OPTICAL ARTICLE COMPRISING A DYE RESISTANT TO PHOTO-DEGRADATION

Abstract

The present invention relates to optical articles and optical filtering coatings comprising at least one absorbing dye comprising one of the groups of formulae of formulae (I), (II), (III) and (IV), wherein R represents an aryl or alkyi group, and the groups of formulae (I), (II), (III) and (IV) have at least one carbon atom substituted with a group chosen from OH, CN, bromo, NO.sub.2, alkoxy, aryloxy, COOH, CHO, COalkyl, COaryl, haloalkyl, SH, S-alkyl, S-aryl, SO.sub.2alkyl, OSO.sub.2alkyl, SO.sub.2aryl, OSO.sub.2aryl and sulfonamide, or have at least two carbon atoms substituted with a chloro group.

##STR00001##

Claims

1.-15. (canceled)

16. An optical article comprising at least one absorbing dye comprising any one of the following formulae: ##STR00025## wherein R represents an aryl or alkyl group, X.sup.1 and X.sup.2 independently represent O or a N-R.sup.1 group with R.sup.1 representing an alkyl or aryl group, and the groups of formulae (I), (II) and (III) have at least one carbon atom substituted with a group chosen from OH, CN, bromo, NO.sub.2, alkoxy, aryloxy, CO.sub.2H, CHO, COalkyl, COaryl, haloalkyl, SH, S-alkyl, S-aryl, SO.sub.2alkyl, OSO.sub.2alkyl, SO.sub.2aryl and OSO.sub.2aryl, or have at least two carbon atoms substituted with a chloro group, and wherein the dye of formula (III) does not comprise any SO.sub.3H group or a salt thereof, and the dye of formula (II) is not a compound having any one of the following formulae: ##STR00026##

17. The optical article of claim 16, wherein the absorbing dye at least partially inhibits transmission of light in at least one selected wavelength range included within a 100-380 nm wavelength range, a 380-780 nm wavelength range, and/or a 780-1400 nm wavelength range.

18. The optical article of claim 16, wherein the optical article has a substrate into which said at least one absorbing dye is incorporated.

19. The optical article of claim 16, wherein said at least one absorbing dye is incorporated into a coating deposited onto a main surface of said optical article.

20. The optical article of claim 19, wherein said coating is an antireflection coating, an abrasion- and/or scratch-resistant coating or a primer coating.

21. The optical article of claim 19, wherein said coating is an epoxy coating.

22. The optical article of claim 19, wherein said at least one absorbing dye is present in an amount ranging from 0.01 to 1.25% relative to the weight of the coating.

23. The optical article of claim 16, wherein the groups of formulae (I), (Ia), (II) and (III) have at least one carbon atom substituted with a group chosen from OH, CN, bromo, NO.sub.2, alkoxy and aryloxy.

24. The optical article of claim 16, wherein the groups of formulae (I), (II) and (III) have at least one carbon atom substituted with an electron donating group, and at least one carbon atom substituted with an electron withdrawing group, and the group of formula (Ia) has at least one carbon atom substituted with an electron donating group.

25. An optical filtering coating for an optical article comprising at least one absorbing dye comprising any one of the following formulae: ##STR00027## wherein R represents an aryl or alkyl group, X.sup.1 and X.sup.2 independently represent O or a N-R.sup.1 group with R.sup.1 representing an alkyl or aryl group, and the groups of formulae (I), (II), (III) and (IV) have at least one carbon atom substituted with a group chosen from OH, CN, bromo, NO.sub.2, alkoxy, aryloxy, CO.sub.2H, CHO, COalkyl, COaryl, haloalkyl, SH, S-alkyl, S-aryl, SO.sub.2alkyl, OSO.sub.2alkyl, SO.sub.2aryl, OSO.sub.2aryl and sulfonamide, or have at least two carbon atoms substituted with a chloro group, and wherein the dye of formula (III) does not comprise any SO.sub.3H group or a salt thereof.

26. The optical filtering coating of claim 25, wherein the coating is an epoxy coating.

27. The optical filtering coating of claim 25, wherein the coating is an antireflection coating, an abrasion- and/or scratch-resistant coating or a primer coating.

28. The optical filtering coating of claim 25, wherein said at least one absorbing dye is present in an amount ranging from 0.01 to 1.25% relative to the weight of the coating.

