Optical materials obtained from polymerizable compositions containing heterobifunctional alkyne compounds

Abstract

The present invention relates to a polymerizable composition containing at least one polythiol, at least one polyisocyanate or polyisothiocyanate, and at least one polymerizable compound of formula (I), wherein R 1 and R 2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R 1 and R 2 together form a divalent group of the formula -R 1 -R 2 -, -R 1 -R 2 - represents a substituted or unsubstituted alkylene group, Z represents OH, SH, NH2, or NHR 4 where R 4 represents a substituted or unsubstituted alkyl group or a (hetero)aryl group, R3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or a group of CR’ 1 R’ 2 Z’, and R’ 1 , R’ 2 , and Z’ are as defined for R 1 , R 2 , and Z. JPEG2026525351000028.jpg21162

Description

[Technical Field]

[0001] The present invention relates in particular to an optical material having improved thermomechanical properties, especially improved impact resistance, which can be used in optical substrates such as ophthalmic lenses, which generally have a medium or high refractive index. The present invention also relates to a polymerizable composition and a method for producing the optical material. [Background technology]

[0002] Plastic materials have been developed as alternative and replacement materials for glass in applications such as optical lenses, optical fibers, windows, automobiles, ships, and the aerospace industry. Organic polymer materials have advantages over inorganic glass in terms of lightness, impact resistance, moldability, and colorability.

[0003] Optical elements have been developed from various highly durable organic polymers, including polythiourethanes obtained by the condensation of polyiso(thio)cyanates and polythiol monomers. These are disclosed, for example, in International Patent Application Publication No. 00 / 26272, U.S. Patent Application Publication No. 2007 / 098999, International Patent Application Publication No. 2021 / 182526, European Patent No. 3916470, and European Patent No. 3919967.

[0004] Polythiourethane materials exhibit relatively high refractive indices, and this property allows for the manufacture of thinner optical articles, such as lenses, with comparable corrective force, thus attracting considerable interest. However, most of the resulting polythiourethane polymers exhibit insufficient mechanical properties, such as low glass transition temperatures and poor impact resistance.

[0005] U.S. Patent Application Publication No. 2016 / 376453 discloses a curable composition containing a polythiol component, an alkene-containing and / or alkyne-containing component, and an epoxy-containing component. The polythiol component can be derived from mercaptan-containing terpenes or terpenoids, mercaptan-containing cyclic alkenes, mercaptan-containing polycyclic alkenes, linear alkenes, mercaptan-containing alkynes, mercaptan-containing unsaturated fatty acids, mercaptan-containing unsaturated fatty acid esters, or mercaptan-containing polyalkenes. This curable composition is used in the manufacture of cell phone cases and expanded polystyrene foam. However, obtaining this polymerizable composition requires synthesizing and then blending three different chemical substances.

[0006] U.S. Patent Application Publication No. 2008 / 0125570 discloses an optical article comprising a reaction product of (A) a reactive compound having a functional group such as an isocyanate group that reacts with active hydrogen, and (B) a thioether-functional oligomeric polythiol prepared by reacting a compound having at least two thiol functional groups, a hydroxyl-functional compound having a triple bond functional group, and a compound having at least two double bonds.

[0007] European Patent No. 3257876 describes a polymerizable composition comprising 100 parts by weight of a terminal dialkyne compound and 25 to 75 parts by weight of a polythiol, used to obtain a material with a high refractive index. Due to the large amount of dialkyne used, the glass transition temperature of this material is expected to be very low.

[0008] European Patent No. 2980113 discloses a polymerizable composition for optical materials comprising a polythiol compound and a bifunctional compound (e.g., propargyl isocyanate) having a carbon-carbon triple bond and at least one group selected from an isocyanate group and an isothiocyanate group.

[0009] JP-A-2019 / 026755 and JP-A-2019 / 142849 describe an optical material composition containing a compound having two or more alkyne groups polymerizable with a polythiol compound at a terminal position.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] Thus, in the technical field, there is a need to develop a polymeric material having a refractive index and glass transition temperature sufficient for practical use in optical articles and excellent impact resistance / strength at a reasonable cost.

MEANS FOR SOLVING THE PROBLEMS

[0011] The present invention relates to a polymerizable composition containing at least one polythiol, at least one polyisocyanate or polyisothiocyanate, and at least one polymerizable compound of formula (I):

CHEMICAL FORMULA

CHEMICAL FORMULA

[0012] The inventors have found that an alkyne compound of formula (I) having at least one active hydrogen group can be used as a modifier in a standard polythiourethane composition containing a polythiol and a polyiso(thio)cyanate. The addition of this alkyne comonomer makes it possible to improve the mechanical properties of a standard polythiourethane resin, particularly its impact resistance, to meet FDA impact resistance requirements. No special coatings or plasticizers are required to impart this property. In addition to impact resistance, the present invention is believed to be able to improve the glass transition temperature and / or elastic modulus (or Young's modulus E') of the material in some embodiments.

[0013] In some embodiments, the present invention simultaneously improves impact resistance, glass transition temperature, and elastic modulus.

[0014] Furthermore, it was found that the introduction of alkyne comonomers significantly shortens the reaction time required for the polyisocyanate compound or polyisothiocyanate compound in the optical material according to the present invention to reach a predetermined level of conversion rate.

[0015] While not bound by any particular theory, the inventors believe that the present invention provides a modified polythiourethane polymer network by increasing crosslinking via thiol-in reactions that provide thioether functional groups, using specially designed starting materials that are copolymerizable with polythiols and poly(iso)thiocyanates and preferably at least partially curable by photochemical processes. Improving the impact resistance of the material by increasing crosslinking with alkyne-based modifiers is an innovative approach.

[0016] The aforementioned and other objectives, features, and advantages of the present invention will be readily apparent to those skilled in the art by considering the accompanying drawings in conjunction with the following detailed description. [Brief explanation of the drawing]

[0017] [Figure 1] The FTIR spectrum of the initial monomer mixture before the reaction is shown. [Figure 2] The FTIR spectrum of the polymer obtained after a certain reaction time is shown. [Modes for carrying out the invention]

[0018] The terms “comprise” (and its grammatical variations such as “comprises” and “comprising”), “have” (and its grammatical variations such as “has” and “having”), “contain” (and its grammatical variations such as “contains” and “containing”), and “include” (and its grammatical variations such as “includes” and “including”) are open-ended linking verbs. They are used to specify the existence of a feature, integer, process, or component, or a group thereof, but do not preclude the existence or addition of one or more other features, integers, processes, 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 has, but is not limited to having only, one or more of those steps or elements.

[0019] Unless otherwise indicated, all numbers or expressions used herein to refer to quantities, ranges, reaction conditions, etc., of components shall be understood in all cases to be modified by the term “approximately.”

[0020] In this specification, unless otherwise specified, an optical article / material is understood to be transparent if the observation of an image through the optical article is perceived without significant loss of contrast, i.e., if the formation of an image through the optical article is obtained without adversely affecting the quality of the image. This definition of the term “transparent” may apply to all such modifications in the description unless otherwise specified.

[0021] The optical material of the present invention is an organic glass produced from a thermosetting resin. The polymer matrix of the material is obtained by polymerization of a polymerizable composition containing at least one polythiol, at least one polyisocyanate or polyisothiocyanate, and at least one polymerizable compound of formula (I): [ka] (In the formula, R 1 and R 2 Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R 1 and R 2 These two combine to form equation -R 1 -R 2 - It forms a divalent group, -R 1 -R 2 - represents a substituted or unsubstituted alkylene group, and Z represents OH, SH, NH2, or NHR 4 Represents R 4 R represents a substituted or unsubstituted alkyl group or a (hetero)aryl group. 3 is a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or formula: [ka] It represents the base of R' 1 and R' 2 Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R'. 1 and R' 2 These two combine to form the equation -R' 1 -R' 2 - It forms a divalent group, -R' 1 -R' 2 - represents a substituted or unsubstituted alkylene group, and Z' represents OH, SH, NH2, or NHR'. 4 Represents R' 4 (represents a substituted or unsubstituted alkyl group or a (hetero)aryl group).

[0022] The optical material of the present invention can be used as a base material for optical articles, preferably optical lenses or lens blanks, more preferably ophthalmic lenses or lens blanks, such as plastic spectacle lenses. It can also be used as a coating.

[0023] The term "ophthalmic lens" is used to mean a lens adapted to an eyeglass frame for the purpose of protecting the eye and / or correcting vision. The lens may be selected from afocal lenses, monofocal lenses, bifocal lenses, trifocal lenses, progressive lenses, plano lenses, solar lenses, Fresnel lenses, or any other type of lens having discontinuous surfaces.

