POLYMERIZABLE AND POLYMER COMPOSITIONS FOR AN OPTICAL MATERIAL HAVING A REFRACTIVE INDEX OF 1.54-1.58, OPHTHALMIC LENS AND MANUFACTURING METHOD

Abstract

The invention relates to a polymerizable composition intended to form a polymer composition for an optical material, such as a substrate of an ophthalmic lens, to this polymer composition obtained by polymerizing the polymerizable composition and having a refractive index of from 1.54 to 1.58, to an ophthalmic lens comprising this polymer composition and to a method for manufacturing this optical material. The polymerizable composition has a refractive index of from 1.54 to 1.58, the polymerizable composition comprising: - at least one non-aromatic polyisocyanate compound comprising at least two —NCO groups; - at least one non-aromatic polythiol compound comprising at least two —SH groups; - at least one polyol, According to the invention, said at least one polyol comprises a polyether polyol.

Claims

1. A polymerizable composition intended to form a polymer composition for an optical material having a refractive index of from 1.54 to 1.58, the polymerizable composition comprising: at least one non-aromatic polyisocyanate compound comprising at least two —NCO groups; at least one non-aromatic polythiol compound comprising at least two —SH groups; at least one polyol, wherein said at least one polyol comprises a polyether polyol.

2. The polymerizable composition according to claim 1, wherein said at least one non-aromatic polythiol comprises at least three —SH groups, and wherein the composition further comprises at least one dithiol compound.

3. The polymerizable composition according to claim 2, wherein said at least one dithiol compound is an aliphatic dithiol .

4. The polymerizable composition according to claim 1, wherein said polyether polyol has a molecular weight greater than 900 g/mol and less than or equal to 2000 g/mol.

5. The polymerizable composition according to claim 1, wherein said polyether polyol has three to five OH groups.

6. The polymerizable composition according to claim 1, wherein said polyether polyol is selected from glycerol propoxylate, glycerol initiated polyoxypropylene polyols, sorbitol initiated polyoxypropylene polyols, propylene glycol initiated polyoxypropylene polyols, ethylene glycol initiated polyoxypropylene polyols, sucrose-initiated polyoxypropylene polyols and mixtures thereof.

7. The polymerizable composition according to claim 1, wherein said at least one non-aromatic polyisocyanate compound is an aliphatic or alicyclic diisocyanate.

8. The polymerizable composition according to claim 1, wherein said at least one non-aromatic polythiol compound is selected from dipentaerythritol hexakis 3-mercaptopropionate, pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis 3-mercaptoproprionate and mixtures thereof.

9. The polymerizable composition according to claim 1, wherein the molar ratio [SH]:[OH] in the polymerizable composition is greater than or equal to 5 and less than or equal to 24 .

10. The polymerizable composition according to claim 1, wherein the polymerizable composition comprises: 35% by weight or more of said at least one non-aromatic polyisocyanate compound; 20% by weight or more of said at least one non-aromatic polythiol compound; and 1% by weight or more of said at least one polyether polyol.

11. A polymer composition for an optical material having a refractive index of from 1.54 to 1.58, wherein the polymer composition comprises a polymerization product of the polymerizable composition according to claim 1.

12. The polymer composition according to claim 11, wherein the polymer composition has a glass-transition temperature Tg, measured by Dynamic Mechanical Analysis (DMA) or by Differential Scanning Calorimetry (DSC), which is greater than or equal to 100° C. and less than or equal to 150° C.

13. The polymer composition according to claim 11, wherein the polymer composition has a storage modulus E′, measured à 25° C. by Dynamic Mechanical Analysis (DMA), which is greater than or equal to 3.0 GPa.

14. An ophthalmic lens comprising the polymer composition of claim 11.

15. A method for producing an optical material having a refractive index from 1.54 to 1.58, the method comprising: a) mixing: at least one non-aromatic polyisocyanate compound comprising at least two -NCO groups; at least one non-aromatic polythiol compound comprising at least two -SH groups; at least one polyol which comprises a polyether polyol; and optionally at least one dithiol compound, in case said at least one non-aromatic polythiol comprises at least three —SH groups, to form a polymerizable composition; and b) polymerizing the polymerizable composition in a mold to obtain a polymer composition forming said optical material.

