CROSS-REFERENCE TO RELATED PATENT APPLICATIONS This application is a continuation-in-part of patent application Serial No. 273,428 filed November 18, 1988 which is a continuation-in-part of parent application Serial No. 021,913 filed March 4, 1987 which is a continuation-in-part of Serial No. 823,339, filed January 28, 1986 now U.S. Patent No. 4,728,469.

BACKGROUND OF THE INVENTION This invention relates generally to plastic lens compositions and methods and apparatus for making plastic lenses, and in one of its aspects to corrective or piano plastic lenses for use in eyeglasses and the like.

Optical lenses have been produced from the polymer of dierhylene glycol bis(allyl)-carbonate (DEG-BAC) by thermal curing techniques. These techniques for polymerizing DEG-BAC to produce an optical lens, however, have several

disadvantages and drawbacks. One of the mosr significant drawbacks is that it takes approximately 12 hours to produce a lens according to this technique and therefore a lens forming mold can produce at most two lenses per day.

Moreover, the thermal curing process employs a thermal catalyst so that the polymerizable mixture of DEG-BAC and catalyst will slowly polymerize even while refrigerated. The polymerizable mixture therefore has a very short shelf life and must be used within a short time or it will harden in its container.

Furthermore, the thermal catalysts utilized in these procedures are quite volatile and dangerous to work with requiring extreme care in handling.

U.S. Patent No. 4,166,088 discloses the formation of a pias- ic lens by disposing a lens forming material comprising a liquid monomer and a photosensitive initiator into a mold cavity defined in part between a pair of spaced apart molds each having a lens forming surface facing the cavity and an outer opposed surface, and rhen directing rays of ultraviolet light against the outer surface of at least one of the molds to act on rhe lens forming material in the caviτy to produce a lens therefrom.

U.S. Patents Nos. 3,038,210 and 3,222,432 disclose the heating of a lens forming material in a mold cavity by an external heat source.

U.S. Patent No. 4,298,005 discloses an apparatus for generating ultraviolet light having a wavelength in the range of 320 to 450 nm for hardening plastics.

The polymer of DEG-BAC exhibits desirable optical and mechanical properties. These properties include high light transmission, high clarity, and high index of refraction together with high abrasion and impact resistance. These properties in the past made DEG-BAC one of the leading monomers in the manufacture of high quality lenses, face shields, sun and safety glasses. Other

properties of DEG-BAC, however, such as its slow rate of polymerization make it an undesirable monomer in the manufacture of these items.

SUMMARY OF THE INVENTION

One aspect of the present invention is to provide a method and apparatus for making a plastic lens, such as an optical lens for use in eyeglasses and the like.

Another aspect of the present invention is to reduce the yellowing of the plastic lens during the making thereof.

Yellowing of the plastic lens has been found to be ι^ Q-np ^* ^ O"^ ^■ *- I ITΛ-W 4- W Q ~ < QΓ<T* ^■ i **-' r r** "^ -"-^ O n τrι-r Λ-π Q*n+- c; i "i- ^* i ^ i Q/^ ^■ *- r ^* ι form the lens forming material.

According to one embodiment of the present invention, a lens forming composition comprises diethylene glycol bis(allyl carbonate) (DEG-BAC) and one or more mono or multifunctional acrylate monomers that can be radiation cured to produce a hard, tough, clear, and strain-free polymeric material which has excellent optical qualities. The composition further comprises a suitable photoinitiator that is selected preferably from the group consisting of 2-hydroxy-2-methyl-l-phenyl-propan-l-one and 1-hydroxy- cyclohexyl phenyl ketone. Preferably, the mono or multifunctional acrylate monomers of this composition may be selected from tetrahydrofurfuryl acrylate (TFFA) , trimethylol propane triacrylate (TMPTA) and terrahydrofurfuryl-methacrylate (TFFMA) .

It is a further object of the present invention to provide a plastic lens that can be produced in less than two hours and preferably in less than one hour.

It is a still further object of the present invention to provide a plastic lens that has no distortions, cracks, patterns, striations, defects, or aberrations.

It is a still further object of the present invention to provide a plastic lens that is hard, strong and

durabie, and has very little flexibility at high temperatures.

It is a still further object of the present invention to provide a plastic lens that easily releases from the molding apparatus.

Toward the fulfillment of the above and other objects _r according to another embodiment of the present invention, a lens forming composition comprises aromatic-containing bis(all 1 carbonate)-functional monomer and at least one poiyethylenic-functional monomer containing two ethylenically unsaturated groups selected from acrylyl and methacrylyl. The composition further comprises a suitable photoinitiator and optionally comprises one or more of a poiyethylenic-functional monomer containing three ethylenically unsaturated groups selected from acrylyl and methacrylyl, styrene, a mold release agent and. a dye.

According to a further embodiment of the present invention, a lens forming composition comprises at least one poiyethylenic-functional monomer containing two ethylenically unsaturated groups selected from acrylyl and methacrylyl.- The composition further comprises a suitable photoinitiator and optionally comprises one or more of a poiyethylenic-functional monomer containing three ethylenically unsaturated groups selected from acrylyl and methacrylyl, styrene, a mold release agent and a dye.

According to a still further embodiment of the present invention, a lens forming composition comprises a poiyethylenic-functional monomer containing three ethylenically unsaturated groups selected from acrylyl and methacrylyl. The composition further comprises a suitable photoinitiator and optionally comprises one or more of an aromatic-containing bis(allyl carbonate)-functional monomer, styrene, a mold release agent and a dye.

Brief Description of the Drawings The above brief description as well as further objects, features and advantages of the composition, method and apparatus of the present invention will be more fully appreciated by reference to the following detailed description of presently preferred but nonetheless illustrative embodiments in accordance with the present invention when taken in conjunction with the accompanying drawings in which:

Fig. 1 is a perspective view of a plastic lens of the present invention;

Fig. 2 is a reduced top view of a portion of an apparatus cf the present invention that is illustrated in Fig. 3, Fig. 2 being taken substantially on line 2-2 of Fig. 3;

Fig. 3 is an enlarged fragmentary cross-sectional view taken on line 3-3 of Fig. 2 which schematically illustrates an apparatus for producing a plastic lens according to the present invention;

Fig. 4 is an infrared-absorption spectra of DEG-BAC before and after irradiation in the presence cf 2-hydroxy-2-methyl-l-phenylpropan-l-one;

Fig. 5 is a portion of an infrared-absorption spectra of DEG-BAC before, during and after irradiation in the presence of 2-hydroxy-2-methyl-l-phenylpropan-l-one;

Fig. 6 is a fragmentary cross-sectional view of an apparatus for producing a plastic lens according to the present invention; and

Fig. 7 is a fragmentary cross-sectional view of an apparatus for producing a plastic lens according to the present invention.

Description of the Preferred Embodiments While various aspects of the present invention are hereinafter illustrated and described as being particularly adapted for the production of a plastic lens

for use in eyeglasses, it is to be understood that lenses for other uses can also be produced, such as safety glasses and UV-filters as well as lenses having high quality optical use for instrument sightings, photography and light filtration.

Therefore, the present invention is not to be limited to only the embodiments illustrated in the drawings, because the drawings are merely utilized to illustrate one of the wide variety of uses of this invention.

Referring now to Fig. 1, a plastic lens of the present invention is generally indicated by the reference numeral 10. The plastic lens 10 may be formed by an apparatus of the present invention that is generally indicated by the reference numeral 11 in Figs. 2 and 3 and which will be hereinafter described.

The ultraviolet light cured plastic lens 10 of the present invention-can be formed in a substantially shorter time period than lenses formed by thermal curing techniques such as in the manner set forth in U.S. Patents Noε. 3,038,210 and 3,222,432 the disclosures of which are hereby specifically incorporated herein by reference. Approximately 8 to 14 hours are required to form a thermally cured plastic lens whereas a plastic lens can be formed in less than 2 hours according to one embodiment of the composition, method and apparatus 11 of the present invention.

As illustrated in Figs. 2 and 3, the apparatus 11 of the present invention includes a pair of suitably shaped mold members 12 formed of any suitable material that will permit rays of ultraviolet light to pass therethrough. The mold members 12, preferably, are formed of glass. Each mold member 12 has an outer peripheral surface 13 and a pair cf opposed surfaces 14 and 15 with the surfaces 14 being precision ground. In a preferred embodiment the surfaces 15 are frosted to aid in the substantially even

distribution of ultraviolet light and to prevent the setting up of discontinuous intensity gradients in the ultraviolet light. Preferably the molds have desirable ultraviolet light transmission characteristics and the mold surfaces preferably have no surface scratches cr other defects.

The mold members 12 are adapted to be held in spaced apart relation to define a mold cavity 16 between the facing surfaces 14 thereof. The mold members 12 are held in a spaced apart relation by a T-shaped flexible annular gasket 17 that seals the cavity 16 from the exterior of the mold members 12. The mold members 12 are held in assembled relation with the sealing gasket 17 by a pair of annular clamping members 18 that are held together preferably with a suitable spring force, such as a spring force that is provided by the tension springs 19 illustrated in the drawings.

In this manner, in the embodiment of the present invention that is illustrated in Fig. 3 the upper mold member 12 has a concave inner surface 14 while the lower mold member 12 has a convex inner surface 14 so that the resulting mold cavity 16 is shaped to form a lens 10 with a desired configuration. Thus, by selecting the mold members 12 with a desired surface 14, lenses 10 with different characteristics, such as focal lengths, can be made by the apparatus 11. Such techniques are well known to those skilled in the art, and will therefore not be further discussed.

In one embodiment, the apparatus 11 of the present invention includes a device 20 for directing rays of ultraviolet light against the outer surface 15 cf the mold members 12. The rays of ultraviolet light pass through the mold members 12 and act on a lens forming material 21 disposed in the mold cavity 16 in a manner discussed below so as to form a lens 10. Each device 20 includes an

ultraviolet light producing device 22 disposed outboard of a mold member 12 and the rays (not shown) of ultraviolet light from each device 22 are reflected by a suitably shaped hood type reflector 23. The reflected rays of ultraviolet light pass through a suitable filter 24 to engage against the outer surface 15 of the mold members 12. In one embodiment of the present invention, each device 20 is similar to the radiation apparatus disclosed in U. S. Patent No. 4,298,005 the disclosure of which is hereby specifically incorporated herein by reference.

~ ' ~n -- Q -n*rp ^* n ^* *- ή oa πK ^{™ **} ϊ -τ +- source cr device 22 preferably comprises a high pressure mercury lamp with a heavy metal additive, such as iron. This type of lamp produces a significant amount of energy in the 320 nm. range. A standard mercury ultraviolet source can also be used for a longer period to achieve the same results.

The filter 24 for each device 22 preferably comprises a Pyrex glass plate which filters out ultraviolet light having a wavelength below approximately 300 nm. thereby to prevent excessive heat buildup in the mold cavity 16. The lens forming material 21 in the mold cavity 16 is cooled during the curing cycle by passing cooling air over the mold arrangement.

According to this embodiment, it is preferred that the ultraviolet ray generating devices 20 irradiate the lens forming material 21 with ultraviolet light in the range cf approximately 300 nm to 400 nm since the effective wavelength spectrum for curing the material 21 lies in the 300 nm to 400 nm region.

While each filter 24 has been illustrated and described as being a one filter member, it will be recognized by those skilled in the art that each filter 24 could comprise a plurality of filter members or comprise

any other device effective to filter out ultraviolet light having a wavelength below approximately 300 nm. , as desired.

Also according to this embodiment, it is preferred that the glass mold members 12 are formed from a material that will not allow ultraviolet radiation having a wavelength below approximately 300 nm to pass therethrough. One such material is Schott Crown or S-l glass that is manufactured and sold by Schott Optical Glass Inc., of Duryea, Pennsylvania.

