 2,999,835, 3,148,172, 2,991,273, 3,271,367 and 2,999,846, all incorporated herein by reference. Other examples of suitable bisphenols are 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , α '-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3, 5-dimethyl-4-hydroxy-phenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3) , 5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, dihydroxybenzophenone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, a, a '-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2,4-trimethylcyclohexyl-1,1-diphenol and 4,4'-sulfinyl-diphenol. Examples of particularly preferred aromatic bisphenols are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,4-trimethylcyclohexyl- m k ik mik 1,1-diphenol and 1,1-bis (4-hydroxyphenyl) cyclohexane. The most preferred bisphenol is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). The polycarbonates of the invention can carry in their structure units derived from one or more of the suitable bisphenols. A further embodiment of the invention is represented by a composition in which the resinous components contain copolymer block copolymer (carbonatolactone) or random. In this embodiment of the invention, the copolymer contains 1 to 50 mole percent of units that conform to The preparation of said copolycarbonates is well known in the art. Among the resins suitable in the practice of the invention are polycarbonates, copolycarbonates and terpolycarbonates based on phenolphthalein, such as those described in U.S. Pat. 3,036,036 and 4,210,741, both incorporated herein by reference. The polycarbonates of the invention can also be branched, condensed therein by small amounts, for example from 0.05 to 2.0 mol% (relative to the bisphenoles) of polyhydroxyl compounds. Polycarbonates of this type have been described, for example, in German Patent Application Publications 1,570,533, 2,116,974 and 2,113,374; in British Patents 885,442 and 1,079,821, and in US Pat. 3,544,514. The following are some examples of polyhydroxyl compounds that can be used for this purpose: * «** - ^ ^ - l * _ £ -.¿_ ^ _- ^. ^ __ & ..... glucinol, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, tri (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4- (4,4'-dihydroxydiphenyl)] cyclohexylpropane, 2,4-bis (4-hydroxy-1-isopropylidine) phenol, 2,6 -bis (2 '-di-hydroxy-5' -methylbenzyl) -4-methylphenol, 2,4-dihydro-xibenzoic acid, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propan and 1,4-bis (4,4'-dihydroxytriphenylmethyl) benzene. Some of the other polyfunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (4-hydroxyphenyl) -2-OXO-2,3-dihydroindole. In addition to the above-mentioned polycondensation process, other processes for the preparation of the polycarbonates of the invention are polycondensation in a homogeneous phase and transesterification. Suitable procedures are described in US Pat. incorporated herein by reference 3,028,365, 2,999,846, 3,153,008 and 2,991,273. The preferred process for the preparation of polycarbonates is the interfacial polycondensation process. Other synthesis methods can be employed in the formation of the polycarbonates of the invention, such as those described in US Pat. 3,912,688, incorporated herein by reference. Suitable polycarbonate resins can be obtained commercially, for example Makrolon CD 2005, Makrolon FCR 2400, Makrolon 2600, Makrolon 2800 and Makrolon 3100, all of which are homopolycarbonate resins based on bis-phenols which differ in terms of their respective molecular weights and characterized by melt flow indexes (IFF) according to ASTM D-1238 from about 60 to 85, 16.5 to 24, 13 to 16, 7.5 to 13.0 and 3.5 to 6.5 g / 10 min , respectively. You can also use a branched polycarbonate, such i-a-y t ití a as Makrolon 1239. These are products of Bayer Corporation, of Pittsburgh, Pennsylvania. A