vitreous body

Abstract

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 H L > 85 N / mm 2 has, - the layer (4) has a microhardness of Hc < 1000 N / mm 2 and Hc ≥ 0.5 × H L has.

Description

[0001] The present invention relates to a glass body, in particular a spectacle lens, a use of the glass body and a photochromic dye.

[0002] Glass bodies, in particular plastic lenses, preferably plastic spectacle lenses, are generally manufactured from a polymerizable mixture or composition, which is often also referred to as a casting resin. Such a composition generally consists of plastic monomers and is in the form of a castable or moldable mass, which, for example, to produce a plastic lens, is poured into a volume formed between two molding parts arranged at a predetermined distance from one another. The 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 generally being provided by thermal energy.

[0003] In other areas as well, such as the application of functional coatings, particularly functional lacquers, to plastic lenses, these coatings or lacquers are generally applied as a polymerizable composition to the plastic lens to be coated, before solidification or curing takes place during a polymerization step. Such functional coatings generally have a lower hardness or microhardness than the underlying glass body or base body and can therefore be considered soft coatings in terms of their microhardness, especially compared to the underlying base body.Such soft coatings have the disadvantage that they do not have a high level of strength and therefore do not offer sufficient protection against everyday external influences and, accordingly, degrade quickly without an additional outer protective layer, which can be expressed in particular by a diminishing effect of their respective functionality.

[0004] US 11 / 526 031 B2 describes an approach in which such a soft layer is protected by a hard protective layer, particularly one arranged over it. This can protect the soft layer from degrading external influences. However, this approach has the disadvantage that an additional (protective) layer must be applied, which, on the one hand, makes the manufacturing process more complex and time- and material-intensive, and, on the other hand, results in a hard-soft-hard structure consisting of a (relatively) hard base body, a soft functional coating, and then a hard (protective) layer. Due to different material properties, particularly differing hardnesses, such structures are generally undesirable and should be avoided.

[0005] Against this background, it is an object of one aspect of the present application to propose an improved glass body, in particular an improved spectacle lens, which does not have the above-mentioned disadvantages.

[0006] The object is achieved in particular by a glass body having the features of claim 1. The subclaims relate to advantageous developments.

[0007] 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, where: - the base body is made of plastic glass and has a microhardness of H L > 85 N / mm 2 and - the layer has a microhardness of Hc < 1000 N / mm 2 and Hc ≥ 0.5 × H L has.

[0008] The base body is initially not further restricted, except that it has a first side and a second side arranged opposite the first side, wherein the first and second sides are connected to one another by an edge surface. The base body can have a flat shape, in which case the first and second sides are essentially plane-parallel or parallel to one another. The base body can also have a shape deviating from this, in particular a shape in which at least one of the two sides has a non-parallel shape, in particular a curved shape. A curved shape can be described in more detail based on the existing radius of curvature, and a distinction is generally made between a first case in which a positive radius of curvature exists, such a shape also being referred to as a convex shape, and a second case in which a negative radius of curvature exists, such a shape also being referred to as a concave shape.Due to a non-parallel shape, such a base body is preferably suitable as a base body for a glass body, in particular for a lens glass body or a 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 glass body an optical effect, in particular a reduction or magnification effect, whereby such a glass body can preferably be used as a lens or as a spectacle lens.

[0009] 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 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.

[0010] To be suitable for 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 definable, characteristic quantities that can characterize a given object, in particular a base body, with regard to its optical imaging properties, including properties such as spectral transmission, color rendering, or the Abbe number. This is particularly true for the use of plastics as materials for the manufacture of lenses, especially ophthalmic lenses.In recent years, materials such as acrylate, poly(thio)urethane, polyacrylate, polymethyl methacrylate, polycarbonate, polydiethylene glycol bisallyl carbonate, or combinations thereof have emerged as preferred for ophthalmic lenses, although in principle, other transparent plastic materials can also be used. Accordingly, in one embodiment, the base body comprises plastic; in particular, it can be a plastic base body, preferably a plastic base lens.

[0011] Depending on the plastic used, the base body can be formed, as described above, by polymerizing a polymerizable composition, for example, by curing under controlled temperature conditions or by irradiation with electromagnetic waves, particularly UV light. Furthermore, the base body can be formed by thermoplastic deformation, such as injection molding.

[0012] In order to be particularly suitable as a base body for a glass body or for a spectacle lens, the base body is preferably formed from a transparent plastic glass, in particular from a plastic glass that is transparent in the visible spectral range or from a plastic glass that is (at least partially) permeable to visible light.

[0013] The microhardness of an object, particularly the base body and / or the layer, is generally determined by applying a known and well-defined test specimen to the object to be measured with a defined force, or, converted to the surface of the test specimen, with a defined pressure. The deformation observed upon penetration of the test specimen allows a conclusion to be drawn about the hardness. Particularly for penetration depths greater than or equal to approximately one-tenth of the layer thickness of the layer to be determined for hardness, it is important to note, according to the Bückle rule, that the composite hardness of the system is being measured and not the individual hardness of the layer.Such a hardness measurement can be carried out using commercially available hardness measuring devices, such as the FISCHERSCOPE HM2000 from Helmut Fischer GmbH, Sindelfingen, for layers with a thickness of more than 1-2 µm or the PICODENTOR HM500 from the same company for layers with a thickness of 1 µm or less.

[0014] The measurement and calculation of material parameters, such as microhardness or Martens hardness, elastic indentation modulus, indentation creep, and the ratio of elastic to plastic deformation, are carried out in accordance with DIN EN ISO 14577-1. Measurements can be performed with a maximum force of 300 mN, with the maximum force being reached after 20 seconds of measurement time, and the measurement is performed at 30°C. The microhardness can then be determined from the measurement when the maximum force is reached.

