Coated pharmaceutical packaging that blocks ultraviolet light

Abstract

According to one or more embodiments disclosed herein, the coated pharmaceutical packaging can include a glass container having a first surface and a second surface opposite the first surface, where the first surface is an exterior surface of the glass container, and where the glass container in an uncoated state has an average light transmittance in the UVB and UVC spectrums through a single wall of the coated packaging of at least 50%. The coated pharmaceutical packaging can further include a coating positioned on at least a portion of the first surface of the glass container, where the coated pharmaceutical packaging has an average light transmittance in the UVC spectrum through a single wall of the coated packaging of less than 50%.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 074,915, filed September 4, 2020, entitled "Ultraviolet Light-Blocking Coated Pharmaceutical Packages," which is hereby incorporated by reference in its entirety. [Technical Field]

[0002] FIELD OF THE INVENTION This specification relates generally to glass articles, and more particularly to coating glass articles such as pharmaceutical packaging. [Background technology]

[0003] Historically, glass has been used as a preferred material for pharmaceutical packaging due to its hermeticity, optical transparency, and superior chemical durability compared to other materials. Some pharmaceutical compositions are sensitive to ultraviolet light and may be susceptible to degradation when exposed to ultraviolet light. Several glass compositions have been developed that at least partially block UV light. Summary of the Invention [Problem to be solved by the invention]

[0004] However, these glass compositions may have poor properties with respect to, but not limited to, glass delamination and / or exterior surface coefficient of friction. [Means for solving the problem]

[0005] According to one or more embodiments, the coated pharmaceutical packaging can include a glass container having a first surface and a second surface opposite the first surface, where the first surface is an exterior surface of the glass container, and where the glass container in an uncoated state has an average light transmittance in the UVB and UVC spectrums through a single wall of the coated packaging of at least 50%. The coated pharmaceutical packaging can further include a coating positioned on at least a portion of the first surface of the glass container, where the coated pharmaceutical packaging has an average light transmittance in the UVC spectrum through a single wall of the coated packaging of less than 50%, and where the coated pharmaceutical packaging has a light transmittance of less than 20% at all wavelengths from 400 nm to 450 nm.

[0006] According to one or more additional embodiments, the coated pharmaceutical packaging can include a glass container with a first surface and a second surface opposite the first surface, where the first surface is an exterior surface of the glass container, and where the glass container in an uncoated state has an average light transmittance in the UVB and UVC spectrums through a single wall of the coated packaging of at least 50%. The coated pharmaceutical packaging can further include a coating positioned on at least a portion of the first surface of the glass container, where the coated packaging has an average light transmittance in the UVC spectrum through a single wall of the coated packaging of less than 50%, and where the coated pharmaceutical packaging is visibly colorless.

[0007] Additional features and advantages of coatings that can be used to coat glass articles, the coated glass articles, and methods and processes for making same will be set forth in the detailed description that follows, and in part will be readily apparent to those skilled in the art from that description, or will be learned by practicing the embodiments described herein, including the following detailed description, the claims, and the accompanying drawings.

[0008] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view of a glass container with a coating according to one or more embodiments shown and described herein. [Figure 2] 2 is a schematic, enlarged cross-sectional view of the glass container of FIG. 1 with a coating according to one or more embodiments shown and described herein; [Figure 3] 1 is a schematic diagram of a test jig for determining the coefficient of friction between two surfaces according to one or more embodiments shown and described herein; [Figure 4] Scanning electron microscope images of the coatings herein according to one or more embodiments shown and described herein. [Figure 5] Scanning electron microscope images of the coatings herein according to one or more embodiments shown and described herein. [Figure 6] Optical absorption spectrum of a metal oxide layer or sublayer according to one or more embodiments shown and described herein [Figure 7] Optical transmission spectra of example embodiments according to one or more embodiments shown and described herein [Figure 8] Light transmission data of example embodiments according to one or more embodiments shown and described herein [Figure 9] Optical transmission spectra of example embodiments according to one or more embodiments shown and described herein [Figure 10]Optical transmission spectra of example embodiments according to one or more embodiments shown and described herein [Figure 11] Coefficient of Friction Data for Example Embodiments According to One or More Embodiments Shown and Described Herein [Figure 12] Optical transmission spectra of example embodiments according to one or more embodiments shown and described herein [Figure 13] Optical transmission spectra of example embodiments according to one or more embodiments shown and described herein [Figure 14] Optical transmission spectra of example embodiments according to one or more embodiments shown and described herein DETAILED DESCRIPTION OF THE INVENTION

[0010] Conventional glass pharmaceutical packaging designed to block the transmission of ultraviolet light (sometimes referred to herein as "UV"), such as amber glass containers, generally utilizes glass compositions that function to block UV light; that is, the glass itself acts to block UV light. Such glass may not only appear colored in the visible spectrum, but may also contain pigmented materials, as in the case of amber glass compositions, that block UV light. Such conventional packaging does not include coatings applied to the surface of the glass that function to substantially affect UV transmission.

[0011] According to one or more embodiments, glass containers (e.g., pharmaceutical packaging) are described herein that include a coating that blocks all or a portion of UV light. A container without a coating may not substantially block UV light to the desired extent. Such coatings allow for the use of glass compositions that do not block all of the desired UV light. In some embodiments, the coating can generally block UV light while allowing visible light to pass through. Such embodiments can be advantageous because, in one or more embodiments, a "clear" glass with improved properties can be utilized as opposed to traditional amber-colored glass compositions, and / or the coated glass container can appear clear while still functioning as a UV light blocker. In additional embodiments, the coating (and coated article) can appear colored and provide UV blocking functionality. These embodiments can be beneficial because they allow the use of "clear" glass containers rather than colored glass containers, which may be more susceptible to glass degradation and / or more expensive to mass-produce. For example, switching between colored and uncolored glass in a single manufacturing facility can be expensive because a lot of glass is wasted in transitioning between the desired colored and uncolored glass compositions. The coating may further provide desirable properties such as a reduced coefficient of friction compared to the surface of the glass body, and may be thermally stable through depyrogenation (a heating process commonly used in pharmaceutical filling).

[0012] Reference will now be made in detail to various embodiments of coatings, glass articles having such coatings, and methods of making the same, examples of which are illustrated schematically in the drawings. Such coated glass articles may be glass containers suitable for use in various packaging applications, including, but not limited to, pharmaceutical packaging. It should be understood that the coated glass articles may also refer to the coated pharmaceutical packaging described herein. In one or more embodiments, the coatings and / or coated pharmaceutical packaging at least partially block the transmission of ultraviolet light to the container. However, glass compositions and / or uncoated glass containers generally may not have UV-blocking properties that appreciably contribute to the UV blocking of the coated glass article. These pharmaceutical packaging may or may not contain a pharmaceutical composition.

[0013] Various embodiments of coatings, glass articles having coatings, and methods of making the same are described in further detail herein, with particular reference to the accompanying drawings. While the coating embodiments described herein are applied to the exterior surface of a glass container, it should be understood that the described coatings can be used as coatings on a wide variety of materials, including non-glass materials, and on substrates other than containers, including, but not limited to, glass display panels, etc.

[0014] Generally, coatings can be applied to the surface of glass articles, such as containers that can be used for pharmaceutical packaging. The coatings can provide advantageous properties to the coated glass article, such as UV light blocking, a reduced coefficient of friction, and improved damage resistance. A reduced coefficient of friction can impart improved strength and durability to the glass article by reducing frictional damage to the glass. Furthermore, the coatings can maintain these improved strength and durability properties after exposure to high temperatures and other conditions, such as those experienced during packaging and pre-packaging processes used in pharmaceutical packaging, such as depyrogenation, lyophilization, autoclaving, etc. Thus, coatings and glass articles bearing the coatings can be thermally stable under conditions such as those used for depyrogenation.

[0015] FIG. 1 schematically illustrates a cross-section of a coated glass article, specifically a coated glass container 100. The coated glass container 100 includes a glass body 102 and a coating 120. The glass body 102 has a glass container wall 104 extending between an outer surface 108 (i.e., a first surface) and an inner surface 110 (i.e., a second surface). The inner surface 110 of the glass container wall 104 defines an interior volume 106 of the coated glass container 100. The coating 120 is positioned on at least a portion of the outer surface 108 of the glass body 102. As used herein, a coating may be "positioned on" the outer surface 108 even if it is not in direct contact with the outer surface 108, such as when an intermediate layer exists between the outer surface 108 and the coating positioned on the outer surface 108. In some embodiments, the coating 120 may be positioned on substantially the entire outer surface 108 of the glass body 102. In some embodiments, the coating 120 may be bonded to the exterior surface 108 of the glass body 102, as shown in Figure 1. In the embodiment of Figure 1, the coating 120 has an exterior surface 122 and a glass body contact surface 124 at the interface between the glass body 102 and the coating 120.

[0016] In one embodiment, the coated glass container 100 is a pharmaceutical package. For example, the glass body 102 can be in the form of a vial, ampoule, bottle, flask, phial, beaker, bucket, carafe, tub, syringe body, or the like. The coated glass container 100 can be used to contain any composition, and in one embodiment, a pharmaceutical composition. A pharmaceutical composition can include any chemical substance intended for use in the medical diagnosis, cure, treatment, or prevention of disease. Examples of pharmaceutical compositions include, but are not limited to, medicines, drugs, medications, therapeutic agents, and the like. A pharmaceutical composition can be in the form of a liquid, solid, gel, suspension, powder, or the like.

[0017] 1 and 2 , in one embodiment, the coating 120 includes a single layer structure. For example, the coating 120 can have a substantially homogeneous composition including a polymer. When two or more components are included in the coating 120, the coating 120 can be mixed but not completely homogeneous. For example, in one or more embodiments, one or more chemical components of the mixture can aggregate at an interface of the coating 120 (e.g., the interface with the glass body 102 or the exterior surface 122). In such embodiments, the local concentrations of the chemical components can vary across different regions of the coating 120. However, as used herein, the term “mixed” should be understood to refer to a layer having at least some dispersion of at least two chemical components and include layers that are not completely homogeneous. Generally, a mixed layer is deposited as a mixture of two or more chemical components included in the coating mixture. However, according to additional embodiments, the coating 120 can include two or more separate layers. According to additional embodiments, the coating 120 can be multilayered, having two or more separate layers. For example, coating 120 may include a coupling agent layer in contact with exterior surface 108 and a polymer layer over the coupling agent layer.

[0018] The transparency of the electromagnetic spectrum (i.e., light) through an article can be assessed by measuring light transmission using a spectrophotometer. Measurements can be made through uncoated pharmaceutical containers, coated containers, and coated or uncoated flat glass sheets.