16. The polymerizable composition according to claim 3, wherein said at least one dithiol compound is selected from 1,5-pentanedithiol, 1,4-butanedithiol, 1,3-propanedithiol, 1,10-decanedithiol, 1,2-butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol and mixtures thereof.

17. The polymerizable composition according to claim 7, wherein said at least one non-aromatic polyisocyanate compound is selected from isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, butamethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate, trimethyl-1,6-diisocyanatohexane, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane and mixtures thereof.

18. The polymerizable composition according to claim 9, wherein the molar ratio [SH]:[OH] in the polymerizable composition is greater than or equal to 10 and less than or equal to 14.

19. The polymerizable composition according to claim 10, wherein the polymerizable composition comprises: from 45% to 60% of said at least one non-aromatic polyisocyanate compound; from 25% to 35% of said at least one non-aromatic polythiol compound; and from 1.5% to 5% of said at least one polyether polyol.

20. The ophthalmic lens according to claim 14, wherein the composition forms a substrate of the lens.

Description

DETAILED DESCRIPTION OF INVENTION AND PREFERRED EMBODIMENTS

[0061] The terms “comprise” (and any grammatical variation thereof, such as “comprises” and “comprising”), “have” (and any grammatical variation thereof, such as “has” and “having”), “contain” (and any grammatical variation thereof, such as “contains” and “containing”), and “include” (and any grammatical variation thereof, such as “includes” and “including”) are openended linking verbs. They are used to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps or components or groups thereof. As a result, a method, or a step in a method, that “comprises,” “has,” “contains,” or “includes” one or more steps or elements possesses those one or more steps or elements, but is not limited to possessing only those one or more steps or elements.

[0062] Unless otherwise indicated, all numbers or expressions referring to quantities of ingredients, ranges, reaction conditions, etc. used herein are to be understood as modified in all instances by the term “about.” Also unless otherwise indicated, the indication of an interval of values « from X to Y » or “between X to Y”, according to the present invention, means as including the values of X and Y.

General Usable Features of Optical Lenses According to the Present Invention

[0063] In a known way, an ophthalmic lens according to the invention may comprise a multilayer coating surmounting a front main face of said substrate (a rear main face of the substrate being intended to be adjacent the wearer’s eye).

[0064] In certain applications, it is preferable for the front main face of the substrate to be coated with one or more functional coatings prior to the deposition of said multilayer coating. These functional coatings, which are conventionally used in optics, may be, non-limitingly, an anti-shock primer layer, an anti-abrasion and/or anti-scratch coating, a polarizing coating, a photochromic coating or a colored coating. Generally, this front main face of the substrate is thus coated with an anti-shock primer layer, an anti-abrasion coating and/or an anti-scratch coating, or an anti-shock primer layer coated with an anti-abrasion and/or anti-scratch coating.

[0065] These abrasion-and/or scratch-resistant coatings are preferably hard coatings based on poly(meth)acrylates or silanes generally comprising one or more mineral fillers intended to increase the hardness and/or the refractive index of the coating once cured, and they are preferably produced from compositions comprising at least one alkoxysilane and/or one hydrolysate thereof, for example obtained by hydrolysis with a hydrochloric acid solution and optionally condensation and/or curing catalysts. Mention may be made of coatings based on hydrolysates of epoxysilanes such as those described in documents FR 2702486 (EP 0614957), US 4,211,823 and US 5,015,523.

[0066] The anti-abrasion and/or anti-scratch coating composition may be deposited on the main face of the substrate by dip coating or spin coating. It is then cured using the appropriate process (preferably thermally, or under UV). The thickness of the anti-abrasion and/or anti-scratch coating generally varies from 2 .Math.m to 10 .Math.m, and preferably from 3 .Math.m to 5 .Math.m.

[0067] Prior to the deposition of the anti-abrasion and/or anti-scratch coating, it is possible to deposit, on the substrate, a primer coating (also called a tie layer) that improves the resistance to shocks and/or the adhesion of subsequent layers in the final product. This coating may be any anti-shock primer layer conventionally used for articles made of transparent polymer, such as ophthalmic lenses.

[0068] Among preferred primer compositions, mention may be made of compositions based on thermoplastic polyurethanes, such as those described in documents JP 63-141001 and JP 63-87223, poly(meth)acrylic primer compositions, such as those described in document US 5,015,523, compositions based on thermoset polyurethanes, such as those described in document EP 0404111 and compositions based on poly(meth)acrylic latex or polyurethane latex, such as those described in documents US 5,316,791 and EP 0680492. Preferred primer compositions are compositions based on polyurethanes and compositions based on latex, in particular polyurethane latexes optionally containing polyester units.