[0015] The base body has a microhardness H Lgreater than or equal to 85 N / mm 2 preferably greater than or equal to 95 N / mm 2 , more preferably greater than or equal to 100 N / mm 2 , particularly preferably greater than or equal to 150 N / mm 2 , in particular greater than or equal to 175 N / mm 2 A base body which has the above-mentioned microhardness is suitable as a base body for a glass body, since it has a certain strength, toughness or wear resistance and is therefore suitable for everyday use.

[0016] The glass body comprises (at least) one layer which is 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 ply is arranged between the layer and the base body or is located in between. 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 plies of a material different from the layer and the base body are arranged or are located between the layer and the base body. These can preferably be additional layers orThese can be layers which impart an additional property to the glass body, in particular the base body and / or the layer, for example one or two or more additional layers or 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.

[0017] This layer is initially not further restricted; in particular, like the base body, it can be formed from a material that is transparent in the visible spectral range or from a material that is (at least partially) permeable to visible light. This makes the layer particularly suitable as a layer for a glass body, in particular for a spectacle lens.

[0018] The layer has a microhardness Hc of less than or equal to 1000 N / mm 2 preferably less than or equal to 500 N / mm 2, particularly 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 a base body or with which a base body is provided, in particular to protect it from mechanical damage, such as scratching. Such high values ​​for the microhardness of the layer are not desirable, since an (optional) functionalization of the layer, for example, by dyes contained in the layer, in particular photochromic dyes, requires a not too hard or solid environment.

[0019] The layer can in particular be a functional layer and impart properties, preferably (additional) functional properties, to the base body provided therewith. In this way, a glass body has additional properties that the base body does not have, i.e. by means of the layer, a base body can be provided with additional properties or refined in order to obtain a (coated) glass body which has the desired additional properties. The layer can preferably be colored. Alternatively or additionally, the layer can be more easily colorable than the base body due to its material properties, since, for example, dyes penetrate the material of the layer more easily or more quickly and / or adhere to the layer surface. The coloring can take place in an immersion bath.

[0020] The layer has a microhardness Hc which is greater than or equal to half the microhardness of the base body H L is, ie HC ≥ 0.5 × H L is, preferably H C ≥ 0.6 × H L , especially preferred H C ≥ 0.70 × H L . Because the layer has a microhardness which corresponds to at least half the microhardness of the base body, it is characterized by an increased hardness compared to common layers and, associated with this, an increased strength, toughness and wear resistance.

[0021] Advantageously, this makes it possible to obtain a glass body comprising a base body and a layer arranged directly or indirectly thereon, which imparts at least one additional property to the glass body and, at the same time, is not too soft. A soft layer within the meaning of the invention, in particular a layer that is too soft, has a microhardness of Hc < 0.4 × H LIn particular, because the layer has a hardness greater than or equal to 50% of the hardness of the base body, a functional layer or coating can be realized without an additional protective layer, in particular one that protects the functional coating. Advantageously, this makes it possible to obtain a (functionally coated) glass body which does not require an additional protective layer and is thus, on the one hand, cost-effective to produce and, on the other hand, particularly in the absence of an additional hard protective layer, does not have a hardness profile comprising a hard base body, a soft layer, and then a hard protective layer.

[0022] The layer is preferably formed by polymerizing a polymerizable composition. Advantageously, the layer can be formed or produced particularly favorably by preparing or providing a polymerizable composition because the polymerizable composition can first be applied to the base body in a simple manner and then polymerized on the base body by polymerization, thus forming a firm 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, or even sprue coating. This allows the layer to be formed particularly favorably, particularly in the case of a base body that has at least one curved side.For forming the layer by polymerization of the polymerizable composition, the person skilled in the art is also familiar with common methods, in particular thermal polymerization, triggered or caused by supplying or exposing 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.

[0023] A preferred polymerizable composition has at least isocyanates or protected isocyanates and isocyanate-reactive components as main components. This advantageously makes it possible to form a polymerized poly(thio)urethane layer which combines very good optical properties with high suitability for everyday use. Likewise preferred are polymerizable compositions having two- and / or three-functional (meth)acrylates as main components, which are particularly suitable for forming a polymethyl (meth)acrylate layer. Such layers are also known for their good optical properties coupled with high suitability for everyday use. In addition to the preferred main components mentioned above, such polymerizable compositions can also have further components, in particular various additives, which fulfill additional functions orThe chemical and / or mechanical properties of such a polymerizable composition can be specifically modified. It may also be advantageous to add additives such as light and / or radical stabilizers to improve the resistance of such a layer, particularly to environmental influences and climatic conditions.

[0024] The layer preferably has a thickness of greater than or equal to 10 µm, preferably greater than or equal to 30 µm, particularly preferably greater than or equal to 50 µm, but in particular less than or equal to 350 µm or less than or equal to 750 µm. This advantageously allows for the formation of a comparatively thin layer, in particular a very thin layer compared to the base body. In this way, the amount of material required can be advantageously reduced.

[0025] Preferably, the base body has a microhardness H L greater than or equal to 85 N / mm2 and the layer has a microhardness Hc greater than or equal to 43 N / mm 2 preferably greater than or equal to 50 N / mm 2 Further preferably, the base body has a microhardness H L greater than or equal to 100 N / mm 2 and the layer has a microhardness Hc greater than or equal to 60 N / mm 2 The base body particularly preferably has a microhardness H L greater than or equal to 160 N / mm 2 and the layer has a microhardness Hc of greater than or equal to 120 N / mm 2 Combinations of base body and layer that meet the above-mentioned values ​​are characterized by particularly high suitability for everyday use as glass bodies or spectacle lenses and can be manufactured, in particular, using known plastic lens materials familiar to those skilled in the art.

