CA2247298A1 - Color-neutral uv blocking coating for plastic lens - Google Patents

Abstract

Polymeric coatings containing both UV absorbers and dyes are employed to produce transparent, durable film coatings that can significantly increase the level of UV radiation blockage when coated onto substrates including ophthalmic lenses. The dye comprises 1-¢(4-methylphenyl)amino!-4-hydroxy-9,10-anthracenedione. The color-neutral film coatings are resistant to weather and UV degradation.

Description

W O 97130362 PCTrUS97/02378 COLOR-NEUTR~L UV BLOCKING C'OATING FOR PLASTIC LENS

Reference to Provisional Application This application claims the benefit of U.S. Provisional Application Serial No. 60/01 1,537 filed February 13, 1996.
Field of the Invention This invention relates to stable color-neutral, abrasion resistant coatings with ultraviolet radiation blocking properties Such coatings are useful on substrates such as plastic ophthalmic lenses. The coatings of this invention have a neutral transmittance, a very desirable property particular]y when the coatingare used with ophthalmic lenses where UV ~locking of the UV-A region below 10 about 400 nrn i5 required.
Back~round of the Invention Ophthalmic lenses are formed from glass or plastics. Plastics include, for example, polymers based on allyl diglycolcarbonate monomers and polycarbonates. Ophthalmic lenses are formed as a single integral body or as laminated lenses that are f'abricated by bonding two lens wafers (i.e., a front wafer and a back wafer) together with a transparent adhesive. T ~ n~tecl lens wafers are described, for example, in U.S. Patent Nos. 5,149,181, 4,857,553, and4,645,317.
Commercially avai]able plastic ophthalmic lenses are commonly coated with a thin polymeric scratch resistance coating. The thickness of the polymericscratch resistance coating will depend, in part, on the substrate material.
Abrasion resistant radiation curable coatings for polycarbonate substrates are described, for example, in U.S. Patent No. 4,954,591. The vast majority of ophthalmic lenses are clear.
Absorption of ultraviolet radiation, especially those having higher wavelengths, by the retina is believed to accelerate or cause retinal injuries such as macular degeneration. Specifically, epiderniological data correlates UV
sunlight exposure with the incidence of lenticular opacities (cataracts) and possibly with pseudo exfoliation in the eyes.