suitable polycarbonate resin is known in the practice of the invention and its structure and methods of preparation have been described, for example, in US Pat. 3,030,331, 3,169,121, 3,395,119, 3,729,447, 4,255,556, 4,260,731, 4,369,303 and 4,714,746, all incorporated herein by reference. The dyes suitable in the context of the invention are photochromic compounds selected from the group consisting of benzopyrans, naphthopyrans, spirobenzopyranes, spironaphthopyrans, spirobenzoxazines, spironaphthoxazines, fulgides and fulgimides. Said photochromic compounds have been described in the literature, including US Pat. 4,826,977, 4,931,221, 5,106,998, 5,552,090, 5,628,935 and 5,565,147 (all of which are incorporated herein by reference). The color range of the naphthopyrans suitable in the present invention is from 410 to 500 nm, whereby they impart a yellow or orange coloration in their obscured state. In the discolored or bleached condition, the materials exhibit a colorless or clear coloration. The present invention can be used in a mixture or combined with suitable organic photochromic compounds to obtain, after activation, the formation of a neutral coloration, such as green, brown and gray. Particularly useful for this purpose are the photochromic compounds belonging to the group of naphthopyrans, spiroindolinooxazines and spiroin-dolinopyrans, which are known and can be purchased commercially. These have a high quantum efficiency to give color, a good sensitivity and a saturated optical density and an acceptable rate of whitening or paling-foundation. These compounds can be represented by the following graphic formulas IA1, IA2 and IA3, where the letters a to n represent the sides of the rings of naftopira- j ^ ml ^ no and the numbers represent the numbering of the ring atoms of the naphthopyrans: * | In the graphic formulas IA1, IA2 and IA3, the group represented by A is a heterocyclic ring of five or six members, substituted or unsubstituted, fused to the g, i or 1 side of the naphthopyran and is represented by the following graphic formulas IIA to IIF: HE HAS IIB IIC IID ¿^ ¡^ ^ ^^^ IIE IIF In graphic formulas IIA to IID, X can be an oxygen or nitrogen atom, the nitrogen atom of which is substituted with hydrogen or a C? -C4 alkyl. R 1 may be hydrogen, C 1 -C 6 alkyl, substituted or unsubstituted phenyl, carboxy or C 1 -C 6 alkoxycarbonyl. Preferably Ri is hydrogen, C 1 -C 3 alkyl, substituted or unsubstituted phenyl, carboxy or C 1 -C 3 alkoxycarbonyl. R 2 can be hydrogen, C 1 -C 6 alkyl or substituted or unsubstituted phenyl. Preferably, R 2 is hydrogen, C 1 -C 3 alkyl or substituted or unsubstituted phenyl. R3 and R4 can each be hydrogen, C-C6 alkyl or phenyl. Preferably, R3 and R4 are each hydrogen, C?-C3 alkyl or phenyl. R5 and R6 can each be hydrogen, C6-C6 alkyl, phenyl, hydroxy, C6-C6 alkoxy or acetoxy. Preferably, R5 and R6 are each hydrogen, C? -C3 alkyl, phenyl, hydroxy, C? -C3 alkoxy or acetoxy. R7, s and Rio can each be hydrogen, C? -C6 alkyl or phenyl, always .AA-.3 ** > - ~ * - that, when R7 is phenyl, R8 is hydrogen or C? -C6 alkyl and that, when Ra is phenyl, R7 is hydrogen or Cx-C6 alkyl. Preferably, R7, R8 and Rio are each hydrogen, C? -C3 alkyl or phenyl. More preferably, R1 t R2, R3, R4, R5, R6, R7, e and Rio are each hydrogen or methyl. R11 # Ri2, R13 / Ri, R15 and R16 can each be hydrogen, C? -C6 alkyl, Ci-C6 alkoxy or phenyl. Preferably, R n, R 12, R 3, Ri 4, R 15 and R a are each hydrogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or phenyl. More preferably, Rn, 12, R? 3, 14, R15 and Rie are each hydrogenated, methyl or methoxy. In the graphic formulas IIE and IIF, Ri7 can be hydrogen, C? -C6 alkyl, substituted or unsubstituted phenyl or halogen. Preferably, R 17 is hydrogen, C 1 -C 3 alkyl, substituted or unsubstituted phenyl or halogen. More preferably, Ri7 is hydrogen, methyl or chloro. R 8 can be hydrogen, C 1 -C 6 alkyl, phenyl, carboxy, C 1 -C 6 alkoxycarbonyl or C 1 -C 6 haloalkoxycarbonyl. Preferably, R18 is hydrogen, C?