US20030134060A1 - Glass container for medicinal purposes - Google Patents

Glass container for medicinal purposes Download PDF

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Publication number
US20030134060A1
US20030134060A1 US09/564,758 US56475800A US2003134060A1 US 20030134060 A1 US20030134060 A1 US 20030134060A1 US 56475800 A US56475800 A US 56475800A US 2003134060 A1 US2003134060 A1 US 2003134060A1
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Prior art keywords
glass container
coating
weight
adherent coating
glass
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US09/564,758
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US6599594B1 (en
Inventor
Marten Walther
Andreas Geiger
Petra Auchter-Krummel
Michael Spallek
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Schott AG
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Schott Glaswerke AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/282—Carbides, silicides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C03C2218/153—Deposition methods from the vapour phase by cvd by plasma-enhanced cvd
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S215/00—Bottles and jars
    • Y10S215/03—Medical
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • Y10T428/1317—Multilayer [continuous layer]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • Y10T428/1317—Multilayer [continuous layer]
    • Y10T428/1321—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to a glass container for medicinal purposes, and, more particularly, to a glass container for storing and preserving pharmaceutical or diagnostic solutions for medicinal purposes, which is provided with an anti-adherent coating on its interior surface or surfaces.
  • Glass containers for medicinal purposes i.e. containers having pharmaceuticals or diagnostics as contents
  • containers having pharmaceuticals or diagnostics as contents are on the market in a most wide variety of embodiments, in order to take into account their respective purposes, associated administration forms and the respective contents.
  • Glass containers for medicinal contents should have interior surfaces which have the least possible adherence for their contents, i.e. as large as possible a wetting angle for aqueous contents, in order to permit a complete emptying of residues from the container. This is particularly true for comparatively small glass containers with very expensive contents.
  • silicone oil is dispensed from the surfaces and that the silicone oil may be introduced into human or animal bodies. Furthermore undesirable adsorption phenomenon occur on the silicone-coated surface, which are remarkable, especially protein-binding. Furthermore heavy metal impurities are unavoidably present in the silicone oil. Thus suitable expensive testing is prescribed in European formularies. Furthermore auxiliary substances (e.g. detergents), which must be used for stabilizing silicone emulsions, are critical.
  • a glass container for storing and preserving pharmaceutical or diagnostic solutions for medicinal purposes comprising a container closure device and an amorphous, transparent and pharmaceutically acceptable anti-adherent coating provided on the entire interior surface of the glass container over the entire interior surface up to the closure device, and wherein the anti-adherent coating has a contact angle for wetting with water of ⁇ 80°, even after autoclaving at about 120° C. for about 20 min, contains the elements Si, O, C and H and is deposited by means of a plasma-enhanced chemical vapor deposition method (PECVD), preferably by means of a plasma-pulsed chemical vapor deposition method (PICVD).
  • PECVD plasma-enhanced chemical vapor deposition method
  • PICVD plasma-pulsed chemical vapor deposition method
  • Medicinal glass containers of this type i.e. according to the invention, have interior surfaces that to a large extent reject water or wetting with water, which permits a nearly complete emptying of the container. It also has the great medically related advantage that no silicone substances are introduced into the pharmaceutical or diagnostic contents and thus into the human body.
  • the anti-adherent layer or coating according to the invention is equal to typical pharmaceutical stress test conditions, e.g. typical sterilization conditions, without loosing its function.
  • the glass container according to the invention is thus to a large extent pharmaceutically acceptable.
  • the anti-adherent layer comprises at least 1% by weight silicon and at least 5% by weight carbon.
  • the hydrophobic properties of the coating can be augmented, when the anti-adherent coating contains fluorine according to a further embodiment of the invention.
  • the percentage content of fluorine in the anti-adherent layer is related to the percentage content of carbon by the following reciprocal relationship:
  • FIGURE is a partially side, partially cutaway cross-sectional view through a glass container for medicinal purposes according to the invention.
  • the sole FIGURE shows a glass container 1 for medicinal purposes in a configuration suitable for a typical application, which is provided with a conventional closure device 2 .
  • the glass container 1 serves for storage and preservation of a pharmaceutical or diagnostic solution 5 .
  • the glass container 1 is preferably made from a glass type I according to German Dispensatory, 10th Edition, corresponding to a borosilicate glass.
  • the particular glass type mentioned above and the shape of the glass bottle are features of preferred embodiments.
  • the glass bottle may also have other shapes and can be made from other types of glass, which have the required properties for other applications.
