Ultraviolet light-blocking coated pharmaceutical packaging

Abstract

We provide coated pharmaceutical packaging. [Solution] According to one or more embodiments disclosed herein, a coated pharmaceutical packaging may include a glass container having a first surface and a second surface opposite to the first surface, wherein the first surface is the outer surface of the glass container, and the uncoated glass container has an average light transmittance of at least 50% of the UVB and UVC spectrum passing through a single wall of the coated packaging. The coated pharmaceutical packaging may further include 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 of less than 50% of the UVC spectrum passing through a single wall of the coated packaging.

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] This specification generally relates to glass articles, and more particularly to coatings for glass articles such as pharmaceutical packages.

Background Art

[0003] Historically, glass has been used as a preferred material for pharmaceutical packaging due to its hermeticity, optical transparency, and excellent chemical durability compared to other materials. Some pharmaceutical compositions are sensitive to ultraviolet light and may be prone to decomposition when exposed to ultraviolet light. Some glass compositions that at least partially block UV light have been developed.

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, these glass compositions may be inferior in properties, including but not limited to, delamination between glass layers and / or the coefficient of friction of the outer surface.

Means for Solving the Problems

[0005] According to one or more embodiments, the coated pharmaceutical packaging may include a glass container having a first surface and a second surface opposite to the first surface, wherein the first surface is the outer surface of the glass container, and the uncoated glass container has an average light transmittance of at least 50% of the UVB and UVC spectra passing through a single wall of the coated packaging. The coated pharmaceutical packaging may further include 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 of less than 50% of the UVC spectrum passing through a single wall of the coated packaging, and 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 may include a glass container having a first surface and a second surface opposite to the first surface, wherein the first surface is the outer surface of the glass container, and the uncoated glass container has an average light transmittance of at least 50% of the UVB and UVC spectrum passing through a single wall of the coated packaging. The coated pharmaceutical packaging may further include a coating positioned on at least a portion of the first surface of the glass container, wherein the coated packaging has an average light transmittance of less than 50% of the UVC spectrum passing through a single wall of the coated packaging, and the coated pharmaceutical packaging is visibly colorless.

[0007] Further features and advantages of coatings that can be used to coat glass articles, coated glass articles, and methods and processes for manufacturing them are described in the following detailed description, some of which will be readily apparent to those skilled in the art from that description, or will be recognized by carrying out the embodiments described herein, including the following detailed description, claims, and accompanying drawings.

[0008] It should be understood that both the above summary and the following detailed description illustrate various embodiments and are intended to provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments and are incorporated into this specification, forming part of it. The drawings illustrate the various embodiments described herein and, together with their descriptions, serve to illustrate the principles and operation of the claimed subject matter. [Brief explanation of the drawing]

[0009] [Figure 1] A schematic cross-sectional view of a coated glass container according to one or more embodiments shown and described herein. [Figure 2] A schematic enlarged cross-sectional view of the glass container of Figure 1 with a coating, according to one or more embodiments shown and described herein. [Figure 3] 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 coatings according to this specification, according to one or more embodiments shown and described herein. [Figure 5] Scanning electron microscope images of coatings according to this specification, according to one or more embodiments shown and described herein. [Figure 6] Optical absorption spectra of a metal oxide layer or sublayer according to one or more embodiments shown and described herein. [Figure 7] Exemplary light transmission spectra of one or more embodiments shown and described herein. [Figure 8] Exemplary embodiment light transmission data from one or more embodiments shown and described herein [Figure 9] Exemplary light transmission spectra of one or more embodiments shown and described herein. [Figure 10]Exemplary light transmission spectra of one or more embodiments shown and described herein. [Figure 11] Exemplary embodiment friction coefficient data from one or more embodiments shown and described herein. [Figure 12] Exemplary light transmission spectra of one or more embodiments shown and described herein. [Figure 13] Exemplary light transmission spectra of one or more embodiments shown and described herein. [Figure 14] Exemplary light transmission spectra of one or more embodiments shown and described herein. [Modes for carrying out the invention]

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

[0011] According to one or more embodiments, glass containers (such as pharmaceutical packaging) comprising a coating that blocks all or part of UV light are described herein. Containers without a coating may not substantially block UV light to the desired extent. Such coatings make it possible to use glass compositions that do not block all of the UV light that is to be blocked. In some embodiments, the coating can block UV light generally while allowing the transmission of visible light. Such embodiments may be advantageous because, in one or more embodiments, “transparent” glass with improved properties in contrast to conventional amber-colored glass compositions, and / or the coated glass container may appear transparent while having the function of blocking UV light. In additional embodiments, the coating (and coated articles) may appear colored while providing the UV blocking function. These embodiments may be advantageous because they can use “transparent” glass containers rather than colored glass containers (colored glass may be more prone to degradation and / or may be more expensive to mass-produce). For example, switching between colored and uncolored glass in a single manufacturing apparatus may be costly because a lot of glass is wasted when transitioning between the desired colored and uncolored glass compositions. The coating can further provide desirable properties such as a reduced coefficient of friction compared to the surface of the glass itself, and can become thermally stable through the removal of exothermic substances (a heating process commonly used in pharmaceutical filling).

[0012] Hereafter, we will refer in detail to various embodiments of coatings, coated glass articles, and methods for manufacturing them, examples of which are schematically shown in the drawings. Such coated glass articles may be glass containers suitable for use in a variety of packaging applications, including but not limited to pharmaceutical packaging. It should be understood that coated glass articles may refer to coated pharmaceutical packaging as described in this disclosure. In one or more embodiments, the coating and / or coated pharmaceutical packaging blocks at least partially the transmission of ultraviolet light to the container. However, glass compositions and / or uncoated glass containers may not generally have UV blocking properties that contribute noticeably to the UV blocking of coated glass articles. These pharmaceutical packaging may or may not contain a pharmaceutical composition.

[0013] Various embodiments of coatings, glass articles having coatings, and methods for manufacturing the same are described in further detail herein, with particular reference to the accompanying drawings. While the embodiments of coatings described herein are applied to the outer surface of glass containers, it should be understood that the coatings described 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.

[0014] Generally, the coating can be applied to the surface of a glass article such as a container that can be used as pharmaceutical packaging. The coating can provide advantageous properties to the coated glass article, such as blocking UV light, reducing the coefficient of friction, and improving damage resistance. Reducing the coefficient of friction can give the glass article improved strength and durability by reducing damage due to friction on the glass. Further, the coating can maintain the aforementioned improved strength and durability characteristics after exposure to high temperatures and other conditions experienced during packaging and pre-packaging processes such as, for example, heat-generating substance removal, lyophilization, autoclaving, etc. used in the packaging of pharmaceuticals. Thus, the coating and the glass article having the coating can be thermally stable under conditions such as those utilized for heat-generating substance removal.

