Glass body

Abstract

One aspect relates to a glass body, in particular a spectacle lens, comprising a base body (2) having a first and a second side, and a layer (4) on at least one side of the base body (2), the base body (2) being composed of plastic glass and having a microhardness of H L > 90 N / mm2, and the layer (4) having a microhardness of H c < 1000 N / mm2 and H c 0.5 x H L.

Description

[0001] Glass body

[0002] The present invention relates to a glass body, in particular a spectacle lens, a use of the glass body and a photochromic dye.

[0003] Glass bodies, especially plastic lenses, preferably plastic spectacle lenses, are generally manufactured from a polymerizable mixture or composition, often also referred to as casting resin. Such a composition typically consists of plastic monomers and is in the form of a pourable or moldable mass, which, for example, to produce a plastic lens, is poured into a volume formed between two mold components arranged at a predetermined distance from each other. The resulting structure is then cured by the application of energy, i.e., the polymerizable composition or casting resin is polymerized, with the energy required for this process generally being supplied by thermal energy.

[0004] In other areas, such as the application of functional coatings, particularly functional lacquers, to plastic lenses, these coatings or lacquers are generally applied to the plastic lens as a polymerizable composition before solidification or curing occurs during a polymerization step. Such functional coatings typically exhibit lower hardness or microhardness than the underlying glass or substrate and can therefore be considered soft coatings, especially in comparison to the underlying substrate, with regard to their microhardness.Such soft coatings have the disadvantage that they do not have high strength and therefore do not offer sufficient protection against everyday external influences, and consequently degrade quickly without an additional outer protective layer, which can manifest itself in particular in a diminishing effect of their respective functionality.

[0005] US 11 / 526 031 B2 describes an approach in which such a soft layer is protected by a hard protective layer, in particular one placed over it. This provides protection for the soft layer against degrading external elements.

[0006] Confirmation copies can be obtained by influencing factors, but this approach has the disadvantages that an additional (protective) layer must be applied. This makes the manufacturing process more complex, time-consuming, and material-intensive, and also results in a hard-soft-hard structure consisting of a (comparatively) hard base body, a soft functional coating, and subsequently a hard (protective) layer. Due to differing material properties, especially differing hardnesses, such structures are generally undesirable and should be avoided.

[0007] Against this background, one aspect of the present application aims to propose an improved glass body, in particular an improved spectacle lens, which does not have the aforementioned disadvantages.

[0008] The problem is solved in particular by a glass body having the features of claim 1. The dependent claims relate to advantageous embodiments.

[0009] One aspect of the present invention relates to a glass body, in particular a spectacle lens, comprising: a base body with a first and second side, a layer which is arranged on at least one side of the base body, wherein: the base body is made of plastic glass and has a microhardness of HL > 85 N / mm² 2 exhibits a microhardness of Hc < 1000 N / mm 2 and has Hc 0.5 x HL.

[0010] The basic body is initially unrestricted except that it has a first side and a second side opposite the first, the first and second sides being connected by a boundary surface. The basic body can have a planar shape, in which case the first and second sides are essentially plane-parallel or parallel to each other. The basic body can also have a different shape, in particular a shape in which at least one of the two sides has a non-parallel shape, especially a curved shape. A curved shape can be described in more detail based on the radius of curvature, and a distinction is generally made between a first case, in which there is a positive radius of curvature, such a shape being called a convex shape, and a second case, in which there is a negative radius of curvature, such a shape being called a concave shape.Due to its non-parallel shape, such a base body is particularly suitable as a base body for a vitreous body, especially for a lens or spectacle lens, since the presence of at least one curved side of the base body, preferably the presence of two curved sides of the base body, gives the vitreous body an optical effect, in particular a minification or magnification effect, which makes such a vitreous body preferably suitable for use as a lens or spectacle lens.

[0011] The base body can be an unprocessed base body with respect to its first and / or second side, also referred to as a substrate or blank. In particular, if one of the two sides has already been processed with respect to its current shape, it is also referred to as a semi-finished part or product, since a glass body comprising such a base body generally undergoes at least one further processing step, preferably two or more processing steps, before its use as a lens or spectacle lens, in particular a surface processing step in which the still unprocessed side undergoes (surface) processing.

[0012] To be suitable for its later use as a lens, the base body should possess sufficient optical quality with regard to its optical imaging properties. Those skilled in the art understand optical imaging properties to be a multitude of determinable, characteristic quantities that can characterize a given object, such as a base body in particular, with respect to its optical imaging properties, including properties such as spectral transmission, color rendering, and the Abbe number. This is especially relevant in the use of plastics as materials for the manufacture of lenses, particularly ophthalmic lenses.For spectacle lenses, materials such as acrylate, poly(thio)urethane, polyacrylate, polymethyl methacrylate, polycarbonate, polydiethylene glycol bisallyl carbonate, or combinations thereof have proven preferred in recent years, although other transparent plastic materials can also be used in principle. Accordingly, the base body in one embodiment is made of plastic, and can in particular be a plastic base body, preferably a plastic lens base.

[0013] Depending on the plastic used, the base body can be formed, as described in the introduction, by polymerizing a polymerizable composition, for example by curing under controlled temperature conditions or by irradiation with electromagnetic waves, especially UV light. Alternatively, the base body can be formed by thermoplastic deformation, such as (injection) molding.

[0014] In order to be particularly suitable as a base body for a glass body or for a spectacle lens, the base body is preferably made of a transparent plastic glass, in particular of a plastic glass that is transparent in the visible spectral range or of a plastic glass that is (at least partially) transparent to visible light.

[0015] The microhardness of an object, particularly of the substrate and / or the layer, is generally determined by applying a known and well-defined test specimen to the object with a defined force, or, converted to the area of ​​the test specimen, with a defined pressure. The deformation observed upon penetration of the test specimen provides information about the hardness. Especially at penetration depths greater than or equal to approximately one-tenth of the layer thickness of the layer being tested for hardness, it is important to note, according to Bückle's rule, that this measures the composite hardness of the system and not the individual hardness of the layer.Such hardness measurements can be performed using commercially available hardness testers, such as the FISCHERSCOPE HM2000 from Helmut Fischer GmbH, Sindelfingen, for coatings thicker than 1-2 pm, or the PICODENTOR HM500 from the same company for coatings 1 pm thick or less. The measurement and calculation of material properties, such as microhardness (or Martens hardness), elastic indentation modulus, indentation creep, and the ratio of elastic to plastic deformation, are carried out according to DIN EN ISO 14577-1. Measurements can be performed with a maximum force of 300 mN, which is reached after a measurement time of 20 seconds at a temperature of 30°C. The microhardness can then be determined from the measurement once the maximum force is reached.

[0016] The base body has a microhardness HL of greater than or equal to 85 N / mm². 2on, preferably greater than or equal to 95 N / mm 2 , preferably greater than or equal to 100 N / mm 2 , particularly preferably of greater than or equal to 150 N / mm 2 , especially of greater than or equal to 175 N / mm 2 A base body exhibiting the aforementioned microhardness is suitable as a base body for a glass body, as it possesses a certain strength, toughness, and wear resistance, and thus good everyday usability.