  • Especially the glass bottle may be made from glass of a lower hydrolytic class, especially the so-called neutral glass.
  • the interior of the glass bottle should reject water to a large extent. That means that it should have as large as possible a wetting angle for its aqueous contents 5 , especially in order to permit complete emptying so as to minimize any residue left in the bottle. This is also true for a comparatively small glass container with very expensive contents.
  • a special coating 4 is provided over the whole interior surface of the wall 3 of the glass bottle 1 .
  • This coating comprises an anti-adherent layer with a contact angle for water of ⁇ 80°, which is pharmaceutically acceptable, i.e. free of heavy metals and stable under the usual test conditions, especially autoclaving for 20 minutes at 121° C. and/or in hot air sterilization for 30 minutes at 300° C.
  • the layer is amorphous, clear and transparent and contains the elements Si, O, C and H, with silicon content of at least 1% by weight and a C content of at least 5% by weight.
  • the layer 4 also contains fluorine, whose content is in a reciprocal relationship to the carbon content.
  • the coating or layer 4 is produced by means of a plasma-enhanced chemical vapor deposition process (PECVD).
  • PECVD plasma-enhanced chemical vapor deposition process
  • PICVD plasma-pulsed chemical vapor deposition process
  • the container for medical purposes according to the present invention has the following properties:
  • a contact angle of 95° to 102° (relative to water) is produced in all bottles by this process. This contact angle becomes 85° to 95° during autoclaving at 121° C. for 20 minutes. All bottles were filled with an aqueous suspension. After a storage time of 1 week the pouring behavior was tested. In contrast to the uncoated bottles, in which a residue of flecks of the suspension remained over the entire interior surface after emptying the bottles, the bottles coated in the above-described manner according to the invention, could be completely emptied without leaving a residue.
  • German Patent Application 199 21 303.8 of May 7, 1999 is incorporated here by reference.
  • This German Patent Application describes the invention described hereinabove and claimed in the claims appended hereinbelow and provides the basis for a claim of priority for the instant invention under 35 U.S.C. 119.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Surface Treatment Of Glass (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)

Abstract

The glass container stores and preserves pharmaceutical or diagnostic solutions for medicinal purposes. In order to provide a silicone-free but residue free bottle after emptying, the glass container is provided with an amorphous transparent and pharmaceutically acceptable anti-adherent coating (4) over the entire interior surface of the glass container from its bottom over the wall (3) to the closure device (2). This anti-adherent coating (4) has a contact angle for wetting with water of ≧80°, even after autoclaving at about 120° C. for about 20 min, contains silicon, oxygen, carbon and hydrogen and is deposited according to a PECVD method, especially a PICVD method.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0001]
  • The present invention relates to a glass container for medicinal purposes, and, more particularly, to a glass container for storing and preserving pharmaceutical or diagnostic solutions for medicinal purposes, which is provided with an anti-adherent coating on its interior surface or surfaces. [0002]
  • 2. Prior Art [0003]
  • Glass containers for medicinal purposes, i.e. containers having pharmaceuticals or diagnostics as contents, are on the market in a most wide variety of embodiments, in order to take into account their respective purposes, associated administration forms and the respective contents. [0004]
  • Glass containers for medicinal contents should have interior surfaces which have the least possible adherence for their contents, i.e. as large as possible a wetting angle for aqueous contents, in order to permit a complete emptying of residues from the container. This is particularly true for comparatively small glass containers with very expensive contents. [0005]
  • Glass containers for medicinal purposes have been treated with silicone oils (polydimethylsiloxane oil) or silicone oil emulsions, in order to produce anti-adherent interior surfaces. This has been disclosed in U.S. Pat. No. 2,504,482, among other prior art references. This method is also described in European medical formularies. [0006]
  • The main disadvantage of this method is that silicone oil is dispensed from the surfaces and that the silicone oil may be introduced into human or animal bodies. Furthermore undesirable adsorption phenomenon occur on the silicone-coated surface, which are remarkable, especially protein-binding. Furthermore heavy metal impurities are unavoidably present in the silicone oil. Thus suitable expensive testing is prescribed in European formularies. Furthermore auxiliary substances (e.g. detergents), which must be used for stabilizing silicone emulsions, are critical. [0007]
  • Methods for modification of the interior surfaces of the glass container using silanes, silazanes, etc, are known (GB 2,230,260 A) as well as by application of silicone oil. A monolayer is deposited on the surfaces from the liquid or gas phase after an expensive cleaning process, which often uses reactive acids, such as chromo-sulfuric acid, etc. [0008]