[0026] Preferably, the layer is formed by casting, i.e., the layer is produced in particular by a casting process, wherein the base body is first arranged at a distance from a mold shell to form a cavity, the resulting cavity is sealed accordingly, and the cavity is subsequently 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 layer thickness of less than 750 µm.

[0027] The polymerizable composition for forming the layer preferably comprises at least one crosslinker. This can advantageously promote the formation of crosslinks during polymerization, whereby the formed layer has greater microhardness. Preferably, microhardness values ​​of Hc ≥ 0.9 × H can be achieved for the formed layer by adding compounds from the group of multifunctional thiols or multifunctional alcohols. L , more preferably Hc ≥ 1.0 × H L , particularly preferably Hc ≥ 1.1 × H LIn addition, inorganic or organic nanoparticles surface-modified with thiols or alcohols can be used. Furthermore, multifunctional isocyanates or inorganic or organic nanoparticles modified with isocyanates can be used. In other words, this allows the formation of a layer with excellent strength and, in particular, a microhardness that roughly corresponds to the hardness of the base material and, in refinements, even exceeds it.

[0028] The base body of the glass body is preferably 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 the person skilled in the art, particularly commercially available plastic materials for transparent lens bodies, can be used. The aforementioned materials, in particular, are characterized by very good optical properties combined with high suitability for everyday use as base materials for lens bodies.

[0029] The base body has preferably been produced or formed by polymerising a polymerisable composition, the polymerisable composition of the base body comprising essentially the same substances or compounds as the polymerisable composition for forming the layer. Advantageously, by selecting a composition that is as similar as possible, preferably very similar, particularly preferably essentially identical, between the respective polymerisable compositions of the base body and layer, a particularly strong and long-lasting adhesion between the base body and layer can be achieved. On the other hand, very comparable optical properties can also be achieved in this way, due to essentially the same substances or compounds, which leads to a glass body which is characterised by low interference phenomena. Further advantageously, the casting layer can comprise essentially the same substances or compounds.be colored exactly like the base body, so that no disturbing optical effects arise due to different colors.

[0030] Preferably, the difference Δn between the refractive index n L of the base body and the refractive index n C of the layer at least at one wavelength, in particular determined at a wavelength of about 550 nm, Δn = |n L - n C | ≤ 0.2. The preferred difference is Δn = |n L - n C | ≤ 0.1. More preferably, the difference Δn = |n L - n C | ≤ 0.01, particularly preferably Δn = |n L - n C | ≤ 0.001, in particular Δn = |n L - n C| ≤ 0.0001 and thus approximately identical. Interference phenomena that arise at interfaces with different refractive indices can advantageously 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, particularly preferably at the majority of all wavelengths in the visible spectral range. The base body may have a refractive index of approximately 1.5 or approximately 1.6 or approximately 1.67 or approximately 1.72 or approximately 1.74, where the term "approximately" may refer to a deviation of less than 5%, preferably less than 1%.

[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 body, i.e. the glass body has acquired an additional property by providing the base body with a photochromic layer, in particular photochromic behavior, which is understood in particular to mean 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 referred to as isomerization. A photochromic dye thus changes its absorption behavior in response to irradiation with UV light.If the UV light irradiation subsides, the photochromic dye returns to its original molecular structure and thus also to its original absorption behavior. A photochromic dye thus enables reversible switching between a dark and a light tint. Naphthopyrans, spirooxazines and / or spiropyrans are particularly suitable as photochromic dyes, as they exhibit rapid darkening behavior on the one hand and a high longevity on the other. In particular, the polymerizable composition can comprise not only one photochromic dye from the aforementioned compound groups, but also two or more, whereby the selected photochromic dyes can also be different. By means of such a composition supplemented with photochromic dyes, a photochromic layer can be formed on a base body ora photochromic glass body is obtained, which can preferably be used as a self-tinting lens and is very comfortable to wear, since switching between conventional prescription glasses, for example reading glasses, and sunglasses is made obsolete by the self-tinting effect.

[0032] The layer is preferably colored, in particular permanently colored, and the polymerizable composition of the layer comprises at least one permanent dye. Permanent means, particularly in contrast to photochromic, that the dye has a constant absorption behavior and cannot reversibly switch between an excited (absorbing) and a non-excited (non-absorbing) state due to UV radiation. Permanent coloration therefore means a lasting, largely unchanging coloration. The dye can, for example, impart a characteristic coloration or special absorption properties, such as a filtering effect, to the composition. A composition modified in this way then has a pre-coloration or, with respect to a composition without a dye, a different transmission characteristic as a new or additional property.This results in, in particular, a colored composition, whereby a colored layer is advantageously formed on the base body or a colored glass body is obtained. These are preferably azo dyes, cyanine dyes, anthraquinone dyes, or the like, as are frequently used in the conventional coloring of glass bodies, in particular plastic spectacle lenses. In particular, the polymerizable composition can comprise not just one dye from the aforementioned groups of compounds, but also two or more, whereby the selected dyes can also be different. The skilled person routinely selects a suitable dye or a mixture of suitable dyes.

[0033] In a further development, the layer is preferably photochromic and, in particular, permanently colored. By combining these two forms, a permanently pre-colored layer can be obtained which has a first absorption characteristic or a first transmission behavior and, upon irradiation with UV radiation, has a different second absorption characteristic or a different second transmission behavior. Advantageously, by providing a base body with such a layer, a layer with a permanent color and a photochromic behavior can be obtained, which thereby has special properties, such as an initial darkening and, in a further development, a second, even deeper darkening upon irradiation with UV radiation.Such a glass body is therefore particularly suitable for use as a sunglass lens, which has a first darkening and, upon exposure to UV radiation, particularly 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 thereof on both sides, on which the layer is arranged, which is selected from: - an anti-reflective coating; and / or - a mirror coating; and / or - an easy-to-clean coating; and / or - an antistatic coating; and / or - an anti-fog coating; and / or - a UV protection coating; and / or - an IR protection coating; and / or - a blue protection coating.