[0019] In one or more embodiments, the glass body 102 can transmit UV light (at least compared to commercially available amber vials). The coating 120 can provide a majority of the UV blocking. Additionally, while the coating can provide UV blocking, in one or more embodiments, the coating can be transparent to visible light and therefore not tinted. In some embodiments, the coated glass container 100 can be transparent to visible light but can block UV light. In other embodiments, the coated glass container can block some visible light (i.e., be tinted) and also block UV light. These light transmission properties are described quantitatively herein. As described herein, when UV light is "blocked," it is understood that all or a portion of the UV light is blocked, and even in glass compositions that are said not to block UV light, some small amount of UV radiation may not be transmitted at all wavelengths.

[0020] As used herein, UV light (sometimes referred to as light in the UV spectrum) refers to light having a wavelength of 200 to 400 nm. UV light can include UVA light, UVB light, and UVC light. As used herein, UVA light refers to light having a wavelength of 200 to 290 nm. As used herein, UVB light refers to light having a wavelength of 290 to 320 nm. As used herein, UVC light refers to light having a wavelength of 320 to 400 nm. As used herein, visible light refers to light having a wavelength of 400 to 700 nm. As used herein, "average light transmittance" over a wavelength range refers to the average transmittance that can be determined by a spectrophotometer over a particular wavelength range. "Maximum light transmittance" in a wavelength range refers to the maximum transmittance at a single wavelength within the wavelength range.

[0021] When light transmittance is stated for a glass composition, glass container, or glass wall in the "uncoated state," the measurement can be obtained by testing the uncoated container or glass substrate. Unless otherwise stated herein, light transmittance is measured through a single wall of a coated glass container. The uncoated state refers to a glass article that does not have a coating.

[0022] It should be understood that the recited transmittances disclosed herein for the coated glass container 100, the glass body 102 (uncoated), or the coating 120 can be measured through a coated or uncoated container (through two walls), or through a single wall of a container (coated or uncoated), or through a flat glass sheet (coated or uncoated) having a thickness similar to pharmaceutical packaging. The light transmittance of the coating 120 can be determined by separately measuring the light transmittance through the substrate material (e.g., the glass body 120) and the coated glass container 100 and determining the difference between the two measured specimens.

[0023] According to one or more embodiments, the coated glass container 100 may have an average light transmittance in the UV spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0024] According to one or more embodiments, the coated glass container 100 may have an average light transmittance in the UVA spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0025] According to one or more embodiments, the coated glass container 100 may have an average light transmittance in the UVB spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0026] According to one or more embodiments, the coated glass container 100 may have an average light transmittance in the UVC spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0027] According to one or more embodiments, the coated glass container 100 may have a maximum light transmittance in the UV spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0028] According to one or more embodiments, the coated glass container 100 may have a maximum light transmittance in the UVA spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0029] According to one or more embodiments, the coated glass container 100 may have a maximum light transmittance in the UVB spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0030] According to one or more embodiments, the coated glass container 100 may have a maximum light transmittance in the UVC spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0031] According to one or more embodiments, the glass body 102 (uncoated) may have an average light transmittance in the UV spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0032] According to one or more embodiments, the glass body 102 (uncoated) may have an average light transmittance in the UVA spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0033] According to one or more embodiments, the glass body 102 (uncoated) may have an average light transmittance in the UVB spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0034] According to one or more embodiments, the glass body 102 (uncoated) may have an average light transmittance in the UVC spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0035] According to one or more embodiments, the glass body 102 (uncoated) may have a minimum light transmittance in the UV spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0036] According to one or more embodiments, the glass body 102 (uncoated) may have a minimum light transmittance in the UVA spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0037] According to one or more embodiments, the glass body 102 (uncoated) may have a minimum light transmittance in the UVB spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0038] According to one or more embodiments, the glass body 102 (uncoated) may have a minimum light transmittance in the UVC spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%.

[0039] According to one or more embodiments, the coating 120 may have an average light transmittance in the UV spectrum of 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0040] According to one or more embodiments, coating 120 may have an average light transmittance in the UV spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0041] According to one or more embodiments, the coating 120 may have an average light transmittance in the UVA spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0042] According to one or more embodiments, coating 120 may have an average light transmittance in the UVB spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0043] According to one or more embodiments, coating 120 may have an average light transmittance in the UVC spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0044] According to one or more embodiments, coating 120 may have a maximum light transmittance in the UV spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0045] According to one or more embodiments, the coating 120 may have a maximum light transmittance in the UVA spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0046] According to one or more embodiments, coating 120 may have a maximum light transmittance in the UVB spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0047] According to one or more embodiments, coating 120 may have a maximum light transmittance in the UVC spectrum of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 7.5% or less, 5% or less, 2.5% or less, or even 1% or less.

[0048] In one or more embodiments, the coated glass container 100 is U.S.P. <660> These standards generally meet the requirements of the USP "Spectral Transmission for Colored Glass Containers." <660> The UV-Vis spectroscopic analysis is defined in [the text missing or illegible] and utilizes UV-Vis spectroscopy, which measures wavelengths between 290 and 450 nm. In some embodiments, the coated glass container 100 may be perceived as colorless and transparent to the unaided human eye when viewed at any angle. In other embodiments, the coating 120 may have a perceptible tint, such as when the coating 120 includes a colored polymer. In one or more embodiments, the light transmittance through the coated glass container 100 is about 55% or more, about 60% or more, about 65% or more, about 70% or more, about 75% or more, about 80% or more, or even about 90% or more of the light transmittance through an uncoated glass container at wavelengths from about 400 nm to about 700 nm. However, in additional embodiments, the coated glass container 100 may be colored, such as amber, brown, or yellow.

[0049] In one or more embodiments, the coated glass container 100 is coated in accordance with the USP <660> The coated glass container 100 may have protection from radiation in the wavelength range of 400-450 nm, consistent with the standards of the International Electrotechnical Commission (IEC) 20010-10010. For example, the coated glass container 100 may have a light transmittance of less than 20% at all wavelengths from 400 nm to 450 nm. In additional embodiments, the coated glass container 100 may have a light transmittance of less than 15%, less than 10%, or even less than 5% at all wavelengths from 400 nm to 450 nm. In such embodiments, if the coating does not significantly block higher wavelength visible radiation, the coated glass container 100 may have a perceptible color of amber or brown.

[0050] In one or more embodiments, the coated glass container 100 may have an average light transmittance in the visible spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%. In additional embodiments, the glass body 102 may have such an average light transmittance in the 400-450 nm, 450-500 nm, 500-550 nm, 550-600 nm, 600-650 nm, 650-700 nm spectrum, or any combination of these ranges.

[0051] In one or more embodiments, the coated glass article 100 may have a minimum light transmittance in the visible spectrum of at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even at least 99%. In additional embodiments, the glass body 102 may have such a minimum light transmittance in the ranges of the spectrum described for the wavelength ranges of 400-450 nm, 450-500 nm, 500-550 nm, 550-600 nm, 600-650 nm, 650-700 nm, or any combination of these ranges.

[0052] As described herein, light transmittance can be measured before or after an environmental treatment, such as a heat treatment, as described herein. For example, the disclosed light transmittance properties can be observed after heat treatment for 30 minutes at about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C, or after exposure to freeze-drying conditions, or after exposure to autoclave conditions.

[0053] In one or more embodiments, the glass body 102 (uncoated) is visibly colorless, or at least not colored like traditional amber-tinted glass. For example, the glass body 102 in its uncoated state may be perceived as colorless and transparent to the unaided human eye when viewed at any angle. As described herein, visibly colorless refers to a color that is not perceptible to the average human eye. In one or more embodiments, the light transmittance through the glass body 102 in its uncoated state may be about 55% or greater, about 60% or greater, about 65% or greater, about 70% or greater, about 75% or greater, about 80% or greater, or even about 90% or greater at all wavelengths in the visible spectrum. For reference, clear aluminosilicate or borosilicate glass has a light transmittance of about 87-88% at all wavelengths in the visible spectrum.

[0054] The coating 102 can have a wide variety of compositions and structures. In some embodiments, a coating can be applied that provides UV blocking properties. In one or more embodiments, the coating can include a thickness sufficient to reduce the transmission of ultraviolet light. In one or more embodiments, a thickness sufficient to reduce ultraviolet light can be at least 10 nm. For example, the coating thickness can be at least 10 nm, at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 100 nm, at least 200 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 600 nm, at least 700 nm, at least 800 nm, at least 900 nm, or even at least 1000 nm, at least 2 μm, at least 3 μm, at least 4 μm, at least 5 μm, at least 6 μm, at least 7 μm, at least 8 μm, at least 9 μm, at least 10 μm, at least 15 μm, at least 20 μm, or even at least 25 μm.

[0055] In one or more embodiments, the coating can include one or more polymers. In one or more embodiments, the one or more polymers, when deposited thick enough to reduce the transmission of ultraviolet light, can exhibit a color detectable by the human eye. In one or more embodiments, the color can be a warm color. For example, the coating can exhibit a red, yellow, orange, or amber color visible to the human eye.

[0056] In one or more embodiments, the one or more polymers can provide a transparent coating. In one or more embodiments, the coating can be sufficiently transparent to allow automated visual inspection of the contents of a vial containing the coating. The coating can also be sufficiently transparent to allow manual inspection of the contents of the container, such as manual inspection by a medical professional or end user. This can be particularly important for detecting delamination of the glass within the container.

[0057] In one or more embodiments, the coating may be a visibly colored, heat-stable coating that includes a polymer, such as a polyimide, and optionally a coupling agent, such as a silane or metal oxide. In some embodiments, the polymer and / or coupling agent may include a metal, such as silver, copper, iron, or a combination thereof, that acts as a pigment, provides protection from at least UV light, and creates a colored appearance. Coatings that include copper, iron, and / or silver may be coated with a coating composition according to U.S.P. <660> The coating may have an amber or brown appearance that may be required to qualify under the REACH Standard. Examples of suitable coating systems including polymers and / or coupling agents that may incorporate silver, copper, or iron include U.S. Pat. No. 9,763,852, entitled "Glass Articles with Low-Friction Coatings," U.S. Patent Application Publication No. 2017 / 0121058, entitled "Glass Articles With Mixed Polymer and Metal Oxide Coatings," and U.S. Patent Application Publication No. 2017 / 0088459, entitled "Halogenated Polyimide Siloxane Chemical Compositions and Glass Articles with Halogenated Polyimide Siloxane Low-Friction Coatings," the contents of which are incorporated herein by reference. As described herein, metals that promote UV protection and visually color the coating can be incorporated into the polymer layer, the coupling agent layer, or the coating having a mixed layer of coupling agent and polymer.

[0058] According to some embodiments, the coating material applied to the container prior to the optional curing step can include a polyimide containing colloidal metal particles. The colloidal metal particles can be suspended in a polyimide or polyamic acid solution or can be prepared in situ within the polymer layer by reduction of metal ions. In such embodiments, the coating can include a reducing agent. Contemplated metal ions are selected from silver ions, copper ions, and iron ions. For in-situ reduction processes, soluble metal ions are dissolved in the polyimide or polyamic acid solution in the presence of a reducing agent. This reducing agent can be omitted if the reduction of the metal ions is carried out in a reducing atmosphere, although the addition of a reducing agent may be desirable. For example, the reduction can be carried out in a normal atmosphere, such as air, and thus the addition of a reducing agent may be desirable.

