阅读说明：本技术 具有低摩擦涂层的玻璃制品及用于涂覆玻璃制品的方法 (Glass article having a low friction coating and method for coating a glass article ) 是由 A·G·法捷耶夫 王吉 于 2018-11-29 设计创作，主要内容包括：提供了用于形成具有低摩擦涂层的玻璃容器的方法。方法包括：使玻璃管与偶联剂溶液接触以形成具有偶联剂层的经涂覆的玻璃管,其中,所述偶联剂包括无机材料,使经涂覆的玻璃管与至少一种牺牲材料接触以形成至少部分覆盖偶联剂层的牺牲层,在使经涂覆的玻璃管与至少一种牺牲材料接触后,由经涂覆的玻璃管形成至少一个经涂覆的玻璃容器,所述至少一个经涂覆的玻璃容器包括偶联剂层,在离子交换盐浴中对所述至少一个经涂覆的玻璃容器进行离子交换强化,以及向所述至少一个经涂覆的玻璃容器施涂聚合物化学成分溶液以形成低摩擦涂层。(A method for forming a glass container having a low friction coating is provided. The method comprises the following steps: contacting a glass tube with a coupling agent solution to form a coated glass tube having a coupling agent layer, wherein the coupling agent comprises an inorganic material, contacting the coated glass tube with at least one sacrificial material to form a sacrificial layer at least partially covering the coupling agent layer, forming at least one coated glass container from the coated glass tube after contacting the coated glass tube with the at least one sacrificial material, the at least one coated glass container comprising the coupling agent layer, ion exchange strengthening the at least one coated glass container in an ion exchange salt bath, and applying a polymer chemical composition solution to the at least one coated glass container to form a low friction coating.)

1. A method for forming a glass container having a low friction coating, the method comprising:

contacting a glass tube with a coupling agent solution to form a coated glass tube having a coupling agent layer, wherein the coupling agent comprises an inorganic material;

contacting the coated glass tube with at least one sacrificial material to form a sacrificial layer at least partially covering the coupling agent layer;

forming at least one coated glass container from the coated glass tube after contacting the coated glass tube with the at least one sacrificial material, the at least one coated glass container comprising a coupling agent layer;

ion-exchange strengthening the at least one coated glass container in an ion-exchange salt bath; and

applying a polymer chemical solution to the at least one coated glass container to form a low friction coating.

2. The method of claim 1, wherein contacting the glass tube with the coupling agent solution comprises: the glass tube was immersed in a dilute solution containing a coupling agent.

3. The method of any of the preceding claims, wherein contacting the glass tube with the coupling agent solution comprises: chemical vapor deposition of dilute solutions containing a coupling agent.

4. The method of any of the preceding claims, wherein the coupling agent layer comprises a thickness of less than about 1 μ ι η.

5. The method of any of the preceding claims, wherein the coupling agent layer comprises a discontinuous layer.

6. A method as claimed in any preceding claim, wherein the sacrificial material comprises a lubricant.

7. The method of any one of the preceding claims, wherein the sacrificial material is selected from the group consisting of: water-soluble materials, water-insoluble materials, and fatty acids.

8. The method of any of the preceding claims, wherein forming at least one coated glass container from the coated glass tube further comprises: the sacrificial layer is removed from the coated glass tube.

9. The method of any one of the preceding claims, wherein the inorganic material is selected from the group consisting of: titanates, zirconates, tin, titanium, and oxides thereof.

10. The method of any of the preceding claims, wherein the glass tube comprises a glass composition capable of ion exchange.

11. The method of any of the preceding claims, wherein the glass tube comprises a type 1B glass composition.

12. The method of any of the preceding claims, wherein the coupling agent layer is in direct contact with the outer surface of the at least one coated glass container.

13. The method of any of the preceding claims, wherein applying the polymer chemical composition solution to the at least one coated glass container comprises: the coupling agent layer is contacted directly with the solution of the polymer chemical composition.

14. The method of any one of the preceding claims, wherein the polymer chemistry is selected from the group consisting of: polyimides, polybenzimidazoles, polysulfones, polyether ether ketones, polyetherimides, polyamides, polyphenylenes, polybenzothiazoles, polybenzoxazoles, polybisthiazoles, polyaromatic heterocyclic polymers with and without organic or inorganic fillers, and mixtures thereof.

15. The method of any of the preceding claims, wherein the polymer chemistry solution comprises a polymerizable monomer, and wherein applying the polymer chemistry solution to the at least one coated glass container further comprises: the polymer chemical composition solution is cured.

16. The method of any of the preceding claims, wherein the polymer chemical composition solution comprises a polymeric composition.

17. The method of any one of the preceding claims, wherein the ion exchange salt bath comprises a molten salt.

18. The method of claim 17, wherein the molten salt is selected from the group consisting of: KNO₃、NaNO₃And combinations thereof.

19. The method of any of the preceding claims, wherein ion exchange strengthening the at least one coated glass container comprises: a depth of layer of up to about 50 μm and a compressive stress of at least about 300MPa are formed in the at least one glass container.

20. The method of any of the preceding claims, wherein ion exchange strengthening the at least one coated glass container comprises: the at least one glass container is held in the ion-exchange salt bath for less than about 30 hours.

21. The method of any of the preceding claims, wherein the coated glass container is selected from the group consisting of: vials, ampoules, cartridges, and syringe bodies.

22. A coated glass article comprising a coupling agent layer, wherein the coated glass article is a glass tube comprising a pharmaceutical glass, and wherein the coupling agent comprises an inorganic material.

23. The coated glass article of claim 22, wherein the coupling agent layer comprises a thickness of less than about 1 μ ι η.

24. The coated glass article of any of claims 22-23, wherein the coupling agent layer comprises a discontinuous layer.

25. The coated glass article of any of claims 22-24, further comprising a sacrificial layer at least partially covering the coupling agent layer.

26. The coated glass article of claim 25, wherein the sacrificial layer comprises a sacrificial material comprising a lubricant.

27. The coated glass article of claim 25, wherein the sacrificial layer comprises a sacrificial material selected from the group consisting of: water-soluble materials, water-insoluble materials, and fatty acids.

28. The coated glass article of any of claims 22-27, wherein the inorganic material is selected from the group consisting of: titanates, zirconates, tin, titanium, and oxides thereof.

29. The coated glass article of any of claims 22-28, wherein the medicinal glass comprises an ion-exchangeable glass composition.

30. The coated glass article of any of claims 22-29, wherein the pharmaceutical glass comprises a type 1B glass composition.

Technical Field

The present disclosure relates generally to coatings, and more particularly, to low friction coatings applied to glass articles, such as pharmaceutical packaging.

Background

Historically, glass has been used as a preferred material for many applications, including food and beverage packaging, pharmaceutical packaging, kitchen and laboratory glassware and windows or other architectural features, due to its gas tightness, optical clarity and excellent chemical durability relative to other materials.

However, the use of glass for many applications is limited by the mechanical properties of the glass. In particular, glass breakage is an anxiety problem, especially in the packaging of foods, beverages and pharmaceuticals. In the food, beverage and pharmaceutical packaging industry, the cost of rupturing may be high because rupturing, for example, in a filling line may require discarding an adjacent, uncracked container because the container may contain fragments from the ruptured container. Cracking also requires that the filling line be slowed or stopped, thus reducing throughput. Furthermore, non-catastrophic breakage (i.e., when the glass is cracked but not broken) can cause the contents of the glass package or container to lose their sterility, which in turn can lead to costly product recalls.

One root cause of glass breakage is the introduction of flaws in the surface of the glass during processing and/or subsequent filling of the glass. These flaws may be introduced into the surface of the glass from a variety of sources, including contact between adjacent pieces of glassware and contact between the glass and equipment (e.g., handling and/or filling equipment). Regardless of the source, the presence of these flaws can ultimately lead to glass breakage.

The ion exchange treatment is a process for strengthening a glass article. Ion exchange imparts compression (i.e., compressive stress) onto the surface of the glass article by chemically replacing smaller ions within the glass article with larger ions from the molten salt bath. The compression on the surface of the glass article raises the mechanical stress threshold for crack propagation, thereby increasing the overall strength of the glass article. In addition, the addition of a coating to the surface of the glass article may also increase damage resistance and impart improved strength and durability to the glass article.