-C3 alkyl, phenyl, carboxy, C alco-C3-alkoxycarbonyl or haloalkoxy-C?-C3-carbonyl. Ri9 and R20 can each be hydrogen, C? -C6 alkyl or phenyl. Preferably, R19 and R2o are each hydrogen, Cx-C3 alkyl or phenyl. More preferably, R? 8, RX9 and R20 are each hydrogen or methyl. In R! -R20, the substituents of the phenyl may be C1-C3 alkyl and the halogen (or halo) groups may be chloro or bromo. IA1 In graphic formulas, IA2 and IA3, B and B 'may each be selected from the group consisting of (i) the aryl groups phenyl and naphthyl substituted or unsubstituted; (Ii) heterocyclic aromatic groups piri-Dilo, furyl, benzofuryl, thienyl and substituted or unsubstituted benzothienyl, and (iii) B and B 'taken together form the adamantyl group. The aryl and heterocyclyl substituents of B and B 'may each be selected from the group consisting of hydroxy, C1-C3 alkyl, C1-C5 haloalkyl, _ ^ * Jgj¡¡ l AE-ÍilÉtk -E-S- -ÍÉÜ áiÉÍl substituents including mono-, di- and trihalo, Cx-C5 alkoxy, (C1-C5) alkyl C? -C4 dialkylamino C1-C5, acryloxy, methacryloxy and halogen, said groups being halogen (or halo) fluoro, chloro or bromo. Preferably, B and B 'are represented, respectively, by the following graphic formulas: MINE IIIB In graphic formulas IIIA and IIIB, Y1 and Zx pue-den each be selected from the group consisting of hydrogen, C1-C5 alkoxy Cj.-C5, fluoro and chloro; Y2 and Z2 are each selected from the group consisting of C1-C5, C1-C5 alkyl, hydroxy, halogen, for example chloro, fluoro and bromo, acryloxy and methacryloxy, and a and b are each integers from 0 to 2. More preferably, Y and Zi are each hydrogen, C1-C3 alkyl, C1-C3 alkoxy or fluoro; Y2 and Z2 are each C? -C3 alkyl or C1-C3 alkoxy; a is the integer 0 or 1, and b is an integer from 0 to 2. Preferred naphthopyrans of the present invention are represented in the following graphic formula IB. " ^ jsm * js.

In graphic formula IB, group A represents formulas IIA to IID, where X is an oxygen atom, formulas IIE and IIF. The group A is fused, such that the oxygen atom of the formulas IIA to IIF is bonded to the carbon atom number 8 of the naph portion or of the naphthopyran.

IB An even more preferred dye can be described as substituted naphthopyrans in the 3-position of the pyran ring with (i) an aryl substituent and (ii) a phenyl substituent having a 5- or 6-membered heterocyclic ring containing oxygen and / or nitrogen fused at the carbon atoms numbers 3 and 4 of the phenyl substituent and with a heterocyclic ring containing nitrogen at the 6-position of the naphthyl portion of the naphthopyran compound. These compounds can be represented by the following graphic formula: ^ ¡^ ^. ^ h ^. * A ^^.

In graphic formula I, Ri can be Ci-C10 alkyl, halogen or the group -OL, where L is a C? -C? 2 alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl said nonyl, decyl, undecyl and dodecyl, said halogen being chloro, fluoro or bromo, is the integer 0, 1 or 2. Preferably, Ri is C1-C5 alkyl, fluoro, bromo or the group -OL, where L is Cx-C4 alkyl, is already the whole number 0 or 1. More preferably, R is C? -C3 alkyl, fluorine or the group -OL, where L is methyl, is already the integer 0 or 1. In the graphic formula I, R2 can be a saturated, nitrogen-containing, unsubstituted or mono- or disubstituted heterocyclic group selected from the following groups represented by the graphic formulas IA to IG, where E and F in graphic formula IC are each an atom of nitrogen or carbon, provided that, when E is nitrogen, F is a carbon atom, and G in the graphic formula ID is a nitrogen atom, oxygen or carbon and H is a nitrogen or carbon atom, provided that, when H is nitrogen, G is a carbon atom.

