Optical materials derived from polymerizable compounds containing alkynylene and thiol functional groups

Abstract

The present invention relates to an optical material having a refractive index higher than or equal to 1.50, obtained by polymerization of a polymerizable composition comprising at least one polymerizable compound having at least two thiol-SH groups, and at least one alkynylene-C = C-group attached on each side to a carbon atom.

Description

[0001] This invention relates to optical materials with improved optical and mechanical properties, which can be particularly used in optical substrates typically having medium or high refractive indices, such as ophthalmic lenses. The invention also relates to polymerizable compounds and a method for manufacturing such optical materials.

[0002] Background Technology and Summary of the Invention

[0003] Plastic materials have been developed as alternatives and replacements for glass in applications such as optical lenses, optical fibers, windows, and in the automotive, marine, and aerospace industries. Compared to inorganic glass, organic polymer materials are advantageous in terms of light weight, high impact resistance, ease of molding, and dyeability.

[0004] However, many polymer materials have a lower refractive index than glass. Optically transparent plastic materials with higher refractive indices are of primary interest because they allow for the manufacture of optical products, such as lenses with lower thickness for equivalent corrective force.

[0005] Using thiol-olefin chemistry—the organic reaction between thiols and olefins to form thioethers—is generally difficult to achieve polymers with both high glass transition temperatures and high refractive indices using simple, inexpensive, and commercially available monomers. For example, polymerization of a stoichiometric mixture of pentaerythritol tetra(mercaptopropionate) and pentaerythritol tetraacrylate provides polymers with limited glass transition temperatures (13°C) and refractive indices (1.545). Known methods for improving the optical and mechanical properties of polymers obtained via thiol-olefin reactions are unsuitable because they involve the use of very specific monomers, including highly polarizable bonds such as carbon-metal or phosphorus-chalcogenide elements.

[0006] US 2016 / 376453 discloses a curable composition comprising a polythiol component, an olefinic and / or alkyneic component, and an epoxy-containing component. The polythiol component can be derived from thiol-containing terpenes or terpene-like compounds, thiol-containing cyclic olefins, thiol-containing polycyclic olefins, linear olefins, thiol-containing alkynes, thiol-containing unsaturated fatty acids, thiol-containing unsaturated fatty esters, or thiol-containing polyolefins. The cured composition is used to manufacture mobile phone cases or expanded polystyrene foam. However, it is necessary to synthesize several chemicals and then blend them to obtain a polymerizable composition.

[0007] The article “Hyperbranched Polymers by Thiol-Yne Chemistry: From Small Molecules to Functional Polymers”, D. Konkolewicz et al., J. Am. Chem. Soc. [Journal of the American Chemical Society]. 2009, 131, 50, 18075-18077 describes the homopolymerization of monomers such as propargyl 3-mercaptopropionic acid, which contain a terminal alkyne functional group and a thiol functional group. Catalytic amounts of photoinitiator and UV radiation were used to add two thiols to an alkyne bond at room temperature, thereby producing a hyperbranched polymer.

[0008] The article “Hyperbranched Polymers with High Degrees of Branching and Low Dispersity Values: Pushing the Limits of Thiol-Yne Chemistry”, AB Cook et al., Macromolecules, 2016, 49, 4, 1296-1304, discloses the homopolymerization of monomers containing a terminal alkyne functional group and a thiol functional group, or the copolymerization of such monomers with multifunctional core molecules (polyene or polyyne monomers) in the presence of a photoinitiator and under UV irradiation, resulting in the formation of hyperbranched thiol-yne polymers.

[0009] Therefore, there is a need in the art to develop a polymer material at a reasonable cost that has sufficient refractive index and good impact resistance / strength for practical use in optical products.

[0010] The present invention relates to an optical material having a refractive index of 1.50 or higher, which is obtained by polymerization of a polymerizable composition comprising at least one polymerizable compound A having at least two thiol-SH groups and at least one ynynyl-C≡C- group attached to a carbon atom on each side.

[0011] This invention provides a highly crosslinked polymer network derived from a thiol-yne reaction by means of specially designed homopolymerizable starting materials that can be cured by photochemical methods. The same monomer molecule carries two distinct reactive functional groups, which are typically introduced into polymerizable compositions via separate molecules. In the case of this invention, the starting material is characterized by both yne and thiol functional groups.

[0012] Another advantage of this invention is that the starting monomer can be finely tuned by adapting the substitution mode to control its mechanical properties and refractive index. Detailed Implementation

[0013] The terms “comprise” (and any of its grammatical variations, such as “comprises” and “comprising”), “have” (and any of its grammatical variations, such as “has” and “having”), “contain” (and any of its grammatical variations, such as “contains” and “containing”), and “include” (and any of its grammatical variations, such as “includes” and “including”) are all open-ended linking verbs. They are used to specify the presence of the stated feature, whole, step, or component or group thereof, but do not exclude the presence or addition of one or more other features, wholes, steps, or components or groups thereof. Therefore, a method or a step in a method that “comprises,” “has,” “contains,” or “includes” one or more steps or elements possesses, but is not limited to, possessing only those one or more steps or elements.

[0014] Unless otherwise specified, all figures or expressions relating to quantities of ingredients, ranges, reaction conditions, etc., used herein should be understood to be modified by the term “about” in all cases.

[0015] In this specification, unless otherwise specified, an optical article / material shall be understood to be transparent when no significant loss of contrast is perceived when an image is viewed through it, i.e., when image formation is obtained through the optical article without adversely affecting the quality of the image. Unless otherwise specified, this definition of the term "transparent" may be applied to all objects as so defined in this specification.

[0016] The optical material of the present invention is an organic glass made of thermosetting resin. The polymer matrix of the material is obtained by polymerization of a polymerizable composition comprising at least one polymerizable compound having at least two thiol-SH groups and at least one ynyl-C≡C- group attached to a carbon atom on each side.

[0017] The optical material of this invention can be used as a substrate for optical articles, preferably an optical lens or lens blank, more preferably an ophthalmic lens or lens blank, such as a plastic spectacle lens. It can also be used as a coating.