29. The optical filtering coating of claim 25, wherein said at least one absorbing dye has any one of the following formulae: ##STR00028##

30. A process for at least partially inhibiting transmission of light in at least one selected wavelength range, comprising the incorporation in an optical article of an absorbing dye comprising any one of the following formulae: ##STR00029## wherein R represents an aryl or alkyl group, X.sup.1 and X.sup.2 independently represent O or a N-R.sup.1 group with R.sub.1 representing an alkyl or aryl group, and the groups of formulae (I), (II) and (III) have at least one carbon atom substituted with a group chosen from OH, CN, bromo, NO.sub.2, alkoxy, aryloxy, CO.sub.2H, CHO, COalkyl, COaryl, haloalkyl, SH, S-alkyl, S-aryl, SO.sub.2alkyl, OSO.sub.2alkyl, SO.sub.2aryl and OSO.sub.2aryl, or have at least two carbon atoms substituted with a chloro group, and wherein the dye of formula (III) does not comprise any SO.sub.3H group or a salt thereof, and the dye of formula (II) is not a compound having any one of the following formulae: ##STR00030##

Description

EXAMPLES

[0139] The optical articles used in the examples comprised an ORMA plano lens substrate from ESSILOR, having a 65 mm diameter, a refractive index of 1.50, a power of 2.00 diopters and a thickness of 1.2 mm.

[0140] In examples 1-10 and comparative examples C1-C6, the dyes were incorporated into an epoxy coating composition containing UVACure 1500 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, from Allnex USA Inc., 281 g), Erisys GE-60 (sorbitol hexaglycidyl ether, abbreviated as GE-60, from CVC thermoset Specialties, 34 g), Erisys GE-30 (trimethylolpropane triglycidyl ether, abbreviated as GE-30, from CVC thermoset Specialties, 69 g), propylene glycol methyl ether as a solvent (Dowanol PM from Dow Chemical Company, 560 g), a surfactant (EFKA 3034, which is a fluorocarbon containing organically modified polysiloxane, 50% wt. in methoxypropanol sold by CIBA, 1 g), and a Lewis acid polymerization catalyst for the epoxy groups (Nacure Super XC-A218, also named K-pure CXC-1613, metal salt of triflic acid in n-butanol, 25% wt., from King Industries, 55 g).

[0141] In examples 11 and 12, the dyes were incorporated into commercial sol-gel abrasion-resistant coating compositions mainly containing organo-polysiloxanes, silica colloids or titanium dioxide colloids, methanol and/or 1-methoxy-2-propanol, namely Essilor Altius (example 11) and SDC CrystalCoat C-410 (example 12).

[0142] In examples 13 and 14, the dyes were incorporated into the lens substrate by a tinting process.

[0143] The following dyes according to the invention were used: Solvent Yellow 157 ( max=441 nm, quinophthalone dye), Solvent Yellow 114 ( max=446 nm, quinophthalone dye), Solvent Yellow 176 ( max=450 nm, quinophthalone dye), LUMOGEN F Yellow 083 ( max=476 nm, perylene dye), LUMOGEN F Orange 240 ( max=528 nm, perylene dye), LUMOGEN F Red 300 ( max=577 nm, perylene dye), Disperse yellow 42 ( max=415 nm, nitrodiphenylamine dye), Disperse yellow 86 ( max=419 nm, nitrodiphenylamine dye), Disperse yellow 114 ( max=424 nm, diarylazo dye), Disperse yellow 211 ( max=437 nm, diarylazo dye).

[0144] The following comparative dyes were used: Solvent Yellow 33 ( max=442 nm, quinophthalone dye), Food Yellow 13 ( max=442 nm, quinophthalone dye), perylene ( max=440 nm, perylene dye), Solvent Green 5 ( max=460 nm, perylene dye), Disperse yellow 26 ( max=410 nm, nitrodiphenylamine dye), the yellow dye of formula (V) ( max=460 nm, diarylazo dye).

[0145] The structures of the various dyes employed herein are recalled hereunder:

TABLE-US-00001 Solvent Yellow 33 Food Yellow 13 Dye (comparative) (comparative) Structure [00009] [00010] Dye Solvent Yellow 157 Solvent Yellow 114 Structure [00011] [00012]

TABLE-US-00002 Solvent Yellow Perylene Dye 176 (comparative) Structure [00013] [00014] Solvent Green 5 LUMOGEN F Yellow Dye (comparative) 083 Structure [00015] [00016]

TABLE-US-00003 Dye LUMOGEN F Orange 240 LUMOGEN F Red 300 Structure [00017] [00018]

TABLE-US-00004 Disperse yellow 26 Dye (comparative) Disperse Yellow 42 Disperse Yellow 86 Structure [00019] [00020] [00021]

TABLE-US-00005 Yellow dye of formula (V) Dye (comparative) Disperse yellow 114 Disperse yellow 211 Structure [00022] [00023] [00024]

1. Incorporation of Dye into a Coating

[0146] The components of the formulations were mixed together well by a stirrer to obtain a 1000 g epoxy coating solution (examples 1-10, C1-C6). The dye (0.04 g for all examples, except example 3: 0.03 g and examples 11, 12: 0.02 g) was added to 100 g of the coating solution (99.8 g for examples 11, 12) and dissolved with the help of a stirrer or an ultrasonic bath.

