Processing of glass containers

Abstract

A method of treating a glass container by subjecting at least a portion of the inner surface of the glass container to a washing treatment and then subjecting the at least a portion of the inner surface of the glass container to a plasma treatment to obtain an anti-leaching inner surface.

Description

Technical Field

[0001] The present invention relates to a method for treating the surface of a glass container or glass component to enhance anti-leaching properties over a wide pH range. Background Art

[0002] Liquid pharmaceutical compositions have been packaged in glass containers, such as vials, ampoules, cartridges or syringes.

[0003] For some liquid pharmaceutical compositions (e.g., biologics) containing very sensitive drugs, it is beneficial to store them in alkaline buffer solutions. In contrast, other liquid pharmaceutical compositions contain acidic buffer solutions. Typically, the pH values ​​of pharmaceutical compositions are within a range, many of which are not neutral. These non-pH neutral liquids tend to seep from the surface of glass containers, which may cause certain harmful substances in the glass (especially Si) to seep from the glass surface into the pharmaceutical liquid. Summary of the invention

[0004] The present invention is directed to improving the anti-leaching performance of glass surfaces and generally improving the chemical stability of container surfaces by: - rapid production; and / or - reliable application; and / or - low production costs; and / or - Easy to execute.

[0005] Furthermore, the present invention relates to a method for producing a treated container having improved properties, i.e., the treated container having: - Excellent resistance over a wide pH range; and / or - Improved resistance at high pH values; and / or - high chemical stability; and / or - Excellent adhesion properties.

[0006] The subject matter described above can be solved by a method for quality assessment of processed containers, the method comprising the following steps: Provide glass containers; Cleaning at least a portion of the inner surface of the container to obtain a clean surface that can be subjected to subsequent surface treatment; At least a portion of the inner surface of the container is surface treated to obtain a treated surface that is resistant to leaching.

[0007] Furthermore, the above objects can be solved by a treated container, wherein the leaching amount of one or more types of ions and / or compounds, in particular silicon, can be obtained by the method described herein, wherein the leaching amount of one or more types of ions and / or compounds, in particular silicon, is below 6.00 mg / l. Furthermore, it has surprisingly been found that if the treatment process according to the invention is carried out before a subsequent coating process is carried out on the treated glass surface, the adhesion of the coating can be improved.

[0008] Therefore, preferably, the method comprises the steps of: - performing a treatment process on at least a portion of the glass surface of the glass element, wherein the treatment process is one or more of the following: i) cleaning treatment; and / or ii) plasma treatment; Preferably, the treatment process is at least a plasma treatment; preferably, a cleaning process is performed first and then a plasma treatment is performed.

[0009] Without being bound by theory, it was surprisingly realized that by performing the specific treatments described herein, the glass surface has improved anti-leaching properties. Thus, in particular, the combination of the treatments (preferably the specific plasma treatments described herein) can result in a layer with particularly improved properties, namely excellent resistance in a wide pH range, improved resistance at high pH values, and high chemical stability.

[0010] In a preferred embodiment, the cleaning process is to spray water onto at least a portion of the glass surface, wherein one or more of the following parameters are met, preferably all of the following parameters are met: i) the spraying time is from 1 s to 5 h, preferably from 5 s to 60 min, more preferably from 1 min to 40 min, more preferably from 10 min to 40 min; and / or ii) water conductivity of 0.1 μs / cm to 400 μs / cm, preferably 0.5 μs / cm to 10 μs / cm, more preferably 1 μs / cm to 5 μs / cm, more preferably about 2 μs / cm; and / or iii) the temperature of the water is above 10°C, preferably 15°C to 100°C, more preferably 20°C to 80°C, more preferably 25°C to 40°C.

[0011] More preferably, all parameters i) to iii are satisfied. In another preferred embodiment, the spraying time is more than 10 min, and / or the water conductivity is less than 2 μs / cm, and / or the water temperature is at least partially above 30° C. Preferably, water is sprayed onto at least a portion of the glass surface through a needle nozzle, and the inner diameter of the needle nozzle is preferably 0.05 mm to 5 mm, preferably 0.5 mm to 2 mm. The cleaning process is easy to implement in production.