[0018] The term "ophthalmic lens" is used to refer to a lens that is fitted into an eyeglass frame to protect the eyes and / or correct vision. The lens may be selected from afocal lenses, monofocal lenses, bifocal lenses, trifocal lenses, progressive lenses, plano lenses, sunglass lenses, and Fresnel lenses, or any other type of lens with a discontinuous surface.

[0019] Although ophthalmic optics is the preferred field of this invention, it should be understood that the invention can be applied to other types of optical products, such as lenses for optical instruments used in photography or astronomy, optical aiming lenses, eye goggles, optical components of lighting systems, screens, glass windows, windshields, sports masks, face shields, goggles, optical coatings or adhesives, etc.

[0020] If the optical article is an optical lens, it may have one or more functional coatings applied to its front main surface, rear main side, or both sides. As used herein, the back of the substrate is intended to refer to the surface closest to the wearer's eye when the article is in use. The back is typically concave. Conversely, the front of the substrate is the surface furthest from the wearer's eye when the article is in use. The front is typically convex. Optical articles can also be plano articles.

[0021] In the context of this invention, "substrate" should be understood to mean an uncoated substrate and typically has two main surfaces. The substrate may be made, in particular, of the optical materials of this invention having the shape of an optical article (e.g., an ophthalmic lens destined for mounting in eyeglasses). In this context, the term "substrate" should be understood to mean the basic building material of an optical article and, more particularly, an optical lens. Such material may act as a support for a stack of one or more coatings or layers.

[0022] From the perspective of reducing lens thickness, plastic materials with high refractive indices are desirable. The refractive index of the optical material according to the invention is greater than or equal to 1.50, preferably 1.52 or greater, more preferably 1.54 or greater, more preferably 1.56 or greater, more preferably 1.58 or greater, more preferably 1.60 or greater, and even more preferably 1.65 or greater, 1.67 or greater, 1.70 or greater, 1.72 or greater, or 1.74 or greater, and preferably 1.80 or less, more preferably 1.75 or less. Unless otherwise specified, the refractive index mentioned in this application is expressed at a wavelength of 550 nm at 25°C.

[0023] The refractive index of an optical material can be adjusted by adapting the structure of the polymerizable precursor, particularly by the weight amount of sulfur atoms in the monomer. The refractive index of the material can also be increased by the presence of one or more aromatic groups in the structure of the polymerizable precursor.

[0024] In one embodiment, the optical material according to the invention is thin, that is, it preferably has a center thickness of 2 mm or less, more preferably 1.5 mm or less, and even better 1.2 mm or 1.1 mm or less.

[0025] The optical materials according to the invention preferably have a glass transition temperature of 70°C, 75°C, 80°C, or 85°C. It is preferably below or equal to 200°C. The glass transition temperature can be measured by DMA (Dynamic Mechanical Analysis). Due to the high crosslinking density provided by the polymerizable compounds of the invention, the glass transition temperature of the optical materials of the invention is advantageously higher than that of most optical materials obtained through thiol-olefin reactions.

[0026] The elastic modulus E (or Young's modulus, or storage modulus, or tensile modulus) of the optical material according to the present invention is preferably greater than or equal to 2.5, 3, or 3.5 GPa. The elastic modulus E of a material evaluates its ability to deform under applied force. It can be measured by DMA (Dynamic Mechanical Analysis).

[0027] The sulfur content of the optical material according to the invention preferably ranges from 20% to 70% by weight relative to the total weight of the optical material. In one embodiment, the sulfur content by weight of the optical material ranges from 30% to 70% or 50% to 65%. It can be adapted by changing the properties of the polymerizable precursor.

[0028] The optical material according to the invention preferably has a relative light transmittance factor Tv of 70% or higher, more preferably 75% or higher, more preferably 80% or higher, and even better 85% or higher in the visible spectrum.

[0029] The TV factor, also known as the system's "light transmittance," is defined as in ISO standard 13666:1998 and measured according to standard ISO 8980-3. It is defined as the average transmittance over the wavelength range of 380–780 nm, weighted according to the eye's sensitivity at each wavelength within this range, and measured under D65 illumination conditions (daylight). Transmittance is expressed as a 2 mm thick optical article, measured at the center of the optical article and at the point of normal incidence of the beam (0° to the normal).

[0030] The polymerizable composition for producing optical materials comprises a major component containing at least two different reactive (polymerizable) functional groups, namely a polymerizable compound having at least two thiol-SH groups and at least one ynynyl-C≡C- group attached to a carbon atom on each side. This polymerizable compound will be referred to as "Compound A" in this application. In other words, the optical material is obtained by homopolymerizing Compound A (forming thioether bonds) with or without optional comonomers; these compounds are heterobifunctional compounds.

[0031] By convention, compound A is usually referred to as a heterobifunctional compound, but it can actually contain more than two types of reactive functional groups, for example, when its substituents (R... 1 R 2 When at least one of Z (e.g.) contains another type of reactive functional group.

[0032] The polymerizable composition may contain only one type of compound A, or a mixture of compounds A with different structures.

[0033] The polymerizable composition may contain other polymerizable compounds that are not compound A according to the invention. In one embodiment, such other polymerizable compounds are copolymerizable with compound A according to the invention.

[0034] The monomeric compound A according to the invention preferably accounts for at least 50% by weight relative to the total weight of the polymerizable compounds present in the polymerizable composition, more preferably at least 60%, 70%, 80%, 90%, 95%, 99%, or 100% by weight relative to the total weight of the polymerizable compounds present in the polymerizable composition.

[0035] Examples of polymerizable compounds not of compound A according to the present invention include polyols, polyamines, polythiols other than compound A, polyisocyanates, polyisothiocyanates, and epoxy-containing compounds.

[0036] Typically, the polymerizable composition contains a polymerizable compound in an amount adapted such that the molar ratio of SH groups to alkynyl groups present in the polymerizable compound is 1.6 to 2.4, more preferably 1.8 to 2.2, or even more preferably 2. These polymerizable compounds can be the same or different compound A, as well as optional polymerizable compounds that are not compound A.