[0024] While optical systems for the eye are a preferred area of ​​the present invention, it will be understood that the present invention can be applied to other types of optical articles, such as lenses for optical instruments in photography or astronomy, optical sighting lenses, eye visors, optical systems for illumination systems, screens, glazing, windshields, sports masks, face shields, goggles, optical coatings, or adhesives.

[0025] If the optical article is an optical lens, it may have one or more functional coatings on the front principal surface, the rear principal surface, or both sides. As used herein, the rear surface of the substrate is intended to mean the surface closest to the wearer's eye when the article is in use. This is usually a concave surface. In contrast, the front surface of the substrate is the surface furthest from the wearer's eye when the article is in use. This is usually a convex surface. The optical article may also be a plano article.

[0026] In the context of this invention, the substrate should be understood to mean an uncoated substrate and generally having two main surfaces. The substrate can be manufactured from the optical material of this invention, in particular, having the shape of an optical article, such as an eye lens to be mounted on glass. In this context, the term “substrate” is understood to mean the base constituent material of an optical article, more specifically an optical lens. This material can function as a support for one or more coatings or stacks of layers.

[0027] From the viewpoint of reducing lens thickness, a plastic material with a high refractive index is desirable. The refractive index of the optical material according to the present invention is preferably 1.50 or higher, more preferably 1.52 or higher, or 1.54 or higher, more preferably 1.56 or higher, more preferably 1.58 or higher, more preferably 1.60 or higher, even more preferably 1.65 or higher, 1.67 or higher, 1.70 or higher, or 1.72 or higher, and preferably 1.80 or lower, more preferably 1.75 or lower. Unless otherwise specified, the refractive index referred to in this application is expressed at a wavelength of 550 nm at 25°C.

[0028] The refractive index of an optical material can be adjusted by adapting the structure of the polymerizable precursor, particularly the weight represented by sulfur atoms in the monomer, typically polythiol monomers or bifunctional compounds of formula (I). The refractive index of the material can also be increased by the presence of one or more aromatic groups in the structure of at least one polymerizable precursor.

[0029] In one embodiment, the optical material according to the present invention is thin. That is, it preferably has a central thickness of 2 mm or less, more preferably 1.5 mm or less, and even more preferably 1.2 mm or 1.1 mm or less.

[0030] The optical material according to the present invention preferably has a glass transition temperature of 70, 75, 80, 85, 90, 95, 100, or 105°C or higher. Preferably, it is 200°C or lower. The glass transition temperature can be measured by DMA (dynamic mechanical analysis).

[0031] 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 2.5 GPa or higher, 3 GPa or higher, 3.2 GPa or higher, 3.4 GPa or higher, or 3.6 GPa or higher. The elastic modulus E of the material evaluates the ability of the material to deform under the influence of an applied force. This can be measured by DMA (dynamic mechanical analysis).

[0032] The optical material according to the present invention has a relative light transmittance in the visible spectrum Tv of preferably 70% or more, preferably 75% or more, more preferably 80% or more, and even more preferably 85% or more.

[0033] The Tv coefficient, also known as the "luminous transmittance" of a system, is defined in ISO standard 13666:1998 and measured according to standard ISO 8980-3. It is defined as the average transmittance in the wavelength range of 380-780 nm, weighted according to the sensitivity of the eye in each wavelength range, and is measured under D65 illumination conditions (daylight). The transmittance is expressed as the value measured for a 2 mm thick optical article at the center of the optical article with the light rays perpendicularly incident (0° from the normal).

[0034] A polymerizable composition for obtaining optical materials is obtained from three main components: a polythiol, a polyiso(thio)cyanate, and a heterobifunctional alkyne compound of formula (I), the heterobifunctional alkyne compound of formula (I) having at least one alkynylene-C≡C- group and at least one Z group containing a heteroatom (O, S, or N), and having at least one active hydrogen atom.

[0035] In one embodiment, the compound of formula (I) and the polythiol are different compounds.

[0036] Compounds of formula (I) are generally conventionally called bifunctional compounds, but in reality, for example, their substituent R 1 , R 2 , or R 3They may contain more than two reactive functional groups, for example, if at least one of them contains at least one reactive functional group.

[0037] In one embodiment, the polymerizable compound of formula (I) contains two or fewer thiol functional groups, preferably zero or one thiol functional group. In another embodiment, the polymerizable compound of formula (I) contains two or fewer iso(thio)cyanate functional groups, preferably without iso(thio)cyanate functional groups.

[0038] The polymerizable composition may contain only one compound of formula (I), or it may contain a mixture of compounds of formula (I) having different structures.

[0039] The polymerizable composition may contain additional polymerizable compounds other than the compounds of formula (I) according to the present invention, polythiols, and polyiso(thio)cyanates. In one embodiment, such additional polymerizable compounds (comonomers) are copolymerizable with at least one of the compounds of formula (I) according to the present invention, polyiso(thio)cyanates, and polythiols.

[0040] The polythiol, polyiso(thio)cyanate, and compound of formula (I) according to the present invention preferably constitute at least 50% by weight of the total weight of polymerizable compounds present in the polymerizable composition, and more preferably at least 60% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight, 99% by weight, or 100% by weight of the total weight of polymerizable compounds present in the polymerizable composition.

[0041] In one embodiment, the polymerizable composition contains less than 5% by weight, more preferably 4, 3, 2, or 1% by weight, of polymerizable compounds having at least two C=C double bonds, based on the total weight of polymerizable compounds present in the composition, and more preferably does not contain polymerizable compounds having at least two C=C double bonds.

[0042] Examples of polymerizable compounds that are neither compounds of formula (I) according to the present invention, nor polythiols, nor polyiso(thio)cyanates include polyols, polyamines, and epoxy-containing compounds.

[0043] In one embodiment, the polymerizable composition contains 35% to 70% by weight of polythiol, more preferably 38% to 65% by weight or 40% to 60% by weight of polythiol, based on the total weight of polymerizable compounds present in the polymerizable composition. In another embodiment, the polymerizable composition contains 38% to 58% by weight of polythiol, based on the total weight of polymerizable compounds present in the polymerizable composition.

[0044] In one embodiment, the polymerizable composition contains 35% to 42% by weight of trithiol and 3% to 16% by weight of tetrathiol, based on the total weight of polymerizable compounds present in the polymerizable composition.

[0045] In one embodiment, the polymerizable composition contains 20% to 70% by weight, more preferably 25% to 65% by weight, 30% to 60% by weight, or 47% to 55% by weight of polyiso(thio)cyanate based on the total weight of polymerizable compounds present in the polymerizable composition.

[0046] The compound of formula (I) is preferably used as a modifier in polymerizable compositions mainly comprising polythiol and polyiso(thio)cyanate.

[0047] In one embodiment, the polymerizable composition contains 0.2% to 20% by weight, more preferably 0.3% to 15% by weight, 0.4% to 12% by weight, 0.5% to 10% by weight, or 0.5% to 8% by weight of the compound of formula (I) based on the total weight of polymerizable compounds present in the polymerizable composition. As the amount of the alkyne compound of formula (I) increases, the number of thioether bonds formed by the reaction between the alkyne functional group and the thiol functional group that form SC bonds increases in the polymer network. In another embodiment, the polymerizable composition contains 1% to 12% by weight, 1.5% to 10% by weight, or 1.5% to 8% by weight of the compound of formula (I) based on the total weight of polymerizable compounds present in the polymerizable composition.

[0048] In another embodiment, the polymerizable composition contains 1% to 3% by weight of the compound of formula (I) relative to the total weight of polymerizable compounds present in the polymerizable composition.

[0049] In one embodiment, the polymerizable composition contains 80% to 99.8% by weight, more preferably 85% to 99.7% by weight, 88% to 99.6% by weight, 90% to 99.5% by weight, or 92% to 98.5% by weight of polythiols and polyiso(thio)cyanates based on the total weight of polymerizable compounds present in the polymerizable composition.

[0050] To our surprise, the inventors have discovered that adding even a small amount of the alkyne comonomer compound of formula (I) to a polythiourethane polymerizable composition results in a material with improved impact resistance compared to pure polythiourethane materials, which suffer from the problem of low impact resistance.

[0051] While we do not wish to be bound by any theory, the inventors believe that the alkyne compound of formula (I) not only acts as a crosslinking agent in the polymer network but also introduces thioether bonds, thereby further imparting flexibility to the polymer network compared to a pure polythiourethane matrix that does not contain alkyne comonomers.

