Late stage catalysis of fast room temperature polymerization

Abstract

The present application relates to a method for the fast curing of a transparent cast substrate that can be used for the manufacture of optical articles such as ophthalmic lenses, the method comprising the following steps: - providing a fast room temperature polymerizable composition; - providing a catalyst composition; - providing a casting mold assembly containing two unsealed molds each having an inner surface and an outer surface; and optionally providing a light filtering element that is placed or configured to be placed between the two molds - depositing the catalyst composition: - on the inner surface of at least one of the molds; and / or - on at least one surface of the light filtering element, which is positioned in the mold assembly thereafter; - closing the casting mold assembly so that the inner surfaces of the molds together form a mold cavity; - filling the mold cavity of the casting mold assembly with the fast room temperature polymerizable composition, the mold cavity having already contained the catalyst composition deposited on the inner surface of at least one of the molds; - curing the filled mold assembly to obtain a transparent solid substrate, said curing step comprising: a) a first step for polymerizing said composition at room temperature to obtain a gel; and b) a second step for post-curing the gel to obtain the transparent solid substrate; and - recovering the transparent solid substrate from the casting mold assembly.

Description

Technical Field

[0001] The present invention provides a method for rapidly curing a rapidly room-temperature polymerizable composition to obtain a transparent substrate, and particularly an optical substrate such as a lens, especially an ophthalmic lens. Background Technology

[0002] Transparent plastic substrates are well-known and commonly used in the manufacture of optical products such as ophthalmic lenses. Plastic substrates made of thermosetting polymers can be used to manufacture such transparent plastic substrates. These thermosetting polymers are produced by the polymerization of polymerizable compositions comprising monomers and / or oligomers capable of polymerizing under thermal activation to form a polymer. Typically, in the ophthalmic field, a thermosetting polymer refers to a polymer network formed irreversibly through the chemical reaction of monomers under thermal activation.

[0003] The object of this invention is to obtain a transparent plastic substrate that can be used to manufacture optical articles such as ophthalmic lenses from polymerizable compositions at room temperature. By avoiding thermal activation, the manufacturing method is simplified and becomes more environmentally friendly, while requiring less complex equipment.

[0004] Examples of rapidly room-temperature polymerizable compositions are given in US 6,887,401 and US 5,973,098. Both documents describe methods for manufacturing cast transparent polysulfururethane substrates suitable for use in the manufacture of optical articles.

[0005] The methods described in US 5,973,098 and US 6,887,401 are similar and involve a short mixing time between the monomer or prepolymer participating in the polymerization reaction and the catalyst. They describe a method in which one of the monomers or prepolymers participating in the polymerization reaction is first mixed with a catalyst solution, then said mixture is mixed with the remaining monomers or prepolymers to form another mixture, which is then immediately filled into a mold cavity.

[0006] However, once the catalyst solution is added to one of the monomers or prepolymers, the remaining monomers or prepolymers should be added shortly to avoid a decrease in their stability. The resulting mixture containing both the monomer or prepolymer and the catalyst should also be rapidly filled into the mold cavity to avoid any premature gelation during mixing or filling.

[0007] Therefore, there is a need to increase the shelf life of rapidly room-temperature polymerizable compositions. Summary of the Invention

[0008] This invention relates to a method for rapidly curing a transparent casting substrate that can be used to manufacture optical products such as ophthalmic lenses, the method comprising the following steps:

[0009] -Provides fast room temperature polymerizable compositions;

[0010] -Provide catalyst compositions;

[0011] - Provides a casting mold assembly comprising two unsealed molds, each having an inner surface and an outer surface; and optionally provides a filter element placed or configured to be positioned between the two molds.

[0012] -Deposit the catalyst composition:

[0013] - On at least one of the inner surfaces of these molds; and / or

[0014] - On at least one surface of the filter element, it is then positioned in the mold assembly;

[0015] - Close the casting mold assembly so that the inner surfaces of these molds together form a mold cavity;

[0016] - The rapid room temperature polymerizable composition is filled into the mold cavity of the casting mold assembly, the mold cavity already containing a catalyst composition deposited on the inner surface of at least one of these molds;

[0017] - Curing the filled mold assembly to obtain a transparent solid substrate, the curing step comprising:

[0018] a) A first step for polymerizing the composition at room temperature to obtain a gel; and

[0019] b) A second step of post-curing the gel to obtain the transparent solid substrate; and

[0020] - The transparent solid substrate is recovered from the casting mold assembly.

[0021] According to an embodiment, the deposition of the catalyst composition on at least one inner surface of the mold and / or at least one side of the filter element is performed by liquid phase deposition.

[0022] According to embodiments, the deposition of the catalyst composition on at least one inner surface of a mold and / or at least one side of a filter element is performed by spin coating, dip coating, spray coating, brush coating or roll coating.

[0023] According to the examples, the rapid room temperature polymerizable composition has a viscosity at 25°C ranging from 0.1 to 0.3 Pa·s.

[0024] According to the examples, the rapid room temperature polymerizable composition is selected from compositions comprising:

[0025] (a) A poly(thio)urethane prepolymer terminated with at least one poly(iso)thiocyanate monomer or liquid NCO or NCS and a poly(thio)urethane prepolymer terminated with at least one polythiol monomer or liquid SH; or

[0026] (b) One or more polymerizable cyclic sulfide compounds.

[0027] According to an embodiment, the mixture (a) comprises:

[0028] - Component A, comprising a polysulfurethane prepolymer having isocyanate or isothiocyanate (NCX, where X is O or S) end groups and a viscosity at 25°C ranging from 0.02 to 0.4 Pa·s, and with

[0029] - Component B, which comprises a polysulfururethane prepolymer having thiol (SH) end groups and a viscosity at 25°C ranging from 0.2 to 2.0 Pa·s.

[0030] Components A and B are obtained by polymerizing at least one polyisocyanate or polyisothiocyanate monomer and at least one polythiol monomer.

[0031] According to the embodiments, the amounts of polyisocyanate or polyisothiocyanate monomers and polythiol monomers are adjusted such that the ratio of the mixture of polyisocyanate or isothiocyanate monomers and polythiol monomers NCX / SH is in the range of 4:1 to 30:1 to obtain component A, and the ratio of the mixture of polyisocyanate or isothiocyanate monomers and polythiol monomers SH / NCX is in the range of 4:1 to 30:1 to obtain component B.

[0032] According to an example, the polythiol has the following formula: R'(SH)n', where n' is an integer from 2 to 6 and preferably from 3 to 4, and R' is an organic group with a valence equal to n'.

[0033] According to embodiments, the polythiols are selected from the group consisting of: pentaerythritol tetramercaptopropionate, 1-(1'-mercaptoethoxy)-2,3-dimercaptopropane, 1-(2'-mercaptopropylthio)-2,3-dimercaptopropane, 1-(-3'-mercaptopropylthio)-2,3-dimercaptopropane, 1-(-4'-mercaptobutylthio)-2,3-dimercaptopropane, 1-(5'-mercaptopentylthio)-2,3-dimercaptopropane, 1-(6'-mercaptohexylthio)-2,3-dimercaptopropane, 1,2-bis(-4'-mercaptobutylthio)-3-mercaptopropane, 1,2-bis(-5'-mercaptopentylthio)-3-mercaptopropane, 1,2 -bis(-6'-mercaptohexyl)-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, methyl dithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexylthiol-1,2,3-propanetrithiol and 1,2-bis(-2'-mercaptoethylthio)-3-mercaptopropane.

[0034] According to embodiments, the polyisocyanate or polyisothiocyanate is selected from monomers having the following formula:

[0035]

[0036] in

[0037] R1 is independently H or C1-C5 alkyl, preferably CH3 or C2H5;

[0038] R2 is H, a halogen, preferably Cl or Br, or a C1-C5 alkyl group, preferably CH3 or C2H5;

[0039] Z is -N = C = X, where X is O or S;

[0040] a is an integer from 1 to 4, b is an integer from 2 to 4, and a + b ≤ 6.

[0041] x is an integer from 1 to 10, preferably from 1 to 6.

[0042] According to embodiments, the polyisocyanate or isothiocyanate is selected from the group consisting of: toluene diisocyanate or diisothiocyanate, phenylene, diisocyanate or diisothiocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate or diisothiocyanate, dimethylphenylene diisocyanate or diisothiocyanate, diethylphenylene diisocyanate or diisothiocyanate, diisopropylphenylene diisocyanate or diisothiocyanate, trimethylbenzyl Triisocyanate or triisothiocyanate, phenyl diisocyanate or diisothiocyanate, benzyl triiso(thio)cyanate, 4,4'-diphenylmethane diisocyanate or diisothiocyanate, naphthalene diisocyanate or diisothiocyanate, isophorone diisocyanate or diisothiocyanate, bis(isocyanate or isothiocyanate methyl)cyclohexane, hexamethylene diisocyanate or diisothiocyanate and dicyclohexylmethane diisocyanate or diisothiocyanate.

[0043] According to an embodiment, the rapid room temperature polymerizable composition (b) is a composition comprising one or more polymerizable cyclic sulfide compounds having two or more portions having the following formula:

[0044]

[0045] Where X is either S or O.

[0046] According to the embodiments, the filter element is selected from polarizing film, polarizing laminate, photochromic film, photochromic laminate, near-infrared filter, near-infrared laminate, blue light cutoff filter, blue light cutoff laminate, microstructured film and microstructured laminate.