[0069] It is also possible to use in the primer compositions blends of these latexes, in particular polyurethane latex and poly(meth)acrylic latex.

[0070] These primer compositions may be deposited by dip coating or spin coating then dried at a temperature of at least 70° C., possibly of as high as 100° C., and preferably of about 90° C., for a time of 2 minutes to 2 hours, and generally of about 15 minutes, in order to form primer layers having thicknesses, post-bake, of 0.2 .Math.m to 2.5 .Math.m, and preferably of 0.5 .Math.m to 1.5 .Math.m.

[0071] Before the multilayer coating is deposited on the substrate optionally coated for example with an anti-abrasion layer, it is possible to subject the surface of said optionally coated substrate to a chemical or physical activation treatment intended to increase the adhesion of the coating. This pre-treatment is generally carried out under vacuum. It may be a question of a bombardment with energetic species, for example an ion beam (ion precleaning or IPC), of a corona-discharge treatment, of an electron beam, of a UV treatment, or of a treatment by plasma under vacuum, generally an argon or oxygen plasma. It may also be a question of an acid or basic surface treatment and/or of a surface treatment with solvents (water or organic solvent).

[0072] The various layers of the multilayer coating and the optional underlayer are preferably deposited by vacuum deposition using one of the following techniques: [0073] (i) evaporation, optionally assisted by ion beam, [0074] (ii) ion-beam sputtering, [0075] (iii) cathode sputtering, or [0076] (iv) plasma-enhanced chemical vapor deposition.

[0077] These various techniques are described in the works “Thin Film Processes” and “Thin Film Processes II” Vossen & Kern, Ed., Academic Press, 1978 and 1991, respectively. One particularly recommended technique is the technique of vacuum evaporation.

[0078] Preferably and as indicated above, the deposition of each of the layers of said coating and the optional underlayer is carried out by vacuum evaporation.

[0079] The ophthalmic lens of the invention may be made antistatic, i.e. not retain and/or develop an appreciable electrostatic charge, by virtue of the incorporation of at least one electrically conductive layer in said multilayer coating. This electrically conductive layer is preferably located between two layers of said coating, and/or is adjacent to a high-refractive-index layer of this coating. Preferably, this electrically conductive layer is located immediately under a said low-refractive-index layer and ideally forms the penultimate layer of said coating, it being located immediately under the most external (low-index, e.g. silica-based) layer of said coating.

[0080] The electrically conductive layer must be sufficiently thin to not alter the transparency of said coating, and it is preferably manufactured from a highly transparent electrical conductor. In this case, its thickness varies preferably from 1 nm to 15 nm, and better still from 1 nm to 10 nm. This conductive layer preferably comprises an optionally doped metal oxide, chosen from oxides of indium, of tin, of zinc and mixtures thereof. Indium-tin oxide (In2O3:Sn for tin-doped indium oxide), aluminum-doped zinc oxide (ZnO:Al), indium oxide (In2O3) and tin oxide (SnO2) are preferred. Even more preferably, this optically transparent conductive layer is a layer of indium-tin oxide (ITO) or a layer of tin oxide.

[0081] An ophthalmic lens according to the invention may also comprise complementary functionalities such as, non-limitingly: [0082] coatings formed on the external (i.e. exposed) surface of said multilayer inorganic coating and capable of modifying its surface properties, such as for example an anti-fouling or anti-fog top coat (external coating); [0083] specific filtration functionalities such as for example filtration of the UV, of the blue-violet (400 nm-460 nm), or other visible wavelengths, or IR, within a coating, a laminated film, a wafer in or at the surface of the substrate or directly integrated into the substrate either through tinting or in mass in the polymer; and/or [0084] a polarizing function.

[0085] By way of anti-fouling coatings, which may typically be hydrophobic and/or oleophobic and which have a thickness in general smaller than or equal to 10 nm, preferably of 1 nm to 10 nm, and better still of 1 nm to 5 nm, mention may be made of coatings of fluorosilane or fluorosilazane type which may be obtained by depositing a fluorosilane or fluorosilazane precursor, preferably comprising at least two hydrolysable groups per molecule. The precursor fluorosilanes preferably contain fluoropolyether groups and better still perfluoropolyether groups.