[0052] As demonstrated by the experimental section, the addition of the alkyne comonomer compound of formula (I) to the polythiourethane polymerizable composition does not adversely affect the thermomechanical properties of the optical material. Rather, compared to a pure polythiourethane matrix, the glass transition temperature and elastic modulus increase, reaching a maximum value corresponding to the optimal amount of added alkyne. Beyond this optimal amount, the thermomechanical properties of the optical material tend to decrease slightly.

[0053] While we do not wish to be bound by any theory, the inventors believe that the glass transition temperature initially rises due to the increased crosslinking brought about by the alkyne comonomer compound of formula (I), but if the amount of alkyne is too large, the polymer network via thioether bonds increases and the network bonds loosen, causing the glass transition temperature to decrease again.

[0054] In one embodiment, the polymerizable composition (first) contains (NCX group + 2 alkyne groups) / (SH group + OH group, NH2 group, and / or NHR group that may be present in the compound of formula (I)) 4 The mixture contains an amount of polymerizable compound adjusted so that the molar ratio of the base is in the range of 0.9 to 1.1, preferably 1, where X is O or S.

[0055] In fact, in the stoichiometric reaction between polyiso(thio)cyanate, polythiol, and compound of formula (I), if there are no other functional groups that are reactive to these functional groups, (OH, SH, NH2, and NHR in the polymerizable composition) 4 For every 3 equivalents of functional groups, it is necessary to use 2 equivalents of alkyne functional groups and 1 equivalent of NCX functional groups.

[0056] In one embodiment, the polymerizable composition comprises an amount of polymerizable compound adjusted so that the molar ratio of (NCX group + alkyne group) / SH group present in the polymerizable compound is in the range of 0.9 to 1.1, preferably 1, where X is O or S. When this simplified ratio is close to 1, the polymerization reaction is generally close to a balanced state in terms of reactive functional groups.

[0057] In one embodiment, the polymerizable composition comprises an amount of polymerizable compound adjusted so that the molar ratio of SH groups to alkyne groups present (initially) in the polymerizable compound is 1.5 to 45, more preferably 2.5 to 42, 3 to 42, or 5 to 42. In another embodiment, the molar ratio is in the range of 2.5 to 20 or 3 to 15. These polymerizable compounds may be compounds of formula (I) (which may be the same or different), polythiols, or other optionally polymerizable compounds of other categories.

[0058] In one embodiment, the polymerizable composition contains an amount of polymerizable compound adjusted so that the molar ratio of NCX groups to alkyne groups present (initially) in the polymerizable compound is 0.5 to 45, more preferably 1.5 to 42 or 2 to 40. In another embodiment, the molar ratio is in the range of 1.5 to 20 or 2 to 15. These polymerizable compounds may be compounds of formula (I) (which may be the same or different), poly(iso)thiocyanates, or other categories of optional polymerizable compounds.

[0059] In one embodiment, the polymerizable composition comprises an amount of polymerizable compound adjusted so that the molar ratio of NCX (where X is O or S) / SH groups present in the polymerizable compound is 0.3 to 1.2, more preferably 0.5 to 1.

[0060] The compound of formula (I) is a heterodifunctional compound containing at least two different reactive (polymerizable) functional groups, namely a Z group and an alkynylene-C≡CH group.

[0061] A compound of formula (I) is defined as a compound containing at least one alkyne bond. This preferably contains one or two alkyne bonds, more preferably one alkyne bond.

[0062] The compound of formula (I) is OH, SH, NH2, or NHR 4 Defined as a compound containing at least one group selected from R 4represents a substituted or unsubstituted alkyl group or (hetero)aryl group. This is preferably OH, SH, NH2, or NHR 4 It includes one or two groups, more preferably one group, selected from R 4 represents a substituted or unsubstituted alkyl group or (hetero)aryl group. The Z and Z' groups of the compound of formula (I) are reactive groups that can participate in polymerization reactions with iso(thio)cyanate groups.

[0063] In one embodiment, the compound of formula (I) contains OH, SH, NH2, or NHR per molecule of compound (I). 4 (R 4 The group selected from the above definitions has a group / alkyne group ratio of 1 or 2, preferably 1.

[0064] In this application, the term "alkyl" is defined as sp 3 This refers to linear or branched, cyclic or acyclic, saturated or unsaturated hydrocarbon radicals containing preferably 1 to 25 carbon atoms, which are bonded to the rest of the molecule via carbon atoms, and particularly includes acyclic groups containing 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-hexyl groups, preferably cycloalkyl groups containing 3 to 7 carbon atoms, and preferably cycloalkylmethyl groups containing 4 to 8 carbon atoms.

[0065] The "substituted alkyl" group is sp 3 An alkyl group is defined as an alkyl group bonded to the rest of the molecule via a carbon atom, wherein one or more methylene hydrogen atoms are substituted with substituents. A substituted alkyl group may be substituted with one or more aryl groups and / or one or more heteroatoms, such as N, S, O, or halogen atoms (fluorine, chlorine, bromine, or iodine). Examples include arylalkyl groups, such as trityl (-CPh3), benzyl, or 4-methoxybenzyl groups; alkoxyalkyl groups, particularly dialkoxymethyl groups, such as diethoxymethyl or dimethoxymethyl, CH2CO2R 11 Group (R 11Examples include (where represents an alkyl group or aryl group that may be optionally substituted).

[0066] The term "aryl" refers to a single ring (e.g., a phenyl group) or multiple fused rings (e.g., naphthyl or terphenyl groups) including sp 2 This refers to an aromatic monovalent carbon ring radical linked by carbon atoms, which may be optionally substituted by one or more groups such as alkyl (e.g., methyl), hydroxyalkyl, aminoalkyl, hydroxyl, thiol, amino, halogen (fluoro, bromo, iodo, or chloro), nitro, alkylthio, alkoxy (e.g., methoxy), aryloxy, monoalkylamino, dialkylamino, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, hydroxysulfonyl, alkoxysulfonyl, aryloxysulfonyl, alkylsulfonyl, alkylsulfonyl, cyano, trifluoromethyl, tetrazolyl, carbamoyl, alkylcarbamoyl, or dialkylcarbamoyl groups. Alternatively, two adjacent positions of the aromatic ring may be substituted by a methylenedioxyl group or an ethylenedioxyl group. The aryl group preferably contains 6 to 15 carbon atoms.

[0067] The term "heteroaryl" is sp 2A heteroaryl group is an aryl group as defined above, linked to the rest of a molecule via a carbon atom, in which one or more carbon atoms of the aromatic ring are substituted with heteroatoms such as nitrogen, oxygen, phosphorus, or sulfur. A heteroaryl group may have a structure with one or more aromatic rings, or a structure in which one or more aromatic rings are linked to one or more non-aromatic rings. In structures with multiple rings, the rings may be condensed, covalently bonded, or bonded to each other via a common divalent group such as a methylene group, ethylene group, or carbonyl group. Examples of heteroaryl groups include thiophene (2-thienyl, 3-thienyl), pyridine (2-pyridyl, 3-pyridyl, 4-pyridyl), isoxazole, phthalimide, pyrazole, indole, furan group and its benzo-condensed analogs, phenylpyridyl ketone, quinoline, phenothiazine, carbazole, and benzopyranone.

[0068] The term "(hetero)aryl group" refers to either a heteroaryl group or an aryl group.

[0069] The suffix "-ene" is used to indicate a divalent group. Therefore, any monovalent group defined herein can be modified with the suffix "-ene" to indicate the divalent form of its moiety. For example, a divalent aryl group is "arylene," and a divalent alkyl group is "alkylene." An alkylene group has two sp 3 It is linked to the rest of the molecule via carbon atoms. The arylene group has two sp atoms. 2 It is linked to the rest of the molecule via carbon atoms.

[0070] Examples of alkylene groups include linear C1-C10 alkylene groups, such as the methylene group -CH2-, the ethylene group -CH2-CH2-, 1,3-propylene, butylene, or hexylene group, particularly 1,4-butylene and 1,6-hexylene, as well as branched C3-C10 alkylene radicals, such as 1,4-(4-methylpentylene), 1,6-(2,2,4-trimethylhexylene), 1,5-(5-methylhexylene), 1,6-(6-methylheptylene), 1,5-(2,2,5-trimethylhexylene), 1,7-(3,7-dimethyloctylene), 2,2-(dimethylpropylene), 1,5-pentylene, 1,1-dimethylpentylene, and 1,6-(2,4,4-trimethylhexylene) radicals. Preferred cycloalkylene radicals include cyclopentylene radicals and cyclohexylene radicals, which may be optionally substituted with alkyl groups.