  • This process has the disadvantage that a fresh expensive washing process is required after the surface treatment, in order to remove the residual chemicals most completely. Furthermore no silane or silanized layers, which resist the action of the typical pharmaceutical tests sufficiently, which especially withstand autoclaving at 121° C. for 20 minutes, are currently known. [0009]
    • SUMMARY OF THE INVENTION
  • It is an object of the present invention to provide a glass container for medicinal purpose of the above-described kind, so that its interior surface has an outstanding anti-adherent property, it is equal to the typical pharmaceutical stress test conditions and it introduces no silicone into the solution found in the glass container. [0010]
  • According to the invention this object is attained with a glass container for storing and preserving pharmaceutical or diagnostic solutions for medicinal purposes, comprising a container closure device and an amorphous, transparent and pharmaceutically acceptable anti-adherent coating provided on the entire interior surface of the glass container over the entire interior surface up to the closure device, and wherein the anti-adherent coating has a contact angle for wetting with water of ≧80°, even after autoclaving at about 120° C. for about 20 min, contains the elements Si, O, C and H and is deposited by means of a plasma-enhanced chemical vapor deposition method (PECVD), preferably by means of a plasma-pulsed chemical vapor deposition method (PICVD). [0011]
  • Medicinal glass containers of this type, i.e. according to the invention, have interior surfaces that to a large extent reject water or wetting with water, which permits a nearly complete emptying of the container. It also has the great medically related advantage that no silicone substances are introduced into the pharmaceutical or diagnostic contents and thus into the human body. [0012]
  • Tests have shown that the anti-adherent layer or coating according to the invention is equal to typical pharmaceutical stress test conditions, e.g. typical sterilization conditions, without loosing its function. The glass container according to the invention is thus to a large extent pharmaceutically acceptable. [0013]
  • Preferably the anti-adherent layer comprises at least 1% by weight silicon and at least 5% by weight carbon. The hydrophobic properties of the coating can be augmented, when the anti-adherent coating contains fluorine according to a further embodiment of the invention. [0014]
  • According to a preferred embodiment of the invention the percentage content of fluorine in the anti-adherent layer is related to the percentage content of carbon by the following reciprocal relationship: [0015]
  • When fluorine <0.1% by weight, then C≧10% by weight; [0016]
  • When F≧0.1% by weight, then C≧5% by weight.[0017]
    • BRIEF DESCRIPTION OF THE DRAWING
  • The objects, features and advantages of the invention will now be illustrated in more detail with the aid of the following description of the preferred embodiment, with reference to the accompanying sole FIGURE which is a partially side, partially cutaway cross-sectional view through a glass container for medicinal purposes according to the invention. [0018]
    • DESCRIPTION OF THE PREFERRED EMBODIMENT
  • The sole FIGURE shows a glass container [0019] 1 for medicinal purposes in a configuration suitable for a typical application, which is provided with a conventional closure device 2. The glass container 1 serves for storage and preservation of a pharmaceutical or diagnostic solution 5.
  • The glass container [0020] 1 is preferably made from a glass type I according to German Dispensatory, 10th Edition, corresponding to a borosilicate glass. The particular glass type mentioned above and the shape of the glass bottle are features of preferred embodiments. According to the invention the glass bottle may also have other shapes and can be made from other types of glass, which have the required properties for other applications. Especially the glass bottle may be made from glass of a lower hydrolytic class, especially the so-called neutral glass.
  • It is desirable that the interior of the glass bottle should reject water to a large extent. That means that it should have as large as possible a wetting angle for its [0021] aqueous contents 5, especially in order to permit complete emptying so as to minimize any residue left in the bottle. This is also true for a comparatively small glass container with very expensive contents.
  • In order to achieve this behavior, a [0022] special coating 4 is provided over the whole interior surface of the wall 3 of the glass bottle 1. This coating comprises an anti-adherent layer with a contact angle for water of ≧80°, which is pharmaceutically acceptable, i.e. free of heavy metals and stable under the usual test conditions, especially autoclaving for 20 minutes at 121° C. and/or in hot air sterilization for 30 minutes at 300° C. The layer is amorphous, clear and transparent and contains the elements Si, O, C and H, with silicon content of at least 1% by weight and a C content of at least 5% by weight. Preferably the layer 4 also contains fluorine, whose content is in a reciprocal relationship to the carbon content. In other words,
  • when fluorine <0.1% by weight, then C≧10% by weight; [0023]
  • when F≧0.1% by weight, then C≧5% by weight. [0024]
  • The coating or [0025] layer 4 is produced by means of a plasma-enhanced chemical vapor deposition process (PECVD). In this process a plasma-assisted layer deposition from the gas phase occurs, in which the layer material is supplied in the form of so-called precursor gases. These pre-cursor gases are broken down with the required energy being supplied to the system by electrical high frequency plasma, particularly in a plasma-pulsed chemical vapor deposition process (PICVD).