[0017] The glass body comprises (at least) one layer arranged on at least one side of the base body. In a further development, the layer can also be arranged on both sides of the base body. The layer is preferably arranged directly on the base body or on one or both sides of the base body, which means that no further layer or layer is arranged between the layer and the base body. In a variation of this, the layer can also be arranged indirectly, which means that at least one, preferably two or more, additional layers or layers of a material different from the layer and the base body are arranged between the layer and the base body. Preferably, these additional layers or layers can be...Layers are those that give the glass body, in particular the base body and / or the layer, an additional property; for example, one or two or more additional layers arranged between the base body and the layer can improve the adhesion between the base body and the layer or provide an additional property.

[0018] This layer is not initially restricted in any further way; in particular, it can be made of a material that is transparent in the visible spectral range, just like the base material, or of a material that is (at least partially) transparent to visible light. This makes the layer particularly suitable as a coating for a glass body, especially for a spectacle lens.

[0019] The layer exhibits a microhardness Hc of less than or equal to 1000 N / mm². 2 on, preferably less than or equal to 500 N / mm 2, especially preferably less than or equal to 250 N / mm 2 The layer therefore differs from known layers, in particular from known scratch-resistant layers or coatings, or hard lacquer layers or coatings, which are applied to or provided with a substrate to protect it, especially from mechanical damage such as scratching. Such high values ​​for the microhardness of the layer are not desirable, since a not-too-hard or rigid environment is required for the (optional) functionalization of the layer, for example, by dyes contained in the layer, especially photochromic dyes.

[0020] The layer can, in particular, be a functional layer and impart properties, preferably (additional) functional properties, to the base body it contains. In this way, a glass body has additional properties that the base body does not possess; that is, by means of the layer, a base body can be provided with additional properties or refined to obtain a (coated) glass body that exhibits the desired additional properties. Preferably, the layer can be colored. Alternatively or additionally, the layer can be more easily colored than the base body due to its material properties, since, for example, dyes penetrate the material of the layer more easily or quickly and / or adhere to the layer surface. The coloring can be carried out in an immersion bath.

[0021] The layer has a microhardness Hc that is greater than or equal to half the microhardness HL of the base body, i.e., Hc ≤ 0.5 x HL, preferably Hc ≤ 0.6 x HL, and particularly preferably Hc ≤ 0.70 x HL. Because the layer has a microhardness that is at least half the microhardness of the base body, it is characterized by increased hardness compared to conventional layers and, consequently, increased strength, toughness, and wear resistance. Advantageously, this allows a glass body to be obtained that comprises a base body and a layer arranged directly or indirectly thereto, which imparts at least one additional property to the glass body and is simultaneously not too soft. A soft layer within the meaning of the invention, in particular an excessively soft layer, has a microhardness of Hc < 0.4 x HL.In particular, because the layer has a hardness greater than or equal to 50% of the hardness of the base material, a functional layer or coating can be achieved without an additional protective layer, especially one that would protect the functional coating itself. Advantageously, this allows for the creation of a (functionally coated) glass body that requires no additional protective layer and is therefore both cost-effective to manufacture and, especially in the absence of an additional hard protective layer, lacks a hardness profile, consisting of a hard base material, a soft layer, and a subsequent hard protective layer.

[0022] Preferably, the layer is formed by polymerization of a polymerizable composition. Advantageously, the layer can be formed or produced particularly efficiently by preparing or providing a polymerizable composition, because the polymerizable composition can first be easily applied to the substrate and then polymerized on the substrate, thus forming a strong bond with it. Those skilled in the art are familiar with a number of common methods for applying a polymerizable composition, including, in particular, spray coating, spin coating, dip coating, and casting. This method is especially advantageous for forming the layer on a substrate that has at least one curved side.Those skilled in the art are also familiar with common methods for forming the layer by polymerization of the polymerizable composition, in particular thermal polymerization, triggered or caused by the supply of or exposure of the composition to heat, as well as UV-induced polymerization, triggered or caused by the presence of or irradiation of the polymerizable composition with UV radiation, or a combination thereof. A preferred polymerizable composition comprises as its main components at least isocyanates or protected isocyanates and isocyanate-reactive components. This advantageously allows the formation of a polymerized poly(thio)urethane layer that combines very good optical properties with high suitability for everyday use.Polymerizable compositions comprising as their main components two- and / or three-functional (meth)acrylates are also preferred, as they are particularly suitable for forming a polymethyl(meth)acrylate layer. Such layers are also known for their good optical properties combined with high suitability for everyday use. In addition to the aforementioned preferred main components, such polymerizable compositions may contain further components, in particular various additives, which fulfill additional functions or can selectively modify the chemical and / or mechanical properties of such a polymerizable composition. It can also be advantageous to include additives such as light and / or radical stabilizers to improve the resistance of such a layer, especially to environmental influences and climatic conditions.

[0023] Preferably, the layer has a thickness of greater than or equal to 10 pm, more preferably greater than or equal to 30 pm, particularly preferably greater than or equal to 50 pm, but especially less than or equal to 350 pm or less than or equal to 750 pm. Advantageously, this allows the formation of a comparatively thin layer, in particular a very thin layer compared to the substrate. In this way, the amount of material required can advantageously be reduced.

[0024] Preferably, the base body has a microhardness HL of greater than or equal to 85 N / mm². 2 and the layer has a microhardness Hc greater than or equal to 43 N / mm² 2 preferably greater than or equal to 50 N / mm 2 Furthermore, the base body preferably has a microhardness HL of greater than or equal to 100 N / mm². 2 and the layer has a microhardness Hc greater than or equal to 60 N / mm² 2The base body preferably has a microhardness HL of greater than or equal to 160 N / mm². 2 and the layer has a microhardness Hc of greater than or equal to 120 N / mm² 2 Combinations of base material and layer that meet the aforementioned values ​​are characterized by particularly high suitability for everyday use as glass bodies or spectacle lenses and can be manufactured in particular with well-known plastic lens materials familiar to the expert.

[0025] Preferably, the layer is formed by gating, i.e., the layer is produced in particular by a gating process, wherein the base body is first arranged at a distance from a mold shell, forming a cavity, the cavity is appropriately sealed, and then the cavity is filled with the polymerizable composition to form the layer. Advantageously, base bodies can be reproducibly provided with a particularly thin layer in this way, in particular a layer having a thickness of less than 750 pm.

[0026] Preferably, the polymerizable composition for forming the layer comprises at least one crosslinking agent. Advantageously, this promotes the formation of crosslinks during polymerization, resulting in a higher microhardness of the formed layer. Preferably, by adding compounds from the group of multifunctional thiols or multifunctional alcohols, microhardness values ​​of Hc 0.9 x HL, more preferably Hc S 1.0 x HL, and particularly preferably Hc 1.1 x HL, can be achieved for the formed layer. Furthermore, inorganic or organic nanoparticles surface-modified with thiols or alcohols can be used. Multifunctional isocyanates or isocyanate-modified inorganic or organic nanoparticles can also be employed.In other words, this allows a layer to be formed which has excellent strength and, in particular, a microhardness that is approximately equal to the hardness of the base body and, in further developments, even exceeds it.