According to a preferred embodiment of the present

"ϊ O ^■ £ ^{' ■} *- Vi Ω I-T ^* . ■* ^*■ 1 .- mom o r" : 1 "i c frosted. The frosting of the outer surface 15 of the mold members 12 in combination with the ray directing device 20 provides ultraviolet light having no sharp discontinuities throughout the mold cavity 16 thereby leading to a reduction in optical distortions in the lens 10. It is also preferable that there be no sharp gradients of ultraviolet radiation either horizontally or vertically through the material 21 with approximately 50% of the radiation from each device 20 reaching the center of the material 21. To ensure that sufficient radiation is reaching the center of the material 21, it should be possible to measure 1 mW/sqcm of ultraviolet light on the side of the mold cavity opposite the ray directing device 20. Also, any component of the lens forming material 21 that absorbs ultraviolet light in the range of 300 to 400 nm. except the photoinitiator should be eliminated from the lens forming material 21.

In general, photochemical and thermal curing systems are analogous except that light instead of heat is the main driving force for the polymerization reaction. Curing of a lens by ultraviolet light as opposed to thermal curing presents many problems, however, that must be overcome to produce a viable lens. The most

troublesome of these problems include yellowing of the lens, cracking of the lens, production of patterns in the lens and premature release of the lens from the mold.

Yellowing of the finished lens has been found to be related to the monomer composition, the intensity of ultraviolet light, the identity of the photoinitiator and the concentration of the photoinitiator. The effect of the photoinitiator is the strongest but each of the others plays a part.

When casting a lens, particularly a positive lens that is thick in the center, cracking is a very serious ^* ι r» rτ photochemical addition polymerization reactions, are exothermic. During the process, a large temperature gradient builds up and the resulting stress tends to cause the lens to crack. It is believed that with positive lenses it is more-difficult for the heat generated in the polymerization process to migrate to the surface of the lens and be dissipated quickly enough to avoid cracking.

Also, when the lens forming composition includes monomers that tend to be brittle, the lens is more prone to crack. DEG-BAC, without any additives or comonomers produces a very hard but somewhat brittle polymer that is very prone to cracking. In addition, DEG-3AC, without additives tends to stick very tightly to the molds. When a portion of a lens adheres tightly to the mold, cracking often occurs.

When the polymerization reaction proceeds too rapidly, heat buildup inside the system which leads to cracking is inevitable. The likelihood of cracking increases as the temperature difference between the center of the lens forming material and room temperature increases. During the polymerization process, several forces tending to crack the lens, such as shrinkage, adhesion, and thermal gradients, are at work. Other

forces tending to crack the lens occur when the irradiation is stopped and the lens is cooled, especially if the reaction cell is allowed to cool too quickly.

Distortions in the finished lens are very troublesome. If the incident ultraviolet light has sharp discontinuities, visible distortion patterns may appear in the finished lens. Although the incident ultraviolet light was made as uniform as possible, it was found difficult to produce an acceptable product from DEG-BAC alone. It was determined that it is preferable to include additives in the lens forming composition to reduce the

It was found that by mixing DEG-BAC with additives or comcnomers, its cracking tendency was decreased. By varying the raw material composition of DEG-BAC with additives or comono ers, it was possible to produce a wide' variety of materials ranging from hard and tough to rubber-like materials. The rate of polymerization of the composition including DEG-BAC was increased by incorporating one or more compounds containing an acrylate group such as tetraethylene glycol diacrylate (TTEGDA), tripropylene glycol diacrylate (TRPGDA), trimethylolpropane triacrylate (TMPTA) , tetrahydrofurfuryl methacrylate (TFFMA) and tetrahydrofurfuryl acrylate (TFFA). Those skilled in the art will recognize that other compounds that tend to increase the rate of polymerization of a composition including DEG-BAC can also be included.

TTEGDA tends to increase the overall rate cf polymerization and tends to reduce the amount of yellowing in the finished lens. TTEGDA, however, also tends to increase the cracking of the lens. TRPGDA also increases the rate of polymerization. TMPTA and TFFMA tend to prevent the development of patterns and fringes in the finished lenses. TFFA tends to reduce cracking and the

development of patterns in the finished lenses. TFFA also tends to reduce the degree to which the lenses stick to the mold. Preferably, 12-25% by weight of TFFA is incorporated in the composition to yield the desirable effects noted above. Preferably, no more than 25% by weight TFFA is included since a proportion greater than 25% tends to decrease the hardness of the finished lens.

An obstacle to the production cf lenses having no defects or aberrations is the formation of convective striations, cr optical inhomogeneity. These defects are commonly referred to as "patterns" or "wavy patterns". ^H ci ~~~ Λv-π a* ^{- ***■•} ' ι-vτ-1 - ^** *. -C -h i C C O ^ Ω*^ Cir**" C ^Λ CT ¹ ^ S ^" ^ ^* T Λi-> ι ^* > ι « ri -f ^■ ' ^■ π rr the early stages of the polymerization reaction during the transformation of the lens forming composition from the liquid to the gel state. Once patterns form they are almost impossible to eliminate. When gelation occurs there is a rapid t-emperature rise. In positive lenses, the temperature rise can reach 85° C which often leads to the lens fracture. The exothermic polymerization step causes a temperature increase, which in turn causes an increase in the rate of polymerization, which causes a further increase in temperature. If the heat exchange with the surroundings is not sufficient enough there will be a runaway situation that leads to the appearance of thermally caused striations and even breakage. Since the rate of polymerization increases rapidly at the gelation point, this is a critical phase of the reaction.

The best quality lenses according to the present invention were found to result from a smooth reaction process that is not too fast and not too slow. Heat must not be generated by the process so fast that it cannot be exchanged with the surroundings. The incident ultraviolet light intensity must be adjusted because too much incident light can also cause the reaction to proceed too rapidly.

Also, the seal between the gasket and the mold must be as complete as possible.

Conditions that lead to the production of lenses that are free from patterns are when (1) a good seal between the gasket and the mold is achieved; (2) the mold surfaces are free from defects; (3) a formulation is used having an appropriate concentration of initiator that will produce a reasonable rate of temperature rise; (4) the formulation is homogeneous; and (5) shrinkage is minimized. The process cf the present invention is conducted in a manner that maximizes these conditions.

D αmit-'-r "j-o"l oac:o T-T "Ϊ ^" Ϊ result in an incompletely cured lens and the production of lens defects. Factors that contribute to premature release are (1) a poorly ^~ assembled mold; (2) the presence of air bubbles around the sample edges; (3) the covering of a part of the -sample from light; (4) imperfection in gasket lip or mold edge; (5) inappropriate formulation; and (6) high shrinkage. The process of the present invention is conducted in a manner that minimizes these conditions.

The gasket ^* has been found to have a significant effect during the curing process. Specifically, premature release can occur when the molds are held too rigidly by the gasket. There must be enough flexibility in the gasket to permit the molds to follow the lens as it shrinks. In this regard, reference is made to U.S. Patent Nos. 3,038,210 and 3,222,432, the disclosures of which are specifically incorporated herein by reference. Indeed, the lens must be allowed to shrink in diameter slightly as well as in thickness. Breakage of the lens occurs in some cases because there is adhesion between the lens and the gasket. The use of a gasket that has a reduced degree of stickiness with the lens during and after curing is therefore desirable.

In a preferred technique for filling the lens forming cavity, the gasket is placed on the concave mold and the lens forming composition is poured into place. The convex mold is moved into place and a small amount- of the lens forming composition is forced out around the edge. The excess is then removed, preferably, by vacuum. The small amount of liquid which escapes outside the lens body and collects between the top innerεide of the gasket and the top mold edge also presents a problem. During the curing process this liquid will transform to a solid state and will affect the performance of the gasket as well as the m »τ i c- +- ι ^■• & a 1 -ϊ / -pτnp ^* ~l~ r £ -^ e- ^*** . o +- ^*■* -"-. l-i mrt l ^ ^ c trDi* important. Gasket deterioration usually occurs at the top side because of the inherent spill factor. To avoid the alignment and spill problems, the molds, preferably, are clamped in place using a desired amount of pressure and then the lens forming composition is injected.

Despite the above problems, the advantages offered by the radiation cured lens molding system clearly outweigh the disadvantages. The advantages of a radiation cured system include a significant reduction in energy requirements, curing time and other problems normally associated with conventional thermal systems.

According to the present invention, the lens forming material can. comprise any suitable liquid monomer or monomer mixture and any suitable photosensitive initiator. In this embodiment, the liquid lens forming material, preferably, is filtered for quality control and is placed in the mold cavity 16 by pulling the gasket 17 away from one of the mold members 12 and injecting the liquid lens forming material 21 into the cavity 16. Once the cavity 16 is filled with such material 21, the gasket 17 is replaced into its sealing relation with the mold members 12. The material 21 can then be irradiated

with ultraviolet light in the manner described above for a time period that is necessary to cure the lens forming material 21. The ultraviolet light entering the mold cavity 16 preferably has a wavelength in the range of approximately 300 nm. to approximately 400 nm. The surface 15 of the mold members 12 preferably is frosted. The frosted surfaces 15 in combination with the reflectors 23 act to prevent the development of discontinuous gradients in the ultraviolet light as it passes through the lens forming material 21 in the mold cavity 16 during such time period.

The lens forming material 21, preferably, can be cured in the above manner by directing rays of ultraviolet light frc one device 20 through the mold member 12 rather than utilizing both devices 20 as previously described.

Those skilled in the art will recognize that once the cured lens 10 is removed from the mold cavity 16 by disassembling the mold members 12, the lens 10 can be further processed in a conventional manner, such as by . grinding its peripheral edge.

As previously stated one aspect of the first embodiment of the present invention is the prevention of yellowing of the lens forming material 21 during the curing thereof. One means of realizing this aspect is to provide a lens forming material that leads to reduced yellowing.

One component of the lens forming material that leads to reduced yellowing is the photoinitiator. Photoinitiators are the photochemical counterparts of catalysts such as the difficult to handle peroxides that are used mainly in thermal free radical polymerizations. Thermal catalysts are usually very unstable and often dangerous to handle, while the ultraviolet photoinitiators utilized according to the present invention are easily handled and σuite safe.

In general, a photoinitiator having utility in the present invention will exhibit an ultraviolet absorption spectrum over the 300-400 nm range. High absorptivity of a photoinitiator in this range, however, is not desirable, especially when casting a thick positive lens. The following are examples of the illustrative photoinitiator compounds within the scope of the invention: 2-hydroxy-2-methyl-l-phenylpropan-l-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-di-sec- butoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenyl-acetophenone, 2,2-dimethoxy-2- _/ *_-*QCΠ *._-_.*_- ^* wi .*' _* ..**Π>.*. m _fck.t.p+-T- ^* -.—ιτ jτ" -_l__. p C-*t-V-.it p* » -τ-- _/ isobutyl ether, benzoin, benzil, benzyl disulfide, 2,4-dihydroxybenzophenone, benzylideneacetophenone, and acetophenone.

In addition, the polymerization must take place very uniformly. The incident ultraviolet light must be made to have no discontinuous gradients to maximize the uniformity of the polymerization. If one portion of the lens polymerizes faster than another, visible distortions may be produced that remain in the cured lens. A strongly absorbing photoinitiator will absorb most of the incident light in the first millimeter of lens thickness, causing rapid polymerization in that region. The remaining light will produce a much lower rate of polymerization below this depth and will result in a lens that has visible distortions. An ideal photoinitiator will exhibit high activity, but will have a lower extinction coefficient in the useful range. A lower extinction coefficient of photoinitiators at longer wavelengths allows the ultraviolet radiation to penetrate deeper into the reaction system. This deeper penetration of the ultraviolet radiation allows photoinitiator radicals to form uniformly throughout the sample and provide excellent overall cure. Since the sample can be irradiated from

both top and bottom, a system in which appreciable light reaches the center of the lens is essential. The photoinitiator solubility and compatibility with the monomer system is also an essential requirement.

An additional consideration is the effect of the photoinitiator fragments in the finished polymer. Some photoinitiators generate fragments that impart a yellow color to the finished lens. Although such lenses actually absorb very little visible light, they are cosmetically undesirable.

