Polymerizable compositions for anti-glare (meth)acrylate ophthalmic lenses

Abstract

The present invention relates to: polymerizable compositions suitable for producing anti-glare (meth)acrylate ophthalmic lenses having a low or intermediate refractive index, anti-glare (meth)acrylate ophthalmic lenses having a low or intermediate refractive index, and methods for producing the same.

Description

Technical Field

[0001] This invention relates to: polymerizable compositions suitable for producing anti-glare (meth)acrylate eyeglass lenses with low or medium refractive index (i.e., low or medium refractive index), anti-glare (meth)acrylate eyeglass lenses with low or medium refractive index, and methods thereof. Background Technology

[0002] There is growing concern that LED-based light sources may cause more glare for drivers and pedestrians. Glare is considered a serious traffic safety issue because it increases the detection threshold for nearby moving objects and reduces the brightness contrast between an object and its background. With the widespread adoption of LEDs, glare control methods are becoming a hot topic.

[0003] Consumers of eyeglass lenses have repeatedly reported glare from LED headlights with wavelengths between 420 nm and 460 nm in road traffic causing visual distortion. Coating eyeglass lenses with anti-reflective coatings or filters could be a solution; however, currently available anti-reflective coatings have proven problematic due to distracting reflections. Adding filters containing dyes developed to provide selective light filtering could be cumbersome and uneconomical, requiring additional separate processing steps. Furthermore, neither of these alternatives is very economical, as each coating or filter requires a significantly large amount of notch dye to block the desired wavelength, which is extremely expensive.

[0004] In these cases, casting the spectacle lens material together with dyes that selectively block light between 420 nm and 460 nm was considered by the inventors to be the most economical production method. However, the development process was not smooth. Especially for low- or medium-refractive-index spectacle lenses, it was impossible to obtain spectacle lenses that blocked light at the target wavelength after curing with conventional dyes used in coatings or filters. This was attributed to the monomers or polymerization initiators contained in high-refractive-index spectacle lenses. When dyes are cured with monomers and / or polymerization initiators, the monomers and / or polymerization initiators shift the original absorption peaks of the dyes to wavelengths that are not the target, or are in a non-purpose range, or even have no peaks. It was also assumed that polymerization initiators also affected the peak shift to undesirable wavelengths or even eliminated peaks. Therefore, it was concluded that conventional dyes developed for coatings or filters alone to provide selective filtration were unpredictable for anti-glare purposes, or even could not be used as is when producing lenses by casting and curing. Furthermore, the dyes often tended to increase the yellowness index, and even extensively during curing. Cured spectacle lenses with a high yellowness index are unsuitable for ophthalmic use because they significantly limit their application. Therefore, it is difficult to provide cured spectacle lenses that have a transmission notch peak at the desired peak between 420 nm and 460 nm and an acceptable appearance for spectacle lenses (i.e., without exhibiting excessive yellowness).

[0005] Therefore, there is a need to find a specific dye for blue light absorption that can transmit light within the effective wavelength range to reduce glare, even after curing with low-refractive-index or medium-reflectivity spectacle lenses, without significantly increasing the yellowness index. However, allyl monomers are most commonly used in the production of low-refractive-index or medium-reflectivity spectacle lenses, and the polymerization of allyl monomers always requires a peroxide polymerization initiator. Inventors have attempted to find a notch dye that can withstand peroxide inhibitors and still exhibit the desired properties after mixing with a peroxide initiator, but without success. Inventors have considered that low-refractive-index or medium-refractive-index spectacle lenses can be produced based on compositions containing (meth)acrylate monomers and not allyl monomers. Furthermore, the desired anti-glare properties have been achieved by using an azo-based polymerization initiator instead of a peroxide polymerization initiator. Again, the problem is that significant yellowness is observed on the resulting spectacle lenses after curing. Therefore, there is a need to find an absorbing dye for anti-glare purposes that is suitable for use in a (meth)acrylate and azo-based initiator system.

[0006] US 10,605,970 B2 uses a filter with an FL-41 hue to control light exposure in the visible spectral range of 400 nm and 700 nm, with the aim of alleviating migraines and photosensitivity by providing a notch peak from 454 nm to 506 nm. However, as noted in the specification of this patent document, the filter is not intended to prevent LED glare, and therefore light transmission occurs in different wavelength ranges. Furthermore, as acknowledged in the specification of this patent document, this optical layer has a yellow chromaticity, which is unacceptable for ophthalmic lenses.

[0007] US 8,360,574 B2 relates to an ophthalmic lens comprising a filter that transmits at least 80% of light with wavelengths in the 460-700 nm range. The wavelength range clearly indicates that this lens is not intended to reduce glare from LED light. Furthermore, as with other prior art literature, a wide range of dyes are disclosed, and only polycarbonate eyewear systems with a polymerization process different from (meth)acrylate lenses have been validated. No results have been provided regarding specific combinations of low- or medium-refractive-index lenses with specific dyes.

[0008] US 7,556,376 B2 relates to a polycarbonate ophthalmic system comprising a film containing a dye having 85% or greater visible-to-dark light transmittance. Like US 8,360,574 B2, this patent document relates to polycarbonate lenses and laminated films thereon. The curing process has not been demonstrated.

[0009] EP 3 296 799 A1 discloses a transparent optical article comprising a selective filter that at least partially blocks light in the wavelength range of 400 nm to 460 nm and a high-pass filter that partially blocks blue light in the range of 400 nm to 500 nm. This patent document demonstrates that only polycarbonate lenses are compatible with this system, meaning that due to differing chemical compatibility, it is unpredictable whether this system will also be compatible with (meth)acrylate systems.

[0010] US 9,683,102 B2 discloses a selective wavelength filter comprising a Cu-porphyrin compound as a dye that blocks 5% to 50% of light in the wavelength range between 400 nm and 500 nm while transmitting at least 80% of the visible spectrum. That is, this document does not address reducing glare from LED light of a specific wavelength. Furthermore, the ophthalmic system uses an uncured filter. Additionally, one of the lens materials used herein is allyl diethylene glycol carbonate, prepared from an allyl monomer requiring a peroxide polymerization initiator. Moreover, although this document specifies a yellowness index below a certain value, the working examples do not mention the yellowness of the filters prepared for ophthalmic lenses.