[0015] FIG. 1 schematically shows 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 that extends between an outer surface 108 (i.e., the first surface) and an inner surface 110 (i.e., the second surface). The inner surface 110 of the glass container wall 104 defines the inner 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 can be "positioned on" the outer surface 108 even if it is not in direct contact with the outer surface 108, such as when there is an intermediate layer between the outer surface 108 and the coating positioned on the outer surface 108. In some embodiments, the coating 120 can be positioned substantially over the entire outer surface 108 of the glass body 102. In some embodiments, as shown in FIG. 1, the coating 120 can be bonded to the outer surface 108 of the glass body 102. In the embodiment of FIG. 1, the coating 120 has an outer 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 for pharmaceutical packaging. For example, the glass body 102 can be in the shape of a vial, an ampoule, a bottle, a flask, a phial, a beaker, a bucket, a carafe, a vat, a syringe body, etc. The coated glass container 100 can be used to contain any composition, and in one embodiment, can be used to contain a pharmaceutical composition. The pharmaceutical composition can include any chemical substance intended for use in medical diagnosis, cure, treatment, or prevention of diseases. Examples of pharmaceutical compositions include, but are not limited to, pharmaceuticals, drugs, medications, therapeutic agents, etc. The pharmaceutical composition can be in the form of a liquid, a solid, a gel, a suspension, a powder, etc.

[0017] Next, referring to FIGS. 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 containing a polymer. When two or more components are included in the coating 120, the coating 120 may be mixed, but may not be completely homogeneous. For example, in one or more embodiments, one or more chemical components of the mixture can aggregate at the interface of the coating 120 (e.g., the interface with the glass body 102 or the outer surface 122). In such embodiments, the local concentration of the chemical components can vary across different regions of the coating 120. However, the term "mixed" as used herein is to be understood to refer to a layer having at least some dispersion of at least two chemical components and including a layer that is not completely homogeneous. Generally, the 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, the coating 120 can include a coupling agent layer in contact with the outer surface 108 and a polymer layer above the coupling agent layer.

[0018] The transparency of the electromagnetic spectrum (i.e., light) passing through an object can be evaluated by measuring light transmission using a spectrophotometer. Measurements can be performed 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-colored vials). The coating 120 can provide most of the UV blocking. In addition, while the coating can provide UV blocking, in one or more embodiments, the coating can be transparent to visible light and therefore uncolored. 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 colored) and can also block UV light. These light transmission properties are described quantitatively herein. Where UV light is “blocked” as described herein, it should be understood that all or some of the UV light is blocked, and even in glass compositions said not to block UV light, some small amounts of UV radiation may not be transmitted at all wavelengths.

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

[0021] Where light transmittance is described in relation to an "uncoated" glass composition, glass container, or glass wall, the measurement can be obtained by testing the uncoated container or glass substrate. Unless otherwise specified herein, light transmittance is measured through a single wall of a coated glass container. "Uncoated" refers to a glass article without a coating.

[0022] The transmittances disclosed herein with respect to the coated glass container 100, the glass body 102 (uncoated), or the coating 120 should be understood to be that they can be measured through the coated or uncoated container (through two walls), through a single wall of the container (coated or uncoated), or through a flat glass sheet (coated or uncoated) having a thickness similar to that of 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 test 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 more than 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 more than 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 more than 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 more than 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 more than 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 more than 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 more than 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 more than 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, the 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, the 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, the 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, the 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, the 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, the 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 a USP <660> This can meet the requirements for "Spectral Transmission for Colored Glass Containers". Generally, such standards are USP <660> It is defined as utilizing UV-Vis spectroscopy to measure wavelengths of 290–450 nm. In some embodiments, the coated glass container 100 may be perceived as colorless and transparent to the human eye when viewed at any angle. In some other embodiments, the coating 120 may have a perceptible hue, such as when the coating 120 contains 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 the uncoated glass container at wavelengths of about 400 nm to about 700 nm. However, in additional embodiments, the coated glass container 100 may be colored with a color such as amber, brown, or yellow.

[0049] In one or more embodiments, the coated glass container 100 is a USP as described herein. <660> It may have protection from radiation at wavelengths of 400-450 nm, consistent with the standard. 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 visible radiation at higher wavelengths, the coated glass container 100 may have a perceptible amber or brown color.

[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 more than 99%. In additional embodiments, the glass body 102 may have such an average light transmittance in the spectra of 400-450nm, 450-500nm, 500-550nm, 550-600nm, 600-650nm, 650-700nm, 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 more than 99%. In additional embodiments, the glass body 102 may have such minimum light transmittance in the spectra of the wavelength ranges described for 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 environmental treatments such as heat treatment as described herein. For example, the disclosed light transmittance properties can be observed after heat treatment at approximately 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, or 400°C for 30 minutes, 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 uncolored, like traditional amber-colored glass. For example, the uncoated glass body 102 may be perceived as colorless and transparent to the human eye when viewed at any angle. As described herein, visibly colorless means that the color is not perceptible to the average human eye. In one or more embodiments, the light transmittance through the uncoated glass body 102 may be 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 at all wavelengths of the visible spectrum. For reference, transparent aluminosilicate or borosilicate glass has a light transmittance of about 87-88% at all wavelengths of the visible spectrum.

[0054] The coating 102 can have a wide variety of compositions and structures. In some embodiments, a coating that provides UV blocking properties can be applied. In one or more embodiments, the coating may have a thickness sufficient to reduce the transmission of ultraviolet light. In one or more embodiments, the thickness sufficient to reduce ultraviolet light may be at least 10 nm. For example, the coating thickness may 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 may comprise one or more polymers. In one or more embodiments, the one or more polymers may exhibit a color detectable by the human eye when deposited to a thickness sufficient to reduce the transmission of ultraviolet light. In one or more embodiments, the color may be a warm color. For example, the coating may exhibit a red, yellow, orange, or amber color visible to the human eye.

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

[0057] In one or more embodiments, the coating may be a visibly colored, heat-stable coating comprising a polymer such as polyimide and, optionally, a coupling agent such as silane or a metal oxide. In some embodiments, the polymer and / or coupling agent may include metals such as silver, copper, iron, or a combination thereof, which function as pigments, providing protection from at least UV light and producing a colored appearance. Coatings containing copper, iron, and / or silver are subject to USP <660> It may have an amber or brown appearance, which may be required to qualify under the relevant regulations. Examples of suitable coating systems comprising polymers and / or coupling agents that may incorporate silver, copper, or iron include U.S. Patent 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 may be incorporated into the polymer layer, the coupling agent layer, or into a coating having a mixed layer of the coupling agent and polymer.

[0058] According to several embodiments, the coating material applied to the container before any curing step may contain polyimide containing colloidal metal particles. The colloidal metal particles can be suspended in a polyimide or polyamic acid solution, or prepared in-situ within the polymer layer by reduction of metal ions. In such embodiments, the coating may contain a reducing agent. The intended metal ions are selected from silver ions, copper ions, and iron ions. In the case of an in-situ reduction process, the soluble metal ions are dissolved in the polyimide or polyamic acid solution in the presence of a reducing agent. This reducing agent may be omitted if the reduction of the metal ions is carried out in a reducing atmosphere, but the addition of a reducing agent may be desirable. For example, the addition of a reducing agent may be desirable because the reduction can be carried out in a normal atmosphere such as air.

