Method for making coated containers

Abstract

To provide a method of making a coated container, e.g. a syringe, particularly a method of making a container with a lubricant coating on an inner surface.SOLUTION: A method of making a coated container 1 comprises the steps of: providing a container comprising a hollow cylindrical body 7 having a wall surrounding a lumen, the hollow cylindrical body having at least one opening 4; inserting an application body 20 into the lumen through the opening; applying a coating composition 8 to the application body such that the coating composition contacts at least a section of an inner surface of the wall; depositing the coating composition on a deposition area of the inner surface of the wall by moving the application body relative to the hollow cylindrical body; and retracting the application body from the lumen through the opening, where a size of the application body is such that a circumferential gap is present between the application body and the inner surface of the wall during the depositing step.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This disclosure relates to a method for manufacturing coated containers, such as syringes. In particular, this disclosure relates to a method for manufacturing containers having a lubricant coating on their inner surface. This disclosure also relates to coated containers.

[0002] Background technology Pharmaceutical containers must meet very stringent requirements, including resistance to breakage and leakage. These containers must also be optically flawless so as not to undermine the patient's or physician's confidence in the quality of the pharmaceutical composition contained within them.

[0003] Some pharmaceutical containers, such as syringes, require the smooth movement of a stopper to dispense the contents. To achieve this goal, it may be necessary to apply a coating to the inner surface of the pharmaceutical container. Any coating applied to the contact surface between the container and the stopper should improve smooth movement, and it is desirable that heterogeneity does not affect this smooth movement of the stopper. The stopper movement should be very uniform, that is, it should not change abruptly along the path of stopper movement. Otherwise, abrupt changes in sliding force would hinder the easy and effortless administration of the pharmaceutical composition from the container.

[0004] The pharmaceutical container market requires enormous quantities. Simple and robust manufacturing technologies are crucial to facilitating the production of millions or even billions of such containers. For example, pre-filled syringes are a type of pharmaceutical container that has gained significant attention in recent years. Market research indicates a substantial expansion in the pre-filled syringe market. Demand for pre-filled syringes is driven by various factors, including increased vaccine production and the adoption of self-administered biologics for chronic conditions. Recent studies predict that sales of pre-filled syringes will grow at an annual rate of approximately 9% until 2027, reaching a value of approximately US$9 billion.

[0005] A pharmaceutical container and manufacturing method that satisfy one or more of the above-mentioned objectives is required.

[0006] Summary of the Invention In a first aspect, the present disclosure relates to a method for producing a coated container, A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, This invention relates to a method in which the size of the coating is such that a circumferential gap exists between the coating and the volume region during the deposition step.

[0007] Conventional methods for producing coated containers include spray coating. Spray coating is extremely difficult to control, and as a result, a perfectly homogeneous coating layer cannot be achieved. Other methods rely on a hemispherical applicator inserted into a container so as to contact the inner wall of the container. After insertion, a liquid coating composition is applied to the applicator so as to distribute the coating composition as the applicator retracts from the container.

[0008] In contrast to "press-fit" coating processes, the method of the present disclosure is characterized by a circumferential gap between the coating and the deposition area during the deposition step, in particular, the coating does not contact the inner surface of the hollow cylinder. Press-fitting is not used; i.e., the coating is not packed into the hollow cylinder, but a gap is left. This gap allows the coating composition applied to the coating to reach or contact at least a portion of the inner surface of the wall, and the coating thereby bridges the gap between the coating and the inner surface, forming a so-called capillary bridge.

[0009] This capillary bridging technique facilitates a completely different method of coating containers compared to press-fitting. The inventors assume that in the former process, the coating composition flows down the inner surface of the hollow cylinder as a free-moving film. In contrast, the capillary bridging technique lays the silicone cocktail on the surface like a blanket on a bed. Thus, while most of the fluid is dragged away by the moving coater, only a thin liquid layer remains on the inner surface. Due to drag, a constant stress exists along the liquid film. This reliably reduces the greater tendency of the coating composition to accumulate compared to films prepared by press-fitting. While not wishing to be bound by this theory, the inventors believe this contributes to the superior coating quality achievable with this capillary bridging technique.

[0010] In a second aspect, the Disclosure relates to a coated container which may be optionally obtained or may be obtained by the method of aspect 1, comprising a hollow cylindrical body having a wall surrounding a lumen, the hollow cylindrical body having at least one opening, and at least a portion of the inner surface of the wall comprising a coating, The average coating thickness is 100-3000 nm, and The total area of ​​excess coating thickness is less than 10% of the coated area, and excess coating thickness is defined as the area where the coating thickness exceeds twice the average coating thickness. Regarding coated containers.

[0011] As described above, the method of the present disclosure enables the production of coated containers having excellent membrane properties. The coating exhibits little variation in coating thickness, i.e., a small proportion of regions having excessive thickness or very low thickness. This achieves good and uniform sliding properties for stoppers used in pharmaceutical containers, particularly prefilled syringes. A uniform coating thickness also reduces the tendency of the coating to be scraped off from the inner surface by movement of the stopper, since maximum local stresses are reduced. Thereby, the coating technique used in the present disclosure contributes to reducing potential contamination of pharmaceutical preparations in the container, especially when the storage time in the prefilled syringe is long. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] [Figure 1] 1 shows an exemplary pharmaceutical container. [Figure 2] 2 is a schematic view of some of the method steps of the method of the present disclosure. [Figure 3A] 3 is a schematic view of an applicator inserted into a hollow cylindrical body in a press-fit mode. [Figure 3B] 4 is a schematic view of an applicator inserted into a hollow cylindrical body having a circumferential gap according to the present disclosure. [Figure 4A] 5 shows the thickness distribution of a coating applied by a press-fit technique. [Figure 4B] 6 shows the thickness distribution of a coating applied using the capillary bridge technique of the present disclosure. [Figure 5A] 7 is a schematic view of an applicator according to the present disclosure. [Figure 5B] 8 shows the shape of a capillary bridge obtained by the method of the present disclosure.

[0013] Mode for Carrying Out the Invention Method In one embodiment, the present disclosure provides a method of producing a coated container, comprising: A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, This invention relates to a method in which the size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step.

[0014] Pharmaceutical containers and / or walls may be made in part or entirely of materials suitable for the primary packaging of pharmaceuticals. Suitable materials include glass or polymers. Glass may be silicate glass, such as borosilicate glass. Polymers may be amorphous polymers. Transparent polymers are preferred. Suitable polymers can be selected from the group consisting of cyclic olefin copolymers (COC), cyclic olefin polymers (COP), polyethylene terephthalate (PET), polycarbonate (PC), polypropylene (PP), and methyl methacrylate acrylonitrile butadiene styrene polymers (MABS). These polymers have the advantages of low density, high transparency, low birefringence, extremely low water absorption, excellent water vapor barrier properties, high rigidity, strength and hardness, excellent biocompatibility, very good resistance to acids and alkalis, and very good melt processability.

[0015] The walls and / or the pharmaceutical container may be made of polymer. Optionally, a lower density compared to glass, e.g., 0.90–1.20 g / cm³. 3 , or over 1.00 to 1.10 g / cm³ 3A polymer having a density is selected. If a low-density material is used, transportation costs can be reduced. The density can be determined using the method described in ISO 1183-1:2013-04. The wall thickness may be 1 mm to 2.5 mm, or 1.2 mm to 2 mm, or 1.3 mm to 1.9 mm.

[0016] In embodiments, the applicator is inserted and withdrawn through the same opening. If the container is a syringe, this is typically the opening on the flange side. In certain embodiments, the opening through which the applicator is withdrawn faces downward. Typically, the direction of movement in the deposition step is the same as the direction of withdrawal in the withdrawal step of this method. Thus, in some embodiments, at least some of the coating composition is deposited on the deposition area by the downward movement of the applicator. During this movement, the capillary bridge bridges the gap between the applicator and the inner surface of the wall, thereby causing the coating composition to be deposited very uniformly on the deposition area. In this disclosure, “deposition area” is the portion of the inner surface of the wall where the coating is desired and / or formed during the coating process by depositing the coating composition. It should be understood that the insertion, movement, and withdrawal of the applicator include cases where the applicator is stationary, the container is moved, or both the applicator and the container are moved. In other words, the movements described should be understood as relative movements. In some embodiments, more than 80% (vol / vol) of the coating composition, or substantially all of the coating composition, is deposited on the deposition area by the downward movement of the applicator.