[0047] According to the embodiments, the catalyst composition consists of compounds selected from tertiary amines such as triethylamine, organometallic compounds such as dibutyltin dilaurate, and alkali metal, alkaline earth metal, transition metal and ammonium salts or mixtures thereof of acids, wherein these salts satisfy the condition 0.5≤pKa≤14.

[0048] The present invention further relates to an optical article manufactured by the above method.

[0049] Further details relating to different embodiments of the invention will be described in the Detailed Description of the Invention section, without limiting the general methods described above. Detailed Implementation

[0050] In the following description, although various embodiments of manufacture and use are discussed in detail, it should be understood that many inventive concepts, as described herein, can be embodied in a variety of contexts. The embodiments discussed herein are merely illustrative and do not limit the scope of the invention. It will also be apparent to those skilled in the art that all technical features defined with respect to the method can be transposed individually or in combination to the apparatus, and conversely, all technical features with respect to the apparatus can be transposed individually or in combination to the method.

[0051] The words or terms used herein have their simple, ordinary meaning in the field of this disclosure, unless to the extent expressly and clearly defined in this disclosure, or unless the specific context otherwise requires a different meaning.

[0052] If there is any conflict in the use of words or terms in this disclosure or in one or more patents or other documents that may be incorporated by reference, the definitions consistent with those in this specification shall prevail.

[0053] The terms “comprising,” “containing,” “including,” “having,” and all their grammatical variations are intended to have an open, non-limiting meaning. For example, a composition comprising a component does not exclude the presence of additional components, an apparatus comprising a part does not exclude the presence of additional parts, and a method comprising steps does not exclude the presence of additional steps. When such terms are used, compositions, apparatuses, and methods that are “substantially composed of the specified components, parts, and steps” or “composed of the specified components, parts, and steps” are specifically included and disclosed. As used herein, the term “substantially composed of…” and all its grammatical variations are intended to limit the scope of the claims to the specified materials or steps and those that do not substantially affect one or more essential and novel features of the claimed invention.

[0054] The indefinite article “a / an” means one or more of the components, parts or steps introduced by the article.

[0055] Whenever a range of values ​​for a degree or measurement with a lower and upper limit is disclosed, it is also intended to specifically disclose any number and any range that falls within that range. For example, each range of values ​​(in the form of “from a to b” or “from about a to about b” or “from about a to b”, “from approximately a to b”, and any similar expressions, where “a” and “b” represent the numerical values ​​of the degree or measurement) should be understood to list every number and range included within the wider range of values, and to include the values ​​“a” and “b” themselves.

[0056] Terms such as “first,” “second,” and “third” can be arbitrarily assigned and are intended only to distinguish two or more components, parts, or steps that are otherwise similar or corresponding in nature, structure, function, or action. For example, the words “first” and “second” have no other use and are not part of the name or description of the following terms or names. The use of the term “first” alone does not require any “second” similar or corresponding component, part, or step. Similarly, the use of the term “second” alone does not require any “first” or “third” similar or corresponding component, part, or step. Furthermore, it should be understood that the use of the term “first” alone does not require that an element or step be the first in any order, but only that it is at least one of the elements or steps. Similarly, the use of the terms “first” and “second” alone does not necessarily require any order. Therefore, the use of such terms alone does not preclude the insertion of elements or steps between “first” and “second” elements or steps.

[0057] As used herein, polymerization / polymerizing / polymerizable refers to a chemical reaction that produces a combination of two or more monomers and / or oligomers to form a polymer. Polymerization and all grammatical variations include photopolymerizable and / or thermopolymerizable compositions. Photopolymerizable means polymerization that occurs by exposing the composition to activated light. Thermopolymerizable means polymerization that occurs by exposing the composition to temperature variations.

[0058] As used herein, curing refers to the chemical process of converting monomers or oligomers into polymers with higher molar masses and then into networks.

[0059] As used herein, "monomer" and / or "oligomer" means a compound that contains at least a reactive group capable of reacting in the presence of an initiator or catalyst. Further details regarding the "reactive group" involved will be described later in this specification.

[0060] As used herein, a "prepolymer" refers to a monomer or monomer system that has reacted to an intermediate molecular weight state. Such materials can be further polymerized through reactive groups to a fully cured, high molecular weight state. Therefore, a mixture of reactive polymers and unreacted monomers can also be called a prepolymer. The terms "prepolymer" and "polymer precursor" are used interchangeably.

[0061] As used in this article, "viscosity" refers to the fluid's resistance to deformation.

[0062] As used herein, the interchangeable terms "rapid room temperature polymerizable composition" or "rapid curing room temperature polymerizable composition" refer to a composition that cures at room temperature in 10 minutes or less. In other words, the composition gels, resulting in a hard gel after a short time and at room temperature. By forming a hard gel, one means that the resulting polymeric composition is self-supporting, i.e., capable of maintaining its own shape without deformation.

[0063] As used herein, an ophthalmic lens is to be understood as transparent when no significant loss of contrast is perceived when viewing an image through it, i.e., when image formation through the ophthalmic lens is obtained without adversely affecting the quality of the image. Within the scope of this disclosure, this definition of the term "transparent" may be applied to all objects so defined herein.

[0064] The posterior surface (usually a concave surface) of the lens substrate is the surface of the lens substrate that is closest to the wearer's eye during use. The anterior surface (usually a convex surface) of the lens substrate is the surface of the lens substrate that is furthest from the wearer's eye during use.

[0065] According to a first aspect, the present invention relates to a method for rapidly curing a transparent casting substrate that can be used to manufacture optical articles such as ophthalmic lenses, the method comprising the following steps:

[0066] -Provides fast room temperature polymerizable compositions;

[0067] -Provide catalyst compositions;

[0068] - Provides a casting mold assembly comprising two unsealed molds, each having an inner surface and an outer surface; and optionally provides a filter element placed or configured to be positioned between the two molds.

[0069] -Deposit the catalyst composition:

[0070] - On at least one of the inner surfaces of these molds, and / or;

[0071] - On at least one surface of the filter element, it is then positioned in the mold assembly;

[0072] - Close the casting mold assembly so that the inner surfaces of these molds together form a mold cavity;

[0073] - The rapid room temperature polymerizable composition is filled into the mold cavity of the casting mold assembly, the mold cavity already containing a catalyst composition deposited on the inner surface of at least one of these molds;

[0074] - Curing the filled mold assembly to obtain a transparent solid substrate, the curing step comprising:

[0075] a) A first step for polymerizing the composition at room temperature to obtain a gel; and

[0076] b) A second step of post-curing the gel to obtain the transparent solid substrate; and

[0077] - The transparent solid substrate is recovered from the casting mold assembly.

[0078] The method includes the step of providing a casting mold assembly containing two unsealed molds, each having an inner surface and an outer surface.

[0079] A casting mold assembly containing two unsealed molds, each with an inner and outer surface, serves as a template for the final shape of the substrate. The mold cavity thus defines the final shape. According to an embodiment, it has a curved shape to obtain a final substrate with concave and convex surfaces. Therefore, the inner surfaces of the two components of the casting mold are each curved, one showing a convex surface and the other showing a concave surface. Thus, the inner surface of the mold constituting the casting assembly corresponds to the surface forming the mold cavity.

[0080] Optionally, the filter element can be placed between two molds. The filter element can be placed between the inner surfaces of the two molds.

[0081] Before adding the rapid room temperature polymerizable composition, the catalyst composition can be deposited in the mold cavity in various ways.

[0082] According to an embodiment, a catalyst composition is deposited on an inner surface of a mold component forming a mold assembly within a mold cavity.

[0083] According to an embodiment, a catalyst composition is deposited on two inner surfaces of a mold component forming a mold assembly within a mold cavity.

[0084] According to an embodiment, a catalyst composition is deposited on one side or one surface of a filter element, and then added into a mold cavity.

[0085] According to an example, a catalyst composition is deposited on both surfaces of a filter element and then added into a mold cavity.

[0086] According to an embodiment, a catalyst composition is deposited in a mold cavity on an inner surface of a mold component forming a mold assembly and on a surface of a filter element, and then added into the mold cavity.

[0087] According to an embodiment, a catalyst composition is deposited in the mold cavity on an inner surface of a mold component forming a mold assembly and on both surfaces of a filter element, and then added to the mold cavity.

[0088] According to an embodiment, a catalyst composition is deposited in a mold cavity on two inner surfaces of a mold component forming a mold assembly and on one surface of a filter element, and then added into the mold cavity.

[0089] According to an embodiment, a catalyst composition is deposited in the mold cavity on two inner surfaces of the mold component forming the mold assembly and on two surfaces of the filter element, and then added to the mold cavity.

[0090] According to an embodiment, the filter element is first disposed between two mold components forming the mold assembly. Then, a catalyst composition is deposited within the mold cavity on either inner surface of one of the mold components forming the mold assembly.

[0091] According to an embodiment, the filter element is first disposed between two mold components forming the mold assembly. Then, a catalyst composition is deposited within the mold cavity on two inner surfaces of the mold components forming the mold assembly.

[0092] According to an embodiment, a filter element is first disposed on an inner surface of a mold component forming a mold assembly. A catalyst composition is then deposited within the mold cavity on the remaining inner surface of the mold component forming the mold assembly.

[0093] According to an embodiment, the filter element is first disposed on an inner surface of a mold component forming a mold assembly. A catalyst composition is then deposited within the mold cavity on the remaining inner surface of the mold component forming the mold assembly and on the surface of the filter element.