[0037] Compound A is defined as a compound containing at least two sulfhydryl / mercapto groups. It preferably contains 2, 3, or 4 sulfhydryl groups, more preferably 2.

[0038] Compound A is defined as a compound containing at least one alkyne bond. It preferably contains one or two alkyne bonds, more preferably one.

[0039] When no other functional groups are present, a stoichiometric reaction requires two equivalents of thiol functional groups for one equivalent of an alkyne functional group in a polymerizable composition. Compound A does not necessarily contain the stoichiometric ratio of thiols to alkynes that provides the polymerizable functional groups in homopolymerization, i.e., a thiol group / alkynyl group ratio of 2:1. However, in one embodiment, compound A is configured such that the thiol group / alkynyl group ratio per molecule of compound A is equal to 2:1.

[0040] In one embodiment, compound A comprises at least one thioether functional group, preferably two. In another embodiment, compound A comprises at least one ester functional group (C(O)O), preferably two.

[0041] In one embodiment, polymerizable compound A is a compound having formula (I):

[0042] Where R 1 R 2 、R' 1 and R' 2 Each of these can independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or R. 1 and R 2 Together they form a formula -R 1 -R 2 - a divalent group, wherein -R 1 -R 2 - indicates a substituted or unsubstituted alkylene group, or R' 1 and R' 2 Together they form a shape with the formula -R' 1 -R' 2 - a divalent group, wherein -R' 1 -R' 2 - indicates a substituted or unsubstituted alkylene group. Z and Z' independently represent divalent groups that are attached to adjacent thiol-SH groups via carbon atoms, and n = 0 or 1, n' = 0 or 1.

[0043] In this application, the term "hydrocarbon group" refers to a group containing preferably 1 to 25 carbon atoms, via sp... 3A group consisting of a straight or branched, cyclic or acyclic, saturated or unsaturated hydrocarbon group to which a carbon atom is attached to the rest of the molecule, particularly including acyclic groups containing 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl, preferably containing cycloalkyl groups of 3 to 7 carbon atoms, and preferably containing cycloalkylmethyl groups of 4 to 8 carbon atoms.

[0044] "Substituted alkyl" groups should be understood as those derived via sp... 3 An alkyl group as defined above, in which a carbon atom is attached to the remainder of the molecule and one or more methylene hydrogen atoms are replaced by substituents. The substituted alkyl group may be replaced by one or more aryl groups and / or one or more heteroatoms (such as N, S, O) or halogen atoms (fluorine, chlorine, bromine, or iodine). Arylalkyl groups such as triphenylmethyl (-CPh3), benzyl, or 4-methoxybenzyl, alkoxyalkyl groups, particularly dialkoxymethyl groups such as diethoxymethyl or dimethoxymethyl, and the group CH2CO2R will be mentioned by way of example. 11 , where R 11 Indicates an alkyl or aryl group that may be optionally substituted.

[0045] The term "heteroalkyl" indicates that via sp 3 A carbon atom is attached to an alkyl group as defined above, which is the rest of the molecule, wherein one or more carbon atoms of the alkyl chain have been replaced by heteroatoms such as nitrogen (e.g., NH, N-alkyl…), oxygen, phosphorus, or sulfur (e.g., SO, SO2…).

[0046] The term "aryl" refers to a compound containing a single ring (e.g., phenyl) or multiple fused rings (e.g., naphthyl, terphenyl) via sp. 2 The aromatic monovalent carbocyclic group linked to a carbon atom may optionally be substituted with one or more groups, such as, but not limited to, alkyl (e.g., methyl), hydroxyalkyl, aminoalkyl, hydroxyl, thiol, amino, halogen (fluorine, bromine, iodine, chlorine), nitro, alkylthio, alkoxy (e.g., methoxy), aryloxy, monoalkylamino, dialkylamino, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, hydroxysulfonyl, alkoxysulfonyl, aryloxysulfonyl, alkylsulfonyl, alkylsulfinyl, cyano, trifluoromethyl, tetrazolyl, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl. Alternatively, two adjacent positions of the aromatic ring may be substituted with methylenedioxy or ethylenedioxy. The aryl group preferably contains 6 to 15 carbon atoms.

[0047] The term "heteroaryl" indicates that via sp 2A carbon atom is attached to an aryl group as defined above, which is part of the rest of the molecule, wherein one or more carbon atoms of one or more aromatic rings have been replaced by heteroatoms (such as nitrogen, oxygen, phosphorus, or sulfur). A heteroaryl group can have a structure having one or more aromatic rings, or a structure having one or more aromatic rings coupled to one or more non-aromatic rings. In structures with multiple rings, the rings can be fused, covalently bonded, or bonded together via divalent common groups (such as methylene, ethylene, carbonyl). Examples of heteroaryl groups are thiophene (2-thiophene, 3-thiophene), pyridine (2-pyridyl, 3-pyridyl, 4-pyridyl), isoxazole, phthalimide, pyrazole, indole, furan groups and their benzo-fused analogs, phenylpyridinyl ketones, quinoline, phenothiazine, carbazole, and benzopyranone.

[0048] The suffix "-alkyl" is used to describe divalent groups. Therefore, any term defined herein may be modified with the suffix "-alkyl" to describe the divalent form of that part. For example, divalent aryl is "arylene," and divalent alkyl is "alkylene." Alkylenes are derived via two sp... 3 The carbon atom is attached to the rest of the molecule. The aryl group is formed via two sp... 2 Carbon atoms are attached to the rest of the molecule.

[0049] Heteroalkylene refers to heteroalkylene or alkylene. Heteroarylene refers to heteroarylene or arylene.

[0050] Examples of alkylenes include straight-chain C1-C10 alkylenes, such as methylene-CH2-, ethylene-CH2-CH2-, 1,3-propylene, butylene, or hexaneene, especially 1,4-butylene and 1,6-hexaneene, and branched C3-C10 alkylenes, such as 1,4-(4-methylpentanene), 1,6-(2,2,4-trimethylhexanene), 1,5-(5-methylhexanene), 1,6-(6-methylheptanene), 1,5-(2,2,5-trimethylhexanene), 1,7-(3,7-dimethyloctylene), 2,2-(dimethylpropylene), 1,5-pentanene, 1,1-dimethylpentanene, and 1,6-(2,4,4-trimethylhexanene). Preferred cycloalkylenes include cyclopentane and cyclohexane, which are optionally, especially, alkyl-substituted.