Disclosure of Invention

In accordance with embodiments of the present disclosure, methods for forming glass containers with low friction coatings are provided. The method comprises the following steps: contacting a glass tube with a coupling agent solution to form a coated glass tube having a coupling agent layer, wherein the coupling agent comprises an inorganic material, contacting the coated glass tube with at least one sacrificial material to form a sacrificial layer at least partially covering the coupling agent layer, subsequently contacting the coated glass tube with the at least one sacrificial material to form at least one coated glass container from the coated glass tube, the at least one coated glass container comprising the coupling agent layer, ion exchange strengthening the at least one coated glass container in an ion exchange salt bath, and applying a polymer chemical composition solution to the at least one coated glass container to form a low friction coating.

In accordance with an embodiment of the present disclosure, a coated glass article is provided. The coated glass article includes a coupling agent layer, wherein the coated glass article is a glass tube comprising a pharmaceutical glass, and wherein the coupling agent includes an inorganic material.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the various embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and are intended to provide an overview or framework for understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments and, together with the description, serve to explain the principles and operations of the various embodiments.

Drawings

The disclosure will be understood more clearly from the following description and from the drawings, given purely by way of non-limiting example, in which:

FIG. 1 schematically depicts a cross-sectional view of a glass container having a low-friction coating, in accordance with an embodiment of the present disclosure;

FIG. 2 schematically depicts a cross-sectional view of a glass container having a low-friction coating with a polymer layer and a coupling agent layer, according to an embodiment of the disclosure;

FIG. 3 schematically depicts a cross-sectional view of a glass container having a low-friction coating with a polymer layer, a coupling agent layer, and an intervening layer, according to an embodiment of the disclosure;

FIG. 4 illustrates one example of a diamine monomer chemistry, in accordance with an embodiment of the present disclosure;

FIG. 5 illustrates one example of a diamine monomer chemistry, in accordance with an embodiment of the present disclosure;

FIG. 6 depicts the chemical structure of monomers that can be used as a polyimide coating applied to a glass container, according to an embodiment of the present disclosure;

FIG. 7 is a flow chart of a method for forming a glass container with a low friction coating according to an embodiment of the present disclosure;

FIG. 8 schematically depicts steps of the flowchart of FIG. 7, in accordance with an embodiment of the present disclosure;

FIG. 9 illustrates SnO on a 1.00 μm scale on a glass article, according to embodiments of the present disclosure₂SEM image on layer; and

FIG. 10 illustrates 500 nm-scale SnO on a glass article, according to embodiments of the present disclosure₂SEM image on layer.

Detailed Description

Reference will now be made in detail to embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The endpoints of all ranges reciting the same characteristic are independently combinable and inclusive of the recited endpoint. All references are incorporated herein by reference.

As used herein, "having," containing, "" including, "" containing, "and the like are used in their open-ended sense, and typically mean" including, but not limited to.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood in the art. The definitions provided herein are to aid in understanding certain terms used frequently herein and are not to be construed as limiting the scope of the present disclosure.

The present disclosure is first described generally below, and then described in detail on the basis of several exemplary embodiments. The features shown in combination with one another in the various exemplary embodiments do not all have to be realized. In particular, individual features may also be omitted or combined in other ways with other features shown in the same exemplary embodiment or in other exemplary embodiments.

Embodiments of the present disclosure relate to low friction coatings, glass articles having low friction coatings, and methods of producing the same, examples of which are schematically depicted in the accompanying drawings. Such coated glass articles may be glass containers suitable for various packaging applications, including but not limited to as pharmaceutical packaging. These pharmaceutical packages may or may not contain a pharmaceutical composition. While embodiments of the low friction coating described herein are applied to the outer surface of a glass container, it is understood that the low friction coating described herein may be used as a coating on a wide variety of materials, including non-glass materials, as well as on substrates other than containers, including but not limited to glass display panels and the like.

In general, a low friction coating may be applied to the surface of a glass article, which may be used, for example, as a container for pharmaceutical packaging. The low friction coating can provide advantageous properties to the coated glass article, such as a reduced coefficient of friction and increased damage resistance. The reduced coefficient of friction may impart improved strength and durability to the glass article by mitigating frictional damage to the glass. Further, the low friction coating may maintain the above-described improved strength and durability after exposure to elevated temperatures and other conditions, such as those experienced during packaging and pre-packaging steps employed in packaging pharmaceuticals, e.g., depyrogenation, autoclaving, and the like. In addition, the low coefficient of friction coatings described herein may allow for more consistent and predictable alignment of the coated glass articles (as provided by the coatings) during the filling and packaging steps, which in turn may allow for fewer instrument interruptions, downtime, clogging, while enabling higher processing speeds. Thus, the low friction coating and the glass article having the low friction coating are thermally stable.

The low friction coating may generally comprise a coupling agent, such as a metal oxide, and a polymeric chemical component, such as polyimide. The coupling agent can be disposed in a coupling agent layer on a surface of the glass article, and the polymer chemical constituent can be disposed in a polymer layer on the coupling agent layer.

Fig. 1 schematically depicts a cross-sectional view of a coated glass article, in particular a coated glass container 100. The coated glass container 100 includes a glass body 102 and a low friction coating 120. The glass body 102 has a glass vessel wall 104 extending between an outer surface 108 (i.e., a first surface) and an inner surface 110 (i.e., a second surface). The inner surface 110 of the glass container wall 104 defines the interior volume 106 of the coated glass container 100. The low friction coating 120 is located on at least a portion of the outer surface 108 of the glass body 102. The low-friction coating 120 can be located on substantially the entire outer surface 108 of the glass body 102. The low friction coating 120 has an outer surface 122 and a surface 124 that contacts the glass body at the interface of the glass body 102 and the low friction coating 120. The low friction coating 120 can be bonded to the glass body 102 at the outer surface 108.

According to embodiments of the present disclosure, the coated glass container 100 may be a pharmaceutical package. For example, the glass body 102 may be in the following shape: vials, ampoules, bottles, cartridges, flasks, vials, beakers, buckets, glass bottles, jars, syringe bodies, and the like. The coated glass container 100 may be used to contain any composition, for example, a pharmaceutical composition. The pharmaceutical composition may comprise any chemical substance intended for medical diagnosis, cure, treatment or prevention of a disease. Examples of pharmaceutical compositions include, but are not limited to, drugs, medicaments, medicinal agents, and the like. The pharmaceutical compositions may be in the form of liquids, solids, gels, suspensions, powders, and the like.

Referring now to fig. 1 and 2, the low friction coating 120 may comprise a bilayer structure, according to embodiments of the present disclosure. Fig. 2 shows a cross-sectional view of a coated glass container 100 having a low-friction coating 120, the low-friction coating 120 comprising a polymer layer 170 and a coupling agent layer 180. The polymer layer 170 may include a polymer chemical component therein, and the coupling agent layer 180 may include a coupling agent therein. The coupling agent layer 180 may be in direct contact with the outer surface 108 of the glass vessel wall 104. The polymer layer 170 may be in direct contact with the coupling agent layer 180 and may form the outer surface 122 of the low friction coating 120. The coupling agent layer 180 can be bonded to the glass wall 104, and the polymer layer 170 can be bonded and/or mechanically coupled to the coupling agent layer 180 at the interface. According to embodiments of the present disclosure, the polymer layer may be located above the coupling agent layer, meaning that the polymer layer 170 is in an outer layer relative to the coupling agent layer 180 and the glass wall 104. As used herein, a first layer "over" a second layer means that the first layer is in direct contact with the second layer or is spaced apart from the second layer, e.g., a third layer is disposed between the first and second layers.

Referring now to fig. 3, the low friction coating 120 can also include an intervening layer 190 between the coupling agent layer 180 and the polymer layer 170. The intervening layer 190 may comprise one or more chemical constituents in the polymer layer 170 and one or more chemical constituents in the coupling agent layer 180. The interface of the coupling agent layer and the polymer layer forms an intervening layer 190, in which intervening layer 190 bonding and/or mechanical coupling between the polymer chemical constituent and the coupling agent occurs. It is understood, however, that there may be no significant layer at the interface of the coupling agent layer 180 and the polymer layer 170 where the polymer and coupling agent are chemically and/or mechanically bonded to each other as described above with reference to fig. 2.