[0011] US 2021 / 171682 A1 discloses a polymerizable composition comprising "more than" 0% by weight and 30% or less of an allyl carbonate compound and 70% by weight or more and less than 100% by weight of a (meth)acrylate compound, along with two distinct radical polymerization initiators exhibiting different residual radical ratios. This invention utilizes a combination of two specific initiators that generate radicals at lower and higher temperatures, respectively, to stably exhibit the directional effect of the dye. Nevertheless, this invention has an allyl carbonate compound as a fundamental element, and therefore it is difficult to use it for polymerization without the use of a peroxide polymerization initiator. Using a peroxide polymerization initiator with an absorbent dye would be detrimental to the original function of the dye. Furthermore, the type and ratio of polymerization initiators need to be determined independently based on the compositional ratios of the target polymerizable composition, which would make the method cumbersome and inefficient. Summary of the Invention

[0012] Beginning with US 2021 / 171682 A1, the object of this invention is to provide a low- and / or medium-refractive-index (meth)acrylate spectacle lens that provides reduced glare from LED light and an acceptable yellowness index for use as a spectacle lens, and blocks harmful UV light through a simpler and more direct process.

[0013] A first aspect of this invention relates to a polymerizable composition suitable for the curing production of low- and / or medium-refractive-index (meth)acrylate spectacle lenses for anti-glare purposes. Through extensive testing and experimentation, the inventors have discovered that a specific combination of a (meth)acrylate compound, an azo-based polymerization initiator, and a metal complex of a heterocyclic dye compound as a blue light absorber provides an optimal trade-off, wherein glare from LED light is improved by a transmission notch peak at a specific wavelength and a yellowness index within an acceptable range. The core concept of this invention is to provide a low- or medium-refractive-index spectacle lens with reduced glare from LED light and a suitable balance with the yellowness index, wherein the spectacle lens is produced by curing the polymerizable composition of this invention.

[0014] The polymerizable compositions of the present invention comprise (meth)acrylate compounds, metal complexes of heterocyclic dyes exhibiting absorption peaks in the range of 425 ± 10 nm, and azo-based polymerization initiators, while containing neither allyl compounds nor peroxide polymerization initiators.

[0015] The term "spectacles lens" refers to an ophthalmic lens worn in front of the eyeball but not in contact with it (DIN ISO 13666:2019(E), Section 3.5.2), where ophthalmic lenses are lenses intended for the purpose of measuring, correcting and / or protecting the eye or for altering its appearance (ISO 13666:2019(E), Section 3.5.1). Here, spectacle lenses include, but are not limited to, corrective lenses, protective lenses, absorptive lenses, clear lenses, tinted lenses, uniformly tinted lenses, gradient tinted lenses, dual-gradient tinted lenses, photochromic lenses, polarized lenses, balanced lenses, and matching lenses as defined in Sections 3.5.3 to 3.5.13 of DIN ISO 13666:2019(E). Furthermore, according to Section 3.6 of DIN ISO 13666:2019(E), spectacle lenses can have various lens shapes, including but not limited to curved lenses, plano lenses, spherical lenses, cylindrical lenses, spherocylindrical lenses, toric lenses, aspherical lenses, and non-toric lenses.

[0016] The term "anti-glare" refers to the function of reducing glare, thereby improving visual clarity and reducing eye strain. Anti-glare helps minimize reflection by reducing the amount of light of specific wavelengths reflected from the surface of eyeglass lenses. In this invention, this is achieved by reducing the transmission of light with a wavelength of 425 ± 10 nm.

[0017] The articles “a,” “an,” and “the” used in this specification and the appended claims include plural references unless expressly and unambiguously limited to a single reference.

[0018] The term "(meth)acrylate" refers to the monomeric acrylate and / or methacrylate of alcohols. (meth)acrylate monomers and / or oligomers are collectively referred to herein as "(meth)acrylate". (meth)acrylate monomers and / or oligomers can be monofunctional, difunctional, trifunctional, or tetrafunctional. (meth)acrylate monomers and / or oligomers can be aliphatic or aromatic.

[0019] Examples of monofunctional (meth)acrylate monomers and / or oligomers are, but are not limited to, benzyl (meth)acrylate, isodecyl (meth)acrylate, n-butyl (meth)acrylate, and isobornyl (meth)acrylate, with or without an aromatic structure. Difunctional (meth)acrylate monomers and / or oligomers may be, but are not limited to, difunctional aliphatic (meth)acrylates, such as 1,6-hexanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate; difunctional branched alkyl polyether (meth)acrylates, such as triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate; and difunctional ethoxylated bisphenol A type (meth)acrylates, such as bisphenol A (ethoxylate) 4-di(meth)acrylate with or without an aromatic structure and bisphenol A (ethoxylate) 3-di(meth)acrylate with or without an aromatic structure. Trifunctional (meth)acrylate monomers and / or oligomers may be, but are not limited to, trimethylolpropane tri(meth)acrylate, etc., and tetrafunctional methacrylate monomers and / or oligomers may be, but are not limited to, pentaerythritol tetra(meth)acrylate, etc.

[0020] In addition, aliphatic (meth)acrylates can be, but are not limited to, aliphatic urethane (meth)acrylates, aliphatic epoxy (meth)acrylates, aliphatic polyester (meth)acrylates, etc. Aromatic (meth)acrylates can be, but are not limited to, aromatic urethane (meth)acrylates, aromatic epoxy (meth)acrylates, aromatic polyester (meth)acrylates, etc.

[0021] The (meth)acrylate compounds of the present invention may include at least one (meth)acrylate or a mixture thereof. "(meth)acrylate eyeglass lenses" refers to eyeglass lenses produced by the polymerization of one or more (meth)acrylate compounds; in other words, eyeglass lenses based on (meth)acrylates, such as PMMA (polymethyl methacrylate) lenses, SOLA Spectralite, Luxexel Pritoptical (polyacrylate lenses), etc.

[0022] The polymerizable compositions of the present invention do not contain allyl compounds. The term "allyl compound" refers to a compound containing at least one allyl group.

