JP2012526921A - Gas release method for coating surface inspection - Google Patents

Abstract

  A method for coating the surface of a substrate by PECVD is provided, the method comprising a technique for generating a plasma from a gaseous reactant comprising an organosilicon precursor and optionally O2. The lubricity, hydrophobicity and / or barrier properties of the coating are determined by setting the ratio of O2 to organosilicon precursor in the gaseous reactant and / or by setting the power used for plasma generation. In particular, a lubricity coating produced by the method described above is provided. Containers coated by the above method, and the use of such containers to protect the compounds or compositions contained or received in the above coated containers from the mechanical and / or chemical action of the surface of the uncoated container Also provide.

Description

              The present invention relates to the technical field of manufacturing coated containers for storing biologically active compounds or blood. In particular, the present invention relates to a container processing system for coating a container, a container processing system for coating and inspecting a container, a portable container holder for the container processing system, and a plasma enhanced chemical vapor deposition apparatus for coating the inner surface of the container. , Methods for coating the inner surface of a container, methods for coating and inspecting a container, methods of container processing, use of a container processing system, computer readable media, and program elements.

A method for coating the surface of a substrate by PECVD is provided, the method comprising a technique for generating a plasma from a gaseous reactant comprising an organosilicon precursor and optionally O ₂ . The lubricity, hydrophobicity and / or barrier properties of the coating are determined by setting the ratio of O ₂ to organosilicon precursor in the gaseous reactant and / or by setting the power used for plasma generation. . In particular, a lubricity coating produced by the method described above is provided. Containers coated by the above method, and the use of such containers to protect the compounds or compositions contained or received in the above coated containers from the mechanical and / or chemical action of the surface of the uncoated container Also provide.

              The present disclosure also relates to improved methods for processing containers, such as venipuncture and other medical specimen collection, drug storage and delivery, and multiple identical containers used for other purposes. Since such containers are used in large quantities for these purposes, it is essential that the manufacturing cost is relatively low while the storage and use are highly reliable.

              For example, vacuum blood collection tubes are used to draw blood from patients for medical analysis. The tube is sold under vacuum. In order to transfer the patient's blood into the tube, one end of a double-headed hypodermic needle is inserted into the patient's blood vessel, and a vacuum tube tube closure at the other end of the double-ended needle is drilled. Since the inside of the vacuum blood collection tube is evacuated, blood is aspirated (more precisely, the blood is pushed out by the patient's blood pressure) and flows through the needle to the vacuum blood collection tube, increasing the pressure in the tube, thus Incentive pressure difference is reduced. The blood inflow generally continues until the needle is removed or until the pressure difference becomes too small to trigger the inflow.

              The vacuum blood collection tube is provided with a substantial storage period for the purpose of promoting efficient and convenient distribution and storage of the tube before use. For example, a shelf life of 1 year is desirable, and in some cases progressively longer shelf life such as 18 months, 24 months, 36 months is also desirable. The tube must be at least at the level required to aspirate blood necessary for analysis, provided that there is little (preferably no) defective tube provided (common criteria are that the tube is It is desirable to maintain an essentially full vacuum condition by maintaining at least 90%).

              Due to the use of defective tubes, phlebotomists may not be able to draw enough blood. The phlebotomist must then obtain and use one or more additional tubes to collect an appropriate blood sample.

              In another example, prefilled syringes are generally manufactured and sold that saves the effort of filling the syringe with the drug before use. The syringe is in some instances filled with saline, an injectable dye, or a pharmaceutically active formulation.

              Generally, the distal end of a prefilled syringe is covered with a lid and the proximal end is closed with a plunger. The filled syringe may be packaged in a sterile packaging material before use. To use the prefilled syringe, the packaging and lid are removed, and optionally a hypodermic needle or other delivery conduit is attached to the barrel distal end, and the delivery conduit or syringe is moved to the use position (subcutaneous). The needle is inserted into the patient's blood vessel, inserted into a device for washing the syringe contents, etc.), and the plunger is advanced into the barrel to inject the contents of the barrel.

              One important aspect in the manufacture of prefilled syringes is that the contents of the syringe preferably have a substantial shelf life during which the material that fills the syringe contains a barrel containing it. It is important to separate from the wall to prevent leaching of barrel constituents into the filled contents, or vice versa.

              Because many of these containers are inexpensive and used in large quantities, it is useful for certain applications to provide a reliable required shelf life without increasing manufacturing costs to an expensive level. Also, for specific applications, avoid glass containers that can be damaged and that are expensive to manufacture, and rarely break under normal use (even if broken, sharp debris from container residues like glass tubes) It is preferable to use a plastic container. Glass containers have been widely used because of their excellent hermeticity and inertness to filled contents compared to untreated plastic. Also, by traditional usage, it is known that glass is relatively harmless when contacted with medical specimens or pharmaceutical formulations.

              Further considerations regarding the syringe include ensuring that the plunger is movable at a constant speed and a constant force when pushed into the barrel. For this purpose, it is desirable to apply a lubricious coating to either or both of the barrel and the plunger.

              A limited list of patents with potential relevance includes US Patents 6,068,884 and 4,844,986, and US Published Patent Applications 20060046006 and 200040267194.

US Patent 6,068,884 US Patent No. 4,844,986 US Published Patent Application No. 20060046006 US Published Patent Application 20040267194 Specification

              The object of the present invention provides an improved method of manufacturing a coated container.

              Below, the method and apparatus manufactured according to the said method are demonstrated, the said method is performed by the container processing system demonstrated below, and the said apparatus is manufactured by this system.

              The present invention provides a method of coating a surface, for example, the inner surface of a container, with a coating material generated from an organosilicon precursor by PECVD. The present invention further provides a coating material to be produced, a container coated with such a coating material, and a method of using the coating material (such as a lubricating coating material, a hydrophobic coating material, or a barrier coating material). Furthermore, an apparatus and a plurality of devices for carrying out the present invention are provided. The present invention also provides a method for inspecting the coating, and in particular, provides a method that utilizes outgassing of volatile species from the coating surface for such inspection.

PECVD coating method
The present invention relates to a method for producing a coating material by plasma enhanced chemical vapor deposition (PECVD), for example, a method for coating an inner surface of a container.

              A surface, for example, the inner surface of the vessel, is prepared, and a reaction mixture consisting of an organosilicon compound gas, optionally an oxidizing gas, and optionally a hydrocarbon gas is prepared.

              The surface is contacted with the reaction mixture. A plasma is generated in the reaction mixture. Preferably, the plasma is a non-hollow cathode plasma or, in the same conditional formula, the plasma contains substantially no hollow cathode plasma. The covering material is deposited on at least a part of the surface, such as a part of the inner wall of the container.

              The method is performed as follows.

              Prepare a precursor. Preferably, the precursor is an organosilicon compound (hereinafter also referred to as “organosilicon precursor”), more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyltrimethoxy. An organosilicon compound selected from the group consisting of silane, aza analogues of these precursors (linear silazane, monocyclic silazane, polycyclic silazane, polysilsesquiazane), and complexes of two or more of these precursors is there. The precursor is applied to the substrate under conditions effective for PECVD coating production. The precursor is thus polymerized, cross-linked, partially or fully oxidized, or a combination thereof.

              In one embodiment of the present invention, the coating material is a lubricity coating material, that is, forms a surface having a lower frictional resistance than an uncoated substrate.

              In another aspect of the invention, the coating is a hydrophobic coating that results in reduced precipitation of the composition components upon contact with a protective film, such as a coating surface. Such a hydrophobic coating material is characterized by a low wetting tension compared to an uncoated material.

              The lubricity coating of the present invention may be a protective film and vice versa.

In a further aspect of the invention, the dressing is a barrier dressing such as a SiO _x dressing. In general, the barrier membrane blocks gas or fluid and preferably blocks water vapor, oxygen and / or the atmosphere. The barrier membrane is also used to establish and / or maintain a vacuum inside a container (eg, inside a blood collection tube) that is coated with a barrier coating.

The method of the present invention may also consist of application of one or more additional coatings produced from the organosilicon precursor by PECVD. An optional additional procedure includes post-treatment of SiO _{x with} a process gas consisting essentially of oxygen and essentially free of volatile silicon compounds.

Lubricious coating
In certain embodiments, the present invention provides a lubricity coating.

              The dressing is preferably produced by the PECVD method and uses the precursors described above.

For example, the present invention provides a method for setting the lubricity of a coating material on a substrate surface, which method comprises the following steps:
(a) providing a gaseous reactant near the substrate surface comprising an organosilicon precursor and optionally O2, and
(b) generating a plasma from gaseous reactants, and thus forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD);
The lubricity of the coating is determined by setting the ratio of O2 to organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma.

              A desirable precursor for the lubricity coating is a monocyclic siloxane, such as octamethylcyclotetrasiloxane (OMCTS).

              The resulting coated surface has a lower frictional resistance than the untreated substrate. For example, if the coated surface is the inner surface of a syringe barrel and / or syringe plunger, the lubricious coating reduces the activation force, plunger sliding force, or both compared to the case without the lubricious coating. It is effective.

              The material coated with the lubricating coating may be a container having a lubricating coating on the wall, preferably on the inner wall (eg syringe barrel) or on the container contact surface. On a container part or container lid (eg syringe plunger or container lid).

The lubricity coating in one embodiment may have the formula Si _w O _x C _y H _z , for example, w is 1, x is about 0.5 to about 2.4, y is about 0.6 to about 3, and z is about 2 To about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is 6 to about 9.

Protective (eg hydrophobic) coating
The protective coating material described in the present invention is, for example, a hydrophobic coating material.

              A desirable precursor for the protective (eg hydrophobic) coating is a linear siloxane, eg hexamethyldisiloxane (HMDSO).

              The protective coating described in the present invention prevents or reduces the mechanical and / or chemical effects of the uncoated surface on the compound or composition contained within the container. For example, preventing or reducing precipitation and / or clotting or platelet activation of compounds or components that come into contact with the surface, specifically blood clotting or platelet activation or insulin precipitation, or uncoated surface wetting by aqueous humor To prevent.

Specific embodiments of the present invention include a surface coated with a hydrophobic coating having the formula Si _w O _x C _y H _z , for example, w is 1, x is about 0.5 to about 2.4, and y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is 6 to about 9.

              The substance to be coated with the protective covering material is a container having a covering material on a wall, preferably a container part or a container lid having the above-mentioned covering material on an inner wall (for example, a pipe) or on a container contact surface. (Example: Container lid).

Container coating
When coating a container with the above-described coating method using PECVD, the coating method consists of several procedures. A container having an open end, a closed end, and an inner surface is prepared. At least one gaseous reactant is introduced into the vessel. Plasma is generated in the vessel under conditions effective to shape the reaction product of the reactant. That is, a covering material is generated on the inner surface of the container.

              Preferably, the method is performed with the open end of the container loaded onto the container holder as described herein to establish a pass-through seal between the container holder and the interior of the container. In this desirable embodiment, the gaseous reactant is introduced into the vessel through the vessel holder. In certain desirable embodiments of the present invention, a plasma enhanced chemical vapor deposition (PECVD) apparatus comprising a container holder, internal electrodes, external electrodes, and a power supply is used for the coating method described in the present invention.

              The container holder has a port for receiving the container in a loading position for processing. The internal electrode is positioned to be received in a container already loaded on the container holder. The external electrode has an internal portion that is positioned to receive a loaded container on a container holder. The power supply device generates a plasma in a container already loaded on the container holder by causing an electric current to be exchanged with the internal and / or external electrodes. In general, when the internal electrode is grounded, the power supply device exchanges current with the external electrode. In this example, the vessel defines a plasma reaction chamber.

              In a particular embodiment of the present invention, the PECVD apparatus described in the previous paragraph consists of a gas exhaust pipe that does not necessarily include a vacuum source, and defines a closed chamber by transferring gas to / from the inside of a container already loaded on the port. To do.

              In a further specific embodiment of the present invention, the PECVD apparatus comprises a container holder, a first gripping part, a loading part on the container holder, a reactant supply apparatus, a plasma generation apparatus, and a container release apparatus.

              The container holder is set to load the open end of the container. The first gripping unit is set to selectively grip and release the closed end of the container and to transport the container to the vicinity of the container holder while gripping the closed end of the container. The container holder has a loading portion that is set to establish a passing seal between the container holder and the lumen of the first container.

              The reactant supply device is operably connected to introduce at least one gaseous reactant into the first vessel through the vessel holder. The plasma generating apparatus is set to generate plasma in the first container under conditions effective to form a reaction product of the reactant on the inner surface of the first container.

              The container release device is provided to unload the first container from the container holder. The gripping part which is the first gripping part or the other gripping part is set so as to transport the first container away from the container holder in the axial direction and then release the loading of the first container.

              In a particular embodiment of the invention, the method is for coating the restricted opening of a vessel, for example the inner surface of a vessel that is generally tubular, by PECVD. The container includes an outer surface, an inner surface defining a lumen, a larger opening having an inner diameter, and a restrictive opening having an inner diameter defined by the inner surface and smaller than the inner diameter of the larger opening. A processing container having a lumen and a processing container opening is prepared. The processing vessel opening is connected to the restrictive opening of the vessel and the passage between the treated vessel lumen and the processing vessel lumen is established via the restrictive opening. At least a portion is evacuated in the lumen of the container to be processed and in the lumen of the processing container. The PECVD reactant flows through the first opening and then into the lumen of the vessel to be processed, the restrictive opening, and the lumen of the processing vessel. A plasma is generated adjacent to the limiting opening under conditions effective to deposit a PECVD reaction product on the inner surface of the limiting opening.

Coated containers and container parts
The present invention further provides a dressing produced from the method described above, a surface coated with the aforementioned dressing, and a container coated with, for example, the aforementioned dressing.

              The surface to be coated with the coating material, such as the container wall or a part thereof, is made of glass or polymer, preferably is a thermoplastic polymer, more preferably polycarbonate, olefin polymer, cyclic olefin copolymer, and polyester. A polymer selected from the group consisting of For example, a cyclic olefin copolymer, polyethylene terephthalate, or polypropylene.

              In certain embodiments of the invention, the container wall has an inner polymer layer encapsulated with at least one outer polymer layer. The polymers can be the same or different. For example, one polymer layer is a cyclic olefin copolymer (COC) resin (eg, defining water vapor barrier properties) and another polymer layer is a polyester resin. Such a container may be manufactured by a process including a process of introducing a COC layer and a polyester resin layer into an injection mold through a concentric injection nozzle.

              The coated container of the present invention may be prefilled with an empty, vacuum, compound or composition.

              A particular embodiment of the present invention is a container having a protective coating, such as a hydrophobic coating as defined above.

              A further particular aspect of the present invention is a surface having a lubricity coating as defined above, for example. The surface may be a container having a lubricious coating on the wall, preferably a container part or container lid having said coating on the inner wall (eg syringe barrel) or on the container contact surface ( Example: syringe plunger or container lid).

              A particular embodiment of the present invention is a syringe comprising a plunger, syringe barrel, and lubricious coating as defined above on one or both syringe parts, preferably on the inner wall of the syringe barrel. The syringe barrel includes a barrel having an inner surface that slidably receives the plunger. The lubricity coating may adhere to the inner surface of the syringe barrel, the surface of the plunger that contacts the barrel, or both of the aforementioned surfaces. The lubricious coating is effective in reducing the starting force or plunger sliding force required to move the plunger within the barrel.

              A further particular aspect of the present invention is a syringe barrel coated with a lubricity coating as defined in the previous paragraph.

              In certain embodiments of the aforementioned coated syringe barrel, the syringe barrel comprises a barrel having an inner surface that defines a lumen and slidably receives a plunger. The syringe barrel is advantageously made from a thermoplastic material. Lubricant coating is applied to the barrel inner surface, the plunger, or both by plasma enhanced chemical vapor deposition (PECVD). The solute retention member is applied to the lubricity coating by surface treatment in an amount effective to reduce, for example, leaching of the lubricity coating, thermoplastic material, or both into the lumen. The lubricity coating and solute retention member are configured to provide an effective amount to reduce the starting force, plunger sliding force, or both as compared to the case without the lubricity coating and solute retention member. .

Another aspect of the present invention is a syringe that includes a plunger, a syringe barrel, and internal and external dressings. The barrel has an inner surface that slidably receives the plunger and an outer surface. There may be a lubricity coating on the inner surface and an additional barrier SiO _x coating (x from about 1.5 to about 2.9) provided on the barrel inner surface. A barrier coating (eg, resin or additional _SiOx coating) is provided on the outer surface of the barrel.

Another aspect of the invention is a syringe that includes a plunger, a syringe barrel, and a luer fitting. The syringe barrel has an inner surface that slidably receives the plunger. The luer attachment includes a luer taper having an internal path defined by the inner surface. The luer attachment portion is formed as a separate member from the syringe barrel, and is coupled to the syringe barrel by coupling. Internal routing of the luer taper is blocking SiO _X dressing (x is from about 1.5 to about 2.9) having a.

Another aspect of the present invention is a plunger for a syringe that includes a piston and a push rod. The piston has a front surface, a side surface that is generally cylindrical, and a rear portion, the side surface being configured to be movably loaded into a syringe barrel. The plunger has the lubricity coating described in the present invention on its side surface. The push rod is set to engage the rear of the piston and push the piston forward within the syringe barrel. The plunger may also be made of a SiO _x coating material.

              A further aspect of the present invention is a container having only one opening, ie a container for collecting or storing a compound or composition. Such a container is a tube in a particular embodiment, such as a specimen collection tube, such as a blood collection tube. The tube may be closed with a closure, such as a lid or a stop member. Such a lid or stop member may include the lubricity coating described in the present invention on the surface in contact with the tube and / or the protective coating described in the present invention on the surface facing the lumen of the tube. . In certain embodiments, such stop members or parts thereof may be made from an elastomeric material.

              Such a stop member may be made as follows: the stop member is positioned substantially within the vacuum chamber. A reaction mixture is provided comprising an organosilicon compound gas, optionally an oxidizing gas, and optionally a hydrocarbon gas. Plasma is generated in the reaction mixture in contact with the stop member. The dressing is deposited on at least a portion of the stop member.

A further aspect of the present invention is a container having a barrier coating according to the present invention. The container is usually tubular and may be made from a thermoplastic material. The container has a mouth and a lumen that are at least partially bounded by walls. The wall has an inner surface that joins the lumen. In a preferred embodiment, an at least essentially continuous barrier coating made of SiO _{x as} defined above is applied to the inner surface of the wall. The barrier coating is effective to maintain at least 90% of the initial vacuum level and optionally 95% of the initial vacuum level in the container for a shelf life of at least 24 months. A closure is provided to cover the mouth of the container, and the lumen of the container is isolated from the ambient atmosphere.

              PECVD coating methods using PECVD and organosilicon precursors as described herein can also be used to coat a catheter or cuvette to provide a barrier coating, hydrophobic coating, lubricity coating, or Useful for molding those combinations. A cuvette is a small tube having a circular or square cross section and sealed at one end, and is made of polymer, glass, or molten quartz (for ultraviolet rays) as a raw material, and is designed to hold a specimen for spectroscopic experiments. The best cuvettes are infinitely clear and free of impurities that can affect spectroscopic measurements. Like a test tube, a cuvette may have an opening leading to the outside air or a lid that seals it. The PECVD coating of the present invention is very thin, transparent and optically flat and therefore does not interfere with optical testing of the cuvette or its contents.

(Pre) filled coated container
A particular aspect of the present invention is a coated container as described above, wherein the lumen is filled or used to fill a compound or composition. Said compound or composition may be the following:
(i) a biologically active compound or composition, preferably a drug, more preferably a composition comprising insulin or insulin, or
(ii) biological fluids, preferably body fluids, more preferably blood or blood fractions (eg blood cells), or
(iii) blood coagulation or platelets in a blood collection tube, such as a compound or composition that is combined with another compound or composition directly contained within the container, such as citrate or a citrate containing composition A compound for preventing activation.

              The coated containers of the present invention are typically particularly useful for the collection and storage of compounds and compositions that are sensitive to the mechanical and / or chemical action of the surface of an uncoated container substrate, preferably compounds that come into contact with the inner surface of the container Or to prevent and reduce precipitation and / or clotting or platelet activation of the composition components.

              For example, a cell preparation tube having a wall coated with the hydrophobic coating of the present invention and containing a hydrous sodium citrate reagent is suitable for blood collection and prevents / reduces blood clotting. The hydrous sodium citrate reagent adheres to the lumen of the tube in an amount effective to inhibit clotting of blood introduced into the tube.

              A particular embodiment of the present invention is a container for blood collection / reception or a blood containing container. The container has a wall, and the wall has an inner surface defining a lumen. The inner surface of the wall is at least partially coated with the hydrophobic coating material of the present invention. The covering material is as thin as the monomolecular layer thickness or has a maximum layer thickness of about 1000 nm. The blood collected / stored in the container is preferably filled into a lumen that contacts the coating and can be returned to the patient's vasculature. The dressing is effective in reducing clotting or platelet activation of blood exposed to the inner surface compared to the same type of uncoated wall.

              Another aspect of the invention is an insulin containing container including a wall having an inner surface defining a lumen. The inner surface is at least partially coated with the hydrophobic coating material of the present invention. The layer thickness of the coating material is monomolecular to about 1000 nm on the inner surface. Insulin or a composition comprising insulin is deposited in the lumen that contacts the dressing. Optionally, the dressing is effective to reduce precipitate formation from insulin in contact with the inner surface compared to the same type of uncoated wall.

The present invention thus provides the following examples relating to coating methods, coated products, and uses of said products:
(1) A method for setting the lubricity of the coating material on the substrate surface, and the method comprises the following steps:
(a) providing a gaseous reactant near the substrate surface comprising an organosilicon precursor and optionally O2, and
(b) generating a plasma from gaseous reactants, and thus forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD);
The lubricity of the coating is determined by setting the ratio of O2 to organosilicon precursor in the gaseous reactant and / or by setting the power used to generate the plasma.

(2) A method for producing a hydrophobic coating on a substrate, which comprises the following steps:
(a) providing a gaseous reactant near the substrate surface comprising an organosilicon precursor and optionally O2, and
(b) generating a plasma from gaseous reactants, and thus forming a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD);
The hydrophobicity of the coating is determined by setting the ratio of O2 to organosilicon precursor in the gaseous reactant and / or by setting the power used for plasma generation.

              (3) The method according to (1) or (2), wherein the atomic ratio C: O is increased and / or the atomic ratio Si: O is decreased as compared to the summation formula of the organosilicon precursor. A method of producing a dressing that is characterized.

               (4) The volume / volume ratio of the O2 to the gaseous reactant is 0: 1 to 5: 1, optionally 0: 1 to 1: 1, optionally 0: 1 to 0.5: 1, A process according to any of (1) to (3), optionally between 0: 1 and 0.1: 1, desirably at least oxygen is essentially absent from the gaseous reactant.

               (5) The gaseous reactant consists of less than 1 vol% O2, more particularly less than 0.5 vol% O2, most preferably no O2, any of (1) to (4) The method according to any one.

               (6) The method according to any one of (1) to (5), wherein the plasma is non-hollow cathode plasma.

               (7) The substrate is a wall in a container having a lumen, and the void volume of the lumen is 0.5 to 50 mL, preferably 1 to 10 mL, more preferably 0.5 to 5 mL, most preferably 1 to 3 mL. The method according to any one of (1) to (6).

(8) The method according to any one of (1) to (7), which satisfies the following:
(i) The plasma is generated with an electrode that receives sufficient power to generate a coating on the substrate surface, preferably 0.1 to 25 W, more preferably 1 to 22 W, even more preferably 3 to 17 W, More preferably 5-14 W, most preferably 7-11 W, in particular produced with electrodes receiving 8 W of power; and / or
(ii) The electrode power to plasma volume ratio is less than 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, most preferably 2 W / ml 0.2 W / ml.

(9) A method for producing a coating material on a substrate surface, which method comprises the following steps:
(a) providing a gaseous reactant near the substrate surface comprising an organosilicon precursor and optionally O2, and
(b) Generation of non-hollow cathode plasma from gaseous reactants under reduced pressure, ie formation of a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),
The physical and chemical properties of the coating are determined by setting the ratio of O2 to organosilicon precursor in the gaseous reactant and / or by setting the power used for plasma generation.

(10) A method of producing a barrier coating on a substrate, the method comprising the following steps:
(a) providing a gaseous reactant comprising an organosilicon precursor and O2 near the substrate surface; and
(b) Generation of non-hollow cathode plasma from gaseous reactants under reduced pressure, ie formation of a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),
The barrier properties of the coating are determined by setting the ratio of O2 to organosilicon precursor in the gaseous reactant and / or by setting the power used for plasma generation.

(11) The method according to (10), which satisfies the following.
(i) The plasma is generated with an electrode that receives sufficient power to generate a coating on the substrate surface, preferably 8-500 W, more preferably 20-400 W, even more preferably 35-350 W, More preferably produced at 44-300 W, most preferably 44-70 W of electrodes receiving power; and / or
(ii) The electrode power to plasma volume ratio is 5 W / ml or more, preferably 6 W / ml to 150 W / ml, more preferably 7 W / ml to 100 W / ml, most preferably 7 W / ml to 20 W / ml. ml.

               (12) The method according to (10) or (11), wherein the volume / volume ratio of the O2 to the gaseous reactant is from 1: 1 to 100: 1 in the context of the silicon-containing precursor, preferably 5: 1 to 30: 1, more preferably 10: 1 to 20: 1, even more preferably 15: 1.

(13) The method according to any one of (1) to (12), wherein the organosilicon precursor is a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysilsesquioxane, a linear silazane, a single Selected from the group consisting of cyclic silazanes, polycyclic silazanes, polysilsesquiazanes, alkyl trimethoxysiloxanes, and complexes of two or more of these compounds,
A process which is preferably a linear or monocyclic siloxane.

               (14) The method according to (1) or (2), wherein the organosilicon precursor is a monocyclic siloxane, preferably OMCTS.

               (15) The method according to (2) or (10), wherein the organosilicon precursor is a linear siloxane, preferably HMDSO.

               (16) The PECVD is performed at an organosilicon precursor flow rate of 6 sccm or less, preferably 2.5 sccm or less, more preferably 1.5 sccm or less, and most preferably 1.25 sccm or less, (1) to (15) The method described.

               (17) The substrate is a polymer selected from the group consisting of polycarbonate, olefin polymer, cyclic olefin copolymer, and polyester, and is preferably cyclic olefin copolymer, polyethylene terephthalate, or polypropylene. The method according to any one of 1) to (16).

               (18) The substrate surface is a part or all of the inner surface of the container having at least one opening and an inner surface, the gaseous reactant fills the inner lumen of the container, and the plasma is the inner lumen of the container The method according to any one of (1) to (17), wherein the method is produced in part or all of the above.

               (19) The plasma is generated by a high-frequency electrode, and the frequency is preferably 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz, and most preferably 13.56 MHz, (1) to ( The method according to any one of 18).

               (20) The method according to any one of (1) to (19), wherein the plasma is generated under reduced pressure, and the reduced pressure is less than 300 mtorr, preferably less than 200 mtorr, more preferably less than 100 mtorr.

               (21) The method according to any one of (1) to (20), wherein the PECVD deposition time is 1 to 30 seconds, preferably 2 to 10 seconds, more preferably 3 to 9 seconds.

               (22) The method according to any one of (1) to (21), wherein the layer thickness of the resulting coating material is 1 to 100 nm, preferably 20 to 50 nm.

               (23) A covering obtained by the method according to any one of the above claims.

               (24) The coating material according to (23), which is a lubricating and / or hydrophobic coating material.

               (25) the carbon to oxygen atomic ratio is increased compared to the organosilicon precursor and / or the oxygen to silicon atomic ratio is decreased compared to the organosilicon precursor; The coating material described.

               (26) The coating material according to any one of (23) to (25), wherein the precursor is octamethylcyclotetrasiloxane, and the coating material has a density higher than that of the coating material made of HMDSO under the same PECVD reaction conditions.

(27) The coating material according to any one of (24) to (26), wherein the coating material has the following:
(i) Friction resistance lower than uncoated surface, preferably reduced by at least 25%, more preferably reduced by at least 45%, more preferably reduced by at least 60% compared to uncoated surface.

(28) The coating material according to any one of (24) to (27), wherein the coating material has the following:
(i) Wetting tension lower than the uncoated surface, preferably 20-72 dynes / cm, more preferably 30-60 dynes / cm, more preferably 30-40 dynes / cm, preferably 34 dynes / cm, And / or
(iv) Higher hydrophobicity than the uncoated surface.

(29) A coated container in which the coating material according to any one of (23) to (28) is used on at least a part of the inner surface, preferably the following items:
(i) Sample collection tube, especially a collection tube, or
(ii) vials, or
(iii) a syringe or syringe part, a specific syringe barrel or syringe plunger, or
(iv) a conduit, or
(v) cuvette.

(30) The coated container according to (29), further comprising at least one SiOx film (x is 1.5 to 2.9) satisfying the following.
(i) the coating is positioned between the SiOx layer and the substrate surface, or vice versa, or
(ii) the covering is located between the two layers of SiOx, or vice versa, or
(iii) The SiOx layer and coating is a graded composition of SiwOxCyHz to SiOx, or vice versa.

               (31) The coated container according to any one of (29) to (30), further comprising at least one layer, preferably a plastic or SiOx (x is 1.5 to 2.9) on the outer surface.

               (32) containing a compound or composition in the lumen, preferably containing a biologically active compound or composition or biological fluid, more preferably (i) a composition containing citrate or citrate A coated container according to any one of (29) to (31), comprising: a product, (ii) a drug that is in particular insulin or an insulin composition, or (iii) blood or blood cells.

               (33) A syringe barrel produced according to the method of claim 1, wherein the precursor is a siloxane, preferably a monocyclic siloxane, more preferably octamethylcyclotetrasiloxane, and in step (a) the gaseous state The reactant is substantially free of O2, and the force to move the plunger within the coated barrel is at least 25%, more preferably at least 45%, even more preferably 60% compared to the uncoated syringe barrel. The coated container according to any one of (29) to (32), which decreases by%.

(34) Use of a coating material having the summation formula SiwOxCyHz (w is 1, x is 0.5 to 2.4, y is 0.6 to 3, and z is 2 to 9) in the following applications.
(i) a lubricious coating with a lower frictional resistance than the uncoated surface, and / or
(ii) A hydrophobic coating material that is more hydrophobic than the uncoated surface.

               (35) The method according to (34), wherein the coating material is the coating material according to any one of (24) to (28).

               (36) The coating material prevents or reduces precipitation of compounds or composition components that come into contact with the coating material, in particular using an uncoated surface and / or HMDSO as a precursor, a surface coated by the method of (1) Use of (34) or (35) to prevent or reduce insulin precipitation or blood clotting compared to.

               (37) a compound for protecting the compound or composition contained or received in the aforementioned coated container from the mechanical and / or chemical action of the surface of the uncoated container, preferably in contact with the inner surface of the container or Use of the coated container according to any one of (29) to (33) for preventing precipitation and / or coagulation of the composition component.

(38) The use according to (37), wherein the compound or composition satisfies the following.
(i) a biologically active compound or composition, preferably a drug, more preferably a composition comprising insulin or insulin that reduces / prevents insulin precipitation, or
(ii) A blood fraction that reduces or prevents biological fluids, preferably body fluids, more preferably blood or blood clotting and / or platelet activation.

               (39) A medical / diagnostic kit comprising a coated container according to the present invention, the kit further comprising: a drug or diagnostic agent contained in the coated container, and / or a hypodermic needle, a double-ended needle, or Other transport conduits and / or instructions for use.

              The present invention further provides the following examples:

I. Container processing system with multiple processing stations and multiple container holders
In accordance with one aspect of the present invention, a container processing system for coating a container is provided, the system comprising a first processing station, a second processing station, a container holder, and a conveyor equipment. The first processing station is set to perform a first process on the inner surface of the container, for example, an inspection or coating of the inner surface of the container. The second processing station is set apart from the first processing station and is set to perform a second process on the inner surface of the container, for example, inspection or coating of the inner surface of the container. The container holder is adapted to receive and load the container opening at the first processing station and the second processing station for processing (inspecting and / or coating and / or inspecting) the inner surface of the loaded container via the container port. Consists of a container port to be set. The conveyor equipment transports the container holder and the loaded container from the first processing station to the second processing station for the second processing of the inner surface of the loaded container at the second processing station after the first processing. Adapted to do.

              Containers are broadly defined within this specification and include sample tubes that collect / store blood, urine, and other samples, syringes that store / carry biologically active compounds or compositions, biological materials or biology Vials that store biologically active compounds or compositions, catheters that carry biological materials or biologically active compounds or compositions, and cuvettes that hold biological materials or biologically active compounds or compositions Including, but not limited to, any type of container.

              The containers described below are all processed by any of the processing systems or apparatuses described below. In other words, the functions relating to the apparatus or the processing system described below can be implemented as a method procedure and thus may affect the processing vessel.

              A cuvette is a small tube having a circular or square cross section and sealed at one end, and is made of plastic, glass, or molten quartz (for ultraviolet rays) as a raw material and designed to hold a specimen for spectroscopic experiments. The best cuvettes are infinitely clear and free of impurities that can affect spectroscopic measurements. Like a test tube, a cuvette may have an open top that leads to outside air or a lid that seals it.

              The term “inside a container” refers to a hollow space inside the container and may be used to store blood or a biologically active compound or composition as described in another exemplary embodiment. .

              The term “treatment” may include a coating procedure and / or an inspection procedure or a series of coating and inspection procedures, for example, a first inspection procedure, a subsequent coating procedure, followed by a second, third, fourth inspection. Can be mentioned. The second, third, and fourth inspections may be performed at the same time.

              According to an exemplary embodiment of the present invention, the container holder comprises a vacuum duct for drawing gas from the lumen of the loaded container, and the container holder is adapted to keep the interior of the loaded container vacuum. There is no need to use an additional vacuum chamber when processing the vessel. In other words, the container holder together with the loaded container provides a vacuum chamber adapted to keep the container lumen vacuum. This vacuum condition is important in certain processing procedures such as plasma enhanced chemical vapor deposition (PECVD) or other chemical vapor deposition procedures. Furthermore, the vacuum state in the container is important for performing a specific inspection of the container wall, in particular an inspection of the coating on the inner surface of the container wall, for example by measuring the outgassing rate of the wall or the conductivity of the wall.

              In accordance with another exemplary embodiment of the present invention, the first process is performed in 30 seconds or less. The second process is also performed in 30 seconds or less.

              Accordingly, a container processing system for coating the container is provided that allows for rapid manufacture of the container.

              In accordance with another exemplary embodiment of the present invention, the first treatment and / or the second treatment comprises an inspection of the inner surface of the container and a coating on the inner surface.

              In accordance with another exemplary embodiment of the present invention, the container holder comprises a gas inlet port for transporting gas into the container.

              In accordance with another exemplary embodiment of the present invention, the system is adapted to automatically reprocess the container when a defect is detected in the dressing. For example, the container processing system, in particular the container holder, may consist of various detection devices, such as optical detectors, pressure probes, gas detectors, electrodes for electrical measurements.

              Furthermore, in accordance with another exemplary embodiment of the present invention, the container processing system, eg, one or more processing stations, transports the container to the container holder and / or releases the container from the container holder 1 It consists of two or more gripping parts.

              In accordance with another exemplary embodiment of the present invention, the container holder comprises a gas inlet port for transporting gas into the container.

              In accordance with another exemplary embodiment of the present invention, the container processing system is adapted to automatically reprocess the container if a defect is detected in the dressing.

              The gas delivered to the vessel lumen may be used for PECVD coating of the vessel inner surface.

              In accordance with another exemplary embodiment of the present invention, the first treatment and / or the second treatment comprises a coating on the inner surface of the container.

              In accordance with another exemplary embodiment of the present invention, the first processing station and / or the second processing station comprises a PECVD apparatus for coating the inner surface of the vessel.

              In accordance with another exemplary embodiment of the present invention, the system further comprises an external electrode surrounding at least the top of the loaded container.

              In accordance with another exemplary embodiment of the present invention, the container holder comprises a conductive probe that provides a counter electrode within the container.

              According to another exemplary embodiment of the present invention, the first process and / or the second process consists of inspecting the inner surface of the container for defect detection.

              In accordance with another exemplary embodiment of the present invention, the system is further adapted to be inserted into the container via the container port of the first processing station and / or the second processing station for detecting defects. Consists of a first detector for inner surface inspection.

               In accordance with another exemplary embodiment of the present invention, the container processing system further comprises a second detector for inspection of the container inner surface for defect detection outside the container.

               In accordance with another exemplary embodiment of the present invention, the first detector and / or the second detector are mounted on the container holder.

               According to another exemplary embodiment of the present invention, the container holder comprises a mold for forming the container.

               In accordance with another aspect of the present invention, a blood tube for storing blood, a syringe for storing biologically active compound or composition, a vial for storing biologically active compound or composition Use of the container treatment system described above and below to produce a catheter for delivering a biologically active compound or composition, or a pipette for pipetting a biologically active compound or composition Present the law.

               The container handling system may also be adapted for the inspection of containers, in particular the first inspection of containers for defect detection, the application of a first coating material inside the container, the detection of defects Adapted to perform a second inspection of the inner surface of the coated container. Furthermore, the system is adapted to evaluate data acquired during various tests, and the time taken for the second test and the data evaluation is less than 30 seconds.

               In accordance with another aspect of the present invention, a container processing system for coating and inspecting a container is provided, the system comprising: a first inspection of a container for defect detection; application of a first coating material inside the container; Consists of a processing station equipped to perform a second inspection of the inner surface of the coated container for defect detection and evaluation of data acquired during the inspection, and the time required for the second inspection and data evaluation is 30 seconds. Is less than.

               The application of the first coating material may be regarded as the first process or the second process, and the execution of the second inspection of the inner surface of the coated container may be regarded as the second process.

               In accordance with another exemplary embodiment of the present invention, the processing station equipment includes a first process for performing a first test, applying a first coating to the inner surface of the loaded container, and performing a second test. It consists of a station. Further, the processing station equipment is set to receive and load the container opening for inspection and to apply the first coating material to the inner surface of the loaded container via the container port at the first processing station, Consists of a container holder consisting of a container port.

               In accordance with another exemplary embodiment of the present invention, the processing station equipment is further installed remotely from the first processing station, and the second inspection is performed, the second coating material is applied, and the third inspection after the second coating. It consists of a second processing station set up for execution. Further, the container processing system applies the second coating material to the inner surface of the loaded container at the second processing station after the application of the first coating material. Consists of a container holder and conveyor equipment for transporting loaded containers. The container port of the container holder is set to receive and load the container opening for coating, and to inspect the inner surface of the loaded container via the container port at the first and second processing stations Is done.

               In accordance with another exemplary embodiment of the present invention, the container holder comprises a vacuum duct for aspirating gas from within the loaded container, and the container holder is adapted to maintain a vacuum inside the loaded container. There is no need to utilize an additional vacuum chamber for coating and inspection of the container.

               In accordance with another exemplary embodiment of the present invention, each test is performed in 30 seconds or less.

               In accordance with another exemplary embodiment of the present invention, the container processing system is adapted to automatically reprocess the container if a defect is detected in the dressing.

               In accordance with another exemplary embodiment of the present invention, the first processing station and / or the second processing station comprises a PECVD apparatus for applying a coating on the inner surface of the vessel.

               In accordance with another exemplary embodiment of the present invention, the first dressing is a barrier coating and the system is adapted to check for the presence of a barrier layer.

               In accordance with another exemplary embodiment of the present invention, the second dressing is a lubricity dressing and the system is adapted to check for the presence of a lubricity dressing (ie, a lubrication layer).

               In accordance with another exemplary embodiment of the present invention, the first coating material is a barrier coating material, the second coating material is a lubricity coating material, and the system is used to confirm the presence of the barrier layer and the lubricating layer. Have been adapted.

               In accordance with another exemplary embodiment of the present invention, the system is adapted to verify the lubrication layer and the presence or absence of the lubrication layer with at least six sigma level certainty.

               According to another exemplary embodiment of the present invention, the first inspection and / or the second inspection are performed by measuring a gas release rate from the coating container, performing optical monitoring of coating material application, and performing optical monitoring on the inner surface of the coating container. It consists of at least one of measurement of parameters and measurement of electrical properties of the coated container.

               The corresponding measurement data can then be analyzed by the processor.

               In accordance with another exemplary embodiment of the present invention, the processing system further includes a first detector for measuring the outgassing rate and / or a second detector for measuring the diffusivity rate, and / or optical. It consists of a third detector for measuring parameters and / or a fourth detector for measuring electrical parameters.

               According to another exemplary embodiment of the present invention, the first coating material and / or the second coating material has a layer thickness of less than 100 nm.

               In accordance with another exemplary embodiment of the present invention, the processing system further comprises a processor for evaluating the data acquired during the examination.

              One aspect of the present invention is a container processing system comprising a first processing station, a second processing station, a number of container holders, and a conveyor. The first processing station is configured to process a container having a wall defining an opening and an inner surface. The second processing station is set apart from the first processing station and is configured to process a container having a wall defining an opening and an inner surface.

              Some, optionally all such container holders have a container port configured to receive and load the container opening for processing the inner surface of the loaded container via the container port at the first processing station. Including. The conveyor is configured to transport a series of the container holders and loaded containers from the first processing station to the second processing station for processing the inner surface of the loaded containers via the container port at the second processing station. Is done.

II. Container holder
II.A. Container holder without sealing equipment
While holding the inner surface of the container and inspecting it for defects, and while transporting the container from the first processing station to the second processing station of the container processing system, hold the container in the portable container holder of the container processing system. The container holder is configured to load a container opening for processing the inner surface of the loaded container via the container port at the first processing station and the second processing station. Consists of.

               The portable container holder is further in accordance with another exemplary embodiment of the present invention, a second port for receiving or discharging an outside air supply, and between the opening of the loaded container on the container port and the second port. It consists of a gas ventilation duct.

               In accordance with another exemplary embodiment of the present invention, the weight of the portable container holder is less than 2.25 kg.

              In accordance with another exemplary embodiment of the present invention, the portable container holder further comprises a vacuum duct for drawing gas from the inside of the loaded container via a vacuum port and an external vacuum port, the container holder being mounted on the loaded container. Because it is adapted to keep the interior vacuum, there is no need to utilize an additional vacuum chamber when processing the vessel.

               In accordance with another exemplary embodiment of the present invention, the portable container holder further comprises a vacuum duct for drawing gas from the inside of the loaded container via a vacuum port and an external vacuum port, the container holder being mounted on the loaded container. Because it is adapted to keep the interior vacuum, there is no need to utilize an additional vacuum chamber when processing the vessel.

               In accordance with another exemplary embodiment of the present invention, the external vacuum port also incorporates a gas inlet port that is included within the vacuum port for transporting gas into the loaded container.

               In accordance with another exemplary embodiment of the present invention, the container treatment consists of a coating on the inner surface of the loaded container.

               In accordance with another exemplary embodiment of the present invention, the container holder material is essentially a thermoplastic material.

               In accordance with another exemplary embodiment of the present invention, the portable container holder further includes a cylindrical inner surface for receiving the container cylindrical wall, a first groove in the inner and inner coaxial direction of the cylindrical inner surface. A nail groove and a first o-ring disposed in a first grooved nail groove that provides a seal between the loaded container and the container holder.

               In accordance with another exemplary embodiment of the present invention, the portable container holder further comprises a radially extending abutment adjacent to a round cylindrical inner surface against which the loaded container open end can abut.

               In accordance with another exemplary embodiment of the present invention, the portable container holder further comprises a second grooved nail groove that is axially spaced from the first grooved nail groove inside and coaxially with the cylindrical inner surface. . In addition, the container holder comprises a second O-ring disposed in a second grooved nail groove that provides a seal between the loaded container and the container holder.

              In accordance with another exemplary embodiment of the present invention, the portable container holder further comprises a first detector for interrogating the container lumen via the container port and inspecting for defects on the inner surface of the loaded container.

               In accordance with another exemplary embodiment of the present invention, the portable container holder comprises a mold for forming the container.

              In accordance with another exemplary embodiment of the present invention, the container processing system for container coating comprises the container holder described above and below.

              According to another aspect of the present invention, the portable container holder includes a container port, a second port, a duct, and a transportable casing. The container ports are set to load the container openings in a state where they can pass each other. The second port is set to accept or discharge the outside air supply. The duct is set to vent one or more gases between the container opening loaded on the container port and the second port. The container port, the second port, and the duct are attached to the transportable casing in a substantially fixed state. Optionally, the portable container holder weighs less than 5 pounds.

              Another aspect of the present invention is the portable container holder including a container port, a vacuum duct, a vacuum port, and a transportable casing. The container port is set to receive the container opening in a sealed and mutually passable state. The vacuum duct is set to suck gas from the inside of the container loaded on the container port via the container port. The vacuum port is set to allow passage between the vacuum duct and an external vacuum source. The vacuum source may be a pump or reservoir or ballast tank that is at a lower pressure than the vacuum duct. The container port, the vacuum duct, and the vacuum port are attached to the transportable casing in a substantially fixed state. Optionally, the portable container holder weighs less than 5 pounds.

II.B. Container holder including hermetically sealed equipment.
Yet another aspect of the present invention is a container holder for receiving an open end of a container having a substantially cylindrical wall adjacent to the open end. The container holder typically has a cylindrical inner surface (eg, a rounded cylindrical inner surface), a grooved nail groove, and an O-ring. Within this document, containers defined as having round / circular openings or cross-sections are understood to be merely exemplary and are not intended to limit the scope of the disclosure or the claims. If the container has a non-circular opening or cross-section (often seen when the container is a cuvette), the “round” cylindrical surface of the container holder may be non-circular, specifically Can be sealed using a non-circular sealing element such as a gasket or a seal shaped to seal the non-circular cross section. Further, the expression “cylindrical” does not require a cylinder having a circular cross section, but includes other cross sections, such as a square shape with rounded corners.

