Abstract:
A high refractive index, curable, synthetic resin composition comprising a core resin composition composed of a mixture of ethylenically unsaturated compounds, and an initiation system containing both photo and thermal initiators, particularly a photochromic resin composition which further includes at least one photochromic dye. Also a curing process, which includes a combination of multi-step radiation curing and thermal annealing. Articles produced of cured composition exhibit superior physical and, in appropriate cases, photochromic properties and can be easily mass produced on a commercial scale due to short processing time and use of readily available chemicals.

Description:
This application claims the benefit of U.S. Provisional Application Ser. Nos. 60/329,086, filed Oct. 12, 2001, and 60/328,810, filed Oct. 15, 2001. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to a high refractive index curable synthetic resin composition; to a process for curing such a composition; and to a cured article formed thereof. 
     BACKGROUND OF THE INVENTION 
     Currently, commercial photochromic plastic lenses with photochromic dyes dispersed throughout the lens substrate are made by thermal processes. These processes yield product with good mechanical, optical and photochromic properties, but they require normally around 20 hours before the curing is complete. Examples of such thermally cured lenses are disclosed in U.S. Pat. No. 5,763,511, to Chan et al.; U.S. Pat. No. 5,973,039, to Florent et al.; and U.S. Pat. No. 6,034,193, to Henry et al. 
     Attempts have also been made to produce synthetic resin lenses by radiation curing. Examples of such attempts to produce radiation cured lenses are described in U.S. Pat. No. 5,621,017, to Kobayakawa et al., and U.S. Pat. No. 5,910,516, to Imura et al. Although the use of radiation curing makes it possible to reduce processing time, the resulting lenses have not found successful commercial application due to one or more of the following reasons:
         (1) inferior thermal/mechanical properties,   (2) poor optical and/or photochromic properties, and   (3) lack of commercial capability for mass production.
 
Thus, despite the efforts of the prior art to make synthetic resin lenses through radiation curing, there are still no commercial photochromic lenses produced via radiation cure in the market. There has remained a need to solve these problems by finding a proper radiation curable photochromic composition, along with the process to produce superior synthetic resin lenses.
       

     SUMMARY OF THE INVENTION 
     The goal of the invention is thus to develop a curable core resin composition which can be cured rapidly by radiation curing methods and/or thermally to produce synthetic resin lenses with desirable thermal and mechanical properties, good optical characteristics and, in the case of photochromic lenses, photochromic characteristics, and which are capable of mass production on a commercial scale. This goal is fulfilled by the present invention as described and claimed hereinafter. 
     Specifically, we have discovered a new curable core resin composition suitable for photochromic dyes, along with a new initiation system containing both photo and thermal initiators. The unique cure process includes combination of both step radiation cure and thermal annealing, leading to lenses with superior physical and/or photochromic properties in as little as one hour. 
     In a first aspect, the present invention discloses a high refractive index curable synthetic resin composition comprising a core resin composition of ethylenically unsaturated compounds and a photo initiator and a thermal initiator. 
     In accordance with a further aspect of the invention the synthetic resin composition further comprises at least one photochromic dye and is suitable for the production of photochromic lenses. The disclosed photochromic composition provides superior photochromic properties and physical properties, short processing time through both step radiation and thermal curing, and easy commercial capability for mass production. 
     The present invention also describes a radiation curing process of the disclosed compositions via a single stage cure or via a multiple stage cure with an appropriate cooling period at the end of each cure stage, followed by thermal annealing. 
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     The present invention may be understood more readily by reference to the following detailed description of particular embodiments of the invention and the specific examples included therein. Before the present compositions and their process are disclosed and described, it is to be understood that this invention is not limited to a particular formulation and a process, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the term “(meth)acrylate” is intended to refer generally to both acrylate and methacrylate functional groups. 
     The present invention discloses a high refractive index curable core resin composition suitable for photochromic application. When proper photochromic dyes, initiation system containing both photo and thermal initiators and additives are incorporated into the disclosed composition, lenses with superior physical and photochromic properties can be made through the disclosed curing process. 
     In one aspect, the core resin composition suitable for photochromic application comprises per 100 parts by weight, and may include: 
     (i) from 2 to 70 parts by weight of at least one first compound corresponding to formula (I): 
                        
 
wherein
     n and n′ independently are 0-30   R 1 -R 4  independently represent H or C 1 -C 6  alkyl,   X is O, S, SO 2 , CO 2 , CH 2 , CH═CH, C(CH 3 ) 2  or a single bond, and   y 1 -y 8  independently represent H, OH, halogen, mercaptan or C 1 -C 4  alkyl;   