[0051] Non-limiting examples of heteroalkyl groups include -CH2SCH2-, -CH2CH2SCH2CH2-, -CH2OCH2-, -CH2CH2OCH2CH2-, and -CH2-CH2-S-CH2-CH(CH2SH)-S-CH2-CH2-.

[0052] Examples of arylene groups include 2,4-tolyl, 2,6-tolyl, 2,4-naphthylene, 2,6-naphthylene, 1,5-naphthylene, 1,4-phenylene, and 1,4-bisphenylene (- p -C6H4-p-C6H4-), 2-methyl-1,3-phenylene, 4-methyl-1,3-phenylene, tetramethylbenzylene, 1,4-phenylene-methylene-1,4-phenylene (4,4-biphenylene).

[0053] In this application, the (hetero)alkylene and / or alkyl groups preferably contain 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Short substituent chains, particularly short alkyl and / or alkylene chains, are preferred because long chains tend to reduce the refractive index of the resulting optical material.

[0054] In one embodiment, R 1 = R 2 And R' 1 = R' 2 .

[0055] The group -R defined in this application 1 -R 2 - (and / or the group -R') 1 -R' 2 -) preferably represents a straight-chain alkylene group, such as -(CH2)5- (which forms a cyclohexyl group with the carbon atom attached to the alkyne bond) or -(CH2)4-.

[0056] R 1 R 2 、R' 1 and R' 2 The groups preferably represent hydrogen atoms or substituted or unsubstituted alkyl groups independently of each other, the alkyl group preferably being a C1-C5 alkyl group, more preferably a C1-C2 alkyl group, and ideally a methyl group.

[0057] In a preferred embodiment of the present invention, R 1 = R 2 = H, or R' 1 = R' 2 = H, or R 1 = R 2 = R' 1 = R' 2 = H, or R 1 = R 2 = CH3, or R' 1 = R' 2 = CH3, or R 1 = R 2 = R'1 = R' 2 = CH3, or R 1 = H and R 2 =CH3, or R' 1 = H and R' 2 = CH3, or R 1 = R' 1 = H and R 2 = R' 2 = CH3.

[0058] In one embodiment, Z = Z'. In another embodiment, n = n'.

[0059] In another embodiment, Z and Z' are independently selected from substituted or unsubstituted: - Heteroalkylene, Heteroarylene, - Carbonylheteroalkylene, carbonylheteroaryl, - Oxycarbonylheteroalkylene, Oxycarbonylheteroaryl, - Carbonyloxyalkylene, carbonyloxyaryl, -Oxyalkylene, Oxyarylene, - Thioheteroalkylene, thioheteroaryl, - sulfonylalkylene, sulfonylaryl, - Amino-heteroalkyl, amino-heteroaryl, - Alkylaminoimide(heteroalkyl), alkylaminoimide(heteroaryl, - arylaminoimide(heteroalkyl), arylaminoimide(heteroaryl, - Aminocarbonylheteroalkylene, aminocarbonylheteroaryl, - Alkylaminocarbonylheteroalkylene, alkylaminocarbonylheteroaryl, - arylaminocarbonylheteroalkylene, arylaminocarbonylheteroalkylene, - Carbonylaminoimide(heteroalkyl), carbonylaminoimide(heteroaryl, - Carbonylalkylaminoimide(heteroalkyl), carbonylalkylaminoimide(heteroaryl, - Carbonylarylaminoimide(heteroalkyl), carbonylarylaminoimide(heteroaryl, And combinations of the aforementioned divalent groups.

[0060] The carbonyl functional group is -C(O)-, the oxycarbonyl functional group is -OC(O)-, the carbonyloxy functional group is -C(O)O-, and the sulfonyl functional group is -SO2-. The oxycarbonyl alkylene group is -OC(O)-alkylene, while the carbonyloxy alkylene group is -C(O)O-alkylene, etc.

[0061] The above combinations of divalent groups include, but are not limited to, combinations of groups of the same or different categories, such as cycloalkylene-alkylene, bicycloalkylene, bicycloalkylene-alkylene, arylalkylene (e.g., benzylene), biarylene (e.g., biphenylene), biarylalkylene, aryloxyalkylene, poly[oxyalkylene], poly[oxy(hetero)arylene], poly[thioalkylene], poly[thio(hetero)arylene].

[0062] In addition to the alkylene and arylene groups mentioned above, specific examples of Z and Z' groups include -S-CH2-, -S-CH2-CH2-, -S-CH2-CH2-S-CH2-CH2-, -CH2SCH2-, -S-CH2-CH2-S-CH2-CH(CH2SH)-S-CH2-CH2-, -OC(O)-CH2-, -OC(O)-CH2-CH2-, -OC(O)-CH(CH3)-, -CONH(CH2)3-, -OCH2CH(OH)CH2-, and polyoxyethylene such as -(OCH2CH2). n - (where n is an integer ranging from 2 to 10), polyoxypropylene.

[0063] Other available divalent Z and Z' groups include alkylene or arylene groups attached to any of the following divalent groups: -OC(O)O-, -C(O)C(O)-, -OC(O)C(O)O-, -C(O)OC(O)-, -C(S)-.

[0064] In one embodiment, group Z and / or Z' comprises an alkenyl or alkyneyl group.

[0065] The most preferred Z and Z' groups are thioarylene, thioalkylene, and oxycarbonylarylene, wherein the alkylene and arylene are substituted or unsubstituted.

[0066] In one embodiment, the polymerizable compound A is selected from compounds having formula (I):

[0067] Where R 1 R 2 、R' 1 and R' 2Z and Z' are, as defined above, and preferably independently of each other, hydrogen atoms or substituted or unsubstituted alkyl groups, Z and Z' are, as defined above, and preferably independently of each other, thioarylene, thioalkylene, or poly[thioalkylene], where the alkylene and arylene are substituted or unsubstituted, and n = 0 or 1, n' = 0 or 1.