              The inner surface, usually cylindrical, is sized to receive the cylindrical wall of the container.

              The grooved nail groove is attached to the inside and the coaxial direction of the inner surface which is usually cylindrical. The first grooved nail groove has an opening on the inner surface that is usually cylindrical and a lower wall that is radially separated from the inner surface that is usually cylindrical.

              The O-ring is attached to the first grooved nail groove. The O-ring is sized to extend radially through the opening in relation to the first grooved nail groove and is pushed radially outward by a container received by the inner surface, which is usually cylindrical. . This equipment forms a sealed part between the container and the first grooved nail groove.

               According to another aspect of the present invention, a method for coating and inspecting a container is provided, and after performing a first inspection of the inner surface of the container for defect detection, a coating material is applied to the inner surface of the container. Thereafter, a second inspection is performed on the inner surface of the coating container for defect detection, and data acquired during the first and second inspections is evaluated. The time required for the second examination and the data evaluation is less than 30 seconds.

               In accordance with another aspect of the present invention, a method of treating a container is provided, wherein the container inner surface is coated via the container port after receiving and loading the container opening onto the container port of the container holder. Thereafter, the coating material is inspected for defects via the container port. Thereafter, the container is transported from the first processing station to the second processing station, and the loaded container is held by the container holder during coating, inspection, and transportation.

III. Container Transport Method-Processing of Containers Loaded in Container Holder
III.A. Transport of container holder to processing station
Another aspect of the present invention is a method for treating a container. A first processing station for container processing and a second processing station remote from the first processing station are prepared. A container having a wall defining an opening and an inner surface is provided. Prepare a container holder consisting of container ports. The container opening is loaded onto the container port. The inner surface of the loaded container is processed via the container port at the first processing station. The container holder and loaded container are transported from the first processing station to the second processing station. The inner surface of the loaded container is then processed via the container port at the second processing station.

III.B. Transport of processing equipment to the container holder or vice versa.
Another aspect of the present invention is a method for treating a container including a plurality of parts. Prepare a first processing device and a second processing device for container processing. A container having a wall defining an opening and an inner surface is provided. Prepare a container holder consisting of container ports. The container opening is loaded onto the container port.

              The first processing device is moved and operatively engaged with the container holder or vice versa. The inner surface of the loaded container is processed via the container port using the first processing equipment.

              The second processing device is moved and operatively engaged with the container holder or vice versa. The inner surface of the loaded container is processed via the container port using a second processing device.

III.C. Use of grips to transport tubes to / from the processing station
Yet another aspect of the present invention is a first vessel plasma enhanced chemical vapor deposition (PECVD) method comprising multiple procedures. A first container having an open end, a closed end, and an inner surface is prepared. The first gripper is set to selectively grip and release the closed end of the first container. The closed end of the first container is gripped by the first gripping part, and conveyed to the vicinity of the container holder set to be loaded with the first container opening end while using the first gripping part. Thereafter, the first container is advanced in the axial direction using the first gripping portion, the opening end thereof is loaded on the container holder, and the passage seal between the container holder and the first container is established.

              At least one gaseous reactant is introduced into the first container through the container holder. Plasma is generated in the first container under conditions effective to mold a reaction product of the reactant on the inner surface of the first container.

              Thereafter, the loading of the first container on the container holder is released, and the first container is moved away from the container holder in the axial direction while using the first holding part or another holding part. Thereafter, the first container is released from the grip used to move away from the container holder in the axial direction.

IV. PECVD equipment for container production
IV.A. PECVD equipment including vessel holder, internal electrode, and vessel as reaction chamber
In accordance with another aspect of the present invention, a plasma enhanced chemical vapor deposition (PECVD) apparatus for coating the inner surface of a container is provided. The PECVD apparatus may be part of a container processing system and consists of a container holder such as the holder described above and below, the container holder opening the first container for processing the inner surface of the loaded container via the container port It consists of a container port set to receive and load parts. Further, the PECVD apparatus includes an internal electrode disposed in the lumen of the loaded container and an external electrode having an internal part for receiving the loaded container. In addition, a power supply for generating plasma within the vessel is provided, where the loaded vessel and vessel holder are adapted to define a plasma reaction chamber.

               In accordance with another exemplary embodiment of the present invention, the PECVD apparatus further includes a vacuum source for evacuating the loaded container lumen, wherein the container port and the loaded container are adapted and a vacuum chamber is defined. Become.

               In accordance with another exemplary embodiment of the present invention, the PECVD apparatus further comprises a gas supply device that supplies a reactive gas from a reactive gas source to the lumen of the vessel.

              In accordance with another exemplary embodiment of the claimed invention, the gas supply device is located at a distal portion of the internal electrode.

               In accordance with another exemplary embodiment of the present invention, the internal electrode is a probe having a distal portion positioned to extend concentrically into a loaded container.

               According to another exemplary embodiment of the present invention, the external electrode has a cylindrical portion and extends concentrically to the loaded state.

               In accordance with another exemplary embodiment of the present invention, the PECVD apparatus further selectively grips and releases the closed end of the container, and moves the container closer to the container holder while holding the closed end of the container. And a gripping section for transporting the sheet.

               In accordance with another exemplary embodiment of the present invention, the PECVD apparatus is further adapted to generate a plasma in the vessel lumen that is substantially free of any hollow cathode plasma.

               In accordance with another exemplary embodiment of the present invention, the PECVD apparatus further comprises a detector for interrogating the vessel lumen via the vessel port and inspecting the vessel inner surface for defects.

               In accordance with another exemplary embodiment of the present invention, the PECVD apparatus further includes a processing vessel opening connected to the restrictive second vessel opening for allowing reactive gas to flow from the vessel lumen into the processing vessel. It consists of a processing vessel.

               In accordance with another exemplary embodiment of the present invention, the distal end of the internal electrode is located at less than half the distance from the first large opening to the restrictive second opening of the loaded container.

               In accordance with another exemplary embodiment of the present invention, the distal end of the internal electrode is located outside the first large opening of the loaded container.

               In addition, a method of coating the inner surface of the container is provided, and the container opening is received and loaded onto the container port of the container holder to treat the inner surface of the loaded container. Thereafter, the gas supply device is positioned at the distal portion of the internal electrode after the internal electrode is placed in the lumen of the loaded container. Further, the loaded container is received in the internal part of the external electrode. The loaded container in the container holder is adapted to define a plasma reaction chamber.

              In particular, a vacuum chamber may be defined by the container port and the loaded container, eliminating the need to use an external vacuum chamber during coating by aspirating gas from the lumen of the loaded container.

               In a further procedure, a plasma is generated in the vessel lumen and a dressing is deposited on the inner surface of the loaded vessel.

               In accordance with another exemplary embodiment of the present invention, the process vessel opening is connected to the restrictive vessel opening to allow the reactive gas to enter the process vessel from the vessel lumen.

               In accordance with another aspect of the present invention, a blood tube for storing blood, a syringe for storing biologically active compound or composition, a vial for storing biologically active compound or composition Use of the PECVD apparatus described above and below for the manufacture of a catheter for delivering a biologically active compound or composition, or a cuvette for grasping a biologically active compound or composition Present.

              Another aspect of the present invention is a PECVD apparatus comprising a container holder, internal electrodes, external electrodes, and a power supply device.

              The container holder has a port for receiving the container in a loading position for processing. The internal electrode is positioned to be received in a container already loaded on the container holder. The external electrode has an internal portion that is positioned to receive a loaded container on a container holder. The power supply device exchanges current with the internal and external electrodes to generate plasma in a container already loaded in the container holder. The vessel defines a plasma reaction chamber.

              Another specific aspect of the present invention is the PECVD apparatus described in the previous paragraph, which provides a gas exhaust pipe that does not necessarily include a vacuum source, and transfers gas to / from the inside of a container already loaded in the port. To define a closed chamber.

IV.B. PECVD equipment using grips to transport tubes to / from the coating station
Another aspect of the present invention is an apparatus for PECVD processing of a first container having an open end, a closed end, and a lumen. The apparatus includes a container holder, a first gripping part, a loading part on the container holder, a reactant supply device, a plasma generation device, and a container releasing device.

              The container holder is set to load the open end of the container. The first gripping unit is set to selectively grip and release the closed end of the container and to transport the container to the vicinity of the container holder while gripping the closed end of the container. The container holder has a loading portion that is set to establish a passing seal between the container holder and the lumen of the first container.

              The reactant supply device is operably connected to introduce at least one gaseous reactant into the first vessel through the vessel holder. The plasma generating apparatus is set to generate plasma in the first container under conditions effective to form a reaction product of the reactant on the inner surface of the first container.

              The container release device is provided to unload the first container from the container holder. The gripping part which is the first gripping part or the other gripping part is set so as to transport the first container away from the container holder in the axial direction and then release the loading of the first container.

V. PECVD method
In accordance with another aspect of the present invention, a method for coating (and / or inspecting) the inner surface of a container is provided, and the container opening is received and loaded onto a container holder to treat the inner surface of the loaded container. Note that the term “treatment” may refer to a coating procedure or multiple coating procedures, or a series of coating and inspection procedures.

              Furthermore, the first processing of the inner surface of the loaded container is performed at the first processing station via the container port of the container holder. Thereafter, the container holder and the loaded container are transported to the second processing station after the first processing at the first processing station. Furthermore, in the second processing station, the second processing of the inner surface of the loaded container is performed via the container port of the container holder.

VA PECVD for coating SiO _x barrier coatings using plasma that is substantially free of hollow cathode plasma
Another aspect of the invention is a method of applying a barrier coating of SiO _x (formula x is from about 1.5 to about 2.9, alternatively from about 1.5 to about 2.6, alternatively about 2) to the container surface, preferably the container interior. It is. The method consists of several procedures.

              A surface, for example a vessel wall, is prepared, and a reaction mixture consisting of a plasma generating gas, for example an organosilicon compound gas, optionally an oxidizing gas, optionally a hydrocarbon gas.

A plasma is generated in the reaction mixture that is substantially free of hollow cathode plasma. The container wall is in contact with the reaction mixture, the SiO _x coating material is deposited on at least a portion of the container wall.

PECVD coating covering the restricted opening (syringe capillary) of the VB container
Another specific embodiment of the present invention is a method of coating the inner surface of a restricted opening of a container to be treated, which is usually tubular, by PECVD. The method consists of these procedures.

              A container to be processed which is usually tubular is prepared. The container includes an outer surface, an inner surface defining a lumen, a larger opening having an inner diameter, and a restrictive opening having an inner diameter defined by the inner surface and smaller than the inner diameter of the larger opening.

              A processing container having a lumen and a processing container opening is prepared. The processing vessel opening is connected to the restrictive opening of the vessel and the passage between the treated vessel lumen and the processing vessel lumen is established via the restrictive opening.

              At least a portion is evacuated in the lumen of the container to be processed and in the lumen of the processing container. The PECVD reactant flows through the first opening and then into the lumen of the vessel to be processed, the restrictive opening, and the lumen of the processing vessel. A plasma is generated adjacent to the limiting opening under conditions effective to deposit a PECVD reaction product on the inner surface of the limiting opening.

VC Lubricant coating method
Yet another aspect of the present invention is a method of applying a lubricity coating on a substrate. The method is performed as follows.

              Prepare a precursor. The precursor is preferably organosilicon, more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, or a composite of two or more of these precursors. Other precursors, such as organometallic precursors containing Group III and Group IV metals of the periodic system are also conceivable. The precursor is applied to the substrate under conditions effective to produce a coating material. The dressing is polymerized, cross-linked, or both, and produces a lubricated surface that reduces “plunger sliding force” or “starting force” compared to an untreated substrate.

VI. Container inspection
VI.A. Container handling including pre- and post-coating inspections
Yet another aspect of the present invention is a container processing method for processing a plastic container having a wall defining an opening and an inner surface. The method is executed by inspection for detecting defects on the inner surface of the container at the time of provision, application of a coating material on the inner surface of the container after inspection of the container at the time of provision, and inspection for detecting defects of the coating material. Is done.

              Another aspect of the present invention is a container processing method in which a barrier covering material is applied to the container as inspected after inspection, and the inner surface of the container is inspected for inspection defect detection after the barrier covering material is applied. .

VI.B. Container inspection, for example, by detecting container wall outgassing through a barrier layer
Another aspect of the present invention is a method for inspecting a coating material by measuring volatile species that the coating material outgases (“gas emission method”). The above-described method can be used for inspection of a coated product in which a coating material is applied to a substrate surface and the coated surface is formed. In particular, the method can be used as an inline processing control method for coating material processing to identify and remove coated products or damaged coating materials that do not meet a predetermined standard.

              Typically, the volatile species is a gas or vapor at test conditions, preferably selected from the group consisting of air, nitrogen, oxygen, water vapor, volatile coating components, volatile substrate components, and complexes thereof, More preferred is air, nitrogen, oxygen, water vapor, or a complex thereof. The method can be used to measure one or several volatile species, but preferably a number of different volatile species are measured in step (c), more preferably the substance released from the test substance. Measure all above volatile species in step (c).

The gas release method consists of the following procedures:
(a) Providing products as inspection objects,
(c) measurement of at least one nascent species released from the test substance into the air layer adjacent to the coated surface; and
(d) comparison of the results of procedure (c) with the results of procedure (c) for at least one reference substance under the same test conditions, and therefore the presence or absence of a coating and / or the physical and / or coating Determination of chemical properties.

              The physical and / or chemical properties of the dressing in the gas release method may be selected from the group consisting of barrier properties, wetting tensions, and compositions, preferably barrier properties.

              Advantageously, step (c) is carried out by measuring the mass flow rate or the volumetric flow rate of at least one volatile species in the air layer adjacent to the coating surface.

              Preferably, the reference object (i) is an uncoated substrate, or (ii) is a substrate coated with a reference coating material. This may be done, for example, using a gas release method to determine the presence or absence of a coating (the reference object may be an uncoated substrate), or the properties of the coating may be, for example, a coating with known properties It depends on whether to make a comparison. If a particular dressing is used to identify the dressing, a reference dressing can be typically selected.

              The outgassing method additionally provides a pressure difference across the coated surface between steps (a) and (c), and a higher volatile species mass flow rate or volume flow rate without pressure difference. It consists of the procedure (b) of changing the air pressure in the air layer adjacent to the coated surface, which may be realized. In this case, the volatile species move toward the lower pressure difference side. When the coated object is a container, a pressure difference between the container lumen and the outside is established, and volatile species gas emission from the coated container wall is measured. The pressure difference may be achieved, for example, by at least partially evacuating the gas layer in the container. In this case, the volatile species may be measured as outgassing into the container lumen.

              When a vacuum state is created in order to create a pressure difference, the measurement can be performed using a measurement box interposed between the coating surface of the substrate and the vacuum source.

              In one embodiment, the test substance contacts in step (a) a volatile species, preferably a volatile species selected from the group consisting of air, nitrogen, oxygen, water vapor, and complexes thereof, preferably the test substance. May allow absorption of the volatile species on / in the material. The subsequent release of the volatile species from the test substance is then measured in step (c). If the materials are different (for example, the covering material and the substrate), the amount of absorption and the absorbency are also different, and this may simplify the determination of the presence and characteristics of the covering material.

              The substrate may be a polymer compound, preferably a polyester, polyolefin, cyclic olefin copolymer, polycarbonate, or a composite thereof.

In the context of the present invention, the dressing characterized by the outgassing method is usually a dressing produced by PECVD, for example from an organosilicon precursor as described herein. In certain embodiments of the invention, (i) the coating is a barrier coating, preferably a SiO _x film (x from about 1.5 to about 2.9), and / or (ii) the coating is lubricated And / or a coating material that changes the surface tension of the coated substrate, preferably a Si _w O _x C _y H _z film (w is 1, x is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to about 9).

              If the coating method of the product to be inspected by the gas release method is PECVD coating performed under vacuum conditions, the subsequent gas release measurement may be performed without interrupting the vacuum state used for PECVD.

              The volatile species measured may be volatile species released from the coating, volatile species released from the substrate, or a composite of both. In one embodiment, the volatile species is a volatile species released from the dressing, preferably a volatile dressing component, and a test is performed to determine the presence, nature, and / or composition of the dressing. . In another embodiment, the volatile species are tested to determine the volatile species released from the substrate, the presence of the coating and / or the barrier of the coating.

              The gas release method of the present invention is particularly suitable for determining the presence and characteristics of the coating material on the container wall. Accordingly, the coated substrate is a container having a wall, and at least a part of the inner surface or the outer surface may be coated during the coating process. For example, the covering material adheres to the inner surface of the container wall.

              Less than 1 hour, or less than 1 minute, or less than 50 seconds, or less than 40 seconds, in the conditions effective for determining the presence or absence of the dressing and / or determining the physical and / or chemical properties of the dressing , Or less than 30 seconds, or less than 20 seconds, or less than 15 seconds, or less than 10 seconds, or less than 8 seconds, or less than 6 seconds, or less than 4 seconds, or less than 3 seconds, or less than 2 seconds, or less than 1 second In some cases.

              In order to increase the difference between the reference and test substance with respect to the emission rate and / or the type of volatile species measured, the volatile species emission rate can be changed by changing the ambient pressure and / or temperature and / or humidity Is possible.

In certain embodiments, the outgassing is measured using a microcantilever measurement technique. For example, the measurement can be performed by:
(i) (a) providing at least one microcantilever having the property of moving or changing into a different shape in the presence of a gas releasing substance;
(b) exposure of the microcantilever to the outgassing material under conditions effective to move or change the microcantilever to a different shape; and
(c) Detection of movement or different shape, preferably at a point before and after exposure of the microcantilever to gas release, by incident energy rays from the microcantilever shape change, e.g. by laser beam irradiation and away from the cantilever Detection by measuring the deviation result of the irradiation light of
(ii) (a) providing at least one microcantilever that resonates at different frequencies in the presence of an outgassing material;
(b) exposure of the microcantilever to an outgassing material under conditions that are effective to cause the microcantilever to resonate at different frequencies, and (c) detection of different resonance frequencies, such as the use of harmonic vibration sensors.

              Also contemplated are devices that perform the outgassing method, such as devices consisting of the microcantilevers described above.

              The gas release method of the present invention can be used to inspect, for example, a barrier layer on a substance that emits vapor, and the inspection method consists of several procedures. Prepare a specimen of a substance that will outgas and at least partially be a barrier layer. In certain embodiments of the invention, a pressure differential is provided in the barrier layer so that at least some of the outgassing material is present on the high pressure side of the barrier layer. The emitted gas passing through the barrier layer is measured. If a pressure difference exists, the measurement is optionally performed on the low pressure side of the barrier layer.

VII. PECVD-treated container
VII.A.1.ai Hydrophobic coatings deposited from organosilicon precursors

              Another aspect of the invention is a container having a hydrophobic coating deposited by an organosilicon precursor, such as a hydrophobic coating on the inner wall. The covering material is of a type generated by the following procedure.

              Organometallic compound, preferably organosilicon compound, more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyltrimethoxysilane, linear silazane, monocyclic silazane, polycyclic A precursor is provided that is a compound selected from the group consisting of silazane, polysilsesquiazane, or a complex of two or more of these precursors. Alternatively, organometallic compounds including Group III or Group IV metals may be considered precursors.

              The precursor is applied to the substrate under conditions effective to produce a coating material. The dressing is polymerized, cross-linked, or both, and produces a hydrophobic surface with a high contact angle compared to an untreated substrate.

The resulting dressing may have the following summation formula: Si _w O _x C _y H _z (w is 1, x about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9.

The values of w, x, y, and z used herein should be understood as ratios in empirical formulas (eg for coatings) rather than limiting the number of atoms in a molecule. is there. For example, octamethylcyclotetrasiloxane having the molecular formula Si ₄ O ₄ C ₈ H ₂₄ can be described by the following [change expression by US] empirical formula, where each w, x, y, z in the molecular formula is Dividing by 4 gives the maximum common factor: Si ₁ O ₁ C ₂ H ₆ . The values of w, x, y, and z are also not limited to integers. For example, (non-cyclic) octamethyltrisiloxane having the molecular formula Si ₃ O ₂ C ₈ H ₂₄ can be reduced to Si ₁ O _0.67 C _2.67 H ₈ .

VII.A.1.b. Citrate blood tubes with walls coated with a hydrophobic coating deposited from an organosilicon precursor
Another aspect of the present invention is a cell preparation tube having a wall coated with a hydrophobic coating material and including a hydrous sodium citrate reagent.

              The wall is made of a thermoplastic material and has an inner surface that defines a lumen.

The hydrophobic dressing is provided on the inner surface of the tube. The hydrophobic coating material is an organometallic compound, preferably an organosilicon compound, more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyltrimethoxysilane, linear silazane, monocyclic silazane. Or a polycyclic silazane, a polysilsesquiazane, or a compound selected from the group consisting of two or more of these precursors. PECVD can be used to form a coating on the inner surface. The resulting dressing may have the following chemical structure: Si _w O _x C _y H _z (w is 1, x about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9.

              The hydrous sodium citrate reagent adheres to the lumen of the tube in an amount effective to inhibit clotting of blood introduced into the tube.

VII.A.1.c. SiO _x blocking film to be coated two-layer plastic containers - COC, PET, SiO _x layer
Another aspect of the invention is a container having a wall that at least partially encloses a lumen. The wall has an inner polymer layer encapsulated with an outer polymer layer. One polymer layer is a layer of cyclic olefin copolymer (COC) resin that defines water vapor barrier properties with a layer thickness of at least 0.1 mm. Another polymer layer is a layer of polyester resin with a layer thickness of at least 0.1 mm.

The wall includes an oxygen barrier layer of SiO _x with a thickness of about 10 to about 500 angstroms (the official x is from about 1.5 to about 2.9 or about 1.5 to about 2.6, or about 2).

VII.A.1.d.Method of manufacturing a two-layer plastic container-COC, PET, SiO _x layer
Another aspect of the present invention is a method for manufacturing a container having an inner polymer layer encapsulated by an outer polymer layer, one wall made of COC and the other made of polyester. The said container is manufactured by the process including the process of introduce | transducing a COC layer and a polyester resin layer into an injection mold through a concentric injection nozzle.

              An optional additional procedure includes applying PECVD of the amorphous carbon coating to the vessel as an inner and outer coating or as an intermediate coating located between the layers.

As an optional additional procedure, application of a SiO _x barrier layer to the inner surface of the container wall where SiO _x is defined as described above can be mentioned. Another optional additional procedure includes post-treatment of SiO _{x with} a process gas consisting essentially of oxygen and essentially free of volatile silicon compounds.

Optionally, the SiO _x coating can be molded, at least in part, from a silazane feed gas.

VII.A.1.e. Glass barrier coating
Another aspect of the present invention is a container that includes a container, a barrier covering, and a closure. The container is generally tubular and is made from a thermoplastic material. The container has a mouth and a lumen that is at least partially bounded by a wall having an inner surface that joins the lumen. An at least essentially continuous glass barrier coating is present on the inner surface of the wall. A closure covers the mouth and isolates the lumen of the container from the ambient atmosphere.

              A related embodiment of the present invention includes the container described in the previous paragraph, wherein the barrier coating is made of soda-lime glass, borosilicate glass, or other types of glass.

VII.A.2. Stopping member
VII.A.2.a. Applying a lubricious coating to a stop in a vacuum chamber
Yet another aspect of the present invention is a method of applying a coating, such as a lubricious coating as defined above, onto an elastomeric stop member on a substrate. For example, the stop member is positioned substantially within the vacuum chamber. A reaction mixture is prepared comprising a plasma generating gas, ie, an organosilicon compound gas, optionally an oxidizing gas, and optionally a hydrocarbon gas. Plasma is generated in the reaction mixture in contact with the stop member. Lubricant coatings such as Si _w O _x C _y H _z coatings (w is 1, x about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9) are deposited on at least a portion of the stop member.

VII.A.2.b. Application of Group III or Group IV elements and carbon coating on the stop member by PECVD
Yet another aspect of the present invention is a method of applying a coating of carbon or a composition comprising one or more Group III or Group IV elements to an elastomeric stop member. To perform the method, a stop member is positioned in the deposition chamber.

              A reaction mixture containing a plasma generating gas having a gas source that is a Group III element (eg, Al), a Group IV element (eg, Si, Sn), or a composite of two or more thereof is provided in a deposition chamber. . The reaction mixture optionally includes an oxidizing gas and optionally includes a gaseous compound having one or more C—H bonds. Plasma is generated in the reaction mixture, and the stop member contacts the reaction mixture. A coating material that is a Group III element or compound, a Group IV element or compound, or a composite of two or more thereof is deposited on at least a portion of the stop member.

VII.A.3. Plastic container with a stop member with a barrier covering that maintains a 95% vacuum for 24 months
Another aspect of the present invention is a container that includes a container, a barrier covering, and a closure. The container is generally tubular and is made from a thermoplastic material. The container has a mouth and a lumen that are at least partially bounded by walls. The wall has an inner surface that joins the lumen. At least an essentially continuous barrier coating is applied to the inner surface of the wall. The barrier coating is effective to maintain at least 90% of the initial vacuum level and optionally 95% of the initial vacuum level in the container for a shelf life of at least 24 months. A closure is provided to cover the mouth of the container, and the lumen of the container is isolated from the ambient atmosphere.

VII.B.1.a. Syringe with barrel coated with a lubricious coating deposited by organometallic precursor
Yet another aspect of the present invention is a container having a lubricious coating produced from an organosilicon precursor. Different organometallic precursors as defined herein are also contemplated.

              The covering material may be of a type generated by the following process.

              An organometallic precursor, preferably an organosilicon precursor, more preferably a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, linear silazane, monocyclic silazane, polycyclic silazane, A precursor is provided which is Lucesazan, or a complex of two or more of these precursors.

              The precursor is applied to the substrate under conditions effective to produce a coating material. The dressing is polymerized, cross-linked, or both, and produces a lubricated surface that reduces “plunger sliding force” or “starting force” compared to an untreated substrate.

Another aspect of the invention is a syringe that includes a plunger, a syringe barrel, and a lubrication layer. The syringe barrel has an inner surface that slidably receives the plunger. The lubricating layer is deposited on the syringe barrel inner surface and includes a Si _W O _x C _y H _z lubricating layer coating formed from an organosilicon precursor as defined herein. The lubricating layer has a layer thickness of less than 1000 nm and is effective in reducing the starting force or plunger sliding force required to move the plunger within the barrel.

              Yet another aspect of the present invention is a lubricity coating on the inner wall of a syringe barrel. The dressing is produced by PECVD using the following materials and conditions. Utilizing a cyclic precursor, it is selected from linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, or composites of two or more thereof. At least essentially no oxygen is added to the process. A power input that generates a sufficient plasma is supplied to induce coating generation. The material and conditions utilized are effective in reducing the sliding or activation force of the syringe plunger moving within the syringe barrel by at least 25 percent compared to an uncoated syringe barrel.

The resulting dressing may have the following formula: Si _w O _x C _y H _z (w is 1, x about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9 W is preferably 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9.

VII.B.1.ai Lubricious coating: SiO _x barrier layer, lubrication layer, surface treatment.
Another aspect of the invention is a syringe having an inner surface that consists of a barrel defining a lumen and slidably receives a plunger. The syringe barrel may be made from a thermoplastic base material. A lubricious coating is applied, for example, to the barrel inner surface, the plunger, or both by PECVD. The lubricity coating material may be made of an organosilicon precursor as a raw material and may have a layer thickness of less than 1000 nm. Surface treatment on the lubricious dressing in an amount effective to reduce leaching of the lubricious dressing, thermoplastic substrate, or both into the lumen, i.e. molding the solute retention member on the surface Run in an amount effective to do. The lubricity coating and solute retention member are configured to provide an effective amount to reduce the starting force, plunger sliding force, or both as compared to the case without the lubricity coating and solute retention member. .

VII.B.1.b Syringe with barrel with SiO _X layer coating inside and barrier layer coating outside
Yet another aspect of the present invention is a syringe barrel including a plunger, a barrel, an inner and an outer barrier coating. The barrel is made from a thermoplastic substrate that defines a lumen. The barrel has an inner surface that slidably receives the plunger and an outer surface. A SiO _x barrier coating (x in this formula is about 1.5 to about 2.9, alternatively about 1.5 to about 2.6, or about 2) is provided on the inner surface of the barrel. A resin barrier coating is provided on the outer surface of the barrel.

VII.B.1.c Method of manufacturing a syringe having a barrel with an SiO _X layer coating interior and a barrier layer coating exterior
Yet another aspect of the present invention is a method of manufacturing a syringe comprising a plunger, a barrel, an inner and an outer barrier coating. A barrel having an inner surface for slidably receiving a plunger and an outer surface is provided. A SiO _x barrier coating (x in this formula is about 1.5 to about 2.9, alternatively about 1.5 to about 2.6, or about 2) is prepared on the inner surface of the barrel by PECVD. A resin barrier coating is provided on the outer surface of the barrel. A syringe is prepared by assembling the plunger and barrel.

VII.B.2. Plunger
VII.B.2.a. Front of the shielded coated piston
Another aspect of the present invention is a plunger for a syringe that includes a piston and a push rod. The piston has a front surface, a side surface that is generally cylindrical, and a rear portion, the side surface being configured to be movably loaded into a syringe barrel. The front surface has a barrier coating. The push rod is engaged with the rear portion and set to push the piston forward in the syringe barrel.

VII.B.2.b. Lubricant coating to be joined to the side
Yet another aspect of the present invention is a plunger for a syringe that includes a piston, a lubricity coating, and a push rod. The piston has a front surface, a side surface that is generally cylindrical, and a rear portion. The side is set to be movably loaded into the syringe barrel. The lubricity coating material is bonded to the side surface. The push rod is set to engage the rear of the piston and push the piston forward within the syringe barrel.

VII.B.3. Two-part syringe and luer attachment
Another aspect of the invention is a syringe that includes a plunger, a syringe barrel, and a luer fitting. The syringe barrel contains an inner surface that slidably receives the plunger. The luer attachment includes a luer taper having an internal path defined by the inner surface. The luer attachment portion is formed as a separate member from the syringe barrel, and is coupled to the syringe barrel by coupling. The internal path of the luer taper has a SiO _x barrier coating (formula x is about 1.5 to about 2.9, alternatively about 1.5 to about 2.6, or about 2).

VII.B.4. Lubricating coatings made from in situ polymerized organosilicon precursors
VII.B.4.a. Products by process and lubricity
Yet another aspect of the present invention is a lubricity coating made from an organosilicon precursor. The said coating | covering material is a kind of thing produced | generated by the following processes.

              Preferably selected from organometallic precursors, linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, linear silazanes, monocyclic silazanes, polycyclic silazanes, polysilsesquiazanes, or precursors thereof. A precursor selected from a complex of two or more bodies is provided. The precursor is applied to the substrate under conditions effective to produce a coating material. The dressing is polymerized, cross-linked, or both, and produces a lubricated surface that reduces “plunger sliding force” or “starting force” compared to an untreated substrate.

The resulting dressing may have the following chemical structure: Si _w O _x C _y H _z (w is 1, x about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9.

VII.B.4.b. Products by process and analytical characteristics
Yet another aspect of the present invention is from an organometallic precursor, preferably an organosilicon precursor, more preferably a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, linear silazane, monocyclic Lubricating coatings deposited by PECVD from silazanes, polycyclic silazanes, polysilsesquiazanes, or composites of two or more of these precursors. The density of the covering material is 1.25 to 1.65 g / cm ³ as determined by X-ray reflectivity (XRR).

              Group III metals (ie boron, aluminum, gallium, indium, thallium, scandium, yttrium, lanthanum, etc.) or Group IV metals (ie silicon, germanium, tin, lead, titanium, zirconium, hafnium, thorium, etc.), Alternatively, the use of organometallic precursors including these two or more composites is also contemplated. Other volatile organic compounds are also contemplated. However, organosilicon compounds are desirable for the practice of the present invention.

              Yet another aspect of the invention is a feed gas comprising an organometallic precursor, preferably from an organosilicon precursor, more preferably a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, wire It is a lubricious coating deposited by PECVD from a shaped silazane, monocyclic silazane, polycyclic silazane, polysilsesquiazane, or a composite of two or more of these precursors. The use of precursors including Group III or Group IV metals is also contemplated.

The dressing has one or more oligomers comprising a gas releasing component, a repeating-(Me) ₂ SiO- moiety, as determined by gas chromatography / mass spectrometry. Optionally, the dressing meets the limitations of either Example VII.B.4.a or VII.B.4.b.

              Yet another aspect of the present invention is a feed gas comprising an organometallic precursor, preferably comprising an organosilicon precursor, more preferably a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, wire It is a lubricating coating material deposited by PECVD from a feed gas consisting of a cylindrical silazane, monocyclic silazane, polycyclic silazane, polysilsesquiazane, or a composite of two or more of these precursors. The dressing has atomic concentrations normalized to 100% carbon, oxygen, silicon, and has a silicon atom concentration of less than 50% carbon and greater than 25% as determined by X-ray photoelectron spectroscopy (XPS). Optionally, the dressing meets the limitations of either Example VII.B.4.a or VII.B.4.b.

              The use of organometallic precursors including Group III or Group IV metals is also contemplated.

              Another embodiment of the present invention is deposited by PECVD from a feed gas comprising an organosilicon precursor, preferably a monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or a composite of two or more thereof. A lubricious coating material. The dressing has an atomic concentration of carbon normalized to 100% carbon, oxygen, and silicon, and the atomic concentration of carbon in the atomic formula of the feed gas as determined by X-ray photoelectron spectroscopy (XPS). Exceed. Optionally, the dressing meets the limitations of Example VII.B.4.a or VII.B.4.b.

              An additional aspect of the present invention is by PECVD from a feed gas consisting of an organosilicon precursor, more preferably a monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or a composite of two or more of these. It is a lubricious coating material to be deposited. The covering material has a silicon atomic concentration normalized to 100% carbon, oxygen, and silicon, and as determined by X-ray photoelectron spectroscopy (XPS), the atomic concentration of silicon in the atomic formula of the feed gas is Below. Optionally, the dressing meets the limitations of Example VII.B.4.a or VII.B.4.b.

VII.C.1. A living blood containing container with a coating deposited from an organosilicon precursor
A further particular aspect of the present invention is a blood containing container. The container has a wall, and the wall has an inner surface defining a lumen. The inner surface of the wall has at least a portion of the hydrophobic coating described above, preferably a Si _w O _x C _y H _z hydrophobic coating (preferably w is 1, the formula x is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to about 9, more preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9. The covering material is as thin as the monomolecular layer thickness or has a maximum layer thickness of about 1000 nm. The container includes blood that can be returned to the patient's vasculature that fills the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.2. Coatings deposited from organosilicon precursors that reduce clotting or platelet activation on the vessel wall
Another aspect of the present invention is a container having a wall. The wall has an inner surface defining a lumen and at least part of a protective (eg hydrophobic) coating produced from an organosilicon precursor by PECVD, preferably a Si _w O _x C _y H _z coating Material (preferably w is 1, this formula x is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to about 9, more preferably w is 1, x is about 0.5 to 1, y is about 2 To about 3, z has 6 to about 9). The layer thickness of the coating material is monomolecular to about 1000 nm on the inner surface. The dressing is effective in reducing platelet activation of plasma treated with sodium citrate additive exposed to the inner surface compared to an uncoated wall of the same type. The dressing is effective in reducing clotting of blood exposed to the inner surface compared to the same type of uncoated wall.

VII.C.3. A living blood containing vessel with a coating of a Group III or Group IV metal element
Another aspect of the invention is a blood containing container including a wall having an inner surface defining a lumen. The inner surface is at least partially coated with a coating of a composition comprising carbon, one or more Group III metals, one or more Group IV metals, or a composite of two or more of these. The layer thickness of the covering material is compatible with a single molecule to about 1000 nm on the inner surface. The container includes blood that can be returned to the patient's vasculature that fills the lumen in contact with the dressing.

VII.C.4. Group III or Group IV coatings that reduce blood clotting or platelet activation
Optionally, in the container of the previous paragraph, a Group III or Group IV element coating is effective to reduce clotting or platelet activation of blood exposed to the inner wall of the container.

VII.D.1. Insulin-containing container with coating deposited from organosilicon precursor
Another aspect of the invention is an insulin containing container including a wall having an inner surface defining a lumen. The inner surface has at least part of a protective coating produced from an organosilicon precursor by PECVD, preferably a Si _w O _x C _y H _z coating (preferably w is 1, the formula x about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to about 9, more preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9. The layer thickness of the coating material is monomolecular to about 1000 nm on the inner surface. Insulin is loaded into the lumen in contact with the Si _w O _x C _y H _z dressing.

VII.D.2. Coating material deposited from organosilicon precursor to reduce insulin precipitation in the container
Optionally, in the container of the previous paragraph, the Si _w O _x C _y H _z coating is a precipitate from insulin that contacts the inner surface compared to the same type of Si _w O _x C _y H _z uncoated wall. It is effective in reducing molding.

VII.D.3. Insulin-containing container with Group III or Group IV element coating
Another aspect of the invention is an insulin containing container including a wall having an inner surface defining a lumen. The inner surface is at least partially coated with a coating material of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a composite of two or more of these. The layer thickness of the coating material is monomolecular to about 1000 nm on the inner surface. Insulin is filled into the lumen in contact with the dressing.

VII.D.4. Group III or Group IV coating that reduces the precipitation of insulin in the container
Optionally, in the container of the preceding paragraph, the coating material of the composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a composite of two or more of these is the same type of uncoated Compared to the wall, it is effective in reducing precipitate formation from insulin that contacts the inner surface.

VII.E.Cuvette
The PECVD coating methods described herein are also useful for coating cuvettes to form barrier coatings, hydrophobic coatings, lubricity coatings, or combinations thereof. A cuvette is a small tube having a circular or square cross section and sealed at one end, and is made of plastic, glass, or molten quartz (for ultraviolet rays) as a raw material and designed to hold a specimen for spectroscopic experiments. The best cuvettes are infinitely clear and free of impurities that can affect spectroscopic measurements. Like a test tube or specimen collection tube, a cuvette may have an opening that leads to outside air or a lid that seals it. The PECVD coating of the present invention is very thin, transparent and optically flat and therefore does not interfere with optical testing of the cuvette or its contents.

VII.F.Vial
The PECVD coating methods described herein are also useful for coating vials to form, for example, barrier coatings, hydrophobic coatings, or combinations thereof. Vials are small containers or bottles that are used to store pharmaceutical products, particularly fluids, powders, and lyophilized powders. For example, it may be a sample container used in an automatic sampler apparatus for analytical chromatography. The vial may be in the form of a tube or bottle with a neck. The bottom is usually flat, unlike test tubes or specimen collection tubes, which often have a rounded bottom. The raw material of the vial may be plastic (polypropylene, COC, COP, etc.), for example.

Computer-readable media and program elements
In addition, a computer readable medium is provided that stores a computer program for container coating and / or inspection when executed on a processor of the container processing system, and causes the processor to perform the procedures described above or below:

              In addition, program elements for container coating and / or inspection are provided that, when executed by a processor of the container processing system, cause the processor to perform the procedures described above or below.

Other aspects of the invention will be apparent from the disclosure and the accompanying drawings.

It is the schematic which shows the container processing system as described in the Example of this indication. 2 is a schematic cross-sectional view of a container holder of a coating station according to an embodiment of the disclosure. FIG. FIG. 3 is a diagram of an alternative embodiment of the present disclosure similar to FIG. FIG. 6 is an illustrative plan view of an alternative embodiment of the container holder. FIG. 7 is an illustrative plan view of another alternative embodiment of the container holder. FIG. 3 is a view of a container inspection device similar to FIG. FIG. 3 is a view of another container inspection device similar to FIG. FIG. 3 is a cross-sectional view taken along a cutting line AA in FIG. FIG. 9 is an alternative embodiment of the structure shown in FIG. Figure 3 is a container holder for a coating station that utilizes a CCD detector as described in another embodiment of the present disclosure similar to Figure 2; FIG. 11 is a detailed view of the light source and detector inverted relative to the corresponding parts of FIG. 6 similar to FIG. 3 is a container holder for a coating station that utilizes microwave energy to generate a plasma, as described in another embodiment of the present disclosure similar to FIG. FIG. 3 is a container holder of a coating station where the container can be loaded onto the container holder of the processing station, as described in yet another embodiment of the present disclosure similar to FIG. FIG. 3 is a container holder of a coating station where the electrode can be set as a coil, as described in yet another embodiment of the present disclosure similar to FIG. FIG. 3 is a container holder for a coating station that uses a transfer tube to move a container to / from the coating station, as described in another embodiment of the present disclosure similar to FIG. FIG. 16 is an illustrative view of a process of a container transport system for gripping and positioning a container in a processing station as in the example shown in FIG. FIG. 3 is an illustrative view of a mold for molding a container and a mold cavity according to an embodiment of the present disclosure. FIG. 18 is an illustrative view of the mold cavity of FIG. 17 provided with a container coating apparatus according to an embodiment of the present disclosure. FIG. 18 is a view of another container coating apparatus described in an embodiment of the present disclosure similar to FIG. FIG. 3 is an exploded longitudinal section view of a syringe and lid adapted for use as a prefilled syringe. FIG. 3 shows a covered syringe barrel and container holder of a coating station as described in an embodiment of the present disclosure, typically similar to FIG. FIG. 22 illustrates a lidless syringe barrel and container holder of a coating station as described in yet another embodiment of the present disclosure, typically similar to FIG. FIG. 5 is a perspective view of a blood collection tube assembly having a closure according to still another embodiment of the present invention. FIG. 24 is a fragmentary portion of the blood collection tube and closure assembly of FIG. FIG. 25 is a separated sectional view of the elastomeric insertion portion of the closure portion of FIGS. 23 and 24. FIG. 23 is another embodiment of the present invention for processing a syringe barrel and another container similar to FIG. FIG. 27 is an enlarged detail view of the processing container of FIG. 26. It is the schematic of another processing container. It is the schematic which shows the gas emission of the substance which passes along a coating | covering material. FIG. 4 is a schematic cross-sectional view of a test setting for inducing gas emission from the container wall to the inside of the container and gas emission measurement using a measurement box interposed between the container and the vacuum source. FIG. 31 is a diagram of outgassing mass flow rate measured on the test setup of FIG. 30 for multiple containers. FIG. 32 is a bar graph showing an analysis of the endpoint data shown in FIG. 31. FIG. It is the longitudinal cross-sectional view and gas acceptance amount of the coupling syringe barrel as described in another Example of this invention. FIG. 35 is another embodiment of the present invention including an electrode overhang length similar to FIG. FIG. 35 is a cross-sectional view from section line 35-35 of FIG. 34 showing the distal gas supply opening and protruding electrode of FIG. FIG. 6 is a perspective view of a double wall blood collection tube assembly according to yet another embodiment of the present invention. FIG. 23 is a diagram showing another embodiment similar to FIG. FIG. 23 is a diagram showing another embodiment similar to FIG. FIG. 23 is a diagram showing still another embodiment similar to FIG. FIG. 23 is a view showing still another embodiment similar to FIG. FIG. 41 is a plan view of the embodiment of FIG. 40. For the loading of the container on the container holder, for example of alternative sealing equipment which can be used in conjunction with the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 33 and 37-41. It is fragment | piece detail longitudinal cross-sectional view. FIG. 42 also illustrates a syringe barrel structure that can be used, for example, with the embodiments of FIGS. 2, 3, 6-10, 12-22, 26-28, 33-34, and 37-41. FIG. 43 is an enlarged detail view of the sealing equipment shown in FIG. FIG. 4 is a view showing a gas supply pipe / internal electrode similar to FIG. 2, for example, FIG. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37-43, 46-49. , And 52-54 examples. For example, in another construction of the container holder that can be used with the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26, 28, 33-35, and 37-44. is there. FIG. 6 is a schematic cross-sectional view of a series of gas supply tubes and a mechanism for inserting / removing gas supply tubes into / out of a container holder, showing the gas supply tube in a fully advanced position. FIG. 47 is a view showing a gas supply pipe in an intermediate position similar to FIG. FIG. 47 is a view showing a gas supply pipe in a storage position similar to FIG. The arrangement of the gas supply pipes in FIGS. 46 to 48 is, for example, FIGS. 1, 2, 3, 8, 9, 12 to 16, 18 to 19, 21 to 22, 26 to 28, 33 to 35, 37 to 45, 49, And can be used in combination with Examples 52-54. The mechanism of FIGS. 46-48 is for example the gas of FIGS. 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49, and 52-54. It can be used in combination with the supply pipe embodiment, and can also be used in combination with the probe of the container inspection apparatus of FIGS. FIG. 17 is a view showing a mechanism for transporting a container to be treated and a cleaning reactor similar to FIG. 16 to a PECVD coating material apparatus. The mechanism of FIG. 49 can be used in combination with, for example, the container inspection device of FIGS. 1, 9, 15, and 16. It is an exploded view of a two-part syringe barrel and a luer lock attachment part. The syringe barrel can be used in combination with, for example, the container processing and inspection devices of FIGS. 1 to 22, 26 to 28, 33 to 35, 37 to 39, 44, and 53 to 54. FIG. 51 is an assembly diagram of the two-part syringe barrel and luer lock attachment part of FIG. 50. FIG. 43 shows a treated syringe barrel without a flange or finger stop 440 similar to FIG. The syringe barrel can be used in combination with, for example, the container processing and inspection apparatus of FIGS. 1 to 19, 27, 33, 35, 44 to 51, and 53 to 54. FIG. 3 is a schematic view of a process vessel assembly. The assembly can be used with, for example, the devices of FIGS. 1-3, 8-9, 12-16, 18-22, 26-28, 33-35, and 37-49. FIG. 54 is an illustrative view of the embodiment of FIG. 53. FIG. 3 is an illustrative view of one embodiment of the present invention including a plasma shield similar to FIG. FIG. 6 is a schematic cross-sectional view of a series of gas supply pipes having independent gas supply sources and a mechanism for inserting / removing the gas supply pipes into / from the container holder. 10 is a plot of outgassing mass flow rate measured in Example 19. FIG. 5 shows a linear rack or a view similar to FIG. FIG. 2 is a layout view of a container processing system according to an exemplary embodiment of the present invention. FIG. 6 is a layout view of a container processing system according to another exemplary embodiment of the present invention. 2 shows a processing station of a container processing system according to an exemplary embodiment of the present invention. 2 shows a portable container holder as described in an exemplary embodiment of the invention.