The thickness of the low friction coating 120 may be less than about 100 μm or even less than or equal to about 1 μm. For example, the thickness of the low friction coating 120 may be less than or equal to about 100nm, or less than about 90nm thick, or less than about 80nm thick, or less than about 70nm thick, or less than about 60nm thick, or less than about 50nm, or even less than about 25nm thick. The low-friction coating 120 may not be of uniform thickness throughout the glass body 102. For example, the coated glass container 100 may have a thicker low friction coating 120 in some areas due to the process of contacting the glass body 102 with one or more coating solutions that form the low friction coating 120. In addition, the low friction coating 120 may have a non-uniform thickness. For example, the coating thickness may vary over different regions of the coated glass container 100, which may help protect in selected regions of the glass body 102.

In the case where the low friction coating 120 comprises at least two layers (e.g., the polymer layer 170, the intervening layer 190, and/or the coupling agent layer 180), each layer may have a thickness of less than about 100 μm or even less than or equal to about 1 μm. For example, the thickness of each layer may be less than or equal to about 100nm, or less than about 90nm thick, or less than about 80nm thick, or less than about 70nm thick, or less than about 60nm thick, or less than about 50nm, or even less than about 25nm thick. According to embodiments of the present disclosure, the coupling agent layer 180 may be a discontinuous layer. As used herein, the term "discontinuous layer" means a layer of material having at least two separate and distinct islands with empty space between them, wherein the at least two separate and distinct islands with empty space between them are in a given plane.

As described herein, the coupling agent may improve adhesion or bonding of the polymer chemistry to the glass body 102 and is generally disposed between the glass body 102 and the polymer chemistry. Adhesion as used herein refers to the strength of the adhesion or bond of the low friction coating 120 before and after a treatment (e.g., heat treatment) is applied to the coated glass container 100. Thermal treatments include, but are not limited to, autoclaving, depyrogenation, lyophilization, and the like.

According to embodiments of the present disclosure, the coupling agent may be an inorganic material, such as a metal, metal oxide, and/or ceramic membrane. Non-limiting examples of suitable inorganic materials for use as coupling agents include titanates, zirconates, tin, titanium, and/or oxides thereof.

The coupling agent may be applied to the outer surface 108 of the glass body 102 by a dipping process that contacts the glass body 102 with a dilute solution containing the coupling agent. When applied to the glass body 102, the coupling agent may be mixed in a solvent. Alternatively, the coupling agent may be applied to the glass body 102 by sputtering, spray pyrolysis, and Chemical Vapor Deposition (CVD). The glass body 102 with the coupling agent may then be subjected to a temperature and for any time sufficient to substantially release water and/or other organic solvents present on the outer surface 108 of the glass container wall 104.

As described herein, the low friction coating also includes a polymer chemistry. The polymer chemistry can be a thermally stable polymer or mixture of polymers such as, but not limited to, fluorinated polymers, polyimides, polybenzimidazoles, polysulfones, polyetheretherketones, polyetherimides, polyamides, polyphenyls, polybenzothiazoles, polybenzoxazoles, polybisthiazoles, and polyaromatic heterocyclic polymers with and without organic or inorganic fillers.

The polymer chemistry may be a polyimide chemistry. If the low friction coating 120 comprises polyimide, the polyimide component can be derived from a polyamic acid formed in solution by polymerization of a monomer. One such polyamic acid is800 (commercially available from NeXolve corporation). The curing step imidizes the polyamic acid to form a polyimide. Polyamic acids can be formed from the reaction of a diamine monomer (e.g., a diamine) and an anhydride monomer (e.g., a dianhydride). As used herein, polyimide monomers are described as diamine monomers and dianhydride monomers. It is to be understood, however, that while the diamine monomer has two amine moieties, in the following description, any monomer having at least two amine moieties may be suitable as the diamine monomer. Similarly, it is to be understood that while the dianhydride monomer has two anhydride moieties, in the description below, any monomer having at least two anhydride moieties may be suitable as the dianhydride monomer. The reaction between the anhydride moieties of the anhydride monomers and the amine moieties of the diamine monomers forms the polyamic acid. Thus, as used herein, a polyimide chemical component formed by polymerization of a specified monomer refers to a polyimide formed from a polyamic acid formed from the specified monomer after imidization. Generally, the molar ratio of total anhydride monomer to diamine monomer can be about 1: 1. Although the polyimide may be formed from only two different chemical components (one being an anhydride monomer and one being a diamine monomer), at least one anhydride monomer may be polymerized, and may be polymerized toAt least one diamine monomer to form a polyimide. For example, one anhydride monomer may be polymerized with two different diamine monomers. Any number of monomer combinations may be used. Further, the ratio of one anhydride monomer to a different anhydride monomer, or the ratio of one or more diamine monomers to a different diamine monomer, can be any ratio, for example, about 1:0.1 to 0.1:1, such as about 1:9, 1:4, 3:7, 2:3, 1:1, 3:2, 7:3, 4:1, or 1: 9.

The anhydride monomer that forms the polyimide with the diamine monomer can be any anhydride monomer and can include a benzophenone structure. The diamine monomer may have an anthracene structure, a phenanthrene structure, a pyrene structure or a pentacene structure, including substituted forms of the dianhydrides mentioned above.

The diamine monomer that forms the polyimide with the anhydride monomer may include any diamine monomer. For example, the diamine monomer may include at least one aromatic ring moiety. Fig. 4 and 5 illustrate examples of diamine monomers that, together with one or more selected anhydride monomers, can form a polyimide in a polymer chemistry. The diamine monomer may have one or more carbon molecules linking two aromatic ring moieties as shown in fig. 4, where R of fig. 5 corresponds to an alkyl moiety comprising one or more carbon atoms. Alternatively, the diamine monomer may have two aromatic ring moieties that are directly connected and not separated by at least one carbon molecule as shown in FIG. 5. The diamine monomer may have one or more alkyl moieties as represented by R 'and R' in FIGS. 4 and 5. For example, in fig. 4 and 5, R' and R "may represent alkyl moieties, such as methyl, ethyl, propyl, or butyl moieties, bonded to one or more aromatic ring moieties. For example, a diamine monomer may have two aromatic ring moieties, wherein each aromatic ring moiety has an alkyl moiety attached thereto and an adjacent amine moiety attached to the aromatic ring moiety. It is to be understood that in fig. 4 and 5, R' and R "may be the same chemical moiety or may be different chemical moieties. Alternatively, in fig. 4 and 5, R' and/or R "may represent the complete absence of atoms.

The chemical composition of the two different diamine monomers can form a polyimide. The first diamine monomer may comprise two aromatic ring moieties that are directly linked and not separated by a linking carbon molecule, while the second diamine monomer may comprise two aromatic ring moieties that are linked to at least one carbon molecule that links the two aromatic ring moieties. According to embodiments of the present disclosure, the molar ratio of the first diamine monomer, the second diamine monomer, and the anhydride monomer (first diamine monomer: second diamine monomer: anhydride monomer) may be about 0.465:0.035: 0.5. However, the ratio of the first diamine monomer to the second diamine monomer can vary from about 0.01:0.49 to about 0.40:0.10 while the ratio of the anhydride monomer is maintained at about 0.5.

According to embodiments of the present disclosure, the polyimide component may be formed from the polymerization of at least a first diamine monomer, a second diamine monomer, and an anhydride monomer, wherein the first diamine monomer and the second diamine monomer are different chemical components. The anhydride monomer may be a benzophenone, the first diamine monomer includes two aromatic rings bonded together directly, and the second diamine monomer includes two aromatic rings bonded together with at least one carbon molecule connecting the first aromatic ring and the second aromatic ring. The molar ratio of the first diamine monomer, the second diamine monomer, and the anhydride monomer (first diamine monomer: second diamine monomer: anhydride monomer) may be about 0.465:0.035: 0.5.

For example, the first diamine monomer can be ortho-tolidine, the second diamine monomer can be 4,4' -methylene-bis (2-methylaniline), and the anhydride monomer can be benzophenone-3, 3 ', 4,4' -tetracarboxylic dianhydride. The molar ratio of the first diamine monomer, the second diamine monomer, and the anhydride monomer (first diamine monomer: second diamine monomer: anhydride monomer) may be about 0.465:0.035: 0.5.