[0094] According to an embodiment, the filter element is first disposed on an inner surface of a mold component forming the mold assembly. A catalyst composition is then deposited within the molding cavity onto the surface of the filter element.

[0095] According to an embodiment, the deposition of the catalyst composition on at least one inner surface of the mold and / or at least one side of the filter element is performed by liquid phase deposition.

[0096] According to embodiments, the deposition of the catalyst composition on at least one inner surface of a mold and / or at least one side of a filter element is performed by spin coating, dip coating, spray coating, brush coating or roll coating.

[0097] Typically, the thickness of the catalyst composition layer ranges from 0.5 to 20 μm. According to examples, the thickness of the catalyst composition layer ranges from 1 to 20 μm, or from 1 to 5 μm, or from 1 to 3 μm.

[0098] The compositions disclosed herein are highly reactive at room temperature and can be gelled within polymerization times ranging from 1 to 60 minutes. According to examples, the compositions disclosed herein have short gel times ranging from 1 to 5 minutes.

[0099] Therefore, this disclosure relates to a method for manufacturing casting substrates, such as optical articles and in particular lenses, without any shelf-life issues, for example, by mixing the required amounts of each component (except the catalyst) of the composition according to this disclosure as described above just before casting.

[0100] Traditional molds consist of two parts, referred to herein as components, typically made of mineral glass, with annular closures such as washers or tapes around their perimeter, which together define the desired mold cavity.

[0101] According to an embodiment, when the annular closure of the two-part mold assembly is removed, the polymeric composition is self-supporting within the mold assembly.

[0102] Typically, filling the mold cavity is achieved using a conduit connected to a pressurized molding material reservoir and applied to the casting opening like a filling nozzle. Injector filling can be connected to an electric or pneumatic device. In this way, the precise amount of composition can be easily adjusted and fixed for accurate delivery. Polymerization can then begin immediately after filling.

[0103] After a short period at room temperature, a gel is obtained. Gel formation within the mold occurs at room temperature and has a duration ranging from 1 to 60 minutes or from 1 minute to less than 15 minutes, typically around 10 minutes, although shorter gel times of 1 to 5 minutes may still be preferred.

[0104] The gel is then cured in an oven at elevated temperatures to complete the polymerization, such as an air oven, typically at temperatures ranging from 50°C to 150°C or from 100°C to 130°C, and usually for 2 to 4 hours. According to an example, the mold assembly is placed in an air oven and heated at 120°C for 2 hours.

[0105] Next, the mold assembly is removed from the oven, the annular closure is removed, and the mold parts are disassembled to recover the substrate. The recovered substrate or product can then be edge-machined to obtain the finished lens.

[0106] Subsequently, the substrate or product can be colored, coated to improve scratch resistance, and anti-reflective treatments can be added. Furthermore, as explained below, microstructured films and laminates can be added.

[0107] Rapid room temperature polymerizable compositions that can be used in this disclosure

[0108] According to the examples, the rapid room temperature polymerizable composition has a viscosity at 25°C ranging from 0.1 to 0.3 Pa·s.

[0109] A major problem associated with molding methods, especially those used to manufacture optical substrates such as ophthalmic lenses, is obtaining defect-free, particularly streaky, substrates. If the liquid monomer mixture has a relatively low viscosity, i.e., less than 3.10⁻³ Pa·s at 25°C, the gelation time is relatively long. In that case, localized hot spots appearing within the mixture during polymerization generate convection, resulting in so-called "convection-induced streaks" within the final polymerized substrate.

[0110] As the viscosity of the mixture decreases, the formation rate of such convection-induced streaks increases. On the other hand, filling the mold cavity with only the monomer mixture produces so-called "filling-induced streaks." The relaxation time required to eliminate such filling-induced streaks increases with increasing monomer mixture viscosity.

[0111] Furthermore, when using monomer mixtures with relatively high viscosity, it is difficult to eliminate air bubbles that may be trapped within the liquid monomer mixture.

[0112] As a result, the rapid room temperature polymerizable compositions according to this disclosure, having a viscosity ranging from 0.1 to 0.3 Pa·s at 25°C, allow for the acquisition of transparent casting substrates that overcome the shortcomings of prior art methods and are therefore substantially free of optical defects, particularly convection and / or fill-induced streaks.

[0113] According to this disclosure, the rapid room temperature polymerizable composition is selected from compositions comprising:

[0114] (a) A poly(thio)urethane prepolymer terminated with at least one poly(iso)thiocyanate monomer or liquid NCO or NCS and a poly(thio)urethane prepolymer terminated with at least one polythiol monomer or liquid SH; or

[0115] (b) One or more polymerizable cyclic sulfide compounds.

[0116] Therefore, the fast room temperature polymerizable composition (a) is a mixture selected from the following:

[0117] (i) at least one poly(isothiocyanate) monomer and at least one polythiol; or

[0118] (ii) A mixture of at least one liquid NCO or NCS-terminated poly(sulfur)urethane prepolymer and at least one liquid SH-terminated poly(sulfur)urethane prepolymer, or

[0119] (iii) A poly(isothiocyanate) prepolymer with at least one poly(isothiocyanate) monomer and at least one liquid SH-terminated poly(thio)urethane prepolymer; or

[0120] (iv) A poly(thio)urethane prepolymer with at least one polythiol and at least one liquid NCO or NCS-terminated prepolymer.

[0121] Mixture (a)(i)

[0122] According to the examples, the rapid room temperature polymerizable composition is selected from at least one poly(iso)thiocyanate monomer and at least one polythiol.

[0123] As used herein, poly(iso)thiocyanate monomers refer to polyisocyanates or polyisothiocyanate monomers.

[0124] A rapidly room-temperature polymerizable composition containing at least one poly(iso)thiocyanate monomer and at least one polythiol has a viscosity at 25°C ranging from 0.1 to 0.3 Pa·s.

[0125] The NCX / SH and SH / NCX ratios range from 6:1 to 10:1. The amounts of polyisocyanate or polyisothiocyanate monomers and polythiol monomers are adjusted so that the NCX / SH ratio of the mixture ranges from 4:1 to 30:1. The NCX / SH and SH / NCX ratios can also range from 6:1 to 10:1.

[0126] Polyisocyanate or isothiocyanate monomers can be any polyisocyanate or isothiocyanate monomer having two or more isocyanate or isothiocyanate functional groups per molecule, or two or three isocyanate or isothiocyanate functional groups.

[0127] According to the embodiments, the polyisocyanate or isothiocyanate monomers are those having the following formula:

[0128] in

[0129] R 1 It is independently an H or C1-C5 alkyl group;

[0130] R 2 It is H, halogen, or C1-C5 alkyl;

[0131] Z is -N = C = X, where X is O or S;

[0132] a is an integer ranging from 1 to 4, b is an integer ranging from 2 to 4, and a + b ≤ 6; and

[0133] x is an integer from 1 to 10.

[0134] According to the embodiments, R1 is independently CH3 or C2H5.

[0135] According to the examples, R2 is chlorine or bromine.

[0136] According to the embodiments, R2 is CH3 or C2H5.

[0137] According to the embodiment, Z is -N=C=X, where X is O.

[0138] According to the example, x is an integer from 1 to 6.

[0139] Among the polyisocyanate or isothiocyanate monomers, examples include toluene diisocyanate or diisothiocyanate, phenylene diisocyanate or diisothiocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate or diisothiocyanate, dimethyl phenylene diisocyanate or diisothiocyanate, diethyl phenylene diisocyanate or diisothiocyanate, diisopropyl phenylene diisocyanate or diisothiocyanate, trimethylbenzyl triisocyanate or triisothiocyanate, phenyl dimethyl diisocyanate or diisothiocyanate, benzyl triiso(thio)cyanate, 4,4'-diphenylmethane diisocyanate or diisothiocyanate, naphthalene diisocyanate or diisothiocyanate, isophorone diisocyanate or diisothiocyanate, bis(isocyanate or diisothiocyanate methyl)cyclohexane, hexamethylene diisocyanate or diisothiocyanate, and dicyclohexylmethane diisocyanate or diisothiocyanate.

[0140] According to the embodiments, the polyisocyanate monomer is phenyl dimethyl diisocyanate and the polythiol monomer is 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol.

[0141] Single polyisocyanates or isothiocyanate monomers or mixtures thereof can be used.

[0142] The polythiol monomer can be any suitable polythiol having two or more thiol functional groups. It can have two or three thiol functional groups.

[0143] Polythiol monomers can be represented by the formula R'(SH)n', where n' is an integer from 2 to 6, and R' is an organic group with a valence equal to n'. n' can be an integer from 3 to 4.

[0144] Useful polythiol monomers are those disclosed in EP-A-394,495 and U.S. Patent No. 4,775,733 and the polythiols corresponding to the following formula:

[0145]

[0146] C

[0147] C2H5C(CH2COOCH2CH2SH)3

[0148] Among polythiol monomers, aliphatic polythiols can be listed, such as pentaerythritol tetramercaptopropionate, 1-(1'-mercaptoethylthio)-2,3-dimercaptopropane, 1-(2'-mercaptopropylthio)-2,3-dimercaptopropane, 1-(-3'-mercaptopropylthio)-2,3-dimercaptopropane, 1-(-4'-mercaptobutylthio)-2,3-dimercaptopropane, 1-(5'-mercaptopentylthio)-2,3-dimercaptopropane, 1-(6'-mercaptohexylthio)-2,3-dimercaptopropane, 1,2-bis(-4'-mercaptobutylthio)-3-mercaptopropane, 1,2-bis(-5'-mercaptopentylthio)-3-mercaptopropane, 1,2 -bis(-6'-mercaptohexyl)-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, methyl dithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexylthiol-1,2,3-propanetrithiol and 1,2-bis(-2'-mercaptoethylthio)-3-mercaptopropane.