W O 97/30362 PCT~US97/02378 Consequently, there is a demand for finished eyeglass lenses, including sunglasses, with UV-A, absorption capabilities. Conventional methods of fabricating plastie len ,es with UV protection have added UV absorbers into the casting monomer systems that form the ophth~lmic lenses. Unfortunately, UV
S absorbers can interact with the casting monomer system thereby blocking complete polymerization. This results in a variety of lens defects including softness. The efi'ect i, exacerbated in prescription lenses where the thicker regions of the lens Will emit a more intense yellow color. The lens will provideUV-A protection but will be aesthetically undesirable.
U.S. Patent 5,013,608 describes a coatlng composition containing at least about 3% to about 20'Yo(wt) of coating solids of a tintability enhancing compound (i.e.. lJV a~bsorbers) in a base resin comprising an aqueous, aqueous-alcoholic, or alcoholic dispersion of colloidal silica, or a mixture of colloidal silica with a metal oxide, and a partial condensate of an epoxy-functional silanol which is blended with a partia] condensate of another silanol. A crosslinking agent and a curing cat~lyst are added to form purportedly highly tintable abrasion resistant coating compositions. The coating composition upon curing is alleged to forrn hard films that provide both abrasion resistance and high levels of tinting and, op~ionally, absorbance of ultraviolet radiation. Although this coating composition may be suitable for fabricating tinted articles such as sunglasses, it is not suitable for fabricating non-tinted articles. The reason is that these hard films invariably exhibit a yellowish hue.
U.S. Patent 5,3'71,138 describes a UV absorbing polysiloxane resin composition for coatin,g transparent sheets and plastic spectacle lenses. It is formed by adding water-based colloidal silica to a silanol blend, heating, incorporating additives and incorporating a U~f' absorbing material such as 2,2',4,4'-tetrahydroxy-tlenzophenone, benzothiazoles and benzotriazoles, U.S.
Patent 4,233,441 describes an acryloxybenzothiazole copolymerizable UV light absorber that can be copolymerized with monomers and oligomers by free radical or radiatioln curing. JP Patent 55093447 describes polycarbonate articles that are coated with an adhesive and an overcoat, which contains a benzotriazole-type UV absorber. This apparently prevents the substrate from dusting, alkali and solvent attack, and yellowing. U.S. Patent 4,216,267 describes a laminate that comprises a sheet of clear PVC or polycarbonate with a 0.1-10 mil thiek coating of an acrylic polyurethane and an acrylic UV
absorber. U.S. Patent 4,202,834 describes a copolymerizable UV light absorber, cyanodiphenyl-acryloxy-alkyl-allyl or substituted allyl ether, purportedly useful in providing UV protection to radiation cured coatings. U.S. Patent 4,284,485 describes a polyalkylpiperidine derivative as a UV absorber useful in coatings that are applied to various materials. JP Patent 50054670 describes polycarbonate moldings coated with solutions prepared by mixing siloxanes and UV absorbers (benzophenones, triazoles, and salicylates). A
preferred UV absorber is ~-hydroxy-4-octoxybenzophenone is claimed as one of the examples. ll.S. F'atent 5,013,608 describes a coating composition containing3-20% by weight (of coating solids) of a UV absorber used as a tintability 1 5 enhancer.
As is apparenl, the prior art methods of fabricating films with UV
radiation blocking properties are deficient in I number of respects. First~ for UV absorbers which are colorless or nearly colorless, UV blocking is incomplete in the UV-range of 290 nm-380 nm and at longer wavelengths.
These UV absorbers e xhibit maximum absorption at relatively short wavelengths in the UV spectrum. Subsequently, these U~' absorbers have the undesirable side effect of imparting a yellow hue to the coating at the concentrations needed for full UV blocking at these ranges. UV absorbers demonstrating incomplete UV-A blocking include acrylics, benzothiazoles and benzotriazoles, HALS
(hindered amino light absorbers), monohydroxy benzophenones and salicylates.
Second, when a UV absorber is capable of blocking the full UV-A range due to an absorption maximum at relatively long UV wavelengths, the UV
absorber is yellow and imparts a ye11Ow hue to the coating. This is caused by the absorption of visible light, particularly in the blue region (wavelengths above 400 nm) by these UV absorbers. This is part~cularly problematic for ophthalmic lenses where coatings are relative thin, e.g., from 0.1 llm to 25 ,um, and if full CA 02247298 l998-08-06 blocking of the UV-~ range or at longer wavelengths is desired, the UV
absorbers must have a strong absorption in those wavelength ranges. UV-A
absorbers in thii latter category include the dihydroxy benzophenones such as 2,2',4,4'-tetrahydroxy-benzophenone .
Summary of the Invention This invention is based in part on the discovery that the polymer compositions having both UV absorbers and dyes can be employed to produce transparent, durable lilms that can significantly increase the level of UV
radiation blockage when coated onto substrates including ophthalmic lenses. A
feature of the invention is that the addition of the dyes to the polymer compositions significantly enhances the optical qualities of the films by producing a stable, weather resistant coating that is color-neutral, that is, the coating does not exhibit a hue.
In one aspect. the invention is directed to a composition suitable for forming a stable color-neutral, transparent coating which includes:
(a) a polymeric composition;
(b) an ultraviolet absorber;
(c) an effective amount of a dye comprising 1-[(4-methylphenyl)amino]-4-hydroxy-9,10-anthracenedione to neutralize yellow color caused by said ultraviolet absorber; ;md (d) a solvent.
In another aspect, the invention is directed to a transparent article exhibiting low ultraviiolet radiation transmittance which includes:
(a) a substrate; and (b) a stable color-neutral coating on a surface of said substrate wherein the coating includes:
(i) a polymeric matrix;
(ii) an ultraviolet absorber; and (iii) an effective amount of a dye comprising 1-[(4-methylphenyl)amino]-4-hydroxy-9,10-anthracenedione to neutralize yellow color caused by said ultraviolet absorber.