[0059] In the embodiments described herein, metal ions can be used in the form of inorganic salts, such as nitrates, or organic salts, such as acetates. Silver trifluoroacetate and silver trifluoroacetylacetonate are particularly contemplated. However, other materials, including silver, copper, or iron, may also be suitable.

[0060] Examples of reducing agents include, but are not limited to, aminosilanes such as N-[3-(trimethoxysilyl)propyl]ethylenediamine, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(trimethoxysilyl)propyl]ethylenediamine, aminopropylsilsesquioxane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, and other aminosilanes, but this list is not exclusive. In some embodiments, the reducing agent can be a silane. In such embodiments, the reducing agent can act as a coupling agent in the coating and can improve adhesion of the polymer film to the glass.

[0061] In some embodiments, the coating may include a polymer containing copper, iron, or silver in the polymer layer, where a coupling agent layer is present between the glass surface and the polymer layer. The coupling agent layer may include an aminosilane, such as aminopropylsilsesquioxane. In additional embodiments, the coupling agent material may be mixed into the polymer along with the silver, copper, or iron.

[0062] In additional embodiments, the coating includes a coupling agent layer comprising one or more of silver, copper, or iron, and a polymer layer over the coupling agent layer. In such embodiments, the coupling agent layer can provide UV protection, while the polymer layer can provide good coefficient of friction and good thermal properties. For example, the polymer layer can include polyimide.

[0063] The UV-blocking coupling agent layer can be prepared, for example, by dispersing metal nanoparticles in a silane solution, or by forming nanoparticles by in-situ reduction of metal ions. In the latter case, the metal ions can be dissolved in a solution containing an adhesion promoter, such as a silane, and at least one reducing agent. In some embodiments, the reducing agent is a coupling agent, such as a silane, that promotes adhesion. Such coupling agents that act as reducing agents can be selected from aminosilanes, such as, but not limited to, N-[3-(trimethoxysilyl)propyl]ethylenediamine, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(trimethoxysilyl)propyl]ethylenediamine, and aminopropylsilsesquioxane.

[0064] According to additional embodiments, the coating can include one or more of polyimide, silver, copper, or iron, as well as other metal oxides such as alumina, titania, or zirconia. For example, coating embodiments including polyimide and one or more of alumina, titania, or zirconia are disclosed in U.S. Patent Application Publication No. 2017 / 0121058, entitled "Glass Articles with Mixed Polymer and Metal Oxide Coatings." It should be recognized that in addition to alumina, titania, and zirconia, other metal oxides can be utilized that may somewhat reduce UV transmittance but generally do not affect the visible color of the coating.

[0065] In one or more further embodiments, the one or more polymers may include polyimides or other thermally stable polymers that block UV radiation without the use of coloring metals such as silver, copper, or iron. For example, the polymer may include PMDA-ODA polyimide.

[0066] In one or more embodiments, the coating can include a Bragg mirror. As described herein, a "Bragg mirror" is a layered material that uses alternating layers of high and low refractive index materials to cause reflection of oncoming light. In one or more embodiments, the Bragg mirror can include at least one layer of high refractive index material and at least one layer of low refractive index material. The difference in refractive index between the high and low refractive index materials can be at least 0.5. For example, the difference in refractive index between the high and low refractive index materials can be at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, or even at least 1.0.

[0067] In one or more embodiments, the high refractive index layer can include any material having a refractive index at least 0.5 greater than the refractive index of the low refractive index material. In one or more embodiments, the high refractive index material can include a metal oxide. For example, the high refractive index layer can include titania (TiO), zirconia (ZrO), or alumina (AlO). In one or more embodiments, the high refractive index layer can include TiO. Examples of layers including titania, zirconia, or alumina in a polyimide matrix are described in U.S. Patent Application Publication No. 2017 / 0121058, entitled "Glass Articles with Mixed Polymer and Metal Oxide Coatings."

[0068] In one or more embodiments, the low refractive index layer can include a material having a refractive index at least 0.5 less than the refractive index of the high refractive index material. In one or more embodiments, the low refractive index material can include or consist of a visibly colorless polyimide. In additional embodiments, the low refractive index material can include a fluorine compound. In one or more embodiments, the low refractive index material can include a silica compound. For example, the low refractive index material can include SiO2.

[0069] In one or more embodiments, the Bragg mirror can include alternating layers. The alternating layers can be high-index layers and low-index layers. In one or more embodiments, adjacent layers of the Bragg mirror can have a refractive index difference of at least 0.5. For example, the coating can include a first high-index layer, a first low-index layer, and a second high-index layer, where the first low-index layer is positioned between the first high-index layer and the second high-index layer.

[0070] In one or more embodiments, the alternating high and low refractive index layers of the Bragg mirror can reflect ultraviolet light. Without wishing to be bound by theory, the boundaries of each layer can cause partial reflection of waves within a wavelength range. In one or more embodiments, the partial wave reflection can create constructive interference, enhancing the reflection of one or more wavelengths of light. In one or more embodiments, the thicknesses of the alternating high and low refractive index layers can be optimized to enhance the reflection of one or more desired wavelengths. In one or more embodiments, the wavelength range reflected by the Bragg mirror can include wavelengths that include ultraviolet light.

[0071] In one or more embodiments, the coating may include a high-pass filter. A "high-pass filter" as described herein may be a material that transmits light including wavelengths longer than a certain cutoff wavelength. In one or more embodiments, at least one high refractive index layer and at least one low refractive index layer may be positioned to form a high-pass filter. In one or more embodiments, the ultraviolet light may include wavelengths below the cutoff wavelength of the high-pass filter. In one or more embodiments, the high-pass filter may transmit visible light and reduce the transmission of ultraviolet light passing through the coating. For example, the cutoff wavelength may be 400 nm, which may allow the transmission of visible light but prevent the transmission of ultraviolet light.

[0072] According to one or more embodiments, the coating may include a mixed layer of polyimide and one or more of titania, zirconium, or aluminum, as described herein. A layer of polyimide without a substantial amount of metal oxide (less than 1% by weight, or even 0% by weight) may be positioned over this layer. In such embodiments, a Bragg mirror and / or high-pass filter function may be formed.

[0073] In one or more embodiments, the high-pass filter can be a Fabry-Perot cavity. As described herein, a "Fabry-Perot cavity" is a structure that can include two parallel reflective surfaces and can prevent the transmission of light having wavelengths that are not resonant with the Fabry-Perot cavity. In one or more embodiments, the Fabry-Perot cavity can be formed from at least one high-index layer, at least one absorbing layer, and at least one low-index layer. For example, the Fabry-Perot cavity can include a high-index layer and a low-index layer separated by an absorbing layer. The reflective surface of the Fabry-Perot cavity can be located at the interface between the absorbing layer and the high-index layer or the low-index layer. In one or more embodiments, the Fabry-Perot cavity can reduce the transmission of ultraviolet light through the coating. Such embodiments can include alternating layers of a polyimide and metal oxide blend and polyimide layers, as described herein.

[0074] In one or more embodiments, the coating can include a continuous phase and a discontinuous phase. The discontinuous phase can include bodies or inclusions within the continuous phase. In one or more embodiments, the difference in refractive index between one or more materials of the continuous phase and one or more materials of the discontinuous phase can be at least 0.5. For example, the difference in refractive index between one or more materials of the continuous phase and one or more materials of the discontinuous phase can be at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, or even at least 1.0. Without wishing to be bound by theory, it is believed that the difference in refractive index between the continuous phase and the discontinuous phase can cause reflection and scattering of light, which may include ultraviolet light. It is believed that coatings including a continuous phase and a discontinuous phase can optimize reflection and scattering of ultraviolet light by adjusting the coating thickness, inclusion size, inclusion shape, and inclusion dispersion.

[0075] In one or more embodiments, the one or more materials comprising the continuous phase may absorb at least 50% more ultraviolet light than visible light. For example, in one or more embodiments, the material comprising the continuous phase may absorb at least 50%, at least 60%, at least 70%, at least 80%, or even at least 90% more ultraviolet light than visible light. In one or more embodiments, the continuous phase may comprise a metal oxide. For example, the continuous phase may comprise TiO, ZrO, AlO, or a combination thereof. In at least one embodiment, the continuous phase may comprise TiO.

[0076] In one or more embodiments, the discontinuous phase can include one or more polymers or one or more inorganic particles. In one or more embodiments, the one or more polymers can include polyimides. In one or more embodiments, the inorganic particles can be hollow.

[0077] In one or more further embodiments, the coating can include a TiO continuous phase and a discontinuous polyimide inclusion phase. Figures 4 and 5 show coatings including polyimide inclusions within a continuous TiO coating. In one or more embodiments, the irregular shape of the polyimide inclusions and the difference in refractive index between TiO and polyimide can aid in light reflection and scattering.

[0078] In one or more embodiments, the coating can include a cavity, and the refractive index of the coating can be at least 0.5 greater than the refractive index of the cavity. For example, the refractive index of the coating can be at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, or even at least 1.0 greater than the refractive index of the cavity.

[0079] In one or more embodiments, the cavities may be formed by the decomposition or volatilization of a sacrificial material. As described herein, a "sacrificial material" is a material that decomposes or volatilizes during a thermal curing process. In one or more embodiments, the sacrificial material may be introduced into the coating during the coating process and before the thermal curing process. The sacrificial material may then create cavities in the coating during the thermal curing process. In one or more embodiments, the difference in refractive index between the coating and the cavities may result in the reflection and scattering of light. In one or more embodiments, the difference in refractive index between the coating and the cavities may result in the reflection and scattering of ultraviolet light.

[0080] In one or more embodiments, the coating can include a layer at least 10 nm thick, the layer including a material that absorbs ultraviolet light at least 50% more than visible light. For example, the layer can have a thickness of at least 10 nm, at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 100 nm, at least 200 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 600 nm, at least 700 nm, at least 800 nm, at least 900 nm, or even at least 1000 nm. In further examples, the layer can include a material that absorbs ultraviolet light at least 50%, at least 60%, at least 70%, at least 80%, or even at least 90% more than visible light.

[0081] In one or more embodiments, the layer may include a metal oxide. For example, the layer may include one or more of TiO, ZrO, and AlO. In one or more embodiments, the coating may include TiO. In one or more embodiments, TiO may have a high absorbance for ultraviolet light having a wavelength between 250 nm and 400 nm, as shown in the UV-Vis absorption spectrum of TiO in FIG. 6. In one or more embodiments, the thickness of the TiO layer may be adjusted to enhance the ultraviolet light absorption properties of the coating. For example, in one or more embodiments, as the thickness of the TiO layer increases, the absorbance of ultraviolet light by the TiO layer may increase.