[0035] The expert knows how to skillfully combine the above-mentioned coatings in order to obtain glass bodies with different properties.

[0036] Preferably, the at least one further layer is an anti-reflective coating. Such a coating, comprising at least one individual layer, generally preferably comprising alternating individual 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, in order to inhibit or suppress, or largely or completely suppress, the reflection of the incident light for at least one wavelength of incident light, preferably for two or more wavelengths, particularly preferably for a plurality of wavelengths of incident light, by means of destructive interference.This advantageously results in an anti-reflective glass body which is particularly suitable as a lens and / or spectacle lens, since the anti-reflective coating renders it (largely) free from disturbing reflection phenomena and is characterized by high transmission.

[0037] Preferably, and in particular alternatively or in addition to an anti-reflective coating, the at least one further layer is a mirror coating. Such a coating, comprising at least one individual layer, generally preferably comprising alternating individual 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, in order to reflect the incident light by means of constructive interference for at least one wavelength of incident light, preferably for two or more wavelengths, particularly preferably for a plurality of wavelengths of incident light.Advantageously, this results in a mirrored glass body which is particularly suitable as a mirrored lens and / or mirrored spectacle lens, in particular a sunglasses lens, since it reflects light radiated by the mirror coating.

[0038] Preferably, and in particular alternatively or in addition to an anti-reflective and / or mirror coating, the at least one further layer is an easy-to-clean coating, which is characterized by having a low surface energy and in particular hydrophobic and / or oleophobic properties, which result in a glass body provided therewith having a lower tendency towards the adhesion of dirt, grease and / or water. Such a coating often also has an additional property of improved cleanability. Advantageously, this makes it possible to obtain a glass body which is highly suitable for everyday use, has a high resistance to everyday, grease- and / or water-based soiling and is easy to clean.Such an easy-to-clean coating can also be arranged as a final, outermost layer as part of a multilayer (interferometric) coating system.

[0039] Preferably, and in particular alternatively or in addition to an anti-reflective and / or mirror coating and / or easy-to-clean coating, the at least one further layer is an antistatic coating which, in particular, counteracts static charging of the glass body in order to thus 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 preferably used, in particular substoichiometric metal oxides, which thereby exhibit conductivity. Such an antistatic coating can also be arranged as part of a multilayer (interferometric) layer system or be present therein.

[0040] Preferably, and in particular alternatively or in addition to an anti-reflective and / or mirror 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 the fact that it counteracts the formation of fogging. This is understood in particular to mean that it counteracts the formation of (water) droplets when the water vapor contained in the air condenses (in particular when the temperature changes from a cold environment to a warm environment), in order to ensure that no individual droplets form but rather a largely uniform film that enables acceptable transparency or transmission. This advantageously makes it possible to obtain a glass body, in particular a spectacle lens, which is very comfortable to wear.Such an anti-fog coating can also be arranged as a final, outermost layer as part of a multi-layer (interferometric) coating system.

[0041] Preferably, and in particular alternatively or in addition to an anti-reflective and / or mirror coating and / or easy-to-clean coating and / or antistatic coating and / or anti-fog coating, the at least one further layer is a UV protection coating which is characterized by reduced transmission behavior with respect to UV radiation, preferably by inhibited to completely absorbing transmission behavior or reflective behavior with respect to UV radiation. This advantageously results in a glass body which has a blocking effect with respect to the transmission of (harmful) UV radiation and is thus particularly suitable as a lens or spectacle lens. In a lens, such UV protection can be advantageous in order to protect sensitive components, e.g., optical sensors, from irradiation or exposure to UV radiation.For spectacle lenses, protection against harmful UV radiation is beneficial to protect the wearer's eyes. Such a UV-protective coating can also be arranged as part of a multilayer (interferometric) coating system, or a corresponding coating system, optionally an anti-reflective and / or mirror coating, can be designed to suppress light in the visible spectral range (anti-reflective coating) or deliberately reflect it (mirroring coating), while simultaneously providing increased absorption or reflection of UV radiation.

[0042] Preferably, and in particular alternatively or in addition to an anti-reflective and / or mirror 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. This advantageously results in a glass body which 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 in order to protect sensitive components, e.g.optical sensors, from exposure to IR radiation, in particular to reduce, inhibit, or prevent the associated heat energy input. In the case of spectacle lenses, protection against harmful IR radiation is advantageous in order to protect the eyes of the wearer. Such an IR protection coating can also be arranged as part of a multi-layer (interferometric) coating system, or a corresponding coating system, optionally an anti-reflective and / or mirror coating, can be designed so that it suppresses light in the visible spectral range (anti-reflective coating) or deliberately reflects it (mirroring) and at the same time has increased absorption or reflection of IR radiation.In a further development of this, an IR-protective coating can also be designed in combination with a UV-protective coating, in particular 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 by a suitable design of a multilayer (interferometric) coating system.

[0043] Preferably, and in particular alternatively or in addition to an anti-reflective and / or mirror coating and / or easy-to-clean coating and / or antistatic 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-protection coating, which is understood to be a coating which has increased absorption and / or reflection of radiation from the blue spectral range. This advantageously results in a glass body as a lens or spectacle lens which is characterized by protection against radiation from the blue spectral range, which is particularly suspected of disrupting the human circadian rhythm. Such a blue-protection coating can also be arranged as part of a multi-layer (interferometric) layer system.A corresponding coating system, optionally an anti-reflective and / or mirror coating, can be designed to suppress light in the visible spectral range (anti-reflective coating) or deliberately reflect it (mirroring coating), while simultaneously exhibiting increased absorption or reflection of IR radiation. In a further development of this, a blue-shield coating can also be combined with a UV-shield and / or IR-shield coating, particularly as a multilayer (interferometric) coating system, thereby providing advantageous protection against radiation from the aforementioned spectral ranges.