[0023] The term "polymerizable composition" means that the composition can undergo polymerization by applying UV radiation and / or heat. For example, a polymerizable composition according to the invention is placed in a casting mold and then typically cured by applying heat or radiation, preferably by thermosetting and a suitable catalyst or initiator known in the art.

[0024] The compositions of the present invention comprise an azo-based polymerization initiator. The term "azo-based" polymerization initiator refers to a polymerization initiator containing an azo group. Examples may be, but are not limited to, 2,2'-azobis(4-methoxy-2,4-dimethylvalerate) (V-70), 2,2'-azobis(2,4-dimethylvalerate) (V-65), 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 1,1'-azobis(cyclohexane-1-formitrile) (V-40).

[0025] The amount of azo-based polymerization initiator varies depending on the polymerization conditions, the type of initiator, and the composition of one or more monomers, and cannot be unconditionally limited, but is preferably in the range of 0.1% to 3% by weight, and more preferably 0.15% to 1% by weight of the total composition. Within the range described above, polymerization can proceed effectively without affecting the properties of the spectacle lens.

[0026] The term "peroxide polymerization initiator" as used in this invention can refer to a polymerization initiator based on peroxide esters and / or a polymerization initiator based on peroxide dicarbonate.

[0027] In one embodiment, to uniformly cure the lens, a free radical chain transfer agent may be further added to the composition. Typical examples of free radical chain transfer agents are isotretinoin (CAS No. 586-62-9), α-methylstyrene dimer (CAS No. 6362-80-7), a mixture of α-methylstyrene dimers (CAS No. 6144-04-3), and α-methylstyrene (CAS No. 98-93-9). The concentration of the chain transfer agent may be from 0.05% by weight to 1% by weight of the total composition, more likely from 0.1% by weight to 0.7% by weight.

[0028] Conventionally, various blue light absorbers are considered to block light that causes glare from LEDs. A variety of blue light absorbers with absorption peaks in the range of 400 nm to 460 nm have been widely used to block blue light in filters or optical layers. Examples include azo dyes, aryl dyes (e.g., golden amine O), hydrocarbon dyes (e.g., lutein, zeaxanthin), aromatic dyes (e.g., coumarin 343, coumarin 314), and heterocyclic dyes.

[0029] Finding a balance between wavelength range and the amount of blue light effectively blocked to reduce LED glare has always been difficult. This is even more unpredictable, as the monomers / oligomers and / or initiators and / or catalysts in low- or medium-refractive-index spectacle lens materials shift significantly after curing, distorting light absorption. Several cases have been observed where the original absorption peaks of the blue light absorbers are no longer even visible after curing. Furthermore, blocking and / or suppressing blue light also affects the color balance and color perception of spectacle lenses, i.e., the yellowness index.

[0030] First, the inventors successfully minimized the negative impacts from the monomers and polymerization initiators used for curing by carefully selecting (meth)acrylate compounds and azo-based polymerization initiators. Nevertheless, a problem remains: not every absorbent dye functions normally or as expected after curing.

[0031] In particular, a common blue light blocking technology involves coloring or tinting the lenses with blue light absorbers. These absorbers are yellow or even red, thus giving the lenses a yellow or amber hue. This color or hue can therefore interfere with the wearer's normal color perception, making it difficult to correctly perceive the colors of traffic lights or signs, rendering the lenses useless. Furthermore, an inappropriate combination of blue light absorbers and lens materials can lead to an overall reduction in transmittance of light wavelengths other than blue light, which is undesirable. This undesirable reduction can, in turn, lead to decreased visual acuity in the wearer.

[0032] Through in-depth testing and experimentation, the inventors discovered that, within the broad spectrum of blue light absorbers, heterocyclic dye compounds, particularly their metal complexes, can provide sufficient light blocking within an effective range to reduce glare in low- or medium-refractive-index spectacle lenses produced through curing, while also possessing a yellowness index suitable for spectacle lenses. As illustrated in the examples, other types of dyes have proven ineffective in achieving both anti-glare functionality and adequate yellowness.

[0033] Therefore, the present invention overcomes the aforementioned difficulties by providing a polymerizable composition comprising a metal complex of a heterocyclic dye compound exhibiting an absorption peak in the range of 425 ± 10 nm. The absorption peak in the 425 ± 10 nm range provides reduced lens transmittance, which is effective in reducing glare from LED light. Even after the composition has cured, the combination of the (meth)acrylate compound, the azo-based polymerization initiator, and the dye successfully provides reduced transmittance in the 425 ± 10 nm wavelength range without significantly impairing the yellowness of the prepared spectacle lens. It has been determined that wavelengths shorter than the specified range are ineffective in providing anti-glare functionality for LED light, while wavelengths longer than the specified range result in excessively high yellowness indices unsuitable for spectacle lenses. Therefore, reduced transmittance in the 415 nm to 435 nm wavelength range is necessary for effectively reducing glare from LED light.

[0034] The heterocyclic dye compound according to the present invention is a dye compound having one or more heterocycles. A heterocycle is a compound having atoms of at least two different elements as members of one or more of its rings. Typically, the first element is carbon, and the other elements may be selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus, etc. Furthermore, the chemical properties of the heterocyclic dye compound are not particularly limited, and the heterocyclic dye compound can act as a means of at least partially blocking light in the wavelength range of 415 nm to 435 nm, provided that it exhibits a maximum absorption peak in the 415 nm to 435 nm range before curing. In one embodiment, the heterocyclic dye compound is a porphyrin dye compound. The term "porphyrin dye compound" in this invention refers to a compound containing a porphyrin ring structure.

[0035] Heterocyclic compounds can be metal complexes. Metal complexes are coordination complexes, which are compounds composed of a central atom or ion that is metallic and bonded to one or more ligands, which are ions or molecules containing one or more pairs of electrons that can be shared with the metal. Typically, the metal can be selected from the group consisting of: Cu, V, Ni, Cr, Ag, In, Mn, Sn, Fe, Co, Mg, Pt, Pd, Ru, and Zn, etc. In a preferred embodiment, Cu (copper)-complexes and / or V (vanadium)-complexes of heterocyclic dye compounds can be used. In another preferred embodiment, Cu-complexes and / or V (vanadium)-complexes of porphyrin dye compounds can be used.