In a further aspect, the invention is directed to a method of fabricating a transparent article exhibiting low ultraviolet radiation transmittance which comprises the steps of:
(a) providing a substrate; and (b) preparing a stable color-neutral coating on a surface of said substrate wherein the coating comprises:
(i) a polymeric matrix;
(ii~ an ultraviolet absorber; and (ih) an effective amount of a d~e comprising 1-[(4-methylphenyl)amino]-4-hydroxy-9,10-anthracenedione to neutralize yellow color caused by said ultraviolet absorber.
A preferred method of p,~parillg the stable color-neutral coating is by a process comprising:
(i) preparing a composition comprising a polymeric material, an ultraviolet absorber, an effective amount of a dye comprising 1-~(4-methylphenyl)amino]-4-hydroxy-9,l0-anthracenedione to neutralize yellow color caused by said ultraviolet absorber, and a solvent;
(ii) coating a layer of the composition on a surface of the substrate; and (iii) removing solvent from the layer to form the coating.
Preferred ultra~iolet absorbers include 2,2'-dihydroxy-4-methoxy benzophenone~ 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2,2',4,4'-tetrahydroxy benzophenone~ and mixtures thereof. Preferred polymeric materials include silanols, epoxies, acrylates, methacrylates, polyurethanes, melamines, and mixtures thereof.
Preferably, for transparent plastic ophthalmic lens, the color-neutral coating has a UV absorbance of about 98% or more (2% UV transmittance or less) measured at 380 nm and the coating is about l.S to about S.0 ~m thick.
(Transmittance is defined in accordance with ANSI Z 80.1-l99S). The coating can substantially absorb UV-A (315 nm - 380 nm) and UV-B (290 nm - 315 nm) radiation.

WO 97/30362 Pcrluss7/o2378 The coatings have excellent weatherahility, adhesion and abrasion resistance. The blue dyes for these applications are most preferably UV-resistant to avoid degradation of the dye with the consequent destruction of the neutral transmitta]lce. The blue dye is resistant to degradation or change of 5 color by the coating curing conditions and to the catalysts that bring about this curing. The UV absorbers must be also weather and coating-curing resistant and most preferably should be UV stabilizers such as the dihydroxy benzophenones The coatings used in this invention can be tintable or non-tintable.
Brief Description of the Drawin~s Figure I ~s a graph illustrating the spectral transmittance of an uncoated lens and of hard coated lenses (with and without UV absorbers~.
Detailed DescriPtion of the Preferred Embodiments This invention is directed to articles OJ substrates that are coated with a clear transparent, durable, abrasion resistant film (also referred to as a hard coating) which has ul~raviolet radiation absorbing properties. This film can be coated onto any suitable substrate such as pla.stic ophthalmic lenses. The film is prepared from a hard coating composition whlch comprises a mixture of a polymeric composition, an ultraviolet absorber, and a dye. Incorporation of the UV absorber not only significantly reduces UV transmittance, but it also improves the durability of the coated substrate to environmental exposure. The inventive coating apparently shields the coating/substrate interface, which is vulnerable to UV degradation, to excessive exposure to UV radiation.
Furthermore, incorpor;~tion of the dye to the coating composition provides a neutral color to the coating. The dye effectively elimin~tes the yellow hue thatis characteristic of prior art hard coatings and systems where UV cutoff is achieved by adding the UV absorbers to the monomers.
However, prior to describing the invention in further detail, the following terms will be defined:
The term ''substrate" refers to a material which preferably has superior structural and optical properties. Crystalline quart~., fused silica, soda-lime wO 97/30362 PCT/US97102378 silicate glass, and plastics such as from polymers based on allyl diglycol carbonate monomers (available as CR-39TM f1om PPG Industries, Inc., Hartford, Conn.) and polycarbonates such as LexanTM, available from General Electric Co., are preferred substrate materials. Substrates include ophthalmic lenses 5 (including sunglasses). Pret'erred ophthalmic lenses also include l~rnin~e-l lenses that are fabricated by bonding two lens wafers (i.e., a front wafer and a back wafer) together with a transparent adhesive. l ~min~d lens wafers are described, for example, in U.S. Patents 5,149,181, 4,857t~53, and 4,645,317 and U.K. Patent Application, GB 2,260,937A, all of which are incorporated herein.
10 Suitable substrates further include glass ophthalmic lenses, as described, for instance, in U.S. Patents 3,899,315 and 3,899,314, both of which are incorporated herein. Another preferred ophthalmic lens is a plastic lens available as SpectraliteT'~( from SOLA Optical USA and is described in U.S.
Patent 5,373,033. As used herein, the term "lens" refers to both single integral15 body and laminated types.
The material and dimensions (e.g., thickness) of the substrate employed will influence the formulation of the coating compositlon. Specifically, most glasses, for example, absorb ultraviolet light having a wavelength of less than about 260 nm. Thus, the UV absorber used need only be effective for many 20 applications above about 250 nm in this case. ~onversely, many plastics will transmit ultraviolet light having a wavelength of less than 260 nm. Thus, the type of UV absorber can be selected accordingly. Finally, since natural sunlightonly has ultraviolet liyht having a wavelength of about 290 nm and about 400 nm, for ophthalmic lens coatings, the UV absorber employed must be effective 25 in this range.
The term 'coating polymeric composition" or "polymeric composition"
refers to a composition that comprises monomers, oligomers, polymers, and mixtures thereof, which forrns the polymeric structure of the inventive durable,abrasive resistant coatings which are also referred to as hard coatings.
30 Preferably the monomers, oligomers, and/or polymers can be cured by heat, and/or actinic radiation. Initiators and/or catalysts can be added to facilitate W O 97/30362 PCT~US97N2378 polymerization and crosslinking. Preferred monomers, oligomers, and/or polymers for the polymeric composition include, for example, silanols, epoxies, acrylates, methacrylates, melamines, polysiloxanes"?olyurethanes, and mixtures thereof. Preferred siloxanes include, for example, RISiOl 5 an,d RIR2SiO in 5 which Rl and R2 aJe each independently selected from suitable functional groups including, for example, g~mm~lycidoxypropyl, methyl, phenyl, ethyl, propyl, and methacryloxypropyl.
Polysiloxanes are particularly suited for fabricating hard coatings for plastic lens. A preferred polysiloxane resin is available as TS-56HF (Tokuyama 10 Corporation, Japan). This product comes as two separate components A and B, one being the polymer system and the other being a catalyst solution. Coating polymeric compositions are further described in U.S. Patents 4,954,591 and 5,013,608, which an- incorporated herein. The resin compositi,on preferably includes a solvent to facilitate coating the resin composition onto a substrate 1~ surface. Suitable solvents include, for example, alcohols, glycol ethers, and a~et~s ~e.g., propyl and butyl).
The term "ultraviolet absorber" or "'UV absorber" refers to any suitable substance that absor,bs ultraviolet radiant energy, then dissipates the energy.
Preferred ultraviolet absorbers include, for example, substituted benzophenones,20 benzotriazoles and diphenyl acrylates and substituted or unsllbstinlted dihydroxy benzophenones. Particularly useful dihydroxy benzophenones have the structure:

OH O OH

R2~Rl preferably where Rl and R2 are each independently selected from the group consisting of H, OH, ard an alkoxy (i.e., OCnH2n+l) having I to 12 carbons.
Preferred dihydroxy benzophenones include 2,2'-dihydroxy-4-methoxy 30 benzophenone available as Cyasorb UV 24TM from Cytec Corporation, 2,2'-dihydroxy-4,4'dimethoxy benzophenone available as Uvinul D-49TM frorn WO 97l30362 Pcr/uss7l02378 BASF Corp., and 2.2',4.4'tetrahydroxy benzophenone available as Uvinul 3050TM (BASF'~, and mixtures thereof. Use of tetrahydroxybenzophenones in the coating provides for both a UV cut-off less than 400 nm and a smooth, clear, cosmetically superior coated film.
The amount of incident ultraviolet light blocked by the inventive coating can vary depending, for example, on the thickness of the coating and the amount of UV absorbers emp]oyed. For ophthalmic lenses, an absorbance of about 98%
or more (2% UV transmittance or less) measured at 380 nm is preferred. The coating can substantially absorb radiation in both the UV-A and UV-B regions.
The term "dye" generally refers to any suitable substance that neutralizes the yellow color Gaused by some UV absorbing materials. Preferred dyes include, for example, blue dyes or a mixture of solvent soluble dyes imparting ablue hue. The blue dye is used in combination with the dihydroxy benzophenones to obtain a neutral color must be also compatible with the coatings to obtain transparent coatings and preferably must be weather resistant.
A large proportion of prior art blue dyes are not weather resistant. Non-weatherresistant dyes will degrade over a short time relative to the life of the coatedarticle (e.g., ophthalmic lens) so that the yellow color that was being neutralized becomes evident. Further, the by-product of the degradation may also contribute to intensify the yellow hue. The blue dyes must also be resistant to chemical degradation or change of color by ingredients in the coating which normally are very aggressive such as asids, free radicals, and bases. The blue dyes must resist heat and actinic radiation used to cure polymeric compositions. A
particularly useful blue: dye which exhibit these characteristic is comprised of 1-[(4-methylphenyl)amino]4-hydroxy-9,10-anthracenedione that is available as Kayaset Blue A-2RTM (Nippon Kayaku, Japan~ and which has the following structure:

Many organic dyes are sensitive to the elements. particularly to UV
10 radiation. This is due to the high electron mobility in these dyes which accounts for their visual color and to the presence of anilino, imino, and simi~arly UV sensitive chemical groups. Without being bound by theory, the above referenced anthraquinone derivative is UV resistant because of the presence within the rnolecule of a hydroxybenzophenone moiety similar to the 15 one present in tJV absorbers that protect against UV radiation. This chemicalgroup converts UV radiation to non-UV radi~tion and heat as in the case of ordinary 2-hydroxy benzophenones.
METHODOLOGY
The process of fabricating an article coated with a transparent, durable 20 abrasion resiscant film comprises forrning a homogeneous coating polymeric composition comprising the polymeric composition, UV absorber, dye and solvent. Appropriate initiators an~/or catalysts are included where necessary.
The mixture is evenly coated onto a substrate, e.g., plastic lens, by conventional means such as spin coating or dip c~tinE~ The composition is cured to produce 25 a hard coating film. tt has been demonstrated that the UV 380 nm cutoff and higher ophth~lmic pe,~,lllance are achieved without the yellowing of the hard coating. The coatings can be tinted if desired~ for instance, to make "slln~l~c.ces." They can be therrnoplastic or therrnoset, polymerizable or already polymerized, crosslink~hle and non-crosclink~ble. When curing is needed, the 30 coatings can be cured by the known processes such as by thermal energy or actic radiation. Radiation and thermally curable coatings are preferred. The Wo 97l30362 PCT/US97/02378 coatings can be single Jayered or multilayerecl. Typically, the homogeneous coating polymeric composition comprises about 40% to 85% solvent, preferably about 70%. (All percentages herein are based on weight.) The proportion of solvent used wil] depend, in part, on the solubility of the UV absorber and other 5 components. Following removal of the solvent, the coating preferably comprisesabout from 0.5% to 50%, more preferably from 2% to 35% and most preferably from 6% to 2~% of the U~ absorber. High ~JV absorber levels approaching 50% are to be a~oided since this will decrease the abrasion resistance of the coating and consequently reduce the adhesion of the coating to the substrate.
The blue dye preferably comprises from about 0.00l% to 0.2% and more preferably from ().001% to 0.1% of the coating. The ba]ance of the coating comprises predominantly of the polymer matnx. There is generally an inverse relationship between the concentrations of the UV absorber and dye and tl-e thickness of the coating. Specifically, if a thin coating is desired or necessary for a particular application, then high concentrations of UV absorber and dye are required to achieve a desired level of UV blocking.
Typically the color-neutral, transparent coating has a thickness that ranges from about O.l to 20 ,um, and more preferably from 0.8 to 5 ~lm. The coating is expected to be stable or weather resistant in that it will remain substantially color-neutral for the expected life of the article or substrate that is coated. For ophthalmic lenses, it is expected lo be stable for at least about I to 2 years, preferably for about 2 to 3 years. Further, the coatings are resistant to weather and UV degradation with respect to both physical and optical characteristics .
It is expected tllat a coating composition comprising a catalyzed polymer, UV absorber, and dye, that is maintained at ambient temperature, can be employed for continuous coating applications. Indeed, for large scale coating ofophthalmic lenses, it is expected that up to 1(X~ liters or more of such a coating eomposition can be formulated and employed to continuously coat lenses without significant loss of the composition due to excessive polymerization prior wo 97/30362 PCT/USg7/02378 to being coated. The coating formulation (e.g., viscosity) can be adjusted so that uniform, thin films c~n be produced.
The UV absorber does not adversely affect the polymerization of the polymeric composition. Further, the dye remains stable in the resin composition 5 and subsequent abrasion resistant coating. The latter was unexpected since when blue dyes are added to a monomer cast cornposition containing allyl dig}ycol carbonate monomers, which is comrnonly employed to prepare ophthalmic lens, the dyes are degraded by the polymerization initiators.
An important advantage to mixing the dye with the polymeric 10 composition and UV absorber is that this produces color-neutral, UV blocking,abrasion resistant coatings of consistent quality. lt has been found that coating compositions without the dyes produce coatings that have a yellow hue.
Furthermore, the process of dipping the substrate into the dye solution is not acceptable for producing clear, non-tinted lenses because the necessary color 15 absorption is inconsistent from batch to batch and, indeed, within a given batch of lenses.
EXPERIMENTAL
ExamPle I A polymeric coating composition comprising 100 grams of the TS-56HF~TM, 3.13 grams of the UVinul 30~0TM, and 0.01 grams of the Kayaset Blue 20 A-2RTM was prepared as follows: the components A and B of the TS-56HFTM
resin were mixed together and stirred slowly for 24 hours at ambient temperature. The weighed amount of the UV absorber is then added slowly to the resin solution. Upon completing the addition, the solution is stirred for 30minutes more. Then, the blue dye is added to the resin solution and stirred for 25 30 minutes. At this point, the solution is ready for coating application.
Referring to Figure 1, this graph shows the transmittance spectrum curves from an uncoated lens (10), a hard coated lens without UV absorber and the dye (20), and a hard coated lens with UV absorber and blue dye (30). The lenses employed were fabricated from poly (diethylene glycol diallyl carbonate).30 Each lens prior to coating was about 2 mm. thick. A coating solution without the UV absorber and dye was used to coat a lens ~20). A second solution with Wo 97/30362 PCT/US97tO2378 the UA absorber and dye was coated on another lens. Both coatings had a thickness of 2 ~m. 'rhe hard coating which ~id not have the UV absorber and dye exhibited a yellowish hue whereas the hard coating which included the UV
absorber and dye was color neutral.
S Measurements show that the transmitlance for the uncoated lens (curve 10) was almost identical to that of the lens that was coated with the hard coating not having the UV absorber and dye (Curve 20). In contrast, the inventive lens coated with a hard coating with the UV absorber and dye (curve 30) shows a transmittance of less than 2% at 380 nm. The inventive coated lens also exhibits good abrasion resistance properties.
In the following Examples 2-4, the weather resistance of the inventive coating are demonstrated. Inventive and comparative lens substrates were subjected to various physical and optical tests, the procedures of which are described as follows:
1. Abrasion resistance test: A proprietary and automated scrubber having a steel wool #00 surface was utili7.ed. Each sample was scrubbered 75 cycles with the steel wool. Thereafter, abrasion was detected by visual inspection and graded in accordance with the following scale: A-No scratches sustained with rubbing; B-Scratches sustained slightly with rubbing; and C-Scratches sustained even with weak rubbing. (Uncoated CR-39 lenses are in this category.) 2. Adhesiveness test: The so-called cross-cut tape test, where 11 parallel lines each in two perpendicularly crossing directions are cut with a sharp razorblade, was employed. The lines are cut at fixed intervals of approximately I
mm, on the surface of the coating of a given sample to produce a total of 100 squares. Thereafter, adhesive cellophane tape is applied to the cut squares, thetape is peeled, and the squares on which the coat film remains are counted. The adhesiveness is nleasured by the number of squares rem~ining.