Photoinitiators are often very system specific so that photoinitiators that are very efficient in one system may be much poorer in another. The preferred photoinitiators for the system according to the first embodiment cf the present invention are 2-hydroxy-2-methyl-l-phenyl-propan-l-one and l-hydroxycyclohex l phenyl ketone. The identity of the initiator and its concentration are very important for any particular formulation. A concentration of initiator that is too high leads to cracking and yellowing of the lens . Concentrations of initiator that are too low lead to incomplete polymerization and a soft material.

In particular, according to the first embodiment of the present invention, the liquid monomer comprises diethylene glycol bis(allyl)-carbcnate and the initiator utilized therewith comprises 2-hydroxy-2-methyl-l- phenyl-propan-1-one with such initiator comprising approximately 1% to 3% by weight of the lens forming material. The balance of the composition is provided by the monomer alone or preferably with additives as discussed below. The above-noted initiator is commercially available from EM Chemicals under the tradename Darocur 1173.

■Also, according to the first embodiment of the present invention, the liquid monomer comprises diethylene

glycol bis(allyl)-carbonate and the initiator utilized therewith comprises l-hydroxycyclohexyl phenyl ketone with such initiator comprising approximately 2% to 6% by weight of the lens forming material. The balance of the composition being provided by the monomer alone or preferably with additives as discussed below. The above—noted initiator is commercially available from Ciba-Geigy under the tradename Irgacure 184.

In the system according to the first embodiment of the present invention, each of the above two initiators reduce yellowing of the lens forming material during the curing operation because a large amount cf the .same is not required in combination with the above described monomer.

For example, according to the first embodiment of the present invention, when diethylene glycol bis(allyl)- carbonate is used with the photoinitiator Darocur 1173, the preferred amount of Darocur 1173 is approximately 2.5% by weight of the lens forming material. When diethylene glycol bis(allyl)-carbonate is used with the photoinitiator Irgacure 184, the preferred amount of Irgacure 184 is approximately 3.3% by weight of the lens forming material.

Also according to the first embodiment of the present invention, each of the last two above described combinations of the liquid monomer and the photosensitive initiator preferably include one or more additives to improve the plastic lens being made therefrom.

In particular, one such additive is 2-ethyl-2- (hydroxymethyl)-l,3-propanediol triacrylate with such additive comprising approximately 2% to 4% by weight of the lens forming material and being commercially available from Aldrich or Interez. In this system, this additive reduces the amount of optical distortion in the plastic lens.

Another additive that can be used by itself or in combination with the previously described additive is 1,6-hexanediol diacrylate (HDDA) with such additive comprising approximately 2% to 7% by weight of the lens forming material and being commercially available from Rohm Tech.

Other additives such as TFFA (available from Sartomer), TFFMA (available from Sartomer) and TMPTA (available from Aldrich or Interez) may be included to suppress the development of patterns and fringes in the lens and reduce the degree to which the lenses stick to the mold, respectively, as discussed above.

The first embodiment of the invention will now be described in more detail with reference to the following examples. These examples are merely illustrative ^" of the composition and method of the invention and are not intended to be limiting.

Example 1

The photo-initiating efficiency of various commercially available initiator compounds in the polymerization of diethylene glycol bis(allyl)carbonate

(DEG-BAC) was investigated at a constant light intensity of 17mW/cm 2, and initiator concentration of 3%(w/v).

The rate cf polymerization was monitored by IR-stectroscopy -using the absorption band of the stretching vibration of the olefinic double bond at 1650cm ^~ . The results showed that 2-hydroxy-2-methyl-l-phenylpropan-l-one and l-hydroxycyclohexyl phenyl ketone have the highest efficiency as initiators for the polymerization of DEG-BAC. In contrast, benzoin and benzoin ethers produced much lower rates of polymerization and are therefore poor initiators for DEG-BAC.

Apparatus

A Hanovia medium pressure mercury lamp, containing a small amount of iron iodide to improve the spectral output in the UV-region around 350 nm, was used as a UV-light source. The lamp was housed in an air cooled housing equipped with an elliptical reflector. The lamp was operated with a special stabilizer ballast to supply constant power at three different intensities of 125, 200, and 300 Watts/inch. A 1/4 inch filter of Pyrex glass was placed in the path of the beam to absorb short wavelength

UV-light. The total incident light intensity was measured by a digital radiometer εcu pped w th a 1 cm. 2 diffuse-sensor window. This radiometer operates in the spectral range of 320 to 380 nm with a full range reading

2 from zero to 200 mW/cm .

All IR-spectroscopy was performed on a Nicolet 7199 Fourier Transform spectrophotometer equipped with a triglycine sulfate detector.

UV-spectra of the initi or/monomer solutions were recorded on a Shimadzu UV-160, a microcomputer controlled double beam UV-Vis spectrophotometer. Methods

A solution of 3% initiator in monomer was made up on a weight/volume basis. After the initiator was dissolved in the monomer, the solution was transferred into a test tube and flushed with nitrogen for 15 minutes to sweep out dissolved oxygen. A few drops of the solution were sandwiched between two sodium chloride disks which were separated by a 0.05mm stainless steel spacer, and then secured in a demountable cell mount. After the cell was assembled, an IR-spectrum was taken. The sample cell was then irradiated for the desired time, removed, and immediately analyzed on the IR-spctrophotometer. This expoεure-IR-spectrum cycle was repeated seven or eight times for each sample. Duplicate experiments with

different initiators were carried out following the same procedure. The peak area of the IR-bands was calculated using the SETUP computer program which was run from a DEXTER/2 system. Results

Fig. 4 shows an IR-absorption spectra of DEG-BAC before and after irradiation in the presence of 2-hydroxy-2-methyl-l-phenylpropan-l-one, which is commercially available from EM Chemicals under the trademark Darocur 1173. The point of interest is the large decrease of absorption at 1650 cm (band A),

VVi -i pi i e **-Vι Q -P-sP A ^• *-* -t- -t o 2 1 1 τr l portions of the DEG-BAC. As shown in Fig. 5 this absorption band is an excellent index of the extent of polymerization of DEG-BAC. Other changes in the IR absorption spectra occur, but as the absorption band at 1650 cm- is due to a fundamental vibration mode, it is the most reliable criteria of the unsaturation content.

The percent residual unsaturation of DΞG-3AC was calculated using the following equation:

% residual unsaturation = (A _t ) ' 100 (1) where A and A _^ are the absorption peak areas of the band A (base line 1659-1641 cm ), initially and after an irradiation of t seconds, respectively.

Although the demountable cell was used with a fixed spacer, the apparent thickness of the sample was observed to change due to the increase in density as the polymerization proceeds. A band at 1581 cm- (band B) , which did not change appreciably during polymerization, was used as an internal standard. To obtain the correct % unsaturation a correction factor of B /B. was applied to equation 1.

residual unsaturation = (A-j-/B ₀ ) 100 (2)

(A ₀ /B _t ) where B and B. are the absorption peak areas of band B (base line 1592-1572), initially and at time t during the polymerization, respectively. A representative sample of data is given in Table I below.

Table I

Data for the Polymerization of DEG-BAC with 3% 2-Hydroxy-2-m ethyl-I-phenylpropan-l-one and light intensity of 17 mW/cm ² *

As a further check on the validity of this technique or equation 2, two additional analytical methods were used; refractive index and iodometry. The refractive index method was based on data published by Starkweather and Eirich, Ind. Enq. Chem., 47: 2452 (1955) from which the conversion factor was deduced. The iodine value method was that described in ASTM D1541-60. The results are shown in Table II below.

Table I I

Percent Residual Unsaturation of the Irradiated DEG-BAC by Three Different Methods.

Method: IR Refractive Index Iodometry

92.5 92.2 91.3 93.0 89.5 89.5 88.8 89.5 83.3 87.0 73.3 76.1 57.1 60.4 29.0 30.0

Comparison of these two methods with the IR method using equation 2 shows reasonable agreement.

The initial rates of polymerization after sequential UV-irradiation were taken from the slopes of the initial part of the % unsaturation-time curves. Table III summarizes the results obtained for the polymerization of DEG-BAC with various initiators at room temperature.

Table III

Initial Rates (R _Ό ) of Photopolymerization of DEG-BAC with 3% Initiator and Light Intensity of 17 mW/cm ² in the 320-380 nm Region.

Initiator λ ax (logξ) Rp x 10 ⁴ M/sec

2-Hydroxy-2-methyl-l- phenylpropan-1—one 1-Hydroxycyciohexy1 phenyl ketone 2,2-Di-sec-butoxyacetophenone 2,2-Diethoxyacetophenone 2,2-Diethoxy-2-phenyi- acetophenone 39.5

2,2-Dimethoxy-2-phenyl- acetoohenone 37.3

Benzoin methyl ether 18.5

Benzoin isobutyi ether 11.3

Benzoin 9.65

Benzil 5.96

Benzyl disulfide 4.05

2,4- ihydroxybenzόphenone 4.00

Benzylideneacetophenone 3.73

Acetophenone 0.81

Conditions for all runs were 3% initiator(w/v) and 17 mW/cm 2 effective intensity m the 320-380 nm region. The results show that 2-hydroxy-2-methyl-l-phenylpropan-l-one, which is commercially available from EM Chemicals under the trademark Darocur 1173 and 1-hydroxycyclohexyi- phenyl ketone, which is commercially available from Ciba-Geigy under the trademark Irgacure 184 are the best photoinitiators for DEG-BAC in the group studied. Benzoin ethers, however, which showed high efficiency as initiators for vinyl polymerization, are much less effective in the photopolymerization of DEG-BAC.

EXAMPLE 2 The objective of this example was to develop a composition including DEG-BAC and a procedure for the

production of molded eyeglass lenses by ultraviolet photoinitiation.

Composition

It was found to be difficult to prepare an acceptable product by using DEG-BAC and photoinitiator alone in conjunction with the present radiation system. It was determined that the addition cf other monomers was essential to obtain the most desirable combination of optical and mechanical properties in the finished lens. The additional monomers were selected from monofunctional and multifunctional acrylateε or methacrylateε .

The final composition cf the raw material was miscible, clear, and dust free. In addition, the ultraviolet tranεmisεion of the components except for the photoinitiator were at a maximum in the desired range.

The preferred compoεition is εhown in Table IV.

Table IV

Materials Supplier Weight(%) range

2-hydroxy-2-methyl-l-phenyi- EM Chemicals 0.7-1.3 propan-1-one (Darocur 1173)

1-hydroxy cyclohexyl- Ciba-Geigy 1.2-1.8 phenyl ketone (Irgacure 184)

Trimethylol propane- Aldrich, Interez 2.5-3.0 triacrylate (TMPTA)

Tetrahydrofurfuryl- Sartomer (Arco) 3.0-2.5 methacrylate (TFFMA)

Tetrahydrofurfuryl- Sartomer 12.0-25 acrylate (TFFA)

Diethylene glycol PPG Inc. 80.3-72.3 bis(allyl)-carbonate

(DEG-BAC)

Reaction Cell

The reaction cell included two glass windows shaped to produce the lens and a flexible silicon or vinyl gasket. The glass molds reproduced the lens surfaces. The inside curvature of the molds together with the gasket thickness controlled the lens shape and power. To produce good quality lenses it was important that the glass molds had no surface scratches or other defects.

Ultraviolet light radiation system

The spectral range of interest for ultraviolet radiation curing is 320-400 nm where the most efficient photoinitiators absorb and molds of crown glass allow maximum transmission.

Of the high intensity sources of light available, iron added-mercury arc lamps offer a high output within this preferred range and thuε were used in this system. Shorter wavelengths below _. 320 nm. were blocked by a 1/4 inch Pyrex glaεs filter placed at 6-8 inches from the lamp and 5-7 inches from the reaction cell. This blockage of the short wavelengths was found to be absolutely essential. If the full intensity of the ultraviolet light source was allowed to strike the glass mold it broke due to the strong absorption of the shorter wavelengths by the glass. Even small amounts of radiation at this wavelength caused heating problems that were too severe to overcome.

Additional advantages offered by the Pyrex glass filter included a significant reduction in unwanted IR heat problems normally produced by the lamp. Heat was continuously removed, without disturbing the lamp stability, by blowing air past the filter and the reaction cell. The ultraviolet rays emanating from the lamp were passed through two or three sheets of closely spaced tracing paper at 3 inches from the reaction cell or 2-4 inches from the Pyrex glass filter. The tracing paper

increases the uniformity of light distribution with a further reduction in the heating problems.