[0036] Compared to antireflective coatings or filters containing metal complexes of heterocyclic dye compounds, the compositions of the present invention enable the blocking of sufficient amounts of light in the wavelength range that effectively reduces glare from LED light, even with minimal amounts of the metal complexes of heterocyclic dye compounds. This is highly cost-effective, as blue light blocking dyes are typically very expensive. Furthermore, it is also advantageous in terms of the yellowness index of spectacle lenses. This is possible by judiciously selecting the lens material to be cured and the metal complexes of the heterocyclic dye compounds dissolved in the lens material. For example, the filters of US 9,683,102 B2 contain Cu complexes of heterocyclic dye compounds at a concentration of 1% by weight of dye / primer to achieve the desired effect. In contrast, the polymerizable compositions of the present invention contain only minimal concentrations of the metal complexes of heterocyclic dye compounds. In one embodiment, the amount of the metal complexes of heterocyclic dye compounds in the compositions of the present invention is 0.1 to 10 ppm of the total composition, i.e., 0.00001% by weight to 0.001% by weight. In another embodiment, the amount of the metal complex of the heterocyclic dye compound in the composition of the present invention is 0.5 to 3 ppm of the whole composition, that is, 0.00005% to 0.0003% by weight.

[0037] Furthermore, it is necessary to block ultraviolet light to eliminate its harmful effects on the eyes of the lens wearer. For the ultraviolet band, UVB wavelengths are from 290 nm to 320 nm, and UVA wavelengths are from 320 nm to 400 nm. In view of this, the composition of the present invention aims to prepare an anti-glare eyeglass lens that substantially or completely blocks light with wavelengths shorter than 400 nm, preferably from 290 nm to 400 nm, and also has a transmittance peak between 415 nm and 435 nm.

[0038] For this purpose, the composition further comprises a UV absorber having the ability to at least partially, and preferably completely, block light with wavelengths shorter than 400 nm. Any known UV absorber having said ability can be used, including benzophenone and / or benzotriazole derivatives. It has been found that benzophenone and / or benzotriazole UV absorbers exhibit the most desirable properties as spectacle lenses when cured in combination with a spectacle lens material based on low or medium refractive index (meth)acrylates and a metal complex of a heterocyclic dye compound, preferably a Cu- or V-complex of a heterocyclic dye compound, more preferably a Cu- or V-complex of a porphyrin dye compound. In one embodiment, the UV absorber comprises benzophenone and / or a benzotriazole compound.

[0039] In one embodiment, the amount of UV absorber may be 2% by weight or less of the total composition, preferably 1% by weight or less.

[0040] In optional embodiments, for aesthetic reasons, a color balancing agent can be used to further reduce the yellowness of eyeglass lenses. Typically, blocking undesirable blue light wavelengths affects the color balance of eyeglass lenses. This is aesthetically undesirable for eyeglass lenses. For this purpose, the compositions of the present invention may comprise a color balancing agent. A color balancing agent is a compound having an absorption band in the orange to yellow wavelength region of the visible spectrum and a color ranging from green to purple. The color balancing agent is used to at least partially counteract the yellowing effect and is preferably an absorbing dye or a mixture of at least two absorbing dyes used in suitable proportions, which can be used by dissolving it in a solvent. Any conventional color balancing agent known to be suitable for optical applications can be used. In one embodiment, a color balancing agent having a light absorption peak in the wavelength range of 600 nm to 700 nm is used. Many different color balancing agents can be used in combination. Representative, but not exhaustive, examples of color balancing agents may be Kayaset Blue A-2R (CAS No. 81-48-1, from Nippon Kayaku Co Ltd) and Orasol Blue 825 (Kremer). It was observed that, upon mixing with the (meth)acrylate compounds of the present invention, the color balancer blocked light in wavelengths between 600 nm and 630 nm and / or 660 nm and 690 nm. By counteracting yellowness, this significantly contributes to improving the appearance of the composition or even the cured lens. Light blocking was observed in both wavelength ranges when two different color balancers were used. In one embodiment, the amount of blueing agent may be 5 ppm or less, or 3 ppm or less.

[0041] A second aspect of the invention is an eyeglass lens comprising a polymer formed by polymerizing a (meth)acrylate compound and a heterocyclic dye compound having a light absorption peak within 425 ± 10 nm, and substantially free of allyl compounds. The eyeglass lens according to the second aspect is prepared by curing the polymerizable composition of the invention described with respect to the first aspect. Unless otherwise specifically described, all features explained with respect to the first aspect apply to the second aspect. The eyeglass lens of the invention is an anti-glare (meth)acrylate eyeglass lens having a low or medium refractive index.

[0042] According to the present invention, the term "low refractive index or medium refractive index" refers to a refractive index between 1.48 and 1.60, or between 1.48 and 1.58, or between 1.49 and 1.57.

[0043] The spectacle lens of the present invention, prepared by curing the polymerizable composition of the present invention, has a transmittance notch peak within 425 ± 10 nm. In another embodiment, the spectacle lens has a transmittance notch peak within 425 ± 10 nm, wherein the transmittance notch peak is 80% to 20%, or 70% to 20%, or 70% to 25%. In other words, the transmittance profile of the spectacle lens has a minimum transmittance value in this region within the wavelength range of 425 ± 10 nm, wherein the minimum value is 80% to 20%, or 70% to 20%, or 70% to 25%.

[0044] The term "transmittance notch peak" refers to a region in the transmittance spectrum where transmittance drops sharply (notch) at a specific wavelength. This region typically follows a peak followed by an increase in the spectrum, usually another peak in the transmittance spectrum. This is attributed to the absorption of the metal complex of the heterocyclic dye compound, which absorbs light in the wavelength range of 425 ± 10 nm. By having a transmittance notch peak in the wavelength range of 425 ± 10 nm, the spectacle lens of the present invention can be used to filter light of these wavelengths to reduce glare from LED light. Therefore, the spectacle lens of the present invention can at least partially block or cut off light with a wavelength of 425 ± 10 nm. In one embodiment, at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 10%, or at least 15%, or at least 20% of the light is blocked. This feature blocks glare from LED headlights with wavelengths between 420 nm and 460 nm in road traffic, which distorts the wearer's vision.