[0027] Preferably, the base body of the lens body is made of a plastic glass or preferably comprises (meth)acrylate, poly(thio)urethane, polyacrylate, polymethyl methacrylate, polycarbonate, polydiethylene glycol bisallyl carbonate, or combinations thereof. In this way, plastic materials familiar to those skilled in the art, and in particular commercially available ones, can be used for transparent lens bodies. The aforementioned materials, in particular, are characterized by very good optical properties combined with high suitability as base materials for lens bodies in everyday use.

[0028] Preferably, the base body is produced or formed by polymerization of a polymerizable composition, wherein the polymerizable composition of the base body comprises essentially the same substances or compounds as the polymerizable composition for forming the layer. Advantageously, by selecting a composition that is as similar as possible, preferably very similar, and particularly preferably essentially identical, to the respective polymerizable compositions of the base body and the layer, a particularly strong and durable bond between the base body and the layer can be achieved. Furthermore, this also allows for the attainment of very comparable optical properties, due to the essentially identical substances or compounds, resulting in a glass body characterized by low interference phenomena. Advantageously, the sprue layer can also be composed of essentially the same substances or compounds.It should be colored exactly like the base body, so that no disturbing optical effects arise due to different colors.

[0029] Preferably, the difference An between the refractive index n L of the base body and the refractive index n c the layer at least at one wavelength, in particular determined at a wavelength of approximately 550 nm, An = \n L - n c \ < 0.2. The difference An = |n is preferred. L - n c | < 0.1. The difference An = \n is also preferred. L - n c | < 0.01, especially preferred An = |n L - n c | < 0.001, especially An - \n L - n c| < 0.0001 and thus approximately identical. Advantageously, interference phenomena that arise at interfaces with different refractive indices can be prevented if the refractive index of the base body and the layer differs only slightly at at least one wavelength, preferably at two or more wavelengths, and particularly preferably at the majority of all wavelengths in the visible spectral range. The base body can have a refractive index of approximately 1.5, 1.6, 1.67, 1.72, or 1.74, where the term "approximately" can denote a deviation of less than 5%, preferably less than 1%.

[0030] Preferably, the layer has a microhardness Hc of 0.5 x HL Hc HL, meaning that the microhardness of the layer is greater than or equal to 50% of the hardness of the substrate, but at most equal to or less than the hardness of the substrate. This allows the formation of a layer that is particularly suitable for additional functionalization, especially for coloring. Such a layer combines two advantages: firstly, it has sufficient microhardness, which is at least half the microhardness of the substrate, and thus, compared to conventional layers, it is characterized by increased hardness and, consequently, increased strength, toughness, and wear resistance.On the other hand, due to its microhardness, which is at most equal to or less than the microhardness of the glass body, the layer forms a layer that is "soft" enough to allow additional functionalization in an improved way, which can include, for example, the introduction of dyes to obtain a colored or tinted layer.

[0031] Preferably, the layer is photochromic and the polymerizable composition of the layer comprises at least one photochromic dye. Advantageously, a photochromic glass body can be obtained by forming a photochromic layer on the base material; that is, the glass body acquires an additional property by providing the base material with a photochromic layer, in particular photochromic behavior, which is understood to mean, in particular, that the at least one photochromic dye contained in the composition reacts to UV light. Depending on the intensity of the incident UV light, the at least one photochromic dye causes a darkening or lightening through a reversible change in its molecular structure, also known as isomerization. A photochromic dye thus changes its absorption behavior in response to irradiation with UV light.When UV light exposure decreases, the photochromic dye reverts to its original molecular structure and thus also to its original absorption behavior. A photochromic dye therefore enables reversible switching between dark and light tints. Naphthopyrans, spirooxazines, and / or spiropyrans are particularly suitable as photochromic dyes, exhibiting both rapid darkening and high longevity. In particular, the polymerizable composition can contain not only one photochromic dye from the aforementioned compound groups, but also two or more, and the selected photochromic dyes can also differ. Using such a composition supplemented with photochromic dyes, a photochromic layer can be formed on a substrate.a photochromic glass body is obtained, which can preferably be used as a self-tinting spectacle lens and offers a high level of wearing comfort, as the self-tinting effect makes switching between conventional corrective glasses, for example reading glasses, and sunglasses obsolete.

[0032] Preferably, the layer is colored, in particular permanently colored, and the polymerizable composition of the layer comprises at least one permanent dye. "Permanent," in contrast to "photochromic," means that the dye exhibits constant absorption behavior and cannot reversibly switch between an excited (absorbing) and a non-excited (non-absorbing) state due to UV radiation. Permanent coloring therefore refers to a lasting, largely unchanging color. The dye can, for example, impart a characteristic color or special absorption properties, such as a filtering effect, to the composition. Such a modified composition then exhibits a new or additional property: a pre-coloration or a different transmission characteristic compared to a composition without dye.This process yields, in particular, a colored composition, advantageously forming a colored layer on the substrate or producing a colored glass body. Preferably, these are azo dyes, cyanine dyes, anthraquinone dyes, or the like, such as those commonly used in the conventional coloring of glass bodies, especially plastic spectacle lenses. In particular, the polymerizable composition can comprise not only one dye from the aforementioned compound groups, but also two or more, and the selected dyes can also differ. A person skilled in the art routinely selects a suitable dye or a mixture of suitable dyes.

[0033] In a further development of this, the layer is preferably photochromic and, in particular, permanently colored. By combining these two forms, a permanently pre-colored layer can be obtained, which exhibits a first absorption characteristic or a first transmission behavior and, upon irradiation with UV radiation, a second absorption characteristic or a second transmission behavior that differs from the first. Advantageously, by coating a base body with such a layer, a permanently colored and photochromic material can be obtained, which thereby exhibits special properties such as an initial darkening and, upon irradiation with UV radiation, a second, in a further development, even deeper darkening.Such a glass body is therefore particularly suitable for use as a sunglass lens, which exhibits an initial darkening and, upon exposure to UV radiation, especially present in the sunlight spectrum, a second, even deeper darkening.

[0034] Preferably, the glass body has at least one further layer or coating on at least the side, or in a further development, on both sides, on which the layer is arranged, which is selected from: an anti-reflective coating; and / or a mirrored coating; and / or an easy-to-clean coating; and / or an anti-static coating; and / or an anti-fog coating; and / or a UV protection coating; and / or an IR protection coating; and / or a blue light protection coating.

[0035] A person skilled in the art knows how to skillfully combine the aforementioned coatings to obtain glass bodies with different properties. Preferably, the at least one additional layer is an anti-reflective coating. Such a coating, comprising at least one single layer, generally preferably comprising alternating single layers with different refractive indices arranged one after the other, forming an interferometric multi-layer system, is based on the concept of interference, in particular destructive interference, to inhibit or suppress, or largely or completely suppress, the reflection of the incident light by means of destructive interference, at least for one wavelength, preferably for two or more, and particularly preferably for a multitude of wavelengths.Advantageously, this results in an anti-reflective glass body, which is therefore particularly suitable as a lens and / or spectacle lens, since it is (largely) free from disturbing reflections due to the anti-reflective coating and is characterized by high transmission.