[0082] In one or more embodiments, the coating can include one or more compounds that absorb ultraviolet light and dissipate at least 50% of the energy absorbed from the ultraviolet light as heat. For example, the compounds can absorb ultraviolet light and dissipate at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or even at least 99% of the energy absorbed from the ultraviolet light as heat. In one or more embodiments, these compounds can include benzophenones, benzotriazoles, triazines, and oxalanilides.

[0083] In one or more embodiments, the coating may include one or more photochromic compounds. As used herein, a "photochromic compound" may be a compound having an absorption spectrum that changes when the photochromic compound is exposed to ultraviolet light. In one or more embodiments, the absorption spectrum of the photochromic compound may change when the photochromic compound is exposed to ultraviolet light, such that the absorption of ultraviolet light increases. In one or more embodiments, a photochromic compound that undergoes a change in absorption spectrum upon exposure to ultraviolet light may return to its original absorption spectrum when exposure to ultraviolet light ceases. An exemplary photochromic compound is manufactured by Nemoto Lumi Materials Company, YS-A4, Kanagawa, Japan, and is a red-pigmented dye that is white in color and can absorb UV light and transmit red light.

[0084] In one or more embodiments, the photochromic compound can include a first absorption spectrum and a second absorption spectrum, and when exposed to ultraviolet light of sufficient intensity for a sufficient time, the photochromic compound exhibits the second absorption spectrum. In one or more embodiments, the intensity and length of time of ultraviolet light required for the photochromic compound to exhibit the second absorption spectrum can vary depending on the photochromic compound used. In one or more embodiments, sunlight can provide ultraviolet light of sufficient intensity for the photochromic compound to exhibit the second absorption spectrum. In one or more embodiments, the required time can be from 0.5 seconds to 20 minutes. For example, the required time can be 0.5 seconds to 20 minutes, 0.5 seconds to 15 minutes, 0.5 seconds to 10 minutes, 0.5 seconds to 9 minutes, 0.5 seconds to 8 minutes, 0.5 seconds to 7 minutes, 0.5 seconds to 6 minutes, 0.5 seconds to 5 minutes, 0.5 seconds to 4 minutes, 0.5 seconds to 3 minutes, 0.5 seconds to 2 minutes, 0.5 seconds to 1 minute, 0.5 seconds to 50 seconds, 0.5 seconds to 40 seconds, 0.5 seconds to 30 seconds, 0.5 seconds to 20 seconds, 0.5 seconds to 10 seconds, 0.5 seconds to 5 seconds, or even 0.5 seconds to 1 second. In one or more embodiments, the second absorption spectrum can absorb at least 5% more ultraviolet light than the first absorption spectrum. For example, the second absorption spectrum may absorb at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or even at least 99% more ultraviolet light than the first absorption spectrum.

[0085] In one or more embodiments, the molecules of the photochromic compound may undergo a conformational change when the photochromic material is exposed to ultraviolet light, which may cause a change in the absorption spectrum of the photochromic compound.

[0086] In one or more embodiments, the photochromic compound may absorb more visible light upon exposure to ultraviolet light. This may cause the coating to darken or develop color upon exposure to ultraviolet light. In one or more embodiments, this coloration is reversible and disappears when the coating is no longer exposed to ultraviolet light.

[0087] In one or more embodiments, the photochromic compound may be an organic compound or an inorganic compound. For example, the one or more photochromic compounds may be hexaarylbiimidaxols, diarylethenes, photochromic quinones, or zinc compounds. In addition, other suitable photochromic compounds known in the art may be used in the coating, including photochromic compounds suitable for use in photochromic lenses for eyeglasses.

[0088] In one or more embodiments, one or more layers, including coatings, can be applied to the vial surface by spray coating. In one or more embodiments, spray coating can be a suitable method for depositing polymers, polyimides, PMDA-ODA, high refractive index layers, low refractive index layers, absorbing layers, metal oxide layers, titania layers, alumina layers, zirconia layers, silica layers, layers including continuous and discontinuous phases, continuous layers including sacrificial materials, layers including photochromic compounds, and combinations thereof. In one or more embodiments, spray coating can be suitable for depositing layers at least 10 nm thick. For example, spray coating may be suitable for depositing a layer at least 10 nm, at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 100 nm, at least 200 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 600 nm, at least 700 nm, at least 800 nm, at least 900 nm, or even at least 1000 nm thick.

[0089] 1 and 2, the coating 120 can be applied in a single deposition step, where the coating 120 comprises a single layer. Deposition can be by a dip process, or the coating 120 can be applied by spraying or other suitable means and optionally dried. A description of deposition methods suitable for the coating 120 described herein can be found in U.S. Pat. No. 9,763,852, entitled "Glass Articles with Low-Friction Coatings," which is incorporated herein by reference in its entirety. In additional embodiments, multiple depositions can be utilized. For example, multiple depositions of coating precursors can be performed and cured, or each deposition step can be followed by curing, such that a second coating of precursor is applied over the cured layer.

[0090] In one or more embodiments, the coating 120 applied to the glass body 102 can have a thickness of about 100 μm or less, about 10 μm or less, about 8 μm or less, about 6 μm or less, about 4 μm or less, about 3 μm or less, about 2 μm or less, or even about 1 μm or less. In some embodiments, the coating thickness 120 can be about 800 nm or less, about 600 nm or less, about 400 nm or less, 300 nm, about 200 nm or less, or even about 100 nm or less. In other embodiments, the coating 120 can be less than about 90 nm thick, less than about 80 nm thick, less than about 70 nm thick, less than about 60 nm thick, less than about 50 nm thick, or even less than about 25 nm thick. In embodiments, coating 120 can have a thickness of at least about 10 nm, at least about 15 nm, at least about 20 nm, at least about 25 nm, at least about 30 nm, at least about 35 nm, at least about 40 nm, or even at least about 45 nm. Exemplary embodiments can have a thickness of about 20 nm to about 50 nm, about 25 nm to about 45 nm, or about 30 nm to about 40 nm. Without being bound by theory, it is believed that a relatively thin coating (i.e., less than 20 nm) may not adequately protect the glass and may cause shallow cracks in the glass surface during vial-to-vial contact. Additionally, such relatively thin coatings may not withstand the depyrogenation process. On the other hand, a relatively thick coating (i.e., greater than 50 nm) may be more easily damaged and may exhibit coating wear marks due to vial-to-vial contact. It should be noted that for relatively thick coatings, wear marks are believed to be deformation of the coating rather than the glass. As described herein, a wear scar is a visible mark caused by abrasion on a coating, leaving a mark or scratch. In some embodiments, a wear scar can refer to a shallow crack in the glass and / or a relatively high coefficient of friction (e.g., 0.7 or greater).

[0091] In some embodiments, the coating 120 may not be of uniform thickness throughout the glass body 102. For example, the coated glass container 100 may have a thicker coating 120 in some areas due to the process of contacting the glass body 102 with one or more coating solutions that form the coating 120. In some embodiments, the coating 120 may have a non-uniform thickness. For example, the thickness of the coating may vary across different areas of the coated glass container 100, thereby promoting protection in selected areas.

[0092] Glass containers for pharmaceutical packaging, on which coating 120 can be applied, can be formed from a variety of different glass compositions. The specific composition of the glass article can be selected according to the particular application, so that the glass has a desired set of physical properties. According to one or more embodiments, the glass can be a composition known to exhibit chemical durability and low thermal expansion, such as alkali borosilicate glass. According to another embodiment, the glass can be formed from Type I, Class B glass conforming to ASTM Standard E438-922.

[0093] The glass container is approximately 25 x 10 -7 / ℃~80×10 -7The glass body 102 may be formed from a glass composition having a thermal expansion coefficient in the range of 0.1 / °C. For example, in some embodiments described herein, the glass body 102 is formed from an alkali aluminosilicate glass composition suitable for strengthening by ion exchange. Such compositions generally include a combination of SiO, AlO, at least one alkaline earth oxide, and one or more alkali oxides, such as NaO and / or KO. In some of these embodiments, the glass composition may be free of boron and boron-containing compounds. In other embodiments, the glass composition may further include small amounts of one or more additional oxides, such as SnO, ZrO, ZnO, TiO, and AsO. These components may be added as fining agents and / or to further enhance the chemical durability of the glass composition. In another embodiment, the glass surface may include a metal oxide coating including SnO, ZrO, ZnO, TiO, AsO, and the like.

[0094] In some embodiments described herein, the glass body 102 can be strengthened, such as by ion exchange strengthening, and is referred to herein as "ion-exchanged glass." For example, the glass body 102 can have a compressive stress of about 300 MPa or greater, or even about 350 MPa or greater. In some embodiments, the compressive stress can range from about 300 MPa to about 900 MPa. However, it should be understood that in some embodiments, the compressive stress of the glass can be less than 300 MPa or greater than 900 MPa. In some embodiments, the glass body 102 can have a depth of layer of 20 μm or greater. In some of these embodiments, the depth of layer can be greater than 50 μm or even 75 μm or greater. In still other embodiments, the depth of layer can be up to 100 μm, or greater than 100 μm. Ion exchange strengthening can be performed in a molten salt bath maintained at a temperature of about 350° C. to about 500° C. To achieve the desired compressive stress, the glass container (uncoated) can be immersed in the salt bath for less than about 30 hours, or even less than about 20 hours. For example, in one embodiment, the glass container can be immersed in a 100% KNO3 salt bath at 450°C for about 8 hours.

[0095] In one particularly exemplary embodiment, the glass body 102 may be formed from an ion-exchangeable glass composition described in pending U.S. patent application Ser. No. 13 / 660,894, entitled "Glass Compositions with Improved Chemical and Mechanical Durability," filed Oct. 25, 2012, and assigned to Corning, Incorporated.

[0096] However, it should be understood that the coated glass container 100 described herein can be formed from other glass compositions, including, but not limited to, ion-exchangeable and non-ion-exchangeable glass compositions. For example, in some embodiments, the glass container can be formed from a Type 1B glass composition, such as, for example, Schott Type 1B borosilicate glass.

[0097] In some embodiments described herein, glass articles can be formed from glass compositions that meet the standards for pharmaceutical glasses set forth by regulatory authorities, such as the USP (United States Pharmacopoeia), the EP (European Pharmacopoeia), and the JP (Japanese Pharmacopoeia), based on their hydrolytic resistance. According to USP 660 and EP 7, borosilicate glass meets Type I criteria and is routinely used in parenteral packaging. Examples of borosilicate glasses include, but are not limited to, Corning® Pyrex® 7740, 7800, and Wheaton 180, 200, and 400, Schott Duran, Schott Fiolax, KIMAX® N-51A, Gerrescheimer GX-51 Flint, and others. Soda-lime glass meets Type III criteria and is acceptable for packaging dry powders that are subsequently dissolved to form solutions or buffers. Type III glasses are also suitable for packaging liquid formulations that are known to be alkali-insensitive. Examples of Type III soda-lime glasses include Wheaton 800 and 900. Dealkalized soda-lime glasses have higher levels of sodium hydroxide and calcium oxide and meet Type II standards. These glasses are less resistant to leaching than Type I glasses and more resistant than Type III glasses. Type II glasses can be used in products whose pH remains below 7 throughout their shelf life. Examples include ammonium sulfate-treated soda-lime glasses. These pharmaceutical glasses have a variety of chemical compositions and range from 20 to 85 x 10 -7 It has a coefficient of linear thermal expansion (CTE) in the range of °C.