[0012] Preferably, after the cleaning treatment, the glass surface is dried, preferably at 100 to 400° C. for 1 to 100 minutes, preferably at 200 to 300° C. for 35 to 40 minutes. Preferably, the cleaning treatment is performed before the plasma treatment.

[0013] In another preferred embodiment, the plasma treatment is a plasma enhanced chemical vapor treatment (PECVT) process, a plasma pulsed chemical vapor treatment (PICVT) process or a plasma assisted chemical vapor treatment (PACVT) process, comprising the steps of: a) surrounding at least a portion of said glass surface of said glass element with precursor P2; and b) irradiating the precursor P2 to generate plasma; Among them, at least one of the following parameters is met, preferably all of the parameters are met: i) wherein the process temperature PT2 ranges from room temperature to Tg of the glass in the glass element, preferably from room temperature to 450°C, more preferably from room temperature to 400°C, more preferably from room temperature to 320°C, more preferably from room temperature to 280°C; and / or ii) wherein the pulse duration PD2 of the plasma is 50 ms or less, preferably 40 ms or less, preferably 30 ms or less, more preferably 20 ms or less, more preferably 15 ms or less, more preferably 8 ms or less, more preferably 6 ms or less, more preferably 1 ms or less, more preferably 0.5 ms; and / or iii) wherein the pulse duration PD2 of the plasma is greater than 0.1 ms, preferably greater than 0.2 ms, more preferably greater than 0.3 ms, more preferably greater than 0.5 ms; and / or iv) wherein the irradiation is performed by a microwave generator, preferably wherein the frequency of the radiation is 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, more preferably 2.45 GHz; and / or v) wherein the input power IP2, preferably the input power IP2 of the microwave generator is 1000W to 10000W, preferably 2500W to 8000W, more preferably 4000W to 8000W, more preferably 5000W to 7000W, more preferably 5000W to 6500W, more preferably 5250W to 5750W; and / or vi) the precursor P2 comprises argon, oxygen and / or nitrogen, preferably oxygen, more preferably, the precursor P2 is air; and / or vii) wherein the precursor P2 comprises an element N (e.g. N 2 ) and / or O (e.g. O 2 ), preferably N 2 and O 2 , more preferably O 2 , preferably consisting of;; and / or viii) the pulse pause time PP2 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.5 ms to 2.0 ms, more preferably 1.5 ms to 2.0 ms, more preferably 1.8 ms; and / or ix) the total irradiation time TT2 is 0.1 s or more, preferably 1 s or more, more preferably 1 s to 5 min, more preferably 5 s to 15 s; and / or x) the ratio [ms / ms] of all pulse durations PD2 [ms] to all pulse pauses PP2 [ms] is greater than 0.05, preferably greater than 0.1, more preferably from 0.15 to 5, more preferably from 0.2 to 0.5; and / or xi) wherein the process pressure PR2 is 0.01 mbar to 500 mbar, preferably 0.1 mbar to 100 mbar, more preferably 0.5 mbar to 10 mbar, more preferably 0.8 mbar to 6.0 mbar, more preferably 1.0 mbar to 4.0 mbar; and / or xii) wherein, during said plasma treatment, said process temperature PT2 is increased, preferably steadily increased; and / or xiii) wherein the process temperature PT2 is, at least partially, preferably at the end of the plasma treatment process, above 220°C, more preferably above 240°C, more preferably above 250°C, more preferably above 255°C, more preferably above 270°C, more preferably above 280°C; and / or xiv) wherein the flow rate of the precursor P2 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 50 sccm, more preferably 20 to 30 sccm.

[0014] According to the present invention, it has surprisingly been found that the above properties can be further improved if low pressures are used, i.e. below 10 mbar, preferably below 6.0 mbar, more preferably below 4 mbar, in combination with low input power, i.e. below 8000 W, preferably below 7000 W, more preferably below 6500 W, more preferably below 5750 W. Furthermore, the activation of the surface can be further improved if one or more parameters, preferably all parameters, are met. Thus, the properties of the layer, in particular the adhesion, can be improved. It is further preferred that the chemical purity of the precursor P2 should be at least 99%, preferably at least 99.995%.

[0015] In one embodiment, surrounding at least a portion of the glass surface of the glass element with the precursor P2 may be understood as exposing or placing at least a portion of the glass surface of the glass element in the precursor P2.