^ ¡^ Mn mi ^^ & ^^^ & IB IC ID 1E »F IG Examples of R2 groups include aziridino, azetidino, 1-pyrrolidyl, 1-pyrrolinyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, 3-pyrazolin-2-yl, morpholino, piperidino, piperazinyl, methyl-l-piperazinyl, 1,4,5,6-tetrahydropyrimidinyl, 1-indolinyl, hexamethyleneimine and heptamethyleneimino. The substituents for R 2 may be C 1 -C 6 alkyl and / or C 1 -C 6 alkoxy. Preferably, R2 is an unsubstituted or monosubstituted member of the group consisting of indolinyl, morpholino and piperidino. More preferably, R2 is morpholino. B can be the aryl, naphthyl or phenyl group, substituted or unsubstituted, said substituents being aryl C 1 -C 5 alkyl, C 1 -C 4 haloalkyl, hydroxy, C 3 -C 5 alkoxy, C 1 -C 4 alkoxy C 1 -C 4 alkyl , halogen, morpholino, piperidino or R (R ") N-, where R and R" are each hydrogen or C? -C3 alkyl, said halogen (or halo) fluoro or chloro groups being. Preferably, B is represented by the following graphic formula II: p In graphic formula II, R 6 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, fluoro or chloro and each R 7 is a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, chloro or fluoro and d is a whole number from 0 to 2. Preferably, R6 is hydrogen and R7 is selected from the group consisting of fluoro, methyl and methoxy. B 'can be represented by one of the following graphic formulas III or IV: lll IV In graphic formulas III and IV, X is oxygen or nitrogen and Y is carbon or oxygen, provided, when X is nitrogen, Y is carbon; R4 and R5 are each hydrogen or C? -C5 alkyl; each R 3 is a C 1 -C 5 alkyl, C 1 -C 5 alkoxy, hydroxy or halogen, said halogenated substituent being chlorine, fluoro or bromo, and c is an integer from 0 to 3, for example 0, 1, 2 or 3. Preferably, B 'is represented by graphic formula III or IV, where X is oxygen; And it's carbon or oxygen; R 4 and R 5 are each hydrogen or C 1 -C 4 alkyl; each R 3 is a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy or fluoro, and c is the integer 0, 1 or 2. More preferably, B 'is 2,3-di-hydroxybenzofuran-5-yl, 2 - methyldihydroxybenzofuran-5-yl, indolin-5-yl, 1, 2, 3, 4-tetrahydroquinolin-6-yl, chroman-6-yl or 1,3-benzodioxol-5-yl. In graphic formula III; when R4 and R5 are H and when X is oxygen and Y is carbon and c is zero, the group is a 2,3-dihydrobenzofuran-5-yl; when X is oxygen and Y is oxygen and c is zero, the group is 1,3-benzodioxol-5-yl, and when X is nitrogen and Y is carbon and c is zero, the group is indolin-5-yl. In graphic formula IV, when X is oxygen and Y is carbon, the unsubstituted group is a chroman-6-yl; when X is oxygen and Y is oxygen, the unsubstituted group is a 1,4-benzodioxan-6-yl, and when X is nitrogen and Y is carbon, the unsubstituted group is 1, 2, 3, 4-tetrahydroquinone; lin-6-ilo. For reasons of brevity, these groups will be referred to herein as fused heterocyclic phenyl groups. The preferred naphthopyran dye is 3,3-diphenyl-3H-naphtho [2, 1-b] pyran, represented by the formula where Ri to R6 represent hydrogen. The spirooxazines suitable in the present invention are known; see, for example, US Pat. 3,562,172, 3,578,602, 4,215,010 and 4,342,668, all of which are incorporated herein by reference. Essentially, the spirooxazines suitable in the present invention can be described by the formula • As ._ (- 1., wherein: R and R2 independently represent a hydrogen or halogen atom (fluorine, chlorine or bromine) or a group selected from linear or branched Cx-Cs alkyl, C1-C5 perfluoroalkyl, C? -C5 alkoxy, nitro or cyano; R3 and R independently represent linear or branched C1-C5 alkyl groups, phenyl or benzyl; or R3 and R4, when considered together with the carbon atom to which they are attached, form a C5-C8 cycloalkyl group; R5 represents a linear or branched C1-C5 alkyl group, phenyl, benzyl or allyl; R6 represents a hydrogen atom or a straight or branched C1-C5 alkyl group, or the group -NR8R9, where R8 is a linear or branched C? -C5 alkyl group, phenyl or benzyl and R9 is hydrogen or has the same meaning as R8, or R8 and R9, when considered together with the nitrogen atom to which they are attached, form a cyclic structure of 5 to 12 members and possibly containing a more selected heteroatom between oxygen and nitrogen; and R7 represents a hydrogen or halogen atom (fluorine, chlorine or bromine) or a group selected from: linear or branched C1-C5 alkyl, C5-5alkoxy, cyano, thioether and carboxylated ester with 1 to 3 carbon atoms in the ester portion, or represents an aromatic or heterocyclic condensed ring; X represents CH or N-. In particular, the groups Rx and R2, when they are not hydrogen, can be linked in any of positions 4, 5, 6 and 7 of the indoline part of the molecule. In addition, the group R7, if it does not represent hydrogen or an aromatic or heterocyclic condensed ring, can be present in any of the positions 7 ', 8', 9 'and 10' of the