[0017] The insertion of the coating is completed when the coating is in its initial position. “Initial position” refers to the position within the cylinder where the step of applying the coating composition to the coating is performed. If the coating composition is deposited by a withdrawal movement, i.e., in the opposite direction of insertion, the initial position is closer to the opposite end of the deposition area compared to the opening where the coating was inserted. If the coating composition is deposited by a push movement, i.e., in the insertion direction, the initial position is closer to the end of the deposition area adjacent to or near the opening where the coating was inserted. Deposition by a withdrawal movement has been found to be advantageous over push movement in that it results in a more homogeneous coating.

[0018] Optionally, the gap may be an annular gap having an essentially circular cross-section. Generally, if both the coating and the hollow cylinder have essentially round cross-sections, it is easier to obtain a homogeneous coating. In embodiments, if the coating is located within a hollow cylinder, it has a circumferential portion closest to the inner surface of the wall. This portion can be called the “equator” of the coating, whether the coating is spherical or not. The coating can have a spherical, hemispherical, conical, or any other shape suitable for achieving a capillary bridge as discussed herein. Generally, it is desirable that the coating has an essentially spherical, hemispherical, or conical shape on the equatorial side to which the coating composition is applied. In one embodiment, the coating composition can be applied to the upward side of the coating so that the coating composition can flow downward in the direction of the gap, forming a capillary bridge downward in the direction of the gap. In one embodiment, the coating has a shape in which the diameter increases from the upward side toward its equator.

[0019] The size of the circumferential gap can be characterized by the distance D between the coated material and the deposited area during the deposition step. The distance D is defined as the average distance between the coated material and the deposited area during the deposition step. The "average distance" is the average inner diameter D of the hollow cylinder. ID From the average diameter D of the coated material AB It is calculated by subtracting and dividing by 2.

Number

[0020] The relative gap size is D / D AB can be defined as. In one embodiment, D / D AB is 0.0005 to 0.02, 0.001 to 0.01, 0.0015 to 0.006. Optionally, D / D AB is at least 0.0005, at least 0.001, at least 0.0015, or at least 0.002. In certain embodiments, D / D AB is at most 0.02, at most 0.01, at most 0.08, at most 0.06, or at most 0.04.

[0021] It is useful to select a container having a hollow cylindrical body that satisfies strict geometric parameters. In one embodiment, the cylindrical body has a total internal diameter variation in the deposition region of up to 2D, up to 1.5D, or up to D. Optionally, the total internal diameter variation is less than 0.10 mm, less than 0.08 mm, less than 0.06 mm, or less than 0.04 mm. A smaller total internal diameter variation is better. However, in some embodiments, providing a container with an extremely small total internal diameter variation may not be economically feasible. Therefore, in one embodiment, the total internal diameter variation may be at least 0.0001 mm, at least 0.001 mm, or at least 0.01 mm. For example, the total internal diameter variation may be in the range of 0.0001 mm to less than 0.10 mm, 0.001 mm to less than 0.08 mm, or 0.01 mm to less than 0.04 mm.

[0022] To facilitate a highly homogeneous coating, the coating material should also meet stringent quality standards. For example, the coating material may have a total outer diameter variation at its equator of up to 2D, up to 1.5D, or up to D. Optionally, the total outer diameter variation is less than 0.20 mm, less than 0.15 mm, less than 0.10 mm, or less than 0.04 mm. A smaller total outer diameter variation is better. However, in some embodiments, providing a coating material with an extremely small total outer diameter variation may not be economically feasible. Therefore, in one embodiment, the total outer diameter variation may be at least 0.0001 mm, at least 0.001 mm, or at least 0.003 mm. For example, the total outer diameter variation may be in the range of 0.0001 mm to less than 0.20 mm, 0.001 mm to less than 0.15 mm, or 0.003 mm to less than 0.04 mm.

[0023] In one embodiment, the applicator contains or consists of a polymer material. The applicator may or may not be coated. Generally, the material of the applicator is not limited as long as it is available with sufficient dimensional accuracy (see above). In one embodiment, at least a portion of the surface of the applicator that comes into contact with the coating composition during the method of the present disclosure is made of a fluorinated polymer such as PTFE or is coated with a fluorinated polymer.

[0024] In one embodiment, the applicator and / or coating on the applicator contains resins such as fluorinated polymers, including polytetrafluoroethylene (PTFE), densified expanded polytetrafluoroethylene (ePTFE), tetrafluoroethylene (TFE), tetrafluoroethylene-perfluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, trichlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoropropyl vinyl ether, perfluoroalkoxy polymers, and polymers selected from the group consisting of copolymers, blends, and combinations thereof. The coating may also be formed by layers containing polyethylene, polypropylene, polyparaxylxylene, polylactic acid, and copolymers, blends, and combinations thereof. PTFE coating is one coating option. These coatings reduce the coefficient of friction of the body surface on the inner surface of the hollow cylindrical body.

[0025] At least a portion of the surface of the coating, such as the portion of the surface in contact with the capillary bridge, may have a water contact angle of at least 100°, or even at least 110°. This surface may be superhydrophobic.

[0026] The inner surface of the hollow cylinder can have a surface energy of up to 45 mN / m, up to 40 mN / m, or up to 35 mN / m. Optionally, the surface energy is at least 15 mN / m, at least 20 mN / m, or at least 25 mN / m. For example, the inner surface energy may be in the range of 15 mN / m to 45 mN / m, 20 mN / m to 40 mN / m, or 25 mN / m to 35 mN / m. Preferably, the inner surface energy is higher than the surface energy of the coating surface on which the capillary bridge is formed. For example, the coating surface energy may be up to 25 mN / m, or up to 20 mN / m. Optionally, the coating surface energy may be at least 10 mN / m, or at least 15 mN / m. In one embodiment, the surface energy of the coating in which the capillary bridge is formed is in the range of 10 mN / m to 25 mN / m, or 15 mN / m to 20 mN / m. In one embodiment, the surface energy of the inner surface of the hollow cylinder is at least 40%, at least 50%, or at least 60% greater than the surface energy of the coating. The surface energy can be measured indirectly by calculating the value from contact angle measurements using the Owens-Wendt-Rabel-Kaelble (OWRK) method, according to DIN 55660-2:2011-12, Chapter 6.2. The surface energy of the coating composition may be less than the surface energy of the coating and / or the inner surface of the hollow cylinder. Optionally, the surface energy of the coating composition is less than 20 mN / m, less than 17 mN / m, or less than 15 mN / m. In one embodiment, the surface energy of the coating composition is at least 5 mN / m, at least 8 mN / m, or at least 10 mN / m. For example, the surface energy of the coating composition may be in the range of 5 mN / m to 20 mN / m, 8 mN / m to 17 mN / m, or 10 mN / m to 15 mN / m. An appropriate surface energy contributes to the formation of capillary bridges.

[0027] In one embodiment, the applicator comprises one or more ducts suitable for delivering the coating composition through the applicator. One or more ducts are useful because it is not necessary to place a certain volume of the coating composition inside the hollow cylindrical body before inserting the applicator. Instead, the applicator can be appropriately inserted and positioned within the lumen before the coating composition is applied. In one embodiment, one or more ducts terminate near or at the tip of the applicator. The tip of the applicator is typically the top of the applicator when the coating composition is applied. From there, the coating composition can flow toward the circumferential gap, bridging the gap and forming a capillary bridge. Thus, the step of applying the coating composition to the applicator may include delivering the coating composition through one or more ducts. Typically, one or more ducts terminate above the equator of the applicator, allowing the coating composition to flow downwards over the applicator. The step of applying the coating composition to the applicator may include delivering the coating composition to the top section of the applicator, allowing the coating composition to flow downwards over the applicator. In one embodiment, the coating body comprises at least two, at least three, at least four, or at least six ducts. Optionally, the number of ducts may range from a maximum of 24, a maximum of 20, a maximum of 16, or a maximum of 12. For example, the coating body may comprise 1 to 24, 2 to 20, 4 to 16, or 6 to 12 ducts. The ducts may be arranged across the coating body to support a homogeneous distribution of the coating composition.

[0028] The step of applying the coating composition to the coating body may include delivering the coating composition to a section of the coating body, allowing the coating composition to construct a capillary bridge between the coating body and the inner surface of the wall.

[0029] As described above, the coating composition is applied to the applicator such that the coating composition contacts at least one section of the inner surface of the wall. This requires that the coating composition be close enough to the inner surface of the wall to span the circumferential gap. In one embodiment, the size of the circumferential gap is such that the coating composition forms a capillary bridge spanning the circumferential gap during the deposition step. If the gap size is small enough to allow the capillary bridge to occur during the deposition step, especially throughout the deposition step, a very uniform coating can be obtained. On the other hand, if the gap size is too small, the applicator may inadvertently come into contact with the inner surface in the deposition area, hindering the uniform deposition of the coating composition.