[0036] Preferably, and in particular also as an alternative or additional to an anti-reflective coating, the at least one further layer is a reflective coating. Such a coating, comprising at least one single layer, generally preferably comprising alternating single layers with different refractive indices arranged one after the other, forming an interferometric multi-layer system, is based on the concept of interference, in particular constructive interference, to reflect the incident light by means of constructive interference for at least one wavelength, preferably for two or more, and particularly preferably for a plurality of wavelengths.Advantageously, this results in a mirrored glass body, which is therefore particularly suitable as a mirrored lens and / or mirrored spectacle lens, especially sunglass lens, since it reflects incident light through the mirror coating.

[0037] Preferably, and especially as an alternative or additional to an anti-reflective and / or mirrored coating, the at least one further layer is an easy-to-clean coating characterized by low surface energy and, in particular, hydrophobic and / or oleophobic properties. This results in a glass body coated with this coating exhibiting less tendency to adhere to dirt, grease, and / or water. Often, such a coating also offers improved cleanability as an additional property. Advantageously, this results in a glass body that is highly suitable for everyday use, highly resistant to everyday grease- and / or water-based soiling, and easy to clean.Such an easy-to-clean coating can also be arranged as the final, outermost layer as part of a multilayer (interferometric) coating system.

[0038] Preferably, and in particular also as an alternative or additional to an anti-reflective and / or mirrored coating and / or easy-to-clean coating, the at least one further layer is an antistatic coating which counteracts, in particular, a static charge on the glass body in order to prevent the adhesion of dust particles. Preferred materials for such antistatic coatings are generally metallic or at least conductive layers; materials such as ITO (indium tin oxide) and / or metal oxides are particularly preferred, especially substoichiometric metal oxides, which thereby exhibit conductivity. Such an antistatic coating can also be arranged as part of, or be present in, a multilayer (interferometric) coating system.

[0039] Preferably, and in particular also as an alternative or additional to an anti-reflective and / or mirrored coating and / or easy-to-clean coating and / or antistatic coating, the at least one further layer is an anti-fog coating, which is characterized by its ability to counteract fogging. This means, in particular, that it counteracts the formation of (water) droplets when water vapor in the air condenses (especially during temperature changes from a cold to a warm environment), thus ensuring that no individual droplets form, but rather a largely uniform film that allows for acceptable visibility and transmission. Advantageously, this results in a lens, especially a spectacle lens, that offers a high level of wearing comfort.Such an anti-fog coating can also be arranged as the final, outermost layer as part of a multi-layer (interferometric) coating system.

[0040] Preferably, and in particular also as an alternative or additional to an anti-reflective and / or mirrored coating and / or easy-to-clean coating and / or anti-static coating and / or anti-fog coating, the at least one further layer is a UV protection coating characterized by reduced transmission of UV radiation, preferably by inhibited to completely absorbing or reflective transmission of UV radiation. Advantageously, this results in a glass body that has a blocking effect with regard to the transmission of (harmful) UV radiation and is therefore particularly suitable as a lens or spectacle lens. In a lens, such UV protection can be advantageous to protect sensitive components, e.g., optical sensors, from irradiation or exposure to UV radiation.For spectacle lenses, protection against harmful UV radiation is advantageous to protect the wearer's eyes. Such a UV-protective coating can also be incorporated as part of a multi-layered (interferometric) coating system, or a corresponding coating system, optionally an anti-reflective and / or mirrored coating, can be designed to suppress light in the visible spectral range (anti-reflective coating) or deliberately reflect it (mirrored coating), while simultaneously exhibiting increased absorption or reflection of UV radiation.

[0041] Preferably, and in particular also as an alternative or additional to an anti-reflective and / or mirrored coating and / or easy-to-clean coating and / or anti-static coating and / or anti-fog coating and / or UV protection coating, the at least one further layer is an IR protection coating, which is characterized by reduced transmission behavior with respect to IR radiation, preferably by inhibited to completely absorbing transmission behavior or reflective behavior with respect to IR radiation. Advantageously, this results in a glass body that has a blocking effect with respect to the transmission of (harmful) IR radiation and is therefore particularly suitable as a lens or spectacle lens. In a lens, such IR protection can be advantageous to protect sensitive components, e.g.Optical sensors need protection from IR radiation, particularly to reduce, inhibit, or prevent the associated heat energy input. For spectacle lenses, protection from harmful IR radiation is advantageous to protect the wearer's eyes. Such an IR protective coating can also be incorporated as part of a multilayer (interferometric) coating system, or a corresponding coating system, optionally an anti-reflective and / or mirrored coating, can be designed to suppress (anti-reflective) or deliberately reflect (mirrored) light in the visible spectral range while simultaneously exhibiting increased absorption or reflection of IR radiation.Further developing this, an IR protective coating can also be designed in combination with a UV protective coating, particularly as a multilayer (interferometric) coating system, thereby providing advantageous protection against radiation from both radiation ranges adjacent to the visible spectrum. This can preferably be achieved through the suitable design of a multilayer (interferometric) coating system.

[0042] Preferably, and in particular also as an alternative or additional to an anti-reflective and / or mirrored coating and / or easy-to-clean coating and / or anti-static coating and / or anti-fog coating and / or UV protection coating and / or IR protection coating, the at least one further layer is a blue-light protection coating, which is understood to be a coating that exhibits increased absorption and / or reflection of radiation from the blue spectral range. Advantageously, this results in a glass body as a lens or spectacle lens that is characterized by protection against radiation from the blue spectral range, which is particularly suspected of disrupting the human circadian rhythm. Such a blue-light protection coating can also be arranged as part of a multilayer (interferometric) coating system.A suitable layer system, optionally an anti-reflective and / or mirrored coating, can be designed to suppress light in the visible spectral range (anti-reflective coating) or to deliberately reflect it (mirrored coating), while simultaneously exhibiting increased absorption or reflection of IR radiation. Further developing this, a blue-light protection coating can also be designed in combination with a UV-protective and / or IR-protective coating, particularly as a multilayer (interferometric) system, thereby providing advantageous protection against radiation from the aforementioned spectral ranges.

[0043] It goes without saying that the person skilled in the art can select any combinations, in particular synergistic combinations, from the aforementioned coatings in order to obtain a glass body which has a base body and the coating, as well as any number of further layers to obtain further advantageous properties.

[0044] Preferably, at least one of the following coatings is arranged between the layer and at least one further layer or coating, in particular selected from the above list: a buffer coating; and / or a hard coating.

[0045] By applying a buffer coating between the lens layer and at least one other layer, the impact resistance of the coated glass body can be improved or increased. It is known that such buffer coatings are generally formed as incompletely polymerized layers, thereby improving the impact resistance of the glass body. Such buffer coatings are particularly advantageous when base bodies made of relatively hard plastic glass materials, such as polyurethane and / or polymethyl methacrylate, are used as glass bodies or spectacle lenses and must meet specific impact resistance requirements, such as those stipulated by the US Food and Drug Administration (FDA) for the drop ball test.