[0068] Specific examples of such compounds having equation (I) where n = n' = 0 are shown below:

[0069] The available class of compounds having formula (I) where n = n' = 1 includes thioether compounds having formula (III):

[0070] Where R 1 R 2 、R' 1 and R' 2 As defined above, and preferably independently of each other, G and G' represent hydrogen atoms or substituted or unsubstituted alkyl groups, and G and G' represent divalent groups connected to adjacent mercapto-SH groups by carbon atoms and preferably connected to both sides by carbon atoms.

[0071] The G and G' groups are preferably independently selected from substituted or unsubstituted heteroalkylene, substituted or unsubstituted heteroarylene. G and G' are preferably independently selected from substituted or unsubstituted alkylene, typically C2-C4 alkylene, arylene, heteroarylene, or heteroalkylene, such as alkylene-thioalkylene, like the group -(CH2)2-S-(CH2)2-. In one embodiment, G = G'.

[0072] Specific examples of such compounds having formula (III) are shown below:

[0073] Another useful class of polymerizable compounds A includes compounds of formula (II) having an ester functional group (C(O)O):

[0074] Where R 1 and R' 1Y and Y' are, as defined above, and preferably represent hydrogen atoms, substituted or unsubstituted alkyl or aryl groups independently of each other, and Y and Y' represent substituted or unsubstituted heteroalkylene groups independently of each other.

[0075] Specific examples of such compounds are mercaptocarboxylic esters, such as the compounds shown below:

[0076] Compound A can be readily synthesized from widely available and relatively inexpensive raw materials via chemical reactions well known to those skilled in the art, such as 1,4-butynediol, 3-hexyn-2,5-diol, 2,5-dimethyl-3-hexyn-2,5-diol, 1,4-dichloro-2-butynediol, thiolactic acid, mercaptopropionic acid, thioglycolic acid, ethanedithiol, etc. The wide availability of these raw materials used in the synthesis of the monomers of this invention makes the cost highly competitive in terms of the achieved refractive index.

[0077] Compound A can be stored in the presence of antioxidants such as BHT (2,6-bis(1,1-dimethylethyl)-4-methylphenol) to prevent the addition of thiol groups to the alkyne bond.

[0078] The polymerizable compositions according to the invention may also contain additives, in conventional proportions, commonly used in polymerizable compositions intended for use in molding optical articles, particularly ophthalmic lenses, namely catalysts / polymerization initiators, photochromic agents, UV absorbers, fragrances, deodorants, resin modifiers, color balancers, chain extenders, crosslinking agents, free radical scavengers such as antioxidants or hindered amine light stabilizers (HALS), dyes, pigments, fillers, adhesion promoters, inhibitors, anti-yellowing agents, and release agents.

[0079] UV absorbers are often incorporated into optical materials to reduce or prevent UV light from reaching the retina (especially in ophthalmic lens materials). UV absorbers used in this invention preferably have the ability to at least partially block light with wavelengths shorter than 400 nm, but may also have an absorption spectrum extending into the visible blue light range (400-450 nm), particularly 420-450 nm.

[0080] The UV absorber protects the user's eyes from UV light and also protects the optical materials themselves, preventing them from weathering, becoming brittle, and / or yellowing. The UV absorber according to the invention can be, but is not limited to, a benzophenone-based compound, a benzotriazole-based compound, or a dibenzoylmethane-based compound, preferably a benzotriazole compound. Suitable UV absorbers include, but are not limited to, 2-(2-hydroxyphenyl)-benzotriazoles such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (Seesorb). ® 703 / Tinuvin ® 326), or other allyl hydroxymethyl phenyl chlorobenzotriazole, 2-(5-chloro-2H-benzotriazole-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol (Viosorb) ® 550), n-octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate (Eversorb) ® 109), 2-(2-hydroxy-5-methoxyphenyl)benzotriazole, 2-(2-hydroxy-5-butoxyphenyl)benzotriazole, and Tinuvin from BASF. ® CarboProtect ® Preferred absorbers are from the benzotriazole family. Other examples of benzotriazole UV absorbers that protect against blue light can be found in WO 2017 / 137372.

[0081] The amount of the UV absorber compound according to the invention used herein is sufficient to provide satisfactory protection against UV light, but not excessive, to prevent precipitation. The UV absorber compound is generally present in an amount ranging from 0.05% to 4% by weight, preferably from 0.1% to 3% by weight, and more preferably from 0.1% to 2% by weight, relative to the total weight of the optical material (or per 100 parts by weight of the polymerizable compound present in the composition or relative to the weight of the optical material composition).

[0082] Among the mold release agents that can be used in this invention are monoalkyl and dialkyl phosphates, alkyl phosphates, silicones, fluorinated hydrocarbons, fatty acids, and ammonium salts. Preferred mold release agents are monoalkyl and dialkyl phosphates, alkyl phosphates, and mixtures thereof. Such mold release agents are disclosed in particular in US 4975328 and EP 271839. Based on the total weight of the polymerizable compounds present in the polymerizable composition, the mold release agent is preferably used in an amount of less than or equal to 1% by weight.

[0083] The optical material composition is photopolymerizable and may contain at least one system (initiator) for initiating polymerization, preferably a photoinitiator. A photoinitiator is a molecule that absorbs light and generates reactive substances (ions or free radicals) that initiate a chemical reaction or transformation.

[0084] Photoinitiators can be selected from, for example, halogenated alkylated aromatic ketones such as chloromethylbenzophenone, benzoin and benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin, dialkoxyacetophenones such as diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone, benzyl acetophenone, hydroxy ketones such as (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-prop-1-one) (from Ciba Corporation's Irgacure). ® 2959), 2,2-di-sec-butoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone (from Ciba's Irgacure) ® 184) and 2-hydroxy-2-methyl-1-phenylprop-1-one (such as Darocur sold by Ciba) ® 1173), α-amino ketones, especially those containing a benzoyl moiety, are also known as α-aminoacetophenones, such as 2-methyl-1-[4-phenyl]-2-morpholinopropyl-1-one (from Ciba's Irgacure). ® 907), (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-but-1-one (from Ciba's Irgacure) ® 369), monoacyl and diacylphosphine oxides and sulfides, such as phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (Irgacure sold by Ciba). ® 819 and Irgacure ® 2022, which contains Irgacure ® 819 and Darocur ® Blends of 1173), 2,4,6,-trimethylbenzoylethoxydiphenylphosphine oxide, triacylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and mixtures thereof.