[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 intended. However, other materials containing 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, and other aminosilanes such as N-(2-aminoethyl-3-aminopropyl)trimethoxysilane. In some embodiments, the reducing agent may be a silane. In such embodiments, the reducing agent can act as a coupling agent in the coating, improving the 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, with a coupling agent layer present between the glass surface and the polymer layer. The coupling agent layer may contain an aminosilane such as aminopropylsilsesquioxane. In additional embodiments, the coupling agent material may be mixed with the polymer together with silver, copper, or iron.

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

[0063] A 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 acting as reducing agents can be selected from, but are not limited to, N-[3-(trimethoxysilyl)propyl]ethylenediamine, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and aminosilanes such as bis[3-(trimethoxysilyl)propyl]ethylenediamine and aminopropylsilsesquioxane.

[0064] In additional embodiments, the coating may comprise one or more of polyimide, silver, copper, or iron, and other metal oxides, such as alumina, titania, or zirconia. For example, an embodiment of a coating comprising polyimide and one or more of alumina, titania, or zirconia is disclosed in U.S. Patent Application Publication No. 2017 / 0121058, entitled "Glass Articles with Mixed Polymer and Metal Oxide Coatings." In addition to alumina, titania, and zirconia, it should be noted that other metal oxides may be used, which may reduce UV transmittance somewhat but generally do not affect the visible color of the coating.

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

[0066] In one or more embodiments, the coating may include a Bragg mirror. As used herein, a “Bragg mirror” is a layered material that uses alternating layers of high-refractive-index and low-refractive-index materials to cause reflection of approaching light. In one or more embodiments, a Bragg mirror may 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-refractive-index material and the low-refractive-index material may be at least 0.5. For example, the difference in refractive index between the high-refractive-index material and the low-refractive-index material may be at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, or even further at least 1.0.

[0067] In one or more embodiments, the high refractive index layer may include any material having a refractive index at least 0.5 greater than that of the low refractive index material. In one or more embodiments, the high refractive index material may include a metal oxide. For example, the high refractive index layer may include titania (TiO2), zirconia (ZrO2), or alumina (AlO2). In one or more embodiments, the high refractive index layer may include TiO2. An example of a layer containing titania, zirconia, or alumina in a polyimide matrix is ​​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 may include a material having a refractive index at least 0.5 lower than that of the high refractive index material. In one or more embodiments, the low refractive index material may include, or consist of, a visibly colorless polyimide. In additional embodiments, the low refractive index material may include a fluorine compound. In one or more embodiments, the low refractive index material may include a silica compound. For example, the low refractive index material may include SiO2.

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

[0070] In one or more embodiments, alternating high-refractive-index and low-refractive-index layers of a Bragg mirror can reflect ultraviolet light. While we do not wish 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, partial wave reflection can generate constructive interference, enhancing the reflection of light at one or more wavelengths. In one or more embodiments, the thickness of the alternating high-refractive-index 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 may include wavelengths containing 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, a high-pass filter can be formed by positioning at least one high-refractive-index layer and at least one low-refractive-index layer. In one or more embodiments, ultraviolet light may include wavelengths below the cutoff wavelength of the high-pass filter. In one or more embodiments, the high-pass filter can transmit visible light and reduce the transmission of ultraviolet light passing through the coating. For example, the cutoff wavelength may be 400 nm, which allows the transmission of visible light but prevents the transmission of ultraviolet light.

[0072] According to one or more embodiments, the coating may comprise a mixed layer of polyimide and one or more of titania, zirconium, or aluminum, as described herein. A layer of polyimide containing substantially no metal oxides (less than 1% by mass, or even 0% by mass) can be positioned on this layer. In such embodiments, a Bragg mirror and / or high-pass filter function can be formed.

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

[0074] In one or more embodiments, the coating may comprise a continuous phase and a discontinuous phase. The discontinuous phase may contain a body 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 may 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 may 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. While we do not wish to be bound by theory, the difference in refractive index between the continuous and discontinuous phases may cause reflection and scattering of light, which may include ultraviolet light. It is thought that the reflection and scattering of ultraviolet light in a coating comprising a continuous and discontinuous phase can be optimized by adjusting the thickness of the coating, the size of the inclusions, the shape of the inclusions, and the dispersion of the inclusions.

[0075] In one or more embodiments, one or more materials including a continuous phase may absorb at least 50% more ultraviolet light than visible light. For example, in one or more embodiments, a material including a continuous phase may absorb at least 50%, at least 60%, at least 70%, at least 80%, or even more than 90% more ultraviolet light than visible light. In one or more embodiments, the continuous phase may include a metal oxide. For example, the continuous phase may include TiO2, ZrO2, Al2O3, or a combination thereof. In at least one embodiment, the continuous phase may include TiO2.

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

[0077] In one or more further embodiments, the coating may comprise a continuous TiO2 phase and a discontinuous phase of polyimide-containing material. Figures 4 and 5 show a coating comprising polyimide-containing material within a continuous TiO2 coating. In one or more embodiments, the irregular shape of the polyimide-containing material, as well as the difference in refractive index between TiO2 and polyimide, may contribute to the reflection and scattering of light.

[0078] In one or more embodiments, the coating may contain cavities, and the refractive index of the coating is at least 0.5 greater than the refractive index of the cavities. For example, the refractive index of the coating may be at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, or even more than 1.0 greater than the refractive index of the cavities.

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

[0080] In one or more embodiments, the coating may include a layer having a thickness of at least 10 nm, the layer containing a material that absorbs at least 50% more ultraviolet light than visible light. For example, the layer may 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 may contain a material that absorbs at least 50%, at least 60%, at least 70%, at least 80%, or even at least 90% more ultraviolet light than visible light.

[0081] In one or more embodiments, the layer may contain a metal oxide. For example, the layer may contain one or more of TiO2, ZrO2, and Al2O3. In one or more embodiments, the coating may contain TiO2. In one or more embodiments, TiO2 may have high absorbance to ultraviolet light having wavelengths between 250 nm and 400 nm, as shown in the UV-Vis absorption spectrum of TiO2 shown in Figure 6. In one or more embodiments, the thickness of the TiO2 layer can be adjusted to enhance the ultraviolet light absorption properties of the coating. For example, in one or more embodiments, the ultraviolet light absorbance by the TiO2 layer may increase as the thickness of the TiO2 layer increases.

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

[0083] In one or more embodiments, the coating may comprise one or more photochromic compounds. As used herein, “photochromic compound” may mean a compound having an absorption spectrum that changes when exposed to ultraviolet light. In one or more embodiments, the absorption spectrum of the photochromic compound may change such that its absorption of ultraviolet light increases when exposed to ultraviolet light. In one or more embodiments, a photochromic compound that has undergone a change in its absorption spectrum due to exposure to ultraviolet light can return to its original absorption spectrum when exposure to ultraviolet light ceases. An example photochromic compound is a red pigment dye manufactured by Nemoto Lumi Materials Company, located at YS-A4, Kanagawa Prefecture, Japan, which is white in color, absorbs UV light, and transmits red light.