[0149] According to the examples, the polythiol is 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol.

[0150]

[0151] Polythiols have a viscosity of 2.10-1 Pa·s or less, or 10-1 Pa·s or less, or 0.5-10-1 Pa·s or less at 25°C.

[0152] Mixtures (a)(ii)

[0153] According to the embodiments, the rapid room temperature polymerizable composition is selected from a mixture of at least one liquid NCO or NCS-terminated poly(sulfur)urethane prepolymer and at least one liquid SH-terminated poly(sulfur)urethane prepolymer.

[0154] The mixture (ii) comprises:

[0155] - Component A, comprising a polysulfurethane prepolymer having isocyanate or isothiocyanate (NCX, where X is O or S) end groups and a viscosity at 25°C ranging from 0.02 to 0.4 Pa·s, and with

[0156] - Component B, which comprises a polysulfururethane prepolymer having thiol (SH) end groups and a viscosity at 25°C ranging from 0.2 to 2.0 Pa·s.

[0157] Components A and B are obtained by polymerizing at least one polyisocyanate or polyisothiocyanate monomer and at least one polythiol monomer.

[0158] The polyisocyanates or isothiocyanates used to prepare prepolymer components A and B can be any polyisocyanate or isothiocyanate monomer having two or more isocyanate or isothiocyanate functional groups per molecule, preferably two or three isocyanate or isothiocyanate functional groups, and more preferably two isocyanate or isothiocyanate functional groups.

[0159] Components A and B are obtained by polymerizing at least one polyisocyanate or polyisothiocyanate monomer and at least one polythiol monomer, such as those monomers having the formula described in detail in the above reference mixtures (a) and (i).

[0160] The polymerization method is classic; however, in each case, the amounts of polyisocyanate or isothiocyanate monomers and polythiol monomers in the reaction medium should be adjusted. Typically, components A and B can be prepared by classic thermal polymerization (including induction and infrared heating).

[0161] Component A

[0162] Component A comprises a polysulfuric ester prepolymer having isocyanate or isothiocyanate (NCX, where X is O or S) end groups and a viscosity at 25°C ranging from 0.02 to 0.4 Pa·s.

[0163] It is obtained by polymerizing at least one polyisocyanate or polyisothiocyanate monomer and at least one polythiol monomer as described in detail in the above reference mixtures (a)(i).

[0164] Adjust the amounts of polyisocyanate or polyisothiocyanate monomers and polythiol monomers such that the ratio of the mixture of polyisocyanate or isothiocyanate monomers and polythiol monomers NCX / SH ranges from 4:1 to 30:1 to obtain component A.

[0165] Therefore, component A can have a molar ratio of isocyanate or isothiocyanate groups to thiol groups NCX / SH ranging from 4:1 to 30:1.

[0166] According to the embodiments, the NCX / SH ratio ranges from 6:1 to 10:1.

[0167] Component B

[0168] Component B comprises a polysulfururethane prepolymer having thiol (SH) end groups and a viscosity at 25°C ranging from 0.2 to 2.0 Pa·s.

[0169] It is obtained by polymerizing at least one polyisocyanate or polyisothiocyanate monomer and at least one polythiol monomer as described in detail in the above reference mixtures (a)(i).

[0170] Adjust the amounts of polyisocyanate or polyisothiocyanate monomers and polythiol monomers such that the ratio of the mixture of polyisocyanate or isothiocyanate monomers and polythiol monomers SH / NCX ranges from 4:1 to 30:1 to obtain component B.

[0171] Therefore, component B can have a molar ratio of thiol groups to isocyanate or isothiocyanate groups SH / NCX ranging from 4:1 to 30:1.

[0172] According to the embodiments, the SH / NCX ratio ranges from 6:1 to 10:1.

[0173] The preparation of prepolymers with thiol end groups has been described in U.S. Patent No. 6,887,401. A similar method can be used to prepare component B of this disclosure.

[0174] Component A disclosed herein can be prepared in a similar manner, but with the desired ratio of polyisocyanate or isothiocyanate to polythiol monomer to obtain a polythiourethane prepolymer with isocyanate or isothiocyanate end groups. Detailed examples are given below.

[0175] In specific embodiments, the rapid room temperature polymerizable compositions disclosed herein are in the form of two-component polymerizable compositions, i.e., a composition of two separate components formulated to be mixed together immediately before use.

[0176] In this two-component embodiment, the composition comprises a first separate component or premix containing all of the polyisocyanate monomer, possibly some or all of the polythiol monomer, and optionally a UV absorber and a release agent, and a second separate component or premix containing some or all of the polythiol monomer, and optionally a solvent.

[0177] In this two-component embodiment of the composition disclosed herein, the first premix comprises:

[0178] 40-100 parts by weight of polyisocyanate monomer,

[0179] 0-60 parts by weight of polythiol monomers;

[0180] 0-0.3 parts by weight of UV absorber; and

[0181] 0-0.2 parts by weight of internal release agent;

[0182] And the second premix contains:

[0183] 0-100 parts by weight of polythiol monomers;

[0184] 0-1 parts by weight of solvent.

[0185] The following example illustrates the preparation of prepolymer components A and B.

[0186] The mixing of component A and component B can be carried out by any known mixing technique such as those mentioned in U.S. Patent No. 6,887,401, wherein components A and B are mixed in the absence of any catalyst.

[0187] Mixing (which can be mechanical or ultrasonic) typically takes place at room temperature for a duration ranging from 10 to 180 seconds. Components A and B to be mixed can be added to a small reactor chamber and then mixed using a screw mixer.

[0188] Preparation of polythiourethane prepolymer with isocyanate end groups (component A)

[0189] A defined amount of phenyl dimethyl diisocyanate (XDI) was charged into a reactor equipped with a condenser, a heat probe, and a stirrer. The polyisocyanate monomer was then heated to 115°C. Next, 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol was introduced and mixed with the polyisocyanate in an amount such that the molar ratio of isocyanate functional groups to thiol functional groups was...

[0190] It is 6:1.

[0191] The reaction is complete after heating for 3 to 4.5 hours.

[0192] The prepolymer is then cooled, and when the prepolymer temperature reaches 35°C (+ / -5°C), it is transferred to a suitable container, protected with an inert gas (nitrogen or argon), and stored in a cold room.

[0193] The final prepolymer (component A) with isocyanate end groups has a viscosity of 0.219 Pa·s at 25 °C.

[0194] Preparation of polythiourethane prepolymer with thiol end groups (component B)

[0195] A defined amount of 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol is charged into a reactor equipped with a condenser, a heat probe, and a stirrer.

[0196] The polythiol monomer was then heated to 90°C. Next, phenyl dimethyl diisocyanate (XDI) was introduced and mixed with the polythiol in an amount such that the molar ratio of thiol groups to isocyanate groups was...

[0197] It is 8:1.

[0198] The reaction is completed within 3 hours. The reaction ends when the temperature reaches its peak and returns to 90°C (+ / -2°C).

[0199] The prepolymer is then cooled, and when the prepolymer temperature reaches 35°C (+ / -5°C), it is transferred to a suitable container, protected with an inert gas (nitrogen or argon), and stored in a cold room.

[0200] The final prepolymer (component B) with thiol end groups has a viscosity of 0.543 Pa·s at 25 °C.

[0201] Mixtures (a)(iii)

[0202] According to the examples, the rapid room temperature polymerizable composition is selected from a mixture of at least one poly(iso)thiocyanate monomer and at least one liquid SH-terminated poly(thio)urethane prepolymer.

[0203] At least one polyisocyanate or polyisothiocyanate monomer is the monomer described above with respect to mixture (a)(i). At least one liquid SH-terminated poly(thio)urethane prepolymer is the monomer described above with respect to mixture (a)(ii) as component B.

[0204] Mixture (a)(iv)

[0205] According to the examples, the rapid room temperature polymerizable composition is selected from a mixture of at least one polythiol and at least one liquid NCO or NCS-terminated poly(thio)urethane prepolymer.

[0206] At least one polythiol is described above with respect to mixture (a)(i). At least one liquid NCO or NCS-terminated poly(thio)urethane prepolymer is described above with respect to mixture (a)(ii) as component A.

[0207] Mixture (b)

[0208] According to the embodiments, the rapid room temperature polymerizable composition is selected from one or more polymerizable cyclic sulfide compounds.

[0209] The cyclic sulfide compounds used in these compositions disclosed herein are those described in the above-cited European patent applications EP-A-761665 and 785194. These cyclic sulfide compounds have two or more portions having the following formula: Where X is S or O,

[0210] At least one of these parts is a cyclic sulfide group.

[0211] The rapid room temperature polymerizable compositions disclosed herein may contain up to 100% by weight of one or more cyclic sulfide compounds, or the polymerizable compositions may contain one or more cyclic sulfide compounds and one or more copolymerizable monomers.

[0212] Among the copolymerizable monomers that can be used are the polythiol monomers described above.