[0016] In one embodiment, the total irradiation time TT2 is the sum of the duration of all the pulses and the pulse pause time.

[0017] In one embodiment, the process temperature PT2 increases, preferably steadily, during the plasma treatment relative to a total irradiation time TT2, wherein the total irradiation time TT2 is the sum of the durations of all the pulses and the pulse pause time.

[0018] The glass in the glass element is not particularly limited. Preferably, the glass is borosilicate glass, aluminosilicate glass, lithium aluminosilicate (LAS) glass, and more preferably borosilicate glass. Therefore, the strong adhesion of the at least one layer can be improved.

[0019] In a preferred embodiment, the composition of the glass includes, by mass %, SiO 2 : 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%; and / or B 2 O 3 : 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%; and / or Al 2 O 3 : 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%; and / or X 2O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; and / or YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg.

[0020] More preferably, the glass composition is composed of the following in mass %: SiO 2 : 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%; B 2 O 3 : 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%; Al 2 O 3 : 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%; X 2 O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg; and Unavoidable impurities.

[0021] In another preferred embodiment, the composition of the glass comprises, by mass %, SiO 2 : 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%; and / or B 2 O 3 : 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%; and / or Al 2 O 3 : 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%; and / or X 2 O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; and / or YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg.

[0022] More preferably, the glass composition is composed of the following in mass %: SiO 2 : 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%; B 2 O 3 : 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%; Al 2 O 3 : 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%; X 2 O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg; and Preferably unavoidable impurities.

[0023] The shape of the glass element is not particularly limited. The shape may be a tube, a rod, a plate and / or a container. Preferably, the glass element is a container, more preferably a pharmaceutical container, more preferably a vial, a syringe, an ampoule or a cartridge, more preferably a vial. Even if developed for pharmaceutical packaging, the coated glass element can also be used in automobiles, aircraft, technical pipes and many other technical fields due to its improved properties.

[0024] If the glass element is a container, the volume of the container is not particularly limited. Preferably, the brimful volume of the container is 0.1 ml to 1000 ml, preferably 0.5 ml to 500 ml, more preferably 1 ml to 250 ml, more preferably 2 ml to 30 ml, more preferably 2 ml to 15 ml, more preferably about 1 ml, 2 ml, 3 ml, 4 ml, 5 ml, 6 ml, 7 ml, 8 ml, 9 ml, 10 ml, 11 ml, 12 ml, 13 ml, 14 ml or 15 ml; more preferably 5 to 15 ml.

[0025] The location of at least a portion of the glass surface is not particularly limited. Preferably, the glass element (preferably, wherein the glass element is a tube or a container, more preferably, a container) comprises an inner surface, wherein the inner surface comprises at least a portion of the glass surface, preferably at least a portion of the glass surface. Therefore, if a pharmaceutical composition is present in the container, the inner surface of the glass element will be effectively protected.

[0026] In another preferred embodiment, the glass element (preferably, wherein the glass element is a tube or a container, more preferably a container) comprises an outer surface, wherein the outer surface comprises at least a portion of the glass surface, preferably is at least a portion of the glass surface.

[0027] In a preferred embodiment, the glass element is a vial or a cartridge, the vial or cartridge comprising a barrel, a neck and a crown, wherein at least the inner surface of the barrel is coated with the coating. Therefore, if a pharmaceutical composition is present in the container, the inner surface of the glass element is effectively protected.

[0028] In a preferred embodiment, at least a portion of the glass surface of the container includes at least a portion of the inner surface of the container. Preferably, when the container stands stably on the ground and is filled with liquid whose volume is more than 10%, preferably more than 30%, and more preferably more than 90% of the full volume [vol / vol] of the container, at least a portion of the glass surface of the container is the surface in contact with the liquid.

[0029] In a preferred embodiment, the glass element is a vial or cartridge, the vial or cartridge comprising a barrel, a neck and a crown, wherein the crown, preferably the crown and the neck, are uncoated; and / or the glass element is a syringe, the syringe comprising a flange, a barrel and a tip, preferably the syringe comprising a flange, a barrel, a tip and a needle, wherein the needle, preferably the needle and the flange, more preferably the needle and the tip, are uncoated. Thus, the storage stability of the pharmaceutical composition, if any, is improved.