[0030] In one embodiment, the volume of the coating composition initially applied to the coating is sufficient to crosslink the gap throughout the entire deposition step. In another embodiment, one or more additional volumes of the coating composition are applied to the coating during the deposition step, for example, to replenish the volume of the coating composition, and as a result, the capillary bridge remains intact throughout the entire deposition step.

[0031] In one embodiment, the total volume of the coating composition applied to the coating medium initially, and optionally during the deposition step, is at least 2 μl, at least 5 μl, at least 10 μl, at least 25 μl, or at least 50 μl. Optionally, this volume may be up to 200 μl, up to 100 μl, or up to 90 μl. Naturally, the exact volume of the coating composition depends on the deposition area of ​​the coating and the desired thickness. For example, the total volume of the coating composition may be between 2 μl and 200 μl, or between 5 μl and 100 μl.

[0032] In one embodiment, the moving speed of the applicator during the deposition of the coating composition is less than or equal to the flow rate of the coating composition in the direction of the applicator's movement. As described above, during the deposition of the coating composition, the applicator moves relative to the hollow cylinder. During this step, the capillary bridge should remain intact to achieve the most homogeneous result. If the applicator moves too quickly, a significant portion of the coating composition may return to free-flow motion, potentially forming riblets on the inner surface. These riblets remain on the inner surface as serious heterogeneity. Optionally, the moving speed of the applicator is at least 2 mm / s, at least 4 mm / s, at least 5 mm / s, or at least 10 mm / s. In one embodiment, the moving speed is up to 50 mm / s, up to 30 mm / s, up to 20 mm / s, or up to 15 mm / s. For example, the moving speed of the applicator is in the range of 2 mm / s to 50 mm / s, 5 mm / s to 30 mm / s, or 10 mm / s to 15 mm / s.

[0033] In one embodiment, the method may further include the step of air-flushing the container after depositing the coating composition onto the deposition area. Air-flushing can contribute to the evaporation of diluents in the coating composition, which helps to smooth the coating.

[0034] Additionally or alternatively, the method may include the step of depositing the coating composition onto a deposition area and then curing the coating composition to obtain a cured coating. Curing can be used to crosslink and / or polymerize the crosslinkable or polymerizable compounds of the coating composition to form a coating. Curing may also contribute to the evaporation of diluents from the coating composition.

[0035] The coating composition can be applied to obtain a desired coating thickness. The coating may have an average thickness of 100 nm or more, 200 nm or more, or 300 nm or more, 400 nm or more, or 450 nm or more. Optionally, the coating may have an average thickness of up to 3000 nm, up to 2500 nm, up to 2000 nm, up to 1500 nm, up to 1000 nm, or up to 850 nm. An appropriate coating thickness contributes to sealing at low temperatures. In embodiments, the average coating thickness may be 100 nm to 3000 nm, 200 nm to 2000 nm, or 300 nm to 1500 nm, or 400 nm to 1000 nm. Optionally, the indicated average coating thickness is present in at least 90%, at least 95%, or at least 99% of the coated area. In embodiments, the average coating thickness is greater than 400 nm, and in particular at least 450 nm or at least 500 nm. Exemplary preferred ranges for the average coating thickness are over 400 nm to 1500 nm, 450 nm to 1250 nm, or 450 nm to 850 nm.

[0036] The coating composition can be deposited on at least 25%, or at least 50% (by area), of the inner surface of the hollow cylinder. The coating may have a beneficial effect on the sliding properties of the stopper on the inner surface of the hollow cylinder. Therefore, in some embodiments, the coating composition is deposited on at least 65%, or at least 85% (by area), of the inner surface of the hollow cylinder. Optionally, the coating composition is deposited on at least 90%, or essentially all, of the inner surface of the hollow cylinder.

[0037] As used herein, “curing temperature” refers to the effective temperature of the coating for curing the coating. The curing temperature is not the nominal temperature in the oven and may be higher than the effective temperature of the coating during curing. Curing may involve polymerization of polymerizable groups, such as polymerizable end groups. The coating may be cured at curing temperatures below 150°C, below 125°C, or below 110°C. If the curing temperature is too high, a brittle coating may be obtained. On the other hand, if the curing temperature is too low, it may not be sufficient to obtain good performance. Therefore, in embodiments, the curing temperature may be 50°C or higher, 60°C or higher, or 70°C or higher. In particular, the curing temperature is the effective temperature in the coating composition. It should not be confused with the nominal oven temperature. The oven temperature may be much higher than the curing temperature because there may not be enough time for the entire oven to equilibrate at the nominal temperature during the curing time. Optionally, the coating may be cured at 50°C to below 150°C, 60°C to below 125°C, or 70°C to below 110°C. The preferred range is 50°C to less than 110°C. In the embodiment, curing does not involve the application of plasma.

[0038] The curing temperature is maintained for a sufficient time to achieve the desired degree of curing. Optionally, the curing temperature may be maintained for at least 2 seconds, at least 3 seconds, at least 4 seconds, or at least 5 seconds. In embodiments, the curing temperature is maintained for a maximum of 300 seconds, a maximum of 100 seconds, or a maximum of 20 seconds.

[0039] After curing, the average coating thickness may be 100 to 3000 nm. Additionally or alternatively, after curing, the total area of ​​excess coating thickness is less than 10% of the coated area, and excess coating thickness is defined as the area exhibiting a coating thickness greater than twice the average coating thickness, greater than 1.50, or greater than 1.20. After curing, the coating may contain one or more silicon-organic polymers.

[0040] In one embodiment, the method includes a further step of obtaining a coated container according to the disclosure. In one embodiment, the method includes a further step of obtaining a container having a coating as described in more detail below.

[0041] The coating composition can be cured at curing temperatures below 150°C, below 125°C, or below 110°C. If the curing temperature is too high, a brittle coating may be obtained. On the other hand, if the curing temperature is too low, the coating may not have sufficient mechanical resistance. Therefore, in embodiments, the curing temperature may be 50°C or higher, 60°C or higher, or 70°C or higher. In particular, the curing temperature is the effective temperature of the coating composition. It should not be confused with the nominal oven temperature. The oven temperature may be much higher than the curing temperature because there may not be enough time for the entire oven to equilibrate at the nominal temperature during the curing time. Optionally, the coating may be cured at 50°C to below 150°C, 60°C to below 125°C, or 70°C to below 110°C. The preferred range is 50°C to below 110°C.

[0042] In embodiments, the coating can be obtained by applying a coating composition disclosed herein to at least a portion of the surface (e.g., the inner surface) of a container and curing the coating composition on the surface.

[0043] This disclosure is not particularly limited in terms of container volume. In one embodiment, the hollow cylinder encloses a volume of at least 0.10 ml, at least 0.50 ml, or at least 1.00 ml. Optionally, the volume may be up to 1,000 ml, up to 200 ml, up to 100 ml, or up to 25 ml. In embodiments, the volume is in the range of 0.1 ml to 1,000 ml, 0.50 ml to 200 ml, or 1.00 ml to 25 ml. In one embodiment, the hollow cylinder encloses a volume of less than 10.0 ml.

[0044] The hollow cylinder has a lumen surrounded by walls, the walls may have a wall thickness of at least 0.50 mm, at least 0.80 mm, or at least 1.00 mm. Optionally, the wall thickness may be in the range of up to 10.0 mm, up to 8.0 mm, up to 5.0 mm, or up to 4.0 mm. In embodiments, the wall thickness is 0.50 to 10.0 mm, 0.80 mm to 8.0 mm, or 1.00 mm to 4.00 mm. As used herein, the term “wall thickness” refers to the shortest distance between the inner and outer surfaces of the hollow cylinder.

[0045] As used herein, the term “outer diameter” refers to the maximum distance between two points on the outer surface of a hollow cylinder, where the two points are connected by a straight line perpendicular to and intersecting the longitudinal axis of the hollow cylinder. As used herein, the term “inner diameter” refers to the maximum distance between two points on the inner surface of a hollow cylinder, where the two points are connected by a straight line perpendicular to and intersecting the longitudinal axis of the hollow cylinder.

[0046] In the first specific embodiment, this method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of polymers such as COC or COP; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; and The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step.

[0047] In a second specific embodiment, the method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of polymers such as COC or COP; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step; The total volume of the coating composition applied to the coating body is 5 μl to 100 μl; and • The movement speed of the coated object during the deposition of the coating composition is less than or equal to the flow rate of the coating composition in the direction of movement of the coated object.

[0048] In a third specific embodiment, this method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of polymers such as COC or COP; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step; The total volume of the coating composition applied to the coating body is 5 μl to 100 μl; and The movement speed of the coating material during deposition of the coating composition is less than or equal to the flow rate of the coating composition in the direction of movement of the coating material; • The coating composition contains polysiloxane structural units or compounds.