The light intensity in the 320-400 nm. range, under the above conditions, was reduced from 27 mW/sqcm. (in the abεence of the Pyrex glass filter and the tracing paper) to about 6-10 mW/sqcm. with an excellent performance compared with an unmodified radiation system even at comparable light intensity.

Alternatively, it was determined that the high-pressure mercury arc lamps could be replaced by fluorescent tubes without a loss in performance. Sylvania and Philips both produce acceptable fluorescent tubes that generate almost all of their output in the desirable range (320 to 390 nm.). A bank of these lamps was capable of producing at least 8 mW/sqcm. and were effective in this system. These fluorescent tubes provide many advantages over the high-pressure mercury arc lamps as they are inexpensive, compact, and require much less power.

Two illumination sources were used to provide ultraviolet light exposure simultaneously to both sides of the reaction cell. The critical point in the irradiation was found to occur shortly after the gelation point when the rate of polymerization increased drastically and the mobility of the reacting monomer units decreased which resulted in a rapid increase in temperature, especially in thicker εampleε. At this point cracking of the sample occured if the temperature difference became too great. This critical stage was controlled by monitoring the temperature at the mold surface and keeping the difference in temperature between the mold surface and the surroundings to less than 20°C. At room temperature this meant keeping the temperature at the mold surface below 50°C (120F). An alternative was to reduce the intensity of the ultraviolet light radiation, but this resulted in a longer irradiation time. Another possibility waε to reduce

the concentration of photoinitiator, which also increased the irradiation time and caused other problems.

The reaction cell was placed where at least 20% of the incident light passed through the cell, to ensure that regions farthest from the lamps received adequate radiation. Using a value of 6mW/sqcm of incident light it was required that there be 1.2 mW/sqcm passing through the cell.

Two lamps were used to provide εufficient radiation energy throughout the lens forming material so that any deficiency in energy on one side was compensated for by the ~ ^{• ■ •} * f»ι * ^, 1 -~- to obtain, uniform irradiation with only one lamp.

The monomer mixture contained co-monomers that improved the most needed properties. TMPTA was useful in reducing the effect of unequal radiation over the body of the lens. Without TMPTA, visible distortions occured. TFFA was added to add flexibility to the mixture to prevent cracking of the lens . Between 12 and 25% by weight of TFFA waε effective. Above 25% caused too much flexibility and less than 12% failed to prevent cracking. An added bonus was that the addition of TFFA also improved the mold release. A drawback was that TFFA slightly increased the yellowing of the lens. Procedure

The procedure for producing lenses was as follows:

1. The necessary amount of initiator was dissolved in TFFA using adequate agitation.

2. The necessary amount of DEG-BAC and other ingredients waε poured into the photoinitiator-TFFA εolution (with adequate agitation) to obtain a clear fluid free of undiεsolved particles. In some cases, it was helpful to warm the mixture to about 10°C above room temperature to ensure that the mixture attained a good homogeneous εtate.

3. Enough lens solution was placed in the cell container which was composed of the concave part of the cell window supported by the desired flexible gasket. The other window was carefully arranged to allow air to escape freely using a micro εpatula inεerted between the glaεs mold and the gaεket. Once the cell waε filled, the spatula was removed and the gasket returned to a sealing condition.

4. The windows were checked and any spillage was removed by vacuum suction.

5. The reaction cell was placed in position between the two radiation sources and the reaction was begun using both sources . The surface temperature waε not allowed to exceed 50°C in the first 5-10 minutes.

6. At the completion of the curing process (20-60 min. depending on thickness of lens, curvature of ^" lens, the reaction temperature and program of radiation) the reaction cell was allowed to cool to room temperature.

7. The gaεket was removed and the windows were carefully removed using a razor or knife inserted between the cured lens and the glass window with a gentle mechanical shock.

It was found according to the above-described first embodiment of the present invention that the DEG-BAC monomeric material has characteristicε that make its use in ultraviolet light cured plastic lenses undesirable. Specifically, DEG-BAC is very εiow to polymerize and therefore requires a high proportion of initiator which leads to increased yellowing. It was also difficult to produce acceptable poεitive correction ultraviolet light cured plastic lenses from DEG-BAC due to its slow reaction rate and the required thickness of the lens.

According to another embodiment of the present invention a polymerizable lens forming compoεition cσmpriεes an aromatic-containing bis (allyl carbonate) -

functional monomer and at least one poiyethylenic-functional monomer containing two ethylenically unsaturated groups selected from acrylyl and methacrylyl. In preferred embodiments, the composition may include one or more of a poiyethylenic-functional monomer containing three ethylenically unsaturated groups selected from acrylyl and methacrylyl, styrene, a mold releaεe agent and a dye.

According to a further embodiment of the present invention, a lens forming composition comprises at least one poiyethylenic-functional monomer containing two

0-*- ^** -»ττ ^"" Q^-, _ π a l l τr ii- c a-t-iπ- _ ₅ **-Q -l r-y-r.. .-*- _* <_ ^■ col op — o ¹ ^ -r-rxm a /- _* -*--? TT ^** ! ar . ^ methacrylyl. The composition further comprises a suitable photoinitiator and optionally comprises one cr more of a poiyethylenic-functional monomer containing three ethylenically unsaturated groups εelected from acrylyl and methacrylyl, styrene, a mold release agent and a dye.

According to a εtill further embodiment of the present invention, a lens forming compoεition comprises a poiyethylenic-functional monomer containing three ethylenically unsaturated groups selected from acrylyl and methacrylyl . The composition further comprises a suitable photoinitiator and optionally compriseε one or more of an aromatic containing biε(allyl carbonate)-functional monomer, styrene, a mold release agent and a dye.

Aromatic-containing bis(allyl carbonate)-functional monomers which can be utilized in the practice of the present invention are bis(allyl carbonates) of dihydroxy aromatic-containing material. The dihydroxy aromatic-containing material from which the monomer is derived may be one or more dihydroxy aromatic-containing compounds. Preferably the hydroxyl groups are attached directly to nuclear aromatic carbon atoms of the dihydroxy aromatic-containing compounds. The monomers are themselves known and can be prepared by procedures well known in the

art. See, for example, U.S. Pat. Nos. 2,370,567; 2,455,652; 2,455,653; and 2,587,437, the disclosures of which are incorporated herein by reference.

The aromatic-containing bis(allyl carbonate)-functional monomers can be represented by the formula:

Rθ ₀

CH2=CCH ₂ OCO-A ₁ -OCOCH2C=CH ₂ (I)

0 O in which A. is the divalent radical derived from the dihydroxy aromatic-containing material and each R _Q is independently hydrogen, halo, or a C^-C, alkyl group. The alkyl group is usually methyl or ethyl. Examples of R _Q include hydrogen, chlσro, bromo, fluoro, methyl, ethyl, n-propyl, isopropyl and n-butyl. Most commonly R _Q is hydrogen or methyl; hydrogen is preferred. A subclass of the divalent radical A ₁ which is of particular u

in which each ₁ is independently alkyl containing from 1 to about 4 carbon atoms, phenyl, or halo; the average value of each a is independently in the range of from 0 to 4; each Q is independently oxy, sulfonyl, alkanediyl having from 2 to about 4 carbon atoms, or alkylidene having from 1 to about 4 carbon atoms; and the average value of n is the range of from 0 to about 3. Preferably Q is methylethylidene, viz., isopropylidene.

Preferably the value of n is zero, in which case A. is represented by the formula

(III)

in which each R-, each a, and Q are as discussed in respect of Formula II. Preferably the two free bonds are both in the ortho or para positions. The para positions are especially preferred.

The dihydroxy aromatic-containing compounds from which & ₁ is derived may also be polyol-functional chain extended compounds. Examples of such compounds include alkylene oxide extended bisphenols. Typically the alkylene oxide employed is ethylene oxide, propylene oxide, or mixtures thereof. By way of exemplification, when para, para-bisphenols are chain extended with ethylene oxide, the bivalent radical A., may often be represented by the formula

(R _x )a (Rχ)a

—CH ₂ CH ₂ 07 (θ) Q (θ ^OCH ₂ CH ₂ ^- (IV) where each ₁₇ each a, and Q are as discussed in respect 30 Formula II, and the average values of j and k are each independently in the range of from about 1 to about 4.

The preferred aromatic-containing bis(allyl carbonate)-functional monomer is represented by the formula

and is commonly known as bisphenol A bis(allyl carbonate).

A wide variety of compounds may be used as the polyethylenic functional monomer containing two or three ethylenically unsaturated groups. The preferred polyethylenic functional compounds containing two or three ethylenically unsaturated groups may be generally described as the acrylic acid esters and the methacrylic acid esters of aliphatic polyhydric alcohols, such as, for example, the di- and triacrylates and the di- and trimethacrylates of ethylene glycol, triethylene glycol,

tetraethylene glycol, tetramethylene glycol, glycidyl, diethyleneglycol, butyleneglycol, propyleneglycol, pentanediol, hexanediol, trimethylolpropane, and tripropyleneglycol. Examples of specific suitable polyethylenic - functional monomers containing two or three ethylenically unsaturated groups include tri ethylolpropanetriacrylate (TMPTA), tetraethylene glycol diacrylate (TTEGDA), tripropylene glycol diacrylate (TRPGDA) , hexanedioldi ethacryl te (HDDMA) , and hexanedioldiacrylate (HDDA) .

A wide variety of photoinitiator compounds may be used to initiate the polymerization of the lens forming composition. The following are examples of illustrative photoinitiator compounds within the scope of the invention: 2-hydroxy-2-methyl-l-phenylpropan-l-one, l-hydroxycyclohexyl phenyl ketone,

2,2-di-sec-butoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenyl-acetophenone,

2,2-dimethoxy-2-phenyl-acetophenone, benzoin methyl ether, benzoin isobutyl ether, benzoin, benzil, benzyl disulfide, 2,4-dihydroxybenzophenone, benzylideneacetophenone, and acetophenone. An especially preferred photoinitiator compound is l-hydroxycyclohexyl phenyl ketone which is commercially available from Ciba-Geigy as Irgacure 184.

As noted above, styrene having a formula of ^C^ ^* -CH=CH ₂ may optionally be present in the polymerizable composition.

Another material which may optionally be present in the polymerizable composition is a mold release agent. When used, the mold release agent is employed in the composition in amounts sufficient to ensure that the subsequently produced lens releases easily from the mold without breaking or cracking. The mold release agent should be compatible with the polymerizable composition and should not adversely affect the physical properties of

the subsequently produced lens. More particularly, the mold releaεe agent should not adversely affect the physical properties most characteristic of the subsequently produced lens such as its rigidity, hardnesε, index of optical refraction, transmission of visible light and absence of coloring which affects optical clarity. The mold release agent εhould, therefore, be a liquid or, if a εolid, be soluble in the polymerizable composition.

Mold release agents that may be used include alkyl phosphates and εtearateε. Among the alkyl phosphates that may be used as a meld release agent are the mono and dialkyi phosphateε (and mixtures cf mono and dialkyi phosphates) which are commercially available from E.I. DuPont de Nemours & Co. under the trade names ZΞLEC® UN and ZELEC© NE. These alkyl phosphates are reported to have straight chain alkyl groups of from 16 to 18 carbon atoms.

Other mold release agents that may be used include stearic acid, esters of εtearic acid and the metal εaitε of εtearic acid, e.g. , stearic acid salts of the metals zinc, calcium, lead, magnesium, barium, cadmium, aluminum, and lithium. Other fatty acids and fatty acids salts may also be used, provided that they do not adversely affect the physical properties of the casting. Other mold release agents known to the art such as dioctylphthalate may be used.

Dyes and/or pigments are optional materials that may be present when high transmission of light is not necessary.

The listing of optional ingredients discussed above is by no means exhaustive. These and other ingredients may be employed in their customary amounts for their customary purposes so long as they do not seriously interfere with good polymer formulating practice.