     (ii) from 2 to 80 parts by weight of at least one second compound corresponding to formula (II): 
                        
 
wherein
     m is at least 1, and   R 5 -R 7  independently represent H or C 1 -C 6  alkyl;   

     (iii) from 2 to 60 parts by weight of a reactive diluent selected from the group consisting of 1,6-hexanediol di(meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, vinyl benzoate, vinyl 4-t-butyl benzoate, styrene, divinyl benzene, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate and mixtures thereof; and 
     (iv) from 2 to 60 parts by weight of a multi-functional (meth)acrylate or (meth)acrylate derivative with three or more acrylate functional groups selected from the group consisting of trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glyceryl tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, penta(meth)acrylate ester and mixtures thereof. 
     In preferred compounds of formula I, R 1  and R 4  are CH 3 ; R 2 , R 3 , and y 1 -y 8  are hydrogen; and X is C(CH 3 ) 2 . n and n′ are preferably 3 to 5. In preferred compounds of formula II, R 5  and R 7  are CH 3 , and R 6  is hydrogen. 
     To make a photochromic article, the core resin composition of the invention may further comprise an effective photochromic amount of at least one photochromic dye incorporated therein to form photochromic lenses which darken when exposed to bright light and fade when under less intense light exposure. Suitable photochromic dyes may, for example, comprise chromenes, fulgides, fulgimides, spirooxazines, naphthopyrans, and/or mixtures thereof. Examples of useful photochromic dye compounds and/or mixtures are disclosed in U.S. Pat. Nos. 5,399,687; 5,498,686; 5,623,005; 5,645,768; 5,707,557; 5,801,243; 5,932,725; 5,952,515; 5,990,305; 6,022,496; 6,036,890; 6,102,543; 6,146,554; 6,171,525; 6,190,580 and 6,225,466, the entire disclosures of which are incorporated herein by reference. The amount of the photochromic dye or dye mixture may vary depending on the desired photochromic effect, but typically will amount to from 0.0001 to 1, preferably 0.0001 to 0.1, and particularly preferably 0.001 to 0.1, part by weight per 100 parts by weight of the core resin. The selection of specific dyes or dye mixtures to be used in any given case will depend on the desired coloration, as well as the desired performance characteristics of the resulting lens, such as darkening rate and/or fade rate, and is considered to be within the skill of the art. A suitable neutral gray photochromic dye mixture is described in U.S. Pat. No. 6,373,615, at, for example, column 10, line 50+, the entire disclosure of which is incorporated herein by reference. In one preferred aspect, a resin composition includes 0.05 to 0.06%, more preferably 0.056%, photochromic dye mixture by weight of the core resin composition, including 380 to 460 ppm, more preferably 423 ppm, spiro-9-floureno-13′-(6-methoxy-3-(4-N-morpholinyl)phenyl-3-phenyl-indeno[2,1-f]naphtho(1,2-b)pyrane (gray-blue), 40 to 60 ppm, more preferably 46 ppm, of 3-phenyl-3′-(4-N-piperidinyl)-phenyl-6-N-morpholinyl-3H-naphtho[2,1-b]pyrane (ruby), 45 to 65 ppm, more preferably 54 ppm, of 3-phenyl-3′-(4-N-morpholinyl)-phenyl)-6-N-morpholinyl-3H-naphtho[2,1-b]pyrane (orange), and 30 to 50 ppm, more preferably 38 ppm, of 3-phenyl-3′-(4-methoxy)-phenyl-6-N-morpholinyl-3H-naphtho[2,1-b]pyrane (yellow). 
     To form a radiation curable synthetic resin composition, especially a short wavelength, visible light, radiation curable composition, a suitable photo initiator may be incorporated in the core resin composition. Typically the resin composition will include from 0.01 to 3, and preferably 0.02 to 1, part by weight of photo initiator per 100 parts by weight of the core resin. Examples of suitable photo initiators include benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and mixtures thereof. Preferred photo initiators include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or mixtures thereof. 
     If desired, a thermal polymerization initiator may also be incorporated in the synthetic resin composition to facilitate use of thermal curing or combination radiation/thermal curing process techniques. For example, the resin composition may advantageously contain from 0.01 to 3, and preferably 0.02 to 1, part by weight of a thermal initiator per 100 parts by weight of the core resin. Examples of suitable thermal initiators include t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyl-2-methylbenzoate, 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy 2-ethylhexyl carbonate, dibenzoyl peroxide, t-amyl peroxy benzoate, 2,2′-azobis(2,4-dimethylpentanenitrile), 2,2′azobis(2-methylpropanenitrile), 2,2′azobis(2-methylbutanenitrile), 1,1′azobis(cyclohexane-carbonitrile), and mixtures thereof. Particularly preferred thermal initiators include 2,2′-azobis(2,4-dimethylpentanenitrile), 2,2′azobis(2-methylpropanenitrile), 2,2′azobis(2-methylbutanenitrile), 1,1′azobis(cyclohexanecarbonitrile), or mixtures thereof. 