[0049] In the fourth specific embodiment, the method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of polymers such as COC or COP; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step; The total volume of the coating composition applied to the coating body initially, and optionally during the deposition step, is 5 μl to 100 μl; The movement speed of the coating material during deposition of the coating composition is less than or equal to the flow rate of the coating composition in the direction of movement of the coating material; • The coating composition comprises polysiloxane structural units or compounds; and • The surface energy of the inner surface is higher than the surface energy of the surface of the coated material on which the capillary bridge is formed.

[0050] In the fifth specific embodiment, the method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of glass; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; and The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step.

[0051] In the sixth specific embodiment, the method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of glass; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step; The total volume of the coating composition applied to the coating body is 5 μl to 100 μl; and • The movement speed of the coated object during the deposition of the coating composition is less than or equal to the flow rate of the coating composition in the direction of movement of the coated object.

[0052] In the seventh specific embodiment, this method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of glass; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step; The total volume of the coating composition applied to the coating body is 5 μl to 100 μl; and The movement speed of the coating material during deposition of the coating composition is less than or equal to the flow rate of the coating composition in the direction of movement of the coating material; • The coating composition contains polysiloxane structural units or compounds.

[0053] In the eighth specific embodiment, the method is A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The steps include inserting the coating into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The process involves moving the coated material relative to the hollow cylindrical body to deposit the coating composition in the deposition area on the inner surface of the wall, The steps include: retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface during the deposition step. The walls are made of glass; • As the coated material moves downward, at least a portion of the coating composition is deposited in the deposition area; The coating body includes one or more ducts suitable for delivering the coating composition through the coating body; The size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition area during the deposition step; The total volume of the coating composition applied to the coating body initially, and optionally during the deposition step, is 5 μl to 100 μl; The movement speed of the coating material during deposition of the coating composition is less than or equal to the flow rate of the coating composition in the direction of movement of the coating material; • The coating composition comprises polysiloxane structural units or compounds; and • The surface energy of the inner surface is higher than the surface energy of the surface of the coated material on which the capillary bridge is formed.

[0054] Coating composition The coating composition may contain, or be composed of, the raw material components necessary to obtain the coating described herein. The coating composition may contain one or more silicon-organic substances, such as polymers or oligomers. For example, the coating composition may contain polysiloxane structural units or compounds. The polysiloxane compound of the coating composition may include crosslinkable polysiloxane compounds and / or non-crosslinkable polysiloxane compounds. In one embodiment, the polysiloxane compound is a polyalkylsiloxane compound, such as a polydialkylsiloxane compound. Optionally, one or more alkyl groups in the polyalkylsiloxane or polydialkylsiloxane are independently selected from branched or unbranched C1-C8 alkyl groups. Furthermore, the coating composition may contain a catalyst and / or a diluent.

[0055] A polysiloxane compound is considered "crosslinkable" if it contains one or more (particularly two) groups that are polymerizable or crosslinkable under the curing conditions of this disclosure, particularly at curing temperatures below 150°C and curing times below 3000 seconds. A polysiloxane compound is considered "non-crosslinkable" if it does not contain any chemical structures that are polymerizable or crosslinkable under the curing conditions of this disclosure, particularly at curing temperatures below 150°C and curing times below 3000 seconds.

[0056] In one embodiment, the coating composition is One or more crosslinkable polydialkylsiloxane compounds, and One or more non-crosslinkable polysiloxane compounds Includes.

[0057] Optionally, the coating composition is One or more crosslinkable polydialkylsiloxane compounds, One or more non-crosslinkable polysiloxane compounds, and One or more cross-linked polysiloxane compounds Includes.

[0058] Cross-linked polysiloxane compounds The crosslinked polysiloxane compounds are suitable for reacting with a crosslinkable polysiloxane compound, preferably by hydrosilylation, to form a polysiloxane network under the conditions of this disclosure (particularly a curing temperature of less than 150°C and a curing time of less than 3000 seconds).

[0059] Crosslinked polysiloxane compounds may contain alkylsiloxane monomer units, such as dialkylsiloxane monomer units. Optionally, one or more alkyl groups of the monomers in the crosslinked polysiloxane compound are independently selected from branched or unbranched C1-C8 alkyl groups. The alkyl groups may be linear alkyl groups. For example, the alkyl groups may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Optionally, the alkyl groups may be independently selected from methyl and ethyl groups.

[0060] In some embodiments, the crosslinked polysiloxane compound is a polysiloxane having a Si-H group. In exemplary embodiments, the crosslinked polysiloxane compound is a copolymer having dimethylsiloxane and methylhydrosiloxane monomer units. In this case, it has been found to be advantageous to use a copolymer having the following structure (where m is an integer of 1 or more, and n is an integer of 1 or more; n may be 2 or more): [ka] .

[0061] Optionally, crosslinked polysiloxanes are copolymers having dialkylsiloxane and alkylhydrosiloxane monomer units. The alkyl group in the alkylhydrosiloxane monomer unit may be selected from branched or unbranched C1-C8 alkyl groups. The alkyl group may also be a linear alkyl group. For example, the alkyl group may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Optionally, the alkyl group may be independently selected from methyl and ethyl.

[0062] The crosslinked polysiloxane may be present in the coating composition at a concentration of 0.10 to 1.50% by weight, 0.10 to 1.00% by weight, or 0.10 to 0.60% by weight. In the embodiments, the concentration of the crosslinked polysiloxane in the coating composition shall not exceed 1.50% by weight, 1.00% by weight, or 0.60% by weight. A minimum amount of 0.10% by weight is preferred.

[0063] Non-crosslinkable polysiloxane compounds The coating composition may contain two or more non-crosslinkable polysiloxane compounds, such as at least two or at least three. These compounds may have different viscosities. In some embodiments, the coating includes a high-viscosity non-crosslinkable polysiloxane compound having a viscosity greater than 10,000 cSt, and / or a low-viscosity non-crosslinkable polysiloxane compound having a viscosity of 10,000 cSt or less. The viscosity of the polysiloxane compounds is measured at 23°C and 10s. -1 The viscosity can be determined using a coaxial-cylindrical system at the shear rate according to DIN EN ISO 3219:1993. Optionally, high-viscosity non-crosslinkable polysiloxane compounds have a viscosity of at least 15,000 cSt, and / or low-viscosity non-crosslinkable polysiloxane compounds have a viscosity of 5,000 cSt or less.

[0064] Weight ratio of low viscosity non-crosslinkable polysiloxane compound to high viscosity non-crosslinkable polysiloxane compound (mass 高 :mass 低 The ratio may be at least 0.10, at least 0.50, at least 1.00, at least 1.50, or at least 2.00. In some embodiments, this ratio may be in the range of up to 5.00, up to 4.00, or up to 3.00. For example, the weight ratio of the low-viscosity non-crosslinkable polysiloxane compound to the high-viscosity non-crosslinkable polysiloxane compound may be in the range of 0.10 to 5.00, 0.50 to 4.00, or 1.00 to 3.00.

[0065] Optionally, the low-viscosity non-crosslinkable polysiloxane compound has a weight-average molecular weight of 1,200 to 30,000 g / mol, and / or the high-viscosity non-crosslinkable polysiloxane compound has a weight-average molecular weight of 15,000 to 300,000 g / mol. In one embodiment, the high-viscosity non-crosslinkable polysiloxane compound has a weight-average molecular weight of 32,000 to 210,000 g / mol, or 100,000 to 150,000 g / mol. In one embodiment, the low-viscosity non-crosslinkable polysiloxane compound has a weight-average molecular weight of 5,000 to 25,000 g / mol, or 10,000 to 20,000 g / mol.

[0066] In the embodiments, the low-viscosity, non-crosslinkable polysiloxane compound has a weight-average molecular weight of at least 1,200 g / mol, at least 5,000 g / mol, or at least 10,000 g / mol. The weight-average molecular weight may range from a maximum of 30,000 g / mol, a maximum of 25,000 g / mol, or a maximum of 20,000 g / mol.

[0067] In the embodiments, the high-viscosity non-crosslinkable polysiloxane compound has a weight-average molecular weight of at least 15,000 g / mol, at least 32,000 g / mol, or at least 100,000 g / mol. The weight-average molecular weight may range from a maximum of 300,000 g / mol, a maximum of 210,000 g / mol, or a maximum of 150,000 g / mol. The weight-average molecular weight can be determined by gel permeation chromatography (GPC).

[0068] Polydimethylsiloxane is particularly suitable as a non-crosslinkable polysiloxane compound.