[0046] By applying a hard lacquer coating between the layer and at least one further layer, the mechanical strength, and in particular the scratch resistance, of the glass body can be improved. Compared to mineral glass, plastic glass bases exhibit lower scratch resistance and are prone to increased scratching in everyday use, especially as glass bodies or spectacle lenses. To obtain a more resistant glass body, such a hard lacquer coating is applied as an additional layer. This coating preferably consists of siloxanes, which thus exhibits increased scratch resistance. Further developing this by combining a buffer lacquer and a hard lacquer coating yields a particularly resistant glass body that exhibits both increased impact resistance and increased scratch resistance, making it especially suitable as a lens.It's a spectacle lens.

[0047] Preferably, the polymerizable composition of the layer comprises at least one photochromic dye with at least one and at most four naphthopyran subunits and one or more polyether chains. Advantageously, certain photochromic dye molecules with multiple polyether chains at different positions within the molecule, which contains between one and four naphthopyran subunits, exhibit excellent matrix-independent phototropic properties in all types of plastic spectacle lenses. Furthermore, this is achieved without the need for special additives, without which dyes with only one naphthopyran subunit and a longer-chain polyether substituent exhibit unacceptable phototropic properties in tightly cross-linked thiourethane thermoset polymers.In contrast, the naphthopyran subunits—in cases where there is more than one in the molecule—are connected to each other only by relatively short linkers, while several higher-molecular-weight polyether chains are attached to the outside of the molecule. This allows these longer-chain polyether substituents to very efficiently encapsulate the photochromic naphthopyran subunits and thus completely shield them from the respective plastic-glass polymer matrix. For the first time, this makes it possible to achieve excellent phototropic properties independent of the matrix—even in tightly cross-linked thiourethane thermoset polymers.

[0048] Advantageously, or according to one aspect, new higher molecular weight photochromic dyes with at least one (exactly one) and at most four naphthopyran subunits and several polyether chains are thus provided according to the following formula ( I ):

[0049] ( I ) provided (1 ) that at least one and at most four of the residues Ri , R2, R3 or R4 independently represent the following grouping A with a terminal longer-chain polyether substituent: and the remaining residues Ri, R2, R3 or R4 independently represent hydrogen, a methyl residue, an ethyl residue, a phenyl residue or the following group B with a longer-chain polyether substituent: where, in the case of only one group A in the molecule, at least one of the remaining residues must represent group B; or subject to the condition (2) that at least one and at most two of the residues Ri, R2, R3 or R4 independently represent the following group C:

[0050] and of the remaining residues Ri, R2, R3 or R4 at least two represent group B, wherein in the case of a further remaining residue, this may be selected from hydrogen, a methyl residue, an ethyl residue or a phenyl residue; wherein m, n, p, q and r each independently represent an integer from 0 to 1, s represents an integer from 5 to 50 and t represents an integer from 0 to 3, wherein the stylized benzene ring inscribed “Naphthopyran” represents one of the following four discrete naphthopyran subunits “1” - “4”:

[0051] 3 "4 and wherein the foregoing substituents Rs, Re, R7, Rs, R9, R10, R11 and R12 are defined as in claim 1:

[0052] Preferably, phototropic acrylate, allyl carbonate, urea, urethane or thiourethane polymers can be provided, comprising one or more of the above photochromic dyes, in particular to form the layer preferably by means of a sprue.

[0053] The photochromic naphthopyran subunits can be located in close proximity to two or more polyether chains. By arranging these subunits around a central, tetrahedral carbon atom, the entire system can be spatially encapsulated from the polymer matrix. This spatial shielding of the phototropic naphthopyran subunits by means of the longer-chain polyether substituents enables, for the first time, matrix-independent phototropic properties. This means, in particular, that phototropic properties can be obtained with the compounds according to the invention in thiourethanes, urethanes, ureas, acrylates, and allyl carbonates.

[0054] Up to now, achieving good phototropic properties has required either the use of specially adapted polymer matrices with less dense cross-linking—resulting in lower hardness—or the addition of specific additives. These additives, together with the dyes, form domain systems that locally soften the polymer matrix. However, the formation of these domains is highly material-specific and only achievable in certain polymer matrices. Advantageously, increased layer hardness can be achieved because the special structure described above allows the longer-chain polyether substituents to align themselves in close proximity to the pyran ring of the photochromic naphthopyran subunits. This is the site of the greatest structural change during the photochromic switching process when opening to the colored form and closing back to the colorless form.Due to the loose arrangement (“random coil”) of the linear polyether chains with only minor intramolecular interactions, this opening and closing of the photochromic center is not hindered. The photochromic properties of the dyes according to the invention can therefore also be realized in highly cross-linked polymer matrices such as thiourethane polymers.

[0055] Due to the special structure of the dyes and their "separation" from the surrounding polymer matrix, the photochromic dyes according to the invention achieve excellent darkening under sunlight and extremely fast lightening after exposure.

[0056] The connection of the naphthopyran subunits to the central, tetrahedral carbon atom of formula (I) occurs either directly (for n = p = 0), via a succinyl-oxy bridge (for n = 1 and p = 0) or via an ethyleneoxy-succinyloxy bridge (for n = p = 1).

[0057] The use of a succinyloxy bridge is advantageous because ester bonds can be formed at very mild reaction temperatures (including room temperature) when using modern coupling reagents, i.e., without thermal stress on the molecule upon heating and the resulting thermal decomposition reactions. Other coupling reactions, such as Williamson ether syntheses, require higher reaction temperatures and more drastic reaction conditions (e.g., the use of strong bases).

[0058] The use of an ethyleneoxy bridge between the naphthopyran subunit and the succinyloxy bridge is generally necessary when an even higher lightening rate is desired. The lightening from the darkened state is generally faster for naphthopyran systems the better the electron-donating properties of the substituents on the two benzene rings bonded to the carbon atom adjacent to the pyran oxygen. Therefore, it is advantageous to use two strongly electron-donating alkoxy substituents, since the acyloxy substituent of a succinyloxy bridge directly on the naphthopyran subunit is too weak an electron donor and often results in an insufficient lightening rate.The same applies to a succinyloxy bridge (for r = 1 ) as a connection between the naphthopyran subunit and the longer-chain polyether substituent in the compounds according to the invention, for which provision (1 ) applies.

[0059] Preferred compounds, for which condition (1) applies, have between one and four naphthopyran subunits and a total of two to four longer-chain polyether substituents (distributed across groups A and B). The latter are linked to the neighboring naphthopyran subunits via optional ethyleneoxy (for q = 1) and succinyloxy bridges (for r = 1) or, if there are fewer than four naphthopyran subunits in the molecule, are optionally also linked directly to the central, tetrahedral carbon atom of formula (I), as group B, via a succinyloxy bridge. This non-optional succinyloxy bridge in group B is present for synthetic reasons. The coupling of the longer-chain polyether substituents to the central, tetrahedral carbon atom is achieved here via ester bridges under very mild reaction conditions.