[0213] Catalyst compositions that can be used in this disclosure

[0214] Catalyst compositions that can be used in the methods described herein include tertiary amines such as triethylamine, organometallic compounds such as dibutyltin dilaurate, and alkali metal, alkaline earth metal, transition metal, and ammonium salts or mixtures thereof of acids, which satisfy the condition 0.5 ≤ pKa ≤ 14.

[0215] These salts are defined as having the following formula: Mm P+ Y n - ,in:

[0216] Mm P+ It is a cation selected from the group consisting of: alkali metals, alkaline earth metals, transition metals, and cations with the formula NR. + 4-Ammonium group, where R is an alkyl group,

[0217] Y- is an anion, such as the corresponding acid YH, which has a pKa that satisfies the condition 0.5 ≤ pKa ≤ 14.

[0218] p is the valence of the cation, and

[0219] n = mxp.

[0220] The catalyst composition may consist of only salts or mixtures of such salts.

[0221] The metal cation of the salt is Li + Na + K + 、Rb + Mg 2+ Ca 2+ Ba 2+ And Al 3+ The particularly preferred metal cation is Li. + Na + and K + Because they do not have color or solubility in the composition.

[0222] Transition metals are less preferred because their salts cause coloring of the composition and thus the polymeric resin.

[0223] NR +The 4 groups can be those in which R is a C1-C8 alkyl group, and more preferably methyl, ethyl, propyl, butyl, or hexyl.

[0224] Salt should be used in a sufficient amount (i.e., an amount sufficient to promote room temperature polymerization of the composition) in rapidly room temperature polymerizable compositions.

[0225] Typically, based on the total weight of the polymerizable monomers, the salt will be present in amounts ranging from 5 to 2000 parts per million (ppm), or from 10 to 500 ppm, or from 40 to 100 ppm.

[0226] Y- can be an anion, such as the corresponding acid YH that satisfies the condition 0.5≤pKa≤10 and more preferably 0.5≤pKa≤8.

[0227] The anion Y- can be selected from the group consisting of: thiocyanate, carboxylate, thiocarboxylate, acetylacetonate, diketone, acetoacetate, malonate, cyanoacetate, ketone nitrile and anion having the formula RS-, where R is a substituted or unsubstituted alkyl or phenyl group.

[0228] Alkyl groups can be C1-C6 alkyl groups, such as methyl, ethyl, and propyl.

[0229] The anion Y- is thiocyanate (SCN) - ), acetylacetonate, acetate, thioacetate, formate and benzoate.

[0230] According to the example, the salt is KSCN.

[0231] Typically, the salt will be present in an amount ranging from 0.001% to 2.5%, preferably from 0.001% to 1%, based on the total weight of the polymerizable monomers. Electron-donating compounds may be used in combination with the salt and are selected from the group consisting of acetonitrile compounds, amide compounds, sulfones, sulfoxides, trialkyl phosphites, nitro compounds, glycol ethers, crown ethers, and kryptates.

[0232] Examples of acetonitrile compounds are:

[0233] N≡C-CH2-C≡N and in

[0234] R stands for alkyl. It can be a C1-C6 alkyl group, such as methyl, ethyl, propyl, or butyl.

[0235] Amide compounds can be primary, secondary, or tertiary amide compounds.

[0236] Trialkyl phosphite and triaryl phosphite can be represented by the following formula:

[0237] in

[0238] R, R', R"' are alkyl groups, preferably C1-C6 alkyl or aryl such as phenyl. Trialkyl phosphites are preferred, for example (C2H5O)3P.

[0239] Electron donor compounds can also be selected from crown ethers and krypton esters.

[0240] These cyclic molecules are typically chosen to exhibit a good compromise between the size of heteroatoms or metals and the size of the "cage," that is, between the number and size of heteroatoms and the size of the "cage," that is, between the number of heteroatoms and the size of the ring.

[0241] Preferred crown ethers and krypton esters can be represented by the following formula:

[0242] in

[0243] X 1 Represents 0, S, or NH, where x1 is an integer from 3 to 6, preferably from 3 to 4.

[0244] X 2 X 3 and X 4 This indicates that O, S, n2, n3, n4, y2, y3, y4 are 2 or 3 and x2, x3, x4 are 2 or 3.

[0245] Among the preferred crown ethers and krypton esters, the following compounds can be listed:

[0246]

[0247] Based on the total weight of the polymerizable monomers, the electron donor compound is present in an amount ranging from 0% to 5% by weight, preferably from 0% to 1% by weight, and most preferably crown ethers such as 18-crown ether-6, 18-crown ether-7, 15-crown ether-5 and 15-crown ether-6.

[0248] For compositions containing cyclic sulfide compounds, reactivity increases with the cation size of the thiocyanate (potassium salts are more reactive than sodium salts, and sodium salts are more reactive than lithium salts).

[0249] Furthermore, for compositions containing cyclic sulfide compounds, the presence of crown ethers is highly recommended to promote polymerization. Increasing the size of the crown ether appears to decrease reactivity.

[0250] According to a specific embodiment, the catalyst composition is mixed with a portion of one of the monomers used in mixtures (a)(i) or (iii) or (iv): a poly(iso)thiocyanate monomer or a polythiol monomer. The resulting composition is then deposited on at least one inner surface of a mold and / or at least one surface of a filter element, and subsequently positioned in a mold assembly. The method continues by closing the casting mold assembly such that the inner surfaces of the molds together form a cavity and filling the cavity of the casting mold assembly with the remaining rapid room temperature polymerizable composition, which already contains the deposited catalyst composition and the portion of one of the monomers on the inner surface of at least one mold. As used in the context of this embodiment, the remaining rapid room temperature polymerizable composition comprises the remaining portion of the monomer previously mixed with the catalyst and at least one other monomer as described in mixture (a)(i) or a prepolymer as described in mixtures (a)(iii) or (iv). An example is given where, as described above, the catalyst composition is further mixed with a portion of a selected polythiol and deposited on the inner surface of the mold. Since no other monomers are added, the polymerization reaction cannot be triggered. The remaining portion of the polythiol is then filled together with other monomers (i.e., poly(iso)thiocyanate monomers) to trigger the polymerization reaction.

[0251] According to a specific embodiment, the catalyst composition is mixed with a portion of one of the prepolymers used in mixtures (a) and (ii): a liquid NCO or NCS-terminated poly(sulfur)urethane prepolymer or a liquid SH-terminated poly(sulfur)urethane prepolymer. The resulting composition is then deposited on at least one inner surface of a mold and / or at least one surface of a filter element, and subsequently positioned in a mold assembly. The method continues by closing the casting mold assembly such that the inner surfaces of the molds together form a cavity and filling the cavity of the casting mold assembly with the remaining rapid room temperature polymerizable composition, which already contains the deposited catalyst composition and the portion of one of the prepolymers on the inner surface of at least one mold. As used in the context of this embodiment, the remaining rapid room temperature polymerizable composition comprises the remaining portion of the prepolymer previously mixed with the catalyst and at least one other prepolymer as described in mixtures (a) and (ii). An example is given: as described above, the catalyst composition is further mixed with a portion of the prepolymer defined above as component B and deposited on the inner surface of the mold. Since no other prepolymers defined as component A were added above, the polymerization reaction could not be triggered. The remaining portion of prepolymer B was then added along with the other prepolymers A, thereby triggering the polymerization reaction.

[0252] Other components

[0253] The catalyst composition used may contain a solvent to promote the dissolution of the salt catalyst.

[0254] Any polar organic compound can be used, such as acetonitrile, tetrahydrofuran, or dioxane. Other suitable solvents are methanol, ethanol, thioethanol, acetone, acetonitrile, and 3-methyl-2-buten-1-ol.

[0255] Based on the total weight of the polymerizable monomers present, the amount of solvent is typically kept less than 2% by weight and preferably between 0% and 0.5% by weight, or between 0.0001% and 0.5% to avoid turbidity and foaming.

[0256] The rapid room temperature polymerizable compositions disclosed herein may also contain conventional proportions of additives commonly used in polymerizable compositions intended for use in molding optical articles, particularly ophthalmic lenses, namely inhibitors, dyes, photochromic agents, UV absorbers, fragrances, deodorants, antioxidants, antiyellowing agents, and release agents.

[0257] Fragrances can mask the odor of a composition, especially during surface treatment or grooving operations.

[0258] In particular, common UV absorbers, such as those commercially available under trade names UV 5411(R), UV 9(R), Tinuvin 400(R), Tinuvin P(R), Tinuvin 312(R), Seesorb 701(R) and Seesorb 707(R), can be used in amounts up to 2% by weight of the total polymerizable monomers.

[0259] In addition, the compositions disclosed herein may contain a release agent in an amount of up to 0.1% by weight of the total polymerizable monomer / prepolymer.

[0260] Release agents include monoalkyl phosphates and dialkyl phosphates, silicones, fluorinated hydrocarbons, fatty acids, and ammonium salts. Preferred release agents are monoalkyl phosphates and dialkyl phosphates, and mixtures thereof. Such release agents are particularly described in U.S. Patent Nos. 4,662,376, 4,975,328, and EP-271,839.

[0261] Filter element

[0262] According to the embodiments, the filter element is selected from polarizing film, polarizing laminate, photochromic film, photochromic laminate, near-infrared filter, near-infrared laminate, blue light cut-off filter, blue light cut-off filter laminate, microstructured film and microstructured laminate.

[0263] As used in this article, a “filter element” is an optical filter that limits or alters the total amount of light passing through the element.