[0069] Crosslinkable polysiloxane compounds Crosslinkable polysiloxane compounds may be crosslinkable via one or more, preferably two, end groups. In particular, the end groups may have double bonds, making them available for hydrosilylation reactions, for example, under the conditions of this disclosure (especially curing temperatures below 150°C and curing times below 3000 seconds). The end groups may be selected from vinyl, acrylic, methacrylic, styrene, and combinations thereof.

[0070] In one embodiment, a crosslinkable polysiloxane compound and a crosslinked polysiloxane compound may form a hydrosilylation reaction product under the conditions of the present disclosure (particularly a curing temperature of less than 150°C and a curing time of less than 3000 seconds). A suitable crosslinkable polysiloxane compound is a vinyl-polysiloxane compound. The crosslinked polysiloxane may be crosslinked by the reaction of multiple Si-H groups with the vinyl groups of the crosslinkable polysiloxane. The reaction may be catalyzed with platinum.

[0071] Crosslinkable polysiloxane compounds may contain alkylsiloxane monomer units, such as dialkylsiloxane monomer units. Optionally, one or more alkyl groups of the monomers in the crosslinkable polysiloxane compound are independently selected from branched or unbranched C1-C8 alkyl groups. The alkyl groups may be linear alkyl groups. For example, the alkyl groups may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Optionally, the alkyl groups may be independently selected from methyl and ethyl groups.

[0072] Diluent The coating composition may further contain one or more diluents. Diluents in the context of this disclosure may be Si-containing solvents to which crosslinkable polysiloxane compounds and non-crosslinkable polysiloxane compounds are soluble. To ensure good solubility of the polysiloxane compounds, nonpolar solvents can be used as diluents. In this case, it has been found useful to use silicon-organic compounds having up to six silicon atoms as diluents.

[0073] Examples of diluents are as follows: Cyclic silicones, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, Hexamethyldisiloxane (HMDSO), Octamethyltrisiloxane, Decamethyltetrasiloxane.

[0074] In particular, a mixture containing one or more of the above-mentioned substances can also be used as a diluent.

[0075] The coating composition is a liquid. In embodiments, the coating composition has a viscosity of 1.0–50 mPas, 2.0–25 mPas, or 3.0–15 mPas. Optionally, the coating composition has a viscosity of at least 1.0 mPas, at least 2.0 mPas, at least 3.0 mPas, or at least 3.5 mPas. For example, the viscosity of the coating composition may range from a maximum of 50 mPas, a maximum of 25 mPas, or a maximum of 15 mPas. The viscosity of the coating composition can be determined according to DIN EN ISO 3219:1993 using a coaxial-cylindrical system at 25°C and a shear rate of 16.8 s⁻¹.

[0076] Catalyst / Inhibitor The coating composition may further contain a catalyst for the crosslinking reaction of a multicomponent compound. A soluble platinum-containing catalyst, such as chloroplatinic acid, may be used. A Karstedt catalyst can be used.

[0077] In some embodiments, the coating composition includes at least one inhibitor to prevent spontaneous reactions of the composition. This facilitates handling of the composition up to the application of the coating. The inhibitor can enter into a reversible complex formation with the catalyst, thereby preventing spontaneous crosslinking reactions of the composition.

[0078] Coating composition In one embodiment, the coating composition includes a high-viscosity, non-crosslinkable polysiloxane compound, but does not necessarily include a low-viscosity, non-crosslinkable polysiloxane compound.

[0079] In one embodiment, the coating composition comprises the following components: [Table 1]

[0080] In one embodiment, the coating composition comprises the following components by weight percentage: [Table 2]

[0081] In certain embodiments, the weight ratio of the crosslinked polysiloxane compound to the crosslinkable polysiloxane compound is at least 0.01, at least 0.015, or at least 0.02. Optionally, this ratio must not exceed 0.5, 0.4, 0.2, or 0.1. In some embodiments, this ratio is in the range of 0.01 to 0.5, 0.015 to 0.4, or 0.02 to 0.2.

[0082] Optionally, the ratio of the weight of the crosslinkable polysiloxane compound to the weight of the non-crosslinkable polysiloxane compound in the coating composition is less than 3.00, less than 2.50, less than 1.80, or less than 1.20. The ratio of the weight of the crosslinkable polysiloxane compound to the weight of the non-crosslinkable polysiloxane compound in the coating may be at least 0.40, at least 0.60, or at least 0.70. In embodiments, this ratio is in the range of 0.40 to 3.00, 0.60 to 2.50, or 0.70 to 1.80.

[0083] In one embodiment, the coating composition comprises the following components by weight percentage: [Table 3]

[0084] In one embodiment, the coating composition comprises the following components by weight percentage: [Table 4]

[0085] In one embodiment, the coating composition comprises the following components by weight percentage: [Table 5]

[0086] In one embodiment, the coating composition comprises the following components by weight percentage: [Table 6]

[0087] More specific coating compositions Crosslinked polysiloxane structural units, low-viscosity non-crosslinked polysiloxane structural units, and / or high-viscosity non-crosslinked polysiloxane structural units may include or consist of dialkylsiloxane monomer units, particularly dimethylsiloxane monomer units.

[0088] In some embodiments, the crosslinkable polysiloxane is a vinyl-functionalized polysiloxane, and / or the crosslinkable polysiloxane compound is a polysiloxane having Si-H groups. One exemplary embodiment includes a vinyl-functionalized polydimethylsiloxane as the crosslinkable polysiloxane compound, and / or a copolymer having dimethylsiloxane and methylhydrosiloxane monomer units as the crosslinkable polysiloxane compound. In this case, it has been found advantageous to use a copolymer having the following structure (where m is an integer of 1 or more, and n is an integer of 1 or more; n may be 2 or more): [ka] .

[0089] In a more specific variation, the coating composition includes the following components: [Table 7]

[0090] In a more specific variation, the coating composition contains the following components by weight percentage: [Table 8]

[0091] In a more specific variation, the coating composition contains the following components by weight percentage: [Table 9]

[0092] In a more specific variation, the coating composition contains the following components by weight percentage: [Table 10]

[0093] In a more specific variation, the coating composition contains the following components by weight percentage: [Table 11]

[0094] In a more specific variation, the coating composition contains the following components by weight percentage: [Table 12]

[0095] Optionally, crosslinkable polysiloxane structural units, low-viscosity non-crosslinkable polysiloxane structural units, and / or high-viscosity non-crosslinkable polysiloxane structural units may include dialkylsiloxane monomer units, particularly dimethylsiloxane monomer units. Crosslinkable polysiloxane structural units may be crosslinkable via one or more polymerizable terminal groups.

[0096] Coated container In one embodiment, the present disclosure relates to a coated container. The coatings described in detail herein can be obtained by the methods described above. The coated container may or may be obtained by the methods of the present disclosure. The coated container comprises a hollow cylindrical body having a wall surrounding a lumen, the hollow cylindrical body having at least one opening, and at least a portion of the inner surface of the wall includes a coating.

[0097] The average coating thickness can range from 100 to 3000 nm.

[0098] Optionally, the total area of ​​excess coating thickness is less than 10% of the coated area, and excess coating thickness is defined as an area exhibiting a coating thickness greater than twice the average coating thickness, greater than 1.50, or greater than 1.20. In certain embodiments, the total area of ​​excess coating thickness is less than 7%, less than 5%, or less than 3% of the coated area.

[0099] In one embodiment, the coating contains one or more silicon-organic polymers.

[0100] In certain useful embodiments, the total area of ​​insufficient coating thickness is less than 5% of the coated area, and the insufficient coating thickness is the area exhibiting a coating thickness of less than 100 nm or less than 50 nm. The total area of ​​insufficient coating thickness may be less than 3% or less than 2% of the coated area.

[0101] The coated containers of this disclosure may have a coating comprising one or more crosslinked polysiloxane structural units and one or more non-crosslinked polysiloxane structural units, wherein the ratio of the weight of crosslinked polysiloxane structural units to the weight of non-crosslinked polysiloxane structural units in the coating is less than 3.00 and optionally at least 0.40.

[0102] The coating may be placed on the inner surface of the hollow cylindrical body of the container. The coating can have an average thickness of 100 nm or more, 200 nm or more, or 300 nm or more, 400 nm or more, or 450 nm or more. Optionally, the coating may have an average thickness of up to 3000 nm, up to 2000 nm, up to 1500 mm, up to 1000 mm, or up to 850 nm. An appropriate coating thickness contributes to sealing at low temperatures. In embodiments, the average coating thickness may be 100 nm to 3000 nm, 200 nm to 2000 nm, or 300 nm to 1500 nm, or 400 nm to 1000 nm. Optionally, the indicated average coating thickness is present in at least 90%, at least 95%, or at least 99% of the coated area. In embodiments, the average coating thickness is greater than 400 nm, and in particular at least 450 nm or at least 500 nm. Exemplary preferred ranges for the average coating thickness are over 400 nm to 1500 nm, 450 nm to 1250 nm, or 450 nm to 850 nm.