[0060] Preferred compounds that comply with requirement (2) have either one or two naphthopyran subunits and either two or three longer-chain polyether substituents. The latter are linked to the naphthopyran subunits via the central, tetrahedral carbon atom as group B. In contrast to requirement (1), no further longer-chain polyether substituents are bonded to the naphthopyran subunits here, but only "smaller" substituents Re, which can be used to influence the darkening color and the lightening rate.

[0061] Suitable naphthopyran starting materials can be used for the synthesis of the preferred compounds and, for example, reacted with 1,3-difunctional propane derivatives (for m = m' = 1) to form molecules with two naphthopyran subunits and at least two longer-chain polyether substituents.

[0062] One aspect concerns the use of a glass body according to the invention in lenses and glasses for spectacles of all kinds, such as corrective glasses, driving glasses, ski goggles, sunglasses, motorcycle goggles, for visors of protective helmets and the like, or for sun protection purposes in vehicles or in the construction sector, in the form of windows, protective screens, covers, roofs and the like.

[0063] The invention is described in more detail below with reference to the figures. It is understood that the present invention is not limited to the embodiments shown in the figures, and that individual features of different embodiments can be combined to form further embodiments within the scope of the accompanying claims. Identical reference numerals indicate identical or recurring elements. The figures show:

[0064] Fig. 1 shows a first embodiment of the glass body; and

[0065] - Fig. 2 showing a second embodiment of the glass body with optional features; and

[0066] Fig. 3 shows a third embodiment of the glass body.

[0067] - Fig. 4 a schematic diagram microhardness measurements

[0068] Figure 1 shows a first embodiment of a glass body 1 comprising a base body 2 and a layer 4 arranged on at least one side of the base body 2. In this embodiment, the layer 4 is arranged directly on the base body 2.

[0069] Base body 2 is formed from polythiourethane, the preferred plastic lens material. The base body is formed from a polymerizable composition, also known as a casting resin mixture, wherein the polymerizable composition comprises isocyanates and isocyanate-reactive components as its main constituents. Isocyanate-reactive components are understood to be, in particular, thiols or alcohols with two or more functional groups, i.e., SH or OH groups. Plastic lenses made from polythiourethane exhibit high suitability for everyday use, combined with very good optical imaging properties and an increased refractive index of approximately 1.60, determined at a wavelength of approximately 550 nm.They are therefore particularly suitable as lens bodies for spectacle lenses, which can also correct (somewhat) higher refractive errors, expressed in spherical equivalents of more than + / - 3.0 diopters, very well with acceptable lens (center) thickness, which offers particular aesthetic advantages. The lens body 2 can be produced as a polythiourethane casting, using a correspondingly curved mold, so that the resulting lens body 2 already has a curved shape on one side, expressed in a base curve (BC) of BC = 3.0. The lens body 2 can have a microhardness of approximately 180 N / mm². 2 exhibit.

[0070] The resulting base body 2 and a further mold shell can then be spaced apart from each other, so that a cavity forms between the curved first side of the base body 2 and the spaced-apart mold shell, which can be sealed by means of a suitable tape or adhesive tape. The cavity can then be filled with a casting resin using a filling device, wherein the casting resin is a preferred embodiment of a polymerizable composition which may comprise isocyanates and isocyanate-reactive components as further preferred main components. In addition to these main components, the composition may also include photochromic dyes, in particular naphthopyran dyes as preferred photochromic dyes.In this way, using the above-described method, which is also called the casting method, a layer 4, in particular a photochromic layer, can be formed directly on the base body, which can have a layer thickness of about 30 pm to about 400 pm, in particular about 300-350 pm.

[0071] The (photochromic) layer 4, which forms directly on the substrate, can have a microhardness of approximately 130 N / mm². 2 The base body 2 is provided with a photochromic layer 4, resulting in a glass body 1 that exhibits photochromic properties. The glass body 1 thus obtained therefore comprises a base body 2 which, in this embodiment, acquires an additional property through the functional layer 4 formed directly onto it. The layer 4 has a microhardness (Martens hardness) of approximately 130 N / mm². 2The resulting glass body 1 exhibits a microhardness approximately 70% of that of the base body 2, thus possessing a microhardness significantly greater than half that of the base body 2 and consequently displaying above-average strength. The glass body 1 obtained in this way can be further processed as a semi-finished product in subsequent production steps, for example, by one- or two-sided surface treatment to achieve a desired optical effect, optionally by a hard lacquer coating for even higher scratch resistance, or optionally by an anti-reflective coating for higher transmission. In this way, it can be further processed into a coated lens or a coated spectacle lens. Preferably, only one-sided (machining) surface treatment is performed on the side of the base body 2 facing away from layer 4.

[0072] It goes without saying that layer 4 can also be formed on the substrate 2 using any other method. Likewise, layer 4 can be made of a different material; for example, instead of polythiourethane, it can also be made of a polymerizable composition comprising, for example, functional (meth)acrylates, in particular non-cyclic two- and / or three-functional methacrylates or acrylates, which are preferably suitable for forming a (thermoset) layer 4 of polymethyl methacrylate or polyacrylate having a refractive index of about 1.54, determined at a wavelength of about 550 nm.

[0073] It is also understood that the photochromic dyes added to the polymerizable composition in the embodiment described above for the formation of layer 4 represent only an exemplary form of the achievable functionalization and that the person skilled in the art can add any further substances to such a composition in order to obtain a layer 4 with corresponding functions, whereby a glass body 1 having a base body 2 provided with such a layer 4 acquires the corresponding functions.

[0074] Figure 2 shows a second embodiment of a glass body 1, wherein a glass body 1 can serve as a semi-finished product, as described in Figure 1.

[0075] The resulting glass body 1 can be further coated with additional layers in subsequent production steps as a semi-finished product. The glass body T was initially coated with a hard lacquer as a preferred buffer and / or hard lacquer coating 6 using an immersion coating process. This increased the scratch resistance of the glass body 1' and made it more suitable for everyday use, as it is better protected against (minor) scratches.

[0076] Subsequently, a multilayer anti-reflective coating was formed on the glass body T as a preferred, further coating 8. This anti-reflective coating was formed in a dedicated high-vacuum coating system by vapor deposition, wherein in such a system, low-refractive-index and high-refractive-index coating material is alternately vaporized by means of an electron beam, and the vapor deposits are deposited as alternating, thin layers on the glass body T, in particular on the surface of the formed hard lacquer coating 6.

[0077] In this way, an anti-reflective, hard-lacquer coated glass body 1 ' was obtained, which, due to the hard lacquer coating, has increased scratch resistance and, due to the anti-reflective coating, a high suitability for everyday use, due to high transmission capacity and the absence of disturbing reflections or residual reflections.