naphthalene part of the molecule. In a preferred embodiment, photochromic compounds corresponding to the general formula (I) are employed, wherein: R x and R 2 independently represent a hydrogen atom or the methyl group; R3 and R4 each represent the methyl group or together represent the cyclohexyl group; R5 represents the methyl group; Re represents a hydrogen atom or the group -NR8R9, where the groups R8 and R9, together with the nitrogen atom to which they are attached, form a ring structure of piperidyl, morpholyl, pyrrolidyl or hexamethyleneimine, and R7 represents a hydrogen atom, and X represents CH. Examples of preferred photochromic compounds used according to the present invention are 1,3,3,4,5- or 1,3,3,5,6-pentamethylpyrroindoline-2,3 '- [3 H] naphtho (2, lb) - (1,4) oxazine), 1/3, 3-trimethylspiro (in-dolin-2, 3 '- [3 H] -naphtho (2, lb) - (1,4) oxazine), 1,3, 3-trime-tillerspiro (indoline-6- (1-piperidyl) -2,3' - [3H] naphtho (2, lb) - (1,4) oxazine, 1,3,3-trimethylspiro (indoline-6 '- (1-morfo-lyl) -2,3' - [3 H] -naphtho (2, 1-b) ) - (1,4) oxazine), 1,3,3,4,5- or 1,3,3,5,6-pentamethylpyrro (indoline-6 '- (1-piperidyl) -2,3'- [ 3H] naphtho (2, lb) - (1,4) oxazine) and 1,3,3-trimethyl-pyro (indoline-6 '- (1-piperidyl) -9' - (methoxy) -2,3'- [3H] naf-to (2, lb) - (1,4) oxazine.) Spiropyrans useful for the purposes of the present invention are photochromatic organic compounds which can be defined by the following general formulas (II), (III) , (IV) and (V): (II) Indolinanaf topirans (MY) Benzothiazinespiropyrans (IV) Benzoxazinespiropyrans (V) In the above general formulas io and Rn represent alkyl or aryl groups; R 12 represents an alkyl group, an aryl group or a substituted alkyl group (such as hydroxyalkyl, haloalkyl, carbalkoxyalkyl, alkoxyalkyl and aminoalkyl); R 14 represents hydrogen or an alkyl, aryl or alkoxy. R13 and R15 represent hydrogen or mono- or poly-substitution groups, selected from alkyl and substituted alkyl groups, or halogen, nitro or alkoxy. The fulgides and fulgimides suitable in the context of the invention are known and have been described in the literature (see, for example, Applied Photochromic Polymer Systems, Edited by C.B. McArdle, Blackie USA: Chapman &; Hall, New York, 1992, pp. 80-120, incorporated herein by reference). The matrices of the film (PCL / PC) and of the len-te (PC) are sufficiently similar and there are no adhesion / delamination problems associated with the combination. Moreover, since the pressure of the molding operation conforms the film to the surface of the lens, bifocal and progressive lenses can be produced easily. In making the lens of the invention, the well-known practice of "insert molding" can be employed. According to this, the photochromic film is placed first in a mold and the polycarbonate resin is then introduced into the mold. The introduction of the resin behind the film is preferably carried out by injection. The thickness of the film is preferably 5 mils. The invention is further illustrated, but without intending to limit it, by the following examples, in which all parts and percentages are by weight unless otherwise specified. EXPERIMENTAL EXAMPLES Suitable compositions were prepared for the preparation of the photochromic film of the invention and 'B-áMaafa «efe.A ..- -JWfc determined their photochromic properties. In order to measure the darkening rate, the samples were exposed to UV radiation (Spectrolin lamp of long wavelength -365 nm) for ten minutes. Absorbance was recorded at the maximum peak of the dye (424 nm for Yellow L Variacol) at four-second intervals over a period of ten minutes using a spectrophotometer (Perkin-Elmer Lambda 9 UV / Vis). The paling rate was measured in a similar manner after first removing the source of UV radiation. When the UV radiation affects the samples that were studied, the incorporated photochromic dye begins to change from a colorless to a colored state. More color develops as exposure to UV radiation continues. Until the intensity of color reaches a plateau substantially constant. Since the absorbance also increases as the photochromic dye is converted from a colorless state to a colored state, this value is a convenient measure of the rate at which the material darkens. In the following Table, T / 2 refers to the time (in seconds) needed to revert to 50% absorbance. As the results shown in the following Table show, the control composition containing only polycarbonate and the dye of the invention showed to have a slow rate of darkening and paleness; their Tx / 2 values were 4 minutes and 5 seconds. The molded articles of PCL are opaque and the compositions containing only PCL and the dye of the invention are unsuitable for applications in which transparency is a requirement. The compositions, which were prepared and evaluated as tabulated below, contained, as PCL, Tone 767, of Union Carbide, a