[0103] In embodiments, the hollow cylindrical body described in this disclosure as part of a container may have an essentially constant inner diameter to allow the stopper to discharge essentially all of the composition present inside the cylinder. In this regard, “essentially constant” includes inner diameter variations of 200 μm or less, 100 μm or less, or 50 μm or less.

[0104] The container may be any type of container, including vials, syringes, or cartridges. In one embodiment, the container is a syringe or a cartridge.

[0105] The coating may contain one or more silicon-organic polymers. A “silicon-organic polymer” is a polymer material composed of monomer units, each containing both silicon (Si) and carbon (C) atoms. An example of a silicon-organic polymer is polysiloxane. In embodiments, the coating may contain one or more polysiloxane structural units. A “polysiloxane structural unit” may refer to a polysiloxane structure within a larger molecule (e.g., covalently bonded to a larger molecule or part of a larger molecule) or the polysiloxane molecule itself. For example, a crosslinked polysiloxane structural unit is part of a polymer network (covalently bonded), while a non-crosslinked polysiloxane structural unit exists in the coating as a molecule not covalently bonded to other molecules in the coating. Thus, the coating may contain crosslinked polysiloxane structural units and / or non-crosslinked polysiloxane structural units. In this context, “crosslinked” means that the polysiloxane structural unit is covalently bonded to a polymer network. Specifically, the term "crosslinked" preferably includes the case where a polysiloxane structure is covalently bonded to another polysiloxane structure, for example, via a polymer backbone. Optionally, crosslinked polysiloxane structural units are covalently bonded to other polysiloxane structures as a result of a hydrosilylation reaction. The polymer backbone may be formed, for example, by polymerizing a polysiloxane having polymerizable functional groups such as vinyl groups. In contrast, "non-crosslinked" means that the polysiloxane is not covalently bonded to another polysiloxane structure via a polymer backbone, or to other polysiloxanes in a coating.

[0106] In one embodiment, the crosslinked polysiloxane structural unit is crosslinked via one or more, for example, two, end groups. The end groups may be selected from vinyl, acrylic, methacrylic, styrene, and combinations thereof. In one embodiment, the coating comprises a hydrosilylation reaction product of a crosslinkable polysiloxane compound and a crosslinkable polysiloxane compound, for example, a vinyl-polysiloxane compound and a polysiloxane having at least two Si-H groups. The crosslinked polysiloxane may crosslink the crosslinkable polysiloxane by the reaction of its multiple Si-H groups with the vinyl groups of the crosslinkable polysiloxane. The reaction may be catalyzed with platinum.

[0107] In this disclosure, “polysiloxane” or “polysiloxane structural unit” may refer to a polyalkylsiloxane structural unit such as a polydialkylsiloxane structural unit. Optionally, one or more alkyl groups in the polyalkylsiloxane or polydialkylsiloxane are independently selected from branched or unbranched C1-C8 alkyl groups. The alkyl groups may be linear alkyl groups. For example, the alkyl groups may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. For example, the alkyl groups may be independently selected from methyl and ethyl groups.

[0108] In one embodiment, the coating comprises both crosslinked polydialkylsiloxane structural units and non-crosslinked polysiloxane structural units. Specifically, the coating may comprise crosslinked polydialkylsiloxane structural units and non-crosslinked polysiloxane structural units, where the non-crosslinked polysiloxane structural units may be one or more silicone oils, i.e., polydialkylsiloxane structural units such as polydimethylsiloxane silicone oil.

[0109] Optionally, the ratio of the weight of crosslinked polysiloxane structural units to the weight of non-crosslinked polysiloxane structural units in the coating is less than 3.00, less than 2.50, less than 1.80, or less than 1.20. The ratio of the weight of crosslinked polysiloxane structural units to the weight of non-crosslinked polysiloxane structural units in the coating may be at least 0.40, at least 0.60, or at least 0.70. In embodiments, this ratio is in the range of 0.40 to 3.00, 0.60 to 2.50, or 0.70 to 1.80.

[0110] The coating may contain two or more types of non-crosslinked polysiloxane structural units, such as at least two or at least three types. These types may have different viscosities. In some embodiments, the coating includes high-viscosity non-crosslinked polysiloxane structural units having a viscosity greater than 10,000 cSt and / or low-viscosity non-crosslinked polysiloxane structural units having a viscosity of 10,000 cSt or less. The viscosity of the polysiloxane structural units is measured at 23°C and 10s. -1 The viscosity can be determined using a coaxial-cylindrical system at the shear rate according to DIN EN ISO 3219:1993. Optionally, high-viscosity non-crosslinked polysiloxane structural units have a viscosity of at least 15,000 cSt, and / or low-viscosity non-crosslinked polysiloxane structural units have a viscosity of 5,000 cSt or less.

[0111] In one embodiment, the coating contains high-viscosity non-crosslinked polysiloxane structural units, but does not necessarily contain low-viscosity non-crosslinked polysiloxane structural units.

[0112] Weight ratio of low-viscosity non-crosslinked polysiloxane structural units to high-viscosity non-crosslinked polysiloxane structural units (mass) 高 :mass 低The ratio may be at least 0.10, at least 0.50, at least 1.00, at least 1.50, or at least 2.00. In some embodiments, this ratio may be in the range of up to 5.00, up to 4.00, or up to 3.00. For example, the weight ratio of low viscosity non-crosslinked polysiloxane structural units to high viscosity non-crosslinked polysiloxane structural units may be in the range of 0.10 to 5.00, 0.50 to 4.00, or 1.00 to 3.00.

[0113] Crosslinked polysiloxane structural units, low-viscosity non-crosslinked polysiloxane structural units, and / or high-viscosity non-crosslinked polysiloxane structural units may include or consist of dialkylsiloxane monomer units, particularly dimethylsiloxane monomer units.

[0114] Optionally, low-viscosity non-crosslinked polysiloxane structural units have a weight-average molecular weight of 1,200 to 30,000 g / mol, and / or high-viscosity non-crosslinked polysiloxane structural units have a weight-average molecular weight of 15,000 to 300,000 g / mol. In one embodiment, high-viscosity non-crosslinked polysiloxane structural units have a weight-average molecular weight of 32,000 to 210,000 g / mol, or 100,000 to 150,000 g / mol. In one embodiment, low-viscosity non-crosslinked polysiloxane structural units have a weight-average molecular weight of 5,000 to 25,000 g / mol, or 10,000 to 20,000 g / mol.

[0115] In the embodiments, the low-viscosity non-crosslinked polysiloxane structural units have a weight-average molecular weight of at least 1,200 g / mol, at least 5,000 g / mol, or at least 10,000 g / mol. The weight-average molecular weight may range from a maximum of 30,000 g / mol, a maximum of 25,000 g / mol, or a maximum of 20,000 g / mol.

[0116] In the embodiments, the high-viscosity non-crosslinked polysiloxane structural units have a weight-average molecular weight of at least 15,000 g / mol, at least 32,000 g / mol, or at least 100,000 g / mol. The weight-average molecular weight may range from a maximum of 300,000 g / mol, a maximum of 210,000 g / mol, or a maximum of 150,000 g / mol.

[0117] The coating may have a glass transition temperature of -60°C or lower, optionally -70°C or lower, e.g., -75°C or lower, or -80°C or lower. Optionally, the glass transition temperature may be above -200°C, above -150°C, above -120°C, or above -100°C. The glass transition temperature can be measured using differential scanning calorimetry (DSC) or thermomechanical analysis (TMA). An exemplary method for determining the glass transition temperature of a coating includes, for example, thermomechanical analysis in expansion mode using a TA Instruments Q400 thermomechanical analyzer. A sample can be prepared by coating a container according to the disclosure and then scraping off the coating using a knife, and thermomechanical analysis can be performed in expansion mode, i.e., the expansion or contraction of the sample as a function of temperature can be measured. In embodiments, the glass transition temperature of the coating is in the range of -200°C to -60°C, -150°C to -70°C, -120°C to -75°C, or -80°C to -100°C. In one embodiment, the glass transition temperature is -80°C to -90°C.

[0118] The coating may be amorphous or partially crystalline at room temperature. Optionally, the coating may have a crystallinity of less than 20% (v / v) at 20°C.