[0264] This filter refers to a membrane structure formed by a single membrane layer or a membrane laminate structure formed by multiple membrane layers attached to each other. More precisely, the filter can be formed from an ophthalmic-grade functional membrane (having, for example, polarizing or photochromic properties) and has an ophthalmic-grade protective membrane on one or both sides of the ophthalmic-grade functional membrane. Such a multilayer filter can also be referred to as a laminate, sheet, or laminated sheet.

[0265] During the casting process, such a filter is placed in the front of the mold cavity, and a rapid room temperature polymerizable composition is injected against the filter. According to an example, a catalyst composition is deposited on at least one surface of the filter.

[0266] According to the embodiments, the filter element is a polarizing film or polarizing laminate selected from the group consisting of: a polarizing film of polyvinyl alcohol (PVA), a polarizing laminate consisting of polarizing layers supported on both sides by cellulose triacetate (TAC) / polyvinyl alcohol (PVA) / cellulose triacetate (TAC) laminate, and a polarizing laminate consisting of polarizing layers supported on both sides by polycarbonate (PC) / polyvinyl alcohol (PVA) / polycarbonate (PC) laminate.

[0267] As used in this article, PVOH and PVA can be used interchangeably.

[0268] Photochromic films or laminates are well known and contain photochromic dyes selected from the group consisting of pyrans, oxazines, succinic anhydrides, and succinic imides.

[0269] Polarizing film or laminate

[0270] Polarizing films or sheets are well known in the art and can be any polarizing film or sheet typically used in the manufacture of polarizing optical articles (such as ophthalmic lenses).

[0271] Such filters are known and described in many patents such as US20070202265, US 20180052267 and US20210268755.

[0272] Polarizing films or sheets can contain a variety of different constructions and materials. Such constructions include freestanding or unlaminated films, films with removable protective sheets, films with an external permanent protective coating or supporting plastic layer, as well as laminated films and sheets.

[0273] Among polarizing films, examples include polyethylene terephthalate (PET) film and polyvinyl alcohol (PVOH) film.

[0274] Other polarizing films may include thin, multilayer polymer materials, combined reflective polarizers and dichroic polarizers, or films of mixed polymer phases, such as those described in U.S. Patent Nos. 5,882,774; 6,096,375; and 5,867,316.

[0275] In polarizing films, examples of polycarbonate / PVOH / polycarbonate layered combinations with a thickness of less than 1 mm can be listed.

[0276] Preferably, a polarizing film with a thickness greater than 0.10 mm and more preferably from 0.20 to 0.80 mm, more preferably from 0.30 to 0.80 mm, and even more preferably from 0.40 to 0.80 mm is used.

[0277] Typically, the PVOH core membrane has a thickness of 0.01 to 0.04 mm, preferably 0.02 to 0.04 mm, and the two shell layers have a thickness of about 0.30 mm.

[0278] Materials used for sheet construction, in addition to polycarbonate, may include poly(methyl methacrylate), polystyrene, cellulose acetate butyrate (CAB), cellulose acetate, and cellulose triacetate.

[0279] According to an embodiment, the polarizing film is a CAB / PVOH / CAB multilayer combination.

[0280] According to an embodiment, the polarizing film is a multilayer combination of TAC / PVOH / TAC.

[0281] To improve the adhesion of the polarizing film to the rapidly curing, room-temperature polymerizable composition constituting the substrate, unless otherwise specified, the film can be chemically treated by immersing it in a 5% NaOH or 1N HCl aqueous solution. The immersion time and temperature can vary widely depending on the properties of the film and the polymerizable composition. Typically, immersion is carried out at temperatures ranging from 20°C to 50°C, preferably about 40°C, and lasts for up to 1 hour, preferably about 30 minutes.

[0282] The polarizing film was then rinsed with deionized water for about 15 seconds, then placed in warm deionized water for 1 minute, and finally rinsed with deionized water again for 15 seconds.

[0283] The polarizing film can then be dried. The drying temperature and time can be varied widely. The hydrophilicity of the hydrolyzed CAB layer increases, with a contact angle of approximately 30-35°.

[0284] Microstructured membrane

[0285] Alternatively, or in another embodiment of this disclosure, a microstructured film or microstructured laminate may be added. Such films or laminates are known and described in numerous patents such as EP 3895880. For applications in the field of lenses, they are added for the purposes of myopia control, increasing optical power, and / or providing antireflective properties.

[0286] As used in this article, a microstructured membrane is a membrane with microstructures on its surface.

[0287] As used herein, a microstructured laminate is a membrane having microstructures on its surface and a coating of microstructures formed on and encapsulating the membrane.

[0288] According to an embodiment, the microstructured film may be a structure suitably embedded in a rapidly room-temperature polymerizable composition constituting a substrate. According to another supplementary or alternative embodiment, the microstructured laminate may be a structure suitably applied to the outer surface of the obtained substrate. Examples of microstructures include, but are not limited to, structures for controlling myopia; structures for increasing the refractive power of the substrate, such as Fresnel microstructures; and structures for providing antireflective properties to the substrate, such as moth-eye structures.

[0289] According to embodiments, the microstructured membrane can have a thickness ranging from 50 μm to 2 mm.

[0290] According to embodiments, the microstructured membrane may include, or may be made from, a polymer such as a thermoplastic polymer. Examples of thermoplastic polymers included in or constituting the microstructured membrane include, but are not limited to, polycarbonate, thermoplastic polyurethane, polyacrylate, polyester, copolyester, polymethacrylate, polystyrene, polyamide, polysulfone, polyphenylsulfone, polyetherimide, polypentene, polyolefin, ionomer, ethylene methacrylate, cyclic olefin copolymer, acrylonitrile, and styrene-maleic anhydride.

[0291] Copolymers of these polymers can also be used. A copolymer can have two or more structures derived from different polymers in a single molecule. A copolymer can contain at least one structure derived from a polymer other than those mentioned above.

[0292] Derivatives of the above polymers can also be used. The derivatives may have at least one functional group that is molecularly bonded to the above polymer.

[0293] Mixtures of these polymers, copolymers, and / or derivatives may also be used. The mixture may be a resin containing two or more different polymer molecules. The mixture may contain at least one polymer other than those mentioned above.

[0294] The membrane may contain a variety of additives, dyes, and / or filters. Examples of additives may include, but are not limited to, heat stabilizers, release agents, HALS (hindered amine light stabilizers), and light stabilizers. Dyes may be, for example, color-balancing dyes, photochromic dyes, or dichroic dyes. Filters may be, for example, blue light-cutting dyes, UV-cutting dyes, IR-cutting dyes, or any other functional component. These additives, dyes, and filters may be used individually or in any combination.

[0295] According to an embodiment, the membrane is transparent. Microstructures can be formed on one or both surfaces of the membrane. In one embodiment, microstructures can be formed on one surface of the membrane. Microstructures can be formed by any process or method. For example, microstructures can be formed on the surface of the membrane by embossing the surface of the membrane via an embossing roller.

[0296] Microstructured laminates

[0297] According to an embodiment, the microstructured laminate comprises a membrane as described above and a coating of microstructures formed on and encapsulating the membrane. In one embodiment, the coating completely fills the gaps between the microstructures.

[0298] The coating may contain polymers such as thermoplastic polymers, or may be made from them. The aforementioned thermoplastic polymers, copolymers and derivatives of these polymers, and mixtures thereof may be used. The coating may also contain the aforementioned additives, dyes, and / or filters.

[0299] According to an embodiment, the coating is transparent.

[0300] According to an embodiment, the glass transition temperature (T1) of the film is higher than the glass transition temperature (T2) of the coating. Therefore, one or more materials of the coating can be determined based on the material of the film, and vice versa. T1 and T2 can each be from 80°C to 200°C, preferably from 85°C to 190°C, including all ranges and subranges therein. The difference between T1 and T2 can be from 10°C to 100°C, preferably from 12°C to 75°C, including all ranges and subranges therein.

[0301] For example, when the membrane is made of or contains polycarbonate, the coating may be made of or contain polymethyl methacrylate (PMMA). When the membrane is made of or contains polysulfone, the coating may be made of or contain polyester. When the membrane is made of or contains copolyester, the coating may be made of or contain PMA. When the membrane is made of or contains polyamide, the coating may be made of or contain PMA. When the membrane is made of or contains copolyester, the coating may be made of or contain thermoplastic polyurethane. Furthermore, the membrane and coating may be made of the same polymer, provided that the glass transition temperature (T1) of the membrane is higher than the glass transition temperature (T2) of the coating. For example, when the membrane is made of or contains polyamide, the coating may be made of or contain polyamide with a glass transition temperature lower than that of the polyamide in the membrane. These combinations are provided for illustrative purposes only, and the combination of materials for the film and coating is not particularly limited, provided that the glass transition temperature (T1) of the film is higher than the glass transition temperature (T2) of the coating.

[0302] According to an embodiment, the refractive index (n2) of the coating is different from the refractive index (n1) of the film. n1 and n2 can each be from 1.45 to 1.65, preferably from 1.49 to 1.64, including all ranges and subranges therebetween.

[0303] The coating thickness (h2) can be determined based on the size of the microstructures on the film surface, and / or based on the film thickness (h1) and the modulus of the film and coating.

[0304] Minimum coating thickness (h) 2，最小 The height of the microstructure on the membrane surface can be equal to the height of the microstructure, or it can be calculated using the following equation (1), taking the larger one: h 2(最小) =h1×(E1 / E2)

[0305] Where E1 is the modulus of the film and E2 is the modulus of the coating.