Detailed Description of the Preferred Embodiment
The present invention will now be described in more detail with reference to the accompanying drawings showing a plurality of embodiments. However, the present invention can be implemented in many forms and is not limited to the following examples. Rather, these embodiments are examples of the present invention and the full scope is indicated by the language of the claims. Similar numbers refer to similar or corresponding elements.

In the context of the present invention, the following definitions and abbreviations are used:
RF refers to radio frequency and sccm refers to standard cubic centimeters per minute.

              The term “at least” in the context of the present invention means an integer “greater than or equal to” following the preceding term. The term “consisting of” may include other elements or procedures, and the singular substance may be plural unless otherwise specified.

              `` First '' and `` second '' or similar terms, such as referring to processing stations or equipment, indicate the minimum number of processing stations or equipment present, but do not necessarily represent the order or total number of processing stations and equipment is not. These terms are not intended to limit the number of processing operations performed at or at each station.

当該結合は、酸素原子1つおよび有機炭素原子1つ（有機炭素原子は少なくとも1つの水素原子と結合する炭素原子）と結合する四価ケイ素原子である。PECVD装置内で蒸気として供給される前駆体として定義される揮発性有機ケイ素前駆体が、望ましい有機ケイ素前駆体である。好ましくは当該有機ケイ素前駆体は、線状シロキサン、単環シロキサン、多環シロキサン、ポリシルセスキオキサン、アルキルトリメトキシシラン、線状シラザン、単環シラザン、多環シラザン、ポリシルセスキアザン、およびこれらの前駆体2つ以上の複合体からなる群から選択される。 For the purposes of the present invention, an “organosilicon precursor” is a compound having at least one of the following bonds:

The bond is a tetravalent silicon atom bonded to one oxygen atom and one organic carbon atom (an organic carbon atom is a carbon atom bonded to at least one hydrogen atom). Volatile organosilicon precursors, defined as precursors supplied as vapor in PECVD equipment, are desirable organosilicon precursors. Preferably the organosilicon precursor is a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyltrimethoxysilane, linear silazane, monocyclic silazane, polycyclic silazane, polysilsesquiazane, and These precursors are selected from the group consisting of two or more complexes.

In the context of the present invention, the expression “essentially oxygen-free” or (as synonymous) “substantially oxygen-free” is added for the gaseous reactants of some examples. This means that some residual atmospheric oxygen may be present in the reaction space, and residual oxygen that was supplied in the previous procedure and not completely exhausted may be present in the reaction space. Define the absence of oxygen. Particularly when gaseous reactants consist O ₂ less than 1 vol%, if more preferably consisting of O ₂ of less than 0.5 vol%, if even more preferably does not contain O ₂ at all, the oxygen the gaseous reaction Virtually absent from the substance. Also, if no oxygen is added to the gaseous reactant, or if no oxygen is present during PECVD, it is also in the category of “substantially oxygen-free”.

              A “container” in the context of the present invention may be any kind of container having at least one opening and a wall defining an inner surface. The term “at least” in the context of the present invention means an integer “greater than or equal to” following the preceding term. Thus, a container in the context of the present invention has one or more openings. One or two openings are desirable, such as one specimen tube opening or two syringe barrel openings. If the container has two openings, they may be the same or different sizes. If there is more than one opening, one opening can be used for gas inhalation of PECVD coating method described in the present invention, and the other opening can be capped or open . The container according to the present invention comprises a sample tube for collecting / storing biological fluids such as blood and urine, a syringe for storing / carrying a biologically active compound or composition (drug or pharmaceutical composition) ( Or a portion thereof, such as a syringe barrel), a vial that stores biological material or biologically active compound or composition, a conduit (eg, a catheter) that carries biological material or biologically active compound or composition, a fluid For example, it may be a cuvette that grips biological material or a biologically active compound or composition.

              The container may take any shape, and is preferably a container having a substantially cylindrical wall adjacent to at least one open end, typically the inner wall of the container is cylindrical, such as a sample tube or syringe barrel. It has the shape of Sample tubes or syringes or parts thereof (eg syringe barrels) are particularly desirable.

“Hydrophobic coating” in the context of the present invention means a coating which reduces the wetting tension of the surface coated with said coating compared to an uncoated surface. Hydrophobicity is therefore a function of both the uncoated substrate and the coating. The same with appropriate changes applies to other contexts where the term “hydrophobic” is used. The term “hydrophilic” means the opposite, ie, increased wetting tension compared to a reference analyte. Certain hydrophobic coatings in the context of the present invention are empirical or summation formulas Si _w O _x C _y H _z (w is 1, x is 0.5 to 2.4, y is 0.6 to 3, and z is 2 to 9 ).

              “Wet tension” is a specific measurement of the hydrophobicity or hydrophilicity of a surface. The preferred method of measuring wetting tension in the context of the present invention is an improved method described in ASTM D 2578 or ASTM D 2578. The method uses a standard wetting tension solution (called a dyne solution) to determine how close the solution is to the wet state of the plastic membrane surface in 2 seconds. This is the wetting tension of the film. The procedure used herein is different from that of ASTM D 2578, and the substrate is not a flat plastic membrane, but is manufactured according to the “Protocol for Molding PET Tubes” (except for the control) A tube coated according to the protocol for coating with a hydrophobic coating (see Example 9).

              The “lubricating coating” described in the present invention refers to a lubricating coating having a lower frictional resistance than an uncoated surface. In other words, the coating material reduces the frictional resistance of the coated surface as compared to the uncoated reference surface. “Friction resistance” may be static friction resistance and / or dynamic friction resistance. One preferred embodiment of the present invention includes a syringe part, such as a syringe barrel or plunger, coated with a lubricity coating. In this preferred embodiment, the static frictional resistance in the context of the present invention is the starting force as defined herein, and the dynamic frictional resistance in the context of the present invention is the plunger sliding force as defined herein. For example, the plunger sliding force as defined and determined herein is the presence or absence of lubricious coating and lubrication in the context of the present invention whenever the coating is applied to a syringe or syringe part, eg, the syringe barrel inner wall. Suitable for determining sex characteristics. The activation force is of particular relevance to the evaluation of the coating effect on a filled syringe, ie a syringe that is filled after coating and stored for a long time (months or years) until the syringe is moved again ("activated"). About.

              The “plunger sliding force” in the context of the present invention is the force necessary to maintain the movement of the plunger within the syringe barrel, for example during aspiration or administration. This is advantageously determined utilizing the ISO 7886-1: 1993 test described herein and well known in the art. Synonyms for “plunger sliding force” as used in the art include “plunger force” or “pushing force”.

              “Activation force” in the context of the present invention is the initial power required to move the plunger within the syringe (eg, within a prefilled syringe).

              “Plunger sliding force” and “starting force” and their measurement methods are described in more detail in the following sections.

              “Slidably” means that the plunger can be slid within the syringe barrel.

              In the context of the present invention, “substantially fixed” means that the assembly parts (ports, ducts, housings described further below) are moved as a unit without any significant change in position of the assembly parts relative to each other. It means that it is possible. Specifically, no parts are connected by a hose or similar member that causes substantial relative movement between the parts in normal use. Providing these parts in a substantially fixed state allows the position of the loaded container on the container holder to be known and accurate in much the same way as the position of these parts fixed to the housing. .

              In the following, the apparatus for carrying out the present invention will be described first, and then the coating method, the coating material and the coating container, and the usage method described in the present invention will be described.

I. Container processing system with multiple processing stations and multiple container holders
I. It is considered that the container processing system consists of a first processing station, a second processing station, a number of container holders, and a conveyor. The first processing station is configured to process a container having a wall defining an opening and an inner surface. The second processing station is set apart from the first processing station and is configured to process a container having a wall defining an opening and an inner surface.

              I. Some, optionally all such container holders are configured to receive and load the container opening for processing the inner surface of the loaded container via the container port at the first processing station. Includes ports. The conveyor is configured to transport a series of the container holders and loaded containers from the first processing station to the second processing station for processing the inner surface of the loaded containers via the container port at the second processing station. Is done.

              I. First, referring to FIG. 1, a container processing system (usually 20) is shown. The vessel processing system includes a processing station, more broadly considered a processing equipment. The illustrated example container processing system 20 includes an injection molding machine 22 (which may be considered a processing station or equipment), additional processing stations or equipment 24, 26, 28, 30, 32, and 34, and an output 36. (May be considered a processing station or equipment). As a minimum requirement, the system 20 has at least a first processing station (eg, station 28) and a second processing station (eg, 30, 32, or 34).

              I. Any one of the processing stations 22 to 36 in the illustrated embodiment can be set as the first processing station, and another processing station can be set as the second processing station.

              I. The embodiment illustrated in FIG. 1 includes the following eight processing stations or equipment: 22, 24, 26, 28, 30, 32, 34, and 36. The exemplary container processing system 20 includes an injection molding machine 22, a post-mold inspection station 24, a pre-coating inspection station 26, a coating station 28, a post-coating inspection station 30, an optical source transmission station 32 for coating layer thickness determination, An optical source transmission station 34 and an output station 36 for covering material defect detection are included.

              I. The system 20 includes a transport mechanism 72 for moving the container from the injection molding machine 22 to the container holder 38. The transport mechanism 72 is a robot that positions, moves, grips, transports, adapts, loads, and releases the container, for example, to take out the container 80 from the container molding machine 22 and place it in a container holder (38, etc.) It can be set as an arm.

              I. The system 20 also includes a transport mechanism for processing the inner surface of the loaded container (such as 80) at a processing station 74 and then removing the container from one or more container holders (such as 66) ( Figure 1). The container 80 can therefore be moved from the container holder 66 to packaging, storage or other suitable area or processing procedure (usually 36). The transport mechanism 74 is positioned, moved, gripped, transported, adapted, loaded, and released for the container 80 to be taken out from the container molding machine 38 and loaded on other equipment of the station 36, for example. It can be set as a robot arm that performs.

I. The processing station or equipment 32, 34, and 36 shown in FIG. 1 may optionally include one or more appropriate ones in the final stages of the coating and inspection system 20 after the individual containers 80 are removed from the container holder 64, etc. Simple steps can be performed. Some non-limiting examples of functions of the stations or equipment 32, 34, and 36 include the following:
Placement of the treated or inspected container 80 on a conveyor towards the processing equipment,
Addition of chemicals to the container,
Attaching a lid to the container,
Placing the container in a suitable processing rack,
Packaging of the container and sterilization of the packaged container.

              I. The container handling system 20 shown in FIG. 1 also includes a number of container holders (or “packs”, some of which are similar to hockey packs in some embodiments) (38-68 each) and one The above container holders 38-68, and thus the container 80, etc., are typically represented by a circulation zone 70 for transporting to / from the processing stations 22, 24, 26, 28, 30, 32, 34, and 36. Includes conveyor.

              I. The processing station or device 22 may be a device for forming the container 80. One possible device 22 is an injection molding machine. Another possible equipment 22 is a blow molding machine. Also contemplated are vacuum molding machines, casting machines, cutting or milling machines, glass casting machines for glass or other castable materials, or other types of container forming machines. Optionally, if the container is already molded, the container forming station 22 can be omitted.

II. Container holder
II.A. During the container processing, the portable container holders 38-68 are prepared for gripping and transporting the container having the opening. The container holder includes a container port, a second port, a duct, and a transportable casing.

              II.A. The container ports are set to load the container openings in a mutually passable manner. The second port is set to accept or discharge the outside air supply. The duct is set to vent one or more gases between the container opening loaded on the container port and the second port. The container port, the second port, and the duct are attached to the transportable casing in a substantially fixed state. Optionally, the portable container holder weighs less than 5 pounds. By reducing the weight of the container holder, it can be more easily transferred from one processing station to the next.

              II.A. In a particular embodiment of the container holder, the duct is more specifically a vacuum duct, and the second port is more specifically a vacuum port. The vacuum duct is set to suck gas from the inside of the container loaded on the container port via the container port. The vacuum port is set to allow passage between the vacuum duct and an external vacuum source. The container port, the vacuum duct, and the vacuum port can be attached to the transportable housing in a substantially fixed state.

              II.A. The container holder of Examples II.A. and II.A.1. Is shown, for example, in FIG. The container holder 50 has a container port 82 set to receive and load the opening of the container 80. The inner surface of the loaded container 80 can be processed via the container port 82. The container holder 50 includes a duct for sucking gas from the container 80 loaded on the container port 92, for example, a vacuum duct 94. The container holder includes a second port, such as a vacuum port 96, that passes between the vacuum duct 94 and an external vacuum source, such as a vacuum pump 98. The container port 92 and the vacuum port 96 have sealing elements such as O-ring adjacent seals (100 and 102 respectively), or the cylindrical inner / outer wall of the container port 82 and the cylindrical inner / outer wall of the container 80 There may be side seals between the outer walls, thereby allowing passage through the port while receiving and molding the seal with the vessel 80 or external vacuum source 98. Gaskets or other sealing equipment can also be used.

              II.A. The container holder 50 and the like can be made of any material, for example, a thermoplastic material and / or a non-conductive material. Alternatively, the container holder 50 or the like can be made partly or mostly from a conductive material, and in particular in the path defined by the container port 92, the vacuum duct 94, and the vacuum port 96, It is possible to face each other. Examples of suitable materials for the container holder 50 are: polyacetal (eg, Delrin® acetal material sold by EI du Pont De Nemours and Company, Wilmington, Del.), Polytetrafluoroethylene (PTFE) (Eg, Teflon® PTFE, ultra high molecular weight polyethylene (UHMWPE), high density polyethylene (HDPE), or other known or new in the art sold by EI du Pont De Nemours and Company, Wilmington, Delaware Developed material.

              II.A. FIG. 2 also illustrates that the container holder 50 or the like may have a collar 116 for centering the container 80 that is approaching or loaded on the port 92.

Container holder arrangement
II.A. An array of container holders can be used as yet another approach to processing, inspecting, and / or moving parts within a manufacturing system. The array may consist of individual packs or an uninterrupted array of equipment loaded. The arrangement allows testing, transporting, processing / coating to be performed simultaneously on one or more devices, optionally multiple devices. The arrangement may be, for example, a one-dimensional formula that groups to form a linear rack, or a two-dimensional formula similar to a tab or tray.

              II.A. FIGS. 4, 5 and 58 show a three-sequence approach. FIG. 4 shows an uninterrupted arrangement 120 in which the device or container 80 is loaded. In this case, the device or container 80 can be moved through the manufacturing process as an uninterrupted arrangement, but can be removed and transported to individual container holders during the manufacturing process. The single container holder 120 has a plurality of container ports 122 and the like for carrying an array of loaded containers 80 and the like that move as a unit. In this embodiment, a plurality of individual vacuum ports 96, etc. can be provided to receive the array of vacuum sources 98. Alternatively, a single vacuum port connected to the container port 96 or the like can be provided. Multiple gas inlet probes 108 and the like can also be provided in the array. The array of gas suction probes or vacuum sources can be mounted to move multiple containers 80 and the like as a unit at the same time. Alternatively, the plurality of container ports 122 and the like can be processed simultaneously or individually for each row / row in the processing station. The number of devices in the array may relate to the number of devices that are molded in a single procedure, or other tests or procedures for that work efficiency during processing. When processing / coating the array, the electrodes may be coupled (to larger electrodes) or may be individual electrodes with their respective power supplies. All the above approaches are further applicable (in terms of electrode shape, frequency, etc.).

              II.A. In FIG. 5, individual packs or container holders (described above) are enclosed in an outer frame 130 and grouped together. This equipment provides the advantages of the uninterrupted arrangement of FIG. 4 if desired, and the arrangement can be disassembled for other processing procedures that treat the containers 80 in different arrangements or individually. is there.

              II.A. FIG. 58 shows a linear rack or is similar to FIG. In the case of using a linear rack, another option in addition to the above procedure is to convey the rack in a single row in a processing station and sequentially process the containers.

II.B. Container holder including O-ring equipment
FIGS. 42 and 43 are, in turn, fragmentary longitudinal cross-sectional views and detailed views of the container holder 450, which can be used, for example, FIGS. 2, 3, 6, 7, for loading containers onto the container holder. It has alternative sealing equipment that can be used with the 19, 12, 13, 16, 18, 19, 30, and 43 container holder embodiments. Referring to FIG. 42, a container preloaded in the container holder 450, such as a syringe barrel 438, is defined by a generally grooved nail (and generally chamfered or circular) edge 452 and a generally cylindrical side wall 454. And a rear opening 442. Medical fluid collection tubes generally have a similar edge 452 but no flange 440. Therefore, it can be loaded on the container holder 450 instead.

              II.B. The illustrated container holder 450 of the present example includes a generally cylindrical inner surface 456 that receives the generally cylindrical side wall 454 of the syringe barrel 438 in the illustrated example. Functions as a guide surface. The wall is further defined by an abutment 458, which is usually a slotted nail, against which the grooved nail rim 452 abuts when the syringe barrel 438 is loaded on the container holder 450. A pocket or groove 460, which is usually a grooved nail formed by the inner surface 456, is provided to hold the sealing element, eg, the O-ring 462. The radial depth of the pocket 460 is less than the radial cross section of the sealing element, eg, O-ring 462 (shown in FIG. 42), and the inner diameter of the O-ring 462 is the outer diameter of the grooved nail edge 452 It is preferable to be slightly smaller.

              II.B. Due to the relative dimensions, the radial section of the O-ring 462 is at least between the outer wall 464 of the pocket 460 and the generally cylindrical side wall 454 of the syringe barrel 438, as shown in FIG. As shown in FIG. 42, when the container 438 or the like is already loaded, it is compressed in the horizontal direction. By this compression, the support surface of the O-ring 462 is flattened, and a sealed portion is formed at least between the outer wall 464 of the pocket portion 460 and the normal cylindrical side wall 454 of the syringe barrel 438.

              II.B. The pocket 460 is optionally associated with the dimensions of the O-ring 462 to provide two or more seals between the bottom wall 466 / top wall 468 and the side wall 454, and the top wall 468. Can be formed by separating the distance between the bottom wall 466 and the corresponding radial section of the O-ring 462. When the O-ring 462 is squeezed between the outer wall 464 and the normal cylindrical side wall 454 of the pocket portion 460, as shown in FIG. The top wall 466 and the bottom wall 464 are engaged with and flattened. The O-ring 462 optionally deforms accordingly in the vertical and horizontal directions, and tends to have a generally circular cross section that is square. Also, the grooved nail rim 452 loaded in the abutment 458 limits the flow rate of PECVD process reactants and other gases and materials introduced through / adjacent the back opening 442.

              II.B. As a result of this optional structure, as shown in FIG. 43, only the gap in the lower right corner of the O-ring 462 is outside the O-ring and is therefore introduced into the container 438 / Exposure to processing gas, plasma, etc. This structure protects the O-ring 462 and the adjacent surface (of the outer surface of the sidewall 438) from unwanted PECVD deposition and active chemical species in the plasma. Further, the container 438 is positioned more securely by the hard surface of the contact portion 458, and is presented by contact loading of the grooved nail rim 452 directly into the O-ring illustrated in the other figures. In contrast to the elastic surface. Furthermore, since the container 438 is restrained to prevent a large swing, the force to the portion corresponding to the main periphery of the O-ring 462 is uniformly distributed.

              II.B. Alternatively, the pocket portion 460 can be formed on the abutting portion 458 shown in FIG. In another embodiment, one to provide a double or higher level seal and to enhance the restraint against rocking when the container 438 is loaded against the abutment 458. The above axial divergence pocket portion 460 can be provided.

              II.B. FIG. 45 can be used in conjunction with, for example, the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26, 28, 33-35, and 37-44. This is another structure of the container holder 482. The container holder 482 includes an upper portion 484 and a bottom portion 486 that are coupled by a coupling portion 488. A seal, such as an O-ring 490 (the right side of the ring is cut away to describe the pocket that holds it) is constrained between the top 484 and the bottom 486 at the coupling 488. . In the illustrated embodiment, the O-ring 490 is received within a slotted nail pocket 492 for positioning the O-ring when the top 484 is coupled to the bottom 486.

              II.B. In this embodiment, the O-ring 490 is captured by the screws 498 and 500 in this case, and the radial defining a portion of the pocket 492 when the top 484 and the bottom 486 are joined. A wall 496 extending radially and a contact surface 494 extending radially. The O-ring 490 is therefore loaded between the top 484 and the bottom 486. The O-ring 490 captured between the top 484 and the bottom 486 also receives the container 80 (omitted in this figure for clarity of other features) and the container rear opening of FIG. A first O-ring seal of the container port 502 at the opening of the container 80, similar to the 442 O-ring seal equipped, is formed.

              II.B. In this embodiment, although not essential, the container port 502 has both a first O-ring 490 sealing portion and a second axially separated O-ring 504 sealing portion, both of which are the container port 502 and An inner diameter 506 of a size for receiving an outer diameter (similar to the side wall 454 of FIG. 43) such as a container 80 for sealing between the containers 80 and the like. The space between the O-rings 490 and 504 provides a support such as the container 80 at two points that are axially separated from each other, and the O-rings 490 and 504 such as the container 80 or the container port 502 can be distorted. To prevent. In this embodiment, although not required, the radially extending abutment surface 494 is located proximally around the O-rings 490 and 506 seals and the vacuum duct 508.

III. Container Transport Method-Processing of Containers Loaded in Container Holder
III.A. Transport of container holder to processing station
III.A. FIGS. 1, 2 and 10 show how the container 80 is treated. The method can be performed as follows.

              III.A. A container 80 having a wall 86 defining an opening 82 and an inner surface 88 can be provided. As an example, the container 80 can be formed in the mold 22 or the like and then removed. Optionally, within 60 seconds, within 30 seconds, within 25 seconds, within 20 seconds, within 15 seconds, within 10 seconds, within 5 seconds, within 3 seconds, within 1 second, or processing after removal of the container from the mold The container opening 82 can be loaded onto the container port 92 immediately after removing the container 80 without being distorted therein (assuming it is manufactured at high temperature and gradually cooled). By quickly moving the container 80 from the mold 22 to the container port 92, dust or other impurities adhering to the surface 88 can be reduced, and adhesion to the barrier film or other types of coating material 90 can be reduced. Shield or prevent. In addition, as the container 80 is evacuated immediately after production, the possibility that particulate impurities adhere to the inner surface 88 can be reduced.

              A container holder 50 including a container port 92 can be prepared. The opening 82 of the container 80 can be loaded on the container port 92. Before, during, and after loading the opening 82 of the container 80 onto the container port 92, the container holder 40 or the like (for example, in FIG. 6) is transported to the one or more support surfaces 220 to 240. It is possible to engage and position the container holder 40 with respect to the processing equipment or station 24 or the like.

              III.A. As illustrated by the station 24 shown in FIG. 6, one, one or more, or all of the processing stations 24-34, etc. may be loaded into the loaded container 80 at the processing station or equipment 24, etc. A support surface for supporting one or more container holders 40 or the like in place while processing the inner surface 88 thereof, e.g., one or more such support surfaces 220, 222, 224, 226, 228, 230, 232 , 234, 236, 238, or 240. These support surfaces may be part of a stationary or kinetic structure, such as a path or guide that guides and positions the container holder 40 or the like during container processing, for example. For example, the downwardly supported surfaces 222 and 224 position the container holder 40 and function like a reaction surface to move upward of the container holder 40 when the probe 108 is inserted into the container holder 40. To prevent. The reaction surface 236 positions the container holder and prevents the container holder 40 from moving to the left when the vacuum source 98 (FIG. 2) is already loaded on the vacuum port 96. The support surfaces 220, 226, 228, 232, 238, and 240 similarly position the container holder 40 and prevent horizontal movement during processing. Similarly, the support surfaces 230 and 234 position the container holder 40 and the like, and prevent displacement in the vertical direction. Therefore, the first support surface, the second support surface, the third support surface, or later may be provided to each processing station 24-34 or the like.

              III.A. The inner surface 88 of the loaded container 80 can be processed via the container port 92 at the first processing station, and as one example, the coating of the barrier film application or other type of coating material shown in FIG. It may be a station. The container holder 50 and the loaded container 80 are transported from the first processing station 28 to a second processing station, for example, the processing station 32. The inner surface 88 of the loaded container 80 can be processed via the container port 92 in the second processing station 32 or the like.

              III.A. Any of the above methods may include a further step of removing the container 80 from the container holder 66 or the like after processing of the inner surface 88 of the loaded container 80 at a second processing station or instrument. .

              III.A. Any of the above methods may include a further procedure that provides a second container 80 having a wall 86 defining an opening 82 and an inner surface 88 after the removal procedure. An opening 82 such as the second container 80 can be loaded onto a container port 92 such as another container holder 38. The inner surface of the loaded second container 80 can be processed via the container port 92 in the first processing station or the device 24 or the like. The container holder 38 and the like and the loaded second container 80 can be transported from the first processing station or device 24 to the second processing station or device 26 or the like. The loaded second container 80 can be processed via the container port 92 by the second processing station or instrument 26.

III.B. Transport of processing equipment to the container holder or vice versa.
III.B. or the processing station may be a processing device more broadly, transfer of the container holder according to the processing device, transfer of the processing device according to the container holder, or each equipment Any of the provisions in some optional systems is possible. In another arrangement, the container holder can be transported to one or more stations, and the one or more processing equipment can be placed adjacent to / adjacent to at least one of the stations. Accordingly, there is no need for correlated communication between the processing equipment and the processing station.

              III.B. A method for treating containers containing multiple parts is conceivable. A first processing device such as the probe 108 (FIG. 2) and a second processing device such as a light source 170 (FIG. 10) are prepared for the processing container 80 and the like. A container 80 having a wall 86 defining an opening 82 and an inner surface 88 is provided. A container holder 50 including a container port 92 is prepared. The opening 82 of the container 80 is loaded on the container port 92.

              III.B. The first processing device, eg, the probe 108 is moved and operatively engaged with the container holder 50, or vice versa. The inner surface 88 of the loaded container 80 is processed via the container port 92 using the first processing equipment or probe 108.

              III.B. The second processing equipment 170, etc. (FIG. 10) is then moved and operatively engaged with the container holder 50, or vice versa. The inner surface 88 of the loaded container 80 is processed via the container port 92 using a second processing device, such as a light source 170.

              III.B. Optionally, multiple additional processing steps can be provided. For example, a third processing device 34 can be provided for processing the container 80. The third processing device 34 is moved and operatively engaged with the container holder 50, or vice versa. The inner surface of the loaded container 80 can be processed via the container port 92 using the third processing device 34.

              III.B. In another method of container processing, a container 80 having a wall 86 defining an opening 82 and an inner surface 88 can be provided. A container holder 50 including a container port 92 can be prepared. The opening 82 of the container 80 can be loaded on the container port 92. The inner surface 88 of the loaded container 80 can be processed by the first processing device via the container port 92, and as one example, it may be the coating device 28 of the barrier film or other type of coating material shown in FIG. is there. The container holder 50 and loaded container 80 are transported from the first processing device 28 to a second processing device, for example, the processing device 34 shown in FIGS. The inner surface 88 of the loaded container 80 can be processed via the container port 92 by the second processing device 34 or the like.

III.C. Use of grips to transport tubes to / from the coating station
III.C. Yet another embodiment is a method of plasma enhanced chemical vapor deposition (PECVD) treatment of a first vessel that includes multiple procedures. A first container having an open end, a closed end, and an inner surface is prepared. The first gripper is set to selectively grip and release the closed end of the first container. The closed end of the first container is gripped by the first gripping part, and conveyed to the vicinity of the container holder set to be loaded with the first container opening end while using the first gripping part. Thereafter, the first container is advanced in the axial direction using the first gripping portion, the opening end thereof is loaded on the container holder, and the passage seal between the container holder and the first container is established.

              III.C. At least one gaseous reactant is introduced into the first container through the container holder. Plasma is generated in the first container under conditions effective to mold a reaction product of the reactant on the inner surface of the first container.

              III.C. Thereafter, the loading of the first container on the container holder is released, and the first container is moved away from the container holder in the axial direction while using the first holding part or another holding part. Thereafter, the first container is released from the grip used to move away from the container holder in the axial direction.

              III.C. Referring again to FIGS. 16 and 49, a series of conveyors 538 can be used to support and transport the number grippers 204 and the like through the apparatus and processing described herein. The gripper 204 is operatively connected to the series of conveyors 538 to continuously convey at least two containers 80 to the vicinity of the container holder 48, and other of the purification methods described herein. Set the procedure to run.

IV. PECVD equipment for container production
IV.A. PECVD equipment including vessel holder, internal electrode, and vessel as reaction chamber
IV.A. Another embodiment is a PECVD apparatus comprising a container holder, internal electrodes, external electrodes, and a power supply device. The container loaded in the container holder defines a plasma reaction chamber, optionally a vacuum chamber. Optionally, a vacuum source, a reactive gas source, a gas supply device, or a combination of two or more of these can be provided. Optionally, a gas exhaust tube that does not necessarily include a vacuum source is provided, and gas is transferred to / from the interior of the container already loaded into the port to define a closed chamber.

              IV.A. The PECVD apparatus can be used for external pressure PECVD, in which case the plasma reaction chamber need not function as a vacuum chamber.

              In the embodiment illustrated in FIG. 2, the container holder 50 comprises a gas inlet port 104 for conveying gas to a container already loaded on the container port. The gas inlet port 104 has a sliding seal provided by at least one O-ring 106 or a series of two O-rings or a series of three O-rings. Insert through gas inlet port 104. The probe 108 may be a gas inlet conduit that extends to the distal end 110 of the gas supply port. The distal end 110 of the illustrated embodiment can be inserted deep into the vessel 80 to provide one or more PECVD reactants and other process gases.

              IV.A. Optionally, in the embodiment illustrated in FIG. 2, or more generally, for example, FIGS. 1-5, 8, 9, 12-16, 18, 19, 21, 22, 26-28, 33-35. In any disclosed embodiment, such as the 37-49, or 52-55 embodiments, and specifically as disclosed in FIG. 55, the plasma shield 610 typically has a volume that exceeds the plasma shield 610 in the container 80. Provided to contain the plasma generated therein. The plasma shield 610 is a conductive porous material, which in some embodiments is steel wool, porous sintered metal, or a ceramic material coated with a conductive material, such as metal (eg, brass) or other It is a small porous plate or disk made of a conductive material. An example is two metal discs with a central hole that is sized to pass through the gas inlet 108, and the disc further has a radius of 0.02 inch (0.5 mm) with a center-to-center distance of 0.04 inch (1 mm). ), Which provides an open area corresponding to 22% of the surface area of the disc.

              IV.A. The plasma shield 610 is in / near the tube opening 82, syringe barrel, or other processing vessel 80, particularly for embodiments where the probe 108 also functions as a counter electrode. There is a possibility that an intimate electrical contact with the gas inlet 108 may be brought about. Alternatively, the plasma shield 610 may be grounded, and preferably has a common potential with the gas suction part 108. The plasma shield 610 is connected to the container holder 50 and its internal path (eg, near the vacuum duct 94, the gas suction port 104, the O-ring 106, the vacuum port 96, the O-ring 102, and other gas suction 108). To reduce or extinguish the plasma in the device. At the same time, since the plasma shield is porous, it is possible to flow the process gas, the atmosphere, and the like from the container 80 to the vacuum port 96 and the end process equipment.

              IV.A. In the coating station 28 shown in FIG. 3, the vessel holder 112 in turn carries gas (via the probe 108) to the vessel 80 loaded in the vessel port 92 and (via the vacuum source 98). It consists of a synthetic gas inlet port and a vacuum port 96 for drawing gas from a container already loaded in the container port 92, and these communicate with the container port 92. In this embodiment, the gas suction probe 108 and the vacuum source 98 can be provided as a synthetic probe. The two probes can be advanced as a unit or individually as desired. This equipment eliminates the need for the third sealing portion 106 and allows the contact sealing portion to be used everywhere. The contact sealing portion can apply an axial force for deforming the O-ring to reliably load the container 80 and the vacuum source 98, for example, to draw a vacuum in the container 80. The O-ring tends to close the gap left by the presence or absence of unevenness of the sealing surfaces on both sides. In the embodiment of FIG. 3, the axial force applied by the container 80 and the vacuum source 98 on the container holder 112, on the other hand, holds both the container 80 and the container holder 112 together and maintains the respective contact sealing portions. Tend to.

              FIG. 13 is similar to FIG. 2 and is a container holder 48 in a coating station according to yet another embodiment of the present disclosure, the container 80 being loadable onto the container holder 48 of the processing station. is there. This can be used to process a container 80 that does not move with the container holder 48 or the like. Alternatively, it can be used in a barrier membrane or other type of coating station 28 where the container 80 is loaded into a container holder 48 or the like before the loaded container 80 is transported by the system 20 to another apparatus.

              FIG. 13 shows a cylindrical electrode 160 suitable for frequencies from 50 Hz to 1 GHz, as an alternative to the U-shaped electrode of FIGS. The container holder (or the electrode) can be moved in place before the electrode is activated by moving the electrode downward or the container holder upward. Alternatively, the movement of the container holder and electrode in the vertical plane is configured as a clamshell type (the two half-cylinders on the opposite side meet when the container holder is in place and ready for treatment / coating). This can be avoided by forming the electrode 160. IV.A. Optionally, if the process of moving the tube at the coating station 28 or the like is continuous while drawing a vacuum and introducing gas through the probe 108, the vacuum source at the coating station 28 98 creates a seal with a pack or container holder 50 that can be maintained during movement of the container holder. Alternatively, a steady process is used to move the pack or container holder 50 to a stationary position, at which point the probe 108 is pushed up to the instrument and the pump or vacuum source 98 is coupled at the vacuum port 96. And can be activated to create a vacuum. Once the probe 108 is in place and a vacuum is created, plasma can be generated in the tube or container 80 with the external fixed electrode 160 independent of the pack / container holder 50 and the tube / other container 80 It is.

              Fig. 53 shows an additional option detail view of the coating station 28, for example, Fig. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26-28, Can be used with 30, 33-35, 37-44, and 52 examples. The coating station 28 also has a main vacuum valve 574 in a vacuum line 576 that leads to the pressure sensor 152. A manual bypass valve 578 is prepared in the bypass pipeline 580. The vent valve 582 controls the flow rate from the vent hole 404.

              IV.A. The flow rate from the PECVD gas source 144 is controlled by a main reactive gas valve 584 that regulates the flow rate through the main reactant supply line 586. One component of the gas source 144 is an organosilicon fluid reservoir 588. The contents of the reservoir 588 are drawn through the organosilicon capillary wire 590 provided at a length suitable to provide the desired flow rate. The flow rate of the organosilicon vapor is controlled by the organosilicon shutoff valve 592. Apply pressure to the headspace 614 of the fluid reservoir 588 and range from 0 to 15 psi (0 to 78 cm.Hg) from a pressure source 616 such as compressed air connected to the headspace 614 by a pressure line 618 Is applied to establish a repeatable organosilicon fluid supply independent of atmospheric pressure (and its vibration). The reservoir 588 is hermetically sealed and the capillary connection 620 is at the bottom of the reservoir 588 such that only pure organosilicon fluid (not the pressurized gas from the headspace 614) flows through the capillary tube 590. Secured. The organosilicon fluid can optionally be heated above ambient temperature if it is essential or desirable to evaporate the organosilicon fluid to produce temperature, organosilicon vapor. Oxygen is supplied from the oxygen tank 594 via an oxygen supply line 596 controlled by the mass flow controller 598 and equipped with an oxygen shutoff valve 600.

              IV.A. In the embodiment of FIG. 7, the station or instrument 26 has a vacuum source 98 adapted to load on the vacuum port 96, a side channel 134 connected to the probe 108, or both (shown). May include. In the illustrated embodiment, the side channel 134 includes a shut-off valve 136 that regulates the flow rate between the probe port 138 and the vacuum port 140. In the illustrated embodiment, the selection valve 136 has at least two states: the ports 138 and 140 are connected to provide two parallel paths through which gas flows (thus increasing the pump rate or the pumping operation). A vacuum state, and a shut-off state where the ports 138 and 140 are separated. Optionally, the selection valve 136 has a third port, for example, as a PECVD gas inlet port 142 for introducing PECVD reaction / treatment gas from a gas source 144. This means allows the same vacuum supply and probe 108 to be used for leak / permeation testing, or for the application of barrier films or other types of coatings.

              IV.A. In the illustrated embodiment, the vacuum line 146 to the vacuum source 98, etc. also includes a shut-off valve 148. Since the probe 108 and the vacuum source 98 are not connected to the container holder 44 or the like, the shut-off valves 136 and 148 move the side channel 134 and the vacuum pipe line 146 from one container holder 44 to another. Can be closed when it is not necessary to evacuate the vessel 136 and 148 away from the container 80. In order to facilitate the axial removal of the probe 108 from the gas inlet port 104, a flexible conduit 150 is provided to allow axial movement of the probe 108 independent of the vacuum conduit 146 relative to the port 96. ing.

              FIG. 7 also shows another optional feature that can be used with any embodiment—a vent 404 leading to outside air controlled by a valve 406. Immediately after processing of the container 80 to either release the container 80 from the container holder 44, release the vacuum port 96 from the vacuum source 98 of the container holder 44, or optionally both. The vacuum state can be released by opening the valve 406.

              IV.A. In the illustrated embodiment (again, see FIG. 7), the probe 108 is also connectable to a pressure gauge 152 and can communicate with the interior 154 of the container 80, so Can be measured.

IV.A. In the apparatus of FIG. 1, the vessel coating station 28 may, for example, apply a SiO _x barrier film or other type of coating 90, as shown in FIG. It may be a PECVD apparatus that operates under conditions suitable for deposition.

              IV.A. With particular reference to FIGS. 1 and 2, the processing station 28 is fed by a radio frequency power supply 162 for providing an electric field for generating plasma in the vessel 80 during processing. The electrode 160 may be included. In this embodiment, the probe 108 is also conductive and grounded, providing a counter electrode in the container 80. Alternatively, in any embodiment, the external electrode 160 can be grounded and the probe 108 can be directly connected to the power supply 162.

              In the embodiment of FIG. 2, the external electrode 160 may be generally cylindrical as illustrated in FIGS. 2 and 8, or may be generally U-shaped as illustrated in FIGS. (FIGS. 8 and 9 are alternative embodiments of cross-sectional views along section line AA in FIG. 2). Each illustrated embodiment optionally includes one or more sidewalls 164 and 166, etc., having an upper end 168, all of which are attached proximate to the container 80.

              IV.A., IV.B. FIGS. 12-19 show other variants of the container coating station or apparatus 28 described above. Any one or more of the variants can be substituted for the container coating station or device 28 shown in FIGS.

              IV.A. FIG. 12 shows an alternative electrode system that can be used at frequencies above 1 GHz (similar to the previous method using the same container holder and gas inlet). At the frequency, electrical energy from the power supply device can be conveyed into the tube through one or more waveguides connected to a cavity that absorbs the energy or resonates with the energy. The resonance with the energy enables coupling with the gas. The container 80 interacts with the cavity to change its resonance point and generate a plasma for coating and / or processing so that different cavities can be provided for use at different frequencies and containers 80, etc. It is.

              FIG. 12 shows a microwave power supply 190 that directs microwaves to a microwave cavity 194 via a waveguide 192 so as to at least partially surround a target vessel 80 that generates plasma therein. , Indicating that the coating station 28 may include. The microwave cavity 194 can be adjusted according to the frequency of the microwave, the component pressure, and various gases to absorb the microwave and couple it with the plasma generating gas. In FIG. 13, as with any of the illustrated embodiments, a small gap 196 is left between the container 80 and the cavity 194 (or electrode, detector, or peripheral structure), or otherwise rubbed into the container 80 or otherwise. Damage can be prevented. In FIG. 13, since the microwave cavity 194 has a flat end wall 198, the gap 196 is not uniform in width, particularly on the opposite side of the circular edge of the end wall 198. Optionally, the end 198 is curvilinear and provides a substantially uniform gap 196.IV.A. FIG. 44 shows an alternative gas supply tube / internal electrode 470 similar to FIG. 2, for example, FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37 -43, 46-49, and 52-54 can be used in combination. As shown in FIG. 44, the distal portion 472 of the internal electrode 470 comprises an elongated porous sidewall 474 that encloses an internal path 476 in the internal electrode. The internal path 476 is connected to the gas supply device 144 by a proximal port 478 of the internal electrode 470 extending outside the container 80. The distal end 480 of the internal electrode 470 may optionally be porous. Due to the porosity of the porous side wall 474 and the porous distal end 480 (if present), at least a portion of the reactive gas supplied from the gas supply device 144 is transverse from the path 476. The reactive gas is supplied to the adjacent portion of the inner surface of the container 80. In the present embodiment, the porous portion of the porous side wall 474 extends the entire length of the internal electrode 470 in the container 80. However, the porous portion is not wide and may only operate for the length of the internal electrode 470. As shown elsewhere herein, the internal electrode 470 may be longer or shorter than that shown in FIG. 44 in relation to the length of the vessel 80, and the porous portion may be continuous or non- May be continuous.

              IV.A. The outer diameter of the inner electrode 470 is at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the size of the inner diameter of the container adjacent in the lateral direction. There may be. By utilizing the inner electrode 470 having a larger radius, in relation to the inner diameter of the container 80, particularly when the electrode 470 is concentric with the container 80, the outside of the inner electrode 470 and the adjacent inner surface of the container 80 are used. The distance between 88 can be reduced and the plasma can be enclosed in a narrower region and made more uniform. Further, the reactive gas and / or the carrier gas can be more uniformly distributed along the inner surface 80 by using the internal electrode 470 having a larger radius. This is because fresh gas is introduced into the plasma at closely spaced points along the length of the inner surface 88 that is very close to the position of the initial reaction, as opposed to the flow rate from a single point on the inner surface 88. It is.

              IV.A. In one possible equipment, the power supply 162, shown in solid lines, has one power connection to the electrode 200, and the power connection is at any point along the electrode 200. It is possible that the probe 108 can be grounded. In this setting, a capacitive load can be used to generate plasma within the vessel 80. In another possible equipment, each wiring part of the power supply device 162, shown in phantom lines (and excluding the connection shown in solid lines), connects to each end of the coil 200, again for convenience. It can be considered as an “electrode” within this specification. In this setting, an inductive load can be used to generate plasma in the vessel 80. In an alternative embodiment, a combination of inductive and capacitive loads can be used.

              Figures 46-48 show an arrangement of two or more gas supply tubes 108, 510 and 512, etc. (shown in Figure 2), which are also internal electrodes. The array may be linear or circular. Due to the circular arrangement, the electrodes can be reused regularly.

              FIGS. 46-48 also illustrate internal electrode extensions for inserting and removing the gas supply tubes / internal electrodes 108, 510, and 512 into / from one or more container holders 50 or 48, etc. The enclosure 514 is shown. The function is an optional means for using the gas supply pipe.

              IV.A. In the illustrated embodiment, referring to FIGS. 46-48 and 53, the internal electrodes 108, 510, 512 are connected to a common gas supply 144 by flexible hoses 516, 518, and 520, respectively, to a shutoff valve 522. , 524, and 526. (The flexible hose is shortened by omitting the flexible portion in FIGS. 46 to 48). Referring briefly to FIG. 56, the flexible hoses 516, 518, and 520 may alternatively be connected to an independent gas source 144. A mechanism 514 for distracting and retracting the internal electrode 108 and the like is provided. The internal electrode distracter / storage device is set so that the internal electrode is moved between the advance position, the intermediate position, and the storage position with respect to the container holder.

              46 and 56, the internal electrode 108 extends to the operating position in the container holder 50 and container 80, and the shut-off valve 522 is open. In FIG. 46, the standby internal electrodes 510 and 512 are stored, and the shutoff valves 524 and 526 are closed. In the illustrated embodiment, one or more of the standby internal electrodes 510 and 512 are associated with an electrode purification device or station 528. One or more electrodes can be cleaned in the station 528 and other optional replacements. The cleaning operation can remove deposits using chemical reactions or solvent treatment, and as a non-limiting example, milling to physically remove the deposits, or plasma treatment that essentially burns the deposits and so on.

              47. In FIG. 47, the working internal electrode 108 is retracted from the container 80, while the standby internal electrodes 510 and 512 are still left at the distal end of the container holder 50 and the valve 522 Is closed. Under this condition, the container 80 can be removed, and a new container loaded in the container holder 50 can be removed and replaced without risk of contact of the container 80 with the electrode 108. After replacement of the container 80, the internal electrode 108 can be advanced to the position of FIGS. 46 and 56, the shut-off valve 522 is reopened, and the internal electrode 108 is used as before to use the new container 80. The coating can be started. Therefore, in the equipment for loading / removing a series of the containers 80 onto / from the container holder 50, the containers 80 are installed / removed from / to the container holder 50 at the station where the internal electrode 108 is used. Therefore, the internal electrode 108 can be extended many times and partially stored.