[0044] It goes without saying that the person skilled in the art selects any combination, in particular synergistic combinations, from the above-mentioned coatings in order to obtain a glass body which has a base body and the layer, as well as any number of further layers for obtaining further advantageous properties.

[0045] 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 list mentioned above: - a buffer lacquer coating; and / or - a hard lacquer coating.

[0046] By placing a buffer lacquer coating between the layer and at least one other layer, the fracture strength of the glass body coated in this way can be improved or increased. It is known that such buffer lacquer layers are generally formed as incompletely polymerized layers and thus help the glass body achieve improved fracture strength. Such buffer lacquer coatings are particularly advantageous when base bodies made of comparatively hard plastic glass materials, such as poly(thio)urethane and / or polymethyl methacrylate, as glass bodies or spectacle lenses, are required to meet special fracture strength requirements, such as those required by the US Food and Drug Administration (FDA) for the drop ball test.

[0047] By arranging a hard lacquer coating between the layer and at least one further layer, the mechanical strength, in particular the scratch resistance, of the glass body can be improved. In particular, compared to mineral glass, base bodies made of plastic glass have lower scratch resistance and tend to become more scratched in everyday use, particularly as glass bodies or spectacle lenses. In order to obtain a more resistant glass body, such a hard lacquer coating is arranged or formed as an additional coating, which preferably consists of siloxanes and thus has increased scratch resistance. In a further development of this, by combining a buffer lacquer and a hard lacquer coating, a particularly resistant glass body can be obtained which has both increased fracture strength and increased scratch resistance and is therefore particularly suitable as a lens orlens is.

[0048] The polymerizable composition of the layer preferably 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 of the molecule, which contains between one and four naphthopyran subunits, exhibit excellent matrix-independent phototropic properties in all types of plastic ophthalmic 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 only unacceptable phototropic properties in tightly cross-linked thiourethane thermoset polymers.In contrast, the naphthopyran subunits—in the case of 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, completely shielding them from the respective plastic-glass polymer matrix. This makes it possible for the first time to realize outstanding photochromic properties independent of the matrix—even in tightly cross-linked thiourethane thermoset polymers.

[0049] Advantageously, novel higher molecular weight photochromic dyes having at least one and at most four naphthopyran subunits and a plurality of polyether chains according to the following formula (I) are thus provided:with the proviso (1) that at least one and at most four of the radicals R1, R2, R3 and R4, independently of one another, represent the following grouping A with a terminal longer-chain polyether substituent: and the remaining radicals R1, R2, R3 and R4, independently of one another, represent hydrogen, a methyl radical, an ethyl radical, a phenyl radical or the following grouping B with a longer-chain polyether substituent:wherein, in the case of only one grouping A in the molecule, at least one of the remaining radicals must represent the grouping B; or with the proviso (2) that at least one and at most two of the radicals R1, R2, R3 and R4, independently of one another, represent the following group C: and of the remaining radicals R1, R2, R3 and R4, at least two represent the group B, wherein in the case of a further remaining radical, this can be selected from hydrogen, a methyl radical, an ethyl radical or a phenyl radical; 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 with the inscription "Naphthopyran" represents one of the four following discrete naphthopyran subunits "1" - "4": and wherein the above substituents R5, R6, R7, R8, R9, R 10 , R 11 and R 12 as defined in claim 1:

[0050] 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 sprue.

[0051] The photochromic naphthopyran subunits can be located in spatial proximity to two or more polyether chains. The arrangement of these subunits around a central, tetrahedral carbon atom allows the entire system to be spatially isolated from the polymer matrix. This spatial shielding of the phototropic naphthopyran subunits by means of the longer-chain polyether substituents enables matrix-independent phototropic properties for the first time. This particularly means that phototropic properties can be obtained with the compounds according to the invention in thiourethanes, urethanes, ureas, acrylates, and allyl carbonates.

[0052] To date, achieving good photochromic properties has required either the use of specially adapted polymer matrices with less dense cross-linking—associated with lower hardness—or the addition of special 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 can only be achieved in certain polymer matrices. Advantageously, increased layer hardness can be achieved because the special structure described above allows the longer-chain polyether substituents to position themselves in close proximity to the pyran ring of the photochromic naphthopyran subunits. This is the site of greatest structural change during photochromic switching when opening to the colored form or closing back to the colorless form.Due to the loose arrangement ("random coil") of the linear polyether chains with only minimal intramolecular interactions, this opening and closing of the photochromic center is not hindered. The photochromic properties of the dyes according to the invention can thus also be realized in highly cross-linked polymer matrices such as thiourethane polymers.

[0053] Due to the special structure of the dyes and their “isolation” from the surrounding polymer matrix, the photochromic dyes according to the invention can achieve excellent darkening upon exposure to sunlight as well as extremely rapid lightening after the end of exposure.

[0054] The connection of the naphthopyran subunits to the central, tetrahedral carbon atom of formula (I) occurs either directly (for n = p = 0), via a succinyloxy bridge (for n = 1 and p = 0) or via an ethyleneoxy-succinyloxy bridge (for n = p = 1).

[0055] The use of a succinyloxy bridge is advantageous in that, when modern coupling reagents are used, ester bonds can be formed at very mild reaction temperatures (including room temperature), 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).