[0045] The eyeglass lens further comprises a UV absorber to block harmful ultraviolet light at wavelengths of 400 nm or lower, or preferably 290 nm to 400 nm. The eyeglass lens according to the invention blocks light at wavelengths of 400 nm or lower, preferably 290 nm to 400 nm. In one embodiment, the eyeglass lens blocks at least 90%, or at least 95%, or at least 98%, or at least 99% or 100% (i.e., completely) of light with wavelengths of 400 nm or lower, preferably 290 nm to 400 nm.

[0046] In one embodiment, since the spectacle lens of the present invention has a light blocking rate of at least 98%, or at least 99%, or 100% at a wavelength of 400 nm, this means that the light transmittance in this range is 2% or less, 1% or less, or 0%. In this regard, since the spectacle lens of the present invention has a transmittance notch peak at wavelengths between 415 nm and 435 nm, wherein the light transmittance is 80% to 20%, or 70% to 20%, or 70% to 25%, it is estimated that the spectacle lens of the present invention has a light blocking rate of less than 60% at approximately 410 nm.

[0047] This is also a unique feature of the spectacle lenses of the present invention. In contrast, for example, the optical article of EP 3 296 799 A1 blocks at least 66% of light with wavelengths less than or equal to about 410 nm at each wavelength in the wavelength range between 350 nm and 410 nm.

[0048] In another embodiment, at a wavelength of 450 nm, the spectacle lens of the present invention exhibits 80% or greater, or 85% or greater, light transmittance. This high transmittance at this wavelength reflects the low yellowness and high transparency of spectacle lenses suitable for ophthalmic applications.

[0049] In another embodiment, the spectacle lens of the present invention provides an average transmittance of 80% or greater for visible light transmission while suppressing selective wavelengths of blue light, thereby achieving appropriate color vision performance for the wearer and a predominantly color-neutral appearance for observers looking at the wearer.

[0050] In one embodiment using a color balancing agent having a light absorption peak in the wavelength range of 600 nm to 700 nm, the cured spectacle lens of the present invention at least partially blocks light in the wavelength range of 600 nm to 630 nm or 660 nm to 690 nm. That is, transmission within this wavelength is blocked by at least 0.5%, or at least 1%, or at least 2%, or at least 5%, thereby reducing transmittance by up to 0.5%, 1%, 2%, or 5%. This indicates that the spectacle lens according to the present invention has a predominantly color-neutral appearance and is perceived to have good transparency.

[0051] The anti-glare eyeglass lens of the present invention can be further defined as an anti-glare eyeglass lens with a yellowness index (YI) of 9 or less. The yellowness index in this invention is measured according to ASTM D1925.

[0052] The anti-glare eyeglass lens of the present invention can be further defined as an anti-glare eyeglass lens with a haze of 0.5% or less, or 0.4% or less. The haze level in the present invention is measured according to ASTM D1003.

[0053] In addition to the yellowness index, the anti-glare eyeglass lenses of this invention can also be characterized by the subjective perception of colors as represented by the CIE LAB color space (also known as the L*a*b* color space). The L*a*b* color space indicates a color space that represents colors as three values: L* represents perceived brightness, and a* and b* represent the four distinct colors of human vision: red, green, blue, and yellow. The calculation method for parameters L*, a*, and b* is specified in: DIN EN ISO / CIE 11664-4:2019, Colorimetry—Part 4: CIE 1976 L*a*b* color space. The parameter “L*” corresponds to perceived brightness, the parameter “a*” corresponds to the blue-yellow axis, and the parameter “b*” corresponds to the red-green axis. The CIE L*a*b* used in this invention is calculated using the CIE standard D65 illuminant. The term “D65 illuminant” refers to a standard luminescent body, a visible light source with a specific spectral power distribution. It provides a basis for comparing images or colors recorded under different illuminations. A "D" light source is a light source constructed to reproduce natural daylight. The color temperature (i.e., the temperature of an ideal blackbody radiator that emits light with a color equivalent to the color of the light source) of a D65 light source is approximately 6500 K. The D65 light source is defined by the International Commission on Illumination (CIE), such as ISO 11664-2:2007, Colorimetry—Part 2: CIE Standard Light Sources and DIN 5033-7:2014-10, particularly as described in Section 5.1.

[0054] In one embodiment, the spectacle lens of the present invention has a color defined in the CIE L*a*b* space by parameters -5 ≤ a*≤ -1, 3 ≤ b* ≤ 7, and 90 ≤ L* ≤ 100.

[0055] In another embodiment, the spectacle lens of the present invention comprises a hard coating and / or an antireflective coating. Light transmittance can be further affected by such coatings applied subsequently. Spectacle lenses comprising a hard coating and / or an antireflective coating have a yellowness index of 12 or less, or 11 or less, or 10 or less. Furthermore, spectacle lenses comprising a hard coating and / or an antireflective coating have a light transmittance of 90% or greater at a wavelength of 450 nm. This indicates that the spectacle lens of the present invention has a suitable yellowness index for optical applications.

[0056] A third aspect of the invention relates to a method suitable for producing anti-glare spectacle lenses according to a second aspect of the invention by injection and curing a polymerizable composition according to a first aspect of the invention. Unless otherwise specifically described, all features explained with respect to the first and second aspects apply to the third aspect.

[0057] The method of the present invention comprises preparing a polymerizable composition by mixing a (meth)acrylate compound, a metal complex of a heterocyclic dye compound, and an azo-based polymerization initiator. The method of the present invention does not mix the allyl compound or the peroxide-based polymerization initiator. Subsequently, the method of the present invention cures the polymerizable composition.

[0058] In one embodiment, the method of the present invention includes mixing a (meth)acrylate compound, a metal complex of a heterocyclic dye compound (preferably a Cu or V complex of a porphyrin dye compound), and a UV absorber.

[0059] In optional embodiments, the method of the present invention includes mixing a (meth)acrylate compound, a metal complex of a heterocyclic dye compound (preferably a Cu or V complex of a porphyrin dye compound), a UV absorber, and a color balancer.

[0060] In one embodiment, the method further includes applying a hard coating and / or an anti-reflective coating to the surface of a cured spectacle lens.