              48, the container holder 50 and its container 80 are replaced with a new container holder 48 and another container 80. Referring to FIG. 1, in this type of embodiment, each container 80 remains on its container holder 50 or 48, etc., and the internal electrodes 108 etc. are transferred to each container as the container holder reaches the coating station. Inserted.

              48. Also in FIG. 48, the internal electrodes 108, 510, and 512 are fully retracted, and the arrangement of the internal electrodes 108, 510, and 512 is compared to the positions in FIG. 48 and the electrode purification station 528 are moved to the right, so that the internal electrode 108 is removed from its home position and the internal electrode 510 is moved to a position relative to the container holder 48.

              IV.A. It should be understood that the movement of the array of internal electrodes may not depend on the movement of the container holder. These arrangements can be moved together or individually and switched simultaneously or individually to a new container holder and / or a new internal electrode.

              Figures 46-48 show an arrangement of two or more gas supply tubes 108, 510 and 512, etc. (shown in Figure 2), which are also internal electrodes. The array may be linear or circular. Due to the circular arrangement, the electrodes can be reused regularly.

              FIGS. 46-48 also illustrate internal electrode extensions for inserting and removing the gas supply tubes / internal electrodes 108, 510, and 512 into / from one or more container holders 50 or 48, etc. The enclosure 514 is shown. The function is an optional means for using the gas supply pipe.

              IV.A. In the illustrated embodiment, referring to FIGS. 46-48 and 53, the internal electrodes 108, 510, 512 are connected to a common gas supply 144 by flexible hoses 516, 518, and 520, respectively, to a shutoff valve 522. , 524, and 526. (The flexible hose is shortened by omitting the flexible portion in FIGS. 46 to 48). A mechanism 514 for distracting and retracting the internal electrode 108 and the like is provided. The internal electrode distracter / storage device is set so that the internal electrode is moved between the advance position, the intermediate position, and the storage position with respect to the container holder.

              46 and 56, the internal electrode 108 extends to the operating position in the container holder 50 and container 80, and the shut-off valve 522 is open. 46 and 56, the standby internal electrodes 510 and 512 are stored, and the shutoff valves 524 and 526 are closed. In the illustrated embodiment, the standby internal electrodes 510 and 512 are associated with the electrode purification station 528. One part of the electrode can be cleaned in the station 528 and can be replaced as desired. The cleaning operation can remove deposits using chemical reactions or solvent treatment, and as a non-limiting example, milling to physically remove the deposits, or plasma treatment that essentially burns the deposits and so on.

              47. In FIG. 47, the working internal electrode 108 is retracted from the container 80, while the standby internal electrodes 510 and 512 are still left at the distal end of the container holder 50 and the valve 522 Is closed. Under this condition, the container 80 can be removed, and a new container loaded in the container holder 50 can be removed and replaced without risk of contact of the container 80 with the electrode 108. After replacement of the container 80, the internal electrode 108 can be advanced to the position of FIGS. 46 and 56, the shut-off valve 522 is reopened, and the internal electrode 108 is used as before to use the new container 80. The coating can be started. Therefore, in the equipment for loading / removing a series of the containers 80 onto / from the container holder 50, the containers 80 are installed / removed from / to the container holder 50 at the station where the internal electrode 108 is used. Therefore, the internal electrode 108 can be extended many times and partially stored.

              48, the container holder 50 and its container 80 are replaced with a new container holder 48 and another container 80. Referring to FIG. 1, in this type of embodiment, each container 80 remains on its container holder 50 or 48, etc., and the internal electrodes 108 etc. are transferred to each container as the container holder reaches the coating station. Inserted.

              48. Also in FIG. 48, the internal electrodes 108, 510, and 512 are fully retracted, and the arrangement of the internal electrodes 108, 510, and 512 is compared to the positions in FIG. 48 and the electrode purification station 528 are moved to the right, so that the internal electrode 108 is removed from its home position and the internal electrode 510 is moved to a position relative to the container holder 48.

              IV.A. It should be understood that the movement of the array of internal electrodes may not depend on the movement of the container holder. These arrangements can be moved together or individually and switched simultaneously or individually to a new container holder and / or a new internal electrode.

              IV.A. Separate combined gas supply tubes / inner electrodes 108, 510, and 512, in some cases, tend to accumulate polymerization reactive gases or other types of deposits when used to coat a series of vessels 80, etc. As such, an array of two or more internal electrodes 108, 510, and 512 is useful. The deposition may accumulate to a level that impairs the coverage or coating uniformity and may be undesirable. To maintain uniform processing, the internal electrode can be periodically removed from the facility, replaced or cleaned, and a new or cleaned electrode attached to the facility. For example, proceeding from FIG. 46 to FIG. 48, the internal electrode 108 is replaced with a new or adjusted internal electrode 510 and extends to the container holder 48 and the container 80 to apply the new container inner covering material. Ready.

              Therefore, the internal electrode drive 530 can be operated by using the internal electrode distracter / storage device 514 in combination, and the first internal electrode 108 is removed from the distraction position to the storage position. Instead of this, a second internal electrode 510 can be attached and the second internal electrode 510 can be advanced to the extended position (similar to FIGS. 46 and 56, except for electrode replacement).

              46. The arrangement of the gas supply pipes and the internal electrode drive 530 of FIGS. 46 to 48 are, for example, FIGS. 1, 2, 3, 8, 9, 12 to 16, 18 to 19, 21 to 22, 26 to 28, 33. -35, 37-45, 49, and 52-54 examples can be used in combination. The distraction / storage mechanism 514 in FIGS. 46 to 48 is, for example, shown in FIGS. 2, 3, 8, 9, 12 to 16, 18 to 19, 21 to 22, 26 to 28, 33 to 35, 37 to 45, 49, and It can be used together with the gas supply pipe embodiments of 52 to 54, and can also be used with the probe of the container inspection apparatus of FIGS.

              IV.A The electrode 160 shown in FIG. 2 may be a “U” shaped channel with a length to the page, and the pack or container holder 50 passes through the active (power) electrode to the treatment / coating process. It can be moved inside. Note that since external and internal electrodes are used, the device can be used between the frequency 50Hz-1GHz applied to the U-shaped channel electrode 160 from the power supply 162. . The probe 108 can be grounded to complete the electrical circuit, thereby allowing current to flow through the low pressure gas in the vessel 80. The plasma generated by the current makes it possible to select and / or coat the inner surface 88 of the device.

              IV.A The electrode shown in FIG. 2 may have a pulse power supply device as power source power. The pulse allows depletion of reactive gas, removal of by-products before activation, and (again) depletion of reactive gas. A pulsed power system is typically characterized by a duty cycle that determines the time that the electric field (and thus the plasma) is present. The power-on time is relative to the power-off time. For example, a 10% duty cycle may correspond to 10% of the time of a cycle in which the power is interrupted for 90% of the time. As a specific example, the power may be turned on for 0.1 seconds and cut off for 1 second. The pulse power system reduces the active power input of any power supply device 162 because the processing time increases due to the cutoff time. When the system is pulsed, the resulting coating can be very pure (no by-products / contamination). Another consequence of the pulse system is the possibility of atomic layer deposition (ALD). In this case, the duty cycle can be adjusted to produce a single layer deposition of the preferred material with the power-up time. In this approach, a single atomic layer is considered to be deposited at each cycle. With this approach, highly pure and highly chemically structured dressings can be produced (however, the temperature required for deposition on the polymer surface should preferably be kept low (less than 100 ° C.) and The low temperature coating material may be amorphous).

              IV.A. An alternative coating station is disclosed in FIG. 12 and utilizes microwave cavities instead of external electrodes. The applied energy may be a microwave frequency of 2.45 GHz, for example.

IV.B. PECVD equipment using grips to transport tubes to / from the coating station
IV.B. Another embodiment is an apparatus for PECVD processing of a container utilizing the aforementioned gripping part. 15 and 16 show an apparatus (typically 202) for PECVD processing of a first vessel 80 having a lumen defined by an open end 82, a closed end 84, and a surface 88. In the present embodiment, the container holder 48, at least the first gripping portion 204 (in this embodiment, for example, a suction cup), a loading portion defined by the container port 92 on the container holder 48, a reactant supply device 144, a plasma generation device represented by the electrodes 108 and 160, a container release device that may be a vent valve 534, and the same gripping portion 204 or the second gripping portion (effectively, optionally, the second gripping portion 204) Is included.

              IV.B. The first gripping portion 204 and any gripping portion 204 shown are set to selectively grip and release the closed end 84 of the container 80. The first gripper 204 may transport the container to the vicinity of the container holder 48 while gripping the closed end 84 of the container. In the illustrated embodiment, the transport function is facilitated by a series of conveyors 538 on which a plurality of gripping portions 204 are mounted.

              IV.B. The container holder 48 has been previously described in connection with another embodiment and is set to load the open end 82 of the container 80. The loading portion defined by the container port 92 has been previously described in connection with another embodiment and establishes a passing seal between the container holder 48 and the lumen 88 of the first container (any container 80 in this case). Set to do. The reactant supply device 144 has been previously described in connection with another embodiment and is operably connected to introduce at least one gaseous reactant into the first vessel 80 through the vessel holder 48. The The plasma generator defined by electrodes 108 and 160 has been previously described in connection with another embodiment, and under conditions effective to shape the reaction product of the reactant on the inner surface of the first vessel. Thus, it is set to generate plasma in the first container.

              IV.B. Using the container release device 534 or another means, such as reactive gas, carrier gas, or means for introducing a cheap gas such as compressed nitrogen or compressed air into the loaded container 80, the first One container 80 can be unloaded from the container holder 48.

              IV.B. The gripper 204 transports the first container 80 away from the container holder 48 in the axial direction, and then releases the suction from between the gripper 48 and the container end 84, thereby Set to unload container 80.

              IV.B. FIGS. 15 and 16 also show a method of PECVD treatment of a first vessel consisting of multiple procedures. A first container 80 having an open end 82, a closed end 84, and an inner surface 88 is provided. At least the first grip 204 is provided, and the closed end 84 of the first container 80 is set to be selectively gripped and released. The closed end 84 of the first container 80 is gripped by the first gripping portion 204, and accordingly, it is transported to the vicinity of the container holder 48 set to be loaded with the first container open end. In the embodiment of FIG. 16, two container holders 48 are provided, and two containers 80 can be advanced and loaded onto the container holder 48 simultaneously. Therefore, the production efficiency can be increased by a factor of two. Next, the first container 80 is advanced in the axial direction by using the first gripping portion 204, and the opening end 82 is loaded on the container holder 48, and passes between the container holder 48 and the first container. Establish a seal. Next, at least one gaseous reactant is introduced into the first container through the container holder, optionally as in the previous embodiment.

              IV.B. Subsequently, plasma is generated in the first container under conditions effective to mold the reaction product of the reactant on the inner surface of the first container, optionally as in the previous examples. Do. The first container is unloaded from the container holder and optionally performed as in the previous embodiment. Using the first gripper or other gripper, optionally as in the previous embodiment, the first container is transported away from the container holder in the axial direction. Thereafter, the first container can be released from the grip used to move away from the container holder in the axial direction, and can optionally be performed as in the previous embodiment.

              IV.B. Further optional procedures that can be performed according to the method include providing a reaction vessel different from the first vessel, providing the reaction vessel with an open end and a lumen, and the reaction vessel on the vessel holder Loading of the open end of the container, establishing a passage seal between the container holder and the lumen of the reaction vessel. A PECVD reactant conduit can be provided in the lumen. A plasma can be generated within the lumen of the reaction vessel under conditions effective to remove at least a portion of the PECVD reaction product deposit from the reactant conduit. The reaction conditions have been described in connection with the previous examples. Thereafter, the reaction vessel on the vessel holder can be unloaded and moved away from the vessel holder.

IV.B. Additional optional procedures that can be performed according to any embodiment of the method include the following:
Providing at least one second grip;
An operable connection of at least a first and a second gripper to a series of conveyors;
Providing a second container having an open end, a closed end, and an inner surface;
Providing a gripper configured to selectively grip and release the closed end of the second container;
Gripping the closed end of the second container having the gripping portion;
Transporting the second container to the vicinity of the container holder set to load the second container opening end using the gripping part;
Advancing the second container in the axial direction using the gripping portion, loading the open end onto the container holder, establishing a passage seal between the container holder and the interior of the second container;
Introduction of at least one gaseous reactant into the second container through the container holder;
Generation of plasma in the second container under conditions effective to shape a reaction product of the reactant on the inner surface of the second container;
Unloading the second container from the container holder; and transporting the second container axially away from the container holder using the second gripper or other gripper; and the shaft from the container holder Release of the second container from the grip used to move away in the direction.

              Fig. 16 is an embodiment that uses a suction cup type device to grip the end of the sample collection tube (in this embodiment) that is movable within the production line / system. The particular embodiment shown within this specification is one of the possible procedures for coating / processing (many possible procedures described above and below). The tube can be moved to the coating procedure / area, and the tube can be positioned downward to the container holder and (in this example) the cylindrical electrode. The container holder, specimen collection tube, and suction cup can then be moved to the next procedure in which the electrode is powered and the treatment / coating is performed. Any of the above types of electrodes can be used in this embodiment.

              Thus, FIGS. 15 and 16 show the container holder 48 in the coating station 28 similar to FIG. 13 utilizing a container transport device (usually 202) that moves the container 80 to / from the coating station 28. Show. The container transport device 202 can be provided together with the gripper 204, and the transport device 202 shown in the figure may be a suction cup. An adhesive pad, an active vacuum source (actively creating a vacuum with an air suction pump from the gripper), or other means can be used as the gripper. The container transport device 202 can be used, for example, to lower the container 80 to the loaded position of the container port 92 and position the container 80 for coating. The container transport device 202 can also be used to lift the container 80 from the container port 92 after processing at the station 28 is complete. The container transport device 202 can also be used to load the container 80 before the container 80 and the container transport device 48 are advanced together with the station. The container transport device can also be used to forcibly move the container 80 to a loading section on the container port 92. 15 can be adapted to show the vertical movement of the container 80 by the above, but an inverted adaptation is possible in which the container transport device 202 is under the container 80 and supports it from below. Or conceivable.

              FIG. 16 shows that a container transport device 202, for example a suction cup 204, transports the container 80 in the horizontal direction and moves from one station to the next, and (alternatively) transports it vertically in the station 28. An example of the method of putting out and putting in outside is shown. The container 80 can be lifted and transported in all directions. FIG. 16 therefore shows a method of PECVD treatment of the first vessel 80 comprising a plurality of procedures.

              IV.B. In the embodiment of FIG. 13, the external electrode 160 is typically cylindrical with an open end and may be stationary. The container 80 can be advanced through the external electrode 160 until the opening 82 is loaded onto the container port 96. In this embodiment, the probe 108 can optionally be permanently molded or otherwise secured within the gas inlet port 104, and a wiping seal between the port 104 and the probe 108. In contrast to the relative movement of

              FIG. 14 shows an additional alternative method for coupling electrical energy into a 50 Hz to 1 GHz plasma. This may consist of a coil that may be lowered into place or the container holder (with the instrument) that may be pushed up into place. The coil electrode is regarded as an inductive coupling device and can impart a magnetic component to the inside of the device where plasma is generated.

              The IV.B. probe 108 can also be used as described in FIGS. Other aspects of the container holder or the container holder 48 described above remain the same.

              IV.B. For example, as shown in FIG. 49, a reaction vessel 532 different from the first vessel 80 can be provided, and the reaction vessel has a lumen defined by an open end 540 and the inner surface 542. Similar to the vessel 80, the reaction vessel 532 has an open end 540 on the vessel holder 48 and can establish a passing seal between the vessel holder 48 and the lumen 542 of the reaction vessel. .

              FIG. 49 is a view showing a mechanism for transferring the processing target container 80 and the purification reactor 532 similar to FIG. 16 to the PECVD coating material apparatus. In this embodiment, the internal electrode 108 can optionally be purified without being removed from the container holder 48.

              49. FIG. 49 shows that the PECVD reactant conduit 108 is connected to the reaction vessel 532 when the reaction vessel is loaded on the vessel holder 48 instead of the vessel 80 provided for the coating. It is located at a location within the lumen 542. FIG. 49 shows the reactant conduit 108 in this setting, even though the conduit 108 has an external site and an internal distal end. If at least a portion of the reactant conduit 108 extends into the container 80 or 532, this object and the claims are met.

              49. The mechanism of FIG. 49 can be used in combination with, for example, at least the embodiments of FIGS. 1 and 15-16 as shown. The purification reactor 532 can also be provided as a simple loaded container that has been moved onto a container holder 48 or the like in an alternative embodiment. In this setting, the purification reactor 532 is, for example, at least FIGS. 1-3, 8, 9, 12-15, 18, 19, 21, 22, 26-28, 33-35, 37-48, and 52-54. It can be used with other devices.

              IV.B. The plasma generator defined by electrodes 108 and 160 is capable of reacting with the reactor vessel 532 under conditions effective to remove at least a portion of the PECVD reaction product deposit from the reactant conduit 108. It can be configured to generate plasma within the lumen. The internal electrode and gas source 108 may be a conductive tube, such as a metal tube, and the reaction vessel 532 is made of a suitable material, preferably a ceramic, quartz, glass or other material that will withstand higher temperatures than a thermoplastic vessel. It is considered above that it can be manufactured from such a heat-resistant material. The material of the reaction vessel 532 is also preferably chemical or plasma resistant to the conditions used in the reaction vessel for removal of the reaction product deposits. Optionally, the reaction vessel 532 may be manufactured from a conductive material, which itself serves as a special purpose external electrode for removing deposits from the reactant conduit 108. As yet another alternative, the reaction vessel 532 can be configured as a lid that is loaded onto the external electrode 160, in which case the external electrode 160 is preferably loaded onto the vessel holder 48 to provide a closed purification reaction chamber. Define.

              IV.B. Reaction conditions effective to remove at least a portion of the PECVD reaction product deposit from the reactant conduit 108 include oxygen or ozone (both generated separately or by the plasma apparatus) The introduction of the majority of oxidation reactants, power higher than the level used for coating deposition, cycles longer than the level used for coating deposition, other means known as unwanted deposition removal methods on the reaction conduit 108, Is considered to be included. For another embodiment, mechanical milling can be used to remove unwanted deposits. Alternatively, a solvent or other agent can be jetted through the reactant conduit 108 to remove the obstruction. Since the reaction vessel 532 need not be suitable for normal use of the vessel 80, the conditions may be more severe than the resistance of the coated control vessel 80. However, optionally, the container 80 can be used as the reaction container, and the container 80 used as the reaction container in alternative embodiments can be discarded if the deposition removal conditions are excessively severe.

V. PECVD method for container production
V.1 Precursor for PECVD coating
The precursor material for PECVD coating of the present invention is widely defined as an organometallic precursor. The organometallic precursor is a metal element compound from group III and / or group IV of the periodic table having organic residues such as hydrocarbon residues, aminocarbon residues, oxycarbon residues, for all purposes herein. Is defined. Organometallic compounds as defined herein include any precursor having an organic moiety that is bonded directly to silicon or other Group III / Group IV metal atom, or optionally through an oxygen or nitrogen atom. Related periodic table Group III elements are boron, aluminum, gallium, indium, thallium, scandium, yttrium, lanthanum, preferably aluminum and boron. Related Periodic Table Group IV elements are silicon, germanium, tin, lead, titanium, zirconium, hafnium, and thorium, preferably silicon and tin. Other volatile organic compounds are also contemplated. However, organosilicon compounds are desirable for the practice of the present invention.

または

直前の第1の化学構造は、酸素原子1つおよび有機炭素原子1つ（有機炭素原子は少なくとも1つの水素原子と結合する炭素原子）と結合する四価ケイ素原子である。直前の第2の化学構造は、-NH-結合1つおよび有機炭素原子1つ（有機炭素原子は少なくとも1つの水素原子と結合する炭素原子）と結合する四価ケイ素原子である。好ましくは当該有機ケイ素前駆体は、線状シロキサン、単環シロキサン、多環シロキサン、ポリシルセスキオキサン、線状シラザン、単環シラザン、多環シラザン、ポリシルセスキアザン、およびこれらの前駆体2つ以上の複合体からなる群から選択される。また、前述の2つの公式に当てはまらないが前駆体として考えられるものに、アルキルトリメトキシシランがある。 Organosilicon precursors are preferred, and “organosilicon precursors” are most broadly defined herein as compounds having at least one of the following bonds:

Or

The immediately preceding first chemical structure is a tetravalent silicon atom bonded to one oxygen atom and one organic carbon atom (an organic carbon atom is a carbon atom bonded to at least one hydrogen atom). The immediately preceding second chemical structure is a tetravalent silicon atom bonded to one —NH— bond and one organic carbon atom (an organic carbon atom is a carbon atom bonded to at least one hydrogen atom). Preferably, the organosilicon precursor is a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, linear silazane, monocyclic silazane, polycyclic silazane, polysilsesquiazane, and precursors thereof 2 Selected from the group consisting of one or more complexes. Another possible precursor that does not apply to the above two formulas is alkyltrimethoxysilane.

When using oxygen containing precursors (eg siloxane), the typical empirical formula deduced from PECVD under conditions that produce hydrophobic or lubricious coatings is Si _w O _x C _y H _z (Where w is 1, x is about 0.5 to about 1, y is about 2 to about 3, and z is about 6 to about 9). On the other hand, a typical empirical formula deduced from PECVD under conditions that produce a barrier coating is SiO _x (where x is about 1.5 to about 2.9). If a precursor containing nitrogen (eg silazane) is used, the estimated composition is Si _{w *} N _{x *} C _{y *} H _{z *} . That is, in Si _w O _x C _y H _z , according to the present invention, O is replaced with N and the index is adapted so that the valence of N is higher than O (3 instead of 2). The latter fit usually follows the ratio of w, x, y, and z in siloxane to the corresponding aza structure index. In a particular embodiment of the present invention, w *, x *, y *, and z * of Si _{w *} N _{x *} C _{y *} H _{z *} are defined the same as that of siloxane, Treated as an option.

当該公式の各Rは独立して、例えばメチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、t-ブチル、ビニル、アルキン、その他といったアルキル基から選択され、nは1、2、3、4、またはそれ以上であり、好ましくは2以上である。考えられる線状シロキサンのいくつかの例は、
ヘキサメチルジシロキサン（HMDSO）、
オクタメチルトリシロキサン、
デカメチルテトラシロキサン、
ドデカメチルペンタシロキサン、
またはこれら2つ以上の複合体である。上記化学構造における-NH-を酸素原子に置換した類似シラザンもまた、類似被覆材の生成に有用である。考えられる線状シラザンのいくつかの例は、オクタメチルトリシラザン、デカメチルテトラシラザン、またはこれら2つ以上の複合体である。 One type of precursor starting material having the above empirical formula is linear siloxane, such as a material having the following formula:

Each R in the formula is independently selected from alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne, etc., and n is 1, 2, 3, 4, or More than that, preferably 2 or more. Some examples of possible linear siloxanes are:
Hexamethyldisiloxane (HMDSO),
Octamethyltrisiloxane,
Decamethyltetrasiloxane,
Dodecamethylpentasiloxane,
Or these two or more composites. Similar silazanes in which —NH— in the above chemical structure is substituted with oxygen atoms are also useful for the production of similar coating materials. Some examples of possible linear silazanes are octamethyltrisilazane, decamethyltetrasilazane, or a complex of two or more of these.

当該公式のRは線状化学構造のものと同様に定義され「a」は3〜約10であり、または当該類似単環シラザンである。考えられるヘテロ置換および非置換単環シロキサンおよびシラザンのいくつかの例には以下が含まれる：
1,3,5-トリメチル-1,3,5-トリス（3,3,3-トリフルオロプロピル）メチル]シクロトリシロキサン
2,4,6,8-テトラメチル-2,4,6,8-テトラビニルシクロテトラシロキサン、
ペンタメチルシクロペンタシロキサン、
ペンタビニルペンタメチルシクロペンタシロキサン、
ヘキサメチルシクロトリシロキサン、
ヘキサフェニルシクロトリシロキサン、
オクタメチルシクロテトラシロキサン（OMCTS）、
オクタフェニルシクロテトラシロキサン、
デカメチルシクロペンタシロキサン、
ドデカメチルシクロヘキサシロキサン、
メチル（3,3,3-トリフルオロプロピル）シクロシロキサン、
以下のような環状オルガノシラザンも考えられる：
オクタメチルシクロテトラシラザン、
1,3,5,7-テトラビニル-1,3,5,7-テトラメチルシクロテトラシラザン ヘキサメチルシクロトリシラザン、
オクタメチルシクロテトラシラザン、
デカメチルシクロペンタシラザン、
ドデカメチルシクロヘキサシラザン、または
またはこれら2つ以上の複合体。 Another type of VC is a monocyclic siloxane as a precursor starting material, for example a material having the following structural formula:

The formula R is defined the same as that of the linear chemical structure and “a” is from 3 to about 10, or the analogous monocyclic silazane. Some examples of possible hetero-substituted and unsubstituted monocyclic siloxanes and silazanes include:
1,3,5-trimethyl-1,3,5-tris (3,3,3-trifluoropropyl) methyl] cyclotrisiloxane
2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane,
Pentamethylcyclopentasiloxane,
Pentavinylpentamethylcyclopentasiloxane,
Hexamethylcyclotrisiloxane,
Hexaphenylcyclotrisiloxane,
Octamethylcyclotetrasiloxane (OMCTS),
Octaphenylcyclotetrasiloxane,
Decamethylcyclopentasiloxane,
Dodecamethylcyclohexasiloxane,
Methyl (3,3,3-trifluoropropyl) cyclosiloxane,
The following cyclic organosilazanes are also conceivable:
Octamethylcyclotetrasilazane,
1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane hexamethylcyclotrisilazane,
Octamethylcyclotetrasilazane,
Decamethylcyclopentasilazane,
Dodecamethylcyclohexasilazane, or
Or these two or more complexes.

当該公式のYは酸素または窒素である場合があり、Eはケイ素であり、Zは水素原子または有機置換基であり、例えばメチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、t-ブチル、ビニル、アルキン、その他といったアルキル基である。各Yが酸素である場合、それぞれの化学構造は、左から順に、シラトラン、シルクアシラトラン、シルプロアトランである。Yが窒素である場合、それぞれの化学構造はアザシラトラン、アザシルクアシラトラン、アザシルプロアトランである。 Another type of VC precursor precursor is a polycyclic siloxane, for example a material having one of the following structural formulas:

The formula Y may be oxygen or nitrogen, E is silicon, Z is a hydrogen atom or an organic substituent, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, Alkyl and other alkyl groups. When each Y is oxygen, the respective chemical structures are silatrane, silkacilatran, and sylproatrane in order from the left. When Y is nitrogen, the respective chemical structures are azasilatlan, azasilacilatran, and azacilproatran.

当該公式の各Rは水素原子または有機置換基であり、例えばメチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、t-ブチル、ビニル、アルキン、その他といったアルキル基である。この種の2つの市販物質は、各RがメチルであるSST-eM01ポリ（メチルシルセスキオキサン）、および当該R群の90%がメチル、10%が水素原子であるSST-3MH1.1ポリ（メチル-ヒドリドシルセスキオキサン）である。本物質は、例えばテトラヒドロフランの10%溶液において入手可能である。またはこれら2つ以上の複合体も考えられる。 考えられる前駆体のその他の実施例には、CAS No.2288-13-3の各Yが酸素およびZがメチルであるメチルシラトラン、メチルアザシラトラン、各Rが随意にメチルであるSST-eM01ポリ（メチルシルセスキオキサン）、当該R群の90%がメチル、10%が水素原子であるSST-3MH1.1ポリ（メチル-ヒドリドシルセスキオキサン）、またはこれらの2つ以上の複合体がある。 Another type of polycyclic siloxane precursor starting material for VC is the empirical formula RSiO _1.5 and polysilsesquioxanes having the structural formula:

Each R in the formula is a hydrogen atom or an organic substituent, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne, and the like. Two commercially available materials of this type are SST-eM01 poly (methylsilsesquioxane), each R being methyl, and SST-3MH1.1 poly, wherein 90% of the R group is methyl and 10% is a hydrogen atom. (Methyl-hydridosilsesquioxane). This material is available, for example, in a 10% solution of tetrahydrofuran. Alternatively, a complex of two or more of these may be considered. Other examples of possible precursors include SST-, wherein each Y of CAS No. 2288-13-3 is methylsilatrane, methylazasilatrane, where each Y is oxygen and Z is methyl, and each R is optionally methyl. eM01 poly (methylsilsesquioxane), SST-3MH1.1 poly (methyl-hydridosilsesquioxane) in which 90% of the R groups are methyl and 10% are hydrogen atoms, or a combination of two or more of these There is a body.

              V.C. A similar polysilsesquiazane in which —NH— in the above chemical structure is substituted with an oxygen atom is also useful for the production of a similar coating material. Examples of possible polysilsesquiazanes are poly (methylsilsesquiazane) in which each R is methyl, and poly (methyl-hydridosilsesquiazane) in which 90% of the R groups are methyl and 10% are hydrogen atoms It is. Alternatively, a complex of two or more of these is also conceivable.

              V.C. In particular, one possible precursor for the lubricity coating according to the invention includes monocyclic siloxanes, such as octamethylcyclotetrasiloxane.

              In particular, one possible precursor for the hydrophobic coating described in the present invention is a monocyclic siloxane, such as octamethylcyclotetrasiloxane.

              In particular, one possible precursor for the barrier coating described in the present invention is a linear siloxane, such as HMDSO.

              V.C. In any of the coating methods described in the present invention, the coating procedure is optionally performed by vaporization of the precursor and provided near the substrate. For example, OMCTS is vaporized by heating to about 50 ° C. before application to the PECVD apparatus.

V.2 General PECVD method
In the context of the present invention, a PECVD method is generally applied that includes the following procedure:
(a) providing a gaseous reactant comprising a precursor as defined herein, preferably consisting of an organosilicon precursor near the substrate surface and optionally O ₂ ; and
(b) Generation of plasma from gaseous reactants, ie formation of a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD).

In the above method, the properties of the coating are advantageously set by one or more of the following conditions: the nature of the plasma, the pressure applied to the plasma, the power applied to generate the plasma, the O in the gaseous reactant. The presence and relative amount of _2, the volume of plasma, and the organosilicon precursor. Preferably, the properties of the coating are set by the presence and relative amount of O ₂ in the gaseous reactant and / or the power applied for plasma generation.

              In all embodiments of the invention, the plasma in the preferred embodiment is a non-hollow cathode plasma.

              In further desirable embodiments, the plasma is generated under reduced pressure (compared to ambient or atmospheric pressure). Preferably, the reduced pressure is less than 300 mTorr, more preferably less than 200 mTorr, and even more preferably less than 100 mTorr.

              The PECVD is preferably performed by pressurizing a gaseous reactant containing the precursor with an electrode powered by microwave or radio frequency, preferably radio frequency. The radio frequency desired for the implementation of the embodiment of the present invention is also referred to as “RF frequency”. The normal radio frequency range in the practice of the present invention is a frequency of 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, and even more preferably 10 to 15 MHz. A frequency of 13.56 MHz is most desirable, which is a government-approved frequency for carrying out PECVD work.

              There are several advantages of using an RF power source compared to a microwave source: RF operates at low power, which reduces the degree of heating of the substrate / container. Since the focus of the present invention is to coat a plasma coating on a plastic substrate, a low processing temperature is desirable to prevent dissolution / distortion of the substrate. When using microwave PECVD, to prevent overheating of the substrate, the microwave PECVD is applied by a short jet of pulse power. The power pulse increases the cycle time of the dressing, which is not preferred in the present invention. In addition, higher frequency microwaves may cause off-gassing of volatile substances such as residual water, oligomers, and other substances on the plastic substrate. This off-gas may interfere with the PECVD coating. The biggest concern in using microwaves for PECVD is the release of the coating from the substrate. Separation occurs because the microwaves change the surface of the substrate before the coating layer is deposited. In order to reduce the possibility of delamination, interfacial coatings for microwave PECVD have been developed that achieve a good bond between the coating and the substrate. Since RF PECVD has no fear of peeling, such an interfacial coating layer is not necessary. Finally, the lubricity and hydrophobic coatings described in the present invention are advantageously applied using low power. RF power operates at low power and is superior to microwave power in controlling the PECVD process. Nevertheless, microwave power is less desirable but is available under appropriate processing conditions.

Furthermore, for all PECVD methods described herein, a specific correlation is observed between the power used for plasma generation (unit: watts) and the volume of the lumen in which the plasma is generated. Generally, said lumen is the lumen of a container that is coated according to the present invention. The RF power should be measured by the capacity of the vessel when using the same electrode system. If the gaseous reactant composition, such as the precursor to O ₂ ratio, and all other PECVD coating parameters (except power) are set once, the vessel shape is maintained and only its volume changes. In general, those changes are not made. In this case, the power is directly proportional to the capacity. Therefore, starting from the power-to-capacity ratio provided by the present description, it is possible to easily find the power to be applied to obtain the same or similar coating material in containers of the same shape and different sizes. Is possible. The effect of the container shape on applied power is illustrated using the results of a tube example compared to a syringe barrel example.

              For any dressing of the present invention, the plasma is generated by an electrode powered by sufficient power to produce a dressing on the substrate surface. For lubricious or hydrophobic coatings, the plasma is preferably (i) 0.1 to 25 W, more preferably 1 to 22 W, even more preferably 3 to 17 W, in the method described in the examples of the present invention. More preferably 5 to 14 W, most preferably 7 to 11 W, for example generated with an electrode receiving power of 8 W, and / or (ii) the electrode power to plasma volume ratio is less than 10 W / ml, preferably Is 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, most preferably 2 W / ml to 0.2 W / ml. For barrier coatings or SiOx coatings, in the methods described in the examples of the present invention, the plasma is preferably (i) 8 to 500 W, more preferably 20 to 400 W, even more preferably 35 to 350 W, further Preferably 44-300 W, most preferably 44-70 W, and / or (ii) the electrode power to plasma volume ratio is 5 W / ml or more, preferably 6 W / ml ˜150 W / ml, more preferably 7 W / ml to 100 W / ml, most preferably 7 W / ml to 20 W / ml.

              The container shape may also affect the selection of the gas inlet used for the PECVD coating. In certain embodiments, the syringe may be coated with open tube inhalation, and the tube may be coated with a gas intake having a small hole extending into the tube.

              The power (in watts) used for PECVD also affects the properties of the coating. Usually, when the electric power increases, the barrier property of the covering material increases, and when the electric power decreases, the lubricity and hydrophobicity of the covering material increase. For example, for a covering material on the inner wall of a syringe barrel having a capacity of about 3 ml, a power of less than 30 W is passed through a covering material that is mainly a barrier covering material, and a power of 30 W or more is mainly passed through a covering material that is a lubricating covering material Is passed (see example).

Additional parameters that determine coverage include the ratio of O ₂ (or other oxidant) to precursor (eg, organosilicon precursor) in the gaseous reactant used to generate the plasma. Usually, when the O ₂ content in the gaseous reactant increases, the barrier property of the coating increases, and when the O ₂ content decreases, the lubricity and hydrophobicity of the coating increase. Therefore, the PECVD coating method of the present invention can be used to set the lubricity of the coating material produced by the above-described method, the hydrophobicity of the coating material, and the barrier property of the coating material.

When a lubricious coating is desired, preferably the volume / volume ratio of O _{2 to} the gaseous reactant is 0: 1 to 5: 1, more preferably 0: 1 to 1: 1, even more preferably Is from 0: 1 to 0.5: 1, most preferably from 0: 1 to 0.1: 1. Most advantageously, essentially no oxygen is present in the gaseous reactant. Accordingly, the gaseous reactant consists O ₂ of less than 1 vol%, consisting of O ₂ of less than 0.5 vol% and more particularly, and most preferably it is assumed that O ₂ is not included at all. The same applies to the hydrophobic coating material.

On the other hand, if a barrier coating or SiO _x coating is desired, the volume / volume ratio of the O ₂ to gaseous reactants is preferably 1: 1 to 100: 1, preferably 5: 1 to 30. : 1, more preferably 10: 1 to 20: 1, even more preferably
The ratio is 15: 1.

VA PECVD for coating SiO _x barrier coatings using plasma that is substantially free of hollow cathode plasma
VA Specific embodiments of the present invention include SiO _x (oxygen-free) as defined herein (except where otherwise specified) as a coating comprising silicon, oxygen, and optionally other elements. The ratio x to silicon is about 1.5 to about 2.9, alternatively 1.5 to about 2.6, or about 2). These alternative definitions for _x apply to all terms SiO _x as used herein. The barrier coating is applied to the interior of a container, such as a specimen collection tube, syringe barrel, or other type of container. The method consists of several procedures.

              A V.A. vessel wall is provided, and a reaction mixture comprising a plasma generating gas, ie, an organosilicon compound gas, optionally an oxidizing gas, and optionally a hydrocarbon gas.

VA plasma is generated in the reaction mixture that is substantially free of hollow cathode plasma. The container wall is in contact with the reaction mixture, the SiO _x coating material is deposited on at least a portion of the container wall.

In certain VA embodiments, it is desirable that the plasma be generated uniformly through the portion of the container to be coated, since the generation of the SiO _x coating may provide better barrier to oxygen. Uniform plasma means standard plasma that does not contain a large amount of hollow cathode plasma (which has higher emission intensity than standard plasma and appears as a high intensity local area that interferes with the more uniform intensity of the standard plasma). To do.

              The hollow cathode action is generated by a pair of conductive surfaces opposing at the same negative potential with respect to a common anode. When the space is created (depending on pressure and gas type) and the space charge sheath overlaps, the electrons start to oscillate between the reflected potentials of the opposing wall sheath and the potential gradient of the sheath region causes the electrons to As it accelerates, multiple collisions occur. The electrons are contained in the space charge sheath overlap, and a very high ionization and high ion density plasma is generated. This phenomenon is called a hollow cathode action. Those skilled in the art can change processing conditions such as the power level and the gas supply rate or pressure to produce a uniform plasma across the entire area, or to generate a plasma containing varying degrees of hollow cathode plasma. It is possible.

              In an alternative V.A. method, microwave energy can be used to generate a plasma in a PECVD process, for example using the apparatus of FIG. 12 described above. However, the processing conditions may differ because the microwave energy applied to the thermoplastic container excites (vibrates) water molecules. Since a small amount of water is contained in the pure plastic material, the plastic is heated by the microwave. As the plastic is heated, due to the large driving force created by the vacuum inside the equipment relative to the atmospheric pressure outside the equipment, the material is freely or easily detached from the inner surface 88, which Becomes volatile or weakly binds to the surface. The weak binding material then creates an interface that can prevent subsequent coating (deposited from the plasma) from sticking to the plastic inner surface 88 of the device.

VA As a way to negate this anti-coating effect, it is possible to deposit the coating at a very low power (5-20 watts, 2.45 GHz in this example) to produce a capping to which the subsequent coating can adhere. is there. This results in a two-step coating process (and a two-layer coating). In the above example, the initial gas flow (for the capping layer) can be changed to 2 sccm (“cubic centimeter per minute”) HMDSO and 20 sccm oxygen with a processing power of 5-20 watts for about 2-10 seconds. is there. Thereafter, the gas is adjusted to the flow rate in the above embodiment and the power level is increased, for example, from 35 W to 50 W, so that the SiO _x coating material (x in this formula is about 1.5 to about 2.9, or about 1.5 to about 2.6, or about 2) can be deposited. Note that in certain embodiments, the capping layer may perform little or no function except to prevent migration of material to the container inner surface 88 during higher power SiO _x coating deposition. . It should also be noted that easy desorption movement of material within the equipment wall is usually not a problem at low frequencies, such as most RF ranges. This is because the low frequency does not excite (vibrates) the molecular species.

              V.A. As another way to negate the aforementioned anti-coating action, the vessel 80 can be dried to remove stagnant water before applying microwave energy. The drying of the container 80 can be achieved by, for example, thermal heating of the container 80 using an electric heater or forced air heating. Drying of the container 80 can also be accomplished by exposure of the interior of the container 80 to a desiccant or by gas contact within the container 80. Other container drying means such as vacuum drying can also be used. The means can be implemented in one or more of the stations or equipment shown, or by individual stations or equipment.

              V.A. Further, the above-described anti-coating action can be dealt with by selecting or treating the resin as the mold raw material of the container 80 to minimize the amount of water contained in the resin.

PECVD coating covering the restricted opening (syringe capillary) of the VB container
VB FIGS. 26 and 27 show a method and apparatus (usually 290) for coating the inner surface 292 of the restriction opening 294 of the container 250 to be treated, which is generally tubular, for example, the pre-restriction opening 294 of the syringe barrel 250 by PECVD. The foregoing process is modified by connecting the restrictive opening 294 to the process vessel 296 and optionally performing other modifications.

              The VB container 250, which is typically tubular, has an outer surface 298, an inner surface 254 defining a lumen 300, a large opening 302 having an inner diameter, a restriction defined by the inner surface 292 and having an inner diameter smaller than the inner diameter of the large opening 302. A static opening 294 is included.

              VB The processing vessel 296 has a lumen 304 and a processing vessel opening 306, which can optionally provide a second opening that is closed during processing in other embodiments, but optionally It is the only opening. The processing vessel opening 306 is connected to the restrictive opening 294 of the vessel 250, and passage between the lumen 300 of the vessel 250 to be processed and the lumen of the processing vessel is established via the restrictive opening 294.

              V.B. At least a portion of the lumen 300 of the container 250 to be processed and the lumen 304 of the process container 296 are evacuated. PECVD reactant flows from the gas source 144 (see FIG. 7) through the first opening 302 and then into the lumen 300 of the vessel 250 to be processed, the restrictive opening 294, and the lumen 304 of the processing vessel 296. .

              The PECVD reactant can be introduced through the large opening 302 of the vessel 250 by providing an internal electrode 308 that is generally tubular having a VB internal pathway 310, a proximal end 312, a distal end 314, and a distal opening 316. It is. In an alternative embodiment, a plurality of distal openings can be provided adjacent to the distal end 314 and in communication with the internal pathway 310. The distal end of the electrode 308 can be positioned adjacent to / into the large opening 302 of the container 250 to be processed. Reactive gas can be supplied to the lumen 300 of the container 250 to be processed through the distal opening 316 of the electrode 308. To the extent that the PECVD reactant is provided at a pressure higher than the vacuum initially drawn before the PECVD reactant is introduced, the reactant passes through the restrictive opening 294 and then flows into the lumen 304. To do.

              A plasma 318 is generated adjacent to the restrictive opening 294 under conditions effective to deposit a PECVD reaction product on the inner surface 292 of the V.B. restrictive opening 294. In the embodiment shown in FIG. 26, RF energy is supplied to the normal U-shaped external electrode 160 and the internal electrode 308 grounded to generate the plasma. It is possible to disable the supply and ground connection to the electrode, but if the vessel 250 and the internal electrode 308 that are processed during the plasma generation pass through the U-shaped external electrode, this disablement adds complexity. May occur.

              The plasma 318 generated in the vessel 250 during at least a portion of the V.B. process includes a hollow cathode plasma generated within the restrictive opening 294 and / or the process vessel lumen 304. The generation of the hollow cathode plasma 318 provides the ability to successfully apply a barrier coating to the restrictive opening 294. However, the present invention is not limited by the accuracy or applicability of the working theory. Accordingly, in one possible mode of operation, a portion of the process can be performed under conditions that produce a uniform plasma across the vessel 250 and the entire area of the gas inlet, and a portion of the process can be performed, for example, with a hollow cathode plasma. It can be performed under conditions that generate adjacent to the restrictive opening 294.

              VB As described herein and shown in the drawing, the plasma 318 extends substantially across the syringe lumen 300 and the restrictive opening 294, so that the process is operated under such conditions. Is desirable. The plasma 318 also desirably extends over substantially the entire area of the syringe lumen 300, the restrictive opening 294, and the lumen 304 of the processing vessel 296. This assumes that a uniform coating of the interior 254 of the container 250 is desirable. In other embodiments, a non-uniform plasma may be desirable.

              The VB plasma 318 has a substantially uniform color throughout the syringe lumen 300 and restrictive opening 294, and preferably the syringe lumen 300, the restrictive opening 294, and the processing vessel 296. It is usually desirable to have a substantially uniform color over substantially the entire lumen 304 of the tube. The plasma should be substantially invariant throughout the syringe lumen 300 and the restrictive opening 294, and preferably throughout the lumen 304 of the processing vessel 296.

              V.B. The sequence of steps of the method is not considered critical.

              In the embodiment of VB FIGS. 26 and 27, the restrictive opening 294 has a first mounting portion 332 and the processing vessel opening 306 is adapted to be loaded into the first mounting portion 332. And establish a passage between the lumen 304 of the processing vessel 296 and the lumen 300 of the vessel 250 to be processed.

              In the example of VB FIGS. 26 and 27, the first and second attachments are male and female luer lock attachments 332 and 334, which define the restrictive opening 294 and the processing vessel opening 306, respectively. It is integrated with the structure. One of the attachments (in this case, the male luer lock attachment 332) comprises a lock collar 336 having a threaded inner surface and defining an axially opposed normal grooved nail first abutment 338. The one attachment portion 334 includes an axially opposed normal grooved nail second contact portion that faces the first contact portion 338 when the attachment portions 332 and 334 are engaged.

              V.B. In the illustrated embodiment, the sealing portion, for example, the O-ring 342, may be located between the first mounting portion 332 and the second mounting portion 334. For example, the grooved nail sealing portion may be engaged between the first contact portion 338 and the second contact portion 340. The female luer attachment 334 also includes a dog 344 that engages the threaded inner surface of the lock collar 336 to capture the O-ring 342 between the first attachment 332 and the second attachment 334. Optionally, the passage established between the lumen 300 of the container 250 being processed and the lumen 304 of the process container 296 via the restrictive opening 294 is at least substantially leak resistant.