[0098] When the coated glass article described herein is a glass container, the glass body 102 of the coated glass container 100 can take a variety of different forms. For example, the glass bodies described herein can be used to form coated glass containers 100 such as vials, ampoules, cartridges, syringe bodies, and / or any other glass container for storing pharmaceutical compositions. Furthermore, the ability to chemically strengthen the glass container prior to coating can be utilized to further improve the mechanical durability of the glass container. Thus, it should be understood that in at least one embodiment, the glass container can be ion-exchange strengthened prior to applying the coating. Alternatively, other strengthening methods, such as heat tempering, flame polishing, and lamination, as described in U.S. Pat. No. 7,201,965, can be used to strengthen the glass prior to coating.

[0099] Various properties of coated glass containers (i.e., coefficient of friction, horizontal compressive strength, four-point bending strength) can be measured when the coated glass containers are in the as-coated state (i.e., after application of the coating without additional treatment other than curing, if applicable) or after one or more processing steps, such as processes similar or identical to those performed on a pharmaceutical filling line, including, but not limited to, washing, lyophilization, depyrogenation, autoclaving, etc.

[0100] Depyrogenation is a process for removing pyrogens from a substance. Depyrogenation of glass articles, such as pharmaceutical packaging, can be achieved by a heat treatment applied to the sample, in which the sample is heated to an elevated temperature for a period of time. For example, depyrogenation can involve heating the glass container to a temperature between about 250°C and about 380°C for a period of time ranging from about 30 seconds to about 72 hours, including, but not limited to, 20 minutes, 30 minutes, 40 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 24 hours, 48 ​​hours, and 72 hours. After the heat treatment, the glass container is cooled to room temperature. One conventional depyrogenation condition commonly employed in the pharmaceutical industry is a heat treatment at a temperature of about 250°C for about 30 minutes. However, it is contemplated that the heat treatment time can be shortened if a higher temperature is utilized. The coated glass container described herein can be exposed to an elevated temperature for a period of time. The elevated temperatures and heating times described herein may or may not be sufficient to depyrogenate the glass container. However, it should be understood that some of the heating temperatures and times described herein are sufficient to depyrogenate coated glass containers, such as those described herein. For example, as described herein, coated glass containers can be exposed to temperatures of about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for 30 minutes. It is recognized that the depyrogenation process may have a time period other than 30 minutes, and that 30 minutes is used throughout this disclosure in conjunction with the depyrogenation temperature for comparative purposes, such as, for example, coefficient of friction testing after exposure to the defined depyrogenation conditions.

[0101] As used herein, lyophilization conditions (i.e., freeze-drying) refers to a process in which a sample is filled with a liquid containing proteins, then frozen at a low temperature, such as -100°C, followed by sublimation of water under vacuum at a temperature, such as -15°C, for a time, such as 20 hours.

[0102] As used herein, autoclave conditions refer to steam purging a sample at 100°C for a period such as 10 minutes, followed by a 20 minute dwell time in which the sample is exposed to a 121°C environment, followed by heat treatment at 121°C for 30 minutes.

[0103] The coefficient of friction (μ) of the coated portion of a coated glass container may be lower than the surface of an uncoated glass container formed from the same glass composition. The coefficient of friction (μ) is a quantitative measurement of friction between two surfaces and is a function of the mechanical and chemical properties of the first and second surfaces, including surface roughness, and environmental conditions such as, but not limited to, temperature and humidity. As used herein, the coefficient of friction measurement of a coated glass container 100 is reported as the coefficient of friction between the outer surface of a first glass container (having an outer diameter of between about 16.00 mm and about 17.00 mm) and the outer surface of a second glass container substantially identical to the first glass container, where the first and second glass containers have the same body and coating composition (if applied), and are exposed to the same environment before, during, and after manufacture. Unless otherwise specified herein, the coefficient of friction refers to the maximum coefficient of friction measured with a normal load of 30 N measured in a vial-on-vial test jig, as described herein. However, it should be understood that a coated glass container that exhibits a maximum coefficient of friction at a particular load will exhibit the same or a better (i.e., lower) maximum coefficient of friction at a lower load. For example, if a coated glass container exhibits a maximum coefficient of friction of 0.5 or less under a load of 50 N, the coated glass container will also exhibit a maximum coefficient of friction of 0.5 or less under a load of 25 N. To measure the maximum coefficient of friction, the maximum values ​​at or near the start of the test are excluded, since these represent static coefficients of friction. As described in the embodiments herein, the coefficient of friction was measured when the containers were moving at a speed of about 0.67 mm / s relative to each other.

[0104] In the embodiments described herein, the coefficient of friction of glass containers (both coated and uncoated) is measured with a vial-on-vial test jig. Test jig 200 is shown schematically in FIG. 3. The same apparatus can also be used to measure the friction force between two glass containers positioned within the jig. Vial-on-vial test jig 200 includes a first clamp 212 and a second clamp 222 arranged in a cross configuration (i.e., perpendicular to each other). First clamp 212 includes a first fixed arm 214 attached to a first base 216. First fixed arm 214 is attached to a first glass container 210 and holds the first glass container 210 stationary relative to first clamp 212. Similarly, second clamp 222 includes a second fixed arm 224 attached to a second base 226. A second fixed arm 224 is attached to the second glass container 220 and holds it stationary relative to the second clamp 222. The first glass container 210 is positioned on the first clamp 212 and the second glass container 220 is positioned on the second clamp 222 so that the long axes of the first glass container 210 and the second glass container 220 are positioned on the horizontal plane defined by the x- and y-axes at approximately a 90° angle to each other.

[0105] The first glass container 210 is positioned in contact with the second glass container 220 at contact point 230. A normal force is applied in a direction perpendicular to the horizontal plane defined by the x- and y-axes. The normal force can be applied by a stationary weight or other force applied to the second clamp 222 on the stationary first clamp 212. For example, a weight can be positioned on the second base 226, and the first base 216 can rest on a stable surface, thus inducing a measurable force between the first glass container 210 and the second glass container 220 at contact point 230. Alternatively, the force can be applied using a mechanical device such as a UMT (Universal Mechanical Testing) machine.

[0106] The first clamp 212 or the second clamp 222 can move relative to each other in a direction at a 45° angle with the long axes of the first and second glass containers 210 and 220. For example, the first clamp 212 can be held stationary, while the second clamp 222 can be moved so that the second glass container 220 moves in the x-axis direction across the first glass container 210. A similar setup is described by R.L. De Rosa et al. in "Scratch Resistant Polyimide Coatings for Aluminum Silicate Glass Surfaces" in The Journal of Adhesion, 78: 113-127, 2002. To measure the coefficient of friction, the force required to move the second clamp 222 and the normal force applied to the first and second glass containers 210 and 220 are measured with a load cell, and the coefficient of friction is calculated as the quotient of the friction force and the normal force. The jig operates in an environment of 25°C and 50% relative humidity.

[0107] In the embodiments described herein, the coated portion of the coated glass container has a coefficient of friction of about 0.7 or less against a similarly coated glass container, as determined using the vial-on-vial jig described above. In other embodiments, the coefficient of friction may be about 0.6 or less, or even about 0.5 or less. In some embodiments, the coated portion of the coated glass container has a coefficient of friction of about 0.4 or less, or even about 0.3 or less. Coated glass containers having a coefficient of friction of about 0.7 or less generally exhibit improved resistance to abrasive damage and, as a result, have improved mechanical properties. For example, conventional glass containers (uncoated) may have a coefficient of friction greater than 0.7.

[0108] In some embodiments described herein, the coefficient of friction of the coated portion of the coated glass container is at least 20% less than the coefficient of friction of the surface of an uncoated glass container formed from the same glass composition. For example, the coefficient of friction of the coated portion of the coated glass container can be at least 20%, at least 25%, at least 30%, at least 40%, or even at least 50% less than the coefficient of friction of the surface of an uncoated glass container formed from the same glass composition.

[0109] In some embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less after exposure to a temperature of about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for 30 minutes. In other embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after 30 minutes of exposure to a temperature of about 250° C., about 260° C., about 270° C., about 280° C., about 290° C., about 300° C., about 310° C., about 320° C., about 330° C., about 340° C., about 350° C., about 360° C., about 370° C., about 380° C., about 390° C., or about 400° C. In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% after 30 minutes of exposure to a temperature of about 250° C. (or about 260° C.). In other embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after 30 minutes of exposure to temperatures of about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C. In other embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 0.5 (i.e., about 0.45, about 0.4, about 0.35, about 0.3, about 0.25, about 0.2, about 0.15, about 0.1, or even about 0.05) after 30 minutes of exposure to temperatures of about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C.In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase at all after exposure to temperatures of about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for 30 minutes.

[0110] In some embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less after immersion in a water bath for 10 minutes at a temperature of about 70° C. In other embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after immersion in a water bath for 5, 10, 20, 30, 40, 50 minutes, or even 1 hour at a temperature of about 70° C. In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% after immersion in a water bath for 10 minutes at a temperature of about 70° C. In other embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after immersion in a water bath for 5, 10, 20, 30, 40, 50 minutes, or even 1 hour at a temperature of about 70° C. In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase at all after immersion in a water bath for 5, 10, 20, 30, 40, 50 minutes, or even 1 hour at a temperature of about 70° C.

[0111] In some embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less after exposure to freeze-drying conditions. In other embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after exposure to freeze-drying conditions. In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% after exposure to freeze-drying conditions. In other embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after exposure to freeze-drying conditions. In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase at all after exposure to freeze-drying conditions.

[0112] In some embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less after exposure to autoclave conditions. In other embodiments, the coated portion of the coated glass container may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after exposure to autoclave conditions. In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% after exposure to autoclave conditions. In other embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after exposure to autoclave conditions. In some embodiments, the coefficient of friction of the coated portion of the coated glass container may not increase at all after exposure to autoclave conditions.