resin characterized by a weight average molecular weight of 50,000 g / mol. The dye used in the examples, at a level of 0.1 ppcr, was 3,3-diphenyl-3H-naphtho [2, 1-b] pyran. The table shows the reversal rates of discoloration. Table 1 (1) The polycarbonate resin was Makrolon 2458 homopolycarbonate based on bisphenol A, with a Melt Flow rate according to ASTM D-1238 of about 20 g / 10 min. (2) A copolycarbonate based on bisphenol A (65%) and 2,2,4-trimethylcyclohexyl-1,1-diphenol. The results show the effectiveness of the dyes of the invention to make the compositions suitable as photochromic compositions. The photochromic performance of a composition of the invention is further demonstrated by the results of its darkening and paleness as tabulated below. The darkening rates of the above compositions 1-1 and 1-2, by exposing the test samples to a 424 nm light source, are shown in Table 2. The test samples were in the form of a PC substrate. , 100 mils thick, in which a 5 mil film of the indicated composition was laminated.

Table 2 The paling speed when removing these samples (Compositions 1-1 and 1-2) from the light source is shown in Table 3. Table 3 (1) The 50% browning time refers to the time interval from the removal of the totally darkened material from the light source and which ends when the reversion reaches 50% of the maximum darkening. (2) The 30% paling time refers to the time interval from the removal of the totally obscured material from the light source and which ends when the reversion reaches 30% of the maximum darkening. In a further parallel group of experiments, the photochromic compound used was 1, 3-dihydro-1,3,3-trimethylspiro-2H-indole-2,3 '- (3H) -naft (2, lb) -1.4 -. The results are the following: Table 4 Resinous components (% weight) Example Polycarbonate PCL T? / 2 (seconds) 4-1 100 * 1 »0 155 4-2 65 (1) 35 15 4-3 75 (1) 25 47 4-4 100 (2) 0 300 4-5 65 (2) 35 24 (1 > The polycarbonate resin was Makrolon 2458 homopolycarbonate based on bisphenol A, with a Melt Flow rate according to ASTM D-1238 of about 20 g / 10 min. (2) A copolycarbonate based on bisphenol A (65%) and 2,2,4-trimethylcyclohexyl-1,1-diphenol The photochromic performance of the compositions of the invention is further demonstrated by the results of their darkening and paleness as tabulated below. 1 and 4-2 above, when exposing the test samples (100 mils thick) to a light source of 424 nm, are shown in Table 5. Table 5 The paling speed when removing these samples (Compositions 4-1 and 4-2) from the light source is shown in Table 6. Table 6 (1) The 50% browning time refers to the time interval from the removal of the totally obscured material from the light source and which ends when the reversion reaches 50% of the maximum darkening. < 2) The 30% paling time refers to the time interval from the removal of the material totally obscured from the light source and ending when the reversion reaches 30% of the maximum darkening. Suitable films in the context of the invention were evaluated as described below in Table 7. The polycarbonate used was Makrolon FCR 2458. Blue A refers to Blue A Variacrol; Yellow L refers to Yellow L Variacrol, which is 3, 3-diphenyl-3H-naphtho [2, 1-b] pyran. The film, with a thickness of 5 mils, was then inserted into the cavity of an injection mold and a PC disk of 3 inches (100 mils thick) was produced by conventional means. These discs were then compared with control samples, consisting of a PC film that contained the same concentrations of photochromic dyes, but without PCL, which were similarly molded into a 3-inch disc. The samples were irradiated with UV light to completely convert the photochromic dyes to the darkened state. Full conversion to the darkened state was ensured by measuring the darkening of the disks every minute until the transmission reached a steady state. Typically, the samples took approximately 10 minutes to reach equilibrium. The UV light source was then removed and the time required for the samples to reach 50% of their fully clear state was determined and recorded as T? / 2. Table 7 As shown in the table, all the samples offered a photochromic behavior, that is, they became pale and darkened in response to UV radiation. However, samples containing PCL were converted to clear form up to twice as fast as controls. The rate of transition and the degree of darkness were strongly dependent on the concentration of the dye in the film sample (ie, the higher the concentration of dye, the darker the sample after exposure to UV radiation). Although the invention has been described in detail in the foregoing for purposes of illustration, it is to be understood that said detail has only that purpose and that those skilled in the art will be able to make variations therein without deviating from the spirit and scope of the invention, except in what may be limited by the claims.