              V.B. As a further option, either or both of the luer lock attachments 332 and 334 can be made from a conductive material, such as stainless steel. The constituent material forming or adjacent to the restrictive opening 294 may contribute to the generation of the plasma in the restrictive opening 294.

              The desired volume of the lumen 304 of the VB processing vessel 296 is preferably a small volume that does not divert the reactant flow rate from the surface of the product that is preferably coated, and the lumen 304 is sufficiently filled (the With a large capacity to support a generous reactive gas flow rate through the restrictive opening 294 before being reduced to a flow rate lower than desired (by reducing the pressure differential at the restrictive opening 294). It may be a trade-off. The possible volume of the lumen 304 is, in some embodiments, less than three times the volume of the lumen 300 of the container 250 being processed, or less than twice the volume of the lumen 300 of the container 250 being processed. The capacity of the lumen 300 of the container 250 being processed, or less than 50% of the capacity of the lumen 300 of the container 250 being processed, or or the capacity of the lumen 300 of the container 250 being processed Less than 25%. Other effective relationships of the volume of each lumen are also conceivable.

              VB The inventor identified by repositioning the distal end of the electrode 308 relative to the container 250 so that it does not enter the lumen 300 of the container 250 as much as the position of the internal electrode shown in the previous figure. It has been found that the uniformity of the coating material in the examples is improved. For example, in certain embodiments, the distal opening 316 may be positioned adjacent to the restrictive opening 294, while in other embodiments the distal opening 316 may be the reactive gas. It may be located at a location less than 7/8, optionally less than 3/4, optionally less than half of the distance from the large opening 302 of the container being processed at the time of supply to the restrictive opening 294. Alternatively, the distal opening 316 is less than 40%, less than 30%, less than 20%, 15% of the distance from the large opening of the container to be treated to the restrictive opening 294 when the reactive gas is supplied. Less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, less than 1%.

              VB or the distal end of the electrode 308 can be positioned slightly inward or outward, or the large opening 302 of the container 250 being processed while passing into the interior of the container 250 and supplying reactive gas. Can be flushed with. The positioning of the distal opening 316 relative to the container 250 to be processed can be optimized for specific processing and other processing conditions by testing at various locations. One particular location of the electrode 308 that can be considered for the treatment of the syringe barrel 250 is that the distal that penetrates about 1/4 inch (about 6 mm) into the container lumen 300 above the large opening 302. A position with end 314.

              V.B. The present inventor currently considers that it is advantageous, if not necessarily, to position at least the distal end 314 of the electrode 308 in the container 250 to function properly as an electrode. Surprisingly, the plasma 318 generated in the vessel 250 can extend more uniformly through the restrictive opening 294 and into the processing vessel lumen 304, and the electrode 308 can be compared to previous uses. It does not enter the lumen 300. With other equipment such as closed container processing, the distal end 314 of the electrode 308 is generally positioned closer to the closed end of the container than its inlet.

              The distal end 314 of the VB or the electrode 308 may be positioned in the restrictive opening 294 or beyond the restrictive opening 294, for example, in the processing vessel lumen 304 illustrated in FIG. . Various means can optionally be provided, such as shaping the process vessel 296 to improve the gas flow rate through the restrictive opening 294, for example.

              As another alternative illustrated in VB FIGS. 34-35, the synthetic internal electrode and gas supply tube 398 may optionally have a distal gas supply opening 400 located near the large opening 302, etc. Also, a protruding electrode 402 that extends distally of the distal gas supply opening 400, optionally extends to a distal end adjacent to the restrictive opening 294, and optionally further extends to the processing vessel 324. May have. This structure is believed to promote plasma generation in the inner surface 292 adjacent to the restrictive opening 294.

              In yet another possible embodiment, the internal electrode 308 is movable during processing, as shown in FIG. 26, for example, first distracting into the processing vessel lumen 304 and then proceeding with the processing. Can be gradually lifted proximally. This means is particularly conceivable when the vessel 250 is elongated under the selected processing conditions and the internal electrode facilitates more uniform processing of the inner surface 254. When this means is used, the processing conditions such as gas supply rate, vacuum suction rate, electrical energy applied to the external electrode 160, suction rate of the internal electrode 308, or other factors change as the processing proceeds. The process can be customized to different parts of the container to be processed.

              For VB convenience, as in other processes described herein, by loading the large opening 302 of the container 250 to be processed onto the port 322 of the container support 320, the process is typically tubular. The large opening of the container 250 may be positioned on the container support 320. Thereafter, the internal electrode 308 can be positioned in the container 250 loaded on the container support 320 prior to at least partially evacuating the lumen 300 of the container 250 to be processed.

              In an alternative embodiment illustrated in VB FIG. 28, the processing vessel 324 communicates with a first opening 306 secured to the vessel 250 and a vacuum port 330 in the vessel support 320 as shown in FIG. It can be provided in the form of a conduit having two openings 328. In this embodiment, the PECVD process gas flows into the vessel 250 and then flows into the process vessel 324 via the restrictive opening 294 and then returns via the vacuum port 330. Optionally, the vessel 250 can be evacuated through both openings 294 and 302 prior to applying the PECVD reactant.

The VB or lidless syringe barrel 250 is at the front end 260 of the barrel by introducing reactants from the source 144 through an opening at the rear end 256 of the barrel 250, as shown in FIG. By using a vacuum source 98 through the opening and pulling a vacuum, an internal SiO _x coating ( _{x in} this formula is about 1.5 to about 2.9, alternatively about 1.5 to about 2.6, or about 2), a barrier coating, Or it may be coated with other types of PECVD coatings. For example, the vacuum source 98 can be connected through a second attachment portion 266 loaded on the front end portion 260 of the syringe barrel 250. Using this means, the reactants will flow through the barrel 250 in a single direction (upward in FIG. 22, but that direction is not important), and the feed gas will flow into the syringe barrel 250. There is no need to transport the reactant through a probe that separates from the exhaust gas. The front end 260 and the rear end 256 of the syringe barrel 250 can be disabled in connection with the dressing device in alternative equipment. The probe 108 may simply function as an electrode, or may function as a tubular or continuous rod in this embodiment. As described above, the distance between the inner surface 254 and the probe 108 may be uniform over at least almost the entire length of the syringe barrel 250.

              FIG. 37 is a diagram showing another embodiment in which the mounting portion 266 similar to FIG. 22 is independent of the plate electrodes 414 and 416 and is not attached thereto. The attachment portion 266 may have a luer lock attachment portion adapted to secure the corresponding attachment portion of the syringe barrel 250. This embodiment allows the vacuum conduit 418 to pass over the electrode 416 while the container holder 420 and mounted container 250 move between the electrodes 414 and 416 during the coating procedure.

              VB FIG. 38 is similar to FIG. 22 in that the front end 260 of the syringe barrel 250 is open and the syringe barrel 250 is enclosed by a vacuum chamber 422 loaded on the container holder 424. It is a figure which shows an Example. In this embodiment, the pressure P 1 in the syringe barrel 250 and the vacuum chamber 422 are substantially the same, and the vacuum state in the vacuum chamber 422 is optionally pulled through the front end 260 of the syringe barrel 250. When the process gas flows into the syringe barrel 250, they are provided with a stable composition in the syringe barrel 250 and until the electrode 160 is pressurized for molding the coating material, It flows through the front end 260. Due to the larger volume of the vacuum chamber 422 compared to the syringe barrel 250 and the position of the counter electrode 426 in the syringe barrel 250, the process gas passing through the front end 260 is on the wall of the vacuum chamber 422. It is believed that no significant deposits are formed.

              VB FIG. 39 is similar to FIG. 22 where the rear flange of the syringe barrel 250 is secured between the container holder 428 and the electrode assembly 430 and the cylindrical electrode or pair of plate electrodes 160 and the vacuum source 98 are secured. It is a figure which shows another Example. The volume (usually 432) sealed outside the syringe barrel 250 is a relatively small amount in this embodiment, and the volume 432 for performing the PECVD process and the inside of the syringe barrel 250 are evacuated. Minimize the pump operation required for this purpose.

              VB FIG. 40 is similar to FIG. 22 and FIG. 41 is a plan view of an alternative embodiment of FIG. 38, in which a pressure proportional valve 434 is provided. The P1 / P2 pressure ratio is maintained at the desired level. P1 may be in a lower vacuum state, i.e. higher pressure than P2 during PECVD processing, so that the waste processing gas and by-products permeate to the front end 260 of the syringe barrel 250 and are discharged Conceivable. In addition, by providing the vacuum chamber conduit 436 that supplies the vacuum chamber 422 individually, a larger enclosed volume 432 can be evacuated more quickly using an individual vacuum pump.

              41 is a plan view of the embodiment of FIG. 40 and shows the electrode 160 removed from FIG.

VC Lubricant coating method
Another example of VC is a method of applying a lubricity coating derived from an organosilicon precursor. "Lubricant coating" or similar term is usually defined as a coating that reduces the frictional resistance of the coated surface compared to the uncoated surface. When the coated object is a syringe (or syringe part, such as a syringe barrel) or other item usually contained in a plunger or a sliding movable part that contacts the coated surface, the frictional resistance is mainly divided into two types- Has starting force and plunger sliding force.

              The plunger sliding force test is specific to the coefficient of friction of the plunger sliding within the syringe, and the standard force normally associated with the coefficient of sliding friction measured on a flat plate surface is the plan. Explain the fact that it can be accommodated by standardizing the fit between the jar / other sliding components and the tube / other plunger sliding containers. The parallel force associated with the normally measured slide friction coefficient can be compared to the plunger slide force measured as described herein. The plunger sliding force can be measured, for example, as specified in the ISO 7886-1: 1993 test.

              The plunger slide force test can also be adapted with appropriate modifications to the apparatus and procedure to measure other types of frictional resistance, such as, for example, the friction holding the stop member in the tube. In one embodiment, the plunger can be replaced by a closure, and the suction force for removing or inserting the closure can be measured as a control of the plunger slide force.

              Also, the starting force can be measured instead of the plunger sliding force. The activation force is the force required to activate the stationary plunger to move within the syringe barrel or a similar force necessary to unload the loaded stationary closure and begin movement. . The activation force is measured by the force applied to the plunger starting from zero or lower and increasing until the plunger begins to move. When the storage period of the syringe is long, the interstitial lubricant is pushed away by the filled syringe plunger due to the decomposition of the lubricant between the plunger and the barrel or sticking to the barrel occurs. The starting force tends to increase. The starting force is the force necessary to overcome the “sticktion” that is the industry term for the adhesive force between the plunger and the barrel, and this plunger is used to activate the plunger. It must be possible to move.

              Some of the equipment for covering the entire or part of the VC container with a lubricity coating, for example, selectively slides on the surface while making contact with other parts, such as a piston in a syringe or a slide in a sample tube Facilitates insertion or removal of stop members or pathways of formula components. The container may be made of glass, or it may be made of a polymer material, for example, an olefin such as polyester, for example polyethylene terephthalate (PET), cyclic olefin copolymer (COC), polypropylene, or other materials. is there. Application of lubricious coatings by PECVD is generally applied in higher amounts compared to deposition by PECVD treatment. The vessel wall can be sprayed, dipped or otherwise applied with organosilicon or other lubricants. Or the need to cover the closure may be avoided or reduced.

              In any of the above embodiments V.C., plasma, optionally non-hollow cathode plasma, can optionally be generated near the substrate.

              In any of the V.C. Examples V.C., the precursor can optionally be provided to an environment that is substantially free of oxygen. V.C. In any of Examples V.C., the precursor can optionally be provided to an environment substantially free of carrier gas. V.C. In any of Examples V.C., the precursor can optionally be provided to an environment that is substantially free of nitrogen. V.C. In any of Examples V.C., the precursor can optionally be provided to an environment where the absolute pressure is less than 1 Torr.

              In any of the V.C. Examples V.C., the precursor can optionally be provided to an environment near the plasma emission.

              In any of the V.C. Examples V.C., the coating can optionally be applied to the substrate in a layer thickness of 1 to 5000 nm, or 10 to 1000 nm, or 10 to 200 nm, or 20 to 100 nm. The layer thickness of this coating material or other coating materials can be measured, for example, by transmission electron microscopy (TEM).

              V.C.TEM can be executed, for example, as follows. Prepare specimens in two directions for focused ion beam (FIB) cross-section. Either specimen can be first coated with a thin layer of carbon (layer thickness 50-100 nm) and then coated with a platinum sputter layer (layer thickness 50-100 nm) using the K575X Emitech coating system. Alternatively, the specimen can be directly coated with a protective sputtered platinum layer. The coated specimen is placed in the FEI FIB200 FIB system. An additional platinum layer can be FIB deposited by injecting an organometallic gas while rastering a 30 kV gallium ion beam into the region of interest. The region of interest for each specimen can be selected at a location that is half the length of the syringe barrel. A cross section with a length of about 15 μm (“micrometer”), a width of 2 μm, and a depth of 15 μm can be extracted from the mold surface using the original in-situ FIB liftout method. Using FIB deposited platinum, the cross section can be attached to a 200 mesh copper TEM grid. One to two windows of each section size ~ 8 μm wide can be thinned into a watermark using a FEI FIB gallium ion beam.

Cross-sectional image analysis of the VC-prepared specimen can be performed using a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), or both. All image data can be recorded digitally. For STEM images, the grid with thin foil can be transferred to Hitachi HD2300 dedicated to STEM. A scan of the transferred electronic image can be acquired at an appropriate magnification in atomic number contrast mode (ZC) and transfer electronic mode (TE). The following device settings are available:

For VCTEM analysis, the specimen grid can be transferred to a Hitachi HF2000 transmission electron microscope. The transferred electronic image can be acquired at an appropriate magnification. The related device settings used for image acquisition may be as follows.

              In any of VC examples VC, the substrate is glass or a polymer such as polycarbonate polymer, olefin polymer, cyclic olefin copolymer, polypropylene polymer, polyester polymer, polyethylene terephthalate polymer, or a composite of two or more of these. May consist of

              In any of the VC examples VC, the PECVD is optionally as defined above, for example, at a frequency of 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz, and most preferably 13.56 MHz. This can be done by pressurizing a gaseous reactant including a precursor having an electrode powered by an RF frequency.

              In any of the V.C. Examples V.C., the plasma can be generated by pressurizing a gaseous reactant comprising the precursor with electrodes that is supplied with sufficient power to form a lubricity coating. Optionally, the plasma is a precursor having an electrode that receives a power supply of 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, even more preferably 5 to 14 W, most preferably 7 to 11 W, especially 8 W. It is produced by pressurizing a gaseous reactant containing The electrode power to plasma volume ratio is less than 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, most preferably 2 W / ml to 0.2 W / ml. May be ml. This power level is suitable for applying a lubricious coating to syringes and specimen tubes and similarly shaped containers in which PECVD plasma is generated and has a void volume of 1 to 3 mL. For larger or smaller objects, it is believed that the applied power should be increased or decreased accordingly as the substrate size is processed.

              One possible product may optionally be a syringe with a barrel that is processed by the method of one or more of the examples V.C.

VD fluid coating
Another example of a suitable barrier coating or other type of coating that can be used in conjunction with VDPECVD applied coatings or other PECVD processes disclosed herein includes fluid barrier layers, lubricants, Interfacial energy tailoring, or other types of coating 90 applied to the inner surface of the container, applied to the inner surface of the container directly or with one or more intervening PECVD applied Si _w O _x C _y Performed with H _z , SiO _x coating, with lubricity coating, or both.

              A suitable fluid barrier membrane or other type of dressing 90 may also optionally cure the fluid monomer, for example by applying a fluid monomer or other polymer, or a curable material, to the inner surface of the container 80. It can be applied by forming a continuous polymer by cross-linking or cross-linking. A suitable fluid barrier or other type of dressing 90 can also be provided by applying a solvent polymer to the surface 88 and removing the solvent.

              V.D. Any of the above methods may include a procedure for forming the dressing 90 on the interior 88 of the vessel 80 via the vessel port 92 at the processing station or equipment 28. As one example, a fluid coating, such as a curable monomer, prepolymer, or polymer dispersion, is applied to the inner surface 88 of the container 80 and a film that physically isolates the contents of the container 80 from the inner surface 88 is formed. For curing. According to the prior art, polymer coating techniques are described as suitable for coating plastic blood collection tubes. For example, the acrylic and polyvinylidene chloride (PVdC) coatings and coating methods described in US Pat. No. 6,165,566, incorporated herein by reference, can be utilized.

              V.D. In addition, any of the above methods may include a procedure for forming a covering material on the outer wall of the container 80. The coating is a barrier coating, optionally an oxygen barrier coating, and optionally a water barrier coating. One example of a suitable dressing is polyvinylidene chloride that has both water barrier and oxygen barrier functions. Optionally, the barrier coating can be applied as a water-based coating. The dressing can optionally be applied by dipping the container, spraying the container, or other means. Containers having the aforementioned external barrier coating are also conceivable.

VI. Container inspection
VI. The station or equipment shown in Figure 1 can be configured to inspect the inner surface of container 80 for defect detection by measuring atmospheric pressure loss or mass flow rate or volumetric flow rate through outgassing of the container wall or container wall. A processing station or device 30. The device 30 can operate in the same way as the device 26 with the exception that the better performance of the container (lower leakage or permeation under any processing conditions) to pass the inspection provided by the device 30. Degree) may be required. This is because, in the illustrated embodiment, a barrier film or other type of coating is applied by the station or device 28 before reaching the station or device 30. In one embodiment, this inspection of the coated container 80 is comparable to the inspection of the same container 80 at the device or station 26. A lower leakage or permeability at the station or device 30 indicates that the barrier coating is functioning at least to some extent.

              VI. The identity of a container 80 measured at two different stations or instruments is determined by the identification of individual identification labels, such as barcodes, other symbols, or radio frequency identification (RFID) instruments or markers, in each container holder 38- This can be confirmed by sticking to 68 and matching the identity of the containers measured at two or more different points of the circulating conveyor shown in FIG. 1. Since the container holder is reusable, computer data or other data will be generated as soon as they reach the position of the container holder 40 in FIG. 1 immediately after the new container 80 is loaded onto the container holder 40. Can be registered in the data storage structure. Further, at or near the end point of the process, for example, when the position of the container holder 66 in FIG. 1 is reached or later, it can be removed from the data registration, and the process container 80 is removed by the transport mechanism 74. The

              VI. The processing station or device 32 can be configured to inspect the container, for example, to detect defects in a barrier film or other type of coating applied to the container. In the illustrated embodiment, the station or device 32 determines the optical source transmission of the coating material by measuring the layer thickness of the coating material. When the barrier film or other type of coating material is properly applied, the surface becomes more uniform, so that the transparency of the container 80 can be increased even if additional materials are applied. .

              VI. As another method for measuring the layer thickness of the covering material, energy waves that bounce inside the covering material 90 (interface with the atmosphere inside the container 154) and the inner surface 88 of the container 80 (the covering material 90) The use of interferometry is also conceivable to determine the difference in travel distance between the energy wave that bounces off at the external interface. As is well known, the difference in the movement distance can be determined directly by measuring the arrival time of each wave with high accuracy. Alternatively, it can be determined indirectly by determining which wavelengths of the incident energy are enhanced or offset in relation to the test conditions.

              VI. Another measurement technique that can be performed to confirm the integrity of the coating is the ellipsometric measurement of the instrument. In this case, the polarized laser beam can be projected from the inside or the outside of the container 80. When projecting a laser beam from the inside, the laser beam is shown orthogonal to the surface and then measured as a transmitted or reflected beam. Changes in the light polarity can be measured. Since the coating or treatment on the instrument surface affects (changes) the degree of polarization of the laser beam, a change in the polarity may be a desirable result. The change in polarity is a direct result of coating or treating the surface, and the amount of change is related to the amount of treatment or coating.

              VI. When the polarized light is projected from outside the instrument, the detector can be positioned inside to measure the transmitted component of the light (and the polarity determined above). Alternatively, the detector can be positioned outside the instrument, which is a position that can correspond to the point of reflection of the light beam from the interface between the treatment / coating (on the inner surface of the instrument). The polarity change can then be determined as shown in the detailed diagram.

              VI. In addition to the measurement of optical properties and / or leakage rate described above, other probes and / or instruments were inserted into the instrument and measurements were taken with the detector device. The apparatus is not limited by the measurement technique or method. Other test methods that utilize mechanical, electrical, magnetic properties, or other physical, optical, chemical properties can be used.

              VI. During the plasma processing setup, an optical detection system can optionally be used to record the plasma emission spectrum (wavelength and intensity profile) corresponding to the chemical characteristics specific to the plasma environment. This characteristic emission spectrum confirms that the coating material has been applied and processed. The system also provides real-time precision measurements and data archiving tools for each processed part.

              VI. Any of the above methods may include a procedure for inspecting the interior 88 of the vessel 80 for defect detection at the processing station 24, 26, 30, 32, or 34. By inserting the detection probe 172 into the container 80 via the container port 92 and using the probe 172 to detect the state of the container inner surface 88 or the barrier film or other type of coating 90 Inspections can be performed at the stations 24, 32, and 34. As shown in FIG. 11, the inspection can be performed by radiating energy inward through the container wall 86 and the container inner surface 88, and detecting the energy with the probe 172. Alternatively, the inspection can be performed by detecting the energy with a detector located inside the container 80 by reflecting the radiation from the inner surface 88 of the container. Alternatively, the inspection can be performed by detecting the state of the container inner surface 88 at a number of dense points on the container inner surface.

              VI. In any of the above methods, if the barrier film or other type of coating 90 is initially evacuated and its walls are exposed to the ambient atmosphere, the pressure in the container can be stored for one year. In some cases, performing an inspection procedure at a sufficient point across the container inner surface 88 to determine that it is effective to prevent an increase in excess of 20% of ambient atmospheric pressure in between.

              VI. Either of the above methods, 30 seconds or less per container, 25 seconds or less per container, 20 seconds or less per container, 15 seconds or less per container, 10 seconds or less per container, 5 seconds or less per container, 4 seconds or less per container , May include performing inspection procedures within an elapsed time of 3 seconds or less per container, 2 seconds or less per container, and 1 second or less per container. This may be possible, for example, by measuring the effectiveness of the container wall covered with the barrier film or other type of coating, as shown in FIG. May be involved. Alternatively, it may be possible by inspecting many or all test points in parallel using a charge coupled device as the detector 172 shown or substituting as shown in FIGS. . The latter procedure can be used to detect the condition of the barrier film or other type of coating at a number of dense points on the container inner surface 88 in a very short period of time.

              VI. In any embodiment of the method, if desired, data is collected using the charge coupled device 172, the inspected container 80 is unloaded, and the collected data is immediately transferred to the container 80. By processing while the process proceeds to the final stage process, it is possible to further promote the container inspection at a plurality of points. When a defect is later confirmed in the container 80 by the data processing, the container 80 that is a defective product can be removed from the line at an end stage process point of the detection station 34 or the like (FIG. 10).

              VI. In any of the above embodiments, the initial vacuum level in the vessel 80 (ie, the initial vacuum to atmosphere) is at least 12 months when initially evacuated and its walls 86 are exposed to ambient air. Or more than 20%, optionally more than 15%, optionally more than 10%, optionally more than 5%, optionally 2% during a shelf life of at least 18 months, or at least 2 years Perform inspection procedures at sufficient points throughout the inner surface 88 of the container 80 to determine that the barrier film or other type of coating 90 is effective in preventing reduction beyond Is possible.

              VI. The initial vacuum level may be high vacuum, i.e. the residual pressure may be less than 10 torr, or lower vacuum, e.g. positive pressure (i.e. overpressure above full vacuum) less than 20 torr, less than 50 torr, 100 May be less than Torr, less than 150 Torr, less than 200 Torr, less than 250 Torr, less than 300 Torr, less than 350 Torr, less than 380 Torr. The initial vacuum level of the vacuum blood collection tube is often determined, for example, by the type of test that uses the tube, i.e., the type and amount of reagent added to the tube during manufacture. The initial vacuum level is generally set to draw an appropriate amount of blood to bind to the reagent contained in the tube.

              VI. In any of the above embodiments, when the barrier membrane or other type of coating 90 is initially evacuated and its walls are exposed to ambient air, the pressure in the vessel 80 is at least 1 year. At a sufficient point throughout the interior surface 88 of the vessel to determine that it is effective to prevent an increase in ambient atmospheric pressure from exceeding 15% or exceeding 10% during the shelf life. An inspection procedure for a barrier film or other type of dressing 90 may be performed.

VI.A. Container handling including pre- and post-coating inspections
VI.A. Yet another embodiment is a container processing method for processing a molded plastic container having a wall defining an opening and an interior surface. The method includes an inspection for detecting a defect on the inner surface of the container at the time of molding or immediately before coating, an application of the coating material to the inner surface of the container according to a mold after the inspection, and an inspection for detecting a defect of the coating material, Executed.

              VI.A. Another embodiment is a container processing method in which a barrier covering material is applied to a container in accordance with a mold after inspection, and the inner surface of the container is inspected for inspection defect detection after application of the barrier covering material. Is done.

              VI.A. In one embodiment, the station or equipment 26 (which can also function as a station or equipment 28 for coating application) can be used for the following barometric vessel inspections. Either or both of the valves 136 and 148 can be opened to evacuate the container 80 to a desired level, preferably to a very low pressure, such as less than 10 Torr, optionally to less than 1 Torr. Regardless of which of the valves 136 and 148 opens first, it can be closed thereafter, isolating the vacuum interior 154 and the pressure gauge 152 of the vessel 80 from environmental conditions and from the vacuum source 98. Any change in pressure over the measurement time is then sensed regardless of whether gas intrusion through the container wall or outgassing from the wall material and / or coating on the container wall, and the container holder It can be used to calculate the invasion rate of environmental gas into the container 80 at the time of attachment to 44. Outgassing for this purpose is defined as the release of absorbed or shielded gas or water vapor from the vessel wall, optionally at least partially in vacuum.

              VI.A. Another option modification may be to provide the environmental gas at a pressure higher than atmospheric pressure. This also increases the gas transport rate through the barrier membrane or other types of layers and may be able to measure the difference in a shorter time when the ambient pressure is low. Alternatively, it is possible to introduce the gas into the container 80 at a higher ambient pressure and again increase the transport rate through the wall 86.

              Optionally, the container inspection at the station or by the equipment 26 may be performed by providing a test gas, such as helium, either inside or outside the container 80 in the front plate process for the substrate, and It can be corrected by detecting it in the final stage process. Low molecular weight gases such as hydrogen, or inexpensive and easily available gases such as oxygen and nitrogen can also be used as inspection gases.

              VI.A. Helium passes through imperfect barriers or other types of coatings or through leaked seals very quickly compared to common environmental gases such as nitrogen and oxygen in the atmosphere. It is considered as a detection test gas that increases the leak / permeation detection rate. Helium has a high transport rate through many uninterrupted substrates or small gaps due to the following characteristics: (1) because it is inert, so it is not much absorbed by the substrate, (2) because it is not easily ionized, The molecule is very compact, and (3) the molecular weight is 4, so the molecule is more compact as opposed to nitrogen (molecular weight 28) and oxygen (molecular weight 32) It can easily pass through the porous substrate or gap. These elements allow helium to move faster than many other gases through any permeable barrier membrane. In addition, since the atmosphere normally contains a very small amount of helium, especially when helium is introduced into the vessel 80 and detected outside the vessel 80 in order to measure leakage and permeation, the presence of added helium. Can be detected relatively easily. The helium can be detected by a pressure drop upstream of the substrate or by other means such as spectroscopic analysis of downstream gas that has passed through the substrate.

VI.AO ₂ An example of barometer container inspection based on oxygen concentration determination from fluorescence detection is as follows.

VI.A. Excitation source (Ocean Optics USB-LS-450 Pulsed Blue LED), fiber assembly (Ocean Optics QBIF6000-VIS-NIR), spectrometer (USB4000-FL Fluorescence Spectrometer), oxygen sensor probe (Ocean Optics FOXY-R) ), And a vacuum supply device (such as lVFT-1000-VIS-275) connected to the vacuum source via an adapter. If the ambient air can be removed by applying vacuum and the container is at the specified pressure, the detection system can be used to detect the oxygen content that leaks or refills the container from the ambient atmosphere. Can be determined. It is possible to measure the O ₂ concentration by replacing the non-coated tube with a coated tube. O ₂ surface absorption differences (SiO _x surface versus uncoated PET or glass surface) on the cladding due to changes in O ₂ diffusion rate from and / or surface, to the cladding tube, the atmosphere which is different from the uncoated specimen Medium oxygen content is shown with reproducibility. The detection time may be less than 1 second.

              VI.A. The barometric method should not be considered limited to the specific gas being sensed (helium detection or other gases can be considered) or specific equipment / equipment.

              VI.A. The processing station or equipment 34 can also be configured to perform inspections for detection of defects in barrier films or other types of coatings. In the embodiment of FIGS. 1 and 10, the processing station or instrument 34 may be another optical inspection, this time at least a portion of the barrier film or other type of coating 90, or the barrier film or It is contemplated that the substantially overall properties of other types of dressings 90 are scanned or measured individually at a number of dense points on the barrier membrane or other types of dressings 90. The large number of dense spots may be, in all cases or as an average of at least a portion of the surface, for example, about 1 micron spacing, or about 2 micron spacing, or about 3 micron spacing, or about 4 micron spacing, or about 5 microns. The intervals, or about 6 micron intervals, or about 7 micron intervals may be separated, and therefore some or all local minimum points of the barrier film or other type of coating 90 are measured individually. In one embodiment, an individual scan of each small area of the dressing is useful for finding pinholes or other defects, and the local effects of pinhole defects and coatings that are too thin or porous. It may be useful to distinguish from more general defects, such as a wider area with material.

              VI.A. Inspection by the station or equipment 34 may be performed by radiation or light source 170 or other suitable radio frequency, microwave, infrared, visible, ultraviolet, X-ray, or electron source, for example via the container port 92. By inserting into the container 80 and detecting the radiation transmitted from the radiation source using a detector, for example, by detecting the condition of the inner surface of the container such as the blocking coating 90, It is feasible.

              VI.A. The container holder system can also be used for testing the equipment. For example, the probe 108 of FIG. 2 having the gas supply port 110 can be replaced with a light source 170 (FIG. 10). The light source 170 can be illuminated inside the tube, and then subsequent tests can be completed outside the tube by measuring transmission or other properties. The light source 170 can be extended into the tube, and the method is similar to pushing the probe 108 into the pack or container holder 62, but vacuum and sealing are not necessary. The light source 170 may be an optical fiber source, a laser, a point light source (such as an LED), or other radiation source. The source can be irradiated at one or more frequencies from deep ultraviolet (100 nm) to far infrared (100 microns) and any frequency in between. There are no restrictions on the sources that can be used.

              VI.A. See Figure 10 for specific examples. In FIG. 10, the tube or container 80 is located in the pack or container holder 62, and the light source 170 at the end of the probe 108 is inserted into the tube. In this case, the light source 170 may be a blue LED source with sufficient intensity to be received by the detector 172 surrounding the outside of the container 80. The light source 170 may be a three-dimensional charge coupled device (CCD) having an array of pixels 174 on the inner surface 176, for example. The pixel 174 or the like receives and detects radiation emitted through the barrier film or other type of covering 90 and the container wall 86. In this embodiment, the detector 172 has an inner diameter associated with the container 80 that is greater than the distance distance between the electrode 164 and the container 80 of FIG. 2 and a cylindrical top adjacent to the closed end 84 rather than the hemispherical top. . The external detector 172 may have a smaller gap running radially from the container 80 and a more uniformly sized gap at the top adjacent to the closed end 84. This can be achieved, for example, by providing a common center of curvature at the closed end 84 and the top of the detector 172 when the container 80 is loaded. Although both variations are considered appropriate, this variation may result in a more uniform inspection of the container 80 curved closed end 84.

              VI.A. Measure the CCD before turning on the light source and save the result as background (may be subtracted from subsequent measurements). The light source 170 is then turned on, and the measured value is acquired by the CCD. The resulting measured values are then compared to the total light transmittance (determining the coating layer thickness average compared to the uncoated tube) and defect density (individual photon counts for each element in the CCD) If the photon count is low, this may correspond to insufficient light transmission). Low light transmission can lead to a lack of coating or an excessively thin coating, i.e. a defect in the coating on the tube. By measuring the number of adjacent elements having a low photon count, the size of the defect can be estimated. The size and number of defects can be summed to evaluate the quality of the tube. Alternatively, other properties that may be specific to the frequency of radiation from the light source 170 can be determined.

              In the embodiment of FIG. 10, energy can be irradiated to the outside through the inner surface of the container, for example, the covering material 90 and the container wall 86, and can be detected by a detector 172 located outside the container. Various types of detectors 172 can be used.

              VI.A. The incident radiation from the source 170 passing through the barrier membrane or other type of coating 90 and the container wall 80 (as compared to a reference line perpendicular to the container wall 80 at any point) Since the low incident angle may be large, the pixels 174 and the like that are normal through the container wall 86 receive more radiation than neighboring pixels. However, one or more pixels may receive part of the light that passes through any part of the blocking film or other type of covering material, and the blocking film or other type of covering material 90 and the container wall Light passing through one or more arbitrary portions of 80 is received by a specific pixel 174 or the like.

              VI.A. The resolution of the pixel 174, etc., for detecting radiation passing through a specific part of the barrier film or other type of covering 90 and the container wall 86 is determined by the arrangement of the pixel 174, etc. Can be increased by closely fitting the contour of the container wall 86 closely. The resolution can also be increased by selecting a smaller or essentially point light source to illuminate the interior of the container 80, as illustrated in FIG. In addition, the use of smaller pixels improves the resolution of the pixel array in the CCD.

              VI.A. In FIG. 6, a point light source 132 (laser or LED) is located at the end of the rod or probe. ("Point light source" refers to light emitted from a small quantity source similar to a mathematical point that may be generated in any direction from a diffused end of a small LED or fiber optic radiation, or a small cross-section beam, for example This refers to any of the light emitted as coherent light transmitted by the laser.) The point light source 132 is movable axially, for example, during the measurement of the properties of the barrier film or other type of coating 90 and the container wall 80 It can be either stationary or mobile, as can be done. In the case of mobility, the point light source 132 can move up and down in the device (tube) 80. In a manner similar to that described above, the inner surface 88 of the container 80 can be scanned, and subsequent measurements are obtained by the external detector device 134 to determine the integrity of the dressing. An advantage of this approach is that it can utilize linearly polarized light or a similar coherent light source with a specific orientation.

              VI.A. The position of the point light source 132 may be an indicator such as the pixel 174, and the illumination of the detector is determined when the detector is at a right angle with respect to a particular area of the covering 90. In the embodiment of FIG. 10, a cylindrical detector 172 having a curved end that optionally coincides with the curve (if any) of the closed end 84 of the container 80 can be used to detect the characteristics of the cylindrical container 80. .

              Referring to FIG. 10, the inspection station or instrument 24 or 34 can be modified by inverting the position of the light or other radiation source 170 and detector 172 so that the light Can be irradiated from the exterior to the interior of the container 80 through the container wall 86. When this means is selected, in one embodiment, a uniform incident source or other radiation can be provided by inserting the container 80 through the wall 184 of the integrating sphere light source 186 and into the aperture 182. Since the integrating sphere light source splits light or radiation from the source 170 outside the container 80 and inside the integrating sphere, the light passing through each point of the wall 86 of the container 80 becomes relatively uniform. This tends to reduce distortion caused by artifacts associated with portions of the wall 86 having different shapes.

              In the embodiment of FIG. 11, the detector 172 may be displayed to closely fit the barrier membrane or other type of dressing 90 or the inner surface 88 of the container 80. Since the detector 172 may be on the same side of the vessel wall 86, which is the barrier film or other type of covering 80, this proximity tends to increase the resolution of the pixel 174 and the like. However, in this embodiment, the detector 172 is preferably positioned relatively accurately with the barrier film or other type of coating 90 and rubs against each other, and further the coating or CCD array Any damage shall be prevented. The placement of the detector 172 directly adjacent to the dressing 90 may also reduce the refractive effect of the container wall 86, which in the embodiment of FIG. Because it occurs after passing through a barrier film or other type of dressing 90, the detected signal may be refracted differently depending on the local shape of the container 80 and the incident angle of the light or other radiation.

              VI.A. Techniques and equipment for testing other barrier membranes or other types of coatings can also be used. For example, fluorescence measurements can be used to characterize the treatment / coating of the instrument. Use of the same apparatus described in FIGS. 10 and 6 may cause light source 132 or 170 (or other radiation source) that may interact with the polymer material of the wall 86 and / or dopants within the polymer material of the wall 86. ) Can be selected. This can be combined with a detection system and used to characterize a range of properties including defects, layer thickness, and other performance factors.

              VI.A. Another inspection example is the use of X-rays to characterize the treatment / coating and / or the polymer itself. In FIG. 10 or 6, the light source can be replaced with an X-ray source, and the external detector may be of a type that measures X-ray intensity. Elemental analysis of the barrier film or other types of coatings can be performed using this technique.

              After molding the VI.A. equipment 80, there may be several potential problems at the station 22 that apply subsequent processing or coatings incompletely or ineffectively. If the device is inspected before coating for these issues, the device can be coated with a highly optimized process, optionally with 6 sigma control, to ensure the desired result.

VI.A. Some of the potential problems that can interfere with processing and coating include (depending on the nature of the resulting coating material):
VI.A.1. Large density particle contamination defects (for example, each longest dimension of 10 micrometers or more), or low density large particle contamination (for example, each longest dimension of 10 micrometers or more).

              VI.A.2. Chemical or other surface contamination (eg silicon release agents or oils).

              VI.A.3. High surface roughness characterized by a large number of sharp protrusions and / or recesses. This may also be characterized by quantifying the average roughness (Ra), which should be less than 100 nm.

              VI.A.4. Defects in the device, such as holes, that make it impossible to create a vacuum.

              VI.A.5. A defect on the surface of the device used to create a seal (eg, the open end of the specimen collection tube).

              VI.A.6. Significant wall thickness non-uniformity that may interfere with or modify power coupling through the thickness during processing or coating.

              VI.A.7. Other defects that invalidly apply the barrier or other types of coatings.

              VI.A. In order to ensure the success of the treatment / coating operation using the parameters in the treatment / coating operation, the device can be pre-inspected for one or more of the above potential problems or other problems. Previously, devices for gripping equipment (such as packs or container holders 38-68) were disclosed, and the devices were moved through manufacturing processes including various testing and processing / coating operations. Several possible tests can be performed to ensure that the instrument has a suitable surface for treatment / coating. These include the following:

              VI.A.1. Optical inspection, eg transmission of radiation through the device, reflection of radiation from inside or outside the device, absorption of radiation by the device, interference of radiation by the device.

              VI.A.2. Digital inspection-for example, measuring a specific length and shape (eg how “open” the sample collection tube is “circular” or even and accurate compared to a reference) Possible digital camera use.

              VI.A.3. Vacuum leak check or pressure test.

              VI.A.4. Sonic (ultrasonic) testing of the equipment.

              VI.A.5. X-ray analysis.

VI.A.6. Electrical conductivity of the equipment (the electrical resistance of plastic tube material and SiO _x is different-for example, about 1020 Ohm-cm for quartz as bulk material and about 1014 Ohm-cm for polyethylene terephthalate) .

              VI.A.7. Thermal conductivity of the device (for example, the thermal conductivity of quartz as a bulk material is about 1.3 W- ° K / m, and the thermal conductivity of polyethylene terephthalate is 0.24 W- ° K / m. Is).

              VI.A.8. Optionally, outgassing of the vessel wall, which can be measured under post-coating inspection to determine the outgassing baseline as described below.

              VI.A. The above test can be performed at station 24 shown in FIG. 6. In this figure, the device (for example, the specimen collection tube 80) can be grounded at a predetermined position, and the light source (or other source) 132 is connected to the device and an appropriate detector 134 located outside the device. The desired result can be measured by insertion.

              VI.A. If a vacuum leak is detected, the vessel holder and instrument can be coupled to a vacuum pump and measuring instrument inserted into the tube. The test can also be performed as detailed elsewhere in the specification.

              VI.A. The processing station or equipment 24 may be a visual inspection station, which detects one or more container inner surfaces 88, its outer surface 118, or the interior of the container wall 86 between its surfaces 88 and 118, for defect detection. Can be set to inspect for. Inspection of the outer surface 118, the inner surface 88, or the container wall 86 can be performed from the outside of the container 80, particularly when the container is transparent or translucent to the radiation and wavelength used for the inspection. . Inspection of the inner surface 88 can be facilitated, if desired, by providing a fiber optic probe that is inserted into the container 80 via the container port 92 so that the interior of the container 80 is moved into the container 80. Visible from the outside. For example, an endoscope or borescope can be used in this environment.

              Another means illustrated in FIG. 6 may be the insertion of the light source 132 into the container 80. Light transmitted through the container wall 86 and artifacts of the container 80 that are manifested by the light can be detected from the exterior of the container 80 using a detector that measures the device 134. The station or device 24 detects and misaligns containers 80 that are not properly loaded into the container port 96, or containers 80 that have visible distortions, impurities, or other defects in the wall 86, for example. It can be used to correct or remove. Visual inspection of the container 80 can also be performed in addition to / in addition to mechanical inspection by visual inspection of the container 80 by the operator.

              VI.A. The processing station or equipment 26 shown in more detail in FIG. 7 is configured to inspect the inner surface 88 of the vessel 80 for defect detection, for example, to measure the gas pressure loss through the vessel wall 86. Yes, the test can be performed before providing the barrier film or other type of dressing. This test can be performed by creating a pressure difference between both sides of the barrier coating 90. At that time, the inside of the container 80 is pressurized or vacuumed, the inside 154 of the container 80 is isolated, and kept constant so that leakage from the sealed portion or gas permeation from the container wall does not occur due to the pressure. The pressure change is measured every unit time added due to the above problem. This measurement not only clarifies the gas that passes through the vessel wall 86, but also detects a leak at the seal between the vessel port 82 and the O-ring / other seal 100. The leak may point out that there is a problem with either the alignment of the container 80 or the function of the seal 100. In any case, attempt to correct the tube misloading or remove the tube from the processing line to achieve or maintain an appropriate processing vacuum level, and treatment with air leaking from a malfunctioning seal The time required for preventing gas dilution can be saved.

              VI.A. The above system can be integrated into a multi-procedure manufacturing and inspection method.

              VI.A. FIG. 1 (above) shows a layout diagram of possible method steps (although the invention is not limited to a single concept or approach). First, the container 80 is visually inspected at the station or by the device 24. The inspection may include measuring the dimensions of the container 80. If a defect is found, the device or container 80 is rejected, and the pack or container holder 38 is inspected, reused, or removed for defect detection.

VI.A. The leak rate or other characteristics of the other container holder 38 and loaded container 80 assembly is then tested at the station 26 and stored for post-coating comparison. The pack or container holder 38 is then moved to the coating procedure 28, for example. The device or container 80 is coated with SiO _x or other barrier layer or other type of coating, for example at a power supply frequency of 13.56 MHz. The coated container holder is retested for leak rate or other characteristics (this can be done as a second test, such as at the test station 26 or the duplicate / similar station 30-by using a duplicate station System throughput can be increased).

              VI.A. The coverage measurement is comparable to the uncovered measurement. If the ratio of the value exceeds the preset required level, it indicates that the overall performance of the dressing is acceptable, and the container holder and equipment proceed to the next step. The optical test station 32 follows, for example, a blue light source and an external integrating sphere detector that measures the total light transmission through the tube. If the device fails or is reused for additional coating, it may be essential that the value exceed the preset limit. The second optical test station 34 can then be used (for instruments that did not fail). In this case, a point light source is inserted into the tube or container 80, and when a measurement value is obtained, it is gradually taken out of the tube together with the tubular CCD detector array. The data is then subjected to computer analysis to determine the defect density distribution. Based on the measured value, the device is accepted and final packaging is performed or rejected.

              VI.A. The data can optionally be logged or plotted (eg, electronically) using statistical process control techniques to maintain 6 sigma quality.

VI.B. Container inspection by detecting container wall outgassing through barrier layer
VI.B. Another embodiment is a method of inspecting a barrier film or other type of layer on a material that outgases a vapor, the method having multiple steps. Prepare a specimen of a substance that will outgas and at least partially be a barrier layer. Optionally, a pressure differential is provided in the barrier layer so that at least some of the outgassing material is present on the high pressure side of the barrier layer. In another option, the emitted gas may allow diffusion without providing a pressure differential. The released gas is measured. When providing a pressure difference in the barrier layer, the outgassing can be measured on the high pressure side or the low pressure side of the barrier layer.

               VI.B. Also, the effectiveness of the inner coating (applied above) can be measured by measuring the diffusivity of the material absorbed by a particular species or equipment wall (before coating). It is. When compared to uncoated (untreated) tubing, this type of measurement can provide a direct measure of the barrier or other type of nature of the coating or treatment, or the presence or absence of the coating or treatment. The detected coating or treatment is in addition to / in lieu of a barrier layer, a lubricating layer, a hydrophobic layer, a decorative coating, or other type of layer that modifies by increasing or decreasing outgassing of the substrate There is.

              VI.B. As a specific example using the container holder of FIG. 2, and referring again to FIG. 7, an instrument or container 80 can be inserted into the pack or container holder 44 (the test is also covered This can be done on a loaded container 80, such as on a pack or container holder 44 that is moved from another task such as / processing). After the container holder has moved to the blocking test area, the measuring tube or probe 108 can be inserted into the interior (in the same way as the gas tube for coating, except that the measuring tube is There is no need to extend it deep inside the pipe). Both valves 136 and 148 can be opened, and the inside of the tube can be evacuated (vacuum creation).