[0306] The coating can be thick enough that the microstructures on the film surface are substantially or completely embedded in the coating.

[0307] The maximum thickness of the coating (h2, maximum) is not particularly limited and can be determined based on the application of the laminate.

[0308] The coating material can be well compatible with the membrane material, enabling strong adhesion between the coating and the membrane. In one aspect, the coating can bond to the membrane such that the peel strength between the membrane and the coating (measured according to test method ASTM D1876-01) is at least 100 g / 25 mm.

[0309] According to an embodiment, both the microstructured membrane and the microstructured laminate described above can be deformed into a selected shape by applying heat, pressure, or both.

[0310] Deformation can be achieved, for example, through thermoforming using a thermoforming machine or through injection molding using inserts. During deformation, the laminate can be inserted into a mold, thus applying pressure directly to the coating of the laminate. Alternatively, a polymer lens can be inserted into the mold along with the laminate, allowing the laminate and polymer lens to be injection molded together. The polymer lens can be made of or contain the film material. The laminate can also be inserted into the mold close to an insert, and a thermoplastic polymer melt can be injection molded onto the laminate. This also applies to microstructured films.

[0311] Deformation can be performed at a temperature below the glass transition temperature (T1) of the film. In one embodiment, deformation can be performed at a temperature around the glass transition temperature (T2) of the coating and below the glass transition temperature (T1) of the film. By performing deformation at this temperature, the laminate can be deformed while the microstructures formed on the film surface remain unchanged. This also applies to microstructured films.

[0312] According to one aspect, this disclosure relates to an optical article manufactured by the method of the first aspect.

[0313] According to one aspect, this disclosure relates to an ophthalmic lens manufactured by the method of the first aspect.

[0314] The transparent ophthalmic lens manufactured according to the embodiments of this disclosure refers to an ophthalmic lens selected from blank lenses, semi-finished lenses, finished lenses, and lenses adapted to see through a "head-mounted display (HMD)". A "head-mounted display" should be understood as a device that can be mounted on a wearer's head and includes an optical imager for shaping a beam of light from an electronic and optical system that generates a beam of light from electronic signals, such as a miniature screen, laser diode, or light-emitting diode (LED); the optical imager guides the beam of light toward the wearer's eyes to enable access to information content.

[0315] The transparent ophthalmic lens can also refer to a lens selected from the following: afocal (or uncorrected or plano), monofocal, bifocal, trifocal, and progressive lenses. The ophthalmic lens can be mounted on a conventional frame containing two different ophthalmic lenses (one for the right eye and one for the left eye), or on a mask, face shield, helmet sight, or goggle, where one ophthalmic lens faces both the right and left eyes simultaneously. The ophthalmic lens can be manufactured in a conventional geometry as a circle or in a geometry that can be fitted into the intended frame. When the ophthalmic lens is specifically designed for mounting on a see-through "HMD," the lens can be corrective or afocal and can be placed on the front and / or back of the HMD's optical imager. When the ophthalmic lens is placed on the front and back of the optical imager, it means that the optical imager is inserted inside the ophthalmic lens.

[0316] According to this disclosure, an "ophthalmic lens" is defined as a lens adapted for mounting in eyeglasses, whose function is to protect the eyes and / or correct vision; this lens is selected from afocal, monofocal, bifocal, trifocal, and progressive lenses. It should then be understood that the ophthalmic lens can be corrective or uncorrective. The eyeglasses in which the ophthalmic lens will be mounted can be conventional frames containing two different ophthalmic lenses (one for the right eye and one for the left eye), or like masks, face shields, helmet visors, or goggles, where one ophthalmic lens faces both the right and left eyes simultaneously. Ophthalmic lenses manufactured using the methods disclosed herein can be produced in a conventional geometry as a circle or can be manufactured to fit into a desired frame.

[0317] Furthermore, ophthalmic lenses manufactured according to the methods disclosed herein can be functionalized in an optional post-processing step by adding at least one functional coating and / or functional film. Functionality can be added to one or both sides of the ophthalmic lens, and the functionality can be the same or different on each side. Among the functionalities, by way of example and without limitation, those selected from the following can be mentioned: shock resistance, abrasion resistance, stain resistance, antistatic properties, anti-reflective properties, anti-fogging properties, rain resistance, self-healing properties, polarization, tinting, photochromism, and selective wavelength filters, which can be obtained by using absorption filters or reflection filters. Such selective wavelength filters are of particular interest for filtering, for example, ultraviolet radiation, blue light radiation, or infrared radiation.

[0318] Functionality can be added using at least one process selected from dip coating, spin coating, spray coating, vacuum deposition, transfer processes, or lamination processes. A transfer process should be understood as the functionality first deposited on a support like a carrier, and then transferred from the carrier to the ophthalmic lens via an adhesive layer deposited between the two elements. Lamination is defined as achieving permanent contact between a film comprising at least one of the functionalities mentioned above and the surface of the ophthalmic lens to be treated, said permanent contact being achieved by establishing contact between the film and the lens, followed optionally by a polymerization or heating step to complete adhesion and attachment between the two entities. At the end of this lamination process, the assembled film and optical lens form a single entity. Typically, for lamination processes, adhesive is present at the interface between the film and the ophthalmic lens. Examples of microstructured laminates added to one or both sides or surfaces of an ophthalmic lens are detailed above.

[0319] Example

[0320] Example 1

[0321] A catalyst solution containing 0.191 g of 18-crown ether-6, 0.048 g of KSCN, and 0.318 g of thioethanol was spin-coated onto the cc surface of the CX mold. Then, 10.00 g of NCO-terminated prepolymer phenyl diisocyanate (viscosity 0.071 Pa·s at 25°C) prepared in an 8 / 1 ratio of NCO / SH was mixed with 9.39 g of SH-terminated prepolymer 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol (viscosity 0.543 Pa·s at 25°C) prepared in an 8 / 1 ratio of SH / NCO, and the mixture was filled into the mold assembly.

[0322] Gelation occurs in less than 10 minutes at room temperature, and the reaction is completed in an air oven at 135°C for 2 hours.

[0323] Example 2

[0324] A catalyst solution containing 0.191 g of 18-crown ether-6, 0.048 g of KSCN, and 0.318 g of thioethanol was spin-coated onto the CX surface of a CC mold. Then, 10.00 g of NCO-terminated prepolymer phenyl diisocyanate (viscosity 0.071 Pa·s at 25°C) prepared in an 8 / 1 ratio of NCO / SH was mixed with 9.39 g of SH-terminated prepolymer 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol (viscosity 0.543 Pa·s at 25°C) prepared in an 8 / 1 ratio of SH / NCO, and the mixture was filled into the mold assembly. Gelation occurred in less than 10 minutes at room temperature, and the reaction was completed in an air oven at 135°C for 2 hours.

[0325] Example 3

[0326] A catalyst solution comprising 0.191 g of 18-crown ether-6, 0.048 g of KSCN, and 0.318 g of thioethanol was prepared. 50% of this solution was spin-coated onto the cc surface of a CX mold, and another 50% of this solution was spin-coated onto the CX surface of the CX mold. Then, 10.00 g of NCO-terminated prepolymer phenyl diisocyanate (viscosity 0.071 Pa·s at 25°C) prepared in an 8 / 1 ratio of NCO / SH was mixed with 9.39 g of SH-terminated prepolymer 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol (viscosity 0.543 Pa·s at 25°C) prepared in an 8 / 1 ratio of SH / NCO, and the mixture was filled into the mold assembly. Gelation occurred in less than 10 minutes at room temperature, and the reaction was completed in an air oven at 135°C for 2 hours.

[0327] Example 4

[0328] A catalyst solution comprising 0.191 g 18-crown ether-6, 0.048 g KSCN, and 0.318 g thioethanol was prepared. 50% of this solution was spin-coated onto the cc surface of the polar membrane, and another 50% was spin-coated onto the CX surface of the polar membrane. The polar membrane was then positioned in a mold assembly.

[0329] 10.00 g of NCO-terminated prepolymer phenyl diisocyanate (viscosity 0.071 Pa·s at 25°C), prepared in an 8 / 1 ratio of NCO / SH, was mixed with 9.39 g of SH-terminated prepolymer 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol (viscosity 0.543 Pa·s at 25°C), prepared in an 8 / 1 ratio of SH / NCO, and the mixture was filled into a mold assembly. Gelation occurred in less than 10 minutes at room temperature, and the reaction was completed in an air oven at 135°C for 2 hours.

[0330] Example 5

[0331] A catalyst solution comprising 0.191 g 18-crown ether-6, 0.048 g KSCN, 0.318 g thioethanol, and 0.760 g N,N-dicyclohexylmethylamine was prepared. 50% of this solution was spin-coated onto the cc surface of a CX mold. Then, 10.00 g of NCO-terminated prepolymer phenyl dimethyl diisocyanate (viscosity 0.071 Pa·s at 25°C) prepared in an 8 / 1 ratio of NCO / SH was mixed with 9.39 g of SH-terminated prepolymer 3-(2-thioalkylethylthio)-2-(2-thioalkylethylthio)propane-1-thiol (viscosity 0.543 Pa·s at 25°C) prepared in an 8 / 1 ratio of SH / NCO, and the mixture was filled into the mold assembly. Gelation occurs in less than 10 minutes at room temperature, and the reaction is completed in an air oven at 135°C for 2 hours.