Claims (18)

1. CLAIMS 1. An ophthalmic lens consisting of (a) a substantially transparent substrate having a lenticular shape and (b) at least one film that adheres to at least one surface of said substrate, which film consists of polycarbonate resin, PCL and a positive amount of a sufficient photochromic dye to impart photochromicity to said lens. The lens of Claim 1, wherein said film consists of (A) a resinous component selected from the group consisting of (i) a homogeneous mixture of polycarbonate resin and polycaprolactone and (ii) a block or random copolymer of copoly (carbonate lactone), and (B) a photochromic compound selected from the group consisting of spiropyrans, spirooxazines, fulgidae and fulgimides, wherein said compound is present in an amount of 0.01 to 1.0 parts per hundred. parts by weight of said (A). The lens of Claim 1, wherein said film consists of (A) at least one resinous component selected from the group consisting of (i) a homogeneous mixture of polycarbonate resin and polycaprolactone and (ii) a copolymer copolymer (carbonate) lactone) and (B) at least one photochromic compound selected from the group consisting of benzopyrans, naphthopyrans, spirobenzopyrans, spironaphthopyrans, spirobenzoxazines, spironaphthoxazines, fulgides and fulgimides, wherein said compound is present in an amount of 0.01 to 1.0. parts per hundred parts by weight of said (A). 4. The lens of Claim 1, wherein said PCL is a block copolymer containing 1 to 50 mol% of units that conform to 5. The lens of Claim 1, wherein said PCL is a block copolymer containing 1 to 50 mol% of units that conform to 6. The lens of Claim 1, wherein said dye is a benzopyran. 7. The lens of Claim 1, wherein said dye is a naphthopyran. 8. The lens of Claim 1, wherein said dye is a spirobenzopyran. 9. The lens of Claim 1, wherein said dye is a spiro- naphthopyran. 10. The lens of Claim 1, wherein said dye is a spirobenzoxazine. 11. The lens of Claim 1, wherein said dye is a spironophthoxazine. 12. The lens of Claim 1, wherein said dye is a fulgida. 13. The lens of Claim 1, wherein said dye is a fulgimide. 14. The lens of Claim 1, wherein said dye conforms to where R x is C -C 0 alkyl, halogen or the group -O-L, where L is a C 12 -C 12 alkyl; a represents 0, 1 or 2; R2 is a heterocyclic group containing saturated nitrogen; B is an aryl group and B 'is selected from the group consisting of III and IV III where X is oxygen or nitrogen and Y is carbon or oxygen, provided that, when X is nitrogen, Y is carbon, and where R4 and R5 represent hydrogen or C -C5 alkyl; R3 is Cx-Cs alkyl, C? -C5 alkoxy, hydroxy or a halogen atom, and c is an integer from 0 to 3. The lens of Claim 1, wherein said dye conforms to where Rx to R6 represent hydrogen. 16. The lens of Claim 1, wherein said dye conforms to 17. The lens of Claim 1, wherein said dye is present in an amount of 0.03 to 0.5 parts per hundred parts by weight of the total polycarbonate and PCL. 18. An insert molding process for making an ophthalmic lens, comprising placing the film of Claim 1 in a mold and then introducing into said mold a resinous molding composition.