[0056] The use of an ethyleneoxy bridge between the naphthopyran subunit and the succinyloxy bridge is generally necessary if an even higher lightening rate is to be achieved. 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 next 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, often resulting in an insufficient lightening rate. The same applies to a succinyloxy bridge (for r = 1) as a link between the naphthopyran subunit and the longer-chain polyether substituent in the compounds according to the invention, to which condition (1) applies.

[0057] Preferred compounds to 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 each linked to the adjacent naphthopyran subunits via optional ethyleneoxy (for q = 1) and succinyloxy bridges (for r = 1) or, in the case of fewer than four naphthopyran subunits in the molecule, are optionally additionally attached directly to the central, tetrahedral carbon atom of formula (I), specifically as group B, linked via a succinyloxy bridge. This non-optional succinyloxy bridge in group B is again present for synthetic reasons. The coupling of the longer-chain polyether substituents to the central, tetrahedral carbon atom is achieved via ester bridges under very mild reaction conditions.

[0058] Preferred compounds to which condition (2) applies have either one or two naphthopyran subunits and either two or three longer-chain polyether substituents. The latter are each bonded to the naphthopyran subunits via the central, tetrahedral carbon atom as group B. In contrast to condition (1), no further longer-chain polyether substituents are bonded to the naphthopyran subunits, but only "smaller" substituents R6, which can be used to influence the darkening color and lightening rate.

[0059] For the synthesis of the preferred compounds, suitable naphthopyran starting compounds can be used and, for example, reacted with 1,3-difunctional propane derivatives (for m = m' = 1) to form molecules each containing two naphthopyran subunits and at least two longer-chain polyether substituents.

[0060] One aspect relates to the use of a glass body according to the invention in lenses and glasses for spectacles of all kinds, such as, for example, corrective spectacles, driving spectacles, 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 visors, covers, roofs and the like.

[0061] The invention is described in more detail below with reference to 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 appended claims. Like reference numerals indicate like or recurring elements. They show: - Fig. 1 a first embodiment of the glass body; and - Fig. 2 a second embodiment of the glass body having optional features; and - Fig. 3 a third embodiment of the glass body. - Fig. 4 a schematic diagram of microhardness measurements

[0062] Fig. 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.

[0063] The base body 2 is a base body formed from polythiourethane as the preferred plastic lens material. The base body was formed from a polymerizable composition, also referred to as a casting resin mixture, wherein the polymerizable composition has isocyanates and isocyanate-reactive components as its main components. Isocyanate-reactive components are understood to mean, in particular, thiols or alcohols with two or more functional groups, i.e., SH or OH groups. Plastic lenses made of polythiourethane are highly suitable for everyday use, coupled 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 also particularly suitable as base bodies for spectacle lenses, which can also very effectively correct (slightly) higher refractive errors, expressed in spherical equivalents of more than + / - 3.0 dpt, with an acceptable lens (center) thickness, which offers particularly aesthetic advantages. The base body 2 can be manufactured as a polythiourethane cast, using a correspondingly curved mold, so that the resulting base body 2 already has a curved shape on one side, expressed in a base curve (BK), of BK = 3.0. The base body 2 can have a microhardness of approximately 180 N / mm. 2 have.

[0064] Subsequently, the resulting base body 2 and a further mold shell can be arranged at a distance from one another, so that a cavity forms between the curved first side of the base body 2 and the spaced-apart mold shell, which cavity can be sealed using a suitable tape or adhesive tape. Subsequently, the cavity can be filled with a casting resin using a filling device. The casting resin is a preferred embodiment of a polymerizable composition, which can comprise isocyanates and isocyanate-reactive components as further preferred main components. In addition to these main components, the composition can also comprise photochromic dyes, in particular naphthopyran dyes, as preferred photochromic dyes.In this way, with the method described above, which is also referred to as a casting method, a layer 4, in particular a photochromic layer, can be formed, in particular directly, on the base body, which layer can have a layer thickness of approximately 30 µm to approximately 400 µm, in particular approximately 300-350 µm.

[0065] The (photochromic) layer 4 formed directly on the base body can have a microhardness of approximately 130 N / mm 2 By providing the base body 2 with a photochromic layer 4, a glass body 1 was obtained which has photochromic properties. The glass body 1 thus obtained accordingly has a base body 2, which has been given an additional property by the functional layer 4 formed directly thereon in this embodiment. The layer 4 has a microhardness (Martens hardness) of approximately 130 N / mm 2a microhardness corresponding to approximately 70% of the microhardness of the base body 2 and thus possesses a microhardness that is significantly more than half the microhardness of the base body 2 and thus exhibits above-average strength. The glass body 1 thus obtained can, as a semi-finished part, undergo one- or two-sided surface processing in further, downstream production steps, for example, to create a desired optical effect, if necessary, a hard lacquer coating for even greater scratch resistance, if necessary, an anti-reflective coating for higher transmission, and in this way be further processed into a coated lens or a coated spectacle lens. Preferably, only one-sided (machining) surface processing takes place on the side of the base body 2 facing away from layer 4.

[0066] It goes without saying that the layer 4 can also be formed on the base body 2 using any other method. Likewise, the layer 4 can be formed from a different material; for example, instead of polythiourethane, it can also be formed from a polymerizable composition comprising, for example, functional (meth)acrylates, in particular non-cyclic bi- and / or trifunctional methacrylates or acrylates, which are preferably suitable for forming a (thermosetting) layer 4 made of polymethyl methacrylate or polyacrylate having a refractive index of approximately 1.54 determined at a wavelength of approximately 550 nm.

[0067] It is also understood that the photochromic dyes added to the polymerizable composition for forming layer 4 in the above-described embodiment represent only one 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 thereby obtain a layer 4 with corresponding functions, whereby a glass body 1 comprising a base body 2 provided with such a layer 4 receives the corresponding functions.

[0068] Fig. 2 shows a second embodiment of a glass body 1, wherein the starting product is a glass body 1 as a semi-finished part, as in Fig. 1 described.