3. Hot water resistance test: A sample is placed in boiling water for one hour.

4. Yellowness index and white li~ht transmittance test: This test employed a Gardner Pacific Colorimeter XL 835.

W O g7130362 PCTrUS97/02378 5. Transmittance at 380 nm test: Spectrophotometric transmittance measured at 38Q nm.

6. Weatherin~ test: Samples were placed outdoors for five weeks, thereafter, the yellowness index or microcracking of the coatings were measured.
s Example 2 CR-39 plano lenses, 70 mm in diameter and 2 mm in thickness, which had been dipped in an aqueous 35% potassium hydroxide solution at 40~C for 60 seconds and then washed, were spin coated with a polymeric composition comprising hydrolyzed gamma-glycidoxypropryl trimethoxysilane 10 dissolved in methoxypropanol and then cured at 95~C for 4 hours. The solids content for polymeric composition was 30%. The coating thickness was 2.3 lum.

Similarly. after caustic etching, another set of plano lenses were coated with the same polymeric composition but funher including a UV absorber 15 (Cyasorb UV 24'M) and dye (Kayaset Blue A-2RTM). The coated lenses were cured in an oven at 9:5~C for 4 hours. The coating thickness was 2.3 ~m. The coating contained approximately 21.3~o UV absorber and 0.021% dye. The lenses that contained ~:he UV absorber with the blue dye had a neutral color.
The test results were ;tS follows:
I Gn , ~tive) I lnvéntive) coated, coated, UV absorber no additives and blue dye yellowness index 14 1.0 25 1~ . % 92 92 white light abrasion resistance A A
adhesiveness 100 100 hot water l~,;,is~.ce 100 100 30 weall.. ,.illg test, 5 weeks no change no change , %, at 380 nm. 24 0.2 As is apparent, the inventive coating provided excellent UV blocking and other optical propertie,.

W O 97/30362 PCTAUSg7/02378 Example 3 Caustic-erched and washed CR-3'J plano lenses prepared as in Example 2 were coated with a polymeric coating composition comprising 100 grams of TS-56HFTM, 3.13 grams of Uvinul 3050TM and 0.01 grams of Kayaset Blue A-2RTM. An ide:ntical control lens without adding the UV absorber and the 5 blue dye to the composition were also coated. The spin-coated lenses were cured in an oven The coating thickness for both cases was 2 ~m. The inventive coating contained approximately 9.5~o UV absorber and 0.03% dye.
The lenses with IJV absorber and the blue dye had a neutral color. The test results are as follows:
] 0 (Compar~tive) (InventlveJ
coated, co~ted, UV absorber no addi~ives and blue dye yellowness index 1 2 1.() tr~n ~e, %
white ligh~ 92 92 abrasion resistance A A
adhesiveness 100 100 hot water resistance 1()0 100 weathering test, 5 weeks no change no change re~ %, at 380 nm 27 1.~
Again, as in Example 2, the inventive coating provided excellent UV
30 blocking and other oplical p~opellies.

Example 4 SpectraliteTM plano lenses, from SOLA Optlcal USA, 2 mm in thickness, were surface-treated and then spin-coated with TR-65TM, a siloxane coating composition, available from Transitions Corporation. It should be noted 35 that an uncoated SpectraliteTM lens by itself has UV-A blocking capabilities.Another set of SpectraliteTM plano lenses was also coated with TR-65TM that contained UV absorbers comprising Cyasorb UV 24TM and Uvinul 3050TM, and Kayaset Blue A-2RTM. The spin-coated lenses for both formulations were cured in an oven at 105~C for 4 hours. The coating thickness was 2.2 ~Im for all W O 97/30362 PCT~US97/02378 lenses. The inventive coatings contained approximate]y 19% Cyasorb UV24TM, 23% Univul 2050TM, and 0.08% dye. The lenses were all color neutral. The results of the tests are as follows:

(Compara~ive) ~Inventive) coated, coated, UV absorber no additives and blue dye abrasion resistance A B-C
adhesiveness 100 95 As is apparent, high levels of UV absorber content adversely affected the abrasion resistance and adhesiveness.
Example 5 Inventive coated lenses prepared by the methods described in Examples 1, 2 and 3 were subjected to accelerated testing by exposure to radiation from a xenon larnp (without filter) in a HeraeusTM accelerated weathering device manufactured by DSET Laboratory. After 250 hours, the 20 lenses continued to exhibit excellent UV blocking without loss of white light transmittance or color neutrality.
Although only preferred embodiments of the invention are specifically disclosed and described above, it will be appreciated that many modifications and variations of the present invention are possible in light of the above 25 teachings and within the purview of the appended claims without departing from the spirit and intendecl scope of the invention.

Claims (25)

What is Claimed is:

1. A composition suitable for forming a stable color-neutral, transparent coating which comprises:
(a) a polymeric composition;
(b) an ultraviolet absorber;
(c) an effective amount of a dye comprising 1-[(4-methylphenyl)amino]-4-hydroxy-9,10-anthracenedione to neutralize yellow color caused by said ultraviolet absorber; and (d) a solvent.

2. The composition of claim 1 wherein the ultraviolet absorber is selected from the group consisting of 2,2'-dihydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2,2',4,4'-tetrahydroxy benzophenone, and mixtures thereof.