According to a preferred embodiment of the present invention, the preferred aromatic-containing bis(allyl carbonate) functional monomer, bisphenol A bis(allyl carbonate) is admixed with one or more faster reacting polyethylenic functional monomers containing two acrylate or methacrylate groups such as hexanediol dimethacrylate (HDDMA) , hexanediol diacrylate (HDDA) , tetraethylene glycol diacrylate (TTEGDA) , and tripropylene glycol diacrylate (TRPGDA) and optionally a polyethylenic functional monomer containing three acrylate groups such as trimethylolpropane triacrylate (TMPTA) . According to -r-w- pc τ-1 +- " ^■ » -Π TT T +"ϊ ΛΓ πn p or more polyethylenic functional monomerε containing two acrylate or methacrylate groupε such as HDDMA, TTEGDA and TRPGDA iε optionally admixed with a polyethylenic functional monomer containing three acrylate groupε εuch as TMPTA. According tc a further preferred embodiment of the present invention a polyethylenic functional monomer containing three acrylate groups such as TMPTA is optionally admixed with one or more polyethylenic functional monomerε containing two acrylate or methacrylate groupε εuch as HDDMA, TTEGDA and TRPGDA. Generally, compounds containing acrylate groups polymerize much faster than those containing allyl groups. Thuε, by including the faεt polymerizing polyethylenic functional monomerε in the polymerizable lens composition, yellowing iε reduced because less initiator iε required to complete the polymerization proceεs.

TTEGDA has a very long and flexible backbone between its two acrylate groups, so compositionε including a high proportion of TTEGDA on the order of 70% by weight tend to be quite flexible. Preferably, other monomers that provide more stiffness are included in the composition and the proportion of TTEGDA is reduced. Stiffnesε is provided, preferably, by incorporating monomers that have

shorter and stiffer backbones than TTEGDA such as HDDMA or TRPGDA. Stiffness may be provided, according to some embodiments of the present invention, by incorporating polyethylenic functional monomers containing three acrylate groups such as trimethylolpropane triacrylate (TMPTA) .

To reduce the formation of cracks in the lenses, it iε preferable to reduce the rate of polymerization and reduce the maximum temperature of the lens composition during the curing process. Generally, if there is a large enough temperature difference between the hardening lens

The rate of polymerization and the maximum temperature are reduced, preferably, by optimizing three factorε: monomer composition, initiator concentration and incident light intensity. The rate of polymerization, preferably, is sufficiently reduced by decreasing the concentration of photoinitiator and by decreasing the intensity of the incident light. TTEGDA and TRPGDA are very fast reacting monomers although TRPGDA reacts slightly slower than TTEGDA. The higher the proportion of TTEGDA, the faster the reaction, the higher the shrinkage of the lens, the greater the heating effect and the more susceptible the lens is to cracking or premature releaεe from the mold. Slower reacting monomers, preferably, are mixed with these very reactive monomers to bring the rate of polymerization under control and reduce the rate of heat generation. A balance is achieved between εlower monomers and very reactive monomers to avoid lens cracking while at the same time providing a rapid enough rate of polymerization to minimize the concentration of initiator and diminish yellowing.

Conventional high pressure mercury arc lamps used to cure -plastic lenεeε were found to have a detrimental effect on the quality of the produced lenε. Aside from

being cumbersome, expenεive and dangerous, these high intensity lamps contributed to the rapid rise in temperature as well as the rate of polymerization. According to this embodiment of the present invention, conventional high pressure mercury arc lampε are replaced by bulbε that generate approximately 5-10 mW/εqcm of ultraviolet light having wavelengthε between 300 and 400 nm, which light is very uniformly distributed without any- sharp discontinuitieε throughout the reaction process. Such bulbs are commercially available from Sylvania under the trade designation Sylvania Fluorescent (F158T/2052) or Sylvania Fluorescent (F258T8/350BL/18") GTE. As noted above, ultraviolet light having wavelengths between 300 and 400 nm iε preferred because moεt of the preferred photoinitiatorε of the composition of the present invention absorb moεt efficiently at this wavelength and the molds used according to the present invention allow a maximum transmission at this wavelength.

It is preferred that a filter be placed between the light source and the reaction cell to absorb all or substantially all incident light having a wavelength less than 300 nm. Light having a wavelength below 300 nm doeε not induce polymerization but iε absorbed by the monomers and produces a great deal of heat. Also, if the full intensity of the ultraviolet source is allowed to strike the mold, it may break the mold due to a strong absorption of short wavelength radiation by the glasε. The filter, preferably, is a glass filter that can withstand a fair degree of temperature gradation with its surroundings and absorb all wavelengths below 300 nm, such as a boroεiiicate filter or a commercially available filter from Pyrex, Kimax or Crown Glass.

It is preferred according to the present invention that the light source generates light having substantially uniform intensity. It is also preferred that the incident

light have no εharp discontinuities to reduce the possibility of lens cracking. Moreover, it iε preferred that there be no εharp intenεity gradientε of ultraviolet radiation either horizontally or vertically through the lenε compoεition during the curing proceεε because sharp intenεity gradients through the lens lead to defects in the finished lenε. It iε preferred that εeveral light εourceε configured aε a bank cf lightε be utilized to generate the uniform light. It iε also preferred that a suitable light diffuser be diεpoεec between the light εource and the reaction solution to maximize the

^■ » -» -* ^■ - ^■ » ***■ ~ i-w-m ή *+-τr Cn -i -h a K ^' ' p "l -i TV-I -t- diffusers include frosted glass molds or one or more sheetε of tracing paper.

It iε preferred that the maximum temperature of the lenε forming composition during the cure thereof be lesε than 50°C. to reduce the tendency cf the lens to fracture. In addition to the above-noted techniques for reducing the temperature, filters diεposed between the light source and the reaction cell, as well as cooling fans to carry heat away from the reaction cell may be used to reduce the heating effects. Finally, when curing thick positive lenses, intermittent rather than continuous radiation is effective to reduce the heating effect.

According to one embodiment of the present invention, the liquid lens forming composition includes bis phenol A bis(allyl carbonate) as a major liquid monomer in place of DEG-BAC. The bisphenol A bis(allyi-carbonate) monomer has a higher refractive index than DEG-BAC which allows the production of thinner lenses which iε eεpecially important with relatively thick poεitive or negative lenεeε.

Commercially available preparations having utility in the present invention which include bisphenol A bis(allyl

carbonate) aε their major component are available from PPG Inc. under the trade name HIRI II.

In one of its commercially available forms, HIRI II includes approximately 91% bisphenol A bis(allyl carbonate), 7% DEG-BAC and 2% antiyellowing additives. The antiyellowing additives are UV blockers which absorb εtrongly at 326 nm. in the region where the photoinitiatorε absorb. The antiyellowing additives, preferably, are removed before the material is used in a photochemical polymerization reaction. This component, preferably, is removed by passing the HIRI through a column of alumina (basic) . Because cf its high viscoεity, the HIRI II material is preferably mixed with the less viscouε TTEGDA before passing it through an alumina column.

When used in the composition of the present invention, it iε preferred that the bisphenol A bis(allyl carbonate) monomer be obtained without DEG-BAC or the antiyellowing additives. Lenseε made from thiε product sometimes have a very slight, barely detectable, degree of yellowing, A small amount of a blue dye consisting of 9, 10-anthracenedione, l-hydroxy-4-[ ( -methylphenyl)amino] available aε Thermoplaεt Blue 684 from BASF Wyandotte Corp. iε preferably added to the compoεition to counteract the yellowing.

According to a preferred embodiment, the compoεition of the present invention includeε (a) bisphenol A-bis(allyl carbonate); (b) at least one of HDDMA, TTEGDA and TRPGDA; and (c) a photoinitiator. According to this embodiment the composition may optionally include one or more of TMPTA, styrene, a mold release agent, and a dye.

According to another preferred embodimentt, the composition of the present invention includes (a) at least one of HDDMA, TTEGDA and TRPGDA; and (b) a photoinitiator. According to this embodiment the composition may optionally

include one or more of TMPTA, styrene, a mold releaεe agent and a dye.

According to still another preferred embodiment, the composition of the present invention includes (a) TMPTA; and (b) a photoinitiator. According to this embodiment the composition may optionally include one or more of bisphenol A-bis(allyl carbonate), HDDMA, TTEGDA, TRPGDA, εtyrene, a mold releaεe agent and a dye.

According to a further preferred embodiment, the compoεition of the preεent invention includes (a) up to 70 percent by weight of bisphenol A biε(allyl carbonate); (b) up to 100 percent by weight cf HDDMA; (c) up to 100 percent by weight of TTEGDA; (d) up to 100 percent by weight of TRPGDA; (e) up to 100 percent by weight of TMPTA; (f) up to 20 percent by weight of εtyrene; (g) from about 0.01 to about 2.5 percent by weight of l-hydroxycyclohexylphenyl, ketone; and (h) an effective amount of a mold release agent.

According to a more preferred embodiment;, the composition includes 19.0% by weight of biεphenol A biε(allyl carbonate), 15.0% by weight of HDDMA, 17.5% by weight of TTEGDA, 31.0% by weight of TRPGDA, 17.5% by weight of TMPTA, 0.013% by weight of

1-hydroxycyclohexylphenyl ketone and an effective amount of a mold release agent.

According to a preferred embodiment, the composition of the present invention includes (a) bisphenol A-bis( llyl carbonate), (b) a mixture of HDDMA, TTEGDA and TRPGDA; (c) TMPTA; (d) styrene; (e) a photoinitiator; and (f) a mold releaεe agent.

According to a more preferred embodiment, the composition includes from about 22-29% by weight of bisphenol A bis(allyi carbonate), from about 13-26% by weight of HDDMA, from about 12-19% by weight of TTEGDA, and from about 12-19% by weight of TRPGDA; from about 15-19% by weight of TMPTA; from about 2-3% by weight styrene; from

about 0.02 - 0.04% by weight of 1-hydroxycyclohexylphenyl ketone as a photoinitiator; and an effective amount of a mold release agent.

According to a most preferred embodiment, the composition includes 26% by weight of bisphenol A bis(allyl carbonate), 25% by weight of HDDMA, 15% by weight of ^■ TTEGDA, 16% by weight of TRPGDA, 16% by weight of TMPTA, 2% by weight of εtyrene, 0.02% by weight of

1-hydroxycyclohexylphenyl ketone and an effective amount of a mold releaεe agent.

As diεcuεsed above, bisphenol A bis(allyl carbonate) has a much higher refractive index than DΞG-ΞAC and thus allows the production of thinner lenses when compared to DEG-BAC lenses. If more than 30% by weight of bisphenol A-bis(allyl carbonate) is included in the most preferred composition, however, compatability or solubility problems between the various monomers develop resulting in a cloudy, foggy or milky lenε.

TTEGDA iε a diacrylate monomer that, preferably, iε included in the compoεition because it is a fast polymerizing monomer that reduces yellowing and yields a very clear product. If too much TTEGDA is included in the moεt preferred compoεition, i.e. greater than about 18% by weight, however, the finished lens will be prone to cracking and will be too flexible as this material softens at temperatures above 40°C. If TTEGDA is excluded altogether, the finished lens tendε to be brittle.

HDDMA iε a dimethacrylate monomer that has a very εtiff backbone between the two methacrylate groups. HDDMA, preferably, is included in the composition because it yields a stiffer polymer and increases the hardness and strength of the finished lens. This material iε also quite compatible with the bisphenol A bis(allyl carbonate) monomer. HDDMA contributes to high temperature εtiffneεε, polymer clarity and speed of polymerization.

TRPGDA is a diacrylate monomer that, preferably, is included in the composition because it provides good strength and hardness without adding brittlenesε to the finiεhed lenε. Thiε material is also stiffer than TTEGDA.

TMPTA is a triacrylate monomer that, preferably, is included in the composition because it provides much more croεslinking in the finished lens than the difunctional monomers. TMPTA has a shorter backbone than TTEGDA and increases the high temperature stiffneεε and hardness of the finiεhed lens. Moreover, thiε material contributeε to the prevention of patternε in the finiεhed lenε. TMPTA alεc contributes to high shrinkage during polymerization. The inclusion of too much of this material in the most preferred composition, i.e. in excesε of 20% by weight akeε the finished lens too brittle so that it breaks under the drop-ball test.