[0086] Thus, an ophthalmic lens according to the invention may for example comprise a substrate coated in succession on its front main face with an anti-shock primer layer, an anti-abrasion and/or anti-scratch layer, said multilayer coating and a hydrophobic and/or oleophobic top coat.

[0087] As for the rear main face of the substrate, it may for example be coated, in succession, with an anti-shock primer layer, an anti-adhesion and/or anti-scratch layer, an antireflection coating preferably with a low reflectance in the domain of the UV and a hydrophobic and/or oleophobic coating.

[0088] The following examples illustrate the present invention in a more detailed, but non-limiting manner.

Example 1

[0089] A polymer composition according to the invention was prepared in the following manner detailed in Table 1 below, by first preparing two separate parts A and B each consisting of the following ingredients (each being identified by its function, chemical tradename, supplier, CAS number and mass fraction in the whole mixture of monomers and other additives forming the polymerizable composition).

TABLE-US-00001 Function Chemical name Supplier CAS number Content (% wt) Part A Releasing agent Zelec UN Stepan N/A 0.7794 Catalyst DMC 753-73-1 0.0390 UV Absorber Seesorb 701B Shipro Kasei 2440-22-4 1.7537 Diisocyanate IPDI Vencorex 4098-71-9 53.4086 Part B Polythiol PTMA TCI 10193-99-4 25.9566 Dithiol 1,6 hexanedithiol TCI 1191-43-1 16.2564 Polyether polyol Daltolac YT310 Huntsman 25791-96-2 1.8063

IPDI: Isophorone diisocyanate

##STR00002##

PTMA: Pentaerythritol tetrakis (2-mercaptoacetate)

##STR00003##

1,6 hexanedithiol

##STR00004##

Daltolac YT310

##STR00005##

[0090] The polymerizable composition consisting of the above-identified parts A and B was prepared according to the successive steps below: [0091] 1) Preparing Part A by mixing together the diisocyanate and the additive package consisting of the releasing agent, UV absorber and catalyst until complete dissolution of the UV absorber. [0092] 2) Preparing Part B by mixing together the polythiol, dithiol and polyether polyol. [0093] 3) Mixing Part A and Part B at a temperature of less than 11° C. for 1 hour under vacuum. [0094] 4) Purging the N.sub.2 gas to replace the vacuum, before adding part B and continue stirring the mixture for 10 minutes at 0° C. [0095] 5) Degassing for 45 minutes with low speed mixing and degassing for 15 minutes without stirring. [0096] 6) Releasing vacuum by N.sub.2 gas. [0097] 7) Filling the mixture of monomers and additives into a mold by a cleaned syringe.

[0098] The polymerization reaction was carried out in a regulated electronic oven according to the following cycle: 8 hours at about 10-20° C., regular temperature increase from 20° C. to 130° C. during 9 hours at about 5° C./hour to 25° C./hour, and 6 hours at about 120-130° C.

[0099] Table 2 below recites some physical properties of the obtained lens substrates according to the invention, in terms of refractive indexes n.sub.D and n.sub.E and Abbe numbers V.sub.D and V.sub.E, all measured thanks to a Prism Coupler.

TABLE-US-00002 n.sub.D n.sub.E V.sub.D V.sub.E First substrate of the invention 1.554 1.557 42 42

[0100] Table 3 below recites the cosmetic characterization of the obtained lens substrates according to the invention, measured thanks to a Cary machine. No color-balancing was added to the mixture.

TABLE-US-00003 UV cut TvD65 YI L* a* b* C* h* First substrate of the invention 396 89.495 2.01 95.765 -0.625 1.395 1.525 114.25

[0101] Table 4 below recites some mechanical properties of the obtained lens substrate according to the invention.

TABLE-US-00004 Modulus E′ measured at 25° C. Tg measured by Dynamic Mechanical Analysis (DMA: tan δ) Tg measured by Differential Scanning Calorimetry (DSC: onset / midpoint) First substrate of the invention 3.3 GPa 128° C. 106° C. / 113° C.