[0113] The coated glass containers described herein have horizontal compressive strength. The horizontal compressive strength described herein is measured by positioning the coated glass container 100 horizontally between two parallel platens oriented parallel to the long axis of the glass container. A mechanical load is then applied to the coated glass container 100 using the platens in a direction perpendicular to the long axis of the glass container. Prior to placement on the platens, the glass container is wrapped in 2 inches (approximately 5.08 cm) of tape, with the protruding portion either cut off or folded around the bottom of the container. The container is then placed within an index card stapled around the test specimen. The load rate for vial compression is 0.5 inches / minute (approximately 1.27 cm / minute), meaning that the platens move toward each other at a rate of 0.5 inches / minute (approximately 1.27 cm / minute). Horizontal compressive strength is measured at 25°C ± 2°C and 50% ± 5% relative humidity. In some embodiments, it is desirable to conduct horizontal compression testing within 1 hour (and even 24 hours) following depyrogenation to simulate conditions on a pharmaceutical filling line. Horizontal compressive strength is a measure of the load at failure, and the horizontal compressive strength measurement can be obtained as the probability of failure at a selected normal compressive load. As used herein, failure occurs when the glass container breaks under horizontal compression in at least 50% of the samples. Thus, horizontal compression is provided for one group of samples. In some embodiments, the coated glass container may have a horizontal compressive strength that is at least 10%, 20%, or 30% greater than that of an uncoated vial.

[0114] Referring now to Figures 1 and 3, horizontal compression strength measurements can also be performed on abraded glass containers. Specifically, the operation of the test jig 200 can cause damage to the exterior surface 122 of the coated glass container, such as surface scratches or abrasions, which weaken the strength of the coated glass container 100. The glass container is then subjected to the horizontal compression procedure described above, with the container placed between two platens and the scratches facing outward parallel to the platens. The scratches can be characterized by the selected normal pressure applied by the vial-on-vial jig and the length of the scratch. Unless otherwise specified, scratches on abraded glass containers for the horizontal compression procedure are characterized by a scratch length of 20 mm produced by a normal load of 30 N. It may be desirable to make the scratches at an angle of 90° ± 5° relative to the platens.

[0115] Coated glass containers can be evaluated for horizontal compressive strength after heat treatment. The heat treatment can be exposure to temperatures of about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for 30 minutes. In some embodiments, the horizontal compressive strength of the coated glass containers does not decrease by more than about 20%, 30%, or even 40% after exposure to heat treatments such as those described above and then abrasion as described above. In one embodiment, the horizontal compressive strength of the coated glass container does not decrease by more than about 20% after exposure to a heat treatment at about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for 30 minutes and then abraded.

[0116] The coated glass articles described herein may be thermally stable after heating at a temperature of at least 250°C (or 260°C, or 280°C, or 300°C) for 30 minutes. The term "thermally stable," as used herein, means that a coating applied to a glass article remains substantially intact on the surface of the glass article after exposure to high temperatures, such that the mechanical properties of the coated glass article, specifically the coefficient of friction and horizontal compressive strength, are minimally affected, if at all, after exposure. This suggests that the coating remains adhered to the surface of the glass and continues to protect the glass article from mechanical damage, such as abrasion and impact, even after exposure to high temperatures.

[0117] In the embodiments described herein, a coated glass article is considered thermally stable if it meets both the coefficient of friction and horizontal compressive strength criteria after being heated to a specified temperature and remaining at that temperature for a specified time. To determine whether the coefficient of friction criteria are met, the coefficient of friction of a first coated glass article is determined in the as-received state (i.e., before thermal exposure) using the test jig described in FIG. 3 and applying a load of 30 N. A second coated glass article (i.e., a glass article having the same glass composition and coating composition as the first coated glass article) is thermally exposed under specified conditions and cooled to room temperature. The coefficient of friction of the second glass article is then determined by abrading the coated glass article using the test jig shown in FIG. 3 with an applied load of 30 N, resulting in an abrasion (i.e., a "scratch") of approximately 20 mm in length. The coefficient of friction criterion is met for purposes of determining the thermal stability of a coating if the coefficient of friction of the second coated glass article is less than 0.7 and the glass surface of the second glass article in the abrasion area has no observable damage. As used herein, the term "observable damage" means that the glass surface of the glass article in the abrasion area contains fewer than six glass cracks per 0.5 cm length of the abrasion area when observed with a Nomarski or differential interference contrast (DIC) spectroscopic microscope at 100x magnification using an LED or halogen light source. A standard definition of glass cracks or shallow glass cracks is provided by G.D. Quinn, "NIST Recommended Practice Guide: Fractography of Ceramics and Glasses," NIST special publication 960-17 (2006).

[0118] To determine whether the horizontal compressive strength criterion is met, a first coated glass article is abraded under a 30 N load in the test jig described in FIG. 3 to form a 20 mm scratch. The first coated glass article is then subjected to a horizontal compression test as described herein, and the retained strength of the first coated glass article is determined. A second coated glass article (i.e., a glass article having the same glass composition and coating composition as the first coated glass article) is thermally exposed under predetermined conditions and cooled to room temperature. The second coated glass article is then abraded under a 30 N load in the test jig described in FIG. 3. The second coated glass article is then subjected to a horizontal compression test as described herein, and the retained strength of the second coated glass article is determined. If the retained strength of the second coated glass article does not decrease by more than about 20% compared to the first coated glass article (i.e., the failure load does not decrease by more than 20%), the horizontal compressive strength criterion is met for purposes of determining the thermal stability of the coating.

[0119] A coated glass container is considered thermally stable if the coefficient of friction criterion and horizontal compressive strength criterion are met after exposing the coated glass container to a temperature of at least about 250°C (or 260°C or 280°C) for at least about 30 minutes (i.e., the coated glass container is thermally stable at a temperature of at least about 250°C (or 260°C or 280°C) for about 30 minutes). Thermal stability can also be evaluated at temperatures from about 250°C (or 260°C or 280°C) to about 400°C. For example, in some embodiments, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 270°C or even about 280°C for about 30 minutes. In yet other embodiments, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 290°C or even about 300°C for about 30 minutes. In further embodiments, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 310°C or even about 320°C for about 30 minutes. In yet other embodiments, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 330°C or even about 340°C for about 30 minutes. In still other embodiments, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 350°C or even about 360°C for about 30 minutes. In some other embodiments, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 370°C or even about 380°C for about 30 minutes. In still other embodiments, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 390°C or even about 400°C for about 30 minutes.

[0120] The coated glass containers disclosed herein can also be thermally stable over a temperature range, meaning that the coated glass container is thermally stable by meeting the coefficient of friction and horizontal compressive strength criteria at each temperature within the range. For example, in the embodiments described herein, the coated glass container can be thermally stable from at least about 250°C (or 260°C or 280°C) to about 400°C or less. In some embodiments, the coated glass container can be thermally stable from at least about 250°C (or 260°C or 280°C) to about 350°C. In other embodiments, the coated glass container can be thermally stable from at least about 280°C to about 350°C or less. In still other embodiments, the coated glass container can be thermally stable from at least about 290°C to about 340°C. In another embodiment, the coated glass container can be thermally stable at a temperature ranging from about 300°C to about 380°C. In another embodiment, the coated glass container may be thermally stable at temperatures ranging from about 320°C to about 360°C.

[0121] The coated glass containers described herein have four-point bending strength. To measure the four-point bending strength of a glass container, a glass tube, which is a precursor to the coated glass container 100, is used for the measurement. The glass tube has the same diameter as the glass container, but does not have the base or mouth of the glass container (i.e., before the tube is formed into the glass container). The glass tube is then subjected to a four-point bending stress test to induce mechanical failure. The test is performed at a relative humidity of 50%, with the outer contact members spaced 9 inches (approximately 22.86 cm) apart and the inner contact members spaced 3 inches (approximately 7.62 cm) apart, and at a loading rate of 10 mm / min.

[0122] Four-point bend stress measurements can also be performed on coated, abraded tubing. As described in measuring the horizontal compressive strength of abraded vials, the operation of the test jig 200 can cause abrasion to the tube surface, such as surface scratches that weaken the tube. The glass tube is then subjected to a four-point bend stress test to induce mechanical failure. The test is conducted at 25°C and 50% relative humidity, with the outer probes spaced 9 inches (approximately 22.86 cm) apart and the inner contact members spaced 3 inches (approximately 7.62 cm) apart, at a loading rate of 10 mm / min, with the tube positioned so that the scratches are under tension during the test.

[0123] In some embodiments, the four-point bending strength of the coated glass tube after abrasion exhibits, on average, at least 10%, 20%, or even 50% greater mechanical strength than uncoated glass tube abraded under the same conditions.

[0124] In some embodiments, after a coated glass container 100 is abraded by an identical glass container with a normal force of 30 N, the coefficient of friction of the abraded area of ​​the coated glass container 100 does not increase by more than about 20%, or does not increase at all, after another abrasion by the identical glass container at the same location with a normal force of 30 N. In other embodiments, after a coated glass container 100 is abraded by an identical glass container with a normal force of 30 N, the coefficient of friction of the abraded area of ​​the coated glass container 100 does not increase by more than about 15% or even 10%, or does not increase at all, after another abrasion by the identical glass container at the same location with a normal force of 30 N. However, not all embodiments of the coated glass container 100 need exhibit such properties.

[0125] In some embodiments, the coated glass container 100 can have a coating 120 that is capable of accepting an adhesive label. That is, the coated glass container 100 can accept an adhesive label on the coated surface such that the adhesive label will adhere securely. However, the ability to adhere an adhesive label is not a requirement of all embodiments of the coated glass container 100 described herein.

[0126] Several non-limiting embodiments are disclosed herein. A first embodiment includes a coated pharmaceutical package, the coated pharmaceutical package comprising: a glass container having a first surface and a second surface opposite the first surface, the first surface being an exterior surface of the glass container, the glass container in an uncoated state having an average light transmittance in the UVB and UVC spectrums of at least 50% through a single wall of the coated package; and a coating disposed on at least a portion of the first surface of the glass container, the coated pharmaceutical package having an average light transmittance in the UVC spectrum of less than 50% through a single wall of the coated package, and the coated pharmaceutical package having an average light transmittance of less than 20% at all wavelengths from 400 nm to 450 nm.

[0127] Another embodiment is where the coated packaging meets U.S.P. <660> Including any of the preceding aspects, which meets the Spectral Transmission for Colored Glass Containers standard.

[0128] Another embodiment includes any of the preceding embodiments, wherein the glass container in its uncoated state is visibly colorless.

[0129] Another embodiment includes any of the preceding embodiments, wherein the coating includes a polymer and one or more of copper, silver, or iron.

[0130] Another embodiment includes any of the preceding embodiments, wherein the polymer is a polyimide.

[0131] Another embodiment includes any of the preceding embodiments, wherein the coating further comprises a reducing agent.

[0132] Another embodiment includes any of the preceding embodiments, wherein the reducing agent is a silane.

[0133] Another embodiment includes any of the preceding embodiments, wherein the coating includes a coupling agent layer including a silane and one or more of silver, copper, or iron, and further includes a polymer layer including a polyimide.

[0134] Another embodiment includes any of the preceding embodiments, wherein the coating comprises a mixed layer comprising: polyimide; one or more of titania, alumina, or zirconia; and one or more of silver, copper, or iron.