  • These processes and their associated apparatus are well known. Examples are described in DE 196 29 877 C1 and DE 44 38 359 A1, which were produced by the present applicant. [0026]
  • The container for medical purposes according to the present invention has the following properties: [0027]
  • a) its interior surface rejects water, so that its aqueous contents have the greatest possible wetting angle with its interior surface, in order to obtain complete emptying without leaving any residue; [0028]
  • b) its interior surface does not bind proteins; [0029]
  • c) its interior surface is free of silicone (polydimethylsiloxanes); [0030]
  • d) it is stable during typical pharmaceutical stress test conditions and/or terminal sterilization (autoclaving in steam at 121° C. for 20 minutes); [0031]
  • e) it has a high degree of transparency; [0032]
  • f) it has a high stability against washing processes, drying processes, hot air sterilization, filling processes and closing processes, including a washing process with hot distilled water and a hot air sterilization with temperatures up to 300° C. and dwell times of up to 30 minutes; [0033]
  • g) it provides a high degree of chemical purity, i.e. it is not necessary to use solvents and/or aggressive chemicals for surface activation or cleaning; and it may be produced by a simple method. [0034]
  • It has been surprisingly found that not only the adherence of particles in aqueous suspensions on container interior surfaces is drastically reduced, but also that this is also true for suspensions, which contain an inert propellant gas, such as e.g. R134a, R127. This is also true for alcoholic suspensions. [0035]
    • EXAMPLES
  • The following two examples which are representative of numerous other tests are described in the following paragraphs. These examples show that the glass container according to the invention has properties that are superior to those of the prior art. [0036]
    • Example 1 Coating According to a PECVD Method
  • Glass containers in the form of glass bottles are placed in a PECVD reactor, whose structure corresponds principally to that disclosed in DE 44 38 359 A1. A gas nozzle device extends into the mouth of the bottle. The reactor is evacuated to 0.05 mbar by a pump. Then a mixture of HMDSO (5 sccm) and C[0037] 6F10(CF3)2 is conducted into the bottle through the gas nozzle device. RF power is coupled to an electrode in the reactor inductively by means of coils through a matching network and ignites a plasma in the reactor. The entire apparatus is arranged within an electrical shielding. In this process the reaction gas is converted into a coating in the whole bottle at about 300 W HF power (13.56 MHz).
  • A contact angle of 95° to 102° (relative to water) is produced in all bottles by this process. This contact angle becomes 85° to 95° during autoclaving at 121° C. for 20 minutes. All bottles were filled with an aqueous suspension. After a storage time of 1 week the pouring behavior was tested. In contrast to the uncoated bottles, in which a residue of flecks of the suspension remained over the entire interior surface after emptying the bottles, the bottles coated in the above-described manner according to the invention, could be completely emptied without leaving a residue. [0038]
    • Example 2 Coating According to a PICVD Method
  • Glass containers in the form of glass bottles are placed in a PICVD reactor, whose structure corresponds principally to that disclosed in DE 196 29 877 C1. The reactor is evacuated to 0.9 mbar by a pump. In these bottles a gas mixture comprising 10 sccm HMDSO, 5 sccm O[0039] 2 and 2 sccm C6F6 is supplied by a supply device. Pulsed power was provided at 2.45 GHz by a microwave discharge source, which ignites a plasma in the glass bottle. After deposition of a 30 nm layer the microwave power is turned off and the bottles are aerated. The tests found that after the coating is formed the contact angle for water was 91° to 105°. This contact angle is reduced about 6° on average after autoclaving. This behavior of a watery suspension that is poured out of bottles coated in this manner is similar to that described in connection with the previous PECVD method.