              VI.B. Once the desired measured pressure is achieved, the valves 136 and 148 can be closed and the pressure gauge 152 can begin measuring the pressure. By measuring the time at which a certain pressure (above the starting pressure) is achieved, or by measuring the pressure achieved after any time, the tube, container holder, pump channel, and the internal volume It is possible to measure the rate of rise (or leak rate) of all other components that are connected to but isolated by valves 1 and 2. When this value is subsequently compared to an uncoated tube, the ratio of the two measured values (the value of the coated tube divided by the value of the uncoated tube) gives the measured value of the leakage rate through the coated surface of the tube. Obtainable. The measurement technique minimizes the effects of gas permeation or outgassing from the surface, all other connected to the vessel holder, pump channel and the internal volume but isolated by valves 1 and 2. May need to minimize the internal capacity of other parts (excluding the pipe / device).

              VI.B. This disclosure distinguishes between “permeation”, “leakage”, and “surface diffusion” or “outgassing”.

              As used herein in connection with a container, “permeation” refers to a substance that passes through a wall 346 or other obstruction, such as from outside the container along the path 350 in FIG. 29 or vice versa, or vice versa. Refers to movement.

              Outgassing refers to absorption or absorption material, for example gas molecules 354 or 357 or 359, from the inside of the wall 346 or dressing 348 in FIG. 29, eg, through the dressing 348 (if present). And movement to the inside (right side of FIG. 29) of the container 358. Outgassing may also refer to the movement of material 354 or 357, etc., from the wall 346 to the left, and thus out of the vessel 357 shown, as shown in FIG. Outgassing may also refer to the removal of absorbing material from the material surface, such as the gas molecules 355 from the exposed surface of the barrier coating 90.

              Leakage is the movement of a substance around the obstacle represented by the wall 346 and the covering material 348. The leakage is not the separation of the obstacle from the surface of the obstacle, but the closure of the container closed at the closure part. This refers to the passage between the part and the wall.

              VI.B. Permeation is a measure of gas transfer rate through materials that are free of gaps / defects and not related to leakage or outgassing. FIG. 29 shows a container wall or other substrate 346 having a barrier coating 348, and permeation passes completely through the substrate 346 and the coating 348 and through both layers along the path 350. It is. Permeation is considered thermodynamic and is therefore a relatively gradual process.

              The measurement of VI.B. permeation is very time consuming because the permeate gas must pass completely through the walls of the intact plastic material. In the case of a vacuum blood collection tube, gas permeation measurements through the wall are conventionally used as a direct indicator of the tendency of the vessel to lose vacuum over time. However, the measurement is generally very time consuming and usually requires a test period of 6 days, which is not sufficient to support the inspection of the coating material on the line. Such tests are typically used for off-line container specimen testing.

              The VI.B. transmission test also lacks sensitivity in measuring the coating effectiveness of thin coatings on thick substrates. Since all gas flow rates pass through both the dressing and the substrate, variations in flow rates through the thick substrate cause variations that are not due to the barrier effectiveness of the dressing itself.

              VI.B. The inventor has discovered a faster and potentially more sensitive method of measuring the barrier properties of a coating. Specifically, it is a measurement of outgassing of the atmosphere or other gaseous or volatile components that rapidly separate within the vessel wall through the coating. The gaseous or volatile component may be any substance that actually outgases and can be selected from one or more specific substances to be detected. The components include volatile organic substances such as oxygen, nitrogen, air, carbon dioxide, water vapor, helium, alcohol, ketones, hydrocarbons, coating material precursors, substrate components, by-products when adjusting the coating materials such as volatile organic silicon, By-products during preparation of the coated substrate, other components that may be present by chance or caused by spiking the substrate, or mixtures or composites thereof may be included, but are not limited thereto.

              Surface diffusion and outgassing are synonymous. Each term refers to a fluid that was initially absorbed on / in a wall 346, for example a container wall, pulls a vacuum in the container with the wall (creating atmospheric movement as indicated by arrow 352 in FIG. 29) It refers to passing through the adjacent space by some kind of driving force, such as moving into the container. Outgassing or diffusion is considered dynamic and is a relatively rapid process. For a wall 346 that has significant resistance to permeate along the path 350, the molecules 354 closest to the interface 356 between the wall 346 and the barrier layer 348 are quickly removed by outgassing. It is thought that. This differential outgassing is implied by a number of molecules 354 that are proximate to the interface 356 and appear as outgassing, and a number of other molecules 358 away from the interface 356 that do not appear as outgassing.

              Thus, yet another embodiment is considered as a method of inspecting a barrier film on a material that outgases a vapor, including multiple procedures. Prepare a specimen of a substance that will outgas and at least partially be a barrier layer. A pressure differential is provided in the barrier layer so that at least some of the material that initially outgases is present on the high pressure side of the barrier layer. During the test, the released gas conveyed to the low pressure side of the barrier layer is measured to determine information about whether the barrier property exists or how effective the barrier layer is.

              VI.B. In the present method, the outgassing material may comprise a polymer compound, a thermoplastic compound, or one or more compounds having both properties. The outgassing material may include polyester, such as polyethylene terephthalate. The outgassing material may comprise a polyolefin, for the two examples polypropylene, a cyclic olefin copolymer, or a composite thereof. The outgassing material may be a composite of two different materials, at least one outgassing the vapor. One example is a two-layer structure of polypropylene and polyethylene terephthalate. Another example is a two-layer structure of a cyclic olefin copolymer and polyethylene terephthalate. These materials and composites are exemplary and any suitable material or complex of materials can be used.

              VI.B. Optionally, the outgassing material is provided in the form of a container having a wall having an outer surface and an inner surface, the inner surface enclosing the lumen. In this embodiment, the barrier layer adheres to the container wall and optionally to the inner surface of the container wall. The barrier layer may adhere to the container wall and also to the outer surface of the container wall. Optionally, the outgassing material can be provided in the form of a membrane.

              VI.B. The barrier layer may be the entire or partial coating of any barrier layer of this description. The blocking layer is less than 500 nm, or less than 300 nm, or less than 100 nm, or less than 80 nm, or less than 60 nm, or less than 50 nm, or less than 50 nm, or less than 40 nm. It may be a layer thickness, or a layer thickness of less than 30 nm, or a layer thickness of less than 20 nm, or a layer thickness of less than 10 nm, or a layer thickness of less than 5 nm.

In the case of VI.B. coated walls, the inventors have discovered that diffusion / outgassing can be used to determine the coating integrity. Optionally, a pressure differential can be provided in the barrier layer by at least partially evacuating the lumen or interior of the container. This can be done, for example, by connecting the lumen to a vacuum source via a duct and evacuating at least a portion of the lumen. For example, an uncoated PET wall 346 of a container that is exposed to ambient air will release certain oxygen and other gas molecules 354 from its inner surface sometime after evacuation. When the inside of the same PET wall is covered with the barrier coating material 348, the barrier coating material blocks, slows, or reduces the gas emission. This is true for the embodiment of the SiO _x barrier coating 348 that outgases less than the plastic surface. By measuring this differential outgassing between the coated PET wall and the uncoated PET wall, the barrier action of the covering material 348 with respect to the outgassing material can be quickly determined.

              VI.B. If the barrier coating 348 is incomplete due to known or theoretical holes, cracks, gaps, or areas with insufficient layer thickness / density / composition, the PET wall will , Selectively outgassing through the imperfections, thus increasing the total amount of outgassing. The collected gas is supplied primarily from dissolved gases or vaporizable components in the (lower) surface of the plastic material adjacent to the coating, not from outside the material. The amount of outgassing above the base level (eg, the amount passed / released by a standard dressing that has no imperfections, minimal imperfections, or average / acceptable imperfections) ) Can be measured by various methods to determine the integrity of the dressing.

              VI.B. The measurement can be performed, for example, by providing an outgassing measurement box that passes between the lumen and the vacuum source.

              VI.B. The measurement box can implement a variety of different measurement techniques. One example of a suitable measurement technique is the microflow technique. For example, the mass flow rate of the outgassing material can be measured. The measurement can be performed in the molecular flow mode of operation. As an exemplary measurement, there is a determination per time interval of the gas volume to be released through the barrier layer.

              VI.B. The release gas on the low pressure side of the barrier layer can be measured under conditions effective to determine the presence or absence of the barrier layer. Optionally, the conditions effective to determine the presence or absence of the barrier layer are less than 1 minute, or less than 50 seconds, or less than 40 seconds, or less than 30 seconds, or less than 20 seconds, or less than 15 seconds, or Test periods of less than 10 seconds, or less than 8 seconds, or less than 6 seconds, or less than 4 seconds, or less than 3 seconds, or less than 2 seconds, or less than 1 second are included.

              VI.B. Optionally, the measurement of the presence or absence of the barrier layer can be confirmed with at least six sigma level certainty during any of the time intervals identified above.

              VI.B. Optionally, measure the release gas on the low pressure side of the barrier layer under conditions effective to determine the barrier improvement (BIF) of the barrier layer and identify the same material without the barrier layer. Compare. BIF provides the same container, for example divided into two groups, adds a barrier layer to a group of containers, and barrier properties of containers with barrier membranes (eg gas release rate in micrograms per minute or another suitable It is possible to make a determination by performing the same test on a container without a blocking film and obtaining the ratio of the container property to the container without a blocking film. For example, if the gas release rate through the barrier film is one third of the gas release rate without the barrier film, the BIF of the barrier film is 3.

              VI.B. Optionally, a number of different gas emissions can be measured in the presence of one or more gases, for example nitrogen and oxygen in the case of the released atmosphere. Optionally, the outgassing of substantially all or all of the emitted gas can be measured. Optionally, physical measurements such as the combined mass flow rate of all gases can be used to measure the gas emissions of substantially all of the emitted gases simultaneously.

              VI.B. Measuring the number or partial pressure of an individual gas species (such as oxygen or helium) outgassing from the specimen can be performed more quickly than the barometric test, but the test rate depends on the outgassing Only a part is reduced to some extent in the measurement species. For example, if nitrogen and oxygen are outgassed from the PET wall at a ratio of about 4: 1 to the atmosphere, but only oxygen outgassing is measured (to obtain a sufficient statistical quality result to be detected) It may be necessary to perform the test 5 times longer compared to equivalent sensitivity tests that measure all species released from the vessel wall (in terms of the number of molecules).

              VI.B. For any sensitivity level, a method that reveals the volume of all species released from the surface is more desirable than a test that measures the release of certain species, such as oxygen atoms. It will be provided more quickly. As a result, outgassing data that is practical for in-line measurements is generated. Such in-line measurements are optionally feasible for all manufactured containers, thus reducing the number of unique or sequestering defects and potentially eliminating them (at least during the measurement).

              VI.B. In practical measurements, the factors that clearly change the amount of outgassing pass through imperfect seals, such as the seals of the containers that are loaded onto the vacuum receptacle when the vacuum is pulled in the outgassing test. Leaks. Leakage refers to a fluid that bypasses an uninterrupted wall of the substance, such as between a blood tube and its closure, between a syringe plunger and a syringe barrel, between a container and its lid, or filled with the container mouth (not filled). Refers to fluid passing between the container mouth and the seal when it is (due to a fully or misloaded seal). The term “leakage” usually refers to the movement of gas through the opening in the plastic material.

              VI.B. Leakage and permeation (in any situation if necessary) can be incorporated into the basic level of outgassing so that the container is properly loaded onto the vacuum receptacle (and therefore The loaded surface is intact and properly shaped and positioned), the container wall does not support an unacceptable level of permeation (and therefore the container wall is intact and properly shaped), and the coating Both that the material has sufficient barrier integrity is guaranteed by acceptable test results.

              VI.B. Gas can be released in various ways, for example by measuring atmospheric pressure (measuring the change in pressure in the vessel at any time after the initial evacuation) or by partial pressure of the gas released from the sample. Alternatively, it can be measured by measuring the flow rate. Equipment for measuring the mass flow rate in the molecular flow mode of operation is available. An example of this type of instrument that utilizes commercially available microflow technology is the product of ATC, Inc. of Indianapolis, Indiana. For detailed information on this known instrument, see US Pat. Nos. 5,861,546, 6,308,556, 6,848,828, and EP 1,356,260, which are incorporated herein by reference. See also Example 8 herein, which shows an example of outgassing measurements to quickly and reliably distinguish between polyethylene terephthalate (PET) tubes coated with a barrier film and uncoated tubes.

For containers made of polyethylene terephthalate (PET), the microfluidity is different for the SiO _x coated versus uncoated surface. For example, in Example 8 of the present specification, the microfluidity of PET was 8 micrograms or more after the test was performed for 30 seconds, as shown in FIG. The rate of this uncoated PET was much higher than the measured rate of the SiO _x coated PET, which was less than 6 micrograms after the test was performed for 30 seconds, as shown again in FIG.

VI.B. One possible explanation for this difference in flow rate is that uncoated PET contains about 0.7 percent of equilibrium moisture. This is a high moisture content that is believed to cause a high microfluidity. Depending on the SiO _x coated PET plastic, the SiO _x coated material may have a higher level of surface moisture than the uncoated PET surface. Under the test conditions, however, the barrier coating is believed to prevent additional desorption of moisture from the bulk PET plastic and reduce the microfluidity. The microfluidic rate of oxygen or nitrogen from uncoated PET plastic versus SiO _x coated PET is also expected to be distinguishable.

When using other substances, it may be appropriate to modify the above test for PET tubes. For example, polyolefin plastics tend to contain little moisture content. An example of a low moisture content polyolefin is TOPAS® cyclic olefin copolymer (COC), which has a much lower equilibrium moisture content (0.01 percent) and moisture permeability than PET. In the case of COC, uncoated COC plastic may have the same SiO _x coated COC plastic, or even less microfluidic rate. This appears to be due to the high surface moisture content of the SiO _x coating, the low equilibrium bulk moisture content, and the low permeability of the uncoated COC plastic surface. This makes it more difficult to distinguish between uncoated and coated COC materials.

The present invention reveals that microfluidic separation between uncoated COC plastic and SiO _x coated COC plastic improves and remains constant by exposing the COC material surface under test to vapor (uncoated and coated). To do. This is illustrated in Example 19 and FIG. 57 herein. The moisture exposure can be between 35% and 100% in a room controlled to relative humidity, or either direct exposure to a warm or humid source (humidifier) or cold source (nebulizer), the latter being preferred It may be just an exposure to relative humidity in the% range.

VI.B. Although the effectiveness and scope of the present invention is not limited according to the accuracy of this theory, vapor or other outgassing by vapor doping or spiking the uncoated COC plastics It suggests an increase compared to the already saturated SiO _x coated COC surface. This can also be accomplished by exposing the coated and uncoated tubes to other gases including oxygen, nitrogen, or mixtures thereof (eg, the atmosphere).

              VI.B Therefore, before measuring the emitted gas, the barrier layer may come into contact with moisture, for example water vapor. For example, water vapor can be provided by bringing the barrier layer into contact with the atmosphere having a relative humidity of 35% to 100%, alternatively 40% to 100%, alternatively 40% to 50%. Instead of / in addition to moisture, the barrier layer can be contacted with oxygen, nitrogen, or a mixture of oxygen and nitrogen (eg, air). The contact time may be 10 seconds to 1 hour, alternatively 1 minute to 30 minutes, alternatively 5 minutes to 25 minutes, alternatively 10 minutes to 20 minutes.

              Alternatively, for example, by exposing the left side of the wall 346 in FIG. 11 to a substance that absorbs the wall 346 and then releasing it to either the left side or the right side as shown in FIG. The wall 346 can be spiked or supplemented from the side opposite the barrier layer 348. Spiking a wall or other material 346 or the like from the left side by gas absorption and then measuring the outgassing of the spiked material from the right side (or vice versa) is distinct from transmission measurements. This is because, as opposed to measuring the material traveling through the complete path 350 through the wall when the gas through the coating is measured, the spiked material is within the wall 346 when measuring gas release. Because there is. The gas absorption may occur over a long period of time, as shown in one example before application of the dressing 348 and one example after application of the dressing 348 and before the gas release test.

VI.B. Another possible way to increase the separation of the microfluidic reaction between uncoated plastic and SiO _x coated plastic is to modify the measurement pressure and / or temperature. The reduction of the increase or the temperature of the pressure during outgassing measurement, there are cases where water molecules in the SiO _x coating COC is more relative binding than that of the uncoated COC. Thus, the emitted gas may be from 0.1 torr to 100 torr, alternatively from 0.2 torr to 50 torr, alternatively from 0.5 torr to 40 torr, alternatively from 1 torr to 30 torr, alternatively from 5 torr to 100 torr, alternatively from 10 torr to 80 torr, alternatively from 15 torr. It can be measured at a pressure of ~ 50 Torr. The released gas can be measured at a temperature of 0 ° C to 50 ° C, alternatively 0 ° C to 21 ° C, alternatively 5 ° C to 20 ° C.

VI.B. Another possible method for outgassing measurement in any embodiment of the present disclosure is the microcantilever measurement technique. Such techniques are believed to potentially be able to measure smaller gas release mass differences, such as 10 ^-12 g (picogram) to 10 ^-15 g (femtogram). This finer mass detection allows discrimination between the coated and uncoated surfaces and the type of coating material in less than 1 second, optionally in less than 0.1 seconds, and optionally in microseconds.

              VI.B. Microcantilever (MCL) sensors can in some cases respond to the presence or absence of substances that have been outgassed or otherwise provided due to bending, stretching, or movement or shape change due to the molecular absorption. is there. Microcantilever (MCL) sensors can be accommodated by resonant frequency shift in some cases. In other cases, the MCL sensor may be modified in both of these ways or in other ways. They can operate in different environments, such as gaseous environments, fluids, or vacuums. Within the gas, the microcantilever sensor can operate like an artificial nose, so that the bending pattern of the microfabricated array of eight polymer-coated silicon cantilevers exhibits different vapor characteristics from solvents, flavors, and beverages . The use of other types of electronic noses by any technology is also conceivable.

              Multiple MCL electronic designs, including piezoresistive, piezoelectric, and capacitive approaches, are applied and considered to make measurements of movement, shape change, or frequency change of the MCL exposed to chemicals.

              VI.B. One particular embodiment of the outgassing measurement can be performed as follows. At least one microcantilever having the property of moving or changing to a different shape in the presence of a gas releasing material is provided. The microcantilever is exposed to a gas releasing material under conditions effective to move or change the microcantilever to a different shape. This movement or a different shape is then detected.

              VI.B. As an example, the result of the deviation of the irradiated light at a point away from the cantilever by the movement of the microcantilever before or after exposure to the gas release of the microcantilever or by irradiation of an energy incident light from the shape change part It is possible to detect moving or different shapes by measuring Since the deflection width of the light beam under arbitrary conditions is proportional to the distance from the reflection point of the light beam to the measurement point, the shape is preferably measured at a point away from the cantilever.

              VI.B. Some suitable examples of energy incident light include photon light, electron light, or a composite of two or more of these. Alternatively, two or more different rays from the MCL can be reflected along different incidence and / or reflection paths to determine movement or shape change from one or more viewpoints. One specific type of incident energy beam is a coherent photon beam such as a laser beam. As used herein, “photons” are defined interchangeably to include wave energy and particle or photon energy itself.

              An alternative embodiment of VI.B. measurement utilizes the property of certain MCLs that change the resonant frequency when contacted with an amount of environmental material effective to achieve the resonant frequency change. This type of measurement can be performed as follows. At least one microcantilever is provided that resonates at different frequencies in the presence of the outgassing material. The microcantilever can be exposed to an outgassing material under conditions that are effective to resonate the microcantilever at different frequencies. The different resonance frequencies are then detected by appropriate means.

              VI.B. As an example, the different resonance frequencies can be detected by inputting energy into the microcantilever and inducing the resonance before and after exposing the microcantilever to outgassing. . The difference in resonance frequency of the MCL before and after exposure to outgassing is determined. Alternatively, instead of determining the difference in resonance frequency, an MCL can be provided that is known to have a particular resonance frequency when a sufficient concentration or amount of outgassing material is present. The resonance frequency, which indicates the presence of a different resonance frequency or a sufficient amount of the outgassing material, is detected using a harmonic vibration sensor.

As one example utilizing MCL technology for outgassing measurements, the MCL instrument can be mounted on a quartz tube connected to a vessel and a vacuum pump. Harmonic vibration sensors, Wheatstone bridge circuits, positive feedback controllers, excitation piezo actuators and phase locked loop (PLL) demodulators using commercially available piezoresistive cantilevers can be configured. For example,
"Picogram Mass Sensor Using Resonance Frequency Shift of Cantilever" by Hayato Sone, Yoshinori Fujinuma and Sumio Hosaka, Jpn.J. Appl.Phys.43 (2004) 3648,
See “Femtogram Mass Biosensor Using Self-Sensing Cantilever for Allergy Check” Jpn. 43 (2006) 2301 by Hayato Sone, Ayumi Ikeuchi, Takashi Izumi1, Haruki Okano2 and Sumio Hosaka.
Gelatin can be applied to one side of the microcantilever to prepare for detection of MCL. See, for example, Hans Peter Lang, Christoph Gerber, STM and AFM Studies on (Bio) molecular Systems: Unravelling the Nanoworld, Topics in Current Chemistry, Volume 285/2008. Water vapor desorption from the surface of the vacuum coating container is combined with gelatin, and the bending of the cantilever and the fluctuation of its resonance frequency occur, which are measured by the laser deviation from the surface of the cantilever. The change in mass between the uncoated container and the coated container can be solved in just a few seconds and is considered highly reproducible. The above materials related to cantilever technology are hereby incorporated by reference as disclosure of specific MCLs and instrumentation that can be used to detect and quantify the outgassing species.

              Alternative coatings for vapor detection (phosphoric acid) or oxygen detection can be applied to the MCL in addition to / in place of the gelatin coating described above.

VI.B. Furthermore, it is possible that the currently conceivable outgassing test setup can be combined with the SiO _x coating station. In such equipment, the measurement box 362 can be configured as shown above using the main vacuum channel for PECVD as the bypass 386. In one embodiment, the measurement box (usually 362) of FIG. 30 can be mounted on the container holder 50 or the like, in which case the bypass channel 386 is set as the main vacuum duct 94 and the measurement box 362 is a side channel. .

              VI.B. The combination of the measurement box 362 and the container holder 50 allows the outgassing measurement to be performed without interruption of the vacuum optionally used for PECVD. Optionally, the vacuum pump for PECVD can be operated for a short time, preferably a standardized period of time, to discharge some or all residual reactive gas remaining after the coating procedure (less than 1 torr) Pumping down, or flushing or diluting the process gas before pumping down with a small amount of air, nitrogen, oxygen, or other gas). As a result, it is possible to accelerate the combined processing of the coating material test concerning the presence or absence of the coating and the barrier level of the container.

              VI.B. The fact that outgassing measurements and all other described barrier measurement techniques can be used for many purposes besides / in addition to determining barrier effectiveness It will be highly appreciated by those skilled in the art after review of the document. For example, the test can be used on uncoated or coated containers to determine the degree of outgassing of the container wall. This test can be used, for example, when it is essential for the uncoated polymer to release less than a specified amount of gas.

              VI.B. For another embodiment, the gas emission measurements and all other described barrier membrane measurement techniques are used in a static test to measure gas emission fluctuations as the membrane crosses the measurement chamber. Or as an on-line test, it can be used for barrier coated or uncoated films. The test can be used to determine the continuity and barrier effectiveness of other types of coatings, such as aluminum coatings or EVOH barrier coatings or layers of packaging films.

              VI.B. Using the gas release measurement and all other described barrier film measurement techniques, for example, a barrier layer that is applied to the exterior of the container wall and investigated to release gas into the container wall. It is possible to determine the effectiveness of the barrier layer applied to the side wall of the container wall, the membrane, or the like opposite to the measuring box. In this case, the flow rate difference may be related to permeation through the barrier coating and then permeation through the substrate membrane or wall. This measurement may be particularly useful in cases where the substrate membrane or wall is fully permeable, for example, a very thin or porous membrane or wall.

              VI.B. Using the gas release measurement and all other described barrier membrane measurement techniques, the measurement box passes the measurement box and the layer adjacent to the gas release, passes the barrier layer, the The effectiveness of the barrier layer, which is the inner layer of the vessel wall, membrane, or the like, that may detect outgassing of the barrier layer or a more remote layer from the measurement box compared to the barrier layer. Judgment is possible.

              VI.B. Using the gas release measurements and all other described barrier film measurement techniques, the coverage of the pattern of barrier material on the outgassing material can be determined. Specifically, the degree of gas emission of a substance partially covered with a barrier is determined as a ratio of the amount of gas release predicted when no barrier film is present on any part of the substance.

              VI.B. A test technique that can be used in conjunction with any of the gas release test examples in the specification and that can be used to increase the rate of the gas release test of a container, includes a plunger or closure within the container. By inserting, the void volume of the container is reduced. Due to the reduction of the void volume, the container is pumped down more quickly to any vacuum level, thus reducing the test interval.

              VI.B. Many other uses for the currently described outgassing measurements and all other described barrier film measurement techniques will be apparent to those skilled in the art after review of this specification.

VII. PECVD-treated container
VII. The container is believed to have a barrier coating 90 (eg, as shown in FIG. 2) that is at least 2 nm, at least 4 nm, at least 7 nm, at least 10 nm, at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, It may be a SiO _x coating applied to a layer thickness of at least 100 nm, at least 150 nm, at least 200 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 600 nm, at least 700 nm, at least 800 nm, at least 900 nm. The coating material is up to 1000 nm, up to 900 nm, up to 800 nm, up to 700 nm, up to 600 nm, up to 500 nm, up to 400 nm, up to 300 nm, up to 200 nm, up to 100 nm, up to 90 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, The layer thickness may be up to 40 nm, up to 30 nm, up to 20 nm, up to 10 nm, and up to 5 nm. A specific range of layer thickness is explicitly contemplated, consisting of any one of the minimum layer thicknesses and any one or more of the maximum layer thicknesses. The layer thickness of SiO _x or other coating materials can be measured, for example, by transmission electron microscopy (TEM), and the composition can be measured by X-ray photoelectron spectroscopy (XPS).

VII. Depending on the selection of the material that impedes permeation of the coating material and the nature of the applied SiO _x coating material, the barrier properties may be affected. For example, two examples of substances that are generally intended to be excluded are oxygen and water / water vapor. Substances generally have better barrier properties to one than to one. This is believed, at least in part, because oxygen permeates the dressing through a mechanism different from water permeation.

VII. Permeation of oxygen is affected by physical characteristics such as layer thickness of the coating, the presence or absence of cracks, and other physical details of the coating. On the other hand, the permeation of water is generally considered to be influenced by chemical elements (such as the raw material of the coating material) rather than physical elements. The inventor also believes that at least one of the chemical elements is a high concentration of the OH portion of the dressing, thereby increasing the permeability of water through the barrier membrane. SiO _x coatings often contain OH moieties, and thus physically hard coatings that are rich in OH moieties are better at blocking oxygen than water. A physically hard carbon-based barrier film, such as amorphous carbon or diamond-like carbon (DLC), generally has a better barrier to water than a SiO _x coating. This is because the carbon-based barrier film generally has a low concentration of OH part.

VII. However, other factors such as its oxygen barrier and chemical similarity to glass and quartz lead to a preference for SiO _x coatings. Glass and quartz (when used as container raw materials) show two barriers to oxygen and water that have long been known to substantially inactivate many substances commonly contained in containers. It is a substance. Therefore, it is generally desirable to optimize moisture barrier properties, such as the water vapor transmission rate (WVTR) of the SiO _x coating material, rather than selecting a different or additional type of coating material that functions as a moisture permeation barrier layer.

VII. Methods that can be studied to improve the water vapor transmission rate of the SiO _x coating material are shown below.

              VII. The concentration ratio of organic moieties (carbon and hydrogen compounds) to OH moieties in the deposited coating can be increased. This can be done, for example, by increasing the proportion of oxygen in the feed gas (increasing the oxygen feed rate or decreasing the feed rate of one or more other components). The low expression rate of the OH part increases the degree to which the oxygen supply reacts with the hydrogen of the silicon source, generates more volatile water in the PECVD discharge, and traps the low concentration OH part in the coating material. It is believed to be a result that has been done / embedded.

              VII. In the PECVD process, high energy can be applied by increasing the plasma generation power level, applying the power for a longer period, or both. The increase in applied energy can distort the container to be treated to the extent that the tube absorbs the plasma generation power, so use with caution when coating plastic tubes or other equipment. It is essential. This is why RF power is desirable in the context of applications. The medical device is distorted by using the energy in a series of two or more pulses with a cooling period between them, cooling the container during application of energy, and applying the coating material for a short time (generally a thin layer). Reduced) by selection of the coating application frequency with minimal absorption on the substrate selected for coating and / or the application of one or more coatings between each energy application procedure It can be lost. For example, a high power pulse can be used with a duty cycle of 1 ms on and 99 ms off while continuously supplying the process gas. The process gas then becomes a coolant while maintaining flow between pulses. Another alternative is to add more magnetism to contain the plasma to increase the effective power application (in contrast to the wasted power that leads to heating or unwanted coatings, the power that actually leads to the gradual increase in coatings) By doing so, the power application apparatus is reset. By this means, more coating molding energy can be applied per total wattage of applied energy. See, for example, US Pat. No. 5,904,952.

VII. Oxygen post-treatment of the dressing can be applied to remove OH moieties from previously deposited dressings. The treatment may also be removal of residual volatile organosilicon compounds or silicon or oxidation of the coating material for additional SiO _x molding.

              VII. The plastic substrate tube can be preheated.

              VII. Different volatile sources of silicon, such as hexamethyldisilazane (HMDZ) can be used as some or all silicon sources. It is considered that this problem can be addressed by changing the gas supplied to HMDZ. This is because the compound does not have any oxygen moiety at the time of supply. One source of OH moiety in the HMDSO source coating is considered to be hydrogenation of at least some oxygen atoms present in unreacted HMDSO.

VII. Synthetic coatings such as carbon-based coatings combined with SiO _x can be used. This can be done, for example, by changing the reaction conditions or by adding a substituted or unsubstituted hydrocarbon such as an alkane, alkene, or alkyne to the feed gas and organosilicon compound. See, for example, US Pat. No. 5,904,952 in the relevant part: “Contains a low hydrocarbon content such as propyl to provide a carbon part, and most properties of the deposited film (light transmission). The binding analysis shows that the film is essentially silicon dioxide, but the use of methane, methanol, and acetylene produces a film that is essentially silicon. Inclusion of a small amount of gaseous nitrogen in the flow provides a nitrogen portion in the deposited film, increases the deposition rate, improves the transmission and reflection optical properties of the glass, and reacts to various amounts of N ₂ The addition of nitrous oxide to the gas stream increases the deposition rate and improves the optical properties, but the film Hardness tends to decrease.

VII. Diamond-like carbon (DLC) coatings can be formed as the primary or sole deposition coating. This can be done, for example, by changing the reaction conditions or by supplying methane, hydrogen, helium to the PECVD process. Since the reaction feed does not contain oxygen, there is no possibility of forming an OH moiety. For example, the SiO _x coating can be applied to the inside of the tube or the syringe barrel, and the external DLC coating can be applied to the outer surface of the tube or the outer surface of the syringe barrel. Alternatively, both SiO _x and DLC coatings can be applied as single layer or multiple layer coatings on inner tubes or syringe barrels.

VII. Referring to FIG. 2, the barrier membrane or other type of dressing 90 reduces the permeation of atmospheric gas through the inner surface 88 to the vessel 88. Alternatively, the barrier film or other type of dressing 90 reduces the contact of the contents of the container 88 with its inner surface 88. The barrier layer or other type of coating may be composed of, for example, SiO _x , amorphous (eg, diamond-like) carbon, or a composite thereof.

              VII. Any coating described herein can be used to coat a surface, eg, a plastic surface. Further, for example, the barrier film can be used as a barrier layer, such as a barrier film that blocks gas or fluid, and preferably blocks water vapor, oxygen and / or the atmosphere. It can also be used to prevent or reduce mechanical and / or chemical effects that can be exerted on the coated surface compound or composition when the surface is uncoated. Precipitation of the compound or composition can be prevented or reduced, eg, insulin precipitation or blood clotting or platelet activation.

VII.A. Vacuum blood collection container
VII.A.1.Tube
VII.AI With reference to FIG. 2, the container 80 and the like are shown in more detail. The illustrated container 80 may be generally tubular and has an opening 82 at one end of the container and a closed end 84 on the opposite side. The container 80 also has a wall 86 that defines an inner surface 88. One example of such a container 80 is a medical sample tube, such as a vacuum blood collection tube, typically used by a phlebotomy specialist to receive a venipuncture sample of patient blood for use in medical research, for example.

              VII.A.1. The container holder 80 may be made of, for example, a thermoplastic material. Some examples of suitable thermoplastic materials include polyethylene terephthalate or polyolefins, such as polypropylene or cyclic polyolefin copolymers.

VII.A.1. The container 80 can be manufactured by any suitable method such as injection molding, blow molding, machining, manufacturing from tube stock, or other suitable means. PECVD can be used to shape the dressing on the inner surface of the SiO _x.

              VII.A.1. When intended for use as a vacuum blood collection tube, the vessel 80 is subjected to a substantially total internal vacuum that does not substantially deform upon exposure to an external or atmospheric pressure of 760 Torr and other coating processing conditions. It is desirable to have strength to withstand. This property is produced in a thermoplastic container 80 with a suitable material having suitable dimensions and a glass transition temperature higher than the temperature of the coating treatment, such as a cylindrical wall 86 having a sufficient wall thickness with respect to diameter and material. Can be provided by providing a container 80.

              VII.A.1. Medical containers / containers such as specimen collection tubes and syringes are relatively small and are injection molded with relatively thick walls that can be evacuated without being crushed by the ambient atmospheric pressure. . Therefore, it is more robust with carbonated soft drink bottles or other larger thinner walled plastic containers. A specimen collection tube designed for use as a vacuum vessel is typically configured to withstand full vacuum during storage and can be used as a vacuum chamber.

              VII.A.1. Adapting such a container to its own vacuum chamber may eliminate the need to place the container in a PECVD processing vacuum chamber, which is usually performed at very low pressures. By using the container as its own vacuum chamber, the processing time is quick (because it is not necessary to mount / unload components from individual vacuum chambers), and the apparatus setting can be simplified. Further, for specific embodiments, the device can be gripped (to align with a gas pipe or other device) and the device can be created (with the vessel holder attached to a vacuum pump). For this purpose, a container holder is conceivable which seals and moves the device between the mold and the subsequent processing procedure.

              VII.A.1. Container 80, used as a vacuum blood collection tube, is evacuated to a useful vacuum for the intended application, while atmospheric or other atmospheric gases remain It should be designed to withstand external atmospheric pressure without significantly leaking into the tube (by bypassing the closure) or penetrating through the wall 86. If the container 80 at the time of molding does not meet this requirement, it can be treated by coating the inner surface 88 with a barrier film or other type of coating material 90. Treat and / or coat the inner surface of these devices (such as specimen collection tubes and syringe barrels) to provide various properties that provide advantages over and / or mimic existing glassware over existing polymer devices Is desirable. It is desirable to measure various properties of the device before and / or after treatment or coating.

VII.A.1.a. Coating materials deposited from organosilicon precursors using in situ polymerized organosilicon precursors
VII.A.1.a. For example, a treatment in which a lubricating coating material is applied to a substrate such as the inside of the barrel of the syringe can be considered. The treatment provides application to / near the substrate with a layer thickness of 1-5000 nm, optionally 10-1000 nm, optionally 10-200 nm, optionally 20-100 nm, and lubricated surface of the described precursor. Optionally comprising cross-linking or polymerisation (or both) in a PECVD process. The dressing applied by this process is also considered novel.

VII.A.1.a.Si _w O _x C _y H _z coating material applied by PECVD (w is 1, x in this formula is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to 2 About 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9) have further utility as a hydrophobic coating material. This type of dressing is considered hydrophobic and does not depend on functioning as a lubricious dressing. A coating or treatment is defined as “hydrophobic” if it reduces the wetting tension of the surface relative to the corresponding uncoated or untreated surface. Hydrophobicity is therefore a function of both the untreated substrate and the process.

The degree of hydrophobicity of the coating varies depending on its composition, properties, or deposition method. For example, SiOx dressing is a hydrocarbon little free at all are hydrophilic than Si _w O _x C _y H _z coating material having a value of substituents as defined herein. In general, the higher the CH _x content (eg, CH, CH ₂ , or CH ₃ ) content of the dressing, the weight, volume, or molar ratio of the dressing compared to its silicon content Increased hydrophobicity.

              The hydrophobic coating is very thin and is at least 4 nm, or at least 7 nm, or at least 10 nm, or at least 20 nm, or at least 30 nm, or at least 40 nm, or at least 50 nm, or at least 100 nm, or at least 150 nm, or at least 200 nm, or It may have a layer thickness of at least 300 nm, or at least 400 nm, or at least 500 nm, or at least 600 nm, or at least 700 nm, or at least 800 nm, or at least 900 nm. The coating material is up to 1000 nm, up to 900 nm, up to 800 nm, up to 700 nm, up to 600 nm, up to 500 nm, up to 400 nm, up to 300 nm, up to 200 nm, up to 100 nm, up to 90 nm, up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, The layer thickness may be up to 40 nm, up to 30 nm, up to 20 nm, up to 10 nm, and up to 5 nm. A specific range of layer thickness is explicitly contemplated, consisting of any one of the minimum layer thicknesses and any one or more of the maximum layer thicknesses.

VII.A.1.a. One practical use of such a hydrophobic coating is to isolate a thermoplastic tube wall made of, for example, polyethylene terephthalate (PET) from the collected blood in the tube. The hydrophobic coating material can be applied on the hydrophilic SiO _x coating material on the inner surface of the tube. The SiO _x coating increases the barrier properties of the thermoplastic tube, and the hydrophobic coating changes the interfacial energy of the blood contact surface with the tube wall. The hydrophobic dressing can be produced by providing a precursor selected from those identified herein. For example, the hydrophobic coating precursor may be composed of hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).

VII.A.1.a. Another use of hydrophobic coatings is the creation of glass cell preparation tubes. The tube has a wall defining a lumen and a hydrophobic coating on the inner surface of the glass wall and contains a citrate reagent. The hydrophobic dressing can be generated by providing a precursor selected from those identified elsewhere herein. As another example, the hydrophobic coating precursor may comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS). Another raw material for hydrophobic coatings includes the following formula alkyltrimethoxysilane:
R-Si (OCH ₃ ) ₃
Each R in the formula is a hydrogen atom or an organic substituent, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne, epoxide, and the like. Alternatively, a complex of two or more of these may be considered.

              VII.A.1.a. Using the alkyltrimethoxysilane precursors described above, the precursors are condensed (removing ROH by-products) and combined by combining acid or base catalysis and heating. Polymer can be molded. This can optionally be further cross-coupled via alternative methods. One specific example is Shimojima et. Al. J. Mater. Chem., 2007, 17, 658-663.

VII.A.1.a.Si _w O _x C _y H _z coating is applied as a subsequent coating after the SiO _x barrier coating is applied to the inner surface 88 of the container 80, especially when the surface is a fluid organo In the case of a siloxane compound, a lubricious surface can be provided at the end of the coating treatment.

VII.A.1.a. Optionally, post-curing after PECVD treatment is possible after application of the Si _w O _x C _y H _z coating. Radiation, including UV-initiated (free radical or cationic), electron beam (E-beam) and thermal properties described in “Development Of Novel Cycloaliphatic Siloxanes For Thermal And UV-Curable Applications” (Ruby Chakraborty Dissertation, can 2008) A curing approach is available.

              VII.A.1.a. Another approach to providing a lubricious coating is the use of a silicon release agent in the injection molding of the thermoplastic container to be lubricated. For example, it is contemplated that any such release agent and potential monomer that results in the formation of an in-situ thermal lubricity coating during the molding process can be used. Alternatively, the same results can be achieved by doping the above-described monomers into a traditional release agent.

VII.A.1.a. Lubricious surfaces are particularly contemplated for the inner surface of the syringe barrel, as further described below. The lubricious inner surface of the syringe barrel is caused by the plunger sliding force required to advance the plunger in the barrel during syringe operation, or for example, the degradation of the lubricant between the plunger and the barrel After the interstitial lubricant is pushed away by the filled syringe plunger or the sticking to the barrel is generated, the starting force for starting the movement of the plunger can be reduced. As described elsewhere herein, the Si _w O _x C _y H _z coating (where w is 1, x is about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9) can also be applied to the inner surface 88 of the container 80 to improve the adhesion of the subsequent SiO _x coating material.

VII.A.1.a. Therefore, the covering 90 is composed of a SiO _x layer and a Si _w O _x C _y H _z layer (w is 1, x in the formula is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is 6 to about 9. The Si _w O _x C _y H _z layer can be deposited between the SiO _x layer and the container inner surface. Alternatively, the SiO _x layer can be deposited between the Si _w O _x C _y H _z layer and the container inner surface. Alternatively, three or more layers that alternate or transition between these two coating compositions can be used. Alternatively, the SiO _x layer can be deposited adjacent to the Si _w O _x C _y H _z layer with at least one other intervening layer or remotely. Alternatively, the SiO _x layer can be deposited adjacent to the inner surface of the container. Alternatively, the Si _w O _x C _y H _z layer can be deposited adjacent to the inner surface of the container.

VII.A.1.a. In this document, another means considered as adjacent SiO _x layer and Si _w O _x C _y H _z layer is Si _w O _x C _y H _z (w is 1, x is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is about 6 to about 9. Is a stepwise compound for SiO _x . The graded compositions are those separated layers with intermediate composition transitions or interfaces between Si _w O _x C _y H _z and SiO _x or between Si _w O _x C _y H _z and SiO _x Those separated layers with an intermediate singular layer of intermediate composition, or continuously or stepwise from the composition of Si _w O _x C _y H _z to that of SiO _x as the coating proceeds in the normal direction It may be a single layer that changes to

VII.A.1.a. The stage of the staged composite may proceed in either direction. For example, the composition Si _w O _x C _y H _z can be applied directly to the substrate and can transition to a composition that is remote from the SiO _x surface. Alternatively, the composition SiO _x can be applied directly to the substrate and can be transitioned to a composition that is remote from the Si _w O _x C _y H _z surface. A transitional coating material is considered especially when a coating material with a certain composition has better adhesion to the substrate than others, in which case the composition with excellent adhesion may be applied directly to the substrate, for example. is there. It is believed that the more distant portions of the graded dressing are less compatible with the substrate than the adjacent portions of the graded dressing. This is because the properties change gradually at every point of the dressing, so that adjacent parts that are almost the same depth as the dressing have almost the same composition and are at substantially different depths. Parts that are physically separated may have more diverse properties. In addition, the coating part that forms a better barrier against material transfer to / from the substrate is applied directly on the substrate, and the remote coating part forms a blocking film with poor function. It is believed that the membrane can be prevented from being contaminated by substances that are to be excluded or disturbed.

              VII.A.1.a. Instead of being gradual, the dressing can optionally transition abruptly from one layer to another without a substantial gradient in composition. Such a covering material can be generated, for example, by providing the gas to generate a layer that is in a steady flow in a non-plasma state, and then pressurizing for a short time with plasma discharge to form the covering material on the substrate. . When applying a subsequent coating, remove the gas for the first coating, then apply the gas for the next coating in a steady manner before pressurizing the plasma and again, almost again at the interface. Form a separate layer on the surface of the substrate or the outermost first coating without step transitions.

VII.A.1.b. Citrate blood tubes with walls coated with a hydrophobic coating deposited from an organosilicon precursor
VII.A.1.b. Another example is a cell preparation tube having a wall coated with a hydrophobic coating on its inner surface and containing a hydrous sodium citrate reagent. The hydrophobic coating material can be applied onto the hydrophilic SiO _x coating material on the inner surface of the tube. The SiO _x coating increases the barrier properties of the thermoplastic tube, and the hydrophobic coating changes the interfacial energy of the blood contact surface with the tube wall.

              VII.A.1.b. The wall is made of a thermoplastic material and has an inner surface that defines a lumen.

VII.A.1.b. The blood collection tube described in Example VII.A.1.b has a first SiO _x layer on the tube inner surface applied as described herein, and oxygen It can function as a blocking layer and extend the storage period of a vacuum blood collection tube made of a thermoplastic material. Second Si _w O _x C _y H _z layer (where w is 1, x is about 0.5 to 2.4, y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is 6 to about 9) can be applied on the barrier layer of the tube inner surface to provide a hydrophobic surface. The dressing is effective in reducing platelet activation of plasma treated with sodium citrate additive exposed to the inner surface compared to an uncoated wall of the same type.

VII.A.1.b. PECVD can be used to mold a dressing having the following structure on the inner surface: Si _w O _x C _y H _z . Unlike traditional citrate blood collection tubes, these blood collection tubes with a hydrophobic Si _w O _x C _y H _z layer are fired on the silicon on the vessel wall, which is commonly used to produce the hydrophobic surface of the tube Does not require a covering material to be used.

              VII.A.1.b. Both layers can be applied using the same precursor, eg, HMDSO or OMCTS, and different PECVD reaction conditions.

              VII.A.1.b. Sodium citrate anticoagulant is then placed in the tube and evacuated and sealed using the closure to create a vacuum blood collection tube. The ingredients and formulas of the agent are known to those skilled in the art. The hydrous sodium citrate reagent adheres to the lumen of the tube in an amount effective to inhibit clotting of blood introduced into the tube.