[0085] Thermally or photocatalyzed free radical initiators, such as peroxides and azo compounds, as well as Lewis acids, such as triarylsulfonium hexafluoroantimonate or diaryliodonium salts, can also be used.

[0086] Initiators should be used in the polymerizable composition in an amount sufficient to promote the polymerization reaction. They are typically present in an amount ranging from 0.05% to 10% by weight, preferably from 0.2% to 5% by weight, and more preferably from 0.25% to 2% by weight, relative to the total weight of the polymerizable compound present in the polymerizable composition.

[0087] The polymerizable compositions of the present invention may contain a solvent for promoting the dissolution of the additives. Any polar organic solvent may be used, such as acetonitrile, tetrahydrofuran, dioxane, ethanol, 2-mercaptoethanol, acetone, or 3-methyl-2-buten-1-ol. The amount of solvent is generally kept below 2% by weight based on the total weight of the polymerizable compounds present in the composition, and preferably 0% to 0.5% by weight, to avoid turbidity and bubbling.

[0088] The present invention also relates to a method for preparing the optical material as described above, the method comprising polymerizing a polymerizable composition in the presence of at least one initiator, preferably a photoinitiator, followed by thermal post-curing. The method preferably relates to casting polymerization.

[0089] The mixing of different components of a polymerizable composition can be carried out by any known mixing technique (such as those mentioned in US 5973098), preferably by introducing these components into a small reactor chamber and then mixing them with a screw mixer.

[0090] The mixture of reactants can then be used to fill the mold cavity of a casting assembly of any desired shape.

[0091] A molding assembly typically comprises two mold parts defining two molding surfaces that, when moved from an open position to a closed position, engage to form a mold cavity. Depending on the desired article shape, each of the molding surfaces can be concave, convex, or planar. A molding surface can be convex, for example, to form a concave substrate surface, or concave, for example, to form a convex substrate surface.

[0092] More specifically, an optical material composition can be injected into the cavity of two mold parts held together by annular closures (such as gaskets) or tape.

[0093] An annular closure member can be positioned around and attached to the periphery of the two mold pieces. The conventional method of filling such a two-piece mold is to allow a (liquid) optical material composition to flow into the mold cavity through a casting opening provided for this purpose in the closure member. In a process that is at least partially automated, the mold cavity to be filled is vertically aligned with a filling device adapted to deliver a specific amount of molding material through a nozzle.

[0094] Depending on the desired characteristics of the resulting optical material, degassing and / or filtration under pressure or depressurization may be performed before injecting the optical material composition into the mold assembly.

[0095] After the composition is poured into a molding assembly, preferably a lens molding assembly, polymerization of the polymerizable composition is typically carried out by irradiating the composition, preferably by irradiating the composition with ultraviolet light, and more preferably by photopolymerization. Preferably, the UV light wavelength range is 320 to 390 nm. The UV light intensity typically ranges from 40 to 90 mW / cm². 2 Furthermore, whether in a single irradiation or multiple irradiations, the total exposure time to UV light is preferably in the range of 200 to 1650 seconds, more preferably 200 to 600 seconds.

[0096] The final post-curing can be carried out in a water-immersed oven or heating device according to a predetermined temperature program to cure the resin in the mold assembly. Curing temperatures typically range from 60°C to 140°C. Curing time is preferably less than 5 hours, more preferably less than 4, 3, or 2 hours. As used herein, curing refers to the chemical process of converting monomers or oligomers into polymers with higher molar masses and then into networks.

[0097] If necessary, the resin-molded product can then be annealed at a temperature preferably in the range of 100°C to 150°C.

[0098] Afterward, the mold assembly is removed from the heating source, the annular closure component is removed, and the polymerized optical material can be recovered after the mold parts are disassembled.

[0099] The method of the present invention can be used to manufacture finished lenses with both sides having the required geometry, or semi-finished lenses (one side of which still needs to be surface treated according to the required geometry).

[0100] In some applications, it is preferred that the main surface of the optical material be coated with one or more functional coatings to improve optical and / or mechanical properties. The term "coating" is understood to mean any layer, layer stack, or film that can come into contact with a substrate and / or with another coating (e.g., a sol-gel coating or a coating made of an organic resin). Coatings can be deposited or formed by a variety of methods, including wet processing, gas processing, and film transfer. These functional coatings, classically used in optical devices, can be, but are not limited to, impact-resistant and / or adhesive primers, abrasion-resistant and / or scratch-resistant coatings, antireflective coatings, polarizing coatings, photochromic coatings, or antistatic coatings, or stacks of two or more such coatings, especially impact-resistant primer coatings coated with abrasion-resistant and / or scratch-resistant coatings.

[0101] The present invention also relates to a polymerizable compound having formula (I), (II) or (III), wherein R 1 R 2 、R' 1 、R' 2 Z, Z', n, n', G, G', Y, Y' have been previously defined, provided that the polymerizable compound is not:

[0102] In one embodiment, the polymerizable compound is not:

[0103] In another embodiment, the polymerizable compound is not:

[0104] The polymerizable compound is preferably selected from compounds having the following formula:

[0105] The following examples illustrate the invention in more detail, but not in a limiting manner. Unless otherwise stated, all thicknesses disclosed in this application refer to physical thicknesses. Percentages given in the tables are weight percentages.

[0106] Example

[0107] Polymerizable compound A may be selected from, but is not limited to, compounds having the following formula:

[0108] 1. Chemicals used and polymerization conditions

[0109] The optical substrate is prepared by homopolymerization of an ynylene dithiol monomer in the presence of a photoinitiator (2,2-dimethoxy-2-phenylacetophenone, 1% by weight). The polymerizable composition also contains Zelec UN. ® As a release agent.