For example, the polyimide may be formed by polymerization of one or more of the following: 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic dianhydride, cyclopentane-1, 2,3, 4-tetracarboxylic dianhydride 1, 2; 3, 4-dianhydride, bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic dianhydride, 4arH,8acH) -decahydro-1 t,4t:5c,8 c-dimethylnaphthalene-2 t,3t,6c,7 c-tetracarboxylic 2,3:6, 7-dianhydride, 2c,3c,6c,7 c-tetracarboxylic 2,3:6, 7-dianhydride, 5-endo-carboxymethylbicyclo [2.2.1] -heptane-2-exo, 3-exo, 5-exo-tricarboxylic acid 2,3:5, 5-dianhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, bis (aminomethyl) bicyclo [2.2.1] heptane or 4, isomers of 4' -methylenebis (2-methylcyclohexylamine), pyromellitic dianhydride (PMDA)3,3 ', 4,4' -biphenyl dianhydride (4, 4' -BPDA), 3,3 ', 4,4' -benzophenone dianhydride (4, 4' -BTDA), 3,3 ', 4,4' -oxydiphthalic anhydride (4, 4' -ODPA),1, 4-bis (3, 4-dicarboxy-phenoxy) benzene dianhydride (4, 4' -HQDPA), 1, 3-bis (2, 3-dicarboxy-phenoxy) benzene dianhydride (3,3 ' -HQDPA), 4,4' -bis (3, 4-dicarboxyphenoxyphenyl) -isopropylidene dianhydride (4, 4' -BPADA), 4,4' - (2,2, 2-trifluoro-1-pentafluorophenylethylene) diphthalic dianhydride (3FDA), 4,4' -Oxydianiline (ODA), m-phenylenediamine (MPD), p-phenylenediamine (PPD), m-Toluenediamine (TDA), 1, 4-bis (4-aminophenoxy) benzene (1,4,4-APB), 3,3 ' - (m-phenylenebis (oxy)) diphenylamine (APB), 4,4' -diamino-3, 3 ' -dimethyldiphenylmethane (DMMDA), 2,2 ' -bis (4- (4-aminophenoxy) phenyl) propane (BAPP), 1, 4-cyclohexanediamine 2,2 ' -bis [4- (4-amino-phenoxy) phenyl ] hexafluoroisopropylidene (4-BDAF), 6-amino-1- (4 ' -aminophenyl) -1,3, 3-trimethylindane (DAPI), maleic Anhydride (MA), Citraconic Anhydride (CA), Nadic Anhydride (NA), 4- (phenylethynyl) -1, 2-benzenedicarboxylic anhydride (PEPA), 4,4' -Diaminobenzanilide (DABA), 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6-FDA), pyromellitic dianhydride, benzophenone-3, 3 ', 4,4' -tetracarboxylic dianhydride, 3,3 ', 4,4' -diphenyltetracarboxylic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, perylene-3, 4,9, 10-tetracarboxylic dianhydride, 4,4' -oxydiphthalic anhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 4,4' - (4, 4' -isopropylidene) diphenoxy) bis (phthalic anhydride), 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, and those described in U.S. patent No. 7,619,042, U.S. patent No. 8,053,492, U.S. patent No. 4,880,895, U.S. patent No. 6,232,428, U.S. patent No. 4,595,548, international publication No. 2007/016516, U.S. patent publication No. 2008/0214777, U.S. patent No. 6,444,783, U.S. patent No. 6,277,950, and U.S. patent No. 4,680,373, the contents of which are incorporated herein by reference in their entirety. Fig. 6 depicts the chemical structure of some suitable monomers that may be used to form a polyimide coating applied to the glass body 102. As another example, the polyamic acid solution that forms the polyimide may include poly (pyromellitic dianhydride-co-4, 4' -oxydianiline) amic acid (commercially available from Aldrich).

According to embodiments of the present disclosure, the polymer chemistry may include a fluoropolymer. The fluoropolymer may be a copolymer in which both monomers are highly fluorinated. Some of the monomers of the fluoropolymer may be vinyl fluoride. The polymer chemistry may include an amorphous fluoropolymer such as, but not limited to, Teflon (Teflon) AF (commercially available from DuPont). Alternatively, the polymer chemistry may include Perfluoroalkoxy (PFA) resin particles, such as, but not limited to, Teflon PFA TE-7224 (commercially available from DuPont).

According to embodiments of the present disclosure, the polymer chemistry may include a silicone resin. The silicone resin may be a highly branched three-dimensional polymer formed by branched, cage-like oligosiloxanes and having the general formula R_nSi(X)_mO_yWherein R is a non-reactive substituent, typically methyl or phenyl, and X is OH or H. While not wishing to be bound by theory, it is believed that curing of the resin occurs through condensation reactions of Si-OH moieties to form Si-O-Si bonds. The silicone resin may have at least one of four possible functional siloxane monomer units, including M-resins, D-resins, T-resins, and Q-resins, where M-resin refers to a monomer having the general formula R₃SiO resin, D-resin means a resin having the general formula R₂SiO₂The T-resin is a resin having the general formula RSiO₃And Q-resin means a resin having the general formula SiO₄(fused quartz) resin. Optionally, the resin is made of D and T units (DT resin) or of M and Q units (MQ resin). Other combinations (MDT, MTQ, QDT) may also be used.

According to embodiments of the present disclosure, the polymer chemistry may include phenylmethylsilicone resins because they have higher thermal stability than methyl or phenyl silicone resins. The ratio of phenyl to methyl moieties in the silicone resin can vary in the polymer chemistry. For example, the ratio of phenyl to methyl may be about 1.2, or about 0.84, or about 0.5, or about 0.6, or about 0.7, or about 0.8, or about 0.9, or about 1.0, or about 1.1, or about 1.3, or about 1.4, or about 1.5. The silicone resin may be, but is not limited to, DC 255 (commercially available from Dow Corning), DC806A (commercially available from Dow Corning), any of the DC series of resins (commercially available from Dow Corning), and/or the HARDSIL series of AP and AR resins (commercially available from Gelest). The silicone resin may be used without a coupling agent or with a coupling agent.

According to embodiments of the present disclosure, the polymer chemistry may include silsesquioxane-based polymers such as, but not limited to, T-214 (commercially available from Honeywell, Inc.), SST-3M01 (commercially available from Gelest, Inc.), POSS IMICLEAR (commercially available from Hybrid Plastics, Inc.), and FOX-25 (commercially available from Dow Corning, Inc.). The polymer chemistry may include a silanol moiety.

The polymer chemistry may be polyimide, wherein a polyamic acid solution is applied to the coupling agent layer 180. Alternatively, a polyamic acid derivative, for example, polyamic acid salt, polyamic acid ester, or the like can be used. The polyamic acid solution may include a mixture of 1 vol% polyamic acid and 99 vol% organic solvent. The organic solvent may include a mixture of toluene and at least one of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), and 1-methyl-2-pyrrolidone (NMP) solvents or a mixture thereof. The solution of organic solvent may include about 85% by volume of at least one of DMAc, DMF, and NMP and about 15% by volume of toluene. However, other suitable organic solvents may be used. The coated glass container 100 may then be dried at about 150 c for about 20 minutes, or at any temperature and for any time sufficient to substantially release the organic solvent present in the low friction coating 120.

As will be described in greater detail below, embodiments of the present disclosure enable application of a polymeric chemical constituent in polymerized form on the coupling agent layer 180 and without curing. For example, instead of applying a polyamic acid to the glass container 100 and curing to form a polyimide, the polyimide may be applied directly onto the coupling agent layer 180. Such application of the polymer chemistry in polymerized form reduces the need to expose the glass container 100 to high curing temperatures (e.g., temperatures greater than about 300 ℃) during coating of the glass container 100, which reduces the amount of time necessary to form the glass container and reduces the costs associated with such formation.

The glass container to which the low friction coating 120 may be applied may be formed from a variety of different glass compositions. The particular composition of the glass article can be selected to provide a desired set of physical properties to the glass, depending on the particular application.

The glass container may be made of a material having a coefficient of thermal expansion of about 25x10^-7From/° C to 80x10^-7A glass composition in the range/° c. For example, the glass body 102 may be formed from an alkali aluminosilicate glass composition that withstands ion exchange strengthening. Such compositions generally comprise SiO₂、Al₂O₃At least one alkaline earth metal oxide and one or more alkali metal oxides (e.g., Na)₂O and/or K₂O) in combination. The glass composition may be free of boron and boron-containing compounds. In addition, the glass composition may further comprise minor amounts of one or more additional oxides, such as SnO₂、ZrO₂、ZnO、TiO₂、As₂O₃And the like. These components may be added as fining agents and/or to further enhance the chemical durability of the glass composition. In addition, the glass surface may comprise a glass containing SnO₂、ZrO₂、ZnO、TiO₂、As₂O₃And the like.