[0030] definition If not stated otherwise, the following definitions apply throughout the description and claims: In this article, Tg (glass transition temperature) is measured by differential scanning calorimetry (DSC). In this article, ultrapure water is water with a purity of 1 in accordance with DIN ISO 3696, and its conductivity does not exceed 0.1 µS / cm at 25 °C.

[0031] Leaching measurements The amount of Si leached from the treated container can be measured by the following test Q, and its effectiveness can be determined by a leaching test of the inner surface. The test can be applied to both untreated glass containers and treated glass containers.

[0032] Test Q is done using a standard 2R vial, but different sizes such as 5R are also available. Perform the following steps on the inner surface:

[0033] 1. Rinse the vial with water.

[0034] 2. Dry the vials in a vacuum autoclave (e.g. Systec, Model DX-150 (PM-CA-0001-01)) at 121°C for 4 hours with the bottom of the vial facing up.

[0035] 3. Fill to 0.33 brim full level with ultrapure water.

[0036] 4. Place the autoclaved vial of water at 121°C and 1 bar above ambient pressure for 2 hours.

[0037] 5. Analyze the water content (mg / l) of Si ions by FAAS analysis (e.g. using Varian SpectrAA 280 FS (PE 3-004)) to obtain the value of silicon ion leaching amount [mg / l].

[0038] According to the leaching test Q, the Si leaching amount of the treated glass container is less than 6 mg / l, in particular less than 4 mg / l and largely less than 2 mg / l. This is the test result after the vials are treated according to the following example. The leaching test Q carried out on the untreated glass container shows that the Si leaching amount is higher than 6 mg / l.

[0039] Example 1 If not otherwise stated, Example 1 was prepared according to EP 0 821 079 A1, EP 0 811 367 A2, WO 03 015 122 A1 and EP 2 106 461 A1: Two 5R vials (EVERICTM pure from SCHOTT) were provided. As a first treatment, a cleaning treatment was performed in which the vials were cleaned with ultrapure water at 25 °C at a rate of ≤10 μs / cm for 2 minutes at room temperature, at 40 °C for 6 minutes, and then in a laboratory dishwasher (LS-2000 from HAMO AG) at room temperature for 20 minutes. Afterwards, the vials were dried at 290 °C for 20 minutes.

[0040] Subsequently, two vials were treated and coated simultaneously using the apparatus according to WO 03 015 122 A1. For all plasma treatments, microwave irradiation with a frequency of 2.45 GHz was used. The reaction chamber was the inner part of the vial. The outside of the vial was ambient conditions.

[0041] First, the interior of the vial was evacuated until a value of 0.05 mbar was reached. Afterwards, oxygen was charged into the vial (flow rate per vial: 50 sccm) until a pressure of 5 mbar was reached and the plasma treatment was started. The plasma was ignited in pulse mode with an input power of 6700 W (for each vial), a pulse duration of 0.5 ms and a pulse pause time of 1.8 ms. The plasma treatment was carried out for 14 seconds until the temperature of the vial reached 280 °C, which was measured with a pyrometer in the middle of the cylindrical part of the vial.

[0042] Example 2 If not otherwise stated, Example 2 was prepared according to EP 0 821 079 A1, EP 0 811 367 A2, WO 03 015 122 A1 and EP 2 106 461 A1: Two 5R vials (EVERICTM pure from SCHOTT) were provided. As a first treatment, a cleaning treatment was performed in which the vials were cleaned with ultrapure water at 25 °C at a rate of ≤10 μs / cm for 2 minutes at room temperature, at 40 °C for 6 minutes, and then in a laboratory dishwasher (LS-2000 from HAMO AG) for 20 minutes at room temperature. Afterwards, the vials were dried at 290 °C for 20 minutes.

[0043] Subsequently, two vials were treated and coated simultaneously using the apparatus according to WO 03 015 122 A1. For all plasma treatments, microwave irradiation with a frequency of 2.45 GHz was used. The reaction chamber was the inner part of the vial. The outside of the vial was ambient conditions.