[0071] Examples of arylene groups include 2,4-trylene, 2,6-trylene, 2,4-naphthylene, 2,6-naphthylene, 1,5-naphthylene, 1,4-phenylene, 1,4-bisphenylene (-p-C6H4-p-C6H4-), 2-methyl-1,3-phenylene, 4-methyl-1,3-phenylene, tetramethylxylylene, and 1,4-phenylenemethylene-1,4-phenylene (4,4-biphenylenemethylene).

[0072] In this application, the alkyl group preferably comprises 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms.

[0073] In one embodiment, R 1 =R 2 That is the case.

[0074] The defining base-R in this application 1 -R 2 The dash (-) preferably represents a linear alkylene group such as -(CH2)5- (which consequently forms a cyclohexyl group with the carbon atom linked to the alkyne bond) or -(CH2)4-.

[0075] R 1 and R 2 The groups preferably represent, independently of each other, a hydrogen atom or a substituted or unsubstituted alkyl group, and the alkyl group is preferably a C1-C5 alkyl group, more preferably a C1-C2 alkyl group, and ideally a methyl group.

[0076] In a preferred embodiment of the present invention, R 1 =R 2 =H or R 1 =R 2 =CH3, or R 1 =H AND R 2 =CH3, or R 1 =H AND R 2 =3-heptyl, or R 1 =H AND R 2 = i-butyl.

[0077] Useful categories of compounds of formula (I) include R 3 It contains terminal alkynes that are H.

[0078] In one embodiment, the polymerizable compound is selected from the compounds of formula (IV): [ka] (In the formula, R 1 and R 2 These are defined above, and preferably independently of each other, represent a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R 1 and R 2 These two combine to form equation -R 1 -R 2 - It forms a divalent group, -R 1 -R 2 - represents a substituted or unsubstituted alkylene group, and Z is as defined above, preferably representing OH, SH, or NH2).

[0079] In one embodiment, the polymerizable compound is selected from the compounds of formula (II): [ka] (wherein, R 1 and R 2 are as defined above, and preferably, independently of each other, represent a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R 1 and R 2 together form a divalent group of the formula -R 1 -R 2 -, and -R​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​In another embodiment, Z = Z'.

[0083] The base-R' as defined in this application 1 -R' 2 The - preferably represents a linear alkylene group such as -(CH2)5- (which thus forms a cyclohexyl group together with the carbon atom bonded to the alkyne bond) or -(CH2)4-.

[0084] R' 1 base and R' 2 The groups preferably represent, independently of each other, a hydrogen atom or a substituted or unsubstituted alkyl group, and the alkyl group is preferably a C1-C5 alkyl group, more preferably a C1-C2 alkyl group, and ideally a methyl group.

[0085] In a preferred embodiment of the present invention, R' 1 =R' 2 =H or R' 1 =R' 2 =CH3, or R' 1 =H and R' 2 =CH3, or R' 1 =H and R' 2 = i-butyl, or R 1 =R 2 =R' 1 =R' 2 =H or R 1 =R 2 =R' 1 =R' 2 =CH3, or R 1 =R' 1 =H AND R 2 =R' 2 =CH3, or R 1 =R' 1 =CH3 and R 2 =R' 2 = i-butyl.

[0086] In one embodiment, the polymerizable compound is selected from the compounds of formula (V): [ka] (In the formula, R 1, R 2 , R' 1 , and R' 2 These are defined above, and preferably independently of each other, represent a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R 1 and R 2 These two combine to form equation -R 1 -R 2 - It forms a divalent group, -R 1 -R 2 - represents a substituted or unsubstituted alkylene group, or R' 1 and R' 2 These two combine to form the equation -R' 1 -R' 2 - It forms a divalent group, -R' 1 -R' 2 - represents a substituted or unsubstituted alkylene group, and Z and Z' are as defined above, preferably independently representing OH, SH, or NH2).

[0087] In one embodiment, the polymerizable compound is selected from the compounds of formula (IIa): [ka] (In the formula, R 1 , R 2 , R' 1 , and R' 2 These are defined above, and preferably independently of each other, represent a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R 1 and R 2 These two combine to form equation -R 1 -R 2 - It forms a divalent group, -R 1 -R 2 - represents a substituted or unsubstituted alkylene group, or R' 1 and R' 2 These two combine to form the equation -R' 1 -R' 2 - It forms a divalent group, -R' 1 -R' 2 (The hyphen represents a substituted or unsubstituted alkylene group.)

[0088] Specific examples of compounds with such formula (IIa) are shown below: [ka]

[0089] Other examples of useful polymerizable compounds of formula (I) include SH and NH2 analogs of compounds of formula (II) and (IIa), such as propargylamine or propargylthiol.

[0090] Polymerizable compounds of general formulas (I), (II), (IIa), (IV), and (V) are commercially available or can be readily synthesized by chemical reactions well known to those skilled in the art from widely available and relatively inexpensive raw materials such as propargyl alcohol, propargyl chloride, 1-ethynyl-1-cyclohexanol, 3-butyne-2-ol, 2-methyl-3-butyne-2-ol, 2-butyne-1,4-diol, 3-hexyne-2,5-diol, propargylthiol, and propargylamine. By widely utilizing these raw materials for the synthesis of the monomers of the present invention, it is possible to achieve a cost that is highly competitive in terms of the refractive index achieved.

[0091] The polythiols that can be used in the present invention are defined as compounds containing at least two sulfhydryl (mercapto) groups, in other words, dithiols, trithiols, tetrathiols, etc. Polythiol prepolymers or oligomers may be used. The polythiol may be any suitable polythiol having two or more, preferably two, three, or four thiol functional groups.

[0092] A prepolymer refers to a polymer or oligomer that contains a prepolymer molecule. A prepolymer molecule is a polymer or oligomer molecule that can undergo further polymerization via a reactive (polymerizable) group, thereby providing multiple monomer units to at least one chain of the final polymer. Prepolymer molecules are generally formed from two or more different monomers.

[0093] In one embodiment of the present invention, the polythiol is of the formula: R 5 (SH) n1 (III) It is a compound in which n1 represents an integer in the range of 2 to 6, and R 5 This represents an aliphatic group, alicyclic group, heterocyclic group, or aromatic group.

[0094] Preferred polythiol monomers and / or oligomers suitable for the present invention include aliphatic polythiols, such as trimethylolpropanetris(2-mercaptoacetate), trimethylolpropanetris(3-mercaptopropionate), trimethylolethanetris(2-mercaptoacetate), trimethylolethanetris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate). Captopropionate), bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) sulfide, bis(mercaptopropyl) disulfide, formula (VIa) 2,3-bis((2-mercaptoethyl)thio)-1-propanethol, formula (VIIa) 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri Thiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-bis(mercaptomethyl)-1,4-dithiane, and 2,5-bis[(2-mercaptoethyl)thiomethyl]-1,4-dithiane, 1-(1'-mercaptoethylthio)-2,3-dimercaptopropane, 1-(2'-mercappropylthio)-2,3-dimercaptopropane, 1-(3'-mercappropylthio)-2,3-dimercaptopropane, 1-(4'-mercapbutylthio)-2,3-dimercaptopropane, 1-(5'-mercaptomethyl) Pentylthio)-2,3-dimercaptopropane, 1-(6'-mercaphexylthio)-2,3-dimercaptopropane, 1,2-bis-(4'-mercaptobutylthio)-3-mercaptopropane, 1,2-bis-(5'-mercaptopentylthio)-3-mercaptopropane, 1,2-bis-(6'-mercaptohexylthio)-3-mercaptopropane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris-(3'-mercaptopropylthio)propane, 1,2,3-tris-(2'-mercaptoethylthio)propane, 1,2,3-Tris-(4'-mercaptobutylthio)propane, 1,2,3-Tris-(6'-mercaptohexylthio)propane, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanethiol-1,2,3-propanetrithiol, 1,2-bis(2'-mercaptoethylthio)-3-mercaptopropane, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate of formula (VIIIa), 2-mercaptoethyl 2-mercaptopropanurate of formula (IX) Examples include cete, 2-mercaptoethyl 3-mercaptopropionate, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, ethylene glycol bis(3-mercaptopropionate), butylene glycol bis(3-mercaptopropionate), and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane. [ka]

[0095] Further examples of polythiols are shown in the following formula, or can be found in International Publication No. 2014 / 133111, European Patent No. 394495, U.S. Patent No. 4775733, or European Patent No. 1877839: [ka]

[0096] In one embodiment of the present invention, the polythiol is pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), tris(3-mercaptopropionate)trimethylolpropane, tris(2-mercaptoacetate)trimethylolpropane, 2,3-bis((2-mercaptoethyl)thio)-1-propanthol, ethylene glycol bis(3-mercaptopropionate), butylene glycol bis(3-mercaptopropionate), 2-mercaptoethyl 2-mercaptoacetate, 2-mercaptoethyl 3-mercaptopropionate, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-to Lithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)- Examples include 1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, dipentaerythritol hexakis(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, and ethanedithiol.