     In one preferred aspect, the resin composition comprises an initiator mixture comprising both a photo initiator and a thermal initiator. Castable resin compositions according to the invention desirably will have a viscosity of less than 400 cps at room temperature. 
     The curable synthetic resin composition of the invention may also comprise up to 5 parts by weight of other additives, such as light stabilizers, mold release agents and/or other processing agents, per 100 parts by weight of the core resin composition. For example a benzophenone UV absorber, such as 2-hydroxy-4-methoxybenzophenone, may be included in the resin composition in an amount from about 50 ppm to about 1,000 ppm, preferably from about 100 ppm to about 500 ppm, and more preferably about 150 ppm to 300 ppm. In one preferred aspect, a resin composition includes 0.019% 2-hydroxy-4-methoxybenzophenone and 0.056% photochromic dye mixture by weight of the core resin composition. One effective processing agent is isopropylxanthic disulfide, which extends pot life and minimizes yellowing of the resin. Pot life is the time from when a resin batch is prepared until the last acceptable lens can be produced from that particular batch. In manufacturing photochromic resins, the possibility of yellowness increases after initiators are mixed with the resins, thus the ability to extend pot life is a useful benefit. 
     The present invention also discloses a radiation cure process in which a mold assembly is filled with a curable synthetic resin composition as described above and the filled mold assembly is subjected to a source of actinic radiation. Desirably the radiation source is a filtered actinic radiation source having a primary output at or above the cutoff wavelength of the filter. Where the synthetic resin composition is intended to produce a photochromic article and contains a photochromic dye which is activated at certain visible wavelengths, e.g. wavelengths above 400 nm, it is advantageous to use a filter to cut off substantially all (e.g., 99% or more) of the radiation up to the wavelength where the photochromic dye is active, so that the photochromic dye will not be activated or darkened during the curing process. 
     The radiation curing process may comprise either a single stage cure up to 30 minutes in length or a multiple stage cure comprising a plurality of stages from 10 seconds to 20 minutes in duration. The use of the multiple stage procedure is advantageous in order to facilitate control of the rate of reaction and the temperature of the resin during curing depending on the type of lenses being processed. It is also desirable to have adequate cooling time and cooling media at the end of each radiation stage to further control the rate of cure and the temperature of the resin. Suitable cooling media include ambient air, chilled air, ambient water and/or chilled water. The multiple stage radiation and cooling process permits rapid effective curing while keeping the temperature of the lens material below the temperature where thermal polymerization of the resin becomes uncontrollable and the reaction autoaccelerates. This maximizes the yield of the process, optimizing optical, physical, and photochromic properties of the cured article. 
     In one preferred aspect, after the radiation cure it is desirable to have a thermal anneal at a temperature of 50 to 150° C. for up to 2 hours. While various thermal curing processes are suitable subsequent to the radiation exposure process described above, the following temperature profile has provided acceptable results. After a radiated lens is placed in the oven, the oven temperature is maintained at 60° C. for 15 minutes; the temperature is then raised at a rate of 3.3° C./minute to 76° C. and is maintained at 76° C. for 10 minutes. The temperature is then raised at a rate of 3.3° C./minute to 100° C. and is maintained at 100° C. for 35 minutes. Thereafter, the temperature of the oven is allowed to cool to room temperature. The thermal annealing may be carried out prior to and/or after removing the plastic lens from the mold assembly in which it is formed. 
     The invention also relates to an article, especially a photochromic article, made by molding and curing a synthetic resin composition as described above. 
     The following table describes a number of methods for producing lenses with acceptable optical, physical, and photochromic performance when cast using the formulation(s) described in this patent. 
     