[0061] The fourth aspect of the invention relates to a dataset stored on a computer-readable medium or carried by a data signal, the dataset comprising at least one of the following types of data: (i) a virtual representation (analysis or digital) of a polymeric composition according to the second aspect and / or an anti-glare spectacle lens according to the third aspect, and (ii) data containing computer-readable instructions for controlling one or more manufacturing machines to produce anti-glare spectacle lenses. Attached Figure Description

[0062] Based on Figures 1 to 1 4. Description of embodiments of the present invention.

[0063] Figure 1 The intensities of three different types of LED light are shown. The anti-glare eyeglass lenses according to the invention are designed to block such LED light.

[0064] Figure 2 The transmittance diagram of an uncoated spectacle lens prepared according to Example 1 is shown.

[0065] Figure 3 A transmittance diagram of a coated spectacle lens prepared according to Example 1 is shown.

[0066] Figure 4 The transmittance diagram of an uncoated spectacle lens prepared according to Example 2 is shown.

[0067] Figure 5 The transmittance diagram of the coated spectacle lens prepared according to Example 2 is shown.

[0068] Figure 6 The transmittance diagrams of the polymerizable composition and spectacle lens prepared according to Comparative Example 1 are shown.

[0069] Figure 7 The transmittance diagrams of the polymerizable composition and spectacle lens prepared according to Comparative Example 2 are shown.

[0070] Figure 8 Transmittance diagrams of the polymerizable composition and spectacle lens prepared according to Comparative Example 3 are shown.

[0071] Figure 9 Transmittance diagrams of the polymerizable composition and spectacle lens prepared according to Comparative Example 4 are shown.

[0072] Figure 10 The transmittance diagram of an uncoated spectacle lens prepared according to Example 3 is shown.

[0073] Figure 11 The transmittance diagram of the coated spectacle lens prepared according to Example 3 is shown.

[0074] Figure 12 The transmittance diagram of an uncoated spectacle lens prepared according to Example 4 is shown.

[0075] Figure 13 A transmittance diagram of the coated spectacle lens prepared according to Example 4 is shown. Detailed Implementation

[0076] Embodiments of the invention will be described in further detail below. However, it should be understood that the following examples are for illustrative purposes only and do not limit the invention in any way.

[0077] Example 1 (Meth)acrylate monomers / oligomers (35% difunctional ethoxylated bisphenol A type methacrylate, 35% difunctional ethoxylated bisphenol A diacrylate, and 30% difunctional aliphatic methacrylate) were mixed with a Cu-complex of 2.0 ppm heterocyclic dye compound (FDB-001, Yamada Chemical Co., Ltd.) and 0.4 wt% 2,2'-azobis(2,4-dimethylvaleronitrile) as an azo-based initiator. 0.18 wt% of a conventional benzophenone UV absorber was added. 0.3% α-methylstyrene dimer was added as a chain transfer agent. The mixture was dissolved, degassed, and filled into a spectacle lens mold, and then cured by heating in a curing oven. Spectacle lenses with a thickness of 2.09 mm and a refractive index of 1.55 were prepared.

[0078] like Figure 2As shown, transmittance at wavelengths within 400 nm or lower is less than 2%, indicating that harmful UV light is almost completely blocked by the UV absorber. Due to the Cu-complex of the heterocyclic dye compound, a transmittance peak was observed at approximately 422 nm, showing a transmittance of 40%. This indicates that the peak was not destroyed by the polymerization process, and therefore glare from LED light can be successfully reduced by this notch dye in the methacrylate polymer system. For this uncoated sample, the transmittance at 450 nm is 87.7%, indicating that low yellowness and high transparency have been achieved.

[0079] The manufactured spectacle lenses have a yellowness index of 6.84 and a haze of 0.30%, which are within the suitable range for use as spectacle lenses. The average transmittance and CIE L*a*b* in the visible light range were measured and are shown in the table below.

[0080] Subsequently, the cured eyeglass lenses are coated with a hard coating (CrystalCoat® IM-9060) and an anti-reflective coating (DuraVision Platinum (DVP), Zeiss). Figure 3 As shown, the coated lens still reduces glare from LED light, exhibiting a transmittance peak at 422 nm, indicating 44% transmittance. Simultaneously, the yellowness index increases to 9.72, presumably due to the antireflective coating. Haze decreases to 0.17%, presumably due to the cleaning process prior to coating. Transmittance at 450 nm increases to 93%.

[0081] Example 2 (Meth)acrylate monomers / oligomers (35% difunctional ethoxylated bisphenol A type methacrylate, 35% difunctional ethoxylated bisphenol A diacrylate, and 30% difunctional aliphatic methacrylate) were mixed with a vanadium complex of a heterocyclic dye compound (FDB-002, Yamada Chemical Co., Ltd.) at 1.5 ppm and 2,2'-azobis(2,4-dimethylvaleronitrile) as an azo-based polymerization initiator at 0.4 wt%. A conventional benzotriazole UV absorber was added at 1.4 wt%. An α-methylstyrene dimer was added at 0.3 wt% as a chain transfer agent. The mixture was dissolved, degassed, and filled into a spectacle lens mold, and then cured by heating in a curing oven. Spectacle lenses with a thickness of 2.1 mm and a refractive index of 1.54 were prepared.

[0082] like Figure 4As shown, the transmittance at wavelengths within 400 nm or lower is less than 2%, indicating that harmful UV light is almost completely blocked by the UV absorber. Due to the vanadium complex of the heterocyclic dye compound, an absorption peak was observed at approximately 433 nm, showing a transmittance of 62%. This indicates that the absorption peak was not destroyed by the polymerization process, and therefore glare from LED light can be successfully reduced by this absorption dye in the methacrylate polymer system. For this uncoated sample, the transmittance at a wavelength of 450 nm is 87.1%, indicating that low yellowness and high transparency have been achieved.

[0083] The manufactured spectacle lenses have a yellowness index of 6.09 and a haze of 0.11%, which are within the suitable range for use as spectacle lenses.

[0084] Subsequently, the cured eyeglass lenses are coated with a hard coating (CrystalCoat® IM-9060) and an anti-reflective coating (DuraVision Platinum (DVP), Zeiss). Figure 5 As shown, the coated lens still reduces glare from LED light. An absorption peak was observed at 433 nm, indicating 66% transmittance. Simultaneously, the yellowness index increased to 8.57, presumably due to the antireflective coating. Transmittance at 450 nm increased to 92.1%.