  • The disclosure in German Patent Application 199 21 303.8 of May 7, 1999 is incorporated here by reference. This German Patent Application describes the invention described hereinabove and claimed in the claims appended hereinbelow and provides the basis for a claim of priority for the instant invention under 35 U.S.C. 119. [0040]
  • While the invention has been illustrated and described as embodied in a glass container for medicinal purposes, it is not intended to be limited to the details shown, since various modifications and changes may be made without departing in any way from the spirit of the present invention. [0041]
  • Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. [0042]
  • What is claimed is new and is set forth in the following appended claims. [0043]

Claims (8)

We claim:
1. A glass container for storing and preserving pharmaceutical or diagnostic solutions for medicinal purposes, wherein said glass container comprises a closure device (2) and an amorphous, transparent and pharmaceutically acceptable anti-adherent coating (4) provided on an entire interior surface thereof over the entire interior surface up to the closure device, and wherein the anti-adherent coating has a contact angle for wetting by water of ≧80°, even after autoclaving at about 120° C. for about 20 min, and the anti-adherent coating contains silicon, oxygen, carbon and hydrogen and is deposited ny means of a plasma-enhanced chemical vapor deposition process.
2. The glass container as defined in claim 1, wherein said plasma-enhanced chemical vapor deposition process is a plasma-pulsed chemical vapor deposition process.
3. The glass container as defined in claim 1, wherein said anti-adherent coating (4) contains at least 1% by weight of said silicon.
4. The glass container as defined in claim 1, wherein said anti-adherent coating (4) contains at least 5% by weight of said carbon.
5. The glass container as defined in claim 1, wherein said coating (4) contains fluorine.
6. The glass container as defined in claim 5, wherein, according to the following reciprocal relationship, when the coating contains less than 0.1% by weight fluorine, then the coating contains greater than or equal to 10% by weight of said carbon, but when the coating contains greater than or equal to 0.1% by weight fluorine, then the coating contains greater than or equal to 5% by weight carbon.
7. The glass container as defined in claim 1, wherein said anti-adherent coating is free of silicones.
8. The glass container as defined in claim 1, wherein said anti-adherent coating is free of polydimethylsiloxanes.
US09/564,758 1999-05-07 2000-05-04 Glass container for medicinal purposes Expired - Lifetime US6599594B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19921303.8-45 1999-05-07
DE19921303A DE19921303C1 (en) 1999-05-07 1999-05-07 Medical glass container, for holding pharmaceutical or medical diagnostic solution, has an inner PECVD non-stick layer containing silicon, oxygen, carbon and hydrogen
DE19921303 1999-05-07

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US20030134060A1 true US20030134060A1 (en) 2003-07-17
US6599594B1 US6599594B1 (en) 2003-07-29

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US (1) US6599594B1 (en)
EP (1) EP1050517B1 (en)
JP (1) JP4351363B2 (en)
DE (2) DE19921303C1 (en)
HK (1) HK1032776A1 (en)

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CN102349855A (en) * 2011-06-23 2012-02-15 宁波正力药品包装有限公司 Glass bottle with inorganic silicon membranous layer for medical packaging and production process thereof
WO2013038119A2 (en) * 2011-09-16 2013-03-21 Rexam Healthcare La Verpilliere Device for storing and dispensing liquid
CN104098934A (en) * 2013-04-11 2014-10-15 肖特公开股份有限公司 Container with low particulate emission and friction controlled dry sliding surface and methods for producing same
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WO2019064263A1 (en) * 2017-09-29 2019-04-04 Janssen Biotech, Inc. Novel formulations which stabilize low dose antibody compositions
CN110272213A (en) * 2018-03-16 2019-09-24 肖特股份有限公司 The ducted body of surface region with glassy layer and with the contact angle for wetting
EP3560897A1 (en) * 2018-04-26 2019-10-30 Schott AG Process for making a functionalised hollow body, having a layer of glass, including a superposition of one or more siloxanes and contacting with a plasma
US20210187497A1 (en) * 2019-12-20 2021-06-24 Schott Ag Glass container comprising a glass bottom with improved properties
US11376191B2 (en) 2018-05-18 2022-07-05 Schott Ag Glass container with an improved bottom geometry

Families Citing this family (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10300323A1 (en) * 2003-01-09 2004-10-14 Baxter Healthcare S.A. Safety container filled with a biologically active substance, especially a cytostatic agent, is at least partially coated