[0332] Example 6

[0333] A catalyst solution containing 0.012 g of 18-crown ether-6, 0.003 g of KSCN, and 0.318 g of thioethanol was spin-coated onto the CC surface of a CX mold. Then, 10.00 g of phenyl dimethyl diisocyanate monomer was mixed with 9.23 g of 1,2-bis(2'-mercaptoethylthio)-3-mercaptopropane monomer, and the mixture was filled into the mold assembly. Gelation occurred in less than 10 minutes at room temperature, and the reaction was completed in an air oven at 120 °C for 2 hours.

[0334] Example 7

[0335] A catalyst solution comprising 0.012 g of 18-crown ether-6, 0.003 g of KSCN, and 0.318 g of thioethanol was prepared. 50% of this solution was spin-coated onto the cc surface of a CX mold, and another 50% of this solution was spin-coated onto the CX surface of the CX mold. Then, 10.00 g of phenyl dimethyl diisocyanate monomer was mixed with 9.23 g of 1,2-bis(2'-mercaptoethylthio)-3-mercaptopropane monomer, and the mixture was filled into the mold assembly. Gelation occurred in less than 10 minutes at room temperature, and the reaction was completed in an air oven at 120 °C for 2 hours.

[0336] Example 8

[0337] A catalyst solution containing 0.035 g of 15-crown ether-6, 0.002 g of LiSCN, and 0.318 g of acetonitrile was spin-coated onto the CC surface of a CX mold. Then, 10.00 g of phenyl dimethyl diisocyanate monomer was mixed with 12.99 g of pentaerythritol tetramercaptopropionate monomer, and the mixture was filled into the mold assembly. Gelation occurred in less than 10 minutes at room temperature, and the reaction was completed in an air oven at 120 °C for 2 hours.

[0338] Example 9

[0339] A catalyst solution containing 0.008 g of 18-crown ether-6, 0.002 g of KSCN, 0.318 g of thioethanol and 0.030 g of N,N-dicyclohexylmethylamine was spin-coated onto the CC surface of a CX mold. Then, 20.00 g of bis(β-cyclothiopropyl)sulfide monomer was filled into the mold assembly. Gelation occurred at 45°C in less than 1 hour, and the reaction was completed in an air oven at 80°C for 2 hours.

[0340] Although representative methods and articles have been described in detail herein, those skilled in the art will recognize that various alternatives and modifications can be made without departing from the scope described and defined by the appended claims.

Claims

1. A method for rapidly curing a transparent casting substrate suitable for manufacturing optical products, the method comprising the following steps: -Provides fast room temperature polymerizable compositions; -Provide catalyst compositions; - Provides a casting mold assembly comprising two unsealed molds, each having an inner surface and an outer surface; and optionally provides a filter element configured to be placed between the two molds. -Deposit the catalyst composition: -On the inner surface of at least one of the molds; and / or - On at least one surface of the filter element, it is then positioned in the mold assembly; - Close the casting mold assembly so that the inner surface of the mold together forms a mold cavity; - The rapid room temperature polymerizable composition is filled into the cavity of the casting mold assembly, the cavity already containing the catalyst composition deposited on at least one of the inner surfaces of the mold; - Curing the filled mold assembly to obtain a transparent solid substrate, the curing step comprising: a) A first step for polymerizing the composition at room temperature to obtain a gel; and b) A second step of post-curing the gel to obtain the transparent solid substrate; and -Recover the transparent solid substrate from the casting mold assembly; When in contact with the polymerizable composition, the catalyst composition initiates the polymerization of the polymerizable composition.

2. The method as described in claim 1, wherein, The deposition of the catalyst composition on at least one inner surface of the mold and / or at least one side of the filter element is performed by liquid phase deposition.

3. The method as described in claim 1 or 2, wherein, The deposition of the catalyst composition on at least one inner surface of the mold and / or at least one side of the filter element is performed by spin coating, dip coating, spray coating, brush coating or roll coating.

4. The method as described in claim 1 or 2, wherein, The rapid room temperature polymerizable composition has a viscosity at 25°C ranging from 0.1 to 0.3 Pa·s.

5. The method as described in claim 1 or 2, wherein, The rapid room temperature polymerizable composition is selected from compositions comprising: (a) A mixture of at least one polythiocyanate or polyisothiocyanate monomer, or a liquid isocyanate or isothiocyanate-terminated polyurethane or polythiourethane prepolymer, and at least one polythiol monomer, or a liquid thiol-terminated polyurethane or polythiourethane prepolymer; or (b) One or more polymerizable cyclic sulfide compounds.

6. The method of claim 5, wherein, The mixture (a) comprises: - Component A, comprising a polysulfurethane prepolymer having isocyanate or isothiocyanate end groups and a viscosity at 25°C ranging from 0.02 to 0.4 Pa·s, and... - Component B, comprising a polysulfururethane prepolymer having thiol end groups and a viscosity at 25°C ranging from 0.2 to 2.0 Pa·s. Components A and B are obtained by polymerizing at least one polyisocyanate or polyisothiocyanate monomer and at least one polythiol monomer.

7. The method of claim 6, wherein: The amounts of polyisocyanate or polyisothiocyanate monomers and polythiol monomers are adjusted such that the ratio of the mixture of polyisocyanate or isothiocyanate monomers and polythiol monomers is in the range of 4:1 to 30:1 to obtain component A, and the ratio of the mixture of polyisocyanate or isothiocyanate monomers and polythiol monomers is in the range of 4:1 to 30:1 to obtain component B.

8. The method of claim 6, wherein, The polythiol has the following formula: R'(SH)n' Where n' is an integer from 2 to 6, and R' is an organic group with a valence equal to n'.

9. The method of claim 8, wherein, The polythiol is selected from the group consisting of: pentaerythritol tetramercaptopropionate, 1-(1'-mercaptoethoxy)-2,3-dimercaptopropane, 1-(2'-mercaptopropanethio)-2,3-dimercaptopropane, 1-(-3'-mercaptopropanethio)-2,3-dimercaptopropane, 1-(-4'-mercaptobutylthio)-2,3-dimercaptopropane, 1-(5'-mercaptopentylthio)-2,3-dimercaptopropane, 1-(6'-mercaptohexylthio)-2,3-dimercaptopropane, 1,2-bis(-4'-mercaptobutylthio)-3-mercaptopropane, 1,2-bis(-5'-mercaptopentylthio)-3-mercaptopropane, 1,2-bis(-5'-mercaptopentylthio)-3-mercaptopropane, 1,2-bis(-5'-5'-mercaptopentylthio)-3-mercaptopropane, 1,2-bis(-4'-mercaptobutyl ...5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'-5'- (-6'-mercaptohexyl)-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, methyl dithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexylthiol-1,2,3-propanetrithiol, and 1,2-bis(-2'-mercaptoethylthio)-3-mercaptopropane.

10. The method of claim 6, wherein, The polyisocyanate or polyisothiocyanate is selected from monomers having the following formula: in R 1 It is independently an H or C1-C5 alkyl group; R 2 It is H, halogen, or C1-C5 alkyl; Z is -N = C = X, where X is O or S; a is an integer from 1 to 4, b is an integer from 2 to 4, and a + b ≤ 6, and x is an integer from 1 to 10.

11. The method of claim 10, wherein, R 1 and / or R 2 It is CH3 or C2H5.

12. The method of claim 10, wherein, R 2 It is Cl or Br.

13. The method of claim 10, wherein, x is an integer from 1 to 6.

14. The method of claim 10, wherein, The polyisocyanate or isothiocyanate is selected from the group consisting of: toluene diisocyanate or diisothiocyanate, phenylene, diisocyanate or diisothiocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate or diisothiocyanate, dimethylphenylene diisocyanate or diisothiocyanate, diethylphenylene diisocyanate or diisothiocyanate, diisopropylphenylene diisocyanate or diisothiocyanate, trimethylbenzyltriisocyanate. Ester or triisothiocyanate, phenyl diisocyanate or diisothiocyanate, benzyl triisocyanate, benzyl triisothiocyanate, 4,4'-diphenylmethane diisocyanate or diisothiocyanate, naphthalene diisocyanate or diisothiocyanate, isophorone diisocyanate or diisothiocyanate, bis(isocyanate or isothiocyanate methyl)cyclohexane, hexamethylene diisocyanate or diisothiocyanate and dicyclohexylmethane diisocyanate or diisothiocyanate.

15. The method of claim 5, wherein, The rapid room temperature polymerizable composition (b) comprises one or more polymerizable cyclic sulfide compounds having two or more portions having the following formula: Where X is either S or O.

16. The method as claimed in claim 1 or 2, wherein, The filter element is selected from polarizing film, polarizing laminate, photochromic film, photochromic laminate, near-infrared filter, near-infrared laminate, blue light cutoff filter, blue light cutoff laminate, microstructured film and microstructured laminate.

17. The method as claimed in claim 1 or 2, wherein, The catalyst composition comprises compounds selected from tertiary amines, organometallic compounds, and alkali metals, alkaline earth metals, transition metals, and ammonium salts or mixtures thereof, wherein the salts satisfy the condition 0.5 ≤ pKa ≤ 14.

18. The method of claim 17, wherein the tertiary amine is triethylamine.

19. The method of claim 17, wherein the organometallic compound is dibutyltin dilaurate.

20. The method of claim 1 or 2, wherein the optical article is an ophthalmic lens.

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