Styrene is a- high refractive index comonomer that, preferably, is included in the composition because it acts as a coordinating material. If styrene iε not included in some compositionε according to the preεent invention, incompatability problemε may ariεe which reεult in a cloudy lenε. Styrene appearε to act aε a bridging agent which allowε the bisphenol A bis(allyl carbonate) to polymerize with the other monomers. The inclusion of too much styrene in the most preferred composition, i.e. greater than about 3% by weight will result in a loss of strength in the finished lenε, because styrene is a single vinyl group monomer.

Certain of the monomerε that are preferably utilized in the composition of the preεent invention, such as TTEGDA, TRPGDA and TMPTA, include impurities and have a yellow color in certain of their commercially available forms. The yellow color of these monomers is preferably removed by passing them through a column of alumina (basic) which includes aluminum oxide powder - basic. After

paεεage through the alumina column, the monomerε absorb almost no ultraviolet light. Also after passage through the alumina column differences between monomers obtained from different sources are substantially eliminated. It iε preferred, however, that the monomers be obtained from a source which provideε the monomerε with the leaεt amount of impuritieε contained therein. The εtyrene, preferably, iε alεo paεsed through a column of alumina (basic) before use. The composition preferably is filtered prior to polymerization thereof to remove suεpended particleε.

The photoinitiator included in the composition, preferably, is l-hydro ycyclchexylpher.yl ketone which is available from Ciba Geigy aε Irgacure 184. The initiator concentration to a large extent iε dependent on the incident light intenεity and the monomer compoεition. An exceεε of Irgacure 184 will cauεe yellowing in the lenε and will cause the reaction to proceed too rapidly leading to a cracked lens .

A mold release agent, preferably, is included in the composition so the finished lens will not stick to the mold or gasket after it has cured. The effective amount of mold release agent iε very small. Large amounts of mold releaεe agent lead to depoεitε on the molds that are present on the finished lenses. Suitable mold release materials may be εelected from butyl stear te, ZELEC® UN or ZELEC® NE and dioctylphthalate. The composition, preferably, includes 50-150 ppm of butyl stearate, 0.5-1.5 ppm of ZELEC® UN or ZELEC® NE, or 0.3-1.5 ppm of dioctylphthalate.

It is preferred that only one of the enumerated mold release agents and not a combination thereof is used. It is preferable to incorporate the mold release agent in the lens composition rather than spraying it on the surface of the mold faces. While coating the mold faces with a mold release agent such as butyl εtearate provideε effective

mold release it also generates microscopic surface anomalies in the lenses. Such surface anomalies detract from the quality of the finished lens and lenses produced from such εyεtemε do not tint uniformly.

Aε _. noted above, TTEGDA and TRPGDA are highly reactive monomers, with TTEGDA being slightly more active than TRPGDA. Slower reacting monomerε such as TMPTA and HDDMA, preferably, are mixed with the very reactive monomerε to bring the rate of polymerization under control and reduce the rate cf heat generation. The degree of yellowing, preferably, iε diminished by increasing the proportion of ^* T" ^n* 2Q-ns. ^■ —.^ TRPGDA - ^t_ i ^{, ,γ} "eaεe -'"he reaction rate and reduce the concentration of initiator. Lenε hardneεs depends on a balance between initiator concentra ion, exposure time, and formulation. The ultraviolet light cured lenses of the present invention demonstrate excellent organic solvent resistance to acetone, methylethyl ketone, and alcohols. The lenses produced according to the present invention, preferably, are cured in approximately 15 to 30 minutes. -

A reaction cell was also developed according to the present invention. The reaction cell can be uεed with a proper mold arrangement to prepare poεitive or negative lenses that are free from defects.

A first embodiment of the reaction cell of the present invention iε shown in Fig. 6. As shown in Fig. 6, the reaction cell generally indicated at 100 includes opposed glass mold parts 102 and a gasket device 104 which together form a lens molding chamber 106. The polymerizable lens forming composition of the present invention is disposed within the lens molding chamber 106. The glass mold parts 102, gasket device 104 and lens molding chamber 106 are sandwiched between opposed radiation lenses 108. In thiε manner, incident light entering the reaction cell 100 muεt first pass through one of the radiation lenεeε 108.

Fig. 7 illustrates a second embodiment of the reaction cell of the present invention which includes components identical to some components of the previous embodiment which components are given the same reference numerals. Aε shown in Fig. 7, the reaction cell 100 includes the opposed glass mold parts 102 and a gasket device 104 which together form the lens molding chamber 106. The polymerizable lens forming composition of the present invention is diεpoεed within the lens molding chamber 106. The glasε mold parts 102, gaεket device 104 and lenε molding chamber 106 are sandwiched between oppoεed powerless glass molds 108 and thermally insulated by a pair cf gaεkets 110. The powerless glass molds 108 and gasketε 110 together form a thermally insulated radiation chamber. Preferably, the powerless glass molds 108 have a larger diameter than the lens molding chamber 106 so that incident light iε allowed to reach the full, extent of the chamber 106. Preferably, tracing paper (not εhown) iε inεerted between the powerless glasε molds 108 and the glass mold parts 102. In an alternate preferred embodiment, instead of inserting tracing paper between the powerlesε glaεs molds 108 and the glass mold parts 102, the powerleεε glass molds 108 are replaced by frosted glasε molds.

The reaction cell assembly 100 is preferably constructed to minimize heat exchange between the reaction cell and its surroundings. Heat exchange with the εurroundings has been found to cause cracking and other problems.

In one embodiment, the gasket 104 is constructed of vinyl material, has good lip finiεh and maintainε sufficient flexibility at conditions around the T(max) of 45°C. In a preferred embodiment the gasket 104 is constructed of silicon material. In another preferred embodiment the gasket 104 is comprised of copolymerε of ethylene and vinyl acetate which are commercially available

from E. I. DuPont de Nemours & Co. under the trade name ELVAX®. Preferred ELVAX® reεins are ELVAX® 350 having a melt index of 17.3-20.9 dg/min and a vinyl acetate content of 24.3-25.7 wt. %, ELVAX® 250 having a melt index of 22.0—28.0 dg/min and a vinyl acetate content of 27.2-28.8 wt. %, ELVAX® 240 having a melt index of 38.0-48.0 dg/min and a vinyl acetate content of 27.2-28.8 wt. %, and ELVAX© 150 having a melt index of 38.0-48.0 dg/min and a vinyl acetate content of 32.0-34.0 wt. %. The gaskets are prepared by conventional injection molding techniques which are well-known by those of ordinary skill

Premature release often occurs when the molds are held too rigidly by the gasket. There must be εufficient flexibility in the gaskets to permit the molds to follow the lens as it shrinkε. Insufficient sealing, unsuitable gasket material and/or a εmall residual amount of uncured material have been found to contribute to premature release failures.

For best results, both sideε of the mold εurfaces should be as smooth as possible, with no scratches. They should also have a smooth edge finish. Scratches in the molds have been found to be more important than just producing the same defect in the finished lens. During the reaction free radicals are generated and these free radicals may be εenεitive to surface conditions, particularly if no mold releaεe agent is used. Scratches on the εurface may initiate cracking and aberrations. Scratches may cause more or lesε adhesion and premature release often appears to begin at a scratch.

Mold markings cause differential light intensity conditions under the marking, even when the mark is on the outside surface of the mold. The fully exposed region of the lens will be harder, and the sample may have streεses because of this. The portion of the lenε under the mark

will be weaker at the end of the curing period. Thiε effect haε been obεerved and can cauεe premature release or induce cracking.

Mold defects at the edges interfere with the sealing conditions and frequently induce premature release.

The present invention will now be described in more detail with reference to the following examples. These examples are merely illustrative of the compositionε and method of the invention and are not intended to be limiting. In each of the following exampleε, the monomer bisphenol A bis(allyl carbonate) was obtained from PPG Industries, Inc.; the tetraethylene glycol diacrylate (TTEGDA) monomer waε obtained from Interez, the 1,6 hexanedioldimethacrylate (HDDMA) monomer waε obtained from Rohm Tech, Inc. or Sartomer, the tripropylene glycol diacrylate (TRPGDA) and trimethylolpropanetriacrylate (TMPTA) mcnomerε were obtained from Interez cr Sartomer, the styrene monomer was obtained from Fisher and the l-hydroxycyclohexyl phenyl ketone photosensitizer waε obtained from Ciba-Geigy under the trademark Irgacure 184.

Example 3

The objective of thiε Example waε to produce optical lenses incorporating bisphenol A bis(allyl carbonate) that were not brittle, had desirable color and clarity, and did not have any patterns, defects or aberrations.

The results of various representative sample formulations are indicated below. In each trial the following conditions were observed:

1. All liquid materials were treated with alumina powder (basic) before use.

2. Sylvania Fluorescent (F158T/2052) lamps which generate an intensity cf 5.0 to 6.6 mW/sqcm of UV light were used as a light source. UV light reaching the mold

su face, however, was on the order of 1.5 mW/sqcm and the sampleε were irradiated for approximately 20 minutes.

3. The molds had a diameter of 75 mm.

4. The bisphenol A bis(allyl carbonate) monomer was obtained from PPG Industries, Inc., in a formulation that included 91% by weight bisphenol A biε(allyl carbonate), 7% by weight DEG-BAC and 2% by weight antiyellowing additives. The antiyellowing additives, which are UV absorberε, were removed prior to formulating the compositions .

Formulation 1 Λ ϊ n _-~ l.--. aCL o * .."-'. * _* *ι*ι. ^■ _* ^■ » -t_r÷ι~_.-<>_Λι . w consisting of:

22.12 parts by weight of bisphenol A bis(allyl carbonate), (together with 1.69 parts by weight of DEG-BAC), 15.8 parts by weight of TTEGDA, 15.0 parts by weight of TRPGDA 1-9.6 parts by weight of TMPTA, 22.3 parts by weight of HDDMA, 3.50 parts by weight of εtyrene; a photosensitizer conεiεting of 0.05 partε by weight of l-hydroxycyclohexyl phenyl ketone; and a mold releaεe agent consiεting of 76 ppm of butyl εtearate were placed in a reaction chamber disposed between opposed 550 and 775 glasε moldε configured to generate a poεitive correction lens. The molds were separated by a distance of 1.8 mm by a vinyl type gasket. The radiation cell was aε deεcribed above with reference to Fig. 6 and the radiation lenεeε were negative power lenεes.

The compoεition was irradiated for a period of 17 minutes and exhibited a smooth and slow rate of temperature increase.

The lens was an overall good product exhibiting a favorable appearance in terms of color and clarity and having a flexibility resistance that was better than conventional DEG-BAC lenseε.

Formulation 2

A plastic lens composition including a monomer mixture consisting of:

23.70 parts by weight of bisphenol A bis(allyl carbonate), (together with 1.81 parts by weight of DEG-BAC), 15.9 parts by weight of TTEGDA, 15.3 parts by weight of TRPGDA, 16.2 parts by weight of TMPTA, 23.4 partε by weight of HDDMA, 3.60 partε by weight of εtyrene; a photcεenεitizer consisting of 0.051 parts by weight of l-hydroxycyclohexyl phenyl ketone; and a mold releaεe agent conεiεting of 114 ppm of butyl εtearate were placed in a reactior. chamber dispoεed between oppcεed glaεε melds configured to generate a positive (2.7D) correction lens. The glaεε oldε were separated by a vinyl type gasket. The glaεε molds were washed and treated with methylethyl ketone prior to the reaction. The radiation cell was aε described above with reference to Fig. 6 and the radiation lenεeε were negative power lenses.

The composition waε irradiated for a period of 18 minutes and exhibited a smooth reaction that was not too fast and not too slow. The lens did not crack and did not releaεe prematurely. The lenε had a flexibility reεiεtance that waε better than conventional DEG-BAC lenses. The lens, however, was brittle near its edges which is believed to be caused by slight interference with the incident light caused by the lens molding apparatus.