VII.A.1.c. SiO _x barrier film coated two-layer plastic container-COC, PET, SiO _x layer
VII.A.1.c. Another example is a container having a wall that at least partially encloses a lumen. The wall has an inner polymer layer encapsulated with an outer polymer layer. One polymer layer is a layer of cyclic olefin copolymer (COC) resin that defines water vapor barrier properties with a layer thickness of at least 0.1 mm. Another polymer layer is a layer of polyester resin with a layer thickness of at least 0.1 mm.

The VII.A.1.c. the walls include SiO _x oxygen barrier layer having a thickness of about 10 to 500 Angstroms.

VII.A.1.c. In the alternative embodiment illustrated in FIG. 36, the container 80 may be a double-walled container having an inner wall 408 and an outer wall 410, each using the same or different material as a raw material. There is. One particular example of this type consists of a wall molded from a cyclic olefin copolymer (COC) and other walls molded from a polyester such as polyethylene terephthalate (PET), on the inner surface 412 as described above. May have a SiO _x coating material. If necessary, a connecting covering or connecting layer can be inserted between the inner and outer walls to promote adhesion between them. An advantage of this wall structure is that it is possible to form a composite having the respective properties of each wall by combining walls having different properties.

VII.A.1.c. As an example, the inner wall 408 can be generated from a PET coating on the inner surface 412 having a SiO _x barrier layer, and the outer wall 410 can be generated from COC. As shown elsewhere in this specification, a PET coating with SiO _x is a good oxygen barrier layer, while COC is a good water vapor barrier layer, which reduces the water vapor transition rate (WVTR). The synthesis container may have good barrier properties for both oxygen and water vapor. This structure is contemplated, for example, for vacuumed medical specimen collection tubes that contain aqueous reagents at manufacture and have a substantial shelf life, and the outward direction of water vapor through the synthetic wall during the shelf life It has a blocking property to prevent the transfer to the inside or the inward transfer of oxygen or other gas.

VII.A.1.c. As another example, the inner wall 408 can be generated from a COC coating on an inner surface 412 having a SiO _x barrier layer, and the outer wall 410 can be generated from PET. This structure is contemplated for prefilled syringes that contain, for example, an aqueous sterile solution at the time of manufacture. The SiO _x barrier layer prevents oxygen from entering the syringe through the wall. The COC inner wall prevents intrusion or release of other substances, for example water, and thus prevents water in the aqueous sterile liquid from leaching out of the wall material into the syringe. The inner wall of the COC is also conceived to prevent water from the aqueous sterile solution from permeating through the syringe (and thus the aqueous sterile solution is undesirably concentrated). Prevents other fluids from entering through the syringe wall and making the contents non-sterile. It is also believed that the COC inner wall is useful for reducing the plunger breaking force or friction against the inner wall of the syringe.

VII.A.1.d.Method of manufacturing a two-layer plastic container-COC, PET, SiO _x layer
VII.A.1.d. Another embodiment is the manufacture of a container having an inner polymer layer encapsulated by an outer polymer layer and one wall made of COC and the other made of polyester. Is the method. The said container is manufactured by the process including the process of introduce | transducing a COC layer and a polyester resin layer into an injection mold through a concentric injection nozzle.

              VII.A.1.d. As an optional additional step, PECVD of the amorphous carbon coating to the vessel as an inner coating, outer coating, or intermediate coating located between the layers Application may be mentioned.

VII.A.1.d. An optional additional procedure is the application of a SiO _x barrier layer to the inner surface of the vessel wall where SiO _x is defined as described above. Another optional additional procedure includes post-treatment of SiO _{x with} a process gas consisting essentially of oxygen and essentially free of volatile silicon compounds.

VII.A.1.d. Optionally, the SiO _x coating can be formed, at least in part, from a silazane feed gas.

              36, as an example, the container 80 shown in FIG. 36 is formed by injection molding the inner wall into the first mold cavity, and then the core and the molded inner wall are larger than the first mold cavity. It is possible to mold from the inside to the outside by taking out the second wall to the second mold cavity and then injection molding the outer wall to the inner wall in the second mold cavity. Optionally, a tie layer can be provided to the outer surface of the molded inner wall prior to overmolding the outer wall to the tie layer.

              VII.A.1.d. or the container 80 shown in FIG. 36, as an example, the first nucleus is inserted into the mold cavity, the outer wall is injection-molded in the mold cavity, and then the first nucleus is It is possible to mold from the outside to the inside by inserting a second nucleus smaller than the molded first wall and then inserting the second wall into the mold cavity and then subjecting the inner wall to injection molding. Optionally, a tie layer can be provided to the inner surface of the molded outer wall prior to overmolding the inner wall to the tie layer.

              The container 80 shown in VII.A.1.d. or FIG. 36 may be manufactured by two-stage molding. As an example, this can be performed by injection molding the member for the inner wall from the inner nozzle and the member for the outer wall from the concentric outer nozzle. Optionally, a tie layer can be provided from a third concentric nozzle attached between the inner nozzle and the outer nozzle. Each of the wall materials can be simultaneously supplied by the plurality of nozzles. One useful means is to begin feeding the outer wall material through the outer nozzle shortly before feeding the inner wall material through the inner nozzle. If an intermediate concentric nozzle is present, the process sequence begins with the outer nozzle, and then continues with the intermediate nozzle and then with the inner nozzle. Alternatively, the supply start order starts from the internal nozzle and can proceed outward as opposed to the above.

VII.A.1.e. Glass barrier coating
VII.A.1.e. Another example is a container that includes a container, a barrier covering, and a closure. The container is generally tubular and is made from a thermoplastic material. The container has a mouth and a lumen that is at least partially bounded by a wall having an inner surface that joins the lumen. An at least essentially continuous glass barrier coating is present on the inner surface of the wall. A closure covers the mouth and isolates the lumen of the container from the ambient atmosphere.

              VII.A.1.e. The container 80 can be made from any type of glass used for medical or research purposes, such as, for example, soda lime glass, borosilicate glass, or other glass formulations. Other containers having any shape or size manufactured from any material are also contemplated for use with the system 20. One of the functions of the coating of the glass container is from the glass to the contents of the container (such as reagent or blood in the vacuum blood collection tube), into the glass of ions as intentional or impurities (sodium, calcium, etc.) Reducing the intrusion of. Another function of covering the whole or part of the glass container, for example selectively contacting the other part while sliding on the surface, is the insertion of a stop member or path of a sliding component, for example a piston in a syringe. Or to provide lubricity to the dressing for ease of removal. Yet another reason for coating the glass container is to prevent the reagent in the container or the intended specimen (blood, etc.) from adhering to the container wall or increasing the coagulation rate of blood in contact with the container wall. It is done.

              VII.A.1.e.i. A related example is the container described in the previous paragraph, wherein the barrier coating is made of soda-lime glass or borosilicate glass or other type of glass.

VII.A.2. Stopping member
VII.A.2. FIGS. 23-25 illustrate a container 268, which may be a vacuum blood collection tube having a closure 270 that isolates the lumen 274 from the surrounding environment. The closure 270 includes an inner surface 272 that is exposed to the lumen 274 of the container 268 and a contact inner surface 276 that contacts the inner surface 278 of the container wall 280. In the illustrated embodiment, the closure 270 is an assembly of a stop member 282 and a shield 284.

VII.A.2.a. Method of applying the lubricity coating in the vacuum chamber
VII.A.2.a. Another embodiment is a method of applying a coating material on an elastomeric stop member 282 or the like. The stop member 282 is separated from the container 268 and is substantially left in the vacuum chamber. A reaction mixture is prepared comprising a plasma generating gas, ie, an organosilicon compound gas, optionally an oxidizing gas, and optionally a hydrocarbon gas. Plasma is generated in the reaction mixture in contact with the stop member. Si _w O _x C _y H _z coating (where w is 1, x is about 0.5 to about 2.4, y is about 0.6 to about 3, z is about 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is 6 to about 9) are deposited on at least a portion of the stop member.

              VII.A.2.a. In the illustrated embodiment, the wall contact inner surface 276 of the closure 270 is coated with a lubricious coating 286.

VII.A.2.a. In some embodiments, the Si _w O _x C _y H _z coating includes one or more components of the stop member (such as a stop member or a metal ion component of a container wall) ) Has an effect of reducing the permeability to the container cavity. A particular type of elastomeric composition useful in making stop member 282 includes a trace amount of one or more metal ions. The ions should not migrate into the lumen 274 or contact the container contents in large amounts, especially when the sample container 268 is used for sample collection for trace metal analysis. . For example, coatings that are relatively free of organic inclusions (ie, y and z are low or zero) are considered particularly useful as metal ion blocking films in this application. For silica stone powder as a metal ion blocking membrane, see, for example, `` The Effect of Interfacial Chemistry on Metal by Anupama Mallikarjunan, Jasbir Juneja, Guangrong Yang, Shyam P. Murarka, and Toh-Ming Lu, incorporated herein by reference. See Ion Penetration into Polymeric Films "Mat. Res. Soc. Symp. Proc., Vol. 734, pp. B9.60.1 to B9.60.6 (Materials Research Society, 2003), US EP0697378 A2. However, some organic inclusions may be useful in providing a more elastic dressing and attaching the dressing to the elastomeric surface of the stop member 282.

VII.A.2.a. In some embodiments, the Si _w O _x C _y H _z coating includes a first layer and a second layer in which the first / inner layer 288 is bonded to the elastomeric stop member 282. This has the effect of reducing the permeability of one or more components of the stop member 282 to the container cavity. The second layer 286 can be joined to the inner wall 280 of the container, and when the stop member 282 is loaded on / in the container 268, the second layer 286 is interposed between the stop member 282 and the inner wall 280 of the container. It is effective in reducing friction. Such composites are described elsewhere in this specification in connection with syringe dressings.

              VII.A.2.a. Alternatively, the first layer 288 and the second layer 286 are defined by a transitional coating, in which case the y and z values in the first layer are those of the second layer. Become bigger.

VII.A.2.a. The Si _w O _x C _y H _z coating material can be applied substantially by PECVD as described above, for example. The Si _w O _x C _y H _z coating material is, for example, a layer thickness of 0.5 to 5000 nm (5 to 50,000 angstroms), or a layer thickness of 1 to 5000 nm, or a layer thickness of 5 to 5000 nm, or a layer thickness of 10 to 5000 nm, or a layer thickness 20-5000 nm, or layer thickness 50-5000 nm, or layer thickness 100-5000 nm, or layer thickness 200-5000 nm, or layer thickness 500-5000 nm, or layer thickness 1000-5000 nm, or layer thickness 2000-5000 nm, or layer thickness 3000 May be ~ 5000nm or layer thickness 4000 ~ 10,000nm.

              VII.A.2.a. There are certain advantages associated with plasma-coated lubrication layers that are superior to thicker (> 1 micron) conventional spray-coated silicon lubricants. Plasma coatings are much less migratory to blood compared to nebulized or micron silicon. This is because the plasma coating material is very low in quantity and may be a closer application to the coating surface and a better bond in place.

              VII.A.2.a. PECVD coating to provide a lower resistance than adjacent surface slide or adjacent fluid flow micro-coating because the plasma coating tends to provide a smoother surface Nano-coating can be considered.

VII.A.2.a. Another example is to apply a Si _w O _x C _y H _z coating on an elastomeric stop member. The stop member can be used, for example, to close the container. The method consists of several parts. The stop member is substantially placed in the vacuum chamber. A reaction mixture is prepared comprising a plasma generating gas, ie, an organosilicon compound gas, optionally an oxidizing gas, and optionally a hydrocarbon gas. A plasma is generated in the reaction mixture. The stop member contacts the reaction mixture, and a Si _w O _x C _y H _z coating is deposited on at least a portion of the stop member.

              VII.A.2.a. In order to obtain higher y or z values in the practice of the process, it is believed that the reaction mixture may consist of hydrocarbon gas, as described above and further below. Optionally, the reaction mixture may contain oxygen if y and z values are considered low or x values are considered high. Alternatively, the reaction mixture may be essentially free of oxidizing gas, particularly to reduce oxidation and increase the values of y and z.

              VII.A.2.a. In the practice of this method, it is not necessary to project the reaction mixture onto the concave surface of the stop member to cover a particular embodiment of the stop member, such as the stop member 282, for example. Conceivable. For example, the surface 276 that contacts the wall of the stop member 282 and the inwardly facing surface 272 are essentially convex and can therefore be easily processed by batch processing. In that case, multiple stop members 82 and the like may be located and processed in a single reaction chamber that is substantially vacuum. Further, in some embodiments, the dressings 286 and 288 may not need to be shown as stronger barrier films than oxygen or water on the inner surface 280 of the vessel 268. This is because the material of the stop member 282 is responsible for most of this function.

              VII.A.2.a. Many variations of the stop member and coating of the stop member are possible. The stop member 282 can contact the plasma. Alternatively, the plasma can be shaped upstream of the stop member 282 that produces a plasma product, and the plasma product can contact the stop member 282. The plasma can be generated by exciting the reaction mixture with electromagnetic energy and / or microwave energy.

              VII.A.2.a. Variations of the reaction mixture are conceivable. The plasma generating gas may contain an inert gas. The inert gas may be, for example, argon, helium, or other gases described in this disclosure. The organosilicon compound gas may include / are HMDSO, OMCTS, other organosilicon compounds described in this disclosure, or a composite of two or more of these. The oxidizing gas may be oxygen, other gases described in this disclosure, or a composite of two or more of these. The hydrocarbon gas may be, for example, methane, methanol, ethane, ethylene, ethanol, propane, propylene, propanol, acetylene, or a composite of two or more of these.

VII.A.2.b. Application of Group III or Group IV elements and carbon coating on the stop member by PECVD
VII.A.2.b. Another embodiment is a method of applying a coating of carbon or a composition comprising one or more Group III or Group IV elements to an elastomeric stop member. To perform the method, a stop member is positioned in the deposition chamber.

              VII.A.2.b. A reaction mixture comprising a plasma generating gas having a gas source that is a Group III element, a Group IV element, or a combination of two or more thereof is provided in a deposition chamber. The reaction mixture optionally includes an oxidizing gas and optionally includes a gaseous compound having one or more C—H bonds. Plasma is generated in the reaction mixture, and the stop member contacts the reaction mixture. A coating material that is a Group III element or compound, a Group IV element or compound, or a composite of two or more thereof is deposited on at least a portion of the stop member.

VII.A.3. Plastic container with a stop member with a barrier covering that maintains a 95% vacuum for 24 months
VII.A.3. Another example is a container that includes a container, a barrier covering, and a closure. The container is generally tubular and is made from a thermoplastic material. The container has a mouth and a lumen that are at least partially bounded by walls. The wall has an inner surface that joins the lumen. At least an essentially continuous barrier coating is applied to the inner surface of the wall. The barrier coating is effective in providing a substantial shelf life. A closure is provided to cover the mouth of the container, and the lumen of the container is isolated from the ambient atmosphere.

              VII.A.3. Referring to FIGS. 23-25, a container 268, such as a vacuum blood collection tube or other container, is shown.

              VII.A.3. The container in this example is a generally tubular container having at least an essentially continuous barrier covering and a closure. The container is made of a thermoplastic material and has a mouth and a lumen that are at least partially bounded by a wall having an inner surface that joins the lumen. The barrier coating is deposited on the wall inner surface and at least 95% of the initial vacuum level of the container, or at least during a shelf life of at least 24 months, optionally at least 30 months, optionally at least 36 months. Effective to maintain 90%. A closure covers the mouth of the container and isolates the lumen of the container from the ambient atmosphere.

              VII.A.3. The closure, such as the closure 270 or other type of closure shown in the figure, is partly to maintain a vacuum and / or contain the specimen and to its oxygen Provided to limit / prevent exposure or contamination. FIGS. 23-25 are based on the figures contained in US Pat. No. 6,602,206, but the discovery is not limited to this or any other particular type of closure.

              VII.A.3. The closure 270 comprises an inner surface 272 that is exposed to the lumen 274 of the container 268 and a contact inner surface 276 that contacts the inner surface 278 of the container wall 280. In the illustrated embodiment, the closure 270 is an assembly of a stop member 282 and a shield 284.

              VII.A.3. In the illustrated embodiment, the stop member 282 defines the wall contact inner surface 276 and the inner surface 278, while the shield is largely or entirely of the container 268 that has been stopped. There is an external pressure difference between the inside and outside of the container 268 when the container 268 is opened and the atmosphere suddenly increases or decreases to equalize the pressure difference. For this reason, the person who removes the closure part 270 is shielded from being exposed to the contents released from the container 268.

VII.A.3. Further, it is believed that the dressing on the container wall 280 and the wall contact surface 276 of the stop member can be aligned. The stop member can be coated with a lubricious silicon layer, for example, the container wall 280 made of PET or glass can be coated with a harder SiO _x layer or a lower SiO _x layer and a lubricious protective film.

VII.B.Syringe
VII.B. The above description primarily refers to the application of a barrier coating to a tube having one permanent closed end, such as a blood collection tube or more generally a specimen collection tube 80, for example. The apparatus is not limited to such equipment.

VII.B. Another example of a suitable container, shown in FIGS. 20-22, is a syringe barrel for a medical syringe 252. Such a syringe 252 may be prefilled with saline, pharmaceuticals, or the like used in medical technology. The pre-filled syringe 252 can also be a SiO _x barrier layer or other type of inner surface 254 that can keep the contents of the pre-filled syringe 252 out of contact with the syringe plastic, such as a syringe barrel 250 during storage. It is thought that profit can be obtained from the covering material. The barrier film or other type of dressing can be used to prevent the plastic component from leaching through the inner surface 254 into the contents of the barrel.

              VII.B. When a syringe barrel 250 is molded, generally, a rear end portion 256 for receiving the plunger 258 and a hypodermic needle for receiving the substance / material for administering the contents of the syringe 252 into the syringe 252 The front end 260 that receives the nozzle or tab may be open. However, before the prefilled syringe 252 is used, the front end 260 is optionally capped, the plunger 258 is optionally mounted in place, and both ends of the barrel 250 are closed There is. The purpose of installing the lid 262 is to handle the syringe barrel 250 or assembled syringe, or remove the lid 262 (optionally) a hypodermic needle or other transport conduit to prepare the syringe 252 for use. In some cases, the pre-filled syringe 252 is maintained at a predetermined position during the storage period until the front end 260 is mounted.

VII.B.1. Assembly
VII.B.1. FIG. 42 is also a syringe that can be used in conjunction with, for example, the embodiments of FIGS. 21, 26, 28, 30, and 34 and is adapted for use with the container holder 450 of the drawings. The barrel structure is shown.

              VII.B.1. FIG. 50 is an exploded view of the syringe, and FIG. 51 is an assembly view of the syringe. The syringe barrel can be processed, for example, with the container processing and inspection devices of FIGS. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.

VII.B.1. Installation of the lid 262 makes the barrel 250 a closed container that can be dispensed with the SiO _x barrier layer or other type of coating on the inner surface 254 of the previously installed device, and optionally Providing a dressing on the lid interior 264 and bridging the interface between the lid interior 264 and the barrel front end 260. A suitable device suitable for this use is shown in FIG. The figure is similar to FIG. 2 except for replacement of the syringe barrel 250 with lid of the container 80 of FIG. 2 VII.B, for example. VII.B.

              VII.B.1 FIG. 52 shows a treated syringe barrel similar to FIG. 42 but without the flange or finger clamp 440. FIG. The syringe barrel can be used in combination with, for example, the container processing and inspection apparatus of FIGS. 1 to 19, 27, 33, 35, 44 to 51, and 53 to 54.

VII.B.1.a. Syringe having a barrel coated with a lubricity coating deposited by an organosilicon precursor
VII.B.1.a. Another example is a container having a lubricious Si _w O _x C _y H _z coating of the type produced by the following process.

              VII.B.1.a. Prepare a precursor as defined above.

              VII.B.1.a. The precursor is applied to the substrate under conditions effective to produce a coating. The dressing is polymerized, cross-linked, or both, and produces a lubricated surface that reduces “plunger sliding force” or “starting force” compared to an untreated substrate.

              VII.B.1.a. For Example VII and subparts, the coating procedure is optionally performed by vaporization of the precursor and provided near the substrate.

              VII.B.1.a. For Example VII.A.1.a.i, an optional plasma, optionally a non-hollow cathode plasma, is generated near the substrate. Optionally, the precursor is provided to an environment that is substantially free of oxygen. Optionally, the precursor is provided to an environment that is substantially free of carrier gas. Optionally, the precursor is provided to an environment that is substantially free of nitrogen. Optionally, the precursor is provided to an environment where the absolute pressure is less than 1 Torr. Optionally, the precursor is provided to an environment near the plasma emission. Optionally, the precursor and its reaction product are applied to the substrate with a layer thickness of 1 to 5000 nm, or 10 to 1000 nm, or 10 to 200 nm, or 20 to 100 nm. Optionally, the substrate is made of glass. Optionally the substrate is from a polymer, optionally from a polycarbonate polymer, optionally from an olefin polymer, optionally from a cyclic olefin copolymer, optionally from a polypropylene polymer, optionally from a polyester polymer, optionally from a polyethylene terephthalate polymer. Become.

              Optionally, the plasma is powered by an RF frequency as defined above, for example having a frequency of 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz, most preferably 13.56 MHz. It is produced by pressurizing a gaseous reactant including a precursor having an electrode.

              Optionally, the plasma is a precursor having an electrode that receives a power supply of 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, even more preferably 5 to 14 W, most preferably 7 to 11 W, especially 8 W. It is produced by pressurizing a gaseous reactant containing The electrode power to plasma volume ratio is less than 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, most preferably 2 W / ml to 0.2 W / ml. May be ml. This power level is suitable for applying a lubricious coating to syringes and specimen tubes and similarly shaped containers in which PECVD plasma is generated and has a void volume of 1 to 3 mL. For larger or smaller objects, it is believed that the applied power should be increased or decreased accordingly as the substrate size is processed.

              VII.B.1.a Another example is a lubricity coating on the inner wall of the syringe barrel. The dressing is produced by PECVD using the following materials and conditions. Preferably, cyclic precursors are utilized and selected from linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, or composites of two or more thereof as defined elsewhere herein for lubricity coatings. One example of a suitable cyclic precursor consists of octamethylcyclotetrasiloxane (OMCTS), optionally mixed in any proportion with other precursor raw materials. Optionally, the cyclic precursor consists essentially of octamethylcyclotetrasiloxane (OMCTS), ie other precursors change the basic and new properties of the resulting lubricity coating (eg, the coated surface) The amount of the plunger sliding force or starting force is not reduced).

              VII.B.1.a At least essentially no oxygen is added to the process. Some residual atmospheric oxygen may be present in the syringe barrel, and there may be residual oxygen in the syringe barrel that was supplied in the previous procedure and not completely exhausted, so there is essentially oxygen present. Define what not to do. If oxygen is not added to the process, this also falls within the category of “substantially oxygen-free”.

              VII.B.1.a Power input that generates a sufficient plasma, for example, any power level used successfully or described herein in one or more embodiments herein, Induces coating production.

              VII.B.1.a The material and conditions utilized are at least 25 percent, or at least 45 percent, of the sliding or activation force of the syringe plunger moving within the syringe barrel as compared to the uncoated syringe barrel, Or it is effective to reduce at least 60 percent, or more than 60 percent. A range that reduces the plunger sliding force or activation force by 20-95 percent, alternatively 30-80 percent, alternatively 40-75 percent, alternatively 60-70 percent is contemplated.

VII.B.1.a. Another example is a container having a hydrophobic coating on the inner wall having the following chemical structure: Si _w O _x C _y H _z (w, x, y, and z) Is predefined). The coating is produced as described for a lubricating coating of similar composition, but under conditions effective to produce a hydrophobic surface with a high contact angle compared to an untreated substrate.

              VII.B.1.a. For Example VII.A.1.a.ii, the substrate consists of glass or polymer. The glass is optionally a borosilicate glass. The polymer is optionally a polycarbonate polymer, optionally an olefin polymer, optionally a cyclic olefin copolymer, optionally a polypropylene polymer, optionally a polyester polymer, optionally a polyethylene terephthalate polymer.

VII.B.1.a. Another example is a syringe that includes a plunger, a syringe barrel, and a lubrication layer. The syringe barrel contains an inner surface that slidably receives the plunger. The lubricating layer is deposited on the syringe barrel inner surface and includes a Si _w O _x C _y H _z lubricating layer coating. The lubricating layer has a layer thickness of less than 1000 nm and is effective in reducing the starting force or plunger sliding force required to move the plunger within the barrel. The decrease in the plunger sliding force is expressed as a decrease in the sliding friction coefficient of the plunger within the barrel or a decrease in the plunger force (these terms are considered to be synonymous herein). The

VII.B.1.a. The syringe 544 of FIGS. 50-51 consists of a plunger 546 and a syringe barrel 548. The syringe barrel 548 has an inner surface 552 that slidably receives the plunger 546. Further, the inner surface 552 of the syringe barrel 548 is made of a lubricating coating material 554 of Si _w O _x C _y H _z . The lubricating layer has a layer thickness of less than 1000 nm, optionally less than 500 nm, optionally less than 200 nm, optionally less than 100 nm, optionally less than 50 nm, and the starting force necessary to overcome the adhesion state of the plunger after storage, Or it is effective in reducing the plunger sliding force required to move the plunger within the barrel after activation. The lubricity coating is characterized by having a lower plunger sliding force or activation force than the uncoated surface.

              VII.B.1.a. Any of the above precursors can be used alone or in a composite of two or more to provide a lubricity coating.

              VII.B.1.a. In addition to using vacuum processing, low temperature atmospheric (non-vacuum) plasma processing is also used, preferably in a non-oxidizing atmosphere such as helium or argon, through molecular ionization through a precursor monomer vapor supply And can induce deposition. Individually, thermal CVD can be studied via flash pyrolysis deposition.

              VII.B.1.a. The above approach is similar to vacuum PECVD where the surface coating and cross-linking mechanism can occur simultaneously.

              VII.B.1.a. Another possible means for any dressing or dressing described herein includes a dressing that is applied non-uniformly throughout the interior 88 of the container. For example, different or additional dressings can be selectively applied to the cylindrical part inside the container and compared to the hemispherical part at the closed end 84 inside the container, or vice versa. This means is particularly conceivable for the syringe barrel or specimen collection tube described below. In the syringe barrel, a lubricious surface can be provided on part or all of the cylindrical portion of the barrel in which the plunger or piston or closure closes but does not slide elsewhere.

              VII.B.1.a. Optionally, the precursor is in the presence, substantial absence, or absence of oxygen, or in the presence, substantial absence, or absence of nitrogen. Or in the presence, substantial absence, or absence of a carrier gas. In one possible embodiment, the precursor alone is transferred to the substrate, PECVD is applied, and the coating is applied and cured.

              VII.B.1.a. Optionally, the precursor is provided to an environment where the absolute pressure is less than 1 Torr.

              VII.B.1.a. Optionally, the precursor is provided to the environment near the plasma emission.

              VII.B.1.a. Optionally, the precursor and its reaction product are applied to the substrate with a layer thickness of 1 to 5000 nm, or 10 to 1000 nm, or 10 to 200 nm, or 20 to 100 nm.

              VII.B.1.a. In any of the above embodiments, the substrate can be glass or, for example, one or more polycarbonate polymers, olefin polymers (eg, cyclic olefin copolymers or polypropylene polymers), polyester polymers (eg, terephthalate). It may be made of a polymer such as (acid polyethylene polymer).

              VII.B.1.a. In any of the above examples, the plasma is produced by pressurizing the gaseous reactant comprising the precursor having an electrode powered by an RF frequency as defined herein. Is generated.

              VII.B.1.a.In any of the above examples, by pressurizing the gaseous reactant comprising the precursor having an electrode that is supplied with sufficient power to produce a lubricious coating, The plasma is generated. Optionally, the plasma is a precursor having an electrode that receives a power supply of 0.1 to 25 W, preferably 1 to 22 W, more preferably 3 to 17 W, even more preferably 5 to 14 W, most preferably 7 to 11 W, especially 8 W. It is produced by pressurizing a gaseous reactant containing The electrode power to plasma volume ratio is less than 10 W / ml, preferably 5 W / ml to 0.1 W / ml, more preferably 4 W / ml to 0.1 W / ml, most preferably 2 W / ml to 0.2 W / ml. May be ml. This power level is suitable for applying a lubricious coating to syringes and specimen tubes and similarly shaped containers in which PECVD plasma is generated and has a void volume of 1 to 3 mL. For larger or smaller objects, it is believed that the applied power should be increased or decreased accordingly as the substrate size is processed.

              VII.B.1.a. Lubrication that cures the coating by polymerization, cross-linking or both, reducing the “plunger sliding force” or “starting force” compared to the untreated substrate. A surface can be generated. Curing can occur during the coating process, eg, PECVD, or can be performed or at least completed by a separate process.

              VII.B.1.a. This document uses plasma deposition to demonstrate the properties of the coating, but deposits a continuous film that maintains the chemical composition of the starting material and adheres to the bottom substrate. Alternative deposition methods can be used as long as it is possible.

              VII.B.1.a. For example, the coating material can be applied (from the fluid state) onto the syringe barrel by spraying the coating material or immersing the substrate in the coating material, The dressing is either the pure precursor or a solvent diluted precursor (allowing mechanical deposition of thinner dressings). The coating can optionally be cross-linked using thermal energy, UV energy, electron beam energy, plasma energy, or a composite thereof.

              VII.B.1.a. Application of the above silicon precursor to the surface and subsequent individual curing procedures are also conceivable. The conditions of application and curing may be similar to those used for the atmospheric plasma curing of pre-coated polyfluoroalkyl ethers, a process practiced under the trademark TriboGlide®. . For details of this process, refer to http://www.triboglide.com/process.htm.

              VII.B.1.a. In such a process, the area of the area to be coated can optionally be pretreated with atmospheric plasma. Since the surface is cleaned and activated by this pretreatment, the lubricant sprayed in the following procedure can be received.

              VII.B.1.a. The lubricating fluid, in this case one of the aforementioned precursors or polymerization precursors, is then sprayed onto the surface to be treated. For example, IVEK precision dispensing technology can be used to accurately atomize the fluid to create a uniform coating.

              VII.B.1.a. The coating is then bonded or cross-bonded to the part again using the atmospheric plasma field. Thereby, the said coating | covering material can be fixed and the performance of the said lubricant can be improved.

                VII.B.1.a. Optionally, the atmospheric plasma can be generated from the ambient atmosphere in the vessel, in which case the gas supply and vacuuming devices are not required. However, the vessel is preferably substantially closed, at least during plasma generation, to minimize the power requirements and prevent the plasma from contacting the surface / material outside the vessel.

VII.B.1.ai Lubricious coating: SiO _x barrier layer, lubrication layer, surface treatment surface treatment
VII.B.1.ai Another embodiment comprises a barrel defining a lumen and having an inner surface that slidably receives a plunger, i.e., receives a plunger for sliding contact with the inner surface. Syringe.

              VII.B.1.a.i. The syringe barrel is made from a thermoplastic base material.

VII.B.1.ai Optionally, the inner surface of the barrel is coated with a SiO _x barrier layer as described elsewhere herein.

Apply the VII.B.1.ai lubricity coating to the barrel inner surface, the plunger, or both, or the previously applied SiO _x barrier layer. The lubricating layer can be provided, applied or cured as defined in Example VII.B.1.a or elsewhere herein.

              VII.B.1.a.i. For example, the lubricity coating may be applied by PECVD in any embodiment. The lubricity coating material is deposited using an organosilicon precursor as a raw material and has a layer thickness of less than 1000 nm.

              VII.B.1.a.i. Surface treatment on the lubricity coating is performed in an amount effective to reduce leaching or extract of the lubricity coating, thermoplastic substrate, or both. The treated surface thus functions as a solute retaining member. This surface treatment results in a skin coating, e.g. a layer thickness of 1 nm or more, a layer thickness of less than 100 nm, or a layer thickness of less than 50 nm, or a layer thickness of less than 40 nm, or a layer thickness of less than 30 nm, or a layer of less than 20 nm Can be a skin coating with a thickness of less than 10 nm, or less than 5 nm, or less than 3 nm, or less than 2 nm, or less than 1 nm, or less than 0.5 nm There is sex.

              As used herein, “leaching” refers to the transfer of a substance from a substrate, such as a container wall, to the contents of a container, such as a syringe. In general, leachables are measured by storing the container filled with the intended inclusions and then analyzing the inclusions to determine the substances that have leached from the container walls into the intended inclusions. “Extraction” refers to a substance from a substrate by introducing a solvent or dispersion medium in addition to the intended contents of the container and determining the substance that can be removed from the substrate to the extraction medium under the test conditions. Refers to the removal.

Surface treatment to VII.B.1.ai optionally bring solute retention member is SiO _x or Si _w O _x C _y be a H _z covering material is already defined respectively herein. In one embodiment, the surface treatment can be applied by PECVD deposition of SiO _x or _{Si w O x C y H z} . Optionally, the surface treatment can be applied using higher power, stronger oxidation conditions, or both than those used in generating the lubrication layer, and thus a harder, thinner, continuous solute retention member 539. Can be provided. Surface treatment is less than 100 nm deep, optionally less than 50 nm, optionally less than 40 nm, optionally less than 30 nm, optionally less than 20 nm, optionally less than 20 nm, optionally less than 10 nm, optionally less than 5 nm, optionally less than 3 nm, optionally May be less than 1 nm, optionally less than 0.5 nm, optionally 0.1 to 50 nm.

VII.B.1.ai It is believed that the solute retention member provides low solute leaching properties for the lower layer lubricity and, if necessary, other layers including the substrate. This holding member is not a gas (O ₂ / N ₂ / CO ₂ / water vapor) barrier layer, but a solute large molecule and an oligomer (for example, siloxane monomers such as HMDSO, OMCTS, fragments thereof and a mobile oligomer derived from a lubricant, For example, it is only required to be a solute holding member for “exudate holding member”). However, the solute holding member may be a gas barrier film (for example, the SiOx coating material described in the present invention). A good exudate-holding member without gas barrier properties can be created by vacuum or atmospheric PECVD treatment. It is desirable that the “exudate blocking film” is sufficiently thin, and the syringe plunger can be easily moved to the “solute holding member” while exposing the sliding plunger protrusion to the lubricating layer directly below. To create a lubricated surface that reduces the “plunger sliding force” or “starting force” compared to an untreated substrate.

VII.B.1.ai In another embodiment, this can be done by oxidation of the surface of the previously applied lubricant layer, such as exposure of the surface to oxygen in a plasma environment. The plasma environment described herein can be used to form a SiO _x coating. Alternatively, atmospheric plasma conditions can be utilized in an oxygen environment.

              VII.B.1.a.i. The lubrication layer and the solute retention member are, however, shaped and optionally curable simultaneously. In another embodiment, the lubrication layer can be at least partially curable, optionally curable entirely, after which the surface treatment can be provided and applied and the solute retention member can be cured.

              VII.B.1.ai The lubricity coating and solute retaining member are configured to reduce the starting force, plunger sliding force, or both compared to the case without lubrication coating and surface treatment, and the effect In reasonable quantities. In other words, the layer thickness and composition of the solute retention member are intended to reduce leaching of the substance from the lubrication layer into the syringe-containing material and lubricate the plunger with the lower lubricity coating. is there. It is conceivable that the solute retaining member peels off easily and the lubricating layer is thin enough to fulfill the function of lubricating the movement of the plunger.

VII.B.1.ai In one possible embodiment, the lubricity treatment and surface treatment can be applied to the inner surface of the barrel. In another contemplated embodiment, the lubricity treatment and surface treatment can be applied to the plunger. In yet another possible embodiment, the lubricity treatment and surface treatment can be applied to both the barrel inner surface and the plunger. In any of the examples, the optional SiO _x barrier layer inside the syringe barrel may be present or absent.

VII.B.1.ai One possible embodiment is a multi-layer (eg, three-layer) setting that is applied to the inner surface of the syringe barrel. Layer 1 may be a SiO _x gas barrier film produced by MDSO, OMCTS or both PECVD in an oxidizing atmosphere. Such air can be provided, for example, by supplying HMDSO and oxygen gas to the PECVD coating apparatus described herein. Layer 2 may be a lubricating layer using OMCTS applied in a non-oxidizing atmosphere. Such a non-oxidizing atmosphere can be provided, for example, by supplying OMCTS to the PECVD coating apparatus described herein, optionally in the substantial or complete absence of oxygen. As a solute holding member that uses higher power and oxygen using OMCTS and / or HMDSO by processing the secondary solute holding member to produce a thin layer of SiO _x or Si _w O _x C _y H _z , It can be molded.

              VII.B.1.a.i. Certain such multi-layer coatings are believed to have at least some of the following one or more optional advantages. Since the solute holding member may contain the internal silicon and prevent it from moving to the contents of the syringe or to another location, it may be able to cope with the silicon handling difficulties reported by them. . As a result, the silicon particles in the possible syringe contents are reduced, reducing the opportunity for interaction between the lubricity coating and the syringe contents. Moreover, the lubricity of the interface between the syringe barrel and the plunger may be improved by addressing the problem of the lubrication layer moving away from the lubrication point. For example, the breaking force may be reduced, the drag on the moving plunger may be reduced, and both may optionally be reduced.

              VII.B.1.ai If the solute retention member is damaged, the solute retention member continues to adhere to the lubricity coating and the syringe barrel, and any particles into the syringe transportable contents It is thought that there is a possibility of inhibiting the uptake of.

VII.B.1.ai Certain such coatings also have manufacturing advantages, in particular the barrier coatings, lubricity coatings, and surface treatments applied in the same equipment, eg the PECVD equipment shown. To provide. Optionally, the SiO _x barrier coating, lubricity coating, and surface treatment are all applicable in one PECVD apparatus, thus greatly reducing handling requirements.

Further advantages can be obtained by producing the barrier coating, lubricity coating, and solute retention member using the same precursor and by modifying the process. For example, the SiO _x gas barrier layer can be applied using OMCTS precursors under high power / high O ₂ conditions and the lubrication layer can be lOMCTS under low power and / or substantially or completely oxygen-free conditions. The precursor can be applied using a precursor, and finally the surface treatment can be applied using an OMCTS precursor under conditions of intermediate power and oxygen.

VII.B.1.b Syringe with barrel with SiO _X layer coating inside and barrier layer coating outside
VII.B.1.b. Yet another embodiment illustrated in FIG. 50 is a syringe 544 that includes a plunger 546, a barrel 548, and inner and outer barrier coverings 554 and 602. The barrel 548 may be made from a thermoplastic base material that defines the lumen 604. The barrel 548 may have an inner surface 552 that slidably receives the plunger 546 and an outer surface 606. A barrier coating 554 made of SiO _x (x being about 1.5 to about 2.9) may be provided on the inner surface 552 of the barrel 548. In some cases, a resin barrier covering material 602 is provided on the outer surface 606 of the barrel 548.

              VII.B.1.b. In all embodiments, the thermoplastic substrate is optionally a polyolefin such as polypropylene or a cyclic olefin copolymer (eg, a material sold under the trademark TOPAS®), terephthalate May include polyesters such as acid polyethylene and polycarbonate (eg, bisphenol A polycarbonate thermoplastic or other materials). A synthetic syringe barrel having any one material as an outer layer and the same or different material as an inner layer is conceivable. Combinations of the synthetic syringe barrel or sample tube materials described elsewhere herein may also be used.

              VII.B.1.b. In any embodiment, the resin may optionally comprise polyvinylidene chloride in the form of a homopolymer or copolymer. For example, a PvDC homopolymer (common name: Saran) or a copolymer described in US Pat. No. 6,165,566, which is incorporated herein by reference, can be used. The resin may optionally be applied to the outer surface of the barrel in latex or other dispersed form.

VII.B.1.b. In any embodiment, the syringe barrel 548 may optionally include a lubricity coating disposed between the plunger and the barrier SiO _x coating. Suitable lubricity coatings are described elsewhere in this specification.

VII.B.1.b. In any embodiment, the lubricity coating may optionally be applied by PECVD and may optionally include a material having the composition Si _w O _x C _y H _z .

              VII.B.1.b. In any embodiment, the syringe barrel 548 optionally includes a surface treatment covering the lubricity coating to reduce leaching of the lubricity coating, the thermoplastic substrate, or both. Effective amount, may contain.

VII.B.1.c Method of manufacturing a syringe having a barrel with an SiO _X layer coating interior and a barrier layer coating exterior
VII.B.1.c. Further another aspect of the present invention is the manufacture of a syringe according to any embodiment of VII.B.1.b, comprising a plunger, barrel, internal and external barrier coatings There is a way. A barrel having an inner surface for slidably receiving a plunger and an outer surface is provided. The SiO _x barrier coating is provided on the outer surface of the barrel by PECVD. A resin barrier coating is provided on the outer surface of the barrel. A syringe is prepared by assembling the plunger and barrel.

              VII.B.1.c. As an effective (uniform wetting) coating of plastic materials using the aqueous latex, it would be useful to match the surface tension of the latex to the plastic substrate. This may involve multiple approaches such as reducing the surface tension of the latex (using a surfactant or solvent) and / or corona pretreatment of the plastic material and / or chemical priming of the plastic material individually or Can be achieved in combination.

              VII.B.1.c. An improved gas / vapor is optionally applied by dip-coating the latex on the outer surface of the barrel, spray-coating the latex on the outer surface of the barrel, or both. It is possible to provide a plastic material that provides a blocking force. It is possible to produce a polyvinylidene chloride plastic laminate that provides a much better gas barrier than the non-laminate plastic material.

              VII.B.1.c. In any embodiment, the resin is optionally heat curable. The resin can be thermoset by optionally removing moisture. Moisture can be removed by thermal curing of the resin, partial exposure of the resin to a vacuum or low humidity environment, catalytic curing of the resin, or other means.

              VII.B.1.c. As an effective thermosetting schedule, it may be possible to dry at the end to allow PvDC crystallization and provide a blocking force. The primary curing may be performed at a high temperature of, for example, 180 to 310 ° F. (82 to 154 ° C.), and of course depends on the heat resistance of the thermoplastic substrate. The blocking force after primary curing can optionally be about 85% of the ultimate blocking force achieved after final curing.

              VII.B.1.c. Final cure is from long periods at ambient temperatures such as 65-75 ° F (18-24 ° C) (eg 2 weeks) to short periods at high temperatures like 122 ° F (50 ° C) (Up to 4 hours) can be executed.

              VII.B.1.c.In addition to excellent barrier power, the PvDC plastic laminates optionally have one or more desirable properties such as colorless and transparent, good gloss, abrasion resistance, printability, and mechanical strain resistance. It is considered to be provided.

VII.B.2. Plunger
VII.B.2.a. Front of the shielded coated piston
VII.B.2.a. Another example is a plunger for a syringe that includes a piston and a push rod. The piston has a front surface, a side surface that is generally cylindrical, and a rear portion, the side surface being configured to be movably loaded into a syringe barrel. The front surface has a barrier coating. The push rod is engaged with the rear portion and set to push the piston forward in the syringe barrel.

VII.B.2.b. Lubricant coating to be joined to the side
VII.B.2.b. Another example is a plunger for a syringe that includes a piston, a lubricity coating, and a push rod. The piston has a front surface, a side surface that is generally cylindrical, and a rear portion. The side is set to be movably loaded into the syringe barrel. The lubricity coating material is bonded to the side surface. The push rod is set to engage the rear of the piston and push the piston forward within the syringe barrel.

VII.B.3. Two-part syringe and luer attachment
VII.B.3. Another example is a syringe that includes a plunger, a syringe barrel, and a luer fitting. The syringe includes a barrel having an inner surface that slidably receives the plunger. The luer attachment includes a luer taper having an internal path defined by the inner surface. The luer attachment portion is formed as a separate member from the syringe barrel, and is coupled to the syringe barrel by coupling. The inner path of the luer taper has a barrier SiO _x coating.

VII.B.3. Referring to FIGS. 50-51, the syringe 544 optionally includes a luer attachment 556 comprising a luer taper 558 for receiving a cannula mounted on a spare luer taper (not shown, conventional). May include. The luer taper 558 has an internal path 560 defined by the inner surface 562. The luer attachment 556 is optionally formed as a separate member from the syringe barrel 548 and is coupled to the syringe barrel 548 by a coupling 564. As shown in FIGS. 50 and 51, the coupling 564 of the present example includes a male portion 566 and a female portion that engage and fix each other so that the luer attachment portion is at least substantially leak resistant to the barrel 548. Part 568. The inner surface 562 of the luer taper may include a SiO _x barrier coating 570. The barrier coating has a layer thickness of 100 nm and may be effective in reducing oxygen intrusion into the internal path of the luer attachment. The barrier covering material can be applied before the luer attachment portion is engaged with the syringe barrel. The syringe of FIGS. 50-51 also has an optional locking collar 572 that is internally threaded and locks the pre-luer taper of the cannula in place of the taper 558.

VII.B.4. Lubricant composition-Lubricant coatings deposited from organosilicon precursors based on in situ polymerized organosilicon precursors
VII.B.4.a. Products by process and lubricity
VII.B.4.a. Another example is a lubricity coating. The coating material may be of a type generated by the following process.

              VII.B.4.a. Any such precursor described elsewhere herein may be used alone or in a complex. The precursor is applied to the substrate under conditions effective to produce a coating material. The dressing is polymerized, cross-linked, or both, and produces a lubricated surface that reduces “plunger sliding force” or “starting force” compared to an untreated substrate.

              VII.B.4.a. Another embodiment is a method of applying a lubricity coating. The organosilicon precursor is applied to the substrate under conditions effective to produce a coating material. The dressing is polymerized, cross-linked, or both, and produces a lubricated surface that reduces “plunger sliding force” or “starting force” compared to an untreated substrate.