DE10131156A1 (en) * 2001-06-29 2003-01-16 Fraunhofer Ges Forschung Articles with a plasma polymer coating and process for its production
GB0117879D0 (en) * 2001-07-21 2001-09-12 Common Services Agency Storage of liquid compositions
WO2003031362A1 (en) * 2001-10-05 2003-04-17 Dow Global Technologies Inc. Coated glass for use in displays and other electronic devices
DE10231698A1 (en) * 2002-03-26 2003-10-23 Fraunhofer Ges Forschung Process for improving the transfer of additive material to support used in the production of printed circuit boards comprises using template having openings with coating for the structured transfer of the additive material to the support
US8025915B2 (en) * 2006-01-11 2011-09-27 Schott Ag Method of preparing a macromolecule deterrent surface on a pharmaceutical package
DE102006018491A1 (en) * 2006-04-19 2007-10-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Flexible plasma polymer products, corresponding articles, manufacturing methods and use
JP5001015B2 (en) * 2006-09-28 2012-08-15 富士フイルム株式会社 Biochemical instrument having a surface with reduced non-specific adsorption
DE102006058771B4 (en) 2006-12-12 2018-03-01 Schott Ag Container with improved emptiness and method for its production
US7877968B2 (en) 2007-05-15 2011-02-01 Kraft Foods Global Brands Llc Method for forming a container with improved release properties
US8003178B2 (en) * 2007-05-15 2011-08-23 Kraft Foods Global Brands Llc Container with improved release properties
AU2009248885B2 (en) * 2008-05-23 2015-02-05 Hospira, Inc. Packaged iron sucrose products
EP2251454B1 (en) 2009-05-13 2014-07-23 SiO2 Medical Products, Inc. Vessel coating and inspection
DE102009008766A1 (en) * 2009-02-06 2010-08-12 Optima Group Pharma Gmbh Method for coating the inner surfaces of a glass container comprises relieving the pressure of a sterile vapor in the container, adding a determined amount of silicone oil and/or a water/silicone emulsion and further processing
US7985188B2 (en) 2009-05-13 2011-07-26 Cv Holdings Llc Vessel, coating, inspection and processing apparatus
US9458536B2 (en) 2009-07-02 2016-10-04 Sio2 Medical Products, Inc. PECVD coating methods for capped syringes, cartridges and other articles
KR101160270B1 (en) * 2009-11-12 2012-06-27 포항공과대학교 산학협력단 Liquid container
US11624115B2 (en) 2010-05-12 2023-04-11 Sio2 Medical Products, Inc. Syringe with PECVD lubrication
US9878101B2 (en) 2010-11-12 2018-01-30 Sio2 Medical Products, Inc. Cyclic olefin polymer vessels and vessel coating methods
US9272095B2 (en) 2011-04-01 2016-03-01 Sio2 Medical Products, Inc. Vessels, contact surfaces, and coating and inspection apparatus and methods
EP2771301B1 (en) 2011-10-25 2017-12-20 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9517966B2 (en) 2011-10-25 2016-12-13 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US11116695B2 (en) 2011-11-11 2021-09-14 Sio2 Medical Products, Inc. Blood sample collection tube
JP6095678B2 (en) 2011-11-11 2017-03-15 エスアイオーツー・メディカル・プロダクツ・インコーポレイテッド Passivation, pH protection or slippery coatings for pharmaceutical packages, coating processes and equipment
US11497681B2 (en) 2012-02-28 2022-11-15 Corning Incorporated Glass articles with low-friction coatings
US10737973B2 (en) 2012-02-28 2020-08-11 Corning Incorporated Pharmaceutical glass coating for achieving particle reduction
CN104271346B (en) 2012-02-28 2017-10-13 康宁股份有限公司 Glassware with low-friction coating
EP2846755A1 (en) 2012-05-09 2015-03-18 SiO2 Medical Products, Inc. Saccharide protective coating for pharmaceutical package
US10273048B2 (en) 2012-06-07 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
CN104395255A (en) 2012-06-07 2015-03-04 康宁股份有限公司 Delamination resistant glass containers
US9034442B2 (en) * 2012-11-30 2015-05-19 Corning Incorporated Strengthened borosilicate glass containers with improved damage tolerance
ES2634390T3 (en) * 2012-09-26 2017-09-27 Katholieke Universiteit Leuven Glass bottles with means to prevent spillage, use, method
CA2890066C (en) 2012-11-01 2021-11-09 Sio2 Medical Products, Inc. Coating inspection method
WO2014078666A1 (en) 2012-11-16 2014-05-22 Sio2 Medical Products, Inc. Method and apparatus for detecting rapid barrier coating integrity characteristics
US9764093B2 (en) 2012-11-30 2017-09-19 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition
CA2892294C (en) 2012-11-30 2021-07-27 Sio2 Medical Products, Inc. Controlling the uniformity of pecvd deposition on medical syringes, cartridges, and the like
US10117806B2 (en) 2012-11-30 2018-11-06 Corning Incorporated Strengthened glass containers resistant to delamination and damage
US20140202979A1 (en) 2013-01-22 2014-07-24 General Electric Company Apparatus for storage and sampling of de-ionized water samples and the like