[0084] In one or more embodiments, the photochromic compound may include a first absorption spectrum and a second absorption spectrum, and the photochromic compound exhibits the second absorption spectrum when exposed to ultraviolet light of sufficient intensity for a sufficient time. In one or more embodiments, the intensity of ultraviolet light and the length of time required for the photochromic compound to exhibit the second absorption spectrum may 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 may range from 0.5 seconds to 20 minutes. For example, the required time could 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 may 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, molecules of a photochromic compound may undergo conformational changes when the photochromic material is exposed to ultraviolet light. These conformational changes can cause changes in the absorption spectrum of the photochromic compound.

[0086] In one or more embodiments, the photochromic compound may absorb more visible light when exposed to ultraviolet light. This may cause the coating to darken or change color when exposed 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 or inorganic compound. For example, one or more photochromic compounds may be hexaarylbiimidaxoles, diarylethenes, photochromic quinones, or zinc compounds. In addition, other suitable photochromic compounds known in the art, including photochromic compounds suitable for use in photochromic lenses for eyeglasses, can be used for coating.

[0088] In one or more embodiments, one or more layers including a coating can be applied to the vial surface by spray coating. In one or more embodiments, spray coating may be a suitable method for depositing polymers, polyimides, PMDA-ODA, high refractive index layers, low refractive index layers, absorption 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 may be suitable for depositing layers with a thickness of at least 10 nm. For example, spray coating may be suitable for depositing layers with 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.

[0089] Referring again to Figures 1 and 2, the coating 120 can be applied in a single deposition process in which the coating 120 comprises a single layer. The deposition may be by a dipping process, or the coating 120 may be applied by spraying or other suitable means and optionally dried. A description of a suitable deposition method for the coating 120 described herein can be found in U.S. Patent No. 9,763,852, titled "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 coating precursors may be deposited and then cured, or cured following each deposition process, such that a second coating of precursors is applied on a cured layer.

[0090] In one or more embodiments, the coating 120 applied to the glass body 102 may 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 thickness of the coating 120 may 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 may have a thickness of less than about 90 nm, less than about 80 nm, less than about 70 nm, less than about 60 nm, less than about 50 nm, or even less than about 25 nm. In embodiments, the coating 120 may 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 may 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. While not bound by theory, it is thought that relatively thin coatings (i.e., less than 20 nm) may not adequately protect the glass and may result in shallow cracks on the glass surface during contact between vials. In addition, such relatively thin coatings may not withstand the exothermic material removal process. On the other hand, relatively thick coatings (i.e., greater than 50 nm) may be more easily damaged and may show wear marks on the coating due to contact between vials. It should be noted that in the case of relatively thick coatings, the wear marks are considered to be deformation in the coating, not the glass. As described herein, abrasion marks are visible marks caused by abrasion on a coating, leaving traces or scratches. In some embodiments, abrasion marks may mean shallow cracks in the glass and / or relatively high coefficients of friction (e.g., 0.7 or higher).

[0091] In some embodiments, the coating 120 does not have to be of uniform thickness across the entire glass body 102. For example, the coated glass container 100 may have a thicker coating 120 in some areas due to the process of bringing one or more coating solutions that form the coating 120 into contact with the glass body 102. In some embodiments, the coating 120 may have an uneven thickness. For example, the thickness of the coating can be varied across different areas of the coated glass container 100, thereby enhancing protection in selected areas.

[0092] Glass containers for pharmaceutical packaging that can be coated with coating 120 can be formed from a variety of different glass compositions. The specific composition of the glass article can be selected according to the specific application so that the glass has a desired set of physical properties. According to one or more embodiments, the glass may be a composition known to exhibit chemical durability and low thermal expansion, such as alkali borosilicate glass. According to another embodiment, it may be formed from type I, class B glass in accordance with ASTM standard E438-922.

[0093] The glass container is approximately 25 x 10 -7 / ℃~80×10 -7It can be formed from a glass composition having a coefficient of thermal expansion in the range of / °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 SiO2, Al2O3, at least one alkaline earth oxide, and one or more alkali oxides such as Na2O and / or K2O. In some of these embodiments, the glass composition may not contain boron and boron-containing compounds. In some other embodiments, the glass composition may further include small amounts of one or more additional oxides such as SnO2, ZrO2, ZnO, TiO2, and As2O3. These components may be added as clarifiers and / or to further enhance the chemical durability of the glass composition. In another embodiment, the glass surface may include a metal oxide coating containing SnO2, ZrO2, ZnO, TiO2, As2O3, etc.

[0094] In some embodiments described herein, the glass body 102 can be strengthened by means of ion exchange strengthening, which is referred to herein as “ion-exchanged glass.” For example, the glass body 102 may have a compressive stress of about 300 MPa or more, or even more than about 350 MPa. In some embodiments, the compressive stress may be in the range of about 300 MPa to about 900 MPa. However, in some embodiments, it should be understood that the compressive stress of the glass may be less than 300 MPa or more than 900 MPa. In some embodiments, the glass body 102 may have a layer depth of 20 μm or more. In some of these embodiments, the layer depth may be more than 50 μm or even more than 75 μm. In yet other embodiments, the layer depth may be up to 100 μm or more than 100 μm. Ion exchange strengthening can be carried out 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 the pending U.S. Patent Application No. 13 / 660,894, filed on 25 October 2012 and assigned to Corning, Incorporated.

[0096] However, it should be understood that the coated glass container 100 described herein may 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 may be formed from a type 1B glass composition, such as Schott's type 1B borosilicate glass.

[0097] In some embodiments described herein, glass articles may be formed from glass compositions that meet the criteria for pharmaceutical glass described by regulatory authorities such as the USP (United States Pharmacopeia), EP (European Pharmacopoeia), and JP (Japanese Pharmacopoeia) based on their hydrolysis resistance. According to USP 660 and EP 7, borosilicate glass meets the criteria for Type I and is routinely used for parenteral packaging. Examples of borosilicate glass 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 the criteria for Type III and is acceptable for packaging dry powders that are subsequently dissolved to make solutions or buffers. Type III glass is also suitable for packaging liquid formulations that have been found to be insensitive to alkalis. Examples of Type III soda-lime glass include Wheaton 800 and 900. Dealkalized soda-lime glass has high levels of sodium hydroxide and calcium oxide and meets Type II standards. These glasses are less resistant to leaching than Type I glass but more resistant than Type III glass. Type II glass can be used for products where the pH remains below 7 during storage. Examples include ammonium sulfate-treated soda-lime glass. These pharmaceutical glasses have a variety of chemical compositions, ranging from 20 to 85 × 10⁻⁶. -7 It has a linear thermal expansion coefficient (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 on a variety of different forms. For example, the glass body described herein can be used to form coated glass containers 100 such as vials, ampoules, cartridges, syringe bodies, and / or any other glass containers for storing pharmaceutical compositions. Furthermore, the ability to chemically strengthen the glass container before coating can be utilized to further improve the mechanical durability of the glass container. Thus, in at least one embodiment, it should be understood that the glass container can be ion-exchange strengthened before coating. Alternatively, the glass can be strengthened before coating using other strengthening methods such as heat tempering, flame polishing, and lamination, as described in U.S. Patent No. 7,201,965.