Formulation 3

A plastic lens composition including a monomer mixture consisting of:

26.10 parts by weight of bisphenol A bis(allyl carbonate) (together with 2.00 parts by weight of DEG-BAC), 14.0 parts by weight of TTEGDA, 16.8 parts by weight of TRPGDA, 14.3 parts by weight of TMPTA, 24.1 parts by weight of HDDMA, 2.60 parts by weight of styrene; a photosensitizer consisting of 0.048 parts by weight of

1-hydroxycyclohexyl phenyl ketone; were placed in a reaction chamber disposed between opposed 660 and 500 glasε molds configured to generate a negative correction lens. The molds were separated a distance of 4.8 mm by a gaεket. The radiation cell waε as described above with reference to Fig. 6. The molds were sprayed with butyl stearate as a mold release agent prior to the curing process.

The compoεition waε irradiated for a period cf 20 minutes. The finished lens exhibited no hazinesε and good hardneεε but was brittle at itε edgeε. The butyl εtearate εprayed on the mold εurface led to surface anomalies in the finished lens.

Example 4

The objective of thiε Example waε to produce optical lenses incorporating bisphenol A bis(allyl carbonate) that were not brittle, had desirable color and clarity, and did not have any patterns, defects or aberrations.

In each trial of thiε Example, Sylvania Fiuoreεcent (F158T/2052) lampε which generate an intensity of 5.0 to 6.6 mW/sqcm. of UV light were used aε a light source.

The baεic ingredientε of the formulationε according to Example 4 included TTEGDA, TRPGDA, TMPTA, biεphenol A biε(allyl carbonate), εtyrene and l-hydroxycyclohexyl phenyl ketone which are commercially available from the sourceε set forth above.

Zelec® UN waε teεted aε a mold releaεe agent to εupplement butyl εtearate.

Often, the monomers were passed through beds of alumina (basic) to remove i puritieε. Thiε waε eεpecially true for the monomer TRPGDA.

The results of various representative sample formulationε are indicated below.

Sample formulation 4 was irradiated in a reaction cell aε described above with reference to Fig. 6.

Each of sample formulations 5-7 and comparative sample formulations 8-9 was irradiated in a reaction cell as described above with reference to Fig. 7.

As shown in Fig. 7, the lenε forming chamber 106 iε thermally insulated on the sideε by gaεketε 110. According to thiε example, the chamber 106 waε thermally insulated by two large gaskets 110 having the following dimensionε: 92 mm OD, 85 mm ID and 75 mm lip diameter, and on top and bottom by two powerleεε glaεε molds 108 having a 76 mm diameter which fit into the large gaskets 110. Three sheets of tracing paper 108 were inserted between the powerless glass melds 108 and the glaεε molds 102 cf the lens forming chamber 106. Heat exchange between the reaction cell and its εurroundingε waε reduced greatly with thiε arrangement.

Frosted glaεs in place of the glaεε moldε 108 waε tried and worked -aε well aε clear glass molds 108 plus tracing paper. In any case, good sealing was very important to produce high quality lenseε.

Gaεket material and lip finish were also very important. Moεt of the trials were carried out using vinyl gasketε that had been uεed many timeε so that the quality of the lip had deteriorated making sealing difficult.

Imperfect sealing and gasket material, plus a small residual amount of uncured material contributed to premature release.

When the lens cavity was not completely sealed, a small amount of air leaked in and prevented the polymerization of the monomer mixture that it reached resulting in some uncured reεidual liquid remaining at the gasket lip. ^'

Formulation 4

A plastic lens composition including a monomer mixture consisting of:

24.13 parts by weight of bisphenol A bis(allyl carbonate) (together with 1.84 partε by weight of DEG-BAC), 16.05 parts by weight of TTEGDA, 15.64 parts by weight of TRPGDA, 16.59 parts by weight of TMPTA, 23.87 parts by weight of HDDMA, 1.48 parts by weight of styrene; a photosenεitizer consisting of 0.02 partε by weight of l-hydroxycyclohexyl phenyl ketone were placed in a reaction chamber dispoεed between opposed glaεs molds configured to generate a bifocal correction lenε. The glaεε oldε were separated by silicon gaεketε to produce a lenε that was 2mm thick at the edge and 7.7mm thick in the center. The lenε pnm* nc ^, ! ^, '- i nr ya c; i * *2 C Tf ϊ * "÷ c

A.fter 20 minuteε of irradiation mold releaεe occurred at the bifocal. The ultraviolet light paεεing through the cell had an intensity of 1.1 mW/sqcm. Under these conditions the t(max) reached 48°C after 16 minutes of irradiation and fell to 47°C after 20 minutes of irradiation. After the radiation there was found some reεidual liquid around the gaεket lip. The produced lenε had excellent color, no patternε and good hardneεε. The edge of the lens was not perfect but the lens was still an overall acceptable product.

Formulation 5

A plastic lens compoεition including a monomer mixture consisting of:

24.15 parts by weight of bisphenol A bis(allyl carbonate) (together with 1.85 partε by weight of DEG-BAC), 16.0 parts by weight of TTEGDA, 15.6 parts by weight of TRPGDA, 16.6 parts by weight of TMPTA, 23.9 parts by weight of HDDMA, 1.8 parts by weight of εtyrene; and a photosensitizer consiεting of 0.02 partε by weight of 1-hydroxycyclchexyl phenyl ketone were placed in a reaction chamber diεpoεed between opposed 550 and 775 glaεε molds configured to generate a positive 3D correction lens. The glaεs molds were separated by a distance of 1.8 mm by vinyl

gaεkets. The lens composition was irradiated for 40 minutes and the finiεhed lens showed no patterns, had good hardness, and good color and clarity.

Formulation 6

A plastic lenε compoεition including a monomer mixture conεisting of:

24.15 parts by weight of bisphenol A bis(allyl carbonate) (together with 1.85 partε by weight of DEG-BAC), 16.0 partε by weight of TTEGDA, 15.6 parts by weight of TRPGDA, 16.6 parts by weight of TMPTA, 23.9 parts by weight of HDDMA, 1.8 partε by weight of εtyrene; and a phctosensitizer ccnsiεting cf 0.02 parts by weight of l-hydroxycyclohexyl phenyl ketone were placed in a reaction chamber diεpoεed between oppoεed glaεε moldε configured to generate a poεitive 5D or 6.5D correction lens. In these trials the glasε moldε were separated by an ethylene vinyl acetate gasket. The lens compositions were irradiated for 46 minutes and the finished lenses showed no patterns, had good hardness and good color and clarity.

Formulation 7

A plastic lens composition including a monomer mixture consiεting of;

24.15 partε by weight of biεphenol A biε(allyl- carbonate) (together with 1.85 partε by weight of DEG-BAC), 16.0 parts by weight of TTEGDA, 15.6 partε by weight of TRPGDA, 16.6 parts by weight of TMPTA, 23.9 parts by weight of HDDMA, 1.8 parts by weight of styrene; and a photosenεitizer conεisting of 0.02 partε by weight of l-hydroxycyclohexyl phenyl ketone were placed in a reaction chamber diεposed between opposed glasε moldε configured to generate negative correction lenses. The molds were configured to generate a -1 lens or a -4 lens. The lens compoεition was- irradiated for 40 minutes. The -1 lenses were successfully completed while the -4 lenseε prematurely releaεed.

Comparative Formulation 8

A plastic lenε compoεition including a monomer mixture conεiεting of:

23.97 partε by weight of bisphenol A biε(allyl- carbonate) (together with 1.83 parts by weight of DEG-BAC),

16.1 parts by weight of TTEGDA, 15.5 parts by weight of TRPGDA, 16.3 parts by weight of TMPTA, 24.6 partε by weight of KDDA, 1.6 partε by weight of εtyrene; and a photosensitizer consisting of 0.034 parts by weight of l-hydroxycyclohexyl phenyl ketone were placed in a reaction chamber dispoεed between opposed 550 and 775 glaεε moldε configured to generate a positive ccrrecticn lens. The moldε were εeparated by a diεtance of 1.8 mm. The lenε cracked around the central area. The substitution cf HDDA for HDDMA was believed to be responsible for this defect.

Comparative Formulation 9

A plastic lens composition including a monomer mixture consisting of:

29.54 parts by weight of bisphenol A bis(allyl carbonate) (together with 2.26 partε by weight of DEG-BAC),

19.2 parts by weight of TTEGDA, 24.3 parts by weight of TRPGDA, 22.7 parts by weight of TMPTA, 1.9 parts by weight of εtyrene; a photosensitizer consisting of 0.0197 parts by weight of l-hydroxycyclohexyl phenyl ketone; and a mold release agent conεiεting of 1.8 ppm of Zelec® UN were placed in a reaction chamber diεpoεed between oppoεed glaεε moldε configured to generate poεitive ID, 3D and 5D correction lenses as well as negative ID lenses. The produced lenses were not thoroughly cured in the center and were flexible at high temperatures.

Example 5

The objective of thiε Example waε to produce optical lenεes, incorporating bisphenol A bis(allyl carbonate) that

were not brittle, had desirable color and clarity, and did not have any patterns, defects or aberrations.

In each trial of this Example bisphenol A bis(allyl carbonate) waε uεed. It waε determined that any yellowing problemε in lenεeε made from bisphenol A bis(allyl carbonate) could be counteracted and overcome by including a very small amount on the order of one drop or from about 0.2 to 0.4 ppm of styrene containing a blue dye including 9.10-anthracenedione, l-hydroxy-4-[(4-methylphenyl) amino] (available aε Thermoplast Blue 684 from BASF Wyandotte Corp. )

In each trial cf this Example, Sylvania Fluorescent (F158T/2052) lamps which generate an intensity of 5.0 to 6.6 mW/sqcm of UV light were uεed aε a light εource.

Formulation 10A A plaεtic lens composition including a monomer mixture consisting of:

24.50 parts by weight of bisphenol A bis(allyl carbonate), 16.2 partε by weight of TTEGDA, 16.7 partε by weight of TRPGDA, 16.7 partε by weight of TMPTA, 22.7 partε by weight of HDDMA, 3.0 partε by weight of styrene; a photosenεitizer consisting of 0.023 parts by weight of l-hydroxycyclohexyl phenyl ketone; and a mold release agent consiεting of 0.7 ppm of Zelec® UN were placed in a reaction chamber diεpoεed between oppoεed 660 and 520 glass molds configured to generate a negative correction lens. The molds were separated a distance of 4.8 mm by a gaεket. The lenε compoεition waε irradiated for approximately 20 minutes.

The intenεity of ultraviolet light entering the mold waε 2.2 mW/sqcm from above and 2.5 mW/sqcm from below. Frosted glass was used in place of the inεulating powerless glass moldε.

The finished lens had good color and clarity, no patterns and good hardneεε without brittleneεs.

Formulation 10B

A plastic lens composition including a monomer mixture consisting of:

24.50 parts by weight of bisphenol A bis(allyl carbonate), 16.2 parts by weight of TTEGDA, 16.7 parts by weight of TRPGDA, 16.7 parts by weight of TMPTA, 22.7 parts by weight of HDDMA, 3.0 parts by weight of styrene; a photoεenεitizer conεiεting of 0.023 partε by weight of l-hydroxycyclohexyl phenyl ketone; and a mold releaεe agent conεiεting of 0.7 ppm of Zelec® UN were placed in a reaction chamber diεposed between opposed 550 and 775 glasε a * rM ι +"i τrρ ΛΠ T pn c

The moldε were εeparated a distance of 1.8 mm by a gasket. The lens composition was irradiated for approximately 20 minutes.

The intensity of ultraviolet light entering the mold was 2.2 mW/sqcm from above and 2.5 mW/sqcm from below.

Instead of froεted glaεs, clear radiation lenseε were used and tracing paper was used over the lamps with 2 εheetε at top and 1 εheet at bottom.

The finiεhed lenε had more favorable characteriεticε than the lenε of Formulation 10A.