       
         
               
             
               
               
             
               
               
             
           
               
                 TABLE I 
               
             
             
               
                   
               
               
                 Methods for producing lenses 
               
             
          
           
               
                 Cure 
                   
               
               
                 Example 
                 Description 
               
               
                   
               
             
          
           
               
                 1 
                 Using 420 nm peak output low pressure Hg lamps spaced 
               
               
                   
                 three to six inches apart and GG420 glass as a filter, expose 
               
               
                   
                 both sides of the lens or article for 20 minutes. Following the 
               
               
                   
                 radiation exposure, the articles were put into an oven at 
               
               
                   
                 120° C. for 25 to 30 minutes. 
               
               
                 2 
                 Using 420 nm peak output low pressure Hg lamps spaced 
               
               
                   
                 three to six inches apart and GG420 glass as a filter, 
               
               
                   
                 expose both sides of the lens or article for 2.75 to 3 minutes. 
               
               
                   
                 After this initial exposure, the gasket was removed from the 
               
               
                   
                 article and exposed to the actinic light for an additional 9 
               
               
                   
                 minutes. Following the radiation exposure, the articles were 
               
               
                   
                 put into an oven at 80° C. for 25 to 30 minutes. 
               
               
                 3 
                 Using 420 nm peak output low pressure Hg lamps spaced 
               
               
                   
                 three to six inches apart and GG420 glass as a filter, both 
               
               
                   
                 sides of the lens or article were exposed for 12 minutes 
               
               
                   
                 continuously. Following the radiation exposure, the articles 
               
               
                   
                 were put into an oven at 70 to 90° C. for 30 to 60 minutes. 
               
               
                 4 
                 Using 420 nm peak fluorescent tubes spaced three to seven 
               
               
                   
                 inches apart as well as GG420 glass placed between the lamps 
               
               
                   
                 and the lens/article being cured, lenses were cured as follows. 
               
               
                   
                 Lenses were placed on a conveyor belt with 3 curing zones 
               
               
                   
                 and 2 cooling zones. The exposure consisted of an initial 
               
               
                   
                 2.75-minute actinic light exposure followed by a 1.25 minutes 
               
               
                   
                 period out of the light with an ambient temperature of 55° F. 
               
               
                   
                 to 75° F. This was repeated and then followed by another 2.75 
               
               
                   
                 minute exposure and quenching into 20° C. water for 2 
               
               
                   
                 minutes. After the final portion of the radiation exposure 
               
               
                   
                 process, lenses were placed in an oven 45 to 90 minutes at 
               
               
                   
                 temperatures between 60 and 100° C. 
               
               
                 5 
                 Using 420 nm peak fluorescent tubes spaced three to seven 
               
               
                   
                 inches apart as well as GG420 glass placed between the lamps 
               
               
                   
                 and the lens/article being cured, lenses were cured as follows. 
               
               
                   
                 The exposure consisted of an initial 2.75-minute actinic light 
               
               
                   
                 exposure followed by a 1.25 minutes period out of the light. 
               
               
                   
                 This was repeated and then followed by another 2.75 minute 
               
               
                   
                 exposure and quenching into 20° C. water for 2 minutes. After 
               
               
                   
                 the final portion of the radiation exposure process, lenses were 
               
               
                   
                 placed in an oven 45 to 90 minutes at temperatures between 
               
               
                   
                 60 and 100° C. 
               
               
                 6 
                 Using 420 nm peak fluorescent tubes spaced three to seven 
               
               
                   
                 inches apart as well as GG420 glass placed between the lamps 
               
               
                   
                 and the lens/article being cured, lenses were cured as follows. 
               