[0102] The whole measured physical, mechanical and cosmetic parameters of the lens substrates of the invention, as well as their castability in terms of process, have been recited and compared, where possible in Table 5 below, to the same parameters and castability of a prior art lens substrate “1.56 market selection” made of a specific “witness” polymer composition referred above. This “witness” polymer composition “1.56 market selection” was derived from both allylic and acrylic monomers.

TABLE-US-00005 Method Measurement substrate “1.56 market Selection” First substrate of the invention Remarks Physical parameters Refractive index (n.sub.D) Prism coupler ASTM D542 nD20, 20° C. 1.549 1.554 ok Refractive index (n.sub.E) 1.552 1.557 ok Abbe number (V.sub.D) 42 42 ok Abbe number (V.sub.E) 40 42 better Density - ASTM D792 1.24 - - Exotherm DSC - <6 J/g 0 ok Mechanical parameters Modulus E′ (25° C.) DMA Internal 3.0 3.3 better Tg DMA 80-110° C. (91° C.) 128 better Tg DSC 80-110° C. (89° C.) 113 better CTE before Tg Displacement probe Internal 100-140 (116) - - CTE after Tg (.Math.m/m.C.sup.O) 180-200 (190) - - Impact test (FDA & CEN) - 21 CFR 801.410 Not pass - - RedT Internal - 30 - - Cosmetic parameters T.sub.vd65 for UVcut > 390 nm Cary60 At 2 mm, 380-780 nm, UNC 89% 89.5 ok Haze Hazegard ASTM D1003 <0.5% - - Photostab. substrate (ΔE) Q-sun 80 h Internal - - -

[0103] These measurements mainly show overall better performances for the polythiourethane-based lens substrates of the invention having an IR of about 1.56, compared to the allylic/ acrylic-derived lens substrate “1.56 market selection”. In particular, the substrates of this first example of the invention exhibit an improved mechanical resistance to shocks in comparison with that of this “witness” allylic/ acrylic-derived substrate.

Example 2

[0104] Another polymer composition according to the invention was prepared in the following manner detailed in Table 6 below, by first preparing two separate parts A and B each consisting of the following ingredients (each being identified by its function, chemical tradename, supplier, CAS number and mass fraction in the whole mixture of monomers and other additives forming the polymerizable composition).

TABLE-US-00006 Function Chemical name Supplier CAS number Content (% wt) Part A Releasing agent Zelec UN Stepan N/A 0.7794 Catalyst DMC 753-73-1 0.0390 UV Absorber Seesorb 701B Shipro Kasei 2440-22-4 1.7537 Diisocyanate IPDI Vencorex 4098-71-9 51.6054 Part B Polythiol Pentaerythirol tetrakis(3-mercaptoproprionate) Sigma-Aldrich 7575-23-7 28.3696 Dithiol 1,6 hexanedithiol TCI 1191-43-1 13.9623 Polyether polyol Daltolac YT310 Huntsman 25791-96-2 3.4905

[0105] The polymerizable composition consisting of the above-identified parts A and B was prepared as specified in example 1 above.

[0106] Table 7 below recites some physical properties of the obtained lens substrate according to this second example of invention, in terms of refractive indexes n.sub.D and n.sub.E and Abbe numbers V.sub.D and V.sub.E, all measured thanks to a Prism Coupler.

TABLE-US-00007 n.sub.D n.sub.E V.sub.D V.sub.E Second substrate of the invention 1.550 1.553 42 42

[0107] Table 8 below recites the cosmetic characterization of the obtained lens substrate according to this second example of the invention, measured thanks to a Cary machine. No color-balancing was added to the mixture.

TABLE-US-00008 UV cut TvD65 YI L* a* b* C* h* Second substrate of the invention 396 90.785 1.865 96.305 -0.55 1.27 1.385 113.35

[0108] Table 9 below recites some mechanical properties of the obtained lens substrate according to this second example of the invention.

TABLE-US-00009 Modulus E′ measured at 25° C. Tg measured by Dynamic Mechanical Analysis (DMA: tan δ) Tg measured by Differential Scanning Calorimetry (DSC: onset / midpoint) Second substrate of the invention 3.0 GPa 115° C. 106° C. / 112° C.

[0109] These measurements also show better performances for the polythiourethane-based second substrate of the invention having an IR of about 1.56, compared to the allylic/ acrylic-derived lens substrate “1.56 market selection”, with markedly an improved mechanical resistance to shocks in comparison with that of this “witness” allylic/ acrylic-derived substrate.