[0119] In embodiments, the coating may have a crystallization temperature range and a melting temperature range determined using differential scanning calorimetry at a temperature change rate of 10°C / min, where the crystallization temperature range and the melting temperature range overlap at temperatures from -75°C to -100°C, particularly at -80°C. For example, DSC may be performed in a temperature range of -120°C to -60°C. A suitable instrument is the DSC Q2000 (TA Instruments).

[0120] While we do not wish to be bound by this theory, the inventors assume that both crystalline and molten portions of the coating exist within this overlapping range. This is thought to provide the coating with good mechanical resistance. The crystallization and melting temperature ranges are considered to overlap when the crystallization region and the melting peak region extend over the same temperature range. For example, crystallization may begin at -55°C and end at -95°C, i.e., the exothermic crystallization peak region may be in the range of -55°C to -95°C, and melting may begin at -90°C and end at -40°C, i.e., the endothermic melting peak region may be in the range of -90°C to -40°C. In this example, the overlapping temperature range is -90°C to -55°C. This example satisfies the overlap requirement at temperatures of -75°C to -100°C because there is overlap at at least one temperature within the indicated range.

[0121] Generally, this disclosure relates to a container for a pharmaceutical composition comprising a hollow cylindrical body. The container may be configured to receive a stopper that is slidable relative to the hollow cylindrical body from one open end of the container toward the opposite end. In one embodiment, the container has at least two open ends. One open end is provided for the insertion of a stopper. The other open end may be on the opposite side of the container, for example, the tip side in the case of a syringe.

[0122] This disclosure is not particularly limited in terms of container volume. In one embodiment, the hollow cylinder encloses a volume of at least 0.10 ml, at least 0.50 ml, or at least 1.00 ml. Optionally, the volume may be up to 1,000 ml, up to 200 ml, up to 100 ml, or up to 25 ml. In embodiments, the volume is in the range of 0.1 ml to 1,000 ml, 0.50 ml to 200 ml, or 1.00 ml to 25 ml. In one embodiment, the hollow cylinder encloses a volume of less than 10.0 ml.

[0123] The hollow cylinder has a lumen surrounded by walls, the walls may have a wall thickness of at least 0.50 mm, at least 0.80 mm, or at least 1.00 mm. Optionally, the wall thickness may be in the range of up to 10.0 mm, up to 8.0 mm, up to 5.0 mm, or up to 4.0 mm. In embodiments, the wall thickness is 0.50 to 10.0 mm, 0.80 mm to 8.0 mm, or 1.00 mm to 4.00 mm. As used herein, the term “wall thickness” refers to the shortest distance between the inner and outer surfaces of the hollow cylinder.

[0124] As used herein, the term “outer diameter” refers to the maximum distance between two points on the outer surface of a hollow cylinder, where the two points are connected by a straight line perpendicular to and intersecting the longitudinal axis of the hollow cylinder. As used herein, the term “inner diameter” refers to the maximum distance between two points on the inner surface of a hollow cylinder, where the two points are connected by a straight line perpendicular to and intersecting the longitudinal axis of the hollow cylinder.

[0125] A hollow cylindrical container can have an essentially constant inner diameter. This means that the total inner diameter variation is small. "Total inner diameter variation" is the difference between the maximum inner diameter of the hollow cylinder and the minimum inner diameter of the same hollow cylinder. Optionally, the total inner diameter variation is less than 0.10 mm, less than 0.08 mm, less than 0.06 mm, or less than 0.04 mm. A smaller total inner diameter variation is better. However, in some embodiments, it may not be economically feasible to provide a container with an extremely small total inner diameter variation. Therefore, in one embodiment, the total inner diameter variation may be at least 0.0001 mm, at least 0.001 mm, or at least 0.01 mm. For example, the total inner diameter variation may be in the range of 0.0001 mm to less than 0.10 mm, 0.001 mm to less than 0.08 mm, or 0.01 mm to less than 0.04 mm.

[0126] A container according to an embodiment of this disclosure may have a standard sliding force of 5.0 N or less. The sliding force represents the force required to push the stopper within the hollow cylinder, and the release force represents the force required to cause the initial movement of the stopper within the hollow cylinder. "Standard sliding force" is the sliding force (GF) measured under standard conditions. Similarly, "standard release force" is the release force (BLF) measured under standard conditions. Standard conditions include a standard stopper, i.e., available from Datwyler Pharma Packaging International NV, Industrieterrein Kolmen 1519, BE-3570 Alken, Belgium, with a hardness of 52 Shore A and a hardness of 1.355 g / cm³. 3 The Datwyler FM257 / 2 stopper is made of bromobutyl rubber having a density of . BLF and GF can be measured in a single test. The test for BLF and GF may be referred to as the "BLGF" test. Any reference to release force or sliding force in this disclosure means standard release force or sliding force.

[0127] The standard BLGF test is performed at room temperature, i.e., 20°C, using a universal testing machine. For this purpose, a standard BLGF testing device equipped with a 50N test cup is used. The sample was fixed vertically to a TesT AG, CH-6331 Hunenberg, Switzerland, Model 106 (2kN) universal testing machine.

[0128] BLF is the force required to move the stopper from its original position. GF is the force required to keep the stopper moving after it has been released.

[0129] Fill the container with sterile water for injection. After filling with the sample, the sample is either stored or tested immediately, depending on the purpose of the test. Test the sample without attaching a needle.

[0130] The sample is inserted into the holder, and the pressure extruder is moved toward the stopper at a speed of 20 mm / min. When a force of 0.25 N is measured, the machine switches to a test speed of 100 mm / min and begins recording the data. The experiment ends when the measured force exceeds 35 N, which is usually when it reaches the distal end of the hollow cylinder.

[0131] BLF is the highest force measured within the first 4 mm of stopper movement. GF values ​​were measured within a test range starting after 4 mm of movement and ending at 10 mm before reaching the distal end of the hollow cylinder, and GF according to this disclosure is the highest sliding force measured in this experiment.

[0132] The containers of this disclosure may exhibit a standard BLF of 12.0 N or less. In some embodiments, the standard BLF may be limited to upper limits of 9.0 N, 8.0 N, 7.0 N, 6.0 N, 5.0 N, or even 4.0 N. The standard BLF may be at least 0.1 N, at least 0.5 N, or at least 1.0 N to avoid unintended movement of the stopper.

[0133] The container may exhibit a BLF / GF ratio of standard BLF to standard GF greater than 1.30. Optionally, the BLF / GF ratio is characterized by BLF / GF ≤ 3.0. In embodiments, the BLF / GF ratio is greater than 1.40, greater than 1.50, or even greater than 1.60 for the containers of this disclosure. In some embodiments, the BLF / GF ratio may be less than 2.5, less than 2.2, less than 2.0, or even less than 1.9.

[0134] The standard GF of the containers of this disclosure may be less than 7.5N, less than 6.5N, less than 5.5N, less than 4.5N, less than 3.5N, or even less than 2.5N.

[0135] Appropriate sliding and release forces are relevant to the convenient use of the containers of this disclosure. However, a sufficiently high release force may be beneficial in preventing undesirable stopper movement during storage. Optionally, the containers of this disclosure have a standard sliding force of at least 0.5 N.

[0136] To protect the seal by suppressing the movement of the stopper during low-temperature storage, the container of the present disclosure may have a standard release force that exceeds the standard sliding force of the container by at least 30%, at least 60%, at least 100%, or at least 200%.

[0137] In one embodiment, this disclosure relates to a container described herein containing a pharmaceutical composition. The pharmaceutical composition may contain more than 60% by weight of water. Optionally, the pharmaceutical composition may contain a protein or nucleic acid therapeutic agent.

[0138] Examples Exemplary container Referring here to the drawings, Figure 1 shows a container 1, in an exemplary embodiment, a syringe 3 for administering pharmaceuticals or cosmetics. The syringe 3 is made of polymer and has a wall 5 surrounding a lumen. The container comprises a hollow cylindrical body 7, an opening 4, and a nested surface 18 on which, for example, an injection needle or cap can be placed. A stopper 12 is inserted into the cylindrical portion and is axially slidable by the pressure of a push rod 13. The syringe 3 has a flange 15 for handling.

[0139] The container 1 has a coating 10 on its inner surface, specifically on the inner surface of the hollow cylindrical body 7. In this example, the coating 10 covers an area of ​​the inner surface of the hollow cylindrical body 7 on which the stopper 12 can slide when the syringe is being emptied or used for drawing.