               
                   
                 The exposure consisted of an initial 3 minutes actinic light 
               
               
                   
                 exposure after which the gasket was removed. The article was 
               
               
                   
                 then exposed to actinic light two more times for 3.5 minutes 
               
               
                   
                 each time. Following the actinic light exposure, the lenses 
               
               
                   
                 were placed in an oven for 1 hour at 60° C., followed by 1 
               
               
                   
                 hour a 70° C. 
               
               
                 7 
                 Using 420 nm peak output low pressure Hg lamps spaced 
               
               
                   
                 three to six inches apart and GG420 glass as a filter, 
               
               
                   
                 expose both sides of the lens or article for 3 minutes 
               
               
                   
                 continuously. After this initial exposure, lenses were exposed 
               
               
                   
                 using 420 nm peak fluorescent tubes spaced three to seven 
               
               
                   
                 inches apart as well as GG420 glass placed between the lamps 
               
               
                   
                 and the lens/article being cured by continuous exposure from 
               
               
                   
                 both sides for 7 minutes. Following the radiation exposure, the 
               
               
                   
                 articles were put into an oven at 70° C. for 30 to 60 minutes. 
               
               
                 8 
                 Using 420 nm peak fluorescent tubes spaced three to seven 
               
               
                   
                 inches apart as well as GG420 glass placed between the lamps 
               
               
                   
                 and the lens/article being cured, lenses were cured as follows. 
               
               
                   
                 Lenses were placed on a conveyor belt that carries the lenses 
               
               
                   
                 between the lamps. The method consisted of exposing the 
               
               
                   
                 lenses for 4.25 minutes twice. After the final portion of the 
               
               
                   
                 radiation exposure process, lenses were placed in an oven 45 
               
               
                   
                 to 90 minutes at temperatures between 60 and 100° C. 
               
               
                 9 
                 Using 420 nm peak fluorescent tubes spaced three to seven 
               
               
                   
                 inches apart as well as GG420 glass placed between the lamps 
               
               
                   
                 and the lens/article being cured, lenses were cured as follows. 
               
               
                   
                 Lenses were placed on a conveyor belt and exposed to the 
               
               
                   
                 actinic light source described for 9 minutes. After the final 
               
               
                   
                 portion of the radiation exposure process, lenses were placed 
               
               
                   
                 in an oven 30 to 90 minutes at temperatures between 60 and 
               
               
                   
                 100° C. 
               
               
                 10 
                 Using 420 nm peak output low pressure Hg lamps spaced 
               
               
                   
                 three to six inches apart and GG420 glass as a filter, 
               
               
                   
                 expose both sides of the lens or article for 10 minutes 
               
               
                   
                 continuously. Following the radiation exposure, the articles 
               
               
                   
                 were put into an oven at 120° C. for 25 to 30 minutes. 
               
               
                 11 
                 Using 420 nm peak output low pressure Hg lamps spaced 
               
               
                   
                 three to six inches apart and GG420 glass as a filter, 
               
               
                   
                 lenses were exposed from each side separately using shutters 
               
               
                   
                 to control the exposure time from each side. The reaction was 
               
               
                   
                 monitored using a thermocouple embedded in the lens so the 
               
               
                   
                 temperature could be controlled as low as possible. Exposure 
               
               
                   
                 times were from 30 seconds to 4 minutes per side. Following 
               
               
                   
                 the radiation exposure, the articles were put into an oven at 
               
               
                   
                 60 to 120° C. for 20 to 90 minutes. 
               
               
                 12 
                 Using 420 nm peak fluorescent tubes spaced three to seven 
               
               
                   
                 inches apart as well as GG420 glass placed between the lamps 
               
               
                   
                 and the lens/article being cured, lenses were cured as follows. 
               
               
                   
                 Lenses were placed on a conveyor belt with 3 curing zones 
               
               
                   
                 and 2 cooling zones. The exposure consisted of an initial 
               
               
                   
                 2.75-minute actinic light exposure followed by a 1.25 minutes 
               
               
                   
                 period out of the light with an ambient temperature of 55° F. 
               