[0085] Example 3 A mixture of (meth)acrylate monomers / oligomers (20% primary difunctional aliphatic methacrylate, 40% secondary difunctional aliphatic methacrylate, and 40% aliphatic urethane difunctional acrylate oligomers) was prepared with a Cu-complex of 3.0 ppm heterocyclic dye compound (FDB-001, Yamada Chemical Co., Ltd.) and 0.4 wt% of an azo-based initiator, 2,2'-azobis(2,4-dimethylvaleronitrile). 0.23 wt% of a conventional benzophenone UV absorber was added. 0.3 wt% of isoprene was added as a chain transfer agent. 3 ppm of Kayaset Blue A-2R was also added as a color balancer. The mixture was dissolved, degassed, and filled into a spectacle lens mold, and then cured by heating in a curing oven. Spectacle lenses with a thickness of 2 mm and a refractive index of 1.50 were prepared.

[0086] like Figure 10As shown, transmittance at wavelengths within 400 nm or lower is less than 2%, indicating that harmful UV light is almost completely blocked by the UV absorber. Due to the Cu-complex of the heterocyclic dye compound, a transmittance peak was observed at approximately 422 nm, showing 28% transmittance. This indicates that the peak was not destroyed by the polymerization process, and therefore glare from LED light can be successfully reduced by this notch dye in the methacrylate polymer system. For this uncoated sample, the transmittance at 450 nm is 87.0%, indicating that low yellowness and high transparency have been achieved.

[0087] The manufactured spectacle lenses have a yellowness index of 8.01 and a haze of 0.32%, which are within the suitable range for use as spectacle lenses.

[0088] Subsequently, the cured eyeglass lenses are coated with a hard coating (F14) and an anti-reflective coating (DuraVision Platinum (DVP), Zeiss). For example... Figure 11 As shown, the coated lens still reduces glare from LED light, exhibiting an absorption peak at 422 nm and showing 28% transmittance. Simultaneously, the yellowness index increases to 11.55, presumably due to the antireflective coating. Haze decreases to 0.23%, presumably due to the cleaning process prior to coating. Transmittance at 450 nm increases to 89%. CIE L*a*b* measurements are shown in the table below.

[0089] Furthermore, a decrease in transmittance was observed in the wavelength range of 600 nm to 630 nm. This decrease indicates that the produced eyeglass lenses exhibit a more neutral color due to the color balancing agent.

[0090] Example 4 Acrylic monomers / oligomers (40% bifunctional branched alkyl polyether acrylates, 30% bifunctional aliphatic acrylates, and 30% aliphatic urethane bifunctional acrylate oligomers) were mixed with a Cu-complex of 3.0 ppm heterocyclic dye compound (FDB-001, Yamada Chemical Co., Ltd.) and 0.4 wt% of an azo-based initiator, 2,2'-azobis(2,4-dimethylpentanonitrile). 0.23 wt% of a conventional benzophenone UV absorber was added. A chain transfer agent, namely 0.3 wt% isoprene, was added. A color balancer, namely a combination of 2.3 ppm Kayaset Blue A-2R and 1.6 ppm Orasol Blue 825, was also added. The mixture was dissolved, degassed, and filled into a spectacle lens mold, and then cured by heating in a curing oven. Spectacle lenses with a thickness of 2 mm and a refractive index of 1.50 were prepared.

[0091] like Figure 12 As shown, the transmittance at wavelengths within 400 nm or lower is less than 2%, indicating that harmful UV light is almost completely blocked by the UV absorber. Due to the Cu-complex of the heterocyclic dye compound, a transmittance peak was observed at approximately 419 nm, showing a transmittance of 32.5%. This indicates that the peak was not destroyed by the polymerization process, and therefore glare from LED light can be successfully reduced by this notch dye in the methacrylate polymer system. For this uncoated sample, the transmittance at 450 nm is 89.0%, indicating that low yellowness and high transparency have been achieved.

[0092] The manufactured spectacle lenses have a yellowness index of 4.34 and a haze of 0.33%, which are within the suitable range for use as spectacle lenses.

[0093] Subsequently, the cured eyeglass lenses are coated with a hard coating (F14) and an anti-reflective coating (DuraVision Platinum (DVP), Zeiss). For example... Figure 13 As shown, the coated lens still reduces glare from LED light, exhibiting an absorption peak at 419 nm and showing 34% transmittance. Simultaneously, the yellowness index increases to 7.92, presumably due to the antireflective coating. Haze decreases to 0.24%, presumably due to the cleaning process prior to coating. Transmittance at 450 nm increases to 92%.

[0094] Furthermore, a decrease in transmittance was observed in the wavelength ranges of 600 nm to 630 nm and 660 nm to 690 nm. This decrease indicates that the produced eyeglass lenses exhibit a more neutral color due to the color balancing agent.

[0095] The experimental results for the example are summarized in the table below. The average transmittance and CIE L*a*b* in the visible light range were also measured and are shown in the table below. .

[0096] Comparison Example 1 The allyl monomer / oligomer of CR39 (polyallyl diethylene glycol carbonate) was mixed with a Cu-complex of 1.25 ppm heterocyclic dye compound (FDB-001, Yamada Chemical Co., Ltd.). The monomer / oligomer was mixed with a peroxide radical initiator for polymerization. 0.085 wt% of a conventional benzophenone-type UV absorber was added.

[0097] The mixed polymerizable composition exhibits a transmittance notch peak at 420 nm, as shown in... Figure 6 The transmittance peaks are clearly visible in the light transmission curve. However, after curing (polymerization), the transmittance notch peaks are no longer observed in the light transmission curve, as... Figure 6 As shown, this demonstrates that the peroxide polymerization initiator disrupts the Cu-complex of the heterocyclic dye compound, and therefore the transmittance trap peak disappears.

[0098] Comparison Example 2 The allyl monomer / oligomer of CR39 (polyallyl diethylene glycol carbonate) was mixed with a Cu-complex of 4 ppm heterocyclic dye compound (FDB-001, Yamada Chemical Co., Ltd.). The monomer / oligomer was mixed with a peroxide radical initiator for polymerization. 0.085 wt% of a conventional benzophenone-type UV absorber was added.