According to embodiments of the present disclosure, the glass body 102 may be strengthened, for example, by ion exchange, which is referred to herein as "ion exchange glass. For example, the compressive stress of the glass body 102 may be greater than or equal to about 300MPa, or even greater than or equal to about 350MPa, or the compressive stress may range from about 300MPa to about 900MPaAnd (4) the following steps. It is understood that the compressive stress in the glass may be less than 300MPa or greater than 900 MPa. The depth of layer of the glass bodies 102 described herein can be greater than or equal to about 20 μm. For example, the depth of layer may be greater than about 50 μm, or greater than or equal to about 75 μm, or even greater than about 100 μm. The ion exchange strengthening may be performed in a molten salt bath maintained at a temperature of about 350 ℃ to about 500 ℃. To achieve the desired compressive stress, the glass container coated with the coupling agent layer may be immersed in the salt bath for less than about 30 hours or even less than about 20 hours. For example, the glass container may be submerged at 100% KNO at 450 ℃₃The salt bath was left for about 8 hours.

As a non-limiting example, the Glass body 102 can be formed from an ion-exchangeable Glass composition described in pending U.S. patent No. 8,753,994 entitled "Glass Compositions with Improved Chemical and Mechanical Durability" assigned to Corning Incorporated, which is Incorporated herein by reference in its entirety.

It is understood, however, that the coated glass container 100 described herein may be formed from other glass compositions, including but not limited to ion-exchangeable glass compositions and non-ion-exchangeable glass compositions. For example, the glass container may be formed from a type 1B glass composition, such as a type 1B aluminosilicate glass by schottky corporation.

According to embodiments of the present disclosure, a glass article may be formed from a glass composition that meets pharmaceutical glass standards written by regulatory bodies, such as USP (united states pharmacopeia), EP (european pharmacopeia), and JP (japanese pharmacopeia), based on the hydrolysis resistance of pharmaceutical glass. According to USP 660 and EP 7, borosilicate glasses meet the type I standard and are routinely used for parenteral packaging. Examples of borosilicate glasses include, but are not limited to7740,7800 and Wheaton 180, 200 and 400, Schottky Duran, Schottky Filox, Kitthikaron, Kitthi,

N-51A, Grace ham (Gerrescheimer) GX-51Flint, and others. Soda lime glass meets the type III criteria and is acceptable in packaging dry powders that are subsequently dissolved to form a solution or buffer. Type III glass is also suitable for packaging liquid formulations that prove to be insensitive to alkali. Examples of type III soda lime glasses include wheaton 800 and 900. The dealkalized soda-lime glass has higher sodium hydroxide and calcium oxide levels and meets the type II standard. These glasses are less resistant to leaching than type I glasses but are more resistant than type III glasses. Type II glass can be used in products that maintain a pH below 7 during shelf life. Examples include soda lime glass treated with ammonium sulfate. These pharmaceutical glasses have different chemical compositions and a coefficient of linear thermal expansion (CTE) of 20-85x 10^-7℃^-1Within the range of (1).

When the coated glass article described herein is a glass container, the glass body 102 of the coated glass container 100 can take a variety of different forms. For example, the glass bodies described herein may be used to form coated glass containers 100, such as vials, ampoules, cartridges, syringe bodies, and/or any other glass container used to store a pharmaceutical composition. In addition, the ability to chemically strengthen the glass container prior to coating with the polymer layer 170 may be utilized to further improve the mechanical durability of the glass container. Thus, it will be appreciated that the glass container may be ion exchange strengthened prior to application of the polymer layer 170 of the low friction coating. Alternatively, other strengthening methods, such as thermal tempering, flame polishing, and lamination as described in U.S. patent No. 7,201,965 (the contents of which are incorporated herein by reference), may be used to strengthen the glass prior to coating.

According to embodiments of the present disclosure, the low friction coating may adhere more strongly to the ion-exchanged glass body than to the non-ion-exchanged glass body. Without being bound to any particular theory, it is believed that any of several aspects of the ion-exchanged glass may promote bonding and/or adhesion as compared to the non-ion-exchanged glass. First, the ion-exchanged glass can have enhanced chemical/hydrolytic stability, which can affect the stability of the coupling agent and/or the adhesion of the coupling agent to the glass surface. Non-ion-exchanged glasses typically have poor hydrolytic stability and alkali metals can migrate from the glass body to the interface of the glass surface and the coupling agent layer (if present) or even into the coupling agent layer (if present) under humid and/or high temperature conditions. If the alkali metal migrates as described above, and a change in pH occurs, hydrolysis of the Si-O-Si bond at the glass/coupling agent layer interface or in the coupling agent layer itself may weaken the mechanical properties of the coupling agent or its adhesion to the glass. Second, when the ion-exchanged glass is exposed to a strong oxidizing bath (e.g., a potassium nitrite bath) at high temperatures (e.g., 400 ℃ to 450 ℃), and the bath is removed, the organic chemical composition on the glass surface is removed, making it particularly suitable for coating with a coupling agent without further cleaning. For example, non-ion exchanged glass may need to be exposed to additional surface cleaning treatments, which increases the time and cost of the process.

Referring to fig. 7 and 8 together, fig. 7 contains a process flow diagram 500 of a method for producing a coated glass container 100 with a low friction coating, and fig. 8 schematically depicts the process described in this flow diagram. It should be understood that fig. 7 and 8 are merely exemplary of embodiments of the methods described herein and that not all of the steps shown need be performed, and that the steps of embodiments of the methods described herein need not be performed in any particular order.

According to an embodiment of the present disclosure, the method may include 501: the glass tube from which the glass body 102 may be formed is contacted with a coupling agent solution to form a coated glass tube blank 1000 having a coupling agent layer 180 (as described above). Contacting the glass tube blank with the coupling agent solution of 501 may comprise: the glass tube was immersed in a dilute solution containing a coupling agent. Alternatively, contacting the glass tube with the coupling agent of 501 may be performed using sputtering, spray pyrolysis, or Chemical Vapor Deposition (CVD). The thickness of the resulting coupling agent layer 180 may be less than about 100 μm or even less than or equal to about 1 μm. For example, the resulting coupling agent layer 180 may have a thickness of less than or equal to about 100nm, or less than about 90nm thick, or less than about 80nm thick, or less than about 70nm thick, or less than about 60nm thick, or less than about 50nm, or even less than about 25nm thick. According to embodiments of the present disclosure, the resulting coupling agent layer 180 may be a discontinuous layer. In the case where the coupling agent layer 180 is a continuous layer, the thickness of the coupling agent layer 180 may be a thickness that allows the glass container 900 containing the coupling agent layer 180 to be subsequently ion-exchange strengthened. In the case where the coupling agent layer 180 is a discontinuous layer, the empty spaces between the separate and distinct islands may facilitate ion exchange strengthening of the glass container 900.

The method may further include 502: the coated glass blank 1000 with the coupling agent layer 180 is contacted with at least one sacrificial material to form a sacrificial layer at least partially covering the coupling agent layer 180. Contacting the coated glass blank 1000 with the coupling agent layer 180 of 502 with at least one sacrificial material can comprise: a mist comprising the sacrificial material is sprayed onto the surface of the coupling agent layer 180 at a temperature that is sufficiently high to vaporize the droplets. The resulting sacrificial layer is a thin film that is not water-soluble and provides lubricity to the surface of the coated glass blank 1000 having the coupling agent layer 180. As used herein, the term "sacrificial layer" refers to a layer disposed on any substrate surface that is intended to cover the substrate surface and thereby isolate the substrate surface from ambient conditions. The purpose of this isolation may be to protect the substrate surface from environmental conditions. While providing such protection, the sacrificial layer, as the name implies, may be sacrificial, i.e., damaged, destroyed, or removed from the substrate surface. The sacrificial layer may advantageously improve the damage tolerance of the coated glass tubing 1000 when the coated glass tubing 1000 is moved, transported and/or handled in the method for producing the coated glass container 100.

The sacrificial layer may be a liquid or wax material that forms a thin layer when the coated glass blank 1000 with the coupling agent layer 180 is contacted with the at least one sacrificial material 502. The sacrificial material may also be selected such that no residue remains on the coated glass blank 1000 when the sacrificial layer is removed from the surface of the coupling agent layer 180. For example, the sacrificial material may be selected from water soluble materials, water insoluble materials or fatty acids. Exemplary water-soluble materials include, but are not limited to, salts of stearic acid and polyvinyl sorbitol esters, e.g., polysorbate 80 and TWEEN 20. Exemplary water insoluble materials include, but are not limited to, polymers and copolymers of polyethylene glycols, propylene oxide, and ethylene. Exemplary fatty acids include, but are not limited to, oleic acid and stearic acid. Other examples of sacrificial materials include glass-forming lubricants described in U.S. patent No. 8,865,884, the contents of which are incorporated herein by reference in their entirety.