[0110] The following ynyldithiol monomers were used: 2-butyn-1,4-diol dithioglycolate (Example 1), 2-butyn-1,4-dithiol (Example 2), 3-hexyn-2,5-dithiol (Example 3), 2,5-dimethyl-3-hexyn-2,5-dithiol (Example 4), 2-butyn-1,4-diol bis(2-mercaptopropionate) (Example 5), but-2-yn-1,4-diylbis(3-mercaptopropionate) (Example 6), bis(ethane-1,2-dithiol)but-2-yne (Example 7), 5,5'-(but-2-yn-1,4-diylbis(thioalkyldiyl))bis(1,3,4-thiadiazole-2-thiol) (Example 8), bis(mercaptomethylthio)but-2-yne (Example 9), and bis(mercaptomethylthio)hex-3-yne (Example 10).

[0111] Similarly, 4,4'-(but-2-yne-1,4-diylbis(thionidyl))diphenylthiophenol (a compound having formula (III), where G = G' = p-phenylene and R) can be used. 1 = R 2 = R' 1 = R' 2 = H (data not shown).

[0112] In a Duran flask equipped with a magnetic stirrer, an ynynyl dithiol monomer of formula (I) was mixed with a photoinitiator and a release agent. The composition was stirred at room temperature for 30 minutes and then degassed for 10 minutes to avoid air bubbles in the final material.

[0113] Cleaned convex and concave plano glass molds with high refractive index and a diameter of 65-80 mm are assembled using adhesive tape. Center thickness adjustment is performed to obtain a 2 mm thick sample.

[0114] The assembled mold was filled with the monomer formulation described above using a clean syringe, and the polymerization reaction was carried out by UV irradiation for 4 minutes (365 nm), followed by post-curing in an oven from Shenzhen Height-LED Technology Company Limited (80°C, 1 h). The mold was then disassembled to obtain a lens comprising a thermosetting material body.

[0115] 2. Synthesis of ynynyl dithiol monomers

[0116] Preparation of 2-butyn-1,4-diol dithioglycolate (Example 1)

[0117] 2-Butyn-1,4-diol (0.05 mol, 4.305 g), BHT (2,6-bis(1,1-dimethylethyl)-4-methylphenol, 0.1 g), thioglycolic acid (0.105 mol, 9.673 g), and p-toluenesulfonic acid (0.2 g) were introduced into a flask, and the mixture was heated under reduced pressure (7 mbar) at 60°C until the reaction was complete, as shown by FTIR. Ethyl acetate (40 mL) was added, and the organic phase was washed three times with 10% NaHCO3 and once with deionized water, dried over CaCl2, filtered, and stripped under vacuum. The isolated compound was decolorized with carbon in dichloromethane, then filtered and the solvent was stripped. It was sufficiently stable to be stored at 4°C for at least 2 months with an antioxidant (BHT, 300 ppm).

[0118] The monomers of Example 5 (2-butyn-1,4-diol bis(2-mercaptopropionate)) and Example 6 (butyryl-2-yne-1,4-diylbis(3-mercaptopropionate)) can be prepared similarly. 2-Butyn-1,4-dithiol (Example 2) can be synthesized according to known methods via the thiolation of 1,4-dichloro-2-butyne with sodium thioacetate. 3-Hexyn-2,5-dithiol (Example 3) and 2,5-dimethyl-3-hexyn-2,5-dithiol (Example 4) can be prepared similarly. Bis(ethane-1,2-dithiol)butyryl (Example 7) can be prepared from butyryl-1,4-dichloride and ethane-dithiol. Bis(mercaptomethylthio)butyryl (Example 9) and bis(mercaptomethylthio)hexyl-3-yne (Example 10) can be prepared from butyryl-1,4-dichloride and acetylthiomethylthiol according to US... The procedure described in 6770734 is followed by alcoholysis.

[0119] Preparation of 5,5'-(but-2-yn-1,4-diylbis(thioalkyldiyl))bis(1,3,4-thiadiazole-2-thiol) (Example 8) Preparation

[0120] In a 500 mL round-bottom flask equipped with a condenser and a feeding funnel, 15.025 g of 2,5-dimercapto-3,4-thiadiazole (dimercaptothiadiazole, 0.1 mol) was dissolved in 200 mL of ethanol, and 4 g of NaOH in 20 mL of deionized water was slowly added over approximately 10 minutes. The mixture was heated to reflux. In a beaker, 6.419 g of 1,4-dichloro-2-butyne (0.05 mol) was dissolved in 50 mL of ethanol. The solution was transferred to a feeding funnel and slowly added to the half-salt solution of dimercaptothiadiazole. The mixture was heated to reflux for 2 hours. The mixture was cooled to room temperature, and the precipitate was filtered under vacuum. The isolated compound had a melting point of 170°C. It needs to be melted prior to photopolymerization.

[0121] 3. Test methods

[0122] The following test procedures are used to evaluate the optical articles prepared according to the present invention.

[0123] The refractive index and Abbe number were measured by elliptic polarization at a wavelength of 550 nm, as disclosed in WO 2015 / 166144.

[0124] The thermal and mechanical properties (glass transition temperature Tg and elastic modulus E) of the lens were evaluated using DMA (Dynamic Mechanical Analysis) with a Q800 module of a Dynamic Mechanical Analyzer supplied by TA Instruments. Measurements were performed in multi-frequency strain mode. The sample was rectangular in shape, measuring 50 × 8 × 2 mm. The operation was conducted at a heating rate of 2°C / min from 25°C to 130°C, with an amplitude of 30 µm, a preload force of 0.5 N, and force tracking at 150%.

[0125] 4. Prepared optical products and characterization

[0126] The table below indicates the structure of the monomers used, the refractive index of the resulting polymer, and its theoretical sulfur content (by weight).

[0127]

[0128] The resulting new polymer has a high refractive index ranging from 1.60 to 1.74, depending on the structure of the starting monomer.