[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 container is in its as-coated state (i.e., after coating without any additional treatment other than curing, where applicable) or after one or more processing treatments, including but not limited to washing, freeze-drying, exothermic substance removal, and autoclaving, which are similar to or identical to those performed in a pharmaceutical filling line.

[0100] Exothermic removal is the process of removing exothermic substances from a substance. Exothermic removal of exothermic substances from glass articles such as pharmaceutical packaging can be performed by heat treatment applied to the sample, which involves heating the sample to a high temperature for a certain period of time. For example, exothermic removal may involve heating a glass container to a temperature between approximately 250°C and approximately 380°C for a period of time ranging from approximately 30 seconds to approximately 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 exothermic removal condition commonly used in the pharmaceutical industry is heat treatment at a temperature of approximately 250°C for approximately 30 minutes. However, it is expected that the heat treatment time may be shortened when higher temperatures are used. Coated glass containers described herein may be exposed to high temperatures for a certain period of time. The high temperatures and heating times described herein may or may not be sufficient for the removal of exothermic substances from the glass container. However, it should be understood that some of the heating temperatures and times described herein are sufficient for removing exothermic substances from coated glass containers, such as coated glass containers described herein. For example, as described herein, coated glass containers may be exposed to temperatures of approximately 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, or 400°C for 30 minutes. The exothermic substance removal process may have a time other than 30 minutes, and it is recognized throughout this disclosure that 30 minutes is used with the exothermic substance removal temperature for comparative purposes, such as in friction coefficient tests after exposure to defined exothermic substance removal conditions.

[0101] As used herein, freeze-drying conditions refer to a process in which a sample is filled with a protein-containing liquid, then frozen at a low temperature such as -100°C, and subsequently sublimated under vacuum at a temperature such as -15°C for a period of time such as 20 hours.

[0102] As used herein, autoclave conditions refer to purging a sample with vapor at 100°C for a period such as 10 minutes, followed by a residence time of 20 minutes in an environment of 121°C, and then 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 that of the surface of an uncoated glass container formed from the same glass composition. The coefficient of friction (μ) is a quantitative measure of friction between two surfaces and is a function of the mechanical and chemical properties of the first and second surfaces, including surface roughness, as well as environmental conditions such as temperature and humidity, but not limited to these. 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 the first glass container (having an outer diameter between approximately 16.00 mm and approximately 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 the same coating composition (if applied), and are exposed to the same environment before, during, and after manufacture. Unless otherwise stated herein, the coefficient of friction refers to the maximum coefficient of friction measured under 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 exhibiting a maximum coefficient of friction at a particular load will exhibit the same or better (i.e., lower) maximum coefficient of friction at smaller loads. For example, if a coated glass container exhibits a maximum coefficient of friction of 0.5 or less under a load of 50 N, it 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 value at or near the start of the test is excluded, as it represents the static coefficient of friction. As described in the embodiments herein, the coefficient of friction was measured when the relative speed of the containers was approximately 0.67 mm / sec.

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

[0105] The first glass container 210 is positioned in contact with the second glass container 220 at the contact point 230. A perpendicular force is applied in a direction perpendicular to the horizontal plane defined by the x and y axes. The perpendicular force can be applied by a static 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 be placed on a stable surface, so that a measurable force can be induced between the first glass container 210 and the second glass container 220 at the 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 be moved relative to the major axes of the first glass container 210 and the second glass container 220 at an angle of 45°. 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 across the first glass container 210 in the x-axis direction. A similar setup is described by RL De Rosa et al., in “Scratch Resistant Polyimide Coatings for Alumino 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 perpendicular force applied to the first and second glass containers 210, 220 are measured with a load cell, and the coefficient of friction is calculated as the quotient of the friction force and the perpendicular 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 compared to a similarly coated glass container, as determined by the vial-on-vial jig described above. In other embodiments, the coefficient of friction may be about 0.6 or less, or even more 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 more about 0.3 or less. Coated glass containers having a coefficient of friction of about 0.7 or less generally exhibit improved resistance to damage due to friction and, as a result, have improved mechanical properties. For example, a conventional glass container (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 a 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 a coated glass container may 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 a coated glass container may have a coefficient of friction of about 0.7 or less 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 coated portion of a 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 a 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 a coated glass container may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or further 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 a coated glass container may not increase beyond 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 further 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 a coated glass container may not increase at all after 30 minutes of exposure to temperatures of approximately 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, or 400°C.

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

[0111] In some embodiments, the coated portion of a 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 a 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 a 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 a 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 a coated glass container may not increase at all after exposure to freeze-drying conditions.

[0112] In some embodiments, the coated portion of a 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 a 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 a 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 a 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 a 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 perpendicular to the long axis of the glass container. Before positioning on the platens, the glass container is wrapped in 2 inches (approximately 5.08 cm) of tape, with the protruding portion trimmed or folded around the bottom of the container. The container is then positioned within an index card stapled around the test specimen. The loading rate of vial compression is 0.5 inches / min (approximately 1.27 cm / min), meaning the platens move toward each other at a speed of 0.5 inches / min (approximately 1.27 cm / min). The horizontal compressive strength is measured at 25°C ± 2°C and 50% ± 5% relative humidity. In some embodiments, it is desirable to perform a horizontal compression test within 1 hour (and within 24 hours) following the removal of pyrogens in order to simulate the conditions of a pharmaceutical filling line. Horizontal compressive strength is a measure of the load at which fracture occurs, and the measure of horizontal compressive strength can be obtained as the probability of fracture at a selected normal compressive load. As used herein, fracture occurs when the glass container breaks under horizontal compression in at least 50% of the sample. Thus, horizontal compression is provided for one group of samples. In some embodiments, coated glass containers may have a horizontal compressive strength at least 10%, 20%, or 30% greater than that of uncoated vials.

[0114] Next, referring to Figures 1 and 3, the horizontal compressive strength can also be measured on a worn glass container. Specifically, the operation of the test jig 200 can cause damage to the outer surface 122 of the coated glass container, such as scratches or abrasion on the surface that weaken the strength of the coated glass container 100. Next, the glass container is subjected to the horizontal compressive 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 length of the scratches and the selected atmospheric pressure applied by the vial-on-vial jig. Unless otherwise specified, scratches on a worn glass container for the horizontal compressive procedure are characterized by a scratch length of 20 mm produced by a normal load of 30 N. It would be desirable to make scratches at an angle of 90° ± 5° relative to the platens.