[0044] First, the interior of the vial was evacuated until a value of 0.05 mbar was reached. Afterwards, oxygen was charged into the vial (flow rate per vial: 50 sccm) until a pressure of 1.2 mbar was reached and the plasma treatment was started. The plasma was ignited in pulse mode with an input power of 5500 W, a pulse duration of 0.5 ms and a pulse pause time of 1.8 ms. The plasma treatment was carried out for 27 seconds until the temperature of the vial reached 280 °C, which was measured with a pyrometer in the middle of the cylindrical part of the vial.

[0045] The vials that have undergone the cleaning step and plasma treatment may be referred to as uncoated vials since no coating has been applied. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] There are several ways to design and further develop the teaching of the invention in an advantageous manner. For this purpose, reference is made on the one hand to the patent claims that are subordinate to the independent patent claims and on the other hand to the description of the preferred examples of embodiments of the invention shown in the drawings and the accompanying items. On the basis of the explanation of the preferred embodiments of the invention with the aid of the drawings, further preferred embodiments and further developments of the invention will be explained.

[0047] Figure 1 is a schematic side view of an embodiment of the present invention; Figure 2 is a schematic side view of an embodiment of the present invention; Figure 3 is a block diagram of a method according to an embodiment of the present invention.

[0048] In the following description of the embodiments, the same reference numerals denote similar components.

[0049] Reference numerals list 1 Glass surface 2 Coating 3 Treated glass surface 1001 Processing 1002 Coating process 1003 Post-processing DETAILED DESCRIPTION

[0050] Figure 1 and Figure 2 A schematic side view of an embodiment of the present invention is depicted. The treated surface 3 is covered with an optional coating 2. Figure 1 In FIG. 1 , the glass surface 1 is partially coated with a coating 2. The coating depicted is a single-layer coating. Thus, the coating is in direct contact with the glass surface 1 and is the outermost layer. Figure 2 In FIG. 1 , a partially pretreated glass surface 3 is partially coated with a coating 2. The coating depicted is a single-layer coating. Thus, the coating is in direct contact with the glass surface 1 and is the outermost layer.

[0051] Figure 3 A block diagram of a method according to an embodiment of the present invention is shown. After treatment 1001, a coating process 1002 is performed. Afterwards, post-treatment 1003 may be performed.

[0052] project 1. A method, preferably according to any of the preceding items, comprising the steps of: - performing a treatment process on at least a portion of the glass surface of the glass element, wherein the treatment process is one or more of the following: i) cleaning treatment; and / or ii) During plasma treatment, Preferably, the cleaning treatment is performed first, and then the plasma treatment is performed.

[0053] 2. A method according to any of the preceding items, wherein: The cleaning process is to spray water onto the at least a portion of the glass surface, wherein one or more of the following parameters are met, preferably all of the following parameters are met: i) the spraying time is from 1 s to 5 h, preferably from 5 s to 60 min, more preferably from 1 min to 40 min, more preferably from 10 min to 40 min; and / or ii) water conductivity of 0.1 μs / cm to 400 μs / cm, preferably 0.5 μs / cm to 10 μs / cm, more preferably 1 μs / cm to 5 μs / cm, more preferably about 2 μs / cm; and / or iii) the temperature of the water is above 10°C, preferably 15°C to 100°C, more preferably 20°C to 80°C, more preferably 25°C to 40°C.