[0078] Figure 3 shows a third embodiment of a glass body 1, which differs in particular from the glass body 1 of Figure 1, since the glass body 1" has a layer 4 on the first and second sides of its base body 2, i.e., on both sides. This allows for improved or enhanced functionalization of the glass body 1". In particular, as a further development, a first and a second functionalization can be achieved by having different layers 4 on the first and second sides of the base body 2. In the case of identical layers 4 on the first and second sides of the base body 2, this layer 4 can preferably be formed by dip coating, wherein the base body 2 is immersed in a bath containing the polymerizable composition for forming the layer 4, in particular multiple times.The substrate is repeatedly immersed, and upon re-emergence, a thin film of the polymerizable composition adheres to both sides of the substrate 2. This process is repeated several times until the desired layer thickness of layer 4 is reached, followed by polymerization, optionally by heat (thermal) or UV radiation (UV-induced), resulting in the solidification of layer 4. Dip coating is a particularly advantageous manufacturing method, especially for layer 4 that is to be formed on both sides of the substrate 2.

[0079] Figure 4 shows a schematic diagram of microhardness measurements (plotted on the abscissa) at a corresponding penetration depth (plotted on the ordinate) for microhardness measurements on glass objects. The glass objects to be measured were arranged in a FISCHERSCOPE HM2000 microhardness tester from Helmut Fischer GmbH. For the microhardness measurement, a test specimen with a defined geometry was pressed into the glass object with a force of approximately 300 mN (millinewtons). The measuring device determines the resulting microhardness from the deformation of the glass object caused by the pressure of the test specimen, as a function of the penetration depth of the test specimen.

[0080] The solid line 101 shows the microhardness penetration depth curve of a glass body 1 from Figure 1, which has a polythiourethane base body 2 and a photochromic layer 4 formed on it, also having polythiourethane.

[0081] A comparative example is shown as dotted line 102. This is also a polythiourethane substrate, but it has a conventional photochromic layer made from a known photochromic photoresist containing the photochromic dyes, which was formed on the glass substrate by spin coating.

[0082] The curves show that the measurement curve 101 of the glass body exhibits a significantly higher microhardness according to one aspect of the present application and reaches a saturation value that is almost 100 N / mm² even at greater penetration depths. 2The value is higher than that of comparative example 102. It is also evident that, particularly in the initial penetration depth range, from 0 pm to approximately 1 pm, the decrease in microhardness in measurement curve 101 is less pronounced than in comparative example 102. This demonstrates that, according to one aspect of the present application 101, the glass body 1 exhibits a higher microhardness than comparative example 102 not only at greater penetration depths of several micrometers, but also at shallower penetration depths. The glass body thus has an overall higher microhardness, verified across all measurement ranges, and therefore exhibits greater strength. Consequently, it is particularly suitable as a gas body for lenses and spectacle lenses of all kinds, as its higher microhardness results in improved everyday usability.In particular, by combining it with photochromic dyes in the layer 4 formed on the base body, a photochromic glass body 1 with improved microhardness and thus high suitability for everyday use can be produced.

[0083] In the present disclosure, “an X indicates” implies 1 Generally, this is not an exhaustive list, but rather a short form of "has at least one X" and also includes "has two or more X" as well as "has Y in addition to X".

[0084] The numerical values ​​indicated with "approximately" may preferably deviate by + / - 10% from the stated value, more preferably by + / - 5% from the stated value, more preferably by + / - 2% from the stated value, and in particular may be exactly the stated value. This applies to all numerical values ​​so designated in this application.

[0085] In the present disclosure, "essentially" with regard to the similarity of composition implies that two compositions are essentially identical if their principal components, which are understood to be those compounds contained in the composition, constitute a cumulative weight percentage of at least 60% of the composition. That is to say, two compositions are to be considered essentially identical in the present disclosure if they have the same principal components and their weight percentages in the composition differ by less than 20%, preferably by less than 10%, and particularly preferably by less than 5%. Irrespective of the foregoing, two compositions are considered essentially identical if the differences represent minor deviations, in particular those due to metrological or purity factors.

[0086] List of reference signs

[0087] Glass body

[0088] 2 basic shapes

[0089] 4-layer

[0090] 6 Buffer and / or hard lacquer coating 8 Additional, further coating

Claims

Patent claims 1. Glass body (1 , 1', 1"), in particular spectacle lens, comprising: a base body (2) with a first and a second side, a layer (4) which is arranged on at least one side of the base body (2), wherein: the base body (2) is made of plastic glass and has a microhardness of HL > 85 N / mm 2 The layer (4) has a microhardness of Hc < 1000 N / mm² 2 and has Hc > 0.5 x HL.

2. Glass body according to claim 1, wherein the layer (4) is arranged directly on the base body (2).

3. Glass body according to any of the preceding claims, wherein the layer (4) has a layer thickness of greater than or equal to 10 pm.

4. Glass body according to one of the preceding claims, wherein the base body (2) has a microhardness HL of greater than or equal to 100 N / mm². 2 and the layer (4) has a microhardness Hc greater than or equal to 60 N / mm² 2The base body (2) particularly preferably has a microhardness HL of greater than or equal to 160 N / mm². 2 and the layer (4) has a microhardness Hc of greater than or equal to 120 N / mm² 2 on.

5. Glass body according to one of the preceding claims, wherein the layer (4) is formed by polymerization of a polymerizable composition, in particular by casting.

6. Glass body according to any of the preceding claims, wherein the base body (2) and / or the layer (4) is formed from poly(thio)urethane, acrylate, polyacrylate, methacrylate, polymethyl methacrylate, polycarbonate, polydiethylene glycol bisallyl carbonate or combinations thereof.

7. Glass body according to one of the preceding claims, wherein the base body (2) was formed by polymerization of a polymerizable composition and the polymerizable composition for forming the base body (2) comprises substantially the same substances or compounds as the polymerizable composition for forming the layer (4).

8. Glass body according to any of the preceding claims, wherein the difference An between the refractive index n L of the base body (2) and the refractive index n c the layer (4) at least at one wavelength, in particular determined at a wavelength of about 550 nm, An - \n L - n c \ < 0.2 is.

9. Glass body according to one of the preceding claims, wherein the layer (4) has a microhardness Hc of 0.5 x HL Hc HL.

10. Glass body according to any of the preceding claims, wherein the layer (4) is photochromic and the polymerizable composition of the layer (4) comprises at least one photochromic dye.

11. Glass body according to one of the preceding claims, wherein the layer (4) is a, in particular permanently, colored layer (4) and the polymerizable composition of the layer (4) comprises at least one permanent dye.

12. Glass body according to one of the preceding claims, wherein at least one side of the base body (2) on which the layer (4) is arranged has at least one further layer or coating (8) arranged on the layer (4), wherein this is selected from: an anti-reflective coating; and / or a mirrored coating; and / or an easy-to-clean coating; and / or an anti-static coating; and / or an anti-fog coating; and / or a UV protection coating; and / or an IR protection coating; and / or a blue light protection coating.

13. Glass body according to claim 12, wherein one of the following coatings (6) is arranged between layer (4) and at least one further coating (8): a buffer coating; and / or a hard coating.