[0097] The most preferred polythiols are 2-mercaptoethyl 2-mercaptoacetate of formula (IX), pentaerythritol tetrakis(3-mercaptopropionate) of formula (X), and 2,3-bis((2-mercaptoethyl)thio)-1-propantheol of formula (VIa). In particular, a mixture of 2-mercaptoethyl 2-mercaptoacetate and 2,3-bis((2-mercaptoethyl)thio)-1-propantheol can be used.

[0098] In one embodiment, preferably a mixture of at least two different polythiols having different numbers of thiol groups, for example, a mixture of two polythiols, is used. In some embodiments, the polymerizable composition comprises at least one polythiol having three SH groups and at least one polythiol having four SH groups. In one embodiment, the polymerizable composition comprises a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and 2,3-bis((2-mercaptoethyl)thio)-1-propanethol.

[0099] By adjusting the ratio of each polythiol, the refractive index of the material can also be adjusted.

[0100] Polyisocyanate refers to any compound containing at least two isocyanate groups, in other words, diisocyanate, triisocyanate, etc. Polyisocyanate prepolymers may also be used. The polyisocyanate may be any suitable polyisocyanate having two or more, preferably two or three, isocyanate functional groups.

[0101] Polyisocyanates may be selected from aliphatic, aromatic, alicyclic, or heterocyclic polyisocyanates, and mixtures thereof.

[0102] Polyisothiocyanates are defined in the same way as the polyisocyanates described above by replacing the "isocyanate" group with another "isothiocyanate" group.

[0103] In one embodiment of the present invention, the polyisocyanate or polyisothiocyanate is of formula (VI): R 6 (NCX) n2 (VI) It is a compound in which X represents O or S, n² represents an integer in the range of 2 to 6, and R 6 This represents an aliphatic group, alicyclic group, heterocyclic group, or aromatic group.

[0104] Preferred polyisocyanate or polyisothiocyanate compounds are those with the formula: [ka] It has the following characteristics: In these formulas, R 1 This is independently H or a C1-C5 alkyl group, preferably CH3 or C2H5; R 2 This is H, a halogen, preferably Cl or Br, or a C1-C5 alkyl group, preferably CH3 or C2H5; Z is -N=C=X, where X is O or S, preferably O. a is an integer in the range of 1 to 4, b is an integer in the range of 2 to 4, and a + b ≤ 6. x is an integer between 1 and 10, preferably between 1 and 6.

[0105] The polyisocyanate of the present invention is preferably a diisocyanate, such as aria diisocyanate. Among the available diisocyanates, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, paraphenylenediisocyanate, xylylenediisocyanate, biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylenediisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, lysine methyl ester diisocyanate, bis(isocyanatoethyl) fumarate, isophorone diisocyanate, norbornane diisocyanate, ethylene diisocyanate, dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate, cyclo Examples include cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene-2,4-diisocyanate, tetramethylxylylene diisocyanate, hexahydrotoluene-2,6-diisocyanate, perhydrodiphenylmethane-2,4'-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 1,5-naphthalene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate trimer, 1,6-hexamethylene diisocyanate trimer, and mixtures thereof.

[0106] Further polyiso(thio)cyanates suitable for the present invention are described in detail in International Publication No. 98 / 37115, International Publication No. 2014 / 133111, or European Patent No. 1877839.

[0107] Preferred embodiments include combinations of xylylene diisocyanate and pentaerythritol tetrakis(3-mercaptopropionate); combinations of xylylene diisocyanate and 2,3-bis((2-mercaptoethyl)thio)-1-propanethol; and combinations of 2,5 (or 2,6)-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and pentaerythritol tetrakis(3-mercaptopropionate) and 2,3-bis The combinations are ((2-mercaptoethyl)thio)-1-propanethol; xylylene diisocyanate and 4,8 (or 4,7 or 5,7)-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and dicyclohexylmethane diisocyanate and 4,8 (or 4,7 or 5,7)-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0108] The polymerizable mixture according to the present invention may also contain, in conventional proportions, additives conventionally used in polymerizable compositions for molding optical articles, particularly eye lenses, namely catalysts / polymerization initiators, photochromic agents, UV absorbers, fragrances, deodorants, resin modifiers, color balance adjusters, 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.

[0109] UV absorbers are often incorporated into optical materials to reduce or prevent UV light from reaching the retina (particularly in ophthalmic lens materials). UV absorbers that can be used in the present 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 to the visible blue light range of the electromagnetic spectrum (400-450 nm), particularly 420-450 nm.

[0110] The UV absorber protects the user's eyes from UV light and simultaneously protects the optical material itself, thereby preventing the material from weathering, becoming brittle, and / or yellowing. The UV absorber according to the present invention may be, but is not limited to, a benzophenone compound, a benzotriazole compound, or a dibenzoylmethane compound, preferably a benzotriazole compound. Suitable UV absorbers include, but are not limited to, 2-(2-hydroxyphenyl)-benzotriazole, e.g., 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (Seesorb® 703 / Tinuvin® 326), or other allylhydroxymethylphenylchlorobenzotriazoles, 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-benzotriazole-2-yl)phenyl]propionate (Eversorb® 109), 2-(2-hydroxy-5-methoxyphenyl)benzotriazole, 2-(2-hydroxy-5-butoxyphenyl)benzotriazole, and BASF's Tinuvin® CarboProtect®. The preferred absorbers are the benzotriazole class. Other examples of benzotriazole UV absorbers that protect against blue light can be found in International Publication No. 2017 / 137372.

[0111] The amount of the UV absorber compound according to the present invention used herein is sufficient to obtain adequate protection from UV light, but not excessive to prevent precipitation. The UV absorber compound is generally present in an amount of 0.05 to 4% by weight, preferably 0.1 to 3% by weight, and more preferably 0.1 to 2% by weight, relative to the total weight of the optical material (or per 100 parts by weight of polymerizable compound present in the composition, or relative to the weight of the optical material composition).

[0112] Among the release agents that can be used in the present invention are mono and dialkyl phosphates, alkyl ester phosphates, silicones, fluorinated hydrocarbons, fatty acids, and ammonium salts. Preferred release agents are mono and dialkyl phosphates, alkyl ester phosphates, and mixtures thereof. Such release agents are disclosed in particular in U.S. Patent No. 4,975,328 and European Patent No. 2,718,399. The release agent is preferably used in an amount of 1% by weight or less based on the total weight of the polymerizable compounds present in the polymerizable composition.

[0113] In one embodiment, the optical material composition is a dual-curing system in the sense that it possesses both thermal and photopolymerizable properties.

[0114] In one embodiment, the polymerizable optical material composition comprises at least one system (initiator) for initiating and / or promoting the polymerization reaction. The polymerization initiation system may include at least one (thermal) catalyst or at least one photochemical polymerization initiator (photoinitiator), or a mixture of a (thermal) polymerization initiator and a photochemical polymerization initiator. In a preferred embodiment, the polymerizable composition comprises both a photoinitiator and a (thermal) catalyst.

[0115] In another embodiment, the polymerizable optical material composition comprises at least one polymerization initiator, which is a thermal polymerization initiator, and does not include a photochemical polymerization initiator. In this embodiment, the optical material is obtained by thermal curing the polymerizable composition.

[0116] A photoinitiator is a molecule that absorbs light and generates a reactive species (ion or radical) that initiates a chemical reaction or transformation. In this invention, the photoinitiator is preferably used to promote a reaction between a thiol group and an alkyne group (thiol-in reaction).