[0135] Another embodiment includes a coated pharmaceutical packaging, the coated pharmaceutical packaging comprising: a glass container having a first surface and a second surface opposite the first surface, the first surface being an exterior surface of the glass container, the glass container in an uncoated state having an average light transmittance in the UVB and UVC spectrum of at least 50% through the single wall of the coated packaging; and a coating positioned on at least a portion of the first surface of the glass container, the coated pharmaceutical packaging having an average light transmittance in the UVC spectrum of less than 50% through the single wall of the coated packaging, and the coated pharmaceutical packaging being visibly colorless.

[0136] Another embodiment includes any of the preceding embodiments, wherein the coating comprises a Bragg mirror including at least a high refractive index layer and a low refractive index layer, the high refractive index layer having a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

[0137] Another embodiment includes any of the preceding embodiments, wherein the coating comprises a high-pass filter including at least a high refractive index layer and a low refractive index layer, the high refractive index layer having a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

[0138] Another aspect includes any of the preceding aspects, wherein the high pass band filter comprises a Fabry-Perot cavity filter including at least a high index layer and a low index layer separated by an absorbing layer, the high index layer having a refractive index at least 0.5 greater than the refractive index of the low index layer.

[0139] Another embodiment includes any of the preceding embodiments, wherein the coating includes a first layer in contact with the glass container and comprising a polyimide and one or more of alumina, titania, or zirconia; and a second layer over the first layer, the second layer consisting of a polyimide.

[0140] Another embodiment includes any of the preceding embodiments, wherein the coating comprises a cavity, and the refractive index of the coating is at least 0.5 greater than the refractive index of the cavity.

[0141] Another aspect includes any of the preceding aspects, wherein the cavities are formed by decomposition or volatilization of the sacrificial material during the heat treatment.

[0142] Another embodiment includes any of the preceding embodiments, wherein the coating comprises one or more compounds that absorb ultraviolet light and dissipate at least 50% of the absorbed energy as heat.

[0143] Another embodiment includes any of the preceding embodiments, wherein the one or more compounds include one or more of benzophenones, benzotriazoles, triazines, and oxalanilides.

[0144] Another embodiment includes any of the preceding embodiments, wherein the coating comprises one or more photochromic compounds, the one or more photochromic compounds exhibiting a first absorption spectrum and a second absorption spectrum; when exposed to ultraviolet light of sufficient intensity for a sufficient time, the photochromic compounds exhibit the second absorption spectrum; and the second absorption spectrum absorbs at least 5% more ultraviolet light than the first absorption spectrum.

[0145] Another embodiment includes any of the preceding embodiments, wherein the one or more photochromic compounds can include one or more of hexaarylbiimidaxols, diarylethenes, photochromic quinones, or zinc compounds. [Example]

[0146] Various embodiments of the coated glass container will be further clarified by the following examples. The examples are illustrative in nature and should not be understood to limit the subject matter of the present disclosure. It should be understood that in all examples, the uncoated vials were colorless to the naked eye unless otherwise specified. Also, all light transmission is reported as passing through a single wall of the glass vial, but this can be measured by cutting the vial in half or by calculating the light transmission measurement through both walls of the vial.

[0147] Example 1 - Polyimide Single Layer Ion-exchanged alkali aluminosilicate glass vials (16.75 mm outer diameter) were coated with a PMDA-ODA Kapton polyimide coating. The vials were visually colorless prior to coating. Spectral transmittance data are provided in Figure 7 for an uncoated vial (301), a coated vial (302), and a comparative amber vial (303) commonly available on the market. Spectral data for light passing through the two walls of the vial were collected. As shown in Figure 7, the coated vial provided adequate UV protection at many UV wavelengths, comparable to the amber vial. Less than 10% transmittance was observed across the entire UV spectrum.

[0148] Example 2 - Metal oxide / polyimide blend layer Aluminosilicate glass was coated with a coating. The coating was prepared by mixing Tyzor BTP (a commercially available n-butyl polytitanate) with Nexolve CP1 (a commercially available polyimide) in a 95 / 5 weight ratio of Tyzor BTP / CP1. The coating mixture contained 3.35% solids by weight (i.e., Tyzor BTP and CP1), with the remainder being solvent. Additional solids ratios of 7 / 93 and 10 / 90 were also tested. The solvent consisted of n-propyl acetate and Dowanol PMA in an 89 / 7 weight ratio. The coating was sprayed into multiple vials using an airless sprayer. The coating was then cured in a convection oven at 350°C.

[0149] The coating thickness was varied by controlling the spray time and the percentage of solids used. Table 1 shows the spray time and resulting average coating thickness, as well as the number of samples tested. All samples had a coefficient of friction less than 0.5.

[0150] Light transmittance was tested for each of Samples A-K in Table 1. The light transmittance is shown in Figure 13, with the figure number corresponding to each sample provided in Table 1. Light transmittance was determined from one vial, measured in three locations and averaged.

[0151] [Table 1]

[0152] As can be seen from the data in Table 1 and Figure 13, UV protection was relatively good regardless of coating thickness. Additional coatings did not provide substantially more UV protection. It is believed that increasing thickness does not result in a linear increase in attenuation due to thin film optical interference effects resulting from film thickness and high reflectivity.

[0153] Example 3 - Polyimide / Metal Oxide Blend Underlayer and Polyimide Overlayer A coating containing Tyzor BTP (a commercially available n-butyl polytitanate) and Nexolve CP1 (a commercially available polyimide) in a 95 / 5 weight ratio of Tyzor BTP / CP1 was applied at 3.35 wt % solids as in Example 2. The coating was applied and cured as disclosed in Example 2. Next, layers of CP1 alone were applied over the first layer, varying the wt % solids of CP1 in solvent, controlling spray time and / or immersion to achieve the desired thickness of the outer coating layer. The CP1 outer coating layer was similarly cured at 350°C.

[0154] Each of Samples L-O in Table 2 was tested for light transmittance. Sample P represents bare glass (uncoated). Light transmittance is shown in Figure 14, and Table 2 provides the figure number corresponding to each sample. Light transmittance was determined from one vial measured in three locations and averaged. All samples had a coefficient of friction less than 0.5 and were colorless to the naked eye.

[0155] [Table 2]

[0156] As can be seen from the variation in thickness of the polyimide top layer, the attenuation does not increase linearly with increasing thickness due to thin film optical interference effects resulting from the film thickness and high reflectivity.

[0157] Example 4 - Aminopropylsilsesquioxane Underlayer and Polyimide Overlayer Coated pharmaceutical packaging was prepared as follows: Vials to be coated were rinsed with deionized water, blown dry with nitrogen, and finally cleaned by exposure to oxygen plasma for 15 seconds before coating. The vials were then dip-coated as follows: First, an adhesion layer of aminopropylsilsesquioxane (SSQ) was applied to the glass surface by dip coating using 4% by weight SSQ. The 4% by weight SSQ solution was prepared from a 22-25% stock SSQ solution available from ABCR under reference AB127715, CAS number 29159-37-3, and diluted with a mixture of methanol and water.

[0158] An SSQ adhesion layer was deposited by dip coating at a withdrawal speed of 200 mm / min and cured at 150 °C for 8 minutes. The resulting 150 nm-thick SSQ adhesion layer was overcoated with a PMDA-ODA polyimide layer. The polyimide layer was prepared from PMDA-ODA polyamic acid in NMP / xylene (CAS 25038-81-7, available from Sigma-Aldrich under reference 575771), converted to its triethylamine (TEA) salt form, and dissolved in methanol. The concentration of the PMDA-ODA-TEA solution was 3.6 wt%. Coatings of different thicknesses were prepared by dip coating at withdrawal speeds ranging from 50, 200, 400, 700, and 1000 mm / min. The PMDA-ODA coating was cured at 360 °C for 15 minutes to allow the imidization reaction to occur. The coated vials were visibly yellow, with the intensity of the yellow color increasing with thickness.

[0159] The coating thickness was determined using a ZYGO interferometer to accurately measure the total coating thickness. Thicknesses ranging from 0.5 to approximately 2.2 μm were achieved. The measured thicknesses are shown in Figure 8, which also shows the optical transmittance of each sample at 400 nm. An Agilent Cary 5000 spectrophotometer equipped with a DRA 2500 integrating sphere was used to measure the optical transmittance through the two walls of the vial. Figure 10 shows the transmission spectrum of the sample (372) immersed at 400 mm / min relative to the uncoated vial (370).

[0160] The vials were then cut in half lengthwise using a diamond, and the transmittance was measured through a single wall of the prepared SSQ / PMDA-ODA coating at a dip-coating speed of 400 mm / min. Figure 9 shows the transmittance curves obtained for the uncoated and coated vials. Table 3 below shows the dip rates utilized for the deposition of the polyimide layer (i.e., the PMDA-ODA outer layer). One sample was left uncoated as a reference, and another sample was coated with SSQ but without PMDA-ODA as another reference.

[0161] [Table 3]

[0162] As shown in Figure 9, some samples block most or all of the UVB and UVC radiation while still providing relatively good transmittance in the visible range.

[0163] The coated pharmaceutical packaging was depyrogenated at 260°C for 30 minutes and subjected to a scratch test using a vial-on-vial test jig with a 30N load. The coefficient of friction refers to the coefficient of friction measured with the vial-on-vial test jig under a normal load of 30N. The COF test was performed on cured samples, i.e., samples after heat treatment at 360°C for 15 hours followed by heat treatment at 260°C for 0.25 hours. After testing with a 30N load, no scratches or wear were observed on the surface. The average coefficient of friction (COF) was measured to be 0.22.

[0164] Example 5 – Colloidal silver incorporated into polyimide coating This example demonstrates the preparation of glass packaging with a UV-blocking polyimide film produced by in-situ reduction of silver ions. A silver salt particle suspension was prepared by dissolving 0.9 g of AgNO3 in 11 mL of ethanol, followed by the addition of 7.68 g of N-[3-(trimethoxysilyl)propyl]ethylenediamine (CAS No. 1760-24-3, available from Sigma-Aldrich under reference 104884). The suspension was aged at room temperature for 24 hours. A coating composition was then made by adding 10 g of the supernatant of this silver particle suspension to 20 g of a polyamic acid solution consisting of 1.46 g of PMDA-ODA polyamic acid in the form of its triethylamine salt, 13 g of methanol, 4.2 g of NMP, and 1 g of xylene. The solution was homogenized by manual mixing. A clean glass vial was then dip-coated using the polyamic acid / silver mixture solution described above. The coated vials were then dried using hot air delivered by an air gun set at approximately 500°C, followed by heat treatment at 350°C for 0.25 hours.

[0165] The coated vials exhibited a darker brown color than the silver-free PMDA-ODA coating. Using a vial-on-vial test jig, the vials were subjected to scratch tests under a 30 N load. Micrographs of the coating surface after testing with a 30 N load showed that the surface was scratch-free, showed no wear, and had an average coefficient of friction (COF) of 0.22 (shown in Figure 11, where the y-axis represents COF and the x-axis represents the time or distance of the scratch test).