               
                   
                 to 75° F. This was repeated and then followed by another 2.75 
               
               
                   
                 minutes exposure. This whole exposure was repeated and then 
               
               
                   
                 followed by placing the lens into cool water. After the final 
               
               
                   
                 portion of the radiation exposure process, lenses were placed 
               
               
                   
                 in an oven 45 to 90 minutes at temperatures between 60 and 
               
               
                   
                 100° C. 
               
               
                   
               
             
          
         
       
     
     The following tables exhibit examples of photochromic compositions, process and physical properties of the resulting cured articles. Examples 1-28 below, employ formula (Ia) where n=n′=3, R 1 -R 4 =CH 3 , X=C(CH 3 ) 2 , and y 1 -y 8 =H; formula (Ib) where n=n′=5, R 1 -R 4 =CH 3 , X=C(CH 3 ) 2 , and y 1 -y 8 =H; Formula (IIa) where m avg =9, R 5  and R 7 =CH 3 , and R 6 =H (polyethylene glycol 400 dimethacrylate); and Formula (IIb) where m avg =4 to 5, R 5  and R 7 =CH 3 , and R 6 =H (polyethylene glycol 200 dimethacrylate) in the amounts indicated in the table. Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide at 0.04% and 2,2′-azobis(2,4-dimethylpentanenitrile) at 0.05% were used as photo and thermal initiators, respectively, based on 100 parts by weight of core resin. A neutral gray photochromic dye mixture, at 0.073%, and a UV-absorber, 2-hydroxy-4-methoxybenzophenone, at 0.025%, were also employed. Isopropylxanthic disulfide was used at 0.03%, based on 100 parts by weight of core resin, in examples 1-5. During one hour mixing at room temperature with the photochromic dye mixture, nitrogen bubbling was employed, followed by degassing under vacuum for 15 minutes. The dye mixture employed in these examples includes a combination of 550 ppm spiro-9-floureno-13′-(6-methoxy-3-(4-N-morpholinyl)phenyl-3-phenyl-indeno[2,1-f]naphtho(1,2-b)pyrane (gray-blue), 60 ppm of 3-phenyl-3′-(4-N-piperidinyl)-phenyl-6-N-morpholinyl-3H-naphtho[2,1-b]pyrane (ruby), 70 ppm of 3-phenyl-3′-(4-N-morpholinyl)-phenyl)-6-N-morpholinyl-3H-naphtho[2,1-b]pyrane (orange), and 50 ppm of 3-phenyl-3′-(4-methoxy)-phenyl-6-N-morpholinyl-3H-naphtho[2,1-b]pyrane (yellow), which provides a gray photochromic dye blocking visible light. All samples were cured under low pressure Hg lamp with 420 nm peak output for 15 to 20 minutes at an intensity of 2.5 mw/cm 2  with GG420 filter glass (from Schott), followed by annealing at 120° C. for 25 to 30 minutes. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Formulation (by wt) of core resin 
               
             
          
           
               
                 Ex- 
                   
                   
                   
                   
                   
                 Di- 
                   
               
               
                 am- 
                   
                   
                   
                   
                   
                 vinyl 
                 Dipenta- 
               
               
                 ple 
                 Formula 
                 Formula 
                 Formula 
                 Formula 
                 Sty- 
                 Ben- 
                 erythritol 
               
               
                 No. 
                 (Ia) 
                 (Ib) 
                 (IIa) 
                 (IIb) 
                 rene 
                 zene 
                 Pentaacrylate 
               
               
                   
               
             
          
           
               
                 1 
                 0 
                 29.3 
                 41.5 
                 0.0 
                 18.0 
                 0.0 
                 11.3 
               
               
                 2 
                 10 
                 19.3 
                 41.5 
                 0.0 
                 18.0 
                 0.0 
                 11.3 
               
               
                 3 
                 20 
                 9.3 
                 41.5 
                 0.0 
                 18.0 
                 0.0 
                 11.3 
               
               
                 4 
                 0 
                 29.3 
                 31.5 
                 10.0 
                 18.0 
                 0.0 
                 11.3 
               
               
                 5 
                 0 
                 29.3 
                 21.5 
                 20.0 
                 18.0 
                 0.0 
                 11.3 
               
               
                 6 
                 0 
                 39.3 
                 24.0 
                 0.0 
                 18.0 
                 0.0 
                 18.8 
               