Formulation 11

A plastic lens composition including a monomer mixture consiεting of:

25.60 partε by weight of bisphenol A biε(allyl carbonate), 15.1 parts by weight of TTEGDA, 16.1 partε by weight of TRPGDA, 16.5 partε by weight of TMPTA, 24.1 partε by weight of HDDMA, 2.5 partε by weight of εtyrene; a photoεensitizer consisting of 0.0195 parts by weight of 1-hydroxycyclchexyl phenyl ketone; and a mold release agent consisting of 1.0 ppm of Zelec® UN were placed in a reaction chamber dispoεed between oppoεed 550 and 775 glaεε molds configured to generate a positive correction lenε. The molds were separated a distance of 1.8 mm by a gasket.

Two sheetε of tracing paper were inserted between the powerleεs glass mold and the lenε forming mold on both sides of the reaction cell. The lens composition was irradiated for approximately 23 minutes.

The finished lens showed favorable characteriεticε.

Formulation 12 A plastic lenε compoεition including a monomer mixture consisting of:

25.10 parts by weight of bisphenol A bis(allyl- carbonate), 15.5 parts by weight of TTEGDA, 16.3 parts by weight of TRPGDA, 16.7 partε by weight of TMPTA, 23.6 parts by weight cf HDDMA, 2.7 partε by weight of styrene; a photosenεitizer conεiεting of 0.021 partε by weight of l-hydroxycyclohexyl phenyl ketone; a mold releaεe agent consisting of 0.88 ppm of Zelec® UN and one drop of styrene containing a blue dye including 9,10 - anthracenedione, l-hydroxy-4-[ (4-methylphenyl) amino] (available as Thermoplast Blue 684 from BASF Wyandotte Corp.) were placed in a reaction chamber disposed between opposed 550 and 775 glaεε moldε configured to generate a positive 2D correction lenε. The molds were separated a distance of 1.8 mm by a gasket. The lens composition waε irradiated for approximately 36 minutes.

The intensity of ultraviolet light entering the mold was 1.5 mW/sqcm from above and 2.4 mW/sqcm from below. The finished lens showed good color, waε free of diεtortion and waε more rigid than conventional thermally cured DEG-BAC lenεes. The lens alεo paεεed the safety drop-ball test after it had been in boiling water for 10 minutes.

Formulation 13 A plastic lens composition including a monomer mixture consisting of: -

25.82 parts by weight of bisphenol A bis(allyl- carbonate), 15.06 partε by weight of TTEGDA, 16.05 partε by

weight of TRPGDA, 16.30 parts by weight of TMPTA, 24.00 parts by weight of HDDMA, 2.76 parts by weight of styrene; a photosensitizer consisting of 0.025 parts by weight of l-hydroxycyclohexyl phenyl ketone; and a mold release agen consisting of 0.3 ppm of dioctylphthalate (available from Aldrich) were placed in a reaction chamber disposed betwee oppoεed 415 and 775 glaεε moldε configured to generate a positive 4D correction lenε. The moldε were εeparated a diεtance of 1.8 mm by a gaεkεt. The lenε compoεition waε irradiated for approximately 25 minutes.

The finiεhed lenε εhowed favorable characteristics.

A plastic lenε compoεition including a monomer mixtur conεiεting of:

26.70 parts by weight of bisphenol A bis(allyl- carbonate), 15.5 parts by weight of TTEGDA, 16.0 parts by weight of TRPGDA, 16.4 parts by weight of TMPTA, 22.4 part by weight of HDDMA, 3.0 parts by weight of styrene; a photoεenεitizer conεiεting ^' of 0.0204 partε by weight of l-hydroxycyclohexyl phenyl ketone; and a mold releaεe agen conεiεting of 2.5 ppm of Zelec-ϊ UN were placed in a reaction chamber diεpoεed between oppoεed 550 and 775 glas molds configured to generate a positive correction lens. The molds were separated a diεtance of 1.8 mm by a gaεket. The lenε composition waε irradiated for approximately 22 minutes.

The intensity of ultraviolet light at the surface of the light source was 4.8 mW/sqcm. The intensity of ultraviolet light entering the mold waε 3.6 mW/sqcm. The intensity of ultraviolet light exiting the mold was 1.5 mW/sqcm.

The finished lens showed a negligible degree of patterns and had good color. The patte nε that were developed in thiε lenε were believed to be cauεed by toe hich a proportion of Zelec® UN.

Comparative Formulation 15

A plastic lens composition including a monomer mixture consisting of:

26.50 parts by weight of bisphenol A bis(allyl- carbonate), 16.2 partε by weight of TTEGDA, 16.8 partε by weight of TRPGDA, 17.1 parts by weight of TMPTA, 23.3 partε ^• by weight of HDDMA, a photosensitizer consiεting of 0.0277 partε by weight of l-hydroxycyclohexyl phenyl ketone; and a mold releaεe agent consisting of 1.3 ppm of Zelec® UN were placed in a reaction chamber disposed between opposed 550 and 775 glasε moldε configured to generate a pcεitive correction lenε. The glass molds were separated a distance of 1.8 mm by a gaεket. The lenε compoεition was irradiated for approximately 16 minutes. The lens had a slightly frosty appearance and was ^" slightly yellow.

This trial demonεtrates that for some compositions the absence of styrene in the formulation will lead to a lenε having a froεty appearance.

The yellow appearance waε cauεed by a rapid temperature rise during the curing procesε.

The following are additional exampleε of illuεtrative polymeric compounds within the scope of the present invention. In each of the following examples bisphenol A bis(allyl carbonate) waε received from PPG Industries, Inc. in a form that included only the bisphenol A bis(allyl carbonate) monomer. Each acrylate monomer waε treated εeparately through an alumina column (approximately 60-70g alumina/500g monomer) in a 2 cm diameter column. ZELEC® UN waε uεed aε a mold release agent at a rate of 1.0 ppm based on the total weight of the composition. All sampleε were subjected to ultraviolet radiation for 30 minutes. The lens sampleε to be prepared were about -1/2D with a central thickneεs of about 2.2 mm and an edge

thicknesε of about 2.8 mm. Silicone gaskets with 3 mm lips were used for all tests.

In Table V below the following abbreviations have the following meanings:

HIRI meanε the bisphenol A bis(allyl carbonate) monomer, Irg. 184 means Irgacure 184, HD means hardneεε, FL means flexibility, HZ means hazineεε, Y meanε yellowneεε, NO meanε not obεerved, neg. meanε negligible, L meanε low, M means medium, H means high, and TPb meanε Thermoplast Blue 684 blue dye.

Also in Table V below all monomer concentrationε are -"T ^* "*-*-

0 25 cracked at edge 50

47 7 70

TABLE V. Cont

HIRr _„ T^PTA_TTJEGπA_ rRPUJDA-HJ)p Λ _„ .aLyi one

0 25 50 47 75 70.

20 20 60 20 60 20

19 19 57 5 .19 57 19 5

33 ^" 33 33

10 60 30

10 30 0

3 60 10

60 30 10

30 1 60

60 10 30 0 20 60 20 60 20

19 19 57 5 1 57 19 5

TABLE V. Con I

AR

HZ Comments

NO M NO cracked at edge whi le demolding

cracked whi 1o demo1di ng

cracked while demoIding

I cracked wh le σ

.fc- demol cling I

released and cracked at edge

cracked at edge while demolding

ABI K _. Y_(Cont_. )

_? ty_t qrie _ I rg.184 HD FI . HZ Comments

mol cracked due to alignment error

I σ uι

I

cracked at edge while demolding

cracked at edge while demolding cracked at edge while demolding cracked at edge while demol ing cracked whi le demo1 ing; 0.7 ppm TPb

TABLE V ..CP.πt: 1

00

80

00

00

0 100

25 75

50 50 0.019 84 L emo ng

47 47 6 0.018 85 1.

75 25 0.030 07 I.

70.5 23.5 6 0.020 06 L

100 0 0.036 05 L

0 1.00 0.006 77 I.

25 75 0.015 00 L

50 50 0.022 85 I.

47 47 6 _.v .200 03 I.

75 25 0.03 05 I,

70.5 23.5 6 0.028 04 L

100 0 0.036 05 L

TABLE V (Con , )

HIRI HZ Comments

NO neg NO I. N(J M cracked at edge while demolding

NO neg. 100% HDDA; cracked NO neg. 75% HDDA; cracked NO L 50% HDDA; released NO M 47% HDDA; released NO MH 25% HDDA; released NO H 23.5% HDDA; released ©

100 0.036 85 I, NO H 0% HDDA -j

I

NO neg NO L di fficult demolding NO L di f icult demolding NO L di fficult demolding NO LM di ficult demo l ing NO M released, dif icult demold ing

100 NO MH

TABlιE_ _, V _, (C nt_._)

TABLE_V_.{ on _ L

HIRI TMPTA TTEGDA TRPGDA HDDMA sty ne r_r_g _.184 HD FL

0 0.0035 60

25 0.0035 70 M 50 47

75 70. _ 100

0.0035 68

25 0.0045 68 M

50 47 75 70 100

33.3 33.3 33.3 0.0 L4 83 I. NO MH released after cracking during UV exposure

60 10 30 0.023 85 L NO H cracked at edge while demolding

TABLE. V_ Cont.._).

!U.1J ^" TMPTA TTEGDA TRPGDA HDDMA styrone Irg.184 HD EL.

20 60 20 0.015 83 L

60 20 20 0.025 06 1.

19 19 57 L 19 57 19 h 57 19 1.9 L cracking at edge during UV exposure

20 0.015 84 20 0.025 84

60 0.018 78

19 0.015 03

19 5 0.025 85 57 5 0.0L8 77

33.3 33.3 33.3 0.0J5 80

60 0.024 82 30 0.0152 82 60 0.0238 01

30 10 60 0.016 72 M

10 60 30 0.0093 77 10 30 60 0.0095 66 M

TABLE V (Cont.)

HTRT TMPTA TTEGDA TRPGDA HDDMA s rene Irg.184 HD FL HZ Comments

20 60 20 0.005 77 L NO L 60 20 20 0.005 00 1. NO L released at edge after cracking at edge during UV exposure

20 20 60 57 19 19 5

19 19 57 0.008 72

0.015 01

0.023 03 I.

0147 04 L 023 00 L released, cracked while demolding

30 10 0.013 70 I, NO 60% HDDA; cracked, released after cracking

10 60 0 0083 00 I. NO I. 30% HDDA 10 30 0 0075 70 L NO L 60% HDDA; cracked, released after c racking

TAH1,.I _.. V...(Cont. )

HIRT TMPTA TTEGDA TRPGDA HDDMA st rene _L_r_g . _, 104 HD _FL HZ Y Comments 0.01.3 70 M demolding 0.01 79 0.01 80

I

-J IΌ I

40 10 25 25 0.020 82 40 25 10 25 0.020 80

25 25 25 25% HDDA released after cracking

25 40 25 L0% HDDA released

25 10 25 40% HDDA cracked

TABLE__Y_(Cp _. nt_. _.

"J _. ^R T TMPTA TTEGDA TRPGDA HDDMA styrene HZ Y Comments

10

10

40 40 25 while demolding 25 25% HDDA

40 25% HDDA

25 10% HDDA cracked while demolding 25 25% HDDA released, cracked 10 25% HDDA released I

-J ω

I

T erefore, it can be seen that the preεent invention not only provides a method and apparatus for making plastic lenses, but provides lens forming compositions.

It is thus seen that the compositions and process of the present invention provide several advantages. For example, according to certain embodiments of the present invention, the light sources utilized to cure the lenε forming composition are safer, easier to use and consume less energy than conventional high pressure mercury arc lampε. Moreover, according to certain embodiments of the present invention a plastic optical lenε can be cured in 30 minutes or less. Furthermore, in certain embodiments of the present invention, the lens compoεition includes monomers having a higher refractive index than conventional monomer materials allowing the production of thinner lenses.

Although not specifically illustrated in the drawings, it is understood that other additional and necessary equipment and structural components will be provided, and that these and all of the components described above are arranged and supported in an appropriate faεhion to form a complete and operative system.

It is also understood that variations may be made in the present invention without departing from the εpirit and εcope of the invention. Of courεe, other variations can be made by those skilled in the art without departing from the invention as defined by the appended claims.