[0099] The mixed polymerizable composition exhibits a transmittance notch peak at 420 nm, as shown in... Figure 7 The transmittance peaks are clearly visible in the light transmission curve. However, after curing (polymerization), the transmittance notch peaks are no longer observed in the light transmission curve, as... Figure 7 As shown. This demonstrates that despite the increased amount of notch dye used, the peroxide polymerization initiator completely destroys the Cu-complex of the heterocyclic dye compound, and therefore the transmittance notch peak disappears.

[0100] Comparison Example 3 The allyl monomer / oligomer of CR39 was mixed with a V-complex of 1.25 ppm heterocyclic dye compound (FDB-002, Yamada Chemical Co., Ltd.). The monomer / oligomer was mixed with a peroxide polymerization initiator for polymerization. 0.085 wt% of a conventional benzophenone-type UV absorber was added.

[0101] The mixed polymerizable composition exhibits a transmittance notch peak at 430 nm, as shown in... Figure 8 The transmittance peaks are clearly visible in the light transmission curve. However, after curing (polymerization), the transmittance notch peaks are no longer observed in the light transmission curve, as... Figure 8 As shown, this demonstrates that the peroxide polymerization initiator also completely destroys the V-complex of the heterocyclic dye compound, and therefore the transmittance trap peak disappears.

[0102] Comparison Example 4 In this comparative example, the solvent dye FDB-004 from Yamada Chemical Co., Ltd. was selected as the notch dye. FDB-004 is reported to be yellow and has an absorption peak at 445 nm (λ). max ).

[0103] The allyl monomer / oligomer of CR39 was mixed with 4 ppm of solvent dye compound FDB-004 (Yamada Chemical Co., Ltd.). The monomer / oligomer was mixed with a peroxide polymerization initiator for polymerization. 0.085 wt% of a conventional benzophenone-type UV absorber was added.

[0104] The mixed polymerizable composition exhibits a transmittance notch peak at 443 nm, as shown in... Figure 9 The transmittance peaks are clearly visible in the light transmission curve. However, after curing (polymerization), the transmittance notch peaks are no longer observed in the light transmission curve, as... Figure 8 As shown, this demonstrates that the peroxide polymerization initiator also completely destroys the solvent dye compound, and therefore the transmittance notch peak disappears.

Claims

1. A polymerizable composition suitable for producing (meth)acrylate-based spectacle lenses, said polymerizable composition comprising: (i) (meth)acrylate compounds, and (ii) A metal complex of a heterocyclic dye compound, wherein the metal complex of the heterocyclic dye compound has a light absorption peak in the range of 425 ± 10 nm. Its features The composition further comprises (iii) an azo-based polymerization initiator and does not contain an allyl compound.

2. The polymerizable composition according to claim 1, Its features This polymerizable composition is suitable for producing (meth)acrylate-based eyeglass lenses by curing.

3. The polymerizable composition according to claim 1 or 2, Its features The metal complex of this heterocyclic dye is copper (Cu) or vanadium (V).

4. The polymerizable composition according to any one of claims 1 to 3, Its features This heterocyclic dye compound is a porphyrin dye compound.

5. The polymerizable composition according to any one of the preceding claims, Its features Metal complexes containing 0.1 ppm to 10 ppm or 0.5 ppm to 3 ppm of the heterocyclic dye.

6. The polymerizable composition according to any one of the preceding claims, Its features It further includes a free radical chain transfer agent.

7. The polymerizable composition according to any one of the preceding claims, Its features It further comprises at least one color balancing agent having a light absorption peak in the wavelength range of 600 nm to 700 nm.

8. The polymerizable composition according to claim 7, Its features It further contains the color balancing agent at a concentration of 0.1 ppm to 5 ppm.

9. An anti-glare (meth)acrylate eyeglass lens prepared by using the polymerizable composition according to any one of the preceding claims, Its features The spectacle lens has a low or medium refractive index between 1.48 and 1.60, or between 1.48 and 1.58, or between 1.50 and 1.55, and the spectacle lens is a cured spectacle lens.

10. The anti-glare (meth)acrylate spectacle lens according to claim 9, Its features It at least partially blocks the transmission of light in the wavelength range of 425 ± 10 nm.

11. The anti-glare (meth)acrylate spectacle lens according to claim 9 or 10, Its features Block at least 2%, at least 3%, at least 4%, or at least 5% of light transmission in the wavelength range of 425 ± 10 nm.

12. The anti-glare (meth)acrylate spectacle lens according to any one of claims 9 to 11, Its features It has a transmittance notch peak in the wavelength range of 425 ± 10 nm, wherein the transmittance at the transmittance notch peak is 80% to 20%, or 70% to 20%, or 70% to 25%.

13. The anti-glare (meth)acrylate spectacle lens according to any one of claims 9 to 12, Its features It has a yellowness index of 9 or less.

14. The anti-glare (meth)acrylate spectacle lens according to any one of claims 9 to 13, Its features It has 80% or greater, or 85% or greater transmittance at a wavelength of 450 nm.

15. The anti-glare (meth)acrylate spectacle lens according to any one of claims 9 to 14, Its features It has an average transmittance of 80% or more, or 85% or more, of visible light.

16. The anti-glare (meth)acrylate spectacle lens according to any one of claims 9 to 15, Its features It has less than 2% transmittance or 0% transmittance at a wavelength of 400 nm.

17. The anti-glare (meth)acrylate spectacle lens according to any one of claims 9 to 16, Its features The spectacle lens is prepared using the polymerizable composition according to claim 7, and It at least partially blocks light in the wavelength range of 600 nm to 630 nm and / or 660 nm to 690 nm.

18. The anti-glare (meth)acrylate spectacle lens according to claim 17, Its features Block at least 0.5%, or at least 1%, or at least 2%, or at least 5% of light transmission in the wavelength range of 600 nm to 630 nm and / or 660 nm to 690 nm.

19. A method for producing anti-glare (meth)acrylate spectacle lenses according to any one of claims 9 to 18, the method comprising: Curing the polymerizable composition according to any one of claims 1 to 8 in a mold.

Images