[0054] 3. A method according to any of the preceding items, wherein: The plasma treatment is a plasma enhanced chemical vapor treatment (PECVT) process, a plasma pulsed chemical vapor treatment (PICVT) process or a plasma assisted chemical vapor treatment (PACVT) process, which comprises the steps of: a) surrounding said at least a portion of said glass surface of said glass element with precursor P2; and b) irradiating the precursor P2 to generate plasma; Among them, at least one of the following parameters is met, preferably all of the parameters are met: i) wherein the process temperature PT2 ranges from room temperature to Tg of the glass in the glass element, preferably from room temperature to 450°C, more preferably from room temperature to 400°C, more preferably from room temperature to 320°C, more preferably from room temperature to 280°C; and / or ii) wherein the pulse duration PD2 of the plasma is 50 ms or less, preferably 40 ms or less, preferably 30 ms or less, more preferably 20 ms or less, more preferably 15 ms or less, more preferably 8 ms or less, more preferably 6 ms or less, more preferably 1 ms or less, more preferably 0.5 ms or less; and / or iii) wherein the pulse duration PD2 of the plasma is greater than 0.1 ms, preferably greater than 0.2 ms, more preferably greater than 0.3 ms, more preferably greater than 0.5 ms; and / or iv) wherein the irradiation is performed by a microwave generator, preferably wherein the frequency of the radiation is 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, more preferably 2.45 GHz; and / or v) wherein the input power IP2, preferably the input power IP2 of the microwave generator, is 1000W to 10000W, preferably 2500W to 8000W, more preferably 4000W to 8000W, more preferably 5000W to 7000W, more preferably 5000W to 6500W, more preferably 5250W to 5750W; and / or vi) the precursor P2 comprises argon, oxygen and / or nitrogen, preferably oxygen, more preferably, the precursor P2 is air; and / or vii) wherein the precursor P2 comprises element N (e.g. N 2 ) and / or O (e.g. O 2 ), preferably consisting of an element N (e.g. N 2 ) and / or O (e.g. O 2 ) composition; preferably N 2 and O 2 , more preferably O 2 ; and / or viii) the pulse pause time PP2 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.5 ms to 2.0 ms, more preferably 1.5 ms to 2.0 ms, more preferably 1.8 ms; and / or ix) the total irradiation time TT2 is 0.1 s or more, preferably 1 s or more, more preferably 1 s to 5 min, more preferably 5 s to 15 s; and / or x) the ratio [ms / ms] of all pulse durations PD2 [ms] to all pulse pauses PP2 [ms] is greater than 0.05, preferably greater than 0.1, more preferably from 0.15 to 5, more preferably from 0.2 to 0.5; and / or xi) wherein the process pressure PR2 is from 0.01 mbar to 500 mbar, preferably from 0.1 mbar to 100 mbar, more preferably from 0.5 mbar to 10 mbar, more preferably from 0.8 mbar to 6.0 mbar, more preferably from 1.0 mbar to 4.0 mbar; and / or xii) wherein, during said plasma treatment, said process temperature PT2 is increased, preferably steadily increased; and / or xiii) wherein the process temperature PT2 is, at least partially, preferably at the end of the plasma treatment process, above 220°C, more preferably above 240°C, more preferably above 250°C, more preferably above 255°C, more preferably above 270°C, more preferably above 280°C; and / or xiv) wherein the flow rate of the precursor P2 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 50 sccm, more preferably 20 to 30 sccm.

[0055] 4. Use of the pretreated glass element according to any of the preceding items in a method comprising a coating process, preferably the coating process comprises a CVD process, more preferably a PECVD, PICVD or PACVD process, more preferably a PICVD process.

[0056] 5. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any of the preceding items, wherein the glass is borosilicate glass, aluminosilicate glass, lithium aluminosilicate (LAS) glass, preferably borosilicate glass.

[0057] 6. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any one of the preceding items, wherein the composition of the glass comprises, in mass %,: SiO 2 : 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%; and / or B 2 O 3 : 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%; and / or Al 2 O 3 : 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%; and / or X 2 O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; and / or YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg.

[0058] 7. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any of the preceding items, wherein the composition of the glass consists, in mass %, of: SiO 2 : 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%; B 2 O 3 : 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%; Al 2 O 3 : 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%; X 2 O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg; and Preferably unavoidable impurities.

[0059] 8. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any one of the preceding items, wherein the composition of the glass comprises, in mass %,: SiO 2 : 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%; and / or B 2 O 3 : 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%; and / or Al 2 O 3 : 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%; and / or X 2 O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; and / or YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg.

[0060] 9. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any one of the preceding items, wherein the composition of the glass consists, in mass %, of: SiO 2 : 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%; B 2 O3 : 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%; Al 2 O 3 : 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%; X 2 O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, Li, preferably X is Na and / or K; YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, preferably Y is Ca and / or Mg; and Preferably unavoidable impurities.

[0061] 10. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any of the preceding items, wherein: The glass element is a container, more preferably a pharmaceutical container, more preferably a vial, a syringe, an ampoule or a cartridge, more preferably a vial.