3. The composition of claim 1 wherein the ultraviolet absorber absorbs radiation substantially in the entire range between about 290 nm and 380 nm.

4. The composition of claim 1 wherein the polymeric composition comprises material selected from the group consisting of silanols, epoxies, acrylates, methacrylates, polyurethanes, melamines, and mixtures thereof.

5. The composition of claim 2 wherein the polymeric composition comprises material selected from the group consisting of silanols, epoxies, acrylates, methacrylates, polyurethanes, melamines, and mixtures thereof.

6. A transparent article exhibiting low ultraviolet radiation transmittance which comprises:
(a) a substrate; and (b) a stable color-neutral coating on a surface of said substrate wherein the coating comprises:
(i) a polymeric matrix;
(ii) an ultraviolet absorber; and (iii) an effective amount of a dye comprising 1-[(4-methylphenyl)amino]-4-hydroxy-9,10-anthracenedione to neutralize yellow color caused by said ultraviolet absorber.

7. The article of claim 6 wherein the ultraviolet absorber absorbs radiation substantially in the entire range between about 290 nm and 380 nm.

8. The article of claim 6 wherein the ultraviolet absorber is selected from the group consisting of 2,2'-dihydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2,2',4,4'-tetrahydroxy benzophenone,and mixtures thereof.

9. The article of claim 6 wherein the polymeric composition comprises material selected from the group consisting of silanols, epoxies, acrylates, methacrylates, polyurethanes, melamines, and mixtures thereof.

10. The article of claim 6 wherein the substrate is an ophthalmic lens.

11. The article of claim 10 wherein the coating has a thickness of about 0.8 µm to 20 µm.

12. The article of claim 10 wherein the ophthalmic lens is made of material selected from the group consisting of allyl diglycol carbonate monomers and polycarbonates.

13. The article of claim 8 wherein the polymeric composition comprises material selected from the group consisting of silanols, epoxies, acrylates, methacrylates, polyurethanes, melamines, and mixtures thereof.

14. The article of claim 6 characterized in that the coating remains color neutral for at least about 1-2 years.

15. A method of fabricating a transparent article exhibiting low ultraviolet radiation transmittance which comprises the steps of:
(a) providing a substrate; and (b) preparing a stable color-neutral coating on a surface of said substrate wherein the coating comprises:
(i) a polymeric matrix;
(ii) an ultraviolet absorber; and (iii) an effective amount of a dye comprising 1-[(4-methylphenyl)amino]-4-hydroxy-9,10-anthracenedione to neutralize yellow color caused by said ultraviolet absorber.

16. The method of claim 15 wherein the coating is preparing by a process comprising:
(i) preparing a composition comprising a polymeric material, an ultraviolet absorber, an effective amount of the dye to neutralize yellow color caused by said ultraviolet absorber, and a solvent;
(ii) coating a layer of the composition on a surface of the substrate; and (iii) removing solvent from the layer to form the coating.

17. The method of claim 15 wherein the polymeric material is selected form the group consisting of monomers and oligomers and the method comprises curing the polymeric material prior to removing the solvent.

18. The method of claim 15 wherein the ultraviolet absorber absorbs radiation substantially in the entire range between about 290 nm and 380 nm.

19. The method of claim 15 wherein the ultraviolet absorber is selected from the group consisting of 2,2'-dihydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4.4'-dimethoxy benzophenone, 2,2',4,4'-tetrahydroxy benzophenone, and mixtures thereof.

20. The method of claim 15 wherein the polymeric material comprises material selected from the group consisting of silanols, epoxies, acrylates, methacrylates, polyurethanes, melamines, and mixtures thereof.

21. The method of claim 15 wherein the substrate is an ophthalmic lens.

22. The method of claim 21 wherein the coating has a thickness of about 0.8 µm to 20 µm.

23. The method of claim 21 wherein the ophthalmic lens 15 made of material selected from the group consisting of allyl diglycol carbonate monomers and polycarbonates.

24. The method of claim 19 wherein the polymeric material comprises material selected from the group consisting of silanols, epoxies, acrylates, methacrylates, polyurethanes, melamines, and mixtures thereof.

25. The method of claim 15 characterized in that the coating remains color neutral for at least about 1-2 years.