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

[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 the coating applied to the glass article remains substantially intact on the surface of the glass article after exposure to high temperatures, and as a result, the mechanical properties of the coated glass article, specifically the coefficient of friction and horizontal compressive strength, are minimally affected, if any, after exposure. This suggests that the coating remains attached to the glass surface after exposure to high temperatures, continuing to protect the glass article from mechanical damage such as abrasion and impact.

[0117] In the embodiments described herein, a coated glass article is considered thermally stable if, after being heated to a specified temperature and remaining at that temperature for a specified time, it satisfies both the coefficient of friction criterion and the horizontal compressive strength criterion. To determine whether the coefficient of friction criterion is met, the coefficient of friction of a first coated glass article is determined in its as-received state (i.e., before thermal exposure) using the test jig shown in Figure 3 and the application of a load of 30 N. A second coated glass article (i.e., a glass article having the same glass composition and the same coating composition as the first coated glass article) is thermally exposed under predetermined conditions and cooled to room temperature. The coefficient of friction of the second glass article is then determined by abrading the coated glass article with the test jig shown in Figure 3 using the application of a load of 30 N, causing abrasion (i.e., a "scratch") approximately 20 mm in length. The coefficient of friction criterion is met for the purpose of determining the thermal stability of the coating if the coefficient of friction of the second coated glass article is less than 0.7 and there is no observable damage on the glass surface of the second glass article in the abrasion region. The term “observable damage,” as used herein, means that the glass surface of the abrasion region of the glass article contains fewer than six glass cracks per 0.5 cm of abrasion region when observed at 100x magnification using an LED or halogen light source with a Nomarski or differential interference contrast (DIC) spectroscopic microscope. A standard definition of glass cracks or shallow glass fissures is found in GD 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, the first coated glass article is abraded under a load of 30 N using the test jig shown in Figure 3 to form a 20 mm scratch. The first coated glass article is then subjected to a horizontal compression test as described herein to determine the retained strength of the first coated glass article. The second coated glass article (i.e., a glass article having the same glass composition and the same coating composition as the first coated glass article) is thermally exposed under specified conditions and cooled to room temperature. The second coated glass article is then abraded under a load of 30 N using the test jig shown in Figure 3. The second coated glass article is then subjected to a horizontal compression test as described herein to determine the retained strength of the second coated glass article. If the retained strength of the second coated glass article does not decrease by more than approximately 20% compared to the first coated glass article (i.e., the breaking load does not decrease by more than 20%), the horizontal compressive strength criterion is met for the purpose of determining the thermal stability of the coating.

[0119] A coated glass container is considered thermally stable if, after exposure to a temperature of at least about 250°C (or 260°C or 280°C) for at least about 30 minutes, the criteria for the coefficient of friction and the horizontal compressive strength are met (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 further about 280°C for about 30 minutes. In yet another embodiment, a coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 290°C or further about 300°C for about 30 minutes. In further embodiments, the coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 310°C or further about 320°C for about 30 minutes. In yet another embodiment, the coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 330°C or further about 340°C for about 30 minutes. In yet another embodiment, the coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 350°C or further about 360°C for about 30 minutes. In some other embodiments, the coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 370°C or further about 380°C for about 30 minutes. In yet another embodiment, the coated glass container is considered thermally stable if it meets the criteria at a temperature of at least about 390°C or further about 400°C for about 30 minutes.

[0120] The coated glass containers disclosed herein can also be thermally stable over a certain temperature range, meaning that the coated glass container is thermally stable by meeting friction coefficient and horizontal compressive strength criteria at each temperature within the range. For example, in embodiments described herein, the coated glass container may 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 may be thermally stable in the range from at least about 250°C (or 260°C or 280°C) to about 350°C. In some other embodiments, the coated glass container may be thermally stable from at least about 280°C to about 350°C or less. In yet another embodiment, the coated glass container may be thermally stable from at least about 290°C to about 340°C. In yet another embodiment, the coated glass container may be thermally stable in the range of 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 the 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 separated by 9 inches (approximately 22.86 cm) and the inner contact members separated by 3 inches (approximately 7.62 cm), at a loading rate of 10 mm / min.

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

[0123] In some embodiments, the four-point bending strength of a glass tube with a coating after wear is, on average, at least 10%, 20%, or even 50% higher than that of an uncoated glass tube worn under the same conditions.

[0124] In some embodiments, after abrading the coated glass container 100 with a vertical force of 30 N by the same glass container, 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 same glass container with a vertical force of 30 N at the same location. In other embodiments, after abrading the coated glass container 100 with a vertical force of 30 N by the same glass container, 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 same glass container with a vertical force of 30 N at the same location. However, not all embodiments of the coated glass container 100 are required to exhibit such properties.

[0125] In some embodiments, the coated glass container 100 may have a coating 120 that can accept adhesive labels. That is, the coated glass container 100 can accept adhesive labels on its coated surface so that the adhesive labels adhere firmly. However, the ability to adhere adhesive labels is not a requirement for 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 packaging, the coated pharmaceutical packaging being a glass container having a first surface and a second surface opposite to the first surface, the first surface being the outer surface of the glass container, and the uncoated glass container having an average light transmittance of at least 50% of the UVB and UVC spectrum as it passes through a 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 of less than 50% of the UVC spectrum as it passes through a single wall of the coated packaging, and the coated pharmaceutical packaging having a light transmittance of less than 20% at all wavelengths from 400 nm to 450 nm.

[0127] Another aspect is that the coated packaging is USP <660> This includes any of the aforementioned embodiments that meet the criteria for spectral transmission for colored glass containers.

[0128] Another embodiment includes any of the above embodiments, wherein the uncoated glass container is visibly colorless.

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

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

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

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

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

[0134] Another embodiment includes any of the above 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 being a glass container having a first surface and a second surface opposite to the first surface, the first surface being the outer surface of the glass container, and the uncoated glass container having an average light transmittance of at least 50% of the UVB and UVC spectrum passing through a 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 of less than 50% of the UVC spectrum passing through a single wall of the coated packaging, and the coated pharmaceutical packaging being visibly colorless.

[0136] Another embodiment includes any of the above embodiments, wherein the coating includes 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.

[0137] Another embodiment includes any of the above embodiments, wherein the coating includes 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.

[0138] Another embodiment includes any of the above embodiments, wherein the high-pass band filter includes a Fabry-Perot cavity filter comprising at least a high-refractive-index layer and a low-refractive-index layer separated by an absorption 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.

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

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

[0141] Another embodiment includes any of the aforementioned embodiments, in which the cavity is formed during heat treatment by the decomposition or volatilization of the sacrificial material.

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

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

[0144] Another embodiment includes any of the above 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; the photochromic compounds exhibiting a second absorption spectrum when exposed to ultraviolet light of sufficient intensity for a sufficient time; and the second absorption spectrum absorbs at least 5% more ultraviolet light than the first absorption spectrum.