The method may further include 503: a glass container 900 (specifically a glass vial in the example shown in fig. 8) is formed from a coated glass blank 1000, the coated glass blank 1000 having an ion-exchangeable glass composition. 503 forming the glass container 900 may utilize conventional forming and forming techniques. During the forming of 503, the sacrificial layer is removed from the surface of the coupling agent layer 180. For example, in the case where the sacrificial material is an organic material, the sacrificial layer may be removed as a result of the application of heat to the coated glass blank 1000 during the formation of the glass container 900 at 503.

The method may further include 504: the glass containers 900 are loaded into the storage rack 604 using a mechanical storage rack loader 602. The storage rack loader 602 may be a mechanical gripping device, such as a caliper or the like, that is capable of gripping multiple glass containers at a time. Alternatively, the gripping device may utilize a vacuum system to grip the glass container 900. The storage rack loader 602 may be connected to a robotic arm or other similar device capable of positioning the storage rack loader 602 relative to the glass containers 900 and the storage racks 604.

The method may further include 506: the storage rack 604 loaded with glass containers 900 is transferred to the cassette loading area. 506 may be transferred by a mechanical transfer device, such as a conveyor belt 606, an overhead crane, or the like. Subsequently, the method may include 508: the storage racks 604 are loaded into the cassette 608. The cassette 608 is configured to hold a plurality of storage racks so that a large number of glass containers can be processed simultaneously. Each storage rack 604 is placed in a cassette 608 using a cassette loader 610. The cassette loader 610 may be a mechanical gripping device, such as a caliper or the like, capable of gripping one or more storage racks at a time. Alternatively, the gripping device may utilize a vacuum system to grip the storage rack 604. The cassette loader 610 may be connected to a robotic arm or other similar device capable of positioning the cassette loader 610 relative to the cassette 608 and the storage shelf 604.

According to an embodiment of the present disclosure, the method may further include: 510: the cassette 608 containing the storage racks 604 and the glass containers 900 is loaded into the ion exchange tank 614 to facilitate chemical strengthening of the glass containers 900. The cassette 608 is transferred to the ion exchange station using a cassette transfer device 612. The cassette transfer device 612 may be a mechanical gripping device, such as a caliper or the like, capable of gripping the cassette 608. Alternatively, the gripping device may utilize a vacuum system to grip the cassette 608. The cassette transfer device 612 and attached cassette 608 may be automatically transported from the cassette loading area to the ion exchange station using an overhead rail system, such as a gantry crane or the like. The cassette transfer device 612 and attached cassette 608 may be transferred from the cassette loading area to the ion exchange station using a robotic arm. Alternatively, the cassette transfer device 612 and attached cassette 608 may be transferred from the cassette loading area to the ion exchange station using a conveyor, and then transferred from the conveyor to the ion exchange cell 614 using a robotic arm or overhead crane.

Once the cassette transfer device 612 and attached cassette are in the ion exchange station, the cassette 608 and glass container 900 contained therein may be preheated before the cassette 608 and glass container 900 are submerged in the ion exchange tank 614. The cartridge 608 may be preheated to a temperature greater than room temperature and less than or equal to the temperature of the molten salt bath in the ion exchange tank. For example, the glass container may be preheated to a temperature of about 300 ℃ to 500 ℃.

Ion exchange cell 614 may comprise a molten salt bath 616, e.g., a molten alkali metal salt, such as KNO₃、NaNO₃And/or combinations thereof. The molten salt bath is 100% molten KNO₃The temperature is maintained at greater than or equal to about 350 ℃ and less than or equal to about 500 ℃. However, it should be understood that various others may also be usedA bath of molten alkali metal salt of composition and/or temperature to facilitate ion exchange of the glass container.

The method may further include 512: the glass container 900 is ion-exchange strengthened in the ion-exchange tank 614. Specifically, the glass container is submerged in the molten salt and held there for a period of time sufficient to achieve the desired compressive stress and depth of layer in the glass container 900. For example, the glass container 900 may be held in the ion exchange tank 614 for a time sufficient to achieve a depth of layer of up to about 100 μm, and a compressive stress of at least about 300MPa or even 350 MPa. The holding time may be less than 30 hours or even less than 20 hours. It should be understood, however, that the time for which the glass containers are held in trough 614 may vary depending on the composition of the glass containers, the composition of molten salt bath 616, the temperature of molten salt bath 616, and the desired depth of layer and the desired compressive stress.

After ion exchange strengthening at 512, the cassette 608 and glass container 900 are removed from the ion exchange cell 614 using a cassette transfer device 612 in conjunction with a robotic arm or overhead crane. During removal from the ion exchange tank 614, the cassette 608 and glass container 900 are suspended above the ion exchange tank 614, and the cassette 608 is rotated about a horizontal axis to evacuate any molten salt remaining in the glass container 900 back into the ion exchange tank 614. The cassette 608 is then rotated back to its original position and the glass containers are allowed to cool before being cleaned.

The cassette 608 and glass container 900 are then transferred to a cleaning station using a cassette transfer device 612. As described above, the transfer may be performed using a robot arm or an overhead crane, or alternatively, using an automatic conveying device such as a conveyor belt or the like. Subsequently, the method may include 514: the cassette 608 and glass container 900 are cleaned by lowering them into a cleaning bath 618 containing a water bath 620 to remove any excess salt from the surface of the glass container 900. Cassette 608 and glass container 900 may be lowered into washing bath 618 using a robotic arm, overhead crane, or similar device connected to cassette transfer device 612. Next, the cassette 608 and glass container 900 are removed from the sink tank 618, suspended above the sink tank 618, and the cassette 608 is rotated about the horizontal axis to empty any wash water remaining in the glass container 900 back into the sink tank 618. Optionally, the cleaning operation may be performed multiple times before moving the cassette 608 and glass container 900 to the next processing station.

According to embodiments of the present disclosure, the cassette 608 and glass container 900 may be dipped into a water bath at least twice. For example, the cassette 608 may be immersed in a first water bath and subsequently, in a second, different water bath to ensure that all residual alkali metal salt is removed from the surface of the glass article. The water from the first water bath may be sent to a waste water treatment or evaporator.

The method may further include 516: the storage rack 604 is unloaded from the cassette 608 using a cassette loader 610. Subsequently, the method may include 518: the glass container 900 is transferred to a washing station. The glass containers 900 may be unloaded from the storage rack 604 using the storage rack loader 602 and transferred to a washing station where the method may further include 520: the glass container is washed with a jet 624 of deionized water emitted from a nozzle 622. The jet 624 of deionized water may be mixed with compressed air.

Optionally, the method may comprise: the glass container 900 is inspected (not shown in fig. 7 or 8) for flaws, chips, discoloration, etc. Inspecting the glass container 900 may include: the glass containers are transferred to a separate inspection area.

According to an embodiment of the present disclosure, the method may further include 521: the glass container 900 is transferred to a coating station using the storage rack loader 602 where a low friction coating is applied to the glass container 900. At the coating station, the method may include 522: a low friction coating as described herein is applied to the glass container 900. 522 applying the low friction coating may include applying a polymer chemistry on the coupling agent, as described above. 522 the application of the low friction coating may include: the glass container 900 is at least partially submerged into a coating dip tank 630, the coating dip tank 630 being filled with a coating solution 632 of polymer chemistry as described herein. Subsequently, the polymer chemical component solution is dried to removeAny solvent. For example, a coating solution containing the chemical components of the polymer as described above

800, the coating solution may be dried by transferring the glass container 900 to an oven and heating the glass container at 150 c for 20 minutes. Once the coating solution of polymer chemistry is dried, the glass container 900 may (optionally) be dipped again into the coating dip tank 630 of polymer chemistry to apply an additional layer or layers of polymer chemistry. 522 the application of the low friction coating may include: the polymeric chemical composition is applied to the entire outer surface of the container. Alternatively, the applying 522 of the low friction coating may include: a polymeric chemical composition is applied to a portion of the outer surface of the container.