[0117] Photoinitiators include, for example, haloalkylated aromatic ketones (chloromethylbenzophenone), benzoin and benzoin alkyl ethers (benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin, etc.), dialkoxyacetophenones (diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone, etc.), benzylideneacetophenone, and hydroxyketones ((1-[4-(2-hydroxyethoxy)-f [phenyl]-2-hydroxy-2-methyl-1-propan-1-one) (CIBA's Irgacure® 2959), 2,2-di-sec-butoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone (CIBA's Irgacure® 184), and 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur® 1173 sold by CIBA, etc.), α-aminopropyl alcohol Noketones, especially those containing a benzoyl moiety, also known as α-aminoacetophenones, such as 2-methyl-1-[4-phenyl]-2-morpholinopropan-1-one (CIBA's Irgacure® 907), (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (CIBA's Irgacure® 369), monoacyl and bisacylphosphine oxides and sulfides (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide ( You can choose from Irgacure® 819 and Irgacure® 2022 (which is a blend of Irgacure® 819 and Darocur® 1173) sold by CIBA, 2,4,6-trimethylbenzoylethoxydiphenylphosphine oxide, triacylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and mixtures thereof.

[0118] Free radical initiators catalyzed by heat or light, such as peroxides and azo compounds, as well as Lewis acids such as triarylsulfonium hexafluoroantimonate and diaryliodonium salts, can also be used.

[0119] Photoinitiators must 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 0.2 to 5% by weight, and more preferably 0.25 to 2% by weight, relative to the total weight of the polymerizable composition.

[0120] In this invention, the thermal catalyst comprises an iso(thio)cyanate group, thiol, hydroxyl, amino, and NHR. 4 The base selected from (R 4 It promotes the reaction (thiourethane reaction) with substituted or unsubstituted alkyl groups or (hetero)aryl groups. This condensation reaction is accelerated by heat.

[0121] In one embodiment, the (thermal) catalyst is selected from tin compounds such as alkyltin or alkyltin oxide, metal coordination complexes such as cobalt naphthenate, and amines or nitrogen-containing basic compounds. Multiple catalysts can be combined in the polymerizable composition of the present invention.

[0122] The tin catalyst can be selected from the group consisting of tin octoate, tin octanoate (tin 2-ethylhexanoate), dibutyltin diacetate, dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin dimaleate, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin mercaptide, dimethyltin dimaleate, triphenyltin acetate, and triphenyltin hydroxide.

[0123] The amine or nitrogen-containing basic catalyst can preferably be selected from aliphatic or aromatic tertiary amines containing an auxiliary heteroatom or a functional group (e.g., alkyl group or amino group) having a positive inductive effect and / or a positive mesomelic effect within the ring. Examples include 1,4-diazabicyclo[2.2.2]octane (DABCO), triethylamine, quinuclidine, 2,2'-dimorpholinodiethyl ether, N,N-dimethylpiperazine, 1-methylimidazole, 2-methyl-1-vinylimidazole, 1-alliimidazole, 1-phenylimidazole, 1,2,4,5-tetramethylimidazole, 1(3-aminopropyl)imidazole, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, 4-morpholinopyridine, 4-methylpyridine, 3,5-lutidine, N-dodecyl-2-methylimidazole, triazines such as tris(dimethylaminopropyl)hexahydrotriazine, dimethylbenzylamine, N,N-dimethylcyclohexylamine, bis-dimethylamino-ethyl ether, and pentamethyldiethylenetriamine.

[0124] In another embodiment, the catalyst is, [ka] It is a salt compound of, in the formula, M p+ These include alkali metal cations, alkaline earth metal cations, transition metal cations, and formula NR4 + Y is a cation with a valence p selected from the group consisting of ammonium groups (wherein R is preferably an alkyl group having 1 to 10 carbon atoms) and - Here, the corresponding acid YH is an anion having a pKa that satisfies the condition 0.5 ≤ pKa ≤ 14, and m, n, and p are integers such that n = m × p.

[0125] The preferred metal cation of the salt is Li + kaNa + , K + , Cs + Mg 2+ Ca 2+ Mn 2+Ag + Ba 2+ and Al 3+ A particularly preferred metal cation is Li, since it is colorless and soluble in the composition. + kaNa + and K + Transition metals are less preferred because their salts may result in colored compositions and thus colored polymerized resins. In one embodiment, the method according to the present invention does not use a tin-containing catalyst.

[0126] Preferred NR + The four groups are such that R is a C1-C8 alkyl group, more preferably a methyl group, ethyl group, propyl group, butyl group, or hexyl group.

[0127] Preferably, Y - The corresponding acid YH is an anion such that the condition 0.5 ≤ pKa ≤ 10, more preferably 0.5 ≤ pKa ≤ 8. In this application, pKa is preferably expressed at 25°C. The pKa can be measured in water at standard pressure by potentiometric (pH) titration using a glass electrode and a pH meter.

[0128] Preferably, anion Y - These include thiocyanates, carboxylate anions, thiocarboxylate anions, acetylacetonates, diketone anions, acetoacetates, malonic acid anions, cyanoacetates, ketonitrile anions, malononitrile anions, and formula RS - (wherein R is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or preferably an aryl group having 6 to 12 carbon atoms) selected from the group consisting of anions.

[0129] Preferred anion Y - SCN - These include acetylacetonate, acetate, thioacetate, formate, and benzoate. A preferred salt catalyst is potassium thiocyanate (KSCN).

[0130] Such salt catalysts are described in more detail in U.S. Patent Application Publication No. 2007 / 202265. These are preferably used in combination with electron-donating compounds, such as crown ethers, typically 18-crown-6, which are also described in U.S. Patent Application Publication No. 2007 / 202265.

[0131] The (thermal) catalyst must be used in the polymerizable composition in an amount sufficient to promote polymerization of the mixture, i.e., in the range of 0.01% to 5% by weight, more preferably in the range of 0.02% to 2% by weight, relative to the total weight of the polymerizable compounds present in the composition. Too much catalyst should also be avoided to prevent the polymerizable mixture from gelling prematurely before it is introduced into the mold.

[0132] The polymerizable composition of the present invention may contain a solvent to promote the dissolution of additives such as catalysts. Any polar organic solvent such as acetonitrile, tetrahydrofuran, dioxane, ethanol, 2-mercaptoethanol, acetone, or 3-methyl-2-buten-1-ol can be used. The amount of solvent is usually kept to less than 2% by weight, preferably 0-0.5% by weight, based on the total weight of the polymerizable compounds present in the composition, in order to avoid haze and foaming.

[0133] The present invention also relates to optical materials obtained by polymerization of the polymerizable compositions described above. Depending on the structure of the compound of formula (I), these optical materials may contain thioether functional groups and thiourethane functional groups, as well as optionally urethane functional groups (when Z or Z'=OH) and / or urea functional groups (when Z or Z'=NH2 or NHR as defined above). 4 In this case, it possesses both. The thioether bond is obtained by the reaction of an alkyne group with a thiol, the thiourethane bond is obtained by the reaction of an iso(thio)cyanate group with a thiol, the urethane bond is obtained by the reaction of an iso(thio)cyanate group with an alcohol, and the urea bond is obtained by the reaction of an iso(thio)cyanate group with an amine.

[0134] As demonstrated in the experimental section, the optical material according to the present invention can be distinguished from related polythiourethane-based optical materials obtained in the prior art by its improved thermomechanical properties (impact resistance, glass transition temperature) and improved monomer conversion rate.

[0135] The conversion rate of the polyisocyanate or polyisothiocyanate compound in the optical material according to the present invention is preferably 95% or more, more preferably 98% or more. The conversion rate of such a compound can be calculated by methods well known to those skilled in the art, such as by examining the intensity of the NCO / NCS peak by infrared spectroscopy.

[0136] As an example, the calculation of the relative intensity of the NCO / CH peak on a solid lens relative to a monomer using infrared spectroscopy will be described in detail in the experimental section with reference to Figures 1 and 2.

[0137] The present invention further relates to a method for producing the optical material described above, comprising polymerizing a polymerizable composition in the presence of at least one initiator. In one embodiment, the method comprises polymerizing a polymerizable composition in the presence of at least one initiator, preferably a photoinitiator, followed by thermal polymerization in the presence of at least one catalyst (thermal initiator). Alternatively, the method comprises thermal polymerization of a polymerizable composition in the presence of at least one thermal initiator, preferably without a photopolymerization step.

[0138] A preferred method involves polymerizing a polymerizable composition while irradiating it in the presence of at least one photoinitiator, followed by thermal polymerization in the presence of at least one catalyst (thermal initiator). This method yields high levels of conversion and crosslinking.

[0139] This method preferably involves cast polymerization.

[0140] The mixing of different components of the polymerizable composition can be carried out by any known mixing technique, such as that described in U.S. Patent No. 5,973,098, and is preferably carried out by introducing the components into a small reaction chamber and then mixing them with a screw mixer.

[0141] The optical material is obtained by a one-pot process in which a polythiol, poly(iso)thiocyanate, and the compound of formula (I) are simultaneously present in a polymerizable composition.