[0062] 11. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any one of the preceding items, wherein: The full mouth volume of the container is 0.1ml to 1000ml, preferably 0.5ml to 500ml, more preferably 1ml to 250ml, more preferably 2ml to 30ml, more preferably 2ml to 15ml, more preferably about 1ml, 2ml, 3ml, 4ml, 5ml, 6ml, 7ml, 8ml, 9ml, 10ml, 11ml, 12ml, 13ml, 14ml or 15ml; more preferably 5 to 15ml.

[0063] 12. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any of the preceding items, Preferably, wherein the glass element is a tube or a container, more preferably a container, wherein the glass element comprises an inner surface, wherein the inner surface comprises said at least a portion of the glass surface, preferably is said at least a portion of the glass surface.

[0064] 13. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any one of the preceding items, Preferably, wherein the glass element is a tube or a container, more preferably a container, wherein the glass element comprises an outer surface, wherein the outer surface comprises said at least part of the glass surface, preferably is said at least part of the glass surface.

[0065] 14. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any one of the preceding items, wherein: The glass element is a vial or a cartridge, and the vial or the cartridge comprises a barrel, a neck and a crown, wherein at least the inner surface of the barrel is coated with the coating.

[0066] 15. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any one of the preceding clauses, wherein: At least a portion of the glass surface of the container includes at least a portion of the inner surface of the container. Preferably, when the container stands stably on the ground and is filled with liquid whose volume is more than 10%, preferably more than 30%, and more preferably more than 90% of the full volume [vol / vol] of the container, at least a portion of the glass surface of the container is the surface in contact with the liquid.

[0067] 16. The method, the use, the glass element, the coated glass element and / or the filled coated glass element according to any of the preceding items, wherein: The glass element is a vial or a cartridge comprising a barrel, a neck and a crown, wherein the crown, preferably the crown and the neck, are uncoated; and / or Wherein, the glass element is a syringe, the syringe comprising a flange, a barrel and a tip, preferably further comprising a needle, wherein the needle, preferably the needle and the flange, more preferably the needle and the tip are uncoated.

[0068] In summary, embodiments and preferred embodiments are as follows. The scope of protection is determined by the claims. Combinations of two or more embodiments, such as 3, 4 or 8 embodiments, are further preferred. The definitions and general statements herein preferably also apply to the following embodiments and preferred embodiments.

[0069] In a further preferred embodiment, the inner surface of the container, preferably the entire inner surface of the container, is coated. Thus, the pharmaceutical composition is further protected. In a further preferred embodiment, the outer surface of the container is uncoated. In a further preferred embodiment, the inner surface of the container, preferably the entire inner surface of the container, is coated, while the outer surface of the container is uncoated. Thus, the pharmaceutical composition is further protected. More preferably, the coating is obtainable as described in European patent application EP 21 164 784.

Claims

1. A method for treating a glass container, comprising the steps of: ‐Provide glass containers; Cleaning at least a portion of the inner surface of the glass container; The at least a portion of the inner surface of the glass container is plasma treated.

2. The method according to claim 1, wherein: The cleaning process is to spray water onto the at least a portion of the glass surface, wherein one or more of the following parameters are met, preferably all of the following parameters are met: i) the spraying time is from 1 s to 4 h, preferably from 9 s to 50 min, more preferably from 2 min to 40 min, more preferably from 11 min to 39 min; and / or ii) water conductivity of 0.1 μs / cm to 400 μs / cm, preferably 0.5 μs / cm to 10 μs / cm, more preferably 1 μs / cm to 5 μs / cm, more preferably about 2 μs / cm; and / or iii) the temperature of the water is above 10°C, preferably 15°C to 100°C, more preferably 20°C to 80°C, more preferably 25°C to 40°C.