               
                 7 
                 0 
                 45.3 
                 18.0 
                 0.0 
                 18.0 
                 0.0 
                 18.8 
               
               
                 8 
                 0 
                 39.3 
                 18.0 
                 0.0 
                 18.0 
                 0.0 
                 24.8 
               
               
                 9 
                 0 
                 39.3 
                 24.0 
                 0.0 
                 0.0 
                 18.0 
                 18.8 
               
               
                 10 
                 0 
                 45.3 
                 18.0 
                 0.0 
                 0.0 
                 18.0 
                 18.8 
               
               
                 11 
                 0 
                 39.3 
                 18.0 
                 0.0 
                 0.0 
                 18.0 
                 24.8 
               
               
                 12 
                 0 
                 39.8 
                 17.0 
                 0.0 
                 15.8 
                 10.8 
                 16.5 
               
               
                 13 
                 0 
                 34.5 
                 17.0 
                 0.0 
                 15.8 
                 10.8 
                 21.8 
               
               
                 14 
                 0 
                 39.8 
                 17.0 
                 0.0 
                 10.8 
                 15.8 
                 16.5 
               
               
                 15 
                 0 
                 34.5 
                 17.0 
                 0.0 
                 10.8 
                 15.8 
                 21.8 
               
               
                 16 
                 0 
                 36.3 
                 14.0 
                 0.0 
                 24.4 
                 4.0 
                 21.3 
               
               
                 17 
                 0 
                 41.0 
                 14.0 
                 0.0 
                 21.0 
                 7.4 
                 16.6 
               
               
                 18 
                 0 
                 30.0 
                 15.6 
                 0.0 
                 24.4 
                 4.0 
                 26.0 
               
               
                 19 
                 0 
                 41.0 
                 17.1 
                 0.0 
                 21.4 
                 4.0 
                 16.5 
               
               
                 20 
                 0 
                 32.6 
                 17.1 
                 0.0 
                 20.9 
                 5.9 
                 23.5 
               
               
                 21 
                 0 
                 36.3 
                 14.0 
                 0.0 
                 17.6 
                 10.8 
                 21.3 
               
               
                 22 
                 0 
                 41.0 
                 14.0 
                 0.0 
                 13.2 
                 10.8 
                 21.0 
               
               
                 23 
                 0 
                 31.1 
                 24.0 
                 0.0 
                 24.4 
                 4.0 
                 16.5 
               
               
                 24 
                 0 
                 31.6 
                 14.0 
                 0.0 
                 17.6 
                 10.8 
                 26.0 
               
               
                 25 
                 0 
                 41.0 
                 14.0 
                 0.0 
                 21.0 
                 7.4 
                 16.6 
               
               
                 26 
                 0 
                 30.0 
                 24.0 
                 0.0 
                 17.6 
                 10.8 
                 17.6 
               
               
                 27 
                 0 
                 36.0 
                 19.0 
                 0.0 
                 17.6 
                 10.8 
                 16.5 
               
               
                 28 
                 0 
                 36.0 
                 19.0 
                 0.0 
                 24.4 
                 4.0 
                 16.5 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Properties of cured photochromic samples 
               
             
          
           
               
                 Exam- 
                 Compared to ColorMatic extra gray* 
                   
                 Flex 
               
             
          
           
               
                 ple 
                   
                   
                 Deacti- 
                 Refractive 
                 Abbe 
                 modulus 
               
               
                 No. 
                 Activation 
                 Darkness 
                 vation 
                 Index 
                 Value 
                 (kpsi) 
               
               
                   
               
             
          
           
               
                 1 
                 Slower 
                 similar 
                 Faster 
                 1.5413 
                 41.8 
                 123 
               
               
                 2 
                 Slower 
                 similar 
                 Faster 
                 1.5398 
                 40.8 
                 143 
               
               
                 3 
                 Slower 
                 lighter 
                 Faster 
                 1.5423 
                 40.5 
                 152 
               
               
                 4 
                 Slower 
                 lighter 
                 Faster 
                 1.5436 
                 41.2 
                 167 
               
               
                 5 
                 Slower 
                 lighter 
                 Faster 
                 1.5413 
                 41.1 
                 179 
               