US20160015898A1 (en) 2013-03-01 2016-01-21 Sio2 Medical Products, Inc. Plasma or cvd pre-treatment for lubricated pharmaceutical package, coating process and apparatus
EP4234753A3 (en) 2013-03-11 2023-11-01 SiO2 Medical Products, Inc. Coated packaging
US9937099B2 (en) 2013-03-11 2018-04-10 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging with low oxygen transmission rate
US9863042B2 (en) 2013-03-15 2018-01-09 Sio2 Medical Products, Inc. PECVD lubricity vessel coating, coating process and apparatus providing different power levels in two phases
US9839579B2 (en) 2013-04-24 2017-12-12 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717649B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700486B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9713572B2 (en) 2013-04-24 2017-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717648B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700485B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707153B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707154B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707155B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9603775B2 (en) 2013-04-24 2017-03-28 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9849066B2 (en) 2013-04-24 2017-12-26 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
DE102013209709A1 (en) * 2013-05-24 2014-11-27 BSH Bosch und Siemens Hausgeräte GmbH COATING OF USER SURFACES WITH PLASMAPOLYMIC LAYERS UNDER ATMOSPHERE PRESSURE TO IMPROVE CLEANABILITY
BR112016010475B1 (en) * 2014-03-13 2021-07-20 Stevanato Group International A.S. METHOD OF HANDLING A LIQUID PHARMACEUTICAL FORMULATION
US11066745B2 (en) 2014-03-28 2021-07-20 Sio2 Medical Products, Inc. Antistatic coatings for plastic vessels
RU2691189C2 (en) 2014-09-05 2019-06-11 Корнинг Инкорпорейтед Glass articles and methods of improving reliability of glass articles
JP6784671B2 (en) 2014-11-26 2020-11-11 コーニング インコーポレイテッド How to make reinforced and durable glass containers
US20170037568A1 (en) 2015-08-05 2017-02-09 Milliken & Company Installation of Multi-Component Floor Mat
CN108138316A (en) 2015-08-18 2018-06-08 Sio2医药产品公司 Drug and other packagings with low oxygen transmission rate
EP3150564B1 (en) 2015-09-30 2018-12-05 Corning Incorporated Halogenated polyimide siloxane chemical compositions and glass articles with halogenated polylmide siloxane low-friction coatings
BR112018008744B1 (en) 2015-10-30 2022-09-06 Corning Incorporated GLASS ARTICLES WITH METALLIC OXIDE AND MIXED POLYMER COATING
US20180055266A1 (en) 2016-08-24 2018-03-01 Milliken & Company Floor Mat with Hidden Base Component
US10626047B2 (en) 2016-10-18 2020-04-21 Owens-Brockway Glass Container Inc. Glass container coating process
US11709155B2 (en) 2017-09-18 2023-07-25 Waters Technologies Corporation Use of vapor deposition coated flow paths for improved chromatography of metal interacting analytes
US11709156B2 (en) 2017-09-18 2023-07-25 Waters Technologies Corporation Use of vapor deposition coated flow paths for improved analytical analysis
WO2019117267A1 (en) 2017-12-15 2019-06-20 ニプロ株式会社 Medical glass container and method for manufacturing same
JP6856698B2 (en) * 2018-05-18 2021-04-07 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ Glass container with improved bottom geometry
JPWO2020027220A1 (en) * 2018-07-31 2021-08-02 テルモ株式会社 How to remove silicone oil when administering protein preparations
US11918936B2 (en) 2020-01-17 2024-03-05 Waters Technologies Corporation Performance and dynamic range for oligonucleotide bioanalysis through reduction of non specific binding
CN115124258A (en) * 2021-03-25 2022-09-30 肖特股份有限公司 Coated glass element
WO2022200623A1 (en) * 2021-03-25 2022-09-29 Schott Ag Pharmaceutical container
EP4063334A1 (en) * 2021-03-25 2022-09-28 Schott Ag Coated glass element
US20220306525A1 (en) * 2021-03-25 2022-09-29 Schott Ag Coated glass element

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2504482A (en) * 1949-06-17 1950-04-18 Premo Pharmaceutical Lab Inc Drain-clear container for aqueous-vehicle liquid pharmaceutical preparations
US3939834A (en) * 1974-09-24 1976-02-24 Mcmahon Patrick J Metal coated articles
US4778721A (en) * 1986-07-09 1988-10-18 Battelle Memorial Institute Method of forming abrasion-resistant plasma coatings and resulting articles
GB2230260B (en) * 1989-01-17 1992-05-06 United Glass Ltd Strengthening of glass containers
DE69232591T2 (en) * 1991-01-23 2002-08-22 Matsushita Electric Ind Co Ltd Water and oil repellent adsorbed film
JPH05132065A (en) 1991-11-05 1993-05-28 Nichiden Rika Glass Hanbai Kk Surface-treated glass bottle
CH687614A5 (en) * 1994-02-04 1997-01-15 Tetra Pak Suisse Sa A method of providing a packaging with excellent barrier properties with respect to gases.