[0147] The prepared formulations contained around 40% by weight of solids in examples 1-10 and C1-C6 (dry extract weight relative to the weight of the composition). Each of the coating solutions was deposited by dip coating onto both faces of an Orma lens previously cleaned with diluted NaOH, at a speed of 2.0 mm/s. A pre-curing at 75 C. for 15 minutes and a post-curing at 100 C. (110 C. for example 12) for 3 hours were then performed. The coating thicknesses were about 5 m (3-5 m for examples 11, 12).

2. Incorporation of Dye into a Substrate by a Dip Tinting Process

[0148] A tinting bath was prepared by adding to 1 L of water heated at 85 C. 6 g of the dispersing agent Super NSI (Sodium and potassium dinaphthalene methanesulphonate). While the mixture was continuously heated and stirred, 1.5 g of dye was added and the mixture was stirred for 2 hours at 94 C. In the end, the solution was covered with a lid.

[0149] The Orma lens substrates were cleaned with the solvent Techsolv SR to remove potential stains or any foreign materials, placed onto a substrate holder and dipped in the tinting bath for 10 minutes (example 14) or 30-60 minutes (example 13). The tinted substrates still hold by the substrate holder were removed from the tinting bath, cleaned by rinsing in a deionized water bath to remove dye particles adhered to the substrate, placed into an oven and cured at 100 C. for 2 hours.

3. Evaluation of the Coating Performances

[0150] a) Dye photo-degradation in coatings was measured by subjecting the prepared lenses to the Q-sun test. This test uses a Q-SUN Xe-3 xenon chamber, purchased from Q-LAB, at a relative humidity of 20% (5%) and at a temperature of 23 C. (5 C.).

[0151] A sample lens coated with a coating containing at least one dye was measured by a Cary 50 spectrophotometer to get a transmission (T %) spectrum. Then the lens was introduced in the xenon chamber and its convex side was exposed to the light for 40 hours (h) inside the Q-sun chamber. The lens was measured by the Cary 50 spectrophotometer again to get a T % spectrum. An uncoated Orma lens was used as the reference lens, tested before & after the 40 hours of sun exposure test as well. Because there was very little change of the Orma lens spectrum before & after the sun exposure test, its change was neglected during the calculation.

[0152] The formula used to calculate the photo-degradation level of the dye in a coating coated on Orma lens or in a tinted Orma lens is described below, using the transmittance % at max:

Dye photo-degradation=(T %.sub.dye max 40hT %.sub.dye max Oh)/(T %.sub.Orma max 40h T %.sub.dye max Oh)

[0153] For example, an Orma lens coated with a dye containing coating (max of the dye: 580 nm) showed 80% of transmittance initially, which changed to 86% after 40 hours of Q-sun exposure test. The reference Orma lens showed 92% of initial transmittance at 580 nm, which only changed to 91.8% after 40 hours of Q-sun exposure, indicating almost no change of Orma lens at this wavelength. In this case, blue dye photo-degradation=(8680)/(9280)*100=50%.

[0154] b) Haze was measured as disclosed in WO 2012/173596, on a Hazeguard XL 211 Plus apparatus from BYK-Gardner in accordance with the standard ASTM D1003-00. As haze is a measurement of the percentage of transmitted light scattered more than 2.5 from the axis of the incident light, the smaller the haze value, the lower the degree of cloudiness. Generally, for optical articles described herein, a haze value of less than or equal to 0.3% is acceptable, more preferably of less than or equal to 0.2%.

4. Incorporation of Dye into Epoxy and Sol-Gel Coating Compositions: Results

[0155] The various dyes used to prepare the compositions 1-12 according to the invention and the comparative compositions C1-C6 as well as the results of the tests performed are shown in the tables hereunder.

TABLE-US-00006 Example C1 C2 1 2 3 Dye Solvent Food Solvent Solvent Solvent Yellow 33 Yellow 13 Yellow 157 Yellow 114 Yellow 176 Photo- 91 87 19 9 2 degrada- tion (%) Haze 0.1 0.1 1 0.1 0.1 (%)

TABLE-US-00007 Coating C3 C4 4 5 6 Dye Perylene Solvent LUMOGEN F LUMOGEN F LUMOGEN F Green 5 Yellow 083 Orange 240 Red 305 Photo- 86 45 20 21 15 degradation (%) Haze (%) 0.1 0.1 0.1 0.1 0.1

TABLE-US-00008 Coating C5 7 8 C6 9 10 Dye Disperse Disperse Disperse Yellow dye of Disperse Disperse Yellow 26 Yellow 42 Yellow 86 formula XX Yellow 114 Yellow 211 Photo- 50 20 0 >40 15 <10 degradation (%)

TABLE-US-00009 Example 11 12 Dye Solvent Yellow 114 Solvent Yellow 114 Coating solution Essilor Altius SDC CrystalCoat C-410 Photo-degradation (%) 27 23 Haze (%) 0.1 0.1

[0156] The tables show that the photo-degradation of dyes having a structure according to the invention is very limited under the Q-sun test conditions when incorporated into a coating (<27%), while comparative dyes are much more unstable under the same conditions (45-91% of degradation).