[0166] Example 6 - Silver incorporated into another polyimide coating The protocol of Example 5 was repeated, except that the PMDA-ODA polyamic acid was replaced with 6FDA-4-BDAF polyimide, commercially available as LARC-CP1 from NEXOLVE. A solution was prepared by adding 10 ml of an N-(2-aminoethyl-3-aminopropyl)trimethoxysilane-AgNO3-EtOH mixture to 20 ml of 3.5 wt. % LARC-CP1 polyimide dissolved in n-propyl acetate, similar to that prepared in Example 5 but using a different reducing agent. After dip coating, the wet layer was dried under a gentle hot air stream set at approximately 500 °C for 2-3 minutes, revealing an amber-brown color. The coating was then post-cured at 60 °C for 15 minutes. An amber-colored vial was obtained.

[0167] Example 7 - Copper and iron incorporated into the adhesion layer undercoat This example describes the preparation of glass packaging having a UV-blocking adhesion layer made by in-situ reduction of iron and copper ions, and an overcoat made of a clear LARC-CP1 polyimide coating (6FDA-4-BDAF polyimide, commercially available from NEXOLVE Corporation under the reference LARC-CP1).

[0168] A suspension containing both copper and iron salt particles was prepared by dissolving 0.126 g of copper nitrate and 0.91 g of iron nitrate in 13 g of proof ethanol, followed by the addition of 8.75 g of N-[3-(trimethoxysilyl)propyl]ethylenediamine. This solution was aged for 24 hours. Next, a cleaned glass vial was dip-coated with the solution at a withdrawal speed of 300 mm / min. The coated vial was then dried for 3 minutes using hot air supplied by an air gun set at approximately 600 °C. The COF of the adhesive layer alone was approximately 0.52, demonstrating good glass protection against scratches. To further reduce the COF, the vial with the UV-blocking adhesive layer was subsequently dip-coated with a 3.5 wt% clear polyimide solution prepared from LARC-CP1 dissolved in n-propyl acetate. The resulting coating, consisting of an amber adhesive layer with a polyimide top layer, exhibited a COF of approximately 0.27. A diamond was used to cut one vial in two lengthwise and the transmittance was measured through one wall. The transmittance of the uncoated vial (380) and the coated glass vial (382) are shown in Figure 12.

[0169] Example 8 - Iron incorporated into titanium / polyimide composite coating A solution of 3 g of titanium butoxide (5593-70-4, Sigma Aldrich) and 2 g of iron(III) methacrylate (CAS# 94275-77-1, Gelest) in 95 g of n-propyl acetate was prepared and stored at room temperature for 3 days. This solution formed a colored complex with a very yellowish amber color. To this solution, 0.25 g of Nexolve colorless polyimide CP1 was added and mixed until dissolved (2 hours). A vial was immersed in the solution and removed at 240 mm / min. The vial was then blotted dry, placed on a mesh rack, and subsequently cured at 350°C.

[0170] Some samples were coated with an additional outer layer of CP1 polyimide over the first layer and cured. The CP1 polyimide was applied at a dip rate of 240 mm / min in a 3 wt% solids solution and cured at 350°C.

[0171] Example 9 The same coating as in Example 8 was applied, but instead of iron(III) methacrylate, 1.8 g of iron(III) 2,4-pentanedionate (CAS#14024-18-1, Gelest) was added.

[0172] It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the present specification cover modifications and variations of the various embodiments described herein, provided that such modifications and variations come within the scope of the appended claims and their equivalents.

[0173] Preferred embodiments of the present invention will be described below in detail.

[0174] Embodiment 1 In coated pharmaceutical packaging, a glass container having a first surface and a second surface opposite the first surface, the first surface being an exterior surface of the glass container, the glass container in an uncoated state having an average light transmittance in the UVB and UVC spectrum of at least 50% through a single wall of the coated package; a coating positioned on at least a portion of the first surface of the glass container, wherein the coated pharmaceutical packaging has an average light transmittance in the UVC spectrum through a single wall of the coated packaging of less than 50%, and the coated pharmaceutical packaging has a light transmittance of less than 20% at all wavelengths from 400 nm to 450 nm. Coated pharmaceutical packaging, including

[0175] Embodiment 2 The coated pharmaceutical packaging is <660> 2. The coated pharmaceutical packaging of embodiment 1, wherein the coated pharmaceutical packaging meets the Spectral Transmission for Colored Glass Containers standard.

[0176] Embodiment 3 3. The coated pharmaceutical packaging of embodiment 1 or 2, wherein the glass container in an uncoated state is visibly colorless.

[0177] Embodiment 4 4. The coated pharmaceutical packaging of any of embodiments 1 to 3, wherein the coating comprises a polymer and one or more of copper, silver, or iron.

[0178] Embodiment 5 5. The coated pharmaceutical packaging of embodiment 4, wherein the polymer is a polyimide.

[0179] Embodiment 6 5. The coated pharmaceutical packaging of embodiment 4, wherein the coating further comprises a reducing agent.

[0180] Embodiment 7 7. The coated pharmaceutical packaging of embodiment 6, wherein the reducing agent is a silane.

[0181] Embodiment 8 The coating silane and one or more of silver, copper, or iron, and a polymer layer including polyimide a coupling agent layer comprising 8. The coated pharmaceutical packaging of any of embodiments 1 to 7, comprising:

[0182] Embodiment 9 The coating polyimide, one or more of titania, alumina, or zirconia, and One or more of silver, copper, or iron A mixed layer containing 9. The coated pharmaceutical packaging of any of embodiments 1 to 8, comprising:

[0183] Embodiment 10 In coated pharmaceutical packaging, a glass container having a first surface and a second surface opposite the first surface, the first surface being an exterior surface of the glass container, the glass container in an uncoated state having an average light transmittance in the UVB and UVC spectrum of at least 50% through a single wall of the coated package; a coating positioned on at least a portion of the first surface of the glass container, wherein the coated pharmaceutical packaging has an average light transmittance in the UVC spectrum through a single wall of the coated packaging of less than 50%, and the coated pharmaceutical packaging is visibly colorless. Coated pharmaceutical packaging, including

[0184] Embodiment 11 11. The coated pharmaceutical packaging of embodiment 10, wherein the coating comprises a Bragg mirror comprising at least a high refractive index layer and a low refractive index layer, the high refractive index layer having a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

[0185] Embodiment 12 11. The coated pharmaceutical packaging of embodiment 10, wherein the coating comprises a high-pass filter comprising at least a high refractive index layer and a low refractive index layer, the high refractive index layer having a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

[0186] Embodiment 13 13. The coated pharmaceutical packaging of embodiment 12, wherein the high-pass band filter is a Fabry-Perot cavity filter comprising at least a high refractive index layer and a low refractive index layer separated by an absorbing layer, the high refractive index layer having a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

[0187] Embodiment 14 The coating a first layer in contact with the glass container and comprising a polyimide and one or more of alumina, titania, or zirconia; and a second layer on the first layer, the second layer being made of polyimide; 11. The coated pharmaceutical packaging of embodiment 10, comprising:

[0188] Embodiment 15 11. The coated pharmaceutical packaging of embodiment 10, wherein the coating comprises cavities and the refractive index of the coating is at least 0.5 greater than the refractive index of the cavities.

[0189] Embodiment 16 16. The coated pharmaceutical packaging of embodiment 15, wherein the cavities are formed by decomposition or volatilization of a sacrificial material during thermal treatment.

[0190] Embodiment 17 11. The coated pharmaceutical packaging of embodiment 10, wherein the coating comprises one or more compounds that absorb ultraviolet light and dissipate at least 50% of the absorbed energy as heat.

[0191] Embodiment 18 18. The coated pharmaceutical packaging of embodiment 17, wherein the one or more compounds comprise one or more of benzophenones, benzotriazoles, triazines, and oxalanilides.

[0192] Embodiment 19 The coating comprises one or more photochromic compounds, wherein the one or more photochromic compounds exhibit a first absorption spectrum and a second absorption spectrum; the photochromic compound exhibits the second absorption spectrum when exposed to ultraviolet light of sufficient intensity for a sufficient period of time; and the second absorption spectrum absorbs at least 5% more ultraviolet light than the first absorption spectrum; 11. The coated pharmaceutical packaging of embodiment 10.

[0193] Embodiment 20 20. The coated pharmaceutical packaging of embodiment 19, wherein the one or more photochromic compounds may comprise one or more of hexaarylbiimidaxols, diarylethenes, photochromic quinones, or zinc compounds. [Explanation of symbols]

[0194] 100 glass containers 102 Glass body 104 Glass Container Wall 106 Internal volume 108 Exterior 110 Inside 120 Coating 122 External surface 124 Glass body contact surface 200 Vial-on-Vial Test Jigs 210 First Glass Container 212 First Clamp 214 First Fixed Arm 216 First Base 220 Second Glass Container 222 Second Clamp 224 Second Fixed Arm 226 Second Base 230 contact points

Claims

1. In coated pharmaceutical packaging, a glass container having a first surface and a second surface opposite the first surface, the first surface being an exterior surface of the glass container, the glass container in an uncoated state having an average light transmittance in the UVB and UVC spectrum of at least 50% through a single wall of the coated package; a coating positioned on at least a portion of the first surface of the glass container, wherein the coated pharmaceutical packaging has an average light transmittance in the UVC spectrum through a single wall of the coated packaging of less than 50%. Including, the coated pharmaceutical packaging (i) has a light transmittance of less than 20% at all wavelengths from 400 nm to 450 nm, or (ii) is visibly colorless; the coating includes a cavity, the cavity being a Fabry-Perot cavity, the coating being formed from at least one high refractive index layer, at least one absorbing layer, and at least one low refractive index layer, the refractive index of the coating being at least 0.5 greater than the refractive index of the cavity; Coated pharmaceutical packaging.

2. 10. The coated pharmaceutical package of claim 1, wherein the coating comprises a polymer and one or more of copper, silver, or iron.

3. 3. The coated pharmaceutical package of claim 2, wherein the coating further comprises a reducing agent.

4. The coating silane and one or more of silver, copper, or iron, and a polymer layer including polyimide a coupling agent layer comprising 4. The coated pharmaceutical package of claim 1, comprising:

5. The coating polyimide, one or more of titania, alumina, or zirconia, and One or more of silver, copper, or iron A mixed layer containing 5. The coated pharmaceutical package of claim 1, comprising:

6. 10. The coated pharmaceutical package of claim 1, wherein the coating comprises a Bragg mirror including at least a high refractive index layer and a low refractive index layer, the high refractive index layer having a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

7. 10. The coated pharmaceutical package of claim 1, wherein the coating comprises a high-pass filter including at least a high refractive index layer and a low refractive index layer, the high refractive index layer having a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

8. The coating a first layer in contact with the glass container and comprising a polyimide and one or more of alumina, titania, or zirconia; and a second layer on the first layer, the second layer being made of polyimide; 10. The coated pharmaceutical package of claim 1, comprising:

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