US5521351A (en) * 1994-08-30 1996-05-28 Wisconsin Alumni Research Foundation Method and apparatus for plasma surface treatment of the interior of hollow forms
DE4438359C2 (en) * 1994-10-27 2001-10-04 Schott Glas Plastic container with a barrier coating
DE4445427C2 (en) * 1994-12-20 1997-04-30 Schott Glaswerke Plasma CVD method for producing a gradient layer
US5702770A (en) * 1996-01-30 1997-12-30 Becton, Dickinson And Company Method for plasma processing
TW422822B (en) * 1996-04-04 2001-02-21 Matsushita Electric Ind Co Ltd Contamination-resistant float glass and process for producing the same as well as cooking device using said contamination-resistant float glass
DE19622550A1 (en) * 1996-06-05 1997-12-11 Schott Glaswerke Glass containers, in particular for storing pharmaceutical or diagnostic solutions
DE19629877C1 (en) * 1996-07-24 1997-03-27 Schott Glaswerke CVD for internal coating of hollow articles with barrier film
US6112695A (en) * 1996-10-08 2000-09-05 Nano Scale Surface Systems, Inc. Apparatus for plasma deposition of a thin film onto the interior surface of a container
DE19722205A1 (en) * 1997-05-27 1998-12-03 Leybold Systems Gmbh Method and device for coating plastic or glass containers by means of a PCVD coating method

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2413915A2 (en) * 2009-03-30 2012-02-08 F. Hoffmann-La Roche AG A method for avoiding glass fogging
CN102349855A (en) * 2011-06-23 2012-02-15 宁波正力药品包装有限公司 Glass bottle with inorganic silicon membranous layer for medical packaging and production process thereof
WO2013038119A2 (en) * 2011-09-16 2013-03-21 Rexam Healthcare La Verpilliere Device for storing and dispensing liquid
WO2013038119A3 (en) * 2011-09-16 2015-02-19 Rexam Healthcare La Verpilliere Device for storing and dispensing pharmaceutical liquid
CN104334510A (en) * 2012-05-28 2015-02-04 浪越株式会社 Glass container and method for manufacturing same
US20150136723A1 (en) * 2012-05-28 2015-05-21 Namicos Corporation Glass container and method for manufacturing same
CN104583114A (en) * 2012-06-18 2015-04-29 因努瓦动力有限公司 Agglomerate reduction in nanowire suspension stored in container
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WO2019064263A1 (en) * 2017-09-29 2019-04-04 Janssen Biotech, Inc. Novel formulations which stabilize low dose antibody compositions
CN110272213A (en) * 2018-03-16 2019-09-24 肖特股份有限公司 The ducted body of surface region with glassy layer and with the contact angle for wetting
EP3560897A1 (en) * 2018-04-26 2019-10-30 Schott AG Process for making a functionalised hollow body, having a layer of glass, including a superposition of one or more siloxanes and contacting with a plasma
US11167885B2 (en) 2018-04-26 2021-11-09 Schott Ag Process for making a functionalized hollow body, having a layer of glass, including a superposition of one or more siloxanes and contacting with a plasma
US11376191B2 (en) 2018-05-18 2022-07-05 Schott Ag Glass container with an improved bottom geometry
US20210187497A1 (en) * 2019-12-20 2021-06-24 Schott Ag Glass container comprising a glass bottom with improved properties
US20210187496A1 (en) * 2019-12-20 2021-06-24 Schott Ag Glass container comprising a glass bottom with improved properties
US11806716B2 (en) * 2019-12-20 2023-11-07 Schott Pharma Ag & Co. Kgaa Glass container comprising a glass bottom with improved properties
US11980886B2 (en) 2019-12-20 2024-05-14 Schott Pharma Schweiz Ag Bottom forming process

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