[0145] Another embodiment includes any of the above embodiments, wherein one or more photochromic compounds may comprise one or more hexaarylbiimidaxoles, diarylethenes, photochromic quinones, or zinc compounds. [Examples]

[0146] Various embodiments of glass containers with coatings will be further illustrated by the following examples. These examples are illustrative in nature and should not be understood as limiting the subject matter of this disclosure. In all examples, it should be understood that 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, which can be measured by cutting the vial in half or by calculating the light transmission amount passing through two walls of the vial.

[0147] Example 1 - Polyimide Monolayer Ion-exchanged alkali aluminosilicate glass vials (outer diameter 16.75 mm) were coated with PMDA-ODA Kapton polyimide coating. The vials were visually colorless before coating. Spectroscopic transmission data are provided in Figure 7 for the uncoated vial (301), the coated vial (302), and a common amber-colored vial (303) for comparison. Spectral data of light passing through the two walls of the vial were collected. As shown in Figure 7, the coated vial provided adequate UV protection comparable to the amber-colored vial across many UV wavelengths. A transmittance of less than 10% was observed across the entire UV spectrum.

[0148] Example 2 - Metal oxide / polyimide mixed layer Aluminosilicate glass was coated. The coating was prepared by mixing Tyzor BTP (commercially available n-butyl polytitanate) with Nexolve CP1 (commercially available polyimide) in a weight ratio of 95 / 5 Tyzor BTP / CP1. The coating mixture contained 3.35% by mass of solids (i.e., Tyzor BTP and CP1), with the remainder being solvent. Additional solid ratios of 7 / 93 and 10 / 90 were also tested. The solvent consisted of n-propyl acetate and Dowanol PMA in a weight ratio of 89 / 7. The coating was sprayed into numerous 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 spraying time and the proportion of solids used. Table 1 shows the coating spraying time, the average resulting thickness, and the number of samples tested. All samples had a friction coefficient of less than 0.5.

[0150] The light transmittance was tested for each of the samples A through K in Table 1. The light transmittance is shown in Figure 13, and the corresponding figure number is provided in Table 1. The light transmittance was measured at three locations and determined from a single vial 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 the coating thickness. Applying additional coatings did not substantially increase UV protection. It is thought that the attenuation does not increase linearly with increasing thickness due to the optical interference effect of the thin film caused by the film thickness and high reflectivity.

[0153] Example 3 - Polyimide / metal oxide mixed lower layer and polyimide upper layer A coating containing Tyzor BTP (commercially available n-butyl polytitanate) and Nexolve CP1 (commercially available polyimide) in a Tyzor BTP / CP1 weight ratio of 95 / 5 was applied at a solids mass % of 3.35, as in Example 2. The coating was applied and cured as disclosed in Example 2. Next, layers of CP1 alone, with varying solids mass % of CP1 in the solvent, were applied on top of the first layer, and the desired thickness of the outer coating layer was achieved by controlling the spray time and / or immersion. The CP1 outer coating layer was similarly cured at 350°C.

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

[0155] [Table 2]

[0156] As can be seen from the change in the thickness of the polyimide upper layer, the attenuation does not increase linearly with increasing thickness due to the optical interference effect of the thin film caused by the film thickness and high reflectivity.

[0157] Example 4 - Aminopropylsilsesquioxane lower layer and polyimide upper layer The coated pharmaceutical packaging was prepared as follows: The vials to be coated were washed with deionized water, dried with nitrogen, and finally washed again by exposure to oxygen plasma for 15 seconds before coating. Next, the vials were immersion coated as follows: First, an adhesion layer of aminopropylsilsesquioxane (SSQ) was applied to the glass surface by immersion coating using 4% by mass of SSQ. The 4% by mass SSQ solution was prepared from a 22-25% stock SSQ solution available from ABCR, reference AB127715, CAS number 29159-37-3, and diluted with a methanol-water mixture.

[0158] The SSQ adhesion layer was deposited by immersion coating at a pull-up rate 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, reference 575771), converted to its triethylamine (TEA) salt form, and dissolved in methanol. The concentration of the PMDA-ODA-TEA solution was 3.6% by mass. Coatings of different thicknesses were prepared by immersion coating at pull-up rates ranging from 50, 200, 400, 700, and 1000 mm / min. The PMDA-ODA coating was cured at 360°C for 15 minutes to induce the imidization reaction. The coated vials were visibly yellow, and the intensity of the yellow color increased with thickness.

[0159] The coating thickness was determined using a ZYGO interferometer, and the total coating thickness was accurately measured. Thicknesses ranging from 0.5 to approximately 2.2 μm were achieved. The measured thicknesses are shown in Figure 8, where the light transmittance of each sample at 400 nm is also shown. Light transmittance through the two walls of the vial was measured using an Agilent Cary5000 spectrophotometer equipped with an integrating sphere DRA2500. Figure 10 shows the transmission spectra of a sample (372) immersed at 400 mm / min compared to an uncoated vial (370).

[0160] Next, the vials were cut in half lengthwise using a diamond, and the transmittance was measured through a single wall of the SSQ / PMDA-ODA coating prepared at an immersion coating rate of 400 mm / min. Figure 9 shows the transmission curves obtained for the uncoated and coated vials. Table 3 below shows the immersion rates used for depositing the polyimide layer (i.e., the PMDA-ODA outer layer). One sample was used as a reference and was not coated, while another sample was used as a reference and coated with SSQ, but without PMDA-ODA.

[0161] [Table 3]

[0162] As shown in Figure 9, in some samples, most or all of the UVB and UVC radiation is blocked, but the transmittance in the visible range remains relatively good.

[0163] The pyrogen was removed from the coated pharmaceutical packaging at 260°C for 30 minutes, and then subjected to a scratch test with a 30N load using a vial-on-vial test jig. The coefficient of friction refers to the coefficient of friction measured with a 30N vertical load using the vial-on-vial test jig. The COF test was performed on hardened samples, i.e., samples that had been heat-treated at 360°C for 15 hours followed by heat-treated at 260°C for 0.25 hours. After testing with a 30N load, no scratches or abrasion were observed on the surface. The mean coefficient of friction (COF) was measured at 0.22.

[0164] Example 5 - Colloidal silver incorporated into a polyimide coating This example demonstrates the preparation of glass packaging having 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. Next, a coating composition was prepared 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 triethylamine salt, 13 g of methanol, 4.2 g of NMP, and 1 g of xylene. The solution was homogenized by manual mixing. Then, clean glass vials were immersion coated with the polyamic acid / silver mixture solution described above. The coated vials were then dried using hot air supplied by an air gun set to 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. The vials were subjected to scratch testing under a 30N load using a vial-on-vial test jig. Micrographs of the coating surface after testing under a 30N load showed no scratches, no abrasion, and a mean 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 PMDA-ODA polyamic acid was replaced with 6FDA-4-BDAF polyimide, which is commercially available from NEXOLVE as LARC-CP1. A solution was prepared by adding 10 ml of N-(2-aminoethyl-3-aminopropyl)trimethoxysilane-AgNO3-EtOH mixture to 20 ml of 3.5% by mass LARC-CP1 polyimide dissolved in n-propyl acetate, using the same but different reducing agent as in Example 5. After immersion coating, the wet layer was dried for 2-3 minutes under a gentle hot airflow set to approximately 500°C, after which an amber-brown color appeared. 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 embodiment describes the preparation of glass packaging having a UV-blocking adhesion layer created by in-situ reduction of iron and copper ions, and an overcoat made of a transparent LARC-CP1 polyimide coating (6FDA-4-BDAF polyimide, commercially available from NEXOLVE as reference LARC-CP1).