Once the coating solution 632 of the polymer chemical is applied to the glass container 900, the polymer chemical may be cured on the glass container 900. The curing process depends on the type of polymer chemistry coating applied by the coating process and may include: heat curing the coating, curing the coating with UV light, and/or combinations thereof. For example, in the case where the polymer chemistry coating comprises polyimide, for example, the above-described passing

800 polyamic acid coating solution, the glass container 900 is transferred to an oven where the glass container 900 is heated from 150 c to about 350 c in about 5 to 30 minutes. Upon removal of the glass container from the furnace, the polymer chemical composition coating is cured, thereby producing a coated glass container having a low friction coating. As previously described, where the coating solution 632 of polymeric chemical components includes polymeric forms of the polymeric chemical components, the application of the low friction coating 522 may not include curing the coating solution 632 of polymeric chemical components.

After applying 522 the low friction coating to the glass container 900, the method may include 524: the coated glass container 100 is transferred to a packaging process where the container is filled and/or to an additional inspection station.

Various properties (i.e., coefficient of friction, horizontal compressive strength, four-point bending strength) of the coated glass container can be measured while the coated glass container is in the as-coated condition (i.e., 522 after application of the low friction coating to the glass container 900 but without any additional treatment) or after one or more processing treatments, such as similar or identical to those performed on a drug fill line, including but not limited to washing, lyophilization, depyrogenation, autoclaving, and the like.

Depyrogenation is the process of removing pyrogens from a substance. Depyrogenation of glass articles, such as pharmaceutical packaging, may be performed by applying a heat treatment to a sample, wherein the sample is heated to an elevated temperature for a period of time. For example, depyrogenation may include heating the glass container to a temperature of about 250 ℃ to about 380 ℃ for a period of about 30 seconds to about 72 hours, including, but not limited to, 20 minutes, 30 minutes, 40 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 24 hours, 48 hours, and 72 hours. After the heat treatment, the glass container was cooled to room temperature. One conventional depyrogenation condition commonly used in the pharmaceutical industry is heat treatment at a temperature of about 250 ℃ for about 30 minutes. However, it is expected that the time for the heat treatment can be shortened if a higher temperature is used. The coated glass containers described herein may be exposed to elevated temperatures for a period of time. The elevated temperatures and heating periods described herein may or may not be sufficient to depyrogenate the glass containers. It is understood that some of the heating temperatures and times described herein are sufficient to depyrogenation the coated glass containers, such as the coated glass containers described herein. For example, as described herein, the coated glass container can be exposed to a temperature of about 260 ℃, about 270 ℃, about 280 ℃, about 290 ℃, about 300 ℃, about 310 ℃, about 320 ℃, about 330 ℃, about 340 ℃, about 350 ℃, about 360 ℃, about 370 ℃, about 380 ℃, about 390 ℃, or about 400 ℃ for a period of 30 minutes.

Lyophilization conditions (i.e., freeze-drying) as used herein refer to the process of: the sample was filled with a liquid containing the protein, then frozen at-100 ℃ before sublimation of the water at about-15 ℃ for about 20 hours under vacuum.

As used herein, autoclaving conditions refer to steam purging a sample at about 100 ℃ for about 10 minutes, followed by a residence time of about 20 minutes, wherein the sample is exposed to an environment of about 121 ℃ followed by heat treatment at about 121 ℃ for about 30 minutes.

The coefficient of friction (μ) of the portion of the coated glass container having the low friction coating may be lower than the coefficient of friction 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 varies according to the mechanical and chemical properties of the first and second surfaces, including surface roughness and environmental conditions such as, but not limited to, temperature and humidity. As used herein, the coefficient of friction measurement for the coated glass container 100 is reported as the coefficient of friction between the outer surface of a first glass container (having an outer diameter between about 16.00mm to about 17.00 mm) and the outer surface of a second glass container that is identical to the first glass container, wherein the first and second glass containers have the same body and the same coating composition (when applied) and are exposed to the same environment before, during, and after manufacture. Unless otherwise indicated herein, the coefficient of friction refers to the maximum coefficient of friction measured with a normal load of 30N as measured on a test rig with vials on vials as described herein.

The coefficient of friction of the glass containers (coated and uncoated) was measured using a test station with the vials on the vials, as described herein, specifically as described in U.S. patent application publication No. 2013/0224407, assigned to corning incorporated, incorporated herein by reference in its entirety.

According to embodiments of the present disclosure, the portion of the coated glass container having the low friction coating may have a coefficient of friction of less than or equal to about 0.7 relative to a similar coated glass container, as determined with a station having a vial on the vial. The coefficient of friction of the portion of the coated glass container having the low friction coating may be less than or equal to about 0.6, or less than or equal to about 0.5, or less than or equal to about 0.4, or even less than or equal to about 0.3. Coated glass containers having a coefficient of friction less than or equal to about 0.7 generally exhibit increased resistance to frictional damage and, therefore, have improved mechanical properties. For example, the coefficient of friction of a conventional glass container (without a low friction coating) may be greater than 0.7. According to embodiments of the present disclosure, the coefficient of friction of the portion of the coated glass container having the low friction coating may also be less than or equal to about 0.7 (e.g., less than or equal to about 0.6, or less than or equal to about 0.5, or less than or equal to about 0.4, or even less than or equal to about 0.3) after exposure to lyophilization conditions and/or after exposure to autoclaving conditions. The coefficient of friction of the portion of the coated glass container having the low friction coating may increase by no more than about 30% after exposure to lyophilization conditions and/or after exposure to autoclaving conditions. For example, the coefficient of friction of the portion of the coated glass container having the low friction coating may increase by no more than about 25%, or about 20%, or about 15%, or even about 10% after exposure to lyophilization conditions and/or after exposure to autoclaving conditions. The coefficient of friction of the portion of the coated glass container having the low friction coating may not increase at all after exposure to lyophilization conditions and/or after exposure to autoclaving conditions.

The coated glass containers described herein have horizontal compressive strength. The horizontal compressive strength as described herein is measured by placing 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 with the platen in a direction perpendicular to the long axis of the glass container. The load rate for vial compression was 0.5 inches/minute, meaning that the platens moved toward each other at a rate of 0.5 inches/minute. The horizontal compressive strength was measured at 25 ℃ and 50% relative humidity. The measure of horizontal compressive strength may be given as the probability of failure at a selected nominal compressive load. As used herein, failure occurs when a glass container breaks under horizontal compression in at least 50% of the sample. The horizontal compressive strength of the coated glass containers described herein can be at least 10%, 20%, or even 30% greater than an uncoated vial having the same glass composition.

Horizontal compressive strength measurements can also be made on worn glass containers. In particular, operation of the above-described test station may cause damage to the coated glass container outer surface 122, such as surface scratches or abrasion, which weakens the strength of the coated glass container 100. The glass container is then subjected to the horizontal compression procedure described above, in which the container is placed between two press plates and the scratches are directed outwards parallel to the press plates. The scratches may be characterized by applying a selected normal pressure and scratch length by a stage having the vial on the vial. Unless otherwise noted, the scratch of the glass container abraded in the horizontal compression procedure is characterized by a scratch length of 20mm resulting from a normal load of 30N.

The horizontal compressive strength of the coated glass containers can be evaluated after heat treatment. The heat treatment may be exposure to a temperature of about 260 ℃, about 270 ℃, about 280 ℃, about 290 ℃, about 300 ℃, about 310 ℃, about 320 ℃, about 330 ℃, about 340 ℃, about 350 ℃, about 360 ℃, about 370 ℃, about 380 ℃, about 390 ℃, or about 400 ℃ for a period of 30 minutes. The horizontal compressive strength of the coated glass containers described herein may be reduced by no more than about 20%, about 30%, or even about 40% after exposure to a heat treatment (e.g., the heat treatment described above) followed by abrasion as described above.

The coated glass articles described herein can be thermally stable after heating to a temperature of at least 260 ℃ for a period of 30 minutes. The term "thermally stable" as used herein means that the low friction coating applied to the glass article remains substantially intact on the surface of the glass article after exposure to elevated temperatures, and thus the mechanical properties of the coated glass article, particularly the coefficient of friction and the horizontal compressive strength, have minimal, if any, effect after exposure. This indicates that after high temperature exposure, the low friction coating remains adhered to the glass surface and continues to protect the glass article from mechanical damage, e.g., abrasion, impact, etc.