[0129] The optical material of Example 1 has an Abbe number of 39, a glass transition temperature Tg of 89°C, and an elastic modulus E of 3.7 GPa. In comparison, the material obtained by classical thiol-olefin polymerization of a stoichiometric mixture of pentaerythritol tetra(mercaptopropionate) and pentaerythritol tetraacrylate has a much lower glass transition temperature (Tg = 13°C) and refractive index (1.545).

Claims

1. An optical material having a refractive index greater than or equal to 1.50, said optical material being obtained by polymerization of a polymerizable composition, said polymerizable composition comprising at least one polymerizable compound A, said polymerizable compound having at least two thiol-SH groups and at least one ynynyl-C≡C- group attached to a carbon atom on each side, wherein: a) Relative to the total weight of the polymerizable compounds present in the polymerizable composition, the polymerizable compound A having at least two thiol-SH groups and at least one ynylene-C≡C- group attached to a carbon atom on each side accounts for at least 70% by weight, or b) The sulfur content of the optical material, relative to the total weight of the optical material, ranges from 20% to 70% by weight, or c) The polymerizable composition contains a polymerizable compound, the amount of which is adapted such that the molar ratio of SH groups to alkynyl groups present in the polymerizable compound is in the range of 1.6 to 2.

4.

2. The optical material as described in claim 1, wherein, The polymerizable compound A is a compound having formula (I): Where R 1 R 2 、R' 1 and R' 2 Each of these can independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or R. 1 and R 2 Together they form a form with -R 1 -R 2 - a divalent group, wherein -R 1 -R 2 - indicates a substituted or unsubstituted alkylene group, or R' 1 and R' 2 Together they form a shape with the formula -R' 1 -R' 2 - a divalent group, wherein -R' 1 -R' 2 - indicates a substituted or unsubstituted alkylene group. Z and Z' represent divalent groups that are attached to adjacent thiol-SH groups via carbon atoms, and n = 0 or 1, n' = 0 or 1.

3. The optical material as described in any one of the preceding claims, wherein, Z and Z' are independently selected from substituted or unsubstituted: - Heteroalkylene, Heteroarylene, - Carbonylheteroalkylene, carbonylheteroaryl, - Oxycarbonylheteroalkylene, Oxycarbonylheteroaryl, - Carbonyloxyalkylene, carbonyloxyaryl, -Oxyalkylene, Oxyarylene, - Thioheteroalkylene, thioheteroaryl, - sulfonylalkylene, sulfonylaryl, - Amino-heteroalkyl, amino-heteroaryl, - Alkylaminoimide(heteroalkyl), alkylaminoimide(heteroaryl, - arylaminoimide(heteroalkyl), arylaminoimide(heteroaryl, - Aminocarbonylheteroalkylene, aminocarbonylheteroaryl, - Alkylaminocarbonylheteroalkylene, alkylaminocarbonylheteroaryl, - arylaminocarbonylheteroalkylene, arylaminocarbonylheteroalkylene, - Carbonylaminoimide(heteroalkyl), carbonylaminoimide(heteroaryl, - Carbonylalkylaminoimide(heteroalkyl), carbonylalkylaminoimide(heteroaryl, - Carbonylarylaminoimide(heteroalkyl), carbonylarylaminoimide(heteroaryl, And combinations of the aforementioned divalent groups.

4. The optical material as claimed in any one of the preceding claims, wherein, Z and Z' are independently selected from thioheteroaryl, thioheteroalkyl, and oxycarbonylheteroalkyl, wherein the heteroalkyl and heteroaryl groups are substituted or unsubstituted.

5. The optical material as claimed in any one of the preceding claims, wherein, The polymerizable compound A is selected from compounds having formula (I): Where R 1 R 2 、R' 1 and R' 2 Each of the above independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and Z and Z' independently represent a thioarylene, a thioalkylene, or a poly[thioalkylene], wherein the alkylene and arylene are substituted or unsubstituted, and n = 0 or 1, n' = 0 or 1.

6. The optical material according to any one of claims 1 to 4, wherein, The polymerizable compound A is selected from compounds having formula (II): Where R 1 and R' 1 Each of the two groups represents a hydrogen atom, a substituted or unsubstituted alkyl or aryl group, and Y and Y' represent a substituted or unsubstituted heteroalkylene group.

7. The optical material according to any one of claims 2 to 6, wherein, The heteroalkylene and / or alkylene groups contain 1 to 5 carbon atoms.

8. The optical material as claimed in any one of the preceding claims, wherein, a) Relative to the total weight of the polymerizable compounds present in the polymerizable composition, the polymerizable compound A having at least two thiol-SH groups and at least one ynylene-C≡C- group attached to a carbon atom on each side accounts for at least 70% by weight, or b) The sulfur content of the optical material ranges from 20% to 70% by weight relative to the total weight of the optical material.

9. The optical material as described in any of the preceding claims is further defined as having a refractive index of 1.60 or higher, more preferably 1.65 or higher, and even more preferably 1.70 or higher.

10. The optical material as described in any of the preceding claims is further defined as having a glass transition temperature of 85°C or higher.

11. The optical material as described in any of the preceding claims, further defined as a substrate for an optical lens.

12. The optical material as claimed in any one of the preceding claims, wherein, The polymerizable compound A is selected from compounds having the following formula: 。 13. A method for preparing an optical material according to any one of the preceding claims, the method comprising polymerizing the polymerizable composition in the presence of at least one initiator, followed by thermal post-curing.

14. A polymerizable compound having formula (I): (I) Where R 1 R 2 、R' 1 、 and R' 2 Each of these can independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or R. 1 and R 2 Together they form a form with -R 1 -R 2 - a divalent group, wherein -R 1 -R 2 - indicates a substituted or unsubstituted alkylene group. Z and Z' independently represent divalent groups that are linked to adjacent thiol-SH groups via carbon atoms. And n = 0 or 1, n' = 0 or 1, provided that the compound having formula (I) is not: And this is on the premise that the compound having formula (I) is not: 。 15. The polymerizable composition of claim 14, wherein, The polymerizable compound is selected from compounds having the following formula: 。

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