[0157] The haze of all coated lenses was 0.1%, except for example 1. In example 1, the level of haze was higher due to poor solubility of Solvent Yellow 157 in the coating composition. A low haze result demonstrates that there is a good compatibility between the coating components and the dye molecules.

5. Photo-Degradation Results after Deposition of Further Coatings onto the Dye-Containing Coating

[0158] A means to reduce and even eliminate the photo-degradation of the dye is to deposit on the coating containing the dye an antireflection coating acting as an oxygen barrier or an UV shield. Two of such antireflection coatings have been used in the examples shown in the tables below and eliminated the photo-degradation of dyes according to the invention (Solvent Yellow 157 and Solvent Yellow 114) during the Q-sun photo-degradation test, while the same antireflection coatings only allowed to reduce photo-degradation down to 36-57% for comparative dyes (Solvent Yellow 33 and Solvent Green 5). Thus, even if the dyes according to the invention undergo up to 20-25% degradation during the Q-sun photo-degradation test in examples 1-12, they are good candidates for ophthalmic lens applications as such degradation can be suppressed by the presence of an anti-reflection coating.

TABLE-US-00010 Example C1 C1-1 C1-2 C1-3 Epoxy coating Yes Yes Yes Yes containing 0.04% dye Primer + Hard coat No Yes Yes Yes Antireflection coating 1 No No Yes No Antireflection coating 2 No No No Yes Photo-degradation (%) 91 88 57 50

TABLE-US-00011 Example C4 C4-1 C4-2 C4-3 Epoxy coating Yes Yes Yes Yes containing 0.04% dye Primer + Hard coat No Yes Yes Yes Antireflection coating 1 No No Yes No Antireflection coating 2 No No No Yes Photo-degradation (%) 45 45 40 36

TABLE-US-00012 Example 1 1-1 1-2 1-3 Epoxy coating Yes Yes Yes Yes containing 0.04% dye Primer + Hard coat No Yes Yes Yes Antireflection coating 1 No No Yes No Antireflection coating 2 No No No Yes Photo-degradation (%) 19 17 1 0

TABLE-US-00013 Example 2 2-1 2-2 2-3 Epoxy coating Yes Yes Yes Yes containing 0.04% dye Primer + Hard coat No Yes Yes Yes Antireflection coating 1 No No Yes No Antireflection coating 2 No No No Yes Photo-degradation (%) 9 10 0 0

[0159] The primer mentioned in the above tables is a polyurethane-based impact-resistant primer with a thickness of 1 micron (Witcobond latex W-234). The hard coat mentioned in the above tables is an abrasion-resistant coating with a thickness of 3 microns obtained by depositing and curing the composition of example 3 of the patent EP 0614957 (comprising -glycidoxypropyl trimethoxysilane, dimethyldiethoxysilane, colloidal silica and aluminium acetylacetonate; refractive index: 1.5). The antireflection coating 1 is the front face antireflective coating of example 1 of WO 2013/171435, with a 6.5 nm thick indium tin oxide layer interleaved between the 73 nm thick ZrO.sub.2 layer and the 110 nm thick SiO.sub.2 layer. The antireflection coating 2 is the antireflective coating of example 6 of the patent application WO 2008/107325. Said coating was deposited by evaporation under vacuum on the underlying abrasion resistant coating.

[0160] It can be seen that the primer and hard coat, deposited in this order on the dye-containing epoxy coating, hardly alter the resistance to photo-degradation of the dye present in the epoxy coating.

6. Incorporation of Dye into a Substrate: Results

[0161] The levels of photo-degradation observed when the dyes were incorporated into a substrate are comparable with those obtained when the dyes were incorporated into an epoxy coating.

TABLE-US-00014 Example 13 14 Dye Solvent Yellow 157 Disperse Yellow 114 Photo-degradation (%) 17 12 Haze (%) <0.5 <0.5

[0162] Other dyes were also successfully incorporated into the substrate by a tinting process and provided low photo-degradation levels (Solvent yellow 114, Solvent Yellow 176, Disperse Yellow 211, Disperse Yellow 42, and Disperse Yellow 86).