[0069] The glass body 1 thus obtained can be provided with further layers as a semi-finished part in subsequent production steps.

[0070] The glass body 1' was first coated with a hard lacquer as a preferred buffer and / or hard lacquer coating 6 during a dip coating process. This increased the scratch resistance of the glass body 1', and it now has greater everyday usability because it is better protected against (light) scratches.

[0071] Subsequently, a multi-layer anti-reflective coating was formed on the glass body 1' as a preferred further coating 8. This anti-reflective coating was formed by vapor deposition in a dedicated high-vacuum coating system, wherein, in such a system, low-refractive and high-refractive coating materials are alternately evaporated by means of an electron beam, and the vapor deposition is deposited as alternating, thin layers on the glass body 1', in particular on the surface of the formed hard lacquer coating 6.

[0072] In this way, an anti-reflective, hard lacquer coated glass body 1' was obtained, which has an increased scratch resistance due to the formed hard lacquer coating and a high suitability for everyday use due to the anti-reflective coating, due to a high transmittance and the absence of disturbing reflections or residual reflections.

[0073] Fig. 3 shows a third embodiment of a glass body 1, which differs in particular from the glass body 1 of Fig. 1, since the glass body 1" has a layer 4 on the first and the second side of its base body 2, i.e. on both sides. In this way, an improved or increased functionalization of the glass body 1" can be achieved. In particular, in a further development thereof, a first and a second functionalization can be achieved by different layers 4 on the first and second side of the base body 2. In the case of identical layers 4 on the first and second side of the base body 2, this layer 4 can preferably be formed by dip coating, the base body 2 being immersed, in particular several times or repeatedly, in a dip bath containing the polymerizable composition to form the layer 4, wherein on immersion a thin film of the polymerizable composition adheres to both sides of the base body 2.By repeating this process several times until the desired layer thickness of layer 4 is reached and subsequent polymerization, optionally by heat (thermal) or by UV radiation (UV-induced), a solidified formation of layer 4 takes place. Dip coating is a particularly advantageous manufacturing process, particularly for a layer 4 to be formed on both sides of the base body 2.

[0074] Fig. Figure 4 shows a schematic diagram of microhardness measurements (plotted along the abscissa) at a corresponding penetration depth (plotted along the ordinate) for microhardness measurements on glass bodies. The glass bodies to be measured were placed in a FISCHERSCOPE HM2000 microhardness measuring device from Helmut Fischer GmbH. For the microhardness measurement, a test specimen with a defined geometry was pressed into the glass body to be measured with a force of approximately 300 mN (milli-Newtons). The measuring device determines the resulting microhardness, depending on the penetration depth of the test specimen, from the deformation of the glass body resulting from the pressure applied to the test specimen.

[0075] The solid line 101 shows the microhardness-penetration depth curve of a glass body 1 made of Fig. 1, which has a polythiourethane base body 2 and a photochromic layer 4 formed thereon, also comprising polythiourethane.

[0076] A comparative example is shown as the dotted line 102. This is also a polythiourethane base body, but it has a conventional photochromic layer made from a known photochromic photoresist containing the photochromic dyes and formed by spin coating on the glass body.

[0077] From the curves it can be seen that the measurement curve 101 of the glass body according to one aspect of the present application has a significantly higher microhardness and reaches a saturation value even at greater penetration depths, which is almost 100 N / mm 2above Comparative Example 102. It is also evident that, particularly in the first range of the penetration depth, in the range of a penetration depth of 0 µm to approximately 1 µm, the drop in microhardness in measurement curve 101 is smaller or weaker or not as pronounced as in Comparative Example 102. This shows that the glass body 1 according to one aspect of the present application 101 not only has a higher microhardness than Comparative Example 102 at greater penetration depths of several micrometers, but also has a higher microhardness even at shallow penetration depths. The glass body therefore has a higher microhardness overall, i.e. verified in all measurement ranges, and thus has greater strength and is therefore preferably suitable as a gas body for lenses and spectacles of all kinds, since, due to the higher microhardness, it has improved suitability for everyday use.In particular, by combining it with photochromic dyes in the layer 4 formed on the base body, a photochromic glass body 1 of improved microhardness and thus high suitability for everyday use can be produced.

[0078] In the present disclosure, "has an X" generally does not imply an exhaustive list, but is a short form of "has at least one X" and also includes "has two or more Xs" and "has Y in addition to X".

[0079] The numerical values ​​indicated with "approximately" may preferably deviate by + / - 10% from the stated value, particularly preferably by + / - 5% from the stated value, particularly 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.

[0080] In the present disclosure, "essentially" with regard to the similarity of composition implies that two compositions are essentially identical if their main constituents, which are understood to mean those compounds contained in the composition which, when added together, constitute a percentage by weight of at least 60% of the composition. This means that in the present disclosure, two compositions are essentially identical if they have the same main constituents and their percentage by weight in the composition differ by less than 20%, preferably less than 10%, particularly preferably less than 5%. Irrespective of this, two compositions are essentially identical if the differences represent minor deviations, in particular due to measurement technology or purity. List of reference symbols 1.1',1'' glass body 2 basic bodies 4 layer 6 Buffer and / or hard lacquer coating 8 Additional coating QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] US 11 / 526 031 B2

[0004]

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 H L > 85 N / mm 2 has, - the layer (4) has a microhardness of Hc < 1000 N / mm 2 and Hc ≥ 0.5 × H L has. [2] Glass body according to claim 1, wherein the layer (4) is arranged directly on the base body (2). [3] Glass body according to one of the preceding claims, wherein the layer (4) has a layer thickness of greater than or equal to 10 µm. [4] Glass body according to one of the preceding claims, wherein the base body (2) has a microhardness H L greater than or equal to 100 N / mm 2and the layer (4) has a microhardness Hc greater than or equal to 60 N / mm 2 particularly preferably, the base body (2) has a microhardness H L greater than or equal to 160 N / mm 2 and the layer (4) has a microhardness H C greater than or equal to 120 N / mm 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 one 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 one of the preceding claims, wherein the difference Δn 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, Δn = |n L - n C | ≤ 0.