14. Glass body according to any one of claims 5 to 13, wherein the polymerizable composition of the layer (4) comprises at least one photochromic dye with at least one and at most four naphthopyran subunits and one or more polyether chain(s).

15. Photochromic dyes comprising at least one and at most four naphthopyran subunits and one or more polyether chains according to the following formula ( I ): with the proviso (1) that at least one and at most four of the residues Ri, R2, R3 or R4 independently represent the following grouping A with a terminal longer-chain polyether substituent: and the remaining residues Ri, R2, R3 or R4 independently represent hydrogen, a methyl residue, an ethyl residue, a phenyl residue or the following group B with a longer-chain polyether substituent: where, in the case of only one group A in the molecule, at least one of the remaining residues must represent group B; or subject to the condition (2) that at least one and at most two of the residues Ri, R2, R3 or R4 independently represent the following group C: and of the remaining residues Ri, R2, R3 or R4 at least two represent group B, wherein in the case of a further remaining residue this may be selected from hydrogen, a methyl residue, an ethyl residue or a phenyl residue; wherein m, n, p, q and r each independently represent an integer from 0 to 1, s represents an integer from 5 to 50 and t represents an integer from 0 to 3, wherein the residue Rs in the repeating unit of chain length s independently represents either hydrogen or a methyl residue; wherein the residue Re represents a substituent selected from hydrogen, fluorine, a (Ci-Ce) alkyl residue, a (Ca-Cyj) cycloalkyl residue, a (Ci-Ce) thioalkyl residue, a (Ci-Ce) alkoxy residue, a trifluoromethyl residue, a phenyl residue, a 4-methoxyphenyl residue, a phenoxy residue, a 4-methoxyphenoxy residue, a benzyl residue, a 4-methoxybenzyl residue, a benzyloxy residue, a 4-methoxybenzyloxy residue, a biphenyl residue, a biphenyloxy residue, a naphthyl residue, a naphthoxy residue, a piperidinyl residue, a 3,5-dimethylpiperidinyl residue, a morpholinyl residue, a 2,6-dimethylmorpholinyl residue, a thiomorpholinyl residue, an azacycloheptyl residue, an indolinyl residue, a 1,2,3,4-tetrahydroquinolinyl residue, a 1,2,3,4-tetrahydroisoquinolinyl residue, a diphenylamino residue,a ((Ci-C6)-alkoxyphenyl)phenylamino residue, a bis((Ci-Ce)-alkoxyphenyl)amino residue, a 10,10-dimethyl-9,10-dihydroacridine residue, a phenothiazinyl residue, a phenoxazinyl residue, a phenazinyl residue, a carbazolyl residue, a 1,2,3,4-tetrahydrocarbazolyl residue, or a 10,11-dihydro-dibenz[b,f]azepinyl residue; wherein the stylized benzene ring inscribed "Naphthopyran" represents one of the following four discrete naphthopyran subunits "1" - "4": “1” 2” wherein the residues 7, Rs and R10 each independently represent a substituent selected from a (Ci-Ce) alkyl residue or a phenyl residue; the R9 residues each independently represent a substituent selected from a (Ci-Ce) alkyl residue, a (Ca-Cyj) cycloalkyl residue, a (Ci-Ce) alkoxy residue, a benzyl residue, or an unsubstituted or monosubstituted phenyl residue, wherein the substituent may be selected from fluorine, a (C1-Ce) alkyl residue, or a (Ci-Ce) alkoxy residue; and wherein k represents 0, 1, or 2; or two adjacent R9 residues together form an fused benzene ring, which may be unsubstituted, monosubstituted, or disubstituted, wherein the substituents may be selected from a (Ci-Ce) alkyl residue, a (Ci-Cej) alkoxy residue, a phenyl residue, or a benzyl residue;or two adjacent residues R9 together form an fused naphthalene ring system, an fused benzofuran ring system, an fused benzothiophene ring system, an fused 3,3-dimethylindene ring system or an fused 2H-chromene ring system; and residues Rn and R12 each independently represent a substituent selected from hydrogen, a (Ci-Ce) alkyl residue, a (C3-Cyj) cycloalkyl residue, a trifluoromethyl residue, a benzyl residue or an unsubstituted or monosubstituted phenyl residue, wherein the substituent may be selected from fluorine, a (Ci-Cej) alkyl residue or an (O-Cej) alkoxy residue; or the residues Rn and R12 together represent the grouping -(CH?);- where j represents an integer from 1 to 3; with the proviso that if this numerical value is 2 or 3, a benzene ring may also be fused to two adjacent CH2 groups.

16. Photochromic dyes according to claim 15, wherein the dyes are characterized by measure (1).

17. Photochromic dyes according to claim 15, wherein the dyes are characterized by measure (2).

18. Photochromic dyes according to any one of claims 15 to 17, wherein the stylized benzene ring with inscription “Naphthopyran” is selected from one of the aforementioned naphthopyran subunits “1”, “2” or “3”.

19. Photochromic dyes according to any one of claims 15 to 18, wherein the R9 residues each independently represent a substituent selected from a (Ci-Cej) alkyl residue, a (Ca-Czj) cycloalkyl residue, a (Ci-Ce) alkoxy residue, a benzyl residue or an unsubstituted or monosubstituted phenyl residue, wherein the substituent may be selected from fluorine, a (Ci-Cej) alkyl residue or a (Ci-Ce) alkoxy residue; and wherein k represents 0, 1 or 2.

20. Photochromic dyes according to any one of claims 15 to 19, wherein the residues R11 and R12 each independently constitute a substituent selected from hydrogen, a (Ci-Ce) alkyl residue, a (C3-C7) cycloalkyl residue, a benzyl residue or an unsubstituted or monosubstituted phenyl residue, wherein the substituent may be selected from fluorine, a (Ci-Ce) alkyl residue or a (Ci-Ce) alkoxy residue.

21. Phototropic acrylate, allyl carbonate, urea, urethane or thiourethane polymers comprising one or more of the photochromic dyes according to any one of claims 15 to 20.

22. Phototropic product based on a thiourethane polymer according to claim 21, which is a two-component system in which a 0.1 mm to 1 mm thin phototropic polythiourethane functional layer based on the thiourethane polymer is polymerized onto a polymer substrate, or is a sandwich system in which a 0.1 mm to 1 mm thin phototropic polythiourethane functional layer based on the thiourethane polymer is arranged between two polymer bodies.

23. Use of a glass body according to any one of claims 1 to 14 in lenses and glasses for spectacles of all kinds, such as prescription glasses, driving glasses, ski goggles, sunglasses, motorcycle goggles, for visors of protective helmets and the like, or for sun protection purposes in vehicles or in the construction sector, in the form of windows, protective screens, covers, roofs and the like.

24. Use of a photochromic dye according to any one of claims 15 to 21 in lenses and glasses for spectacles of all kinds, such as prescription glasses, driving glasses, ski goggles, sunglasses, motorcycle goggles, for visors of protective helmets and the like, or for sun protection purposes in vehicles or in the construction sector, in the form of windows, protective screens, covers, roofs and the like.

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