3. The method according to claim 2, wherein: The plasma treatment is a plasma enhanced chemical vapor treatment PECVT process, a plasma pulse chemical vapor treatment PICVT process or a plasma assisted chemical vapor treatment PACVT process, comprising the following steps: a) surrounding at least a portion of the (inner) glass surface of the glass element with precursor P2; as well as b) irradiating the precursor P2 to generate plasma; Among them, at least one of the following parameters is met, preferably all of the parameters are met: i) wherein the process temperature PT2 ranges from room temperature to the Tg of the glass in the glass element, preferably from room temperature to 450° C., more preferably from room temperature to 400° C., more preferably from room temperature to 320° C., more preferably from room temperature to 280° C.; and / or ii) wherein the pulse duration PD2 of the plasma is 50 ms or less, preferably 40 ms or less, preferably 30 ms or less, more preferably 20 ms or less, more preferably 15 ms or less, more preferably 8 ms or less, more preferably 6 ms or less, more preferably 1 ms or less, more preferably 0.5 ms; and / or iii) wherein the pulse duration PD2 of the plasma is greater than 0.1 ms, preferably greater than 0.2 ms, more preferably greater than 0.3 ms, more preferably greater than 0.5 ms; and / or iv) wherein the irradiation is performed by a microwave generator, preferably wherein the frequency of the radiation is 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, more preferably 2.45 GHz; and / or v) wherein the input power IP2, preferably, the input power IP2 of the microwave generator is 1000W to 10000W, preferably 2500W to 8000W, more preferably 4000W to 8000W, more preferably 5000W to 7000W, more preferably 5000W to 6500W, more preferably 5250W to 5750W; and / or vi) the precursor P2 comprises argon, oxygen and / or nitrogen, preferably oxygen, more preferably the precursor P2 is air; and / or vii) wherein the precursor P2 comprises, preferably consists of, the elements N (e.g. N2) and / or O (e.g. O2), preferably N2 and O2, more preferably O2; and / or viii) the pulse pause time PP2 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.5 ms to 2 ms, more preferably 1.5 ms to 2.0 ms, more preferably 1.8 ms; and / or ix) the total irradiation time TT2 is 0.1 s or more, preferably 1 s or more, more preferably 1 s to 5 min, more preferably 5 s to 15 s; and / or x) the ratio [ms / ms] of all pulse durations PD2 [ms] to all pulse pauses PP2 [ms] is greater than 0.05, preferably greater than 0.1, more preferably from 0.15 to 5, more preferably from 0.2 to 0.5; and / or xi) wherein the process pressure PR2 is from 0.01 mbar to 500 mbar, preferably from 0.1 mbar to 100 mbar, more preferably from 0.5 mbar to 10 mbar, more preferably from 0.8 mbar to 6.0 mbar, more preferably from 1.0 mbar to 4.0 mbar; and / or xii) wherein, during said plasma treatment, said process temperature PT2 is increased, preferably steadily increased; and / or xiii) wherein the process temperature PT2 is, at least partially, preferably at the end of the plasma treatment process, above 220°C, more preferably above 240°C, more preferably above 250°C, more preferably above 255°C, more preferably above 270°C, more preferably above 280°C; and / or xiv) wherein the flow rate of the precursor P2 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 50 sccm, more preferably 20 to 30 sccm.

4. A method according to any one of the preceding claims, wherein: The glass containers provided are vials, syringes, cartridges or ampoules.

5. The method according to claim 4, wherein: The glass container is a vial with a size of 1R to 9R or 11R to 100R.

6. The method according to any one of the preceding claims, further comprising: A further coating is provided on the at least a portion of the inner surface that has been subjected to the plasma treatment.

7. A pharmaceutical glass container treated according to the method of any one of the preceding claims, wherein: The glass container comprises an inner surface and an outer surface, wherein the leaching amount of Si ions from the inner surface is 6 mg / l or less.

8. The medicinal glass container according to claim 7, wherein: The leaching amount is 6.0 mg / l or less, preferably 5.0 mg / l or less, and more preferably 2.0 mg / l or less.

9. The medicinal glass container according to claim 7 or 8, wherein: The leaching amount is 0.01 mg / l or more, preferably 0.1 mg / l or more.

10. The pharmaceutical glass container according to any one of claims 7 to 9, wherein: The inner surface of the container is uncoated.

11. The pharmaceutical glass container according to any one of claims 7 to 10, wherein: The leaching amount can be obtained by the method described in the specification.

12. The pharmaceutical glass container according to any one of claims 7 to 11, wherein: The glass container is made of glass.

13. The pharmaceutical glass container according to any one of claims 7 to 11, wherein: The container is a vial, a syringe, a cartridge or an ampoule.

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