2. [9] Glass body according to one of the preceding claims, wherein the layer (4) is photochromic and the polymerizable composition of the layer (4) comprises at least one photochromic dye. [10] 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. [11] Glass body according to one of the preceding claims, wherein the 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), which is selected from: - an anti-reflective coating; and / or - a mirror coating; and / or - an easy-to-clean coating; and / or - an antistatic coating; and / or - an anti-fog coating; and / or - a UV protection coating; and / or - an IR protection coating; and / or - a blue protection coating. [12] Glass body according to claim 11, wherein one of the following coatings (6) is arranged between layer (4) and at least one further coating (8): - a buffer lacquer coating; and / or - a hard lacquer coating. [13] Glass body according to one of claims 5 to 12, 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). [14] Photochromic dyes with 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 radicals R1, R2, R3 and R4, independently of one another, represent the following group A with a terminal, longer-chain polyether substituent: and the remaining radicals R1, R2, R3 and R4, independently of one another, represent hydrogen, a methyl radical, an ethyl radical, a phenyl radical 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 radicals must represent the group B; or with the proviso (2) that at least one and at most two of the radicals R1, R2, R3 and R4, independently of one another, represent the following group C: and of the remaining radicals R1, R2, R3 and R4, at least two represent the group B, where a further remaining radical can be selected from hydrogen, a methyl radical, an ethyl radical or a phenyl radical; where 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 radical R5 in the repeating unit of chain length s is each independently hydrogen or a methyl radical, wherein the radical R6 represents a substituent selected from hydrogen, fluorine, a (C1-C6)-alkyl radical, a (C3-C7)-cycloalkyl radical, a (C1-C6)-thioalkyl radical, a (C1-C6)-alkoxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenyl radical, a biphenyloxy radical, a naphthyl radical, a naphthoxy radical, a piperidinyl radical, a 3,5-dimethylpiperidinyl radical, a morpholinyl radical, 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 ((C1-C6)-alkoxyphenyl)-phenylamino residue, a bis((C1-C6)-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-dihydrodibenz[b,f]azepinyl residue;, where the stylized benzene ring with inscription “Naphthopyran” represents one of the four following discrete naphthopyran subunits “1” - “4”: wherein the radicals R7, R8 and R 10 each independently represents a substituent selected from a (C1-C6)alkyl radical or a phenyl radical; the R9 radicals each independently represent a substituent selected from a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a (C1-C6) alkoxy radical, a benzyl radical, or an unsubstituted or monosubstituted phenyl radical, where the substituent may be selected from fluorine, a (C1-C6) alkyl radical, or a (C1-C6) alkoxy radical; and where k represents 0, 1, or 2; or two adjacent R9 radicals together form a fused benzene ring which may be mono- or disubstituted, where the substituents may be selected from a (C1-C6)alkyl radical, a (C1-C6)alkoxy radical, a phenyl radical or a benzyl radical; or two adjacent radicals R9 together form a fused naphthalene ring system, a fused benzofuran ring system, a fused benzothiophene ring system, a fused 3,3-dimethylindene ring system or a fused 2H-chromene ring system; and the residues R 11 and R 12 each independently represent a substituent selected from hydrogen, a (C1-C6)alkyl radical, a (C3-C7)cycloalkyl radical, a trifluoromethyl radical, a benzyl radical or an un- or monosubstituted phenyl radical, wherein the substituent may be selected from fluorine, a (C1-C6) alkyl radical or a (C1-C6) alkoxy radical; or the residues R 11and R 12 together the group -(CH2) j - where j is 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. [15] Photochromic dyes according to claim 14, wherein the dyes are characterized by the measure (1). [16] Photochromic dyes according to claim 14, wherein the dyes are characterized by the measure (2). [17] Photochromic dyes according to any one of claims 14 to 16, wherein the stylized benzene ring inscribed "naphthopyran" is selected from one of the above naphthopyran subunits "1", "2" or "3". [18] Photochromic dyes according to any one of claims 14 to 17, wherein the radicals R9 each independently represent a substituent selected from a (C1-C6)-alkyl radical, a (C3-C7)-cycloalkyl radical, a (C1-C6)-alkoxy radical, a benzyl radical or an unsubstituted or monosubstituted phenyl radical, wherein the substituent may be selected from fluorine, a (C1-C6)-alkyl radical or a (C1-C6)-alkoxy radical; and wherein k represents 0, 1 or 2. [19] Photochromic dyes according to any one of claims 14 to 18, wherein the radicals R 11 and R 12 each independently represent a substituent selected from hydrogen, a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a benzyl radical or an unsubstituted or monosubstituted phenyl radical, where the substituent may be selected from fluorine, a (C1-C6) alkyl radical or a (C1-C6) alkoxy radical. [20] Phototropic acrylate, allyl carbonate, urea, urethane or thiourethane polymers comprising one or more of the photochromic dyes according to any one of claims 14 to 19. [21] Phototropic product based on a thiourethane polymer according to claim 20, 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 base body, 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. [22] Use of a glass body according to one of claims 1 to 13 in lenses and glasses for spectacles of all kinds, such as, for example, corrective spectacles, driving spectacles, 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. [23] Use of a photochromic dye according to any one of claims 14 to 20 in lenses and glasses for spectacles of all kinds, such as, for example, corrective spectacles, driving spectacles, 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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