[0140] Coating composition Two exemplary coating compositions useful in the method disclosed herein are shown in the table below. [Table 13]

[0141] Coating thickness Figure 2 illustrates the press-fitting technique. A coating body 20 is inserted into a pharmaceutical container 1, referred to herein as a syringe, which has an opening 4 and a hollow cylindrical body 7. The coating body 20 is coated with a coating composition 8. The coating body 20 is in direct physical contact with the inner surface of the container. The coating composition 8 is deposited in the deposition area on the inner surface as the coating body 20 moves against the hollow cylindrical body 7, in which case the coating body moves downward, leaving a layer of coating composition 8 on the inner surface. When it reaches the opening 4 of the container 1, the coating body 20 is withdrawn from the container 1. A coated container 1 is obtained having a coating thickness distribution as shown in Figure 4A.

[0142] Figure 3A shows a coating body 20 inserted into a hollow cylindrical body 7 having walls 5 by press-fitting technology, while Figure 3B shows a coating body 20 inserted into a hollow cylindrical body 7 having a circumferential gap 22 between the coating body 20 and the inner surface of the hollow cylindrical body 7. The coating body 20 also includes a duct 23 into which the coating composition can be applied so that it flows downward toward the equator of the coating body 20.

[0143] Figure 5A shows an exemplary coating 20 having an equator 24 and a hemispherical shape in the portion of the coating 20 above the equator 24, h k θ is the height of the capillary bridge on the surface of the coating, and hw is the height of the capillary bridge on the inner surface of the hollow cylinder. Figure 5B shows a geometric diagram of the capillary bridge 25 that may be formed between the coating 20 and the inner surface. D indicates the size of the gap that the capillary bridge spans, R1 is the radius of curvature of the coating, θ1 is the contact angle between the coating composition and the coating, θ2 is the contact angle with the inner surface of the hollow cylinder, l is the azimuthal radius, and r is the meridional radius. β represents the position of the three-phase contact line on the particle surface. The height of the liquid meniscus is h.

[0144] Comparative experiments were conducted comparing the application of a coating by press-fitting technology with the application of another coating using the capillary bridging technology of this disclosure, i.e., using the same method as shown in Figure 2, and further using a smaller diameter applicator to form a capillary bridge. The coating composition and container were the same for both methods. For this experiment, a TopPac® 1 ml lg LL syringe was used. The syringe was made of COC with an inner surface energy of approximately 30 mN / m. The applicator was a hemispherical PTFE head with a surface energy of approximately 18 mN / m. The coating composition had a surface energy of 13 mN / m and a viscosity of approximately 4 mPas. The syringe barrel had an inner diameter of 6.5 mm. The applicator had an equatorial diameter of 6.4 mm.

[0145] Figure 4A shows the thickness analysis of a coating fabricated according to the press-fit method. Figure 4B shows the thickness analysis of a coating fabricated according to the method of this disclosure. The coating in Figure 4B has an average thickness of 730 nm and is clearly very homogeneous. The total area of ​​excess coating thickness was less than 5% of the coated area. The total area of ​​insufficient coating thickness (less than 100 nm) was less than 5% of the coated area.

[0146] The layer thickness distribution shown in Figure 4 was measured using a RapID Layer Explorer measuring device. The Layer Explorer RapID is a computer-aided device equipped with an integrated interferometer. A camera is also connected for positioning. RapID enables the measurement of the average film thickness inside transparent hollow cylindrical bodies, particularly those based on glass and plastic. Other cylindrical primary packaging materials, such as cartridges, can also be measured.

[0147] The thickness of the coating layer is measured using the principle of white light reflectance measurement at multiple points on the coating (each 1 mm × 1 mm), for example, at least 240 or 480 points distributed across the coating area. By measuring several points on the coating, the coating distribution within the body can be quantitatively determined. The relevant measurement mode is called BI mode (coating layer height > 100 nm). RapID can also be used to measure lower (> 20 nm) coating layer heights. The measurement is performed using a laser as the light source. This measurement method is called UT mode (similar to ultrathin). The coating layer height is measured from 5 mm above the flange, and a single point at any given millimeter is measured towards the cone side. In these settings, there are 49 measurement points along the barrel. After measuring the entire length, the sample stage automatically rotates by a predetermined angle and starts measuring a new line again. In this example, the rotation of the sample stage is always kept at 30°, which means 12 × 49 points = 588 points. Any image displayed is based on 588 single measurements. The RapID software represents the data as 2D false colors and converts them into 3D elevation or height profiles. Coating layer thickness is represented by a grayscale (see Figure 4). Black indicates a layer thickness of 2000 nm, and white indicates 0 nm or no measurement. The RapID analyzer was used for layer thicknesses greater than 50 nm, and layers less than 50 nm were counted as non-existent. However, with special settings on the RapID device, layer thicknesses as low as 20 nm can also be measured.

Claims

1. A method for producing a coated container, A step of providing a container comprising a hollow cylindrical body having a wall surrounding a lumen, wherein the hollow cylindrical body has at least one opening, The step of inserting the coating material into the lumen through the opening, The steps include applying the coating composition to the coating body such that the coating composition contacts at least one section of the inner surface of the wall, The steps include: moving the coated body relative to the hollow cylindrical body to deposit the coating composition on the deposition region on the inner surface of the wall; The step of retracting the coating material from the lumen through the opening; Includes, The size of the coating is such that a circumferential gap exists between the coating and the inner surface of the wall during the deposition step. The coating composition comprises one or more crosslinkable polysiloxane compounds, one or more non-crosslinkable polysiloxane compounds, and one or more crosslinkable polysiloxane compounds. The one or more crosslinkable polysiloxane compounds have one or more terminal groups having a double bond, and the terminal groups are available for hydrosilylation reactions at a curing temperature of less than 150°C and a curing time of less than 3000 seconds. A method comprising the above-mentioned one or more crosslinked polysiloxane compounds being polysiloxanes having Si-H groups, reacting with the crosslinkable polysiloxane compounds by a hydrosilylation reaction at a curing temperature of less than 150°C and a curing time of less than 3000 seconds to form a polysiloxane network.

2. The method according to claim 1, wherein the size of the circumferential gap is such that the coating composition forms a capillary bridge across the circumferential gap during the deposition step.

3. The method according to claim 1 or 2, wherein the size of the circumferential gap is characterized by a distance D of less than 0.10 mm between the coating and the deposition region during the deposition step.

4. The method according to claim 3, wherein the distance D is 0.005 to 0.08 mm, or 0.01 to 0.04 mm.

5. The method according to claim 1 or 2, wherein the wall contains or is made of a polymer material or glass.

6. The method according to claim 1 or 2, wherein the coating composition comprises, by weight percentage, the following: Table 1

7. The method according to claim 1 or 2, wherein the movement speed of the coated body during the deposition of the coating composition is in the range of 2 mm / s to 50 mm / s.

8. The steps of depositing the coating composition onto the deposition area and then air-flushing the container, and / or The step involves depositing the coating composition onto the deposition region, and then curing the coating composition to obtain a cured coating. The method according to claim 1 or 2, further comprising:

9. The cylindrical body has a total inner diameter variation of up to 2D in the deposition region, and / or The coated body has a total outer diameter variation of up to 2D, The method according to claim 3.

10. The coating body includes one or more ducts suitable for delivering the coating composition through the coating body, and the step of applying the coating composition to the coating body includes delivering the coating composition through the one or more ducts. , and / or The step of applying the coating composition to the coating body includes delivering the coating composition to the section of the coating body above the equator and allowing the coating composition to flow downwards on the coating body; and / or The step of applying the coating composition to the coating body includes delivering the coating composition to a section of the coating body, enabling the coating composition to construct a capillary bridge between the coating body and the inner surface of the wall, The method according to claim 1 or 2.

11. After hardening, The average coating thickness is 100 to 3000 nm, and / or The total area of ​​excess coating thickness is less than 10% of the coated area, and the excess coating thickness is defined as the area exhibiting a coating thickness exceeding twice the average coating thickness. The method according to claim 8.

12. The method according to claim 8, wherein, after curing, the coating contains one or more silicon-organic polymers.

13. A hollow cylindrical body having a wall surrounding a lumen, obtained by the method of claim 1 or 2, wherein the hollow cylindrical body has at least one opening, and at least a portion of the inner surface of the wall includes a coating, The average coating thickness is 100 to 3000 nm, and The total area of ​​excess coating thickness is less than 10% of the coated area, and excess coating thickness is defined as the area where the coating thickness exceeds twice the average coating thickness. A coated container.

14. The coated container according to claim 13, wherein the coating contains one or more silicon-organic polymers.

15. The coated container according to claim 13, wherein the total area of ​​insufficient coating thickness is less than 5% of the coated area, and the insufficient coating thickness is defined as an area exhibiting a coating thickness of less than 100 nm.

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