[0168] A suspension containing salt particles of both copper and iron 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, washed glass vials were coated with this solution by immersion coating at a pull-up rate of 300 mm / min. The coated vials were then dried for 3 minutes using hot air supplied by an air gun set to approximately 600°C. The COF of the adhesion layer alone was approximately 0.52, indicating good glass protection against scratches. To further reduce the COF, the vials coated with the UV-blocking adhesion layer were subsequently immersion coated with a 3.5% by mass clear polyimide solution prepared from LARC-CP1 dissolved in n-propyl acetate. The resulting coating consisted of an amber-colored adhesion layer with a polyimide upper layer and showed a COF of approximately 0.27. A diamond was used to cut one vial lengthwise into two halves, and the transmittance was measured through one wall. The transmittances of an uncoated vial (380) and a coated glass vial (382) are shown in Figure 12, respectively.

[0169] Example 8 - Iron incorporated into a titanium / polyimide mixed coating A solution was prepared by dissolving 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 and storing it at room temperature for 3 days. This solution formed a very yellowish amber colored complex. To this solution, 0.25 g of Nexolve colorless polyimide CP1 was added and mixed until dissolved (2 hours). The vial was immersed in the solution and removed at 240 mm / min. The vial was then absorbed and dried, placed on a mesh rack, and subsequently cured at 350°C.

[0170] In some samples, an additional outer layer of CP1 polyimide was applied on top of the initial layer and cured. The CP1 polyimide was applied in a 3% solids solution at an immersion rate of 240 mm / min 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-pentanedione (CAS#14024-18-1, Gelest) was added.

[0172] It will be apparent to those skilled in the art that various modifications and changes can be made to the embodiments described herein without departing from the spirit and scope of the subject matter set forth in the claims. Accordingly, this specification is intended to extend to modifications and changes to the various embodiments described herein, insofar as such modifications and changes fall within the scope of the appended claims and their equivalents.

[0173] Preferred embodiments of the present invention are described below in separate sections.

[0174] Embodiment 1 In coated pharmaceutical packaging, A glass container having a first surface and a second surface opposite to the first surface, wherein the first surface is the outer surface of the glass container, and the uncoated glass container has an average light transmittance of at least 50% of the UVB and UVC spectrum passing through a single wall of the coated packaging, and 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 of less than 50% in the UVC spectrum passing through a single wall of the coated packaging, 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 [this].

[0175] Embodiment 2 The aforementioned coated pharmaceutical packaging is subject to USP <660> A coated pharmaceutical packaging according to Embodiment 1, which meets the spectral transmission criteria for colored glass containers.

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

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

[0178] Embodiment 5 The coated pharmaceutical packaging according to Embodiment 4, wherein the polymer is polyimide.

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

[0180] Embodiment 7 The coated pharmaceutical packaging according to Embodiment 6, wherein the reducing agent is silane.

[0181] Embodiment 8 The aforementioned coating Silane and one or more of silver, copper, or iron, Polymer layer containing polyimide coupling agent layer containing A coated pharmaceutical packaging according to any one of embodiments 1 to 7, including the above.

[0182] Embodiment 9 The aforementioned coating Polyimide, One or more of titania, alumina, or zirconia, and One or more of silver, copper, or iron Mixed layer containing A coated pharmaceutical packaging according to any one of embodiments 1 to 8, including the above.

[0183] Embodiment 10 In coated pharmaceutical packaging, A glass container having a first surface and a second surface opposite to the first surface, wherein the first surface is the outer surface of the glass container, and the uncoated glass container has an average light transmittance of at least 50% of the UVB and UVC spectrum passing through a single wall of the coated packaging, and 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 of less than 50% passing through a single wall of the coated packaging, and the coated pharmaceutical packaging is visibly colorless. Coated pharmaceutical packaging, including [this].

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

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

[0186] Embodiment 13 The coated pharmaceutical packaging according to 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 absorption layer, and the high refractive index layer has a refractive index at least 0.5 greater than the refractive index of the low refractive index layer.

[0187] Embodiment 14 The aforementioned coating A first layer in contact with the glass container and comprising polyimide and one or more of alumina, titania, or zirconia, and A second layer, made of polyimide, is located on top of the first layer. A coated pharmaceutical packaging according to Embodiment 10, including the above.

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

[0189] Embodiment 16 The coated pharmaceutical packaging according to Embodiment 15, wherein the cavity is formed by the decomposition or volatilization of the sacrificial material during heat treatment.

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

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

[0192] Embodiment 19 The coating comprises one or more photochromic compounds, where, 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 amount of time, and The second absorption spectrum absorbs at least 5% more ultraviolet light than the first absorption spectrum. Coated pharmaceutical packaging as described in Embodiment 10.

[0193] Embodiment 20 The coated pharmaceutical packaging according to Embodiment 19, wherein the one or more photochromic compounds may comprise one or more 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 Inner self 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 Bass 220 Second glass container 222 Second clamp 224 Second fixed arm 226 Second Bass 230 contact points

Claims

1. In coated pharmaceutical packaging, A glass container having a first surface and a second surface opposite to the first surface, wherein the first surface is the outer surface of the glass container, and the uncoated glass container has an average light transmittance in the UVB and UVC spectrum of at least 50% through a single wall of the coated packaging, and 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 of less than 50% through a single wall of the coated packaging. Includes, 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, and the coating is formed from at least one high refractive index layer, at least one absorption layer, and at least one low refractive index layer, wherein the refractive index of the coating is at least 0.5 greater than the refractive index of the cavity. Coated pharmaceutical packaging.

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

3. The coated pharmaceutical packaging according to claim 2, wherein the coating further comprises a reducing agent.

4. The aforementioned coating Silane and one or more of silver, copper, or iron, Polymer layer containing polyimide coupling agent layer containing A coated pharmaceutical packaging according to any one of claims 1 to 3, including the above.

5. The aforementioned coating Polyimide, One or more of titania, alumina, or zirconia, and One or more of silver, copper, or iron Mixed layer containing A coated pharmaceutical packaging according to any one of claims 1 to 4, including the above.

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

7. The coated pharmaceutical packaging according to claim 1, wherein the coating includes a high-pass filter comprising at least a high-refractive-index layer and a low-refractive-index layer, and the high-refractive-index layer has a refractive index at least 0.5 greater than the refractive index of the low-refractive-index layer.

8. The aforementioned coating A first layer in contact with the glass container and comprising polyimide and one or more of alumina, titania, or zirconia, and A second layer, made of polyimide, is located on top of the first layer. A coated pharmaceutical packaging according to claim 1, comprising:

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