[0142] Subsequently, the mixture of reactants can be filled into the molding cavity of the casting mold assembly having any desired shape.

[0143] A casting mold assembly generally includes two mold components that define two molding surfaces that cooperate to form a molding cavity when moved from an open position to a closed position. Each molding surface may be concave, convex, or planar, depending on the desired shape of the article. The molding surface may be convex, for example, to form a concave substrate surface, or concave, for example, to form a convex substrate surface.

[0144] More specifically, the optical material composition can be poured into the cavity of two mold parts held together using annular fasteners such as gaskets or adhesive tape.

[0145] Annular fastening members can be positioned around and attached to two mold pieces. A conventional method for filling such a two-piece mold is to inject a (liquid) optical material composition into the molding cavity through a casting opening provided for this purpose in the fastening member. In at least a partially automated process, the molding cavity to be filled is positioned perpendicularly to a filling device that is tuned to deliver a specific amount of molding material through a nozzle.

[0146] Depending on the desired properties of the resulting optical material, the optical material composition may be degassed under reduced pressure and / or filtered under pressure or reduced pressure before being poured into the mold assembly.

[0147] Polymerization is initiated after the composition is poured into a casting mold assembly, preferably a lens casting mold assembly.

[0148] Photopolymerization of polymerizable compositions is typically carried out by irradiating the composition with radiation, preferably ultraviolet light. Preferably, the wavelength of the UV light is in the range of 320-390 nm. The intensity of the UV light is typically 40-90 mW / cm². 2 The range is such that the total exposure time to UV light is preferably in the range of 120 to 1650 seconds, more preferably in the range of 200 to 600 seconds, whether in a single irradiation or multiple irradiations.

[0149] Final thermal post-curing can be performed in an oven or in a heating device immersed in water, according to a predetermined temperature program for curing the resin in the mold assembly. Thermal polymerization includes induction heating and infrared heating. The curing temperature is typically in the range of 60°C to 140°C. The curing time is preferably 20 hours, 15 hours, 10 hours, or 5 hours or less, more preferably 4 hours, 3 hours, or 2 hours or less. As used herein, curing refers to a chemical process that converts monomers or oligomers into polymers with a larger molar mass, and then into a network structure.

[0150] The resin molded product may then be annealed as needed, preferably at a temperature in the range of 100°C to 150°C.

[0151] While not bound by any particular theory, the inventors believe that the order of polymerization reactions follows the order in which polymerization initiation is triggered. That is, they believe that the thiol-in reaction occurs first when irradiation is used, followed by the thiourethane reaction (and possibly the formation of urea and / or urethane bonds) upon heating or heat release from the photopolymerization reaction. The thiol / alcohol / amine-iso(thio)cyanate condensation and the thiol-in condensation can proceed independently of each other, especially when polymerizing polymerizable compositions using a combination of thermal catalysts and photoinitiators.

[0152] Subsequently, the mold assembly is removed from the heat source, the annular fasteners are removed, and the polymerized optical material can be recovered after the mold components are disassembled.

[0153] This method can be used to manufacture a finished lens in which both sides have the required geometric shape, or to manufacture a semi-finished lens in which one side still needs to be surface-treated to the required geometric shape.

[0154] In some applications, it is preferable to coat the main surface of an optical material with one or more functional coatings to improve its optical and / or mechanical properties. It is understood that the term “coating” means any layer, layer stack, or film that can come into contact with the substrate and / or another coating, such as a sol-gel coating or an organic resin coating. The coatings may be deposited or formed by a variety of methods, including wet processes, gaseous processes, and film copying. These functional coatings conventionally used in optical systems may include, but are not limited to, impact-resistant and / or adhesive primers, abrasion-resistant and / or scratch-resistant coatings, anti-reflective coatings, polarizing coatings, photochromic coatings, antistatic coatings, or laminates composed of two or more such coatings, particularly impact-resistant primer coatings coated with abrasion-resistant and / or scratch-resistant coatings.

[0155] The following examples illustrate the present invention in a more detailed but non-limiting manner. Unless otherwise specified, all thicknesses disclosed in this application refer to physical thicknesses. Percentages given in the tables are weight percentages. [Examples]

[0156] The polymerizable heterobifunctional dialkyne compounds according to the present invention can be selected from, but are not limited to, compounds of the following formulas: [ka]

[0157] 1. Chemical substances used and polymerization conditions Optical substrates were prepared by polymerizing heterobifunctional alkyne monomers (propargyl alcohol, CAS No. 107-19-7), at least one polythiol monomer, and polyisocyanate monomers (Examples 1-20, C1-C4: isophorone diisocyanate, CAS No. 4098-71-9) in the presence of a photoinitiator (2,2-dimethoxy-2-phenylacetophenone, CAS No. 24650-42-8, 0.25% by weight, excluding Examples C4 and 18-19 where no photoinitiator was used) and a thermal catalyst (dimethyltin dichloride, CAS No. 753-73-1, 0.2% by weight). The polymerizable composition also contained Zelec UN® (0.2% by weight) as a mold release agent.

[0158] The following polythiol monomers were used: 2,3-bis((2-mercaptoethyl)thio)-1-propanthol (CAS No. 131538-00-6), 2-mercaptoethyl-3-mercaptopropionate (CAS No. 59970-59-1), and / or pentaerythritol tetrakis(3-mercaptopropionate) (CAS No. 7575-23-7).

[0159] Cleaned, high-refractive-index convex and concave Planoglass molds with a diameter of 75 mm were assembled using tape. The center thickness was adjusted to obtain a sample with a thickness of 1.1 mm.

[0160] In a Duran flask equipped with a magnetic stirrer, the polyisocyanate monomer and alkyne monomer of formula (I) were mixed with a thermal catalyst, a photoinitiator (except in Examples C4, 18-19, where no photoinitiator was used), and a release agent. The solution was homogenized by stirring at room temperature for 5 minutes (45 minutes in Examples C4, 18-19). The reaction was then cooled to 20-22°C, and one or more polythiol monomers were added. The composition was then mixed, and degassed for 30 minutes to avoid introducing air bubbles into the final material. Degassing was continued for 5 minutes without stirring.

[0161] The polymerizable composition prepared above was filled into the assembled mold using a cleaned syringe, and the polymerization reaction was carried out by UV irradiation (365nm) for 3 to 6 minutes in a UV-LED curing oven (Height-LED, HTBX-II). Subsequently, the assembled mold was placed in a convection oven (hot air oven, Model B: 121218B, Reliance tech-service Co.LTD) and heat-cured (100°C for 2 hours for all examples except Examples C4 and 18-19, which were cured at 120°C for 10 hours) to cure the lens.

[0162] The irradiation times for Examples 1-17 were determined according to the type of polythiol used: 3 minutes for pentaerythritol tetrakis(3-mercaptopropionate), 5 minutes for 2,3-bis((2-mercaptoethyl)thio)-1-propanthol, and 6 minutes for 2-mercaptoethyl-3-mercaptopropionate. Polymerization time was not optimized.

[0163] The mold was removed from the oven and allowed to cool at room temperature for 5-10 minutes. Then, when the surface temperature of the mold fell below 50-60°C, the mold was disassembled to obtain a lens containing the body of the thermosetting material.

[0164] In Comparative Examples 1, 2, 3, and 4 (represented as C1, C2, C3, and C4), no alkyne monomers were used. In Comparative Example 1, since isophorone diisocyanate is bifunctional and pentaerythritol tetrakis (3-mercaptopropionate) is tetrafunctional, the molar ratio of NCO / SH used being 1:1 indicates that 0.5 moles of the latter were used for every 1 mole of the former (see §3).

[0165] 2. Test Method The optical articles fabricated according to the present invention were evaluated using the following test procedure. They were obtained from the integration of five different casting trials.

[0166] In all examples except C2, the thermal and mechanical properties of the lenses (glass transition temperature Tg and elastic modulus E) were evaluated by dynamic mechanical analysis (DMA) using a Q800 module of a dynamic mechanical analyzer supplied by TA Instruments. Measurements were performed in multi-frequency strain mode. The sample was rectangular with dimensions of 50 × 8 × 2 mm. The operation was performed with an amplitude of 30 μm, a preload of 0.5 N, a load track of 150%, and a heating rate of 2 °C / min at 25–130 °C.

[0167] The impact resistance of a 75mm diameter Plano lens (center thickness: 1.1mm) was evaluated according to the FDA drop ball test for eyeglasses (ANSI Z87.1-1989 standard). This test involves dropping a 16g steel ball from a height of 127cm onto the center of the convex surface of the lens, which corresponds to an energy of 200mJ. The lens is considered to have passed the test if it does not break and no star-shaped cracks appear. To ensure reproducibility, the impact test was performed in at least four independent casting trials. The calculation of the NCO conversion % (or conversion rate) will be described later.