               
                 6 
                 Similar 
                 similar 
                 Faster 
                 1.5396 
                 41.9 
                 115 
               
               
                 7 
                 Similar 
                 similar 
                 Faster 
                 1.5396 
                 42.2 
                 120 
               
               
                 8 
                 Similar 
                 darker 
                 Faster 
                 1.5403 
                 41.6 
                 136 
               
               
                 9 
                 Faster 
                 darker 
                 Much 
                 1.5426 
                 41.1 
                 80 
               
               
                   
                   
                   
                 faster 
               
               
                 10 
                 Faster 
                 darker 
                 Much 
                 1.5461 
                 38.4 
                 79 
               
               
                   
                   
                   
                 faster 
               
               
                 11 
                 Faster 
                 darker 
                 Much 
                 1.5451 
                 39.1 
                 81 
               
               
                   
                   
                   
                 faster 
               
               
                 12 
                 Faster 
                 darker 
                 Faster 
                 1.5542 
                 38.8 
                 168 
               
               
                 13 
                 Faster 
                 darker 
                 Faster 
                 1.5516 
                 38.4 
                 159 
               
               
                 14 
                 Faster 
                 darker 
                 Faster 
                 1.5533 
                 38.7 
                 149 
               
               
                 15 
                 Faster 
                 darker 
                 Faster 
                 1.5510 
                 38.8 
                 162 
               
               
                 16 
                 Slower 
                 lighter 
                 Faster 
                 1.5529 
                 39 
                 195 
               
               
                 17 
                 Slower 
                 similar 
                 Faster 
                 1.5522 
                 39 
                 178 
               
               
                 18 
                 Similar 
                 similar 
                 Faster 
                 1.5450 
                 41.8 
                 197 
               
               
                 19 
                 Similar 
                 similar 
                 Faster 
                 1.5496 
                 38.8 
                 168 
               
               
                 20 
                 Faster 
                 darker 
                 Faster 
                 1.5493 
                 39.6 
                 174 
               
               
                 21 
                 Faster 
                 similar 
                 Faster 
                 1.5525 
                 39.7 
                 173 
               
               
                 22 
                 Faster 
                 darker 
                 Faster 
                 1.5493 
                 39.3 
                 132 
               
               
                 23 
                 Similar 
                 similar 
                 Faster 
                 1.5484 
                 40.2 
                 174 
               
               
                 24 
                 Faster 
                 Darker 
                 Faster 
                 1.5506 
                 39.9 
                 175 
               
               
                 25 
                 Faster 
                 Darker 
                 Faster 
                 1.5532 
                 39.1 
                 195 
               
               
                 26 
                 Faster 
                 Darker 
                 Faster 
                 1.5494 
                 39.3 
                 174 
               
               
                 27 
                 Faster 
                 Darker 
                 Faster 
                 1.5514 
                 39.4 
                 174 
               
               
                 28 
                 Slower 
                 Similar 
                 Faster 
                 1.5493 
                 39.6 
                 191 
               
               
                   
               
               
                 *ColorMatic extra gray is the best photochromic lenses in over-all properties on the market and is produced by Optische Werke G. Rodenstock located in Munich, Germany. Photochromic properties were obtained after exposure under the natural sun light.  
               
             
          
         
       
     
     Thicker lenses may also be produced according to the principles of the invention. Because slower heat transfer rates are associated with thicker lenses, the processing temperatures of the material employed in thicker lens tend to be higher and the selection of thermal initiators may be affected. For example, a useful monomer charge for a typical lens may be 24.37% styrene, 3.99% divinylbenzene, 0.05% 2,2′-azobis(2,4-dimethylpentanenitrile), 0.04% bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 0.20% triphenyl phosphine, 6.29% polyethylene glycol (PEG 400), 36.18% bisphenol A, 21.22% dipentaerythritol pentaacrylate, and 7.67% photochromic dyes. The monomer charge for a similar, but thicker, lens may substitute thermal initiator 1,1′azobis(cyclohexane-carbonitrile) for 2,2′-azobis(2,4-dimethylpentanenitrile). 
     The foregoing description and examples have been set forth merely to illustrate the invention and are not intended to be limiting. Since modifications of the described embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed broadly to include all variations falling within the scope of the appended claims and equivalents thereof.