According to embodiments of the present disclosure, a coated glass article is considered to be thermally stable if the coated glass article meets the coefficient of friction criterion and the horizontal compressive strength criterion after being heated to a specified temperature and held at that temperature for a specified time. To determine whether the coefficient of friction criteria was met, the coefficient of friction of the first coated glass article in the as-received state (i.e., prior to any heat exposure) was determined using the test rig and 30N applied load described above. 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 to prescribed conditions and cooled to room temperature. Subsequently, the friction coefficient of the second glass article was determined using a test stand, and the coated glass article was abraded with an applied load of 30N, resulting in an abrasion (i.e., "scratch") of about 20mm in length. The coefficient of friction criterion for determining the thermal stability of the low friction coating is met if the coefficient of friction of the second coated glass article is less than 0.7 and the glass surface of the second glass article does not have any observable damage in the abraded area. As used herein, the term "observable damage" means that the glass surface in the abraded area of the glass article contains less than six glass cracks per 0.5cm length of abraded area when viewed at 100 x magnification with a nomaski (Nomarski) or differential interference phase contrast (DIC) spectroscopic microscope with an LED or halogen lamp source. Standard definitions of glass cracking or glass initiation are described in "NIST Recommended Practice Guide of ceramics and Glasses" by G.D. Quinn (NIST Recommended Practice Guide: fracture analysis of ceramics and glass; NIST Special publication 960-17 (2006).

To determine whether the horizontal compressive strength criteria were met, the first coated glass article was abraded under a 30N load in the above test stand to form a 20mm scratch. The first coated glass article is then subjected to a horizontal compression test as described herein and the residual strength of the first coated glass article is determined. 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 to prescribed conditions and cooled to room temperature. Subsequently, the second coated glass article was abraded in a test rig under a load of 30N. The second coated glass article was then subjected to a horizontal compression test as described herein and the residual strength of the second coated glass article was determined. The level compressive strength criterion for determining the thermal stability of the low friction coating is met if the residual strength of the second coated glass article is reduced by no more than about 20% relative to the first coated glass article.

According to embodiments of the present disclosure, a coated glass container is considered thermally stable (i.e., the coated glass container is thermally stable for a period of about 30 minutes at a temperature of at least about 260 ℃) if it meets the coefficient of friction standard and the horizontal compressive strength standard after exposing the coated glass container to a temperature of at least about 260 ℃ for a period of about 30 minutes. Thermal stability may also be assessed at temperatures of from about 260 ℃ up to about 400 ℃. For example, a coated glass container is considered thermally stable if it is maintained at a temperature of at least about 270 ℃, or about 280 ℃, or about 290 ℃, or about 300 ℃, or about 310 ℃, or about 320 ℃, or about 330 ℃, or about 340 ℃, or about 350 ℃, or about 360 ℃, or about 370 ℃, or about 380 ℃, or about 390 ℃, or even about 400 ℃ for a period of about 30 minutes.

The coated glass containers disclosed herein may also be thermally stable over a range of temperatures, meaning that at each temperature in the range, the coated glass containers are thermally stable in accordance with compliance with the coefficient of friction standard and the horizontal compressive strength standard. For example, the coated glass container is thermally stable at a temperature of at least about 260 ℃ to less than or equal to about 400 ℃, or at a temperature of at least about 260 ℃ to about 350 ℃, or at a temperature of at least about 280 ℃ to less than or equal to about 350 ℃, or at a temperature of at least about 290 ℃ to about 340 ℃, or at a temperature of about 300 ℃ to about 380 ℃, or even at a temperature of about 320 ℃ to about 360 ℃.

After the coated glass container 100 is abraded by the same glass container with a 30N normal force, the coefficient of friction of the abraded area of the coated glass container 100 does not increase by more than about 20% after another abrasion by the same glass container at the same location with a 30N normal force, or does not increase at all. For example, after the coated glass container 100 is abraded by the same glass container with a 30N normal force, the coefficient of friction of the abraded area of the coated glass container 100 may increase by no more than about 15%, or even 10%, or not at all, after another abrasion by the same glass container at the same location with a 30N normal force. However, not all embodiments of the coated glass container 100 need exhibit such properties.

Mass loss refers to a measurable property of the coated glass container 100 that relates to the amount of volatiles released from the coated glass container 100 when the coated glass container is exposed to a selected elevated temperature for a selected period of time. The loss of quality is generally indicative of mechanical degradation of the coating due to thermal exposure. Since the glass body of the coated glass container does not exhibit measurable mass loss at the reported temperatures, the mass loss test generated mass loss data only for low friction coatings applied to the glass container, as described in detail herein. A number of factors can affect the loss of quality. For example, the amount of organic material that can be removed from the coating can affect the quality loss. Cleavage of the carbon backbone and side chains in the polymer will result in 100% theoretical coating removal. Organometallic polymeric materials typically lose all of their organic components, but leave behind inorganic components. Therefore, the mass loss results are normalized based on the amount of organic and inorganic species in the coating at full theoretical oxidation (e.g., silica% of the coating).

To determine mass loss, the coated sample (e.g., coated glass vial) was initially heated to 150 ℃ and held at that temperature for 30 minutes to dry the coating, effectively driving H from the coating₂And O. The sample is then heated from 150 ℃ to 350 ℃ in an oxidizing environment (e.g., air) at a ramp rate of 10 ℃/minute. To determine the mass loss, only data collected from 150 ℃ to 350 ℃ were considered. The coated glass articles described herein include a low friction coating when heated at about 10 ℃/minuteThe low friction coating loses less than about 5% of its mass when heated at a rate from a temperature of 150 ℃ to 350 ℃. For example, the low friction coating has a mass loss of less than about 3%, or less than about 2%, or less than about 1.5%, or even less than about 1% when heated from a temperature of 150 ℃ to 350 ℃ at a ramp rate of about 10 ℃/minute.

As described herein, the mass loss results are based on the following procedure: the weight of the coated glass containers before and after the heat treatment was compared, which was elevated from 150 ℃ to 350 ℃ at 10 °/min. The weight difference of the vial before and after heat treatment is the weight loss of the coating, which can be normalized to the weight loss percentage of the coating, such that the weight of the coating before heat treatment (excluding the weight of the glass body of the container and being the weight after the initial heating step) is known by comparing the weight of the uncoated glass container with the weight of the coated glass container before treatment. Alternatively, the total mass of the coating may be determined by a total organic carbon test or other similar means.

The transparency and color of the coated containers can be evaluated by measuring the light transmittance of the containers in the wavelength range between 400-700nm using a spectrophotometer. Measurements were made to direct the beam perpendicular to the vessel wall so that the beam passed through the low friction coating twice-first on entry into the vessel and then on exit from the vessel. The light transmittance through the coated glass containers described herein may be greater than or equal to about 55% of the light transmittance through the uncoated glass containers for wavelengths from about 400nm to about 700 nm. As described herein, the light transmittance can be measured before or after a heat treatment, such as the heat treatments described herein. For example, the light transmittance may be greater than or equal to about 55% of the light transmittance through the uncoated glass container for each wavelength from about 400nm to about 700 nm. The light transmittance through the coated glass container may be greater than or equal to about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or even about 90% of the light transmittance through the uncoated glass container for wavelengths from about 400nm to about 700 nm.

As described herein, the light transmittance can be measured before or after environmental treatment (e.g., thermal treatment as described herein). For example, the light transmittance through the coated glass container may be greater than or equal to about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or even about 90% of the light transmittance through the uncoated glass container for wavelengths from about 400nm to about 700nm after heat treatment at about 260 ℃, about 270 ℃, about 280 ℃, about 290 ℃, about 300 ℃, about 310 ℃, about 320 ℃, about 330 ℃, about 340 ℃, about 350 ℃, about 360 ℃, about 370 ℃, about 380 ℃, about 390 ℃, or about 400 ℃ for a period of 30 minutes, or after exposure to lyophilization conditions, or after exposure to autoclaving conditions.

The coated glass container 100 described herein may be perceived as colorless and transparent to the unaided human eye when viewed at any angle, or the low friction coating 120 may have a perceived color, such as when the low friction coating 120 comprises a polyimide formed from poly (pyromellitic dianhydride-co-4, 4' -oxydianiline) amic acid (commercially available from aldrich).

The coated glass container 100 described herein may have a low friction coating 120 capable of accepting an adhesive label. That is, the coated glass container 100 may receive an adhesive label on the coated surface to securely attach the adhesive label. However, the ability to attach adhesive labels is not a requirement of all embodiments of the coated glass containers 100 described herein.