[0168] Conversion is associated with the completion of polymerization, which is calculated by comparing the relative NCO values ​​of the lens with the relative NCO values ​​of the monomer.

[0169] PkNCO and PkCH2 are measured on the FTIR spectrum of the initial monomer composition (including isocyanates and thiols, as shown in the typical spectrum in Figure 1) and the FTIR spectrum of the polymer composition after the corresponding reaction time (as shown in the typical spectrum in Figure 2).

[0170] Pk is the peak intensity corresponding to the NCO peak or CH2 peak, minus the baseline %T of the corresponding peak.

[0171] Subsequently, the ratio of NCO to the CH2 internal peak can be calculated according to the following formula:

number

number

[0172] 3. Fabricated optical articles and their characteristics evaluation The table below shows the thermomechanical properties of various monomer formulations prepared and the resulting polymers. NCO / SH, NCO / alkyne, and SH / alkyne are the molar ratios of reactive functional groups introduced into the polymerizable composition. Polyisocyanate / alkyne compound (I) and polythiol / alkyne compound (I) are the molar ratios of monomers introduced into the polymerizable composition. The SH functional group was used in an amount that balanced the amount of NCX+alkyne functional group.

[0173] The presence of alkyne components was observed to help shorten polymerization time. In other words, when the alkyne compound of formula (I) was present in the polymerizable composition, the same conversion rates of polythiol monomers and polyisocyanate monomers were obtained in a shorter time. This effect of shortening polymerization time is particularly pronounced in the early stages of the polymerization process, especially in two-step polymerization processes in which a photocuring step is followed by a thermocuring step.

[0174] [Table 1]

[0175] The optical material according to the present invention passed the FDA impact resistance test while maintaining excellent optical quality, such as low or no visual haze, even with a low amount of alkyne component (0.59% by weight). For comparison, the optical material of Comparative Example 1 (without alkyne monomer) did not pass the impact resistance test.

[0176] The presence of such alkyne components improved the glass transition temperature of the resulting polymer, reaching a maximum of 105°C in Example 4 (an increase of 13°C compared to Comparative Example 1). Furthermore, the presence of such alkyne components also improved the elastic modulus of the resulting polymer, reaching its maximum value in Example 2. The polymers obtained in Examples 4 and 5 maintained a high elastic modulus, albeit slightly lower.

[0177] [Table 2]

[0178] Regarding Examples 1-5, the alkyne compound of formula (I) was introduced into the polythiourethane matrix, allowing the lenses to pass the FDA impact resistance test. In contrast, the lens of Comparative Example 2, which did not contain an alkyne additive, was extremely brittle and broke when the mold was disassembled. Although the glass transition temperature and elastic modulus could not be measured for this reference sample, a similar trend in the effect of alkyne addition on thermomechanical properties was observed in Examples 1-5 and Examples 6-12.

[0179] [Table 3]

[0180] Regarding Examples 1 to 12, the alkyne compound of formula (I) was introduced into the polythiourethane matrix, allowing it to pass the FDA impact resistance test, while the lens of Comparative Example 3, which did not contain an alkyne additive, failed the impact resistance test. The introduction of the alkyne compound of formula (I) into the polythiourethane matrix dramatically increased the glass transition temperature compared to the pure polythiourethane matrix of Comparative Example 3.

[0181] [Table 4]

[0182] In Examples 1-5, the presence of the alkyne component improved the elastic modulus of the resulting polymer.

Claims

1. A compound comprising at least one polythiol, at least one polyisocyanate or polyisothiocyanate, and formula (I): 【Chemistry 1】 (wherein, R １ and R ２ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R １ and R ２ together form a divalent group of the formula -R １ -R ２ -, -R １ -R ２ - represents a substituted or unsubstituted alkylene group, Z represents OH, SH, NH ２ , or NHR ４ , R ４ represents a substituted or unsubstituted alkyl group or a (hetero)aryl group, R ３ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or a formula: 【Chemistry 2】 It represents the base of R' １ and R' ２ Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R'. １ and R' ２ These two combine to form equation -R' １ -R' ２ It forms a divalent group of -R' １ -R' ２ The dash (-) represents a substituted or unsubstituted alkylene group, and Z' represents OH, SH, or NH. ２ , or NHR' ４ Represents R' ４ A polymerizable composition containing at least one polymerizable compound (representing a substituted or unsubstituted alkyl group or a (hetero)aryl group).

2. The polymerizable compound is of formula (II): 【Transformation 3】 (In the formula, R １ and R ２ Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a (hetero)aryl group, or R １ and R ２ Together, they form equation -R １ -R ２ It forms a divalent group of -R １ -R ２ The polymerizable composition according to claim 1, selected from compounds of which (where '-' represents a substituted or unsubstituted alkylene group).

3. The polymerizable compound is a compound of the following formula: 【Chemistry 4】 A polymerizable composition according to claim 1, selected from the following.

4. The polymerizable composition according to any one of claims 1 to 3, comprising 0.2% to 20% by weight of the compound of formula (I) based on the total weight of polymerizable compounds present in the polymerizable composition.

5. The aforementioned polythiol is given by the following formula: R ５ (SH) ｎ１ (III) (wherein n1 represents an integer in the range of 2 to 6, R ５ The polymerizable composition according to any one of claims 1 to 4, wherein (wherein represents an aliphatic group, an alicyclic group, a heterocyclic group, or an aromatic group).

6. The aforementioned polythiols include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), tris(3-mercaptopropionate)trimethylolpropane, tris(2-mercaptoacetate)trimethylolpropane, 2,3-bis((2-mercaptoethyl)thio)-1-propanethol, ethylene glycol bis(3-mercaptopropyl) Butylene glycol bis(3-mercaptopropionate), 2-mercaptoethyl 2-mercaptoacetate, 2-mercaptoethyl 3-mercaptopropionate, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl Lu-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(methylthio) A polymerizable composition according to any one of claims 1 to 5, selected from the group consisting of lucaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, dipentaerythritol hexakis(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, and ethanedithiol.

7. The polyisocyanate or polyisothiocyanate is of formula (VI): R ６ (NCX) ｎ２ (VI) (In the formula, X represents O or S, n² represents an integer in the range of 2 to 6, R ６ The polymerizable composition according to any one of claims 1 to 6, wherein (wherein represents an aliphatic group, an alicyclic group, a heterocyclic group, or an aromatic group).

8. The aforementioned polyisocyanate or polyisothiocyanate is toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, paraphenylenediisocyanate, xylylenediisocyanate, biphenyldiisocyanate, 3,3'-dimethyl-4,4'-diphenylenediisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, lysine methyl ester diisocyanate, bis(isocyanatoethyl) fumarate, isophorone diisocyanate, ethylene diisocyanate, dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-di A polymerizable composition according to any one of claims 1 to 7, selected from the group consisting of socianates, cyclohexane-1,4-diisocyanate, hexahydrotoluene-2,4-diisocyanate, tetramethylxylylene diisocyanate, hexahydrotoluene-2,6-diisocyanate, perhydrodiphenylmethane-2,4'-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 1,5-naphthalene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate trimer, and 1,6-hexamethylene diisocyanate trimer.

9. The polymerizable composition according to any one of claims 1 to 8, comprising an amount of polymerizable compound adjusted so that the molar ratio of (NCX group + alkyne group) / SH group present in the polymerizable compound is in the range of 0.9 to 1.1, wherein X is O or S.

10. The polymerizable composition according to any one of claims 1 to 9, comprising an amount of polymerizable compound adjusted so that the molar ratio of NCX groups / SH groups present in the polymerizable compound is in the range of 0.3 to 1.2, wherein X is O or S.

11. The polymerizable composition according to any one of claims 1 to 10, comprising an amount of polymerizable compound adjusted so that the molar ratio of NCX / alkyne groups present in the polymerizable compound is in the range of 0.5 to 45, wherein X is O or S.

12. A polymerizable composition according to any one of claims 1 to 11, comprising an amount of polymerizable compound adjusted so that the molar ratio of SH / alkyne groups present in the polymerizable compound is in the range of 1.5 to 45.

13. An optical material obtained by polymerization of a polymerizable composition according to any one of claims 1 to 12.

14. The optical material according to claim 13, further defined as a substrate for an optical lens.

15. A method for producing an optical material, comprising polymerizing a polymerizable composition according to any one of claims 1 to 12 in the presence of at least one initiator.

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