VII.B.4.b. Products by process and analytical characteristics
VII.B.4.b. Further another aspect of the present invention is that it comprises an organometallic precursor, preferably an organosilicon precursor, preferably linear siloxane, linear silazane, monocyclic siloxane, monocyclic silazane. A lubricious coating deposited by PECVD from a feed gas consisting of polycyclic siloxane, polycyclic silazane, or a composite of two or more of these. Density of the coating material, as determined by X-ray reflectivity ^{(XRR), 1.25~1.65g / cm 3} , optionally 1.35~1.55g / cm ^3, optionally 1.4~1.5g / cm ^3, optionally 1.44 to 1.48 g / cm ³ .

VII.B.4.b. Further another aspect of the present invention is that it comprises an organometallic precursor, preferably an organosilicon precursor, preferably linear siloxane, linear silazane, monocyclic siloxane, monocyclic silazane. A lubricious coating deposited by PECVD from a feed gas consisting of polycyclic siloxane, polycyclic silazane, or a composite of two or more of these. The dressing has one or more oligomers comprising a gas releasing component, a repeating-(Me) ₂ SiO- moiety, as determined by gas chromatography / mass spectrometry. Optionally, the dressing meets the limitations of either Example VII.B.4.a or VII.B.4.b. Optionally, the dressing outgassing component is substantially free of trimethylsilanol as determined by gas chromatography / mass spectrometry.

VII.B.4.b.Optionally, the coated gas releasing component comprises at least a repeat- (Me) ₂ SiO- moiety as determined by gas chromatography / mass spectrometry using the following test conditions: Has 10 ng oligomer per test.
GC column: 30m X 0.25mm DB-5MS (J & W Scientific),
0.25μm membrane thickness Flow rate: 1.0 ml / min, constant flow mode Detector: Mass selective detector (MSD)
Injection mode: Split injection (split ratio 10: 1)
Outgassing conditions: 1 1/2 inch (37mm) chamber, 3 hours, 85 ° C,
Purge at a flow rate of 60 ml / min. Furnace temperature: Start at 40 ° C (5 minutes) and heat to 300 ° C at 10 ° C / min.
Hold at 300 ° C for 5 minutes.

VII.B.4.b. Optionally, the outgassing component may comprise at least 20 ng of oligomer per test with a repeat- (Me) ₂ SiO— moiety.

              VII.B.4.b. Optionally, the feed gas is from monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or a composite of two or more thereof (eg, octamethylcyclotetrasiloxane). Become.

              VII.B.4.b. The lubricity coatings of all examples are optionally 1-500 nm, optionally 20-200 nm, optionally 20-100 nm, optionally measured by transmission electron microscopy (TEM). Has a layer thickness of 30-100 nm.

              VII.B.4.b. Another embodiment of the present invention is deposited by PECVD from a feed gas consisting of monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or a composite of two or more thereof. Lubricant coating material. The dressing has an atomic concentration of carbon normalized to 100% carbon, oxygen, and silicon, and the atomic concentration of carbon in the atomic formula of the feed gas as determined by X-ray photoelectron spectroscopy (XPS). Exceed. Optionally, the dressing meets the limitations of Example VII.B.4.a or VII.B.4.b.

              VII.B.4.b. Optionally, the atomic concentration of the carbon is 1-80 atomic percent (calculated based on the XPS conditions of Example 15), or from 10-70 atomic percent, alternatively 20-60 atomic percent, or Increase by 30-50 atomic percent, alternatively 35-45 atomic percent, alternatively 37-41 atomic percent.

              VII.B.4.b. Another embodiment of the present invention is deposited by PECVD from a feed gas consisting of monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or a composite of two or more thereof. Lubricant coating material. The covering material has a silicon atomic concentration normalized to 100% carbon, oxygen, and silicon, and as determined by X-ray photoelectron spectroscopy (XPS), the atomic concentration of silicon in the atomic formula of the feed gas is Below. Optionally, the dressing meets the limitations of Example VII.B.4.a or VII.B.4.b.

              VII.B.4.b. Optionally, the atomic concentration of silicon is 1 to 80 atomic percent (calculated based on the XPS conditions of Example 15), or from 10 to 70 atomic percent, alternatively 20 to 60 atomic percent, or Decrease by 30-55 atomic percent, alternatively 40-50 atomic percent, alternatively 42-46 atomic percent.

              VII.B.4.b. Cross-sectional view Lubricant coating materials having a composite of two or more properties listed in VII.B.4 are also explicitly contemplated.

VII.C. General container
VII.C. Coated containers or containers described herein and / or made in accordance with the methods described herein can be used for receipt and / or storage and / or supply of compounds or compositions. is there. The compound or composition may be sensitive, for example, atmospheric sensitivity, oxygen sensitivity, humidity sensitivity and / or mechanical action sensitivity. It may be a drug such as a biologically active compound or composition, for example insulin or a composition comprising insulin. In another embodiment, it may be a biological fluid, preferably a body fluid such as blood or a blood fraction. In certain embodiments of the invention, the compound or composition is a product administered to a subject in need thereof, such as blood (transfusion from a donor to a recipient or blood collected from a patient). Reintroduction to the patient) or infusion products such as insulin.

              VII.C. Coated containers or containers made in accordance with the methods described herein and / or described herein may further include mechanical and surface of the uncoated container material surface of the compound or composition contained in the lumen. Can be used for protection from chemical action. It can be used to prevent or reduce precipitation and / or clotting or platelet activation of said compound or composition component, eg insulin precipitation or blood clotting or platelet activation.

              VII.C. Furthermore, for example, by preventing or reducing the entry of one or more compounds from the environment around the container into the container lumen, the compound or composition contained therein can be removed from the environment outside the container. Can be used to protect against. Such environmental compounds may be gases or fluids, such as atmospheric gases or fluids including oxygen, air, and / or water vapor.

              VII.C. The coated containers described herein are also vacuum and may be stored under vacuum. For example, the covering material can maintain the vacuum state better than the corresponding uncoated container. In one aspect of this embodiment, the coated container is a blood collection tube. The tube may contain an agent for preventing blood clotting or platelet activation, such as EDTA or heparin.

              VII.C. Any of the above embodiments can be, for example, about 1 cm to about 200 cm in length, optionally about 1 cm to about 150 cm, optionally about 1 cm to about 120 cm, optionally about 1 cm to about 100 cm, optionally about 1 cm as the container. It is feasible by providing a tube of about 80 cm, optionally about 1 cm to about 60 cm, optionally about 1 cm to about 40 cm, optionally about 1 cm to about 30 cm, and processed with a probe electrode as described below. In particular, it is considered that the longer the length in the above range, the more useful the relative motion between the probe and the container during molding of the covering material is. This can be done, for example, by moving the container relative to the probe or moving the probe relative to the container.

              VII.C. In these examples, it is believed that the dressing may be thin, or less complete than desirable as a barrier coating. This is because the container in some embodiments does not require high barrier integrity of the vacuum blood collection tube.

              VII.C. As an optional feature of the previous embodiment, the container has a central axis.

              VII.C. As an optional feature of the previous embodiment, a temperature of 20 ° C. in a range that is at least substantially linear with respect to the bending radius at the central axis that does not exceed 100 times the outer diameter of the container. The container wall has sufficient deflection to bend at least once without damaging the wall.

              VII.C. As an optional feature of the previous embodiment, the bend radius at the central axis should not exceed 90 times, not more than 80 times, not more than 70 times, or not more than 60 times the outer diameter of the vessel. No more than 50 times or no more than 40 times or no more than 30 times or no more than 20 times or no more than 10 times or no more than 9 times or no more than 8 times No, no more than 7 times, no more than 6 times, no more than 5 times, no more than 4 times, no more than 3 times, no more than 2 times or 1 size .

              VII.C. As an optional feature of the previous embodiment, the container wall may be a fluid contact surface made of a flexible material.

              VII.C. As an optional feature of the previous embodiment, the container lumen may be the fluid flow path of the pump.

              VII.C. As an optional feature of the previous embodiment, the container may be a blood bag adapted to hold blood in good condition for medical use.

              VII.C., VII.D. As an optional feature of the previous embodiment, the polymer material is, by way of example, a silicone elastomer or a thermoplastic polyurethane, or any material suitable for contact with blood or insulin. There is a case.

              VII.C., VII.D. In an optional embodiment, the container has an inner diameter of at least 2 mm, or at least 4 mm.

              VII.C. As an optional feature of the previous embodiment, the container is a tube.

              VII.C. As an optional feature of the previous embodiment, the lumen has at least two open ends.

VII.C.1. A living blood containing container with a coating deposited from an organosilicon precursor
VII.C.1. Yet another example is a blood containing container. As a non-limiting example of such a container, a blood transfusion bag, a blood sample collection container for collecting a sample, a heart-lung machine tube, a flexible wall blood collection bag, collecting patient blood during surgery and collecting the blood And a tube that is reintroduced into the vasculature of the patient. If the container is a pump that pumps blood, a particularly suitable pump is a centrifugal pump or a peristaltic pump. The container has a wall, and the wall has an inner surface defining a lumen. The inner surface of the wall is coated with Si _w O _x C _y H _z (w is 1, x of the formula is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to about 9, preferably w is 1 , X from about 0.5 to 1, y from about 2 to about 3, and z from 6 to about 9). The covering material is as thin as the monomolecular layer thickness or has a maximum layer thickness of about 1000 nm. The container includes blood that can be returned to the patient's vasculature that fills the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.1. One example is a blood containing container having an inner surface that includes a wall and defines a lumen. The inner surface is at least partially covered with Si _w O _x C _y H _z . The dressing may consist of SiO _x (x is defined herein) or consist essentially of SiO x. The layer thickness of the coating is in the range of monomolecular to about 1000 nm on the inner surface. The container includes blood that can be returned to the patient's vasculature that fills the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.2. Coating materials deposited from organosilicon precursors that reduce blood coagulation or platelet activation in the container
VII.C.2. Another embodiment is a container with walls. The wall has an inner surface defining a lumen, the wall comprising a Si _w O _x C _y H _z coating (preferably w, x, y, and z are as defined: w is 1, x about 0.5 To about 2.4, y is about 0.6 to about 3, z is 2 to about 9, preferably w is 1, x is about 0.5 to 1, y is about 2 to about 3, z is about 6 to about 9) Has some coating. The layer thickness of the coating material is monomolecular to about 1000 nm on the inner surface. The dressing is effective in reducing clotting or platelet activation of blood exposed to the inner surface as compared to the same type of wall not coated with Si _w O _x C _y H _z .

VII.C.2. Incorporation of Si _w O _x C _y H _z coating reduces blood adhesion or clot-forming properties compared to the properties of blood in contact with untreated polymer or SiO _x surfaces I think that. This property reduces the blood concentration of heparin required in patients undergoing a type of surgery that requires blood removal from the patient and subsequent reintroduction to the patient when using heart-lung machines during cardiac surgery. This would reduce / potentially eliminate the need for blood heparinization. By reducing the bleeding complications resulting from the use of heparin, it is believed that surgical complications related to the blood path through such containers are reduced.

VII.C.2. Another example is a container having an inner surface that includes a wall and defines a lumen. The inner surface is at least partially coated with Si _w O _x C _y H _z , and the layer thickness of the coating material is a single molecule to a thickness of about 1000 nm on the inner surface. The dressing is effective in reducing blood clotting or platelet activation exposed to the inner surface.

VII.C.3. A living blood containing container with a coating of a group III or group IV element
VII.C.3. Another example is a blood containing container that includes a wall having an inner surface defining a lumen. The inner surface is at least partially coated with a coating material of a composition comprising one or more Group III elements, one or more Group IV elements, and a composite of two or more of these. The layer thickness of the covering material is compatible with a single molecule to about 1000 nm on the inner surface. The container includes blood that can be returned to the patient's vasculature that fills the lumen in contact with the dressing.

VII.C.4. Group III or Group IV coatings that reduce blood clotting or platelet activation
VII.C.4. Optionally, in the container of the previous paragraph, a Group III or Group IV element coating is effective to reduce blood clotting or platelet activation exposed to the inner wall of the container. .

VII.D. Drug supply container
VII.D. The coated container or container described herein can be used to prevent or reduce leakage of the compound or composition contained in the container to the environment surrounding the container.

              Further use of the dressing and container described herein will be apparent from the description of the part and the claims.

VII.D.1. Insulin-containing container with coating deposited from organosilicon precursor
VII.D.1. Another example is an insulin containing container that includes a wall having an inner surface defining a lumen. The inner surface is Si _w O _x C _y H _z (w, x, y, and z are predefined: w is 1, x is about 0.5 to 2.4, y is about 0.6 to about 3, z is 2 to 9, Preferably, w is 1, x is about 0.5 to 1, y is about 2 to about 3, and z is 6 to about 9). The layer thickness of the coating material is monomolecular to about 1000 nm on the inner surface. Insulin is loaded into the lumen in contact with the Si _w O _x C _y H _z dressing.

VII.D.1. Yet another embodiment is an insulin containing container that includes a wall and has an inner surface that defines a lumen. The inner surface is at least partially coated with Si _w O _x C _y H _z , and the layer thickness of the coating material is a single molecule to a thickness of about 1000 nm on the inner surface. Insulin (eg, FDA approved drug insulin for human use) is loaded into the lumen in contact with the Si _w O _x C _y H _z dressing.

VII.D.1. Incorporation of the Si _w O _x C _y H _z coating reduces the adhesiveness or precipitation molding properties of the insulin in the supply tube of the insulin pump compared to the properties of insulin contacting the untreated polymer surface. It is thought to decrease. This property is believed to reduce / potentially eliminate the need to filter insulin through the supply tube to remove solid precipitate.

VII.D.2. Coating material deposited from organosilicon precursor to reduce insulin precipitation in the container
VII.D.2. Optionally, in the container of the previous paragraph, the Si _w O _x C _y H _z coating is in contact with the inner surface compared to the same type of Si _w O _x C _y H _z uncoated wall. Effective in reducing precipitate formation from insulin.

VII.D.2. Yet another embodiment is again a container having an inner surface that includes a wall and defines a lumen. The inner surface is at least partially covered with Si _w O _x C _y H _z . The layer thickness of the coating is in the range of monomolecular to about 1000 nm on the inner surface. The dressing is effective to reduce precipitate formation from insulin that contacts the inner surface.

VII.D.3. Insulin-containing container with Group III or Group IV element coating
VII.D.3. Another example is an insulin containing container including a wall having an inner surface defining a lumen. The inner surface is at least partially coated with a coating material of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a composite of two or more of these. The layer thickness of the coating material is monomolecular to about 1000 nm on the inner surface. Insulin is filled into the lumen in contact with the dressing.

VII.D.4. Group III or Group IV coating that reduces the precipitation of insulin in the container
VII.D.4. Optionally, in the container of the preceding paragraph, a coating of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a composite of two or more of these, It is effective in reducing the formation of precipitate from insulin in contact with the inner surface as compared to the same type of uncoated wall.

Example 0: Basic protocol for forming and coating tubes and syringe barrels
Containers tested in subsequent examples were molded and coated according to the following exemplary protocol, unless otherwise indicated in individual examples. Certain parameter values (eg, power, process gas flow rate, etc.) given in the basic protocol below are general values. Whenever a parameter value is changed compared to the general value, it is displayed in the subsequent example. The same applies to the type and composition of the processing gas.

Protocol for forming COC tubes (used in Examples 1, 19 etc.)
Cyclic olefin copolymer (COC) tubes of the shape and size commonly used as vacuum blood collection tubes (“COC tubes”) are Topas® 8007-04 cyclic olefin copolymers, sold by Hoechst AG, Frankfurt, Germany Coin (COC) resin was injection molded from the following dimensions: 75 mm long, 13 mm outer diameter, and 0.85 mm wall thickness, each volume approximately 7.25 cm ³ with a rounded closed end.

Protocol for molding PET tubes (used in Examples 2, 4, 8, 9, 10, etc.)
Polyethylene terephthalate (PET) tubes, commonly used as vacuum blood collection tubes (“PET tubes”), are injection molded in the same mold using the “Protocol for forming COC tubes”. The dimensions are as follows: length 75 mm, outer diameter 13 mm, wall thickness 0.85 mm, each volume is about 7.25 cm ³ and has a rounded closed end.

Protocol for coating the inside of the tube with SiO _x (used in Examples 1, 2, 4, 8, 9, 10, 18, 19, etc.)
A particular possible embodiment, the apparatus shown in FIG. 2 with the sealing mechanism of FIG. 45, was used. The container holder 50 is made of Delrin (registered trademark) acetal resin marketed by EI du Pont De Nemours and Co. in Wilmington, Delaware, USA, and has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). Created. The container holder 50 was stored in a Delrin (registered trademark) structure that allows the device to enter and exit the electrode (160).

              The electrode 160 was made from copper and Delrin® shield. The Delrin (registered trademark) shield was conformed to the outer periphery of the copper electrode 160. The dimensions of the electrode 160 were about 3 inches (76 mm) in height and about 0.75 inches (19 mm) in width.

              The tube used as the container 80 is inserted into the bottom of the container holder 50 and Viton® O-rings 490, 504 (Viton® is a trademark of Dupont Performance Elastomers LLC of Wilmington, Delaware, USA The outer periphery of the tube (Fig. 45) was sealed. The tube 80 was carefully moved to a sealed position above the elongated (steady) 1/8 inch (3 mm) diameter brass probe or counter electrode 108 and pressed against the copper plasma shield.

              The copper plasma shield 610 is a perforated copper foil material (K & S Engineering, Chicago, Illinois, USA, part number: LXMUW5 copper mesh) cut to fit the outer diameter of the tube, and the tube is inserted (FIG. 45). And fixed in place by a radially extending abutment surface 494 that functions as a stop. The two copper meshes were fitted tightly around the brass probe or counter electrode 108 to ensure good electrical contact.

              The brass probe or counter electrode 108 was extended to the inside of the tube by about 70 mm, and the 80th wire (diameter = 0.0135 inch or 0.343 mm) was arranged. The brass probe or counter electrode 108 was extended through a Swagelok® attachment (available from Swagelok Co., Solon, Ohio, USA) at the bottom of the container holder 50 and through the bottom structure of the container holder 50. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

              The gas supply port 110 has twelve holes in the probe or counter electrode 108 along the length of the tube (three on the four sides are oriented 90 degrees relative to each other) and the end of the gas supply port 110 There were two holes in the aluminum lid that were inserted into. The gas supply port 110 was connected to a stainless steel assembly consisting of a Swagelok® fitting that contained a manual vent ball valve, thermocouple pressure gauge and bypass valve connected to the vacuum pump line. Further, the gas system is connected to the gas supply port 110 so that the processing gas, oxygen and hexamethyldisiloxane (HMDSO) flow into the pipe through the gas supply port 110 (under processing pressure). I made it.

              The gas system consists of an Aalborg® GFC17 mass flow meter (part number: EW-32661-34, manufactured by Cole-Parmer Instrument Co., Burlington, Ill., USA), which contains 90 sccm of oxygen (or The treatment and the 49.5 inch (1.26 m) length polyetheretherketone ("PEEK") capillary (1/16 inch (1.5 mm) outer diameter, 0.004 inch inner diameter (0.1 mm), with the specific flow reported in the specific example) mm)) for controllable inflow. The PEEK capillary end was inserted into a fluid hexamethyldisiloxane (“HMDSO”, Alfa Aesar® part number L16970, NMR, Grade, Johnson Matthey PLC, London). The fluid HMDSO was aspirated through the capillary due to the low pressure in the tube during processing. The HMDSO then became vapor at the end of the capillary when it reached the low pressure region.

              In order to prevent condensation of the fluid HMDSO beyond this point, the gas flow (including oxygen) that does not flow into the pipe for treatment via the Swagelok (registered trademark) three-way valve is sent to the pump line. And detoured. After the tube was installed, the vacuum pump valve was opened to the container holder 50 and the inside of the tube.

              The vacuum pump system was composed of an Alcatel rotary blade vacuum pump and a blower. The pump system made it possible to reduce the inside of the pipe to a pressure of less than 200 mTorr while flowing the processing gas at the display rate.

              After achieving the bottom vacuum level, the container holder 50 assembly was moved into the electrode 160 assembly. The gas stream (oxygen and HMDSO vapor) was flowed into the brass gas supply port 110 (the three-way valve was adjusted from the pump line to the gas supply port 110). The pressure in the tube was about 300 mTorr as measured by a capacitance manometer (MKS) installed on the pump line close to the valve controlling the vacuum. In addition to the tube pressure, the pressure in the gas supply port 110 and the gas system was also measured with the thermocouple vacuum gauge connected to the gas system. This pressure was usually less than 8 Torr.

              After flowing the gas into the pipe, the RF power supply device was turned on to adjust its power level. An ENI ACG-6 600 watt RF power supply was used (at 13.56 MHz) at a regulated power level of about 50 watts. The output power is calibrated using a Bird Corporation model 43 RF wattmeter connected to the RF output of the power supply during the operation of the coating equipment in all protocols and examples described below. did. The following relationship was found between the dial setting on the power supply and the output power: RF power output = 55 x dial setting. A factor of 100 was used in the previous application to current application ratio, which was incorrect. The RF power supply was connected to a COMDEL CPMX1000 auto-matching device that matched the complex impedance of the plasma (to create in the tube) with the output impedance of the ENI ACG-6 RF power supply of 50 ohms. The applied power was delivered inside the tube because the forward power was 50 watts (or the specific value reported in the specific example) and the reflected power was 0 watts. The RF power supply was controlled by a laboratory timer, and the time to turn on the power was set to 5 seconds (or a specific period reported in a specific example). The RF power was started and the uniform plasma was fixed inside the tube. The plasma was held completely for 5 seconds until the RF power was interrupted by the timer. The plasma produced a silicon oxide coating with a layer thickness of about 20 nm (or the specific layer thickness reported in specific examples) inside the tube surface.

              After coating, the gas flow was returned to the vacuum line and the vacuum valve was closed. The vent valve was then opened and the interior of the tube was returned to ambient atmospheric pressure (about 760 Torr). The tube was then carefully removed from the container holder 50 assembly (after the container holder 50 assembly was removed from the electrode 160 assembly).

Protocol for coating the inside of a tube with a hydrophobic coating (used in Example 9)
A particular possible embodiment, the apparatus shown in FIG. 2 with the sealing mechanism of FIG. 45, was used. The container holder 50 is made of Delrin (registered trademark) acetal resin marketed by EI du Pont De Nemours and Co. in Wilmington, Delaware, USA, and has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). Created. The container holder 50 was stored in a Delrin (registered trademark) structure that allows the device to enter and exit the electrode (160).

              The electrode 160 was made from copper and Delrin® shield. The Delrin (registered trademark) shield was conformed to the outer periphery of the copper electrode 160. The dimensions of the electrode 160 were about 3 inches (76 mm) in height and about 0.75 inches (19 mm) in width.

              The tube used as the container 80 is inserted into the bottom of the container holder 50 and Viton® O-rings 490, 504 (Viton® is a trademark of Dupont Performance Elastomers LLC of Wilmington, Delaware, USA The outer periphery of the tube (Fig. 45) was sealed. The tube 80 was carefully moved to a sealed position above the elongated (steady) 1/8 inch (3 mm) diameter brass probe or counter electrode 108 and pressed against the copper plasma shield.

              The copper plasma shield 610 is a perforated copper foil material (K & S Engineering, Chicago, Illinois, USA, part number: LXMUW5 copper mesh) cut to fit the outer diameter of the tube, and the tube is inserted (FIG. 45). And fixed in place by a radially extending abutment surface 494 that functions as a stop. The two copper meshes were fitted tightly around the brass probe or counter electrode 108 to ensure good electrical contact.

              The brass probe or counter electrode 108 was extended to the inside of the tube by about 70 mm, and the 80th wire (diameter = 0.0135 inch or 0.343 mm) was arranged. The brass probe or counter electrode 108 was extended through a Swagelok® attachment (available from Swagelok Co., Solon, Ohio, USA) at the bottom of the container holder 50 and through the bottom structure of the container holder 50. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

              The gas supply port 110 has twelve holes in the probe or counter electrode 108 along the length of the tube (three on the four sides are oriented 90 degrees relative to each other) and the end of the gas supply port 110 There were two holes in the aluminum lid that were inserted into. The gas supply port 110 was connected to a stainless steel assembly consisting of a Swagelok® fitting that contained a manual vent ball valve, thermocouple pressure gauge and bypass valve connected to the vacuum pump line. Further, the gas system is connected to the gas supply port 110 so that the processing gas, oxygen and hexamethyldisiloxane (HMDSO) flow into the pipe through the gas supply port 110 (under processing pressure). I made it.

              The gas system consists of an Aalborg® GFC17 mass flow meter (part number: EW-32661-34, manufactured by Cole-Parmer Instrument Co., Burlington, Ill., USA), which contains 60 sccm of oxygen (or The treatment and the 49.5 inch (1.26 m) length polyetheretherketone ("PEEK") capillary (1/16 inch (1.5 mm) outer diameter, 0.004 inch inner diameter (0.1 mm), with the specific flow reported in the specific example) mm)) for controllable inflow. The PEEK capillary end was inserted into a fluid hexamethyldisiloxane (“HMDSO”, Alfa Aesar® part number L16970, NMR, Grade, Johnson Matthey PLC, London). The fluid HMDSO was aspirated through the capillary due to the low pressure in the tube during processing. The HMDSO then became vapor at the end of the capillary when it reached the low pressure region.

              In order to prevent condensation of the fluid HMDSO beyond this point, the gas flow (including oxygen) that does not flow into the pipe for treatment via the Swagelok (registered trademark) three-way valve is sent to the pump line. And detoured. After the tube was installed, the vacuum pump valve was opened to the container holder 50 and the inside of the tube.

              The vacuum pump system was composed of an Alcatel rotary blade vacuum pump and a blower. The pump system made it possible to reduce the inside of the pipe to a pressure of less than 200 mTorr while flowing the processing gas at the display rate.

              After achieving the bottom vacuum level, the container holder 50 assembly was moved into the electrode 160 assembly. The gas stream (oxygen and HMDSO vapor) was flowed into the brass gas supply port 110 (the three-way valve was adjusted from the pump line to the gas supply port 110). The pressure in the tube was about 270 mTorr as measured by a capacitance manometer (MKS) installed on the pump line in proximity to the valve controlling the vacuum. In addition to the tube pressure, the pressure in the gas supply port 110 and the gas system was also measured with the thermocouple vacuum gauge connected to the gas system. This pressure was usually less than 8 Torr.

              After flowing the gas into the pipe, the RF power supply device was turned on to adjust its power level. An ENI ACG-6 600 watt RF power supply was used (at 13.56 MHz) at a regulated power level of about 39 watts. The RF power supply was connected to a COMDEL CPMX1000 auto-matching device that matched the complex impedance of the plasma (to create in the tube) with the output impedance of the ENI ACG-6 RF power supply of 50 ohms. Since the forward power was 39 watts (or the specific value reported in the specific example) and the reflected power was 0 watts, the applied power was delivered inside the tube. The RF power supply was controlled by a laboratory timer, and the time to turn on the power was set to 7 seconds (or a specific period reported in a specific example). The RF power was started and the uniform plasma was fixed inside the tube. The plasma was held completely for 7 seconds until the RF power was interrupted by the timer. The plasma produced a silicon oxide coating with a layer thickness of about 20 nm (or the specific layer thickness reported in specific examples) inside the tube surface.

              After coating, the gas flow was returned to the vacuum line and the vacuum valve was closed. The vent valve was then opened and the interior of the tube was returned to ambient atmospheric pressure (about 760 Torr). The tube was then carefully removed from the container holder 50 assembly (after the container holder 50 assembly was removed from the electrode 160 assembly).

Protocol for forming a COC syringe barrel (used in Examples 3, 5, 11-18, 20, etc.)
Syringe barrels ("COC syringe barrels"), CV gripping parts 11447, or plunger displacements, each with a total volume of 2.8mL (excluding the luer fitting) and nominal volume of 1mL, respectively. The following dimensions were injection-molded using Topas (registered trademark) 8007-04 cyclic olefin copolymer (COC) resin commercially available from Hoechst as the raw material: front length approximately 51mm, syringe barrel inner diameter 8.6mm, wall of the cylindrical part A needle capillary luer adapter molded at one end of 1.27mm in thickness and combined length of 9.5mm and two finger flanges molded near the other end.

Protocol for coating the inside of a COC syringe barrel with SiO _x (used in Examples 3, 5, 18 etc.)
The interior of the injection molded COC syringe barrel is coated with SiO _x. A particular possible embodiment, the apparatus shown in FIG. 2 with the sealing mechanism of FIG. 45, was used. The apparatus shown in FIG. 2 having the sealing mechanism of FIG. 45 was modified so as to hold the COC syringe barrel at the contact portion that seals at the bottom of the COC syringe barrel. The lid was made from a polypropylene lid that seals the stainless steel luer attachment and the end of the COC syringe barrel (shown in FIG. 26), allowing the inside of the COC syringe barrel to be evacuated.

              The container holder 50 is made of Delrin (registered trademark) acetal resin as a raw material and has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The container holder 50 was stored in a Delrin (registered trademark) structure that allows the device to enter and exit the electrode 160.

              The electrode 160 was made from copper and Delrin® shield. The Delrin (registered trademark) shield was conformed to the outer periphery of the copper electrode 160. The dimensions of the electrode 160 were about 3 inches (76 mm) in height and about 0.75 inches (19 mm) in width. The COC syringe barrel was inserted into the container holder 50, and the bottom was sealed with Viton (registered trademark) O-ring.

              The COC syringe barrel was carefully moved to a closed position above the extended (steady) 1/8 inch (3 mm) diameter brass probe or counter electrode 108 and pressed against the copper plasma shield. The copper plasma shield is a perforated copper foil material (K & S Engineering, part number: LXMUW5 Copper mesh) cut to fit the outer diameter of the COC syringe barrel and inserted into the COC syringe barrel (see Figure 45) It was fixed at a predetermined position by a radially extending contact part surface 494 functioning as a stop part. The two copper meshes were fitted tightly around the brass probe or counter electrode 108 to ensure good electrical contact.

              The probe or counter electrode 108 was extended about 20 mm into the COC syringe barrel, and its end was opened. The brass probe or counter electrode 108 was extended through the Swagelok® attachment at the bottom of the container holder 50 and extended through the bottom structure of the container holder 50. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

              The gas supply port 110 was connected to a stainless steel assembly consisting of a Swagelok® fitting that contained a manual vent ball valve, thermocouple pressure gauge and bypass valve connected to the vacuum pump line. In addition, the gas system is connected to the gas supply port 110 and the process gas, oxygen and hexamethyldisiloxane (HMDSO) flow into the COC syringe barrel through the gas supply port 110 (under process pressure). I tried to do it.

              The gas system consists of an Aalborg (R) GFC17 mass flow meter (Cole Parmer part number: EW-32661-34), which flows oxygen at 90 sccm (or the specific flow reported in the specific example). This treatment was for controllable flow into a PEEK capillary (outer diameter 1/16 inch (3 mm), inner diameter 0.004 inch (0.1 mm)) 49.5 inches (1.26 m) in length. The PEEK capillary end was inserted into fluid hexamethyldisiloxane (Alfa Aesar® part number L16970, NMR, Grade). The fluid HMDSO was aspirated through the capillary due to the low pressure in the COC syringe barrel tube being processed. The HMDSO then became vapor at the end of the capillary when it reached the low pressure region.

              To prevent condensation of the fluid HMDSO beyond this point, the gas flow (including oxygen) that does not flow into the COC syringe barrel for treatment via the Swagelok (registered trademark) three-way valve Detoured to the line.

              After the installation of the COC syringe barrel, the vacuum pump valve was opened into the container holder 50 and the COC syringe barrel. The vacuum pump system was composed of an Alcatel rotary blade vacuum pump and a blower. The pump system made it possible to reduce the inside of the COC syringe barrel to a pressure of less than 150 mTorr while flowing the processing gas at the display rate. In contrast to the tube, a low pump pressure could be achieved using the COC syringe barrel. This is because the COC syringe barrel has a smaller content.

              After achieving the bottom vacuum level, the container holder 50 assembly was moved into the electrode 160 assembly. The gas stream (oxygen and HMDSO vapor) was flowed into the brass gas supply port 110 (the three-way valve was adjusted from the pump line to the gas supply port 110). The pressure in the COC syringe barrel was about 200 mTorr as measured by a capacitance manometer (MKS) installed on the pump line close to the valve controlling the vacuum. In addition to the COC syringe barrel pressure, the pressure in the gas supply port 110 and gas system was also measured with the thermocouple gauge connected to the gas system. This pressure was usually less than 8 Torr.

              After flowing the gas into the COC syringe barrel, the RF power supply device was turned on to adjust its power level. An ENI ACG-6 600 watt RF power supply was used (at 13.56 MHz) at a regulated power level of about 30 watts. The RF power supply was connected to a COMDEL CPMX1000 auto-matching device that matched the complex impedance of the plasma (to create in the COC syringe barrel) with the output impedance of the 50 ohm ENI ACG-6 RF power supply. . Because the forward power was 30 watts (or whatever value reported in the examples) and the reflected power was 0 watts, power was delivered inside the COC syringe barrel. The RF power supply was controlled by a laboratory timer, and the time to turn on the power was set to 5 seconds (or a specific period reported in a specific example).

              The RF power was started and the uniform plasma was fixed inside the COC syringe barrel. The plasma was held completely for 5 seconds (or other coating time indicated in the specific example) until the RF power was shut off by the timer. The plasma produced a silicon oxide coating with a layer thickness of about 20 nm (or the layer thickness reported in the specific example) inside the COC syringe barrel surface.

              After coating, the gas flow was returned to the vacuum line and the vacuum valve was closed. The vent valve was then opened, and the inside of the COC syringe barrel was returned to ambient atmospheric pressure (about 760 Torr). The COC syringe barrel was then carefully removed from the container holder 50 assembly (after the container holder 50 assembly was removed from the electrode 160 assembly).

Protocol for coating the inside of a COC syringe barrel with OMCTS lubricity coating (used in Examples 11, 12, 15-18, 20, etc.)
The previously identified COC syringe barrel was internally coated with a lubricious coating. A particular possible embodiment, the apparatus shown in FIG. 2 with the sealing mechanism of FIG. 45, was used. The apparatus shown in FIG. 2 having the sealing mechanism of FIG. 45 was modified so as to hold the COC syringe barrel at the contact portion that seals at the bottom of the COC syringe barrel. The lid was made from a polypropylene lid that seals the stainless steel luer attachment and the end of the COC syringe barrel (shown in FIG. 26), allowing the inside of the COC syringe barrel to be evacuated. By installing the beech N O-ring at the luer attachment part, it became possible to hermetically seal, and the inside of the COC syringe barrel could be evacuated.

              The container holder 50 is made of Delrin (registered trademark) acetal resin as a raw material and has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The container holder 50 was stored in a Delrin (registered trademark) structure that allows the device to enter and exit the electrode 160.

              The electrode 160 was made from copper and Delrin® shield. The Delrin (registered trademark) shield was conformed to the outer periphery of the copper electrode 160. The dimensions of the electrode 160 were about 3 inches (76 mm) in height and about 0.75 inches (19 mm) in width. The COC syringe barrel was inserted into the container holder 50, and the bottom of the finger flange and the edge of the COC syringe barrel were sealed with Viton (registered trademark) O-ring.

              The COC syringe barrel was carefully moved to a closed position above the extended (steady) 1/8 inch (3 mm) diameter brass probe or counter electrode 108 and pressed against the copper plasma shield. The copper plasma shield is a perforated copper foil material (K & S Engineering, part number: LXMUW5 Copper mesh) cut to fit the outer diameter of the COC syringe barrel and inserted into the COC syringe barrel (see Figure 45) It was fixed at a predetermined position by a radially extending contact part surface 494 functioning as a stop part. The two copper meshes were fitted tightly around the brass probe or counter electrode 108 to ensure good electrical contact.

              The probe or counter electrode 108 was extended about 20 mm into the COC syringe barrel (unless otherwise indicated), and its end was opened. The brass probe or counter electrode 108 was extended through the Swagelok® attachment at the bottom of the container holder 50 and extended through the bottom structure of the container holder 50. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

              The gas supply port 110 was connected to a stainless steel assembly consisting of a Swagelok® fitting that contained a manual vent ball valve, thermocouple pressure gauge and bypass valve connected to the vacuum pump line. In addition, the gas system is connected to the gas supply port 110 so that the process gas and octamethylcyclotetrasiloxane (OMCTS) (or the specific process gas reported in a specific embodiment) are connected to the gas supply port 110 (process (Under pressure) and into the COC syringe barrel.

              The gas system consisted of a commercially available Horiba VC1310 / SEF8240 OMCTS 10SC 4CR thermal mass flow vaporization system that heats the OMCTS to about 100 ° C. The Horiba system was passed through a 1/8 inch (3 mm) outside diameter 1/8 inch (3 mm) PFA tube with a fluid octamethylcyclotetrasiloxane (Alfa Aesar®, part number: A12540, 98 %). The OMCTS flow rate was set at 1.25 sccm (and the specific organosilicon precursor flow rate reported in the specific examples). In order to prevent condensation of the vaporized OMCTS beyond this point, the gas flow that does not flow into the COC syringe barrel for processing via the Swagelok (registered trademark) 3-way valve is diverted to the pump line. It was.

              After the installation of the COC syringe barrel, the vacuum pump valve was opened into the container holder 50 and the COC syringe barrel. The vacuum pump system was composed of an Alcatel rotary blade vacuum pump and a blower. With the pump system, the inside of the COC syringe barrel can be reduced to a pressure of less than 100 mTorr while the process gas flows at the display rate. In this case, a lower pressure was achieved compared to the tube and COC syringe barrel examples described above. This is because the processing gas flow rate in this case is generally low.

              After achieving the bottom vacuum level, the container holder 50 assembly was moved into the electrode 160 assembly. The gas flow (OMCTS steam) was flowed into the brass gas supply port 110 (the three-way valve was adjusted from the pump line to the gas supply port 110). The pressure in the COC syringe barrel was about 140 mTorr as measured by a capacitance manometer (MKS) installed on the pump line close to the valve controlling the vacuum. In addition to the COC syringe barrel pressure, the pressure in the gas supply port 110 and gas system was also measured with the thermocouple gauge connected to the gas system. This pressure was usually less than 6 Torr.

              After the gas flowed into the COC syringe barrel, the RF power supply device was turned on to adjust the power level. An ENI ACG-6 600 watt RF power supply was used (at 13.56 MHz) at a regulated power level of approximately 7.5 watts (and other power levels indicated in specific examples). The RF power supply was connected to a COMDEL CPMX1000 auto-matching device that matched the complex impedance of the plasma (to create in the COC syringe barrel) with the output impedance of the 50 ohm ENI ACG-6 RF power supply. . Since forward power was 7.5 watts and reflected power was 0 watts, 7.5 watts of power (or different power levels carried in any example) was delivered inside the COC syringe barrel. The RF power supply was controlled by a laboratory timer, and the time to turn on the power was set to 10 seconds (or a different period as described in any of the examples).

              The RF power was started and the uniform plasma was fixed inside the COC syringe barrel. The plasma was held for the entire coating time until the RF power was shut off by the timer. The plasma produced a lubricious coating inside the COC syringe barrel surface.

              After coating, the gas flow was returned to the vacuum line and the vacuum valve was closed. The vent valve was then opened, and the inside of the COC syringe barrel was returned to ambient atmospheric pressure (about 760 Torr). The COC syringe barrel was then carefully removed from the container holder 50 assembly (after the container holder 50 assembly was removed from the electrode 160 assembly).

Protocol for coating the inside of the COC syringe barrel with HMDSO coating (used in Examples 12, 15, 16, 17, etc.)
Further, except when replacing HMDSO with OMCTS, the HMDSO coating material was applied using the “Protocol for coating the inside of the COC syringe barrel with the OMCTS lubricity coating material”.

Example 1:
V. In the following tests, described in the protocol for forming COC tubes using hexamethyldisiloxane (HMDSO) as the organosilicon ("O-Si") that feeds the PECVD equipment in Figure 2 As shown, the SiO _x coating was applied to the inner surface of the cyclic olefin copolymer (COC) tube. The deposition conditions are summarized in the protocol for coating the interior of the tube with SiO _x and Table 1. The control was a similar tube with no barrier coating applied. Subsequently, the oxygen transmission rate (OTR) and the water vapor transmission rate (WVTR) were tested on the coated tube and the uncoated tube.

V. Referring to Table 1, the uncoated COC tube had an OTR of 0.215 cc / tube. Tubes A and B subjected to PECVD for 14 seconds had an average OTR of 0.0235 cc / tube. These results indicate that the SiO _x coating provided 9: 1 oxygen permeable BIF in the ratio of uncoated tube. In other words, the SiO _x barrier coating material has reduced the amount of oxygen permeating the tube to less than 1/9 of the value of the uncoated tube.

Tube C subjected to V.PECVD for 7 seconds had an average OTR of 0.026. This result indicates that the SiO _x coating provided an 8: 3 OTR BIF in the uncoated tube ratio. In other words, the SiO _x barrier coating applied in 7 seconds reduced the amount of oxygen permeating the tube to less than one-eighth of the value of the uncoated tube.

V. The related water vapor transmission rate of the same barrier coating on COC tube was measured. The uncoated COC tube had a WVTR of 0.27 mg / tube / day. Tubes A and B subjected to PECVD for 14 seconds had an average WVTR of 0.10 mg / tube / day or less. Tube C subjected to PECVD for 7 seconds had a WVTR of 0.10 mg / tube / day. This result indicates that the improvement in blocking the water vapor transmission rate of the SiO _x coating (WVTR BIF) was about 2.7 above the uncoated tube. This is a surprising result. This is because the uncoated COC tube already has a very low water vapor transmission rate.

Example 2:
V. A series of PET tubes manufactured according to “Protocols for molding PET tubes” were coated with SiO _x according to “Protocols for coating tube interior with SiO _x ” under the conditions reported in Table 2. . Controls were made according to the protocol for molding PET tubes and were left uncoated. OTR and the water vapor transmission rate specimen of the tube were prepared by epoxy sealing the open end of each tube to the aluminum adapter.

              In a separate test, the OTR BIF was tested using similar coated PET tubes, with various lengths of mechanical abrasion induced by steel needles passing through the inner coating. Controls were uncoated or similar coated tubes with no induced scratching. The OTR BIF decreased but still exceeded the uncoated tubes (Table 2A).

The tubes tested for V.OTR are: Each specimen / adapter assembly was attached to a MOCON® Oxtran 2/21 oxygen permeability measurement device. The specimen can be equilibrated to permeability steady state (1-3 days) under the following test conditions:
Test gas: Oxygen Test gas concentration: 100%
Test gas humidity: 0% relative humidity Test gas pressure: 760mmHg
Test temperature: 23.0 ° C (73.4 ° F)
Carrier gas: 98% nitrogen, 2% hydrogen Carrier gas humidity: 0% relative humidity

              V.OTR is reported in Table 2 as the average of the two decisions.

The tubes tested for V.WVTR are as follows. The specimen / adapter assembly was mounted on a MOCON® Permatran-W 3/31 water vapor permeability measurement device. The specimen can be equilibrated to permeability steady state (1-3 days) under the following test conditions:
Test gas: Water vapor Test gas concentration: Not applicable Test gas humidity: 100% relative humidity Test gas temperature: 37.8 ( ^o C) 100.0 ( ^o F)
Carrier gas: Dry nitrogen Carrier gas humidity: 0% relative humidity

              WVTR is reported in Table 2 as the average of the two determinations.

Example 3:
A series of syringe barrels were made according to the protocol for molding the COC syringe barrel. The syringe barrel was barrier coated with SiO _x or did not comply with the conditions reported in the modified “Protocol for coating the inside of a COC syringe barrel with SiO _x ” as shown in Table 3.

              The syringe barrel OTR and WVTR specimens were prepared by epoxy sealing the open ends of each syringe barrel to the aluminum adapter. Furthermore, the syringe barrel capillary end was sealed with epoxy. The syringe assembly was tested for OTR or WVTR in the same manner as the PET tube specimen, again with the MOCON® Oxtran 2/21 Oxygen Permeability Analyzer and MOCON® Permatran- W 3/31 water vapor transmission A rate measuring device was used. The results are reported in Table 3.

Example 4:
X-ray photoelectron spectroscopy (XPS) / chemical analysis electron spectroscopy (ESCA) surface composition analysis using plasma analysis
A PET tube manufactured according to VA “Protocol for molding PET tube” and coated according to “Protocol for coating tube inside with SiO _x ” is cut in half to expose the inner surface of the tube, and X-ray photoelectron spectroscopy Analysis using the method (XPS).

              V.A. The XPS data was quantified using the associated sensitivity factor and a model assumed to be a uniform layer. The analysis volume is the product of the analysis range (spot size or aperture size) and the information depth. Photoelectrons are generated within the X-ray penetration depth (typically in microns), but only the photoelectrons that fall within the top three photoemission escape depths are detected. The escape depth is about 5 to 35 mm and the analysis depth is 50 to 100 mm or less. In general, 95% of the signal originates at this depth.

VA Table 5 shows the atomic ratio of the detected element. The analysis parameters used for XPS are as follows:

              V.A.XPS does not detect hydrogen or helium. The predetermined value is normalized to Si = 1 for the experiment number (last row) using the detection element, and O = 1 for the uncoated polyethylene terephthalate calculation and examples. The detection limit is about 0.05 to 1.0 atomic percent. The predetermined value is normalized to 100% Si + O + C atoms.

VA The inventive sample has a Si / O ratio of 2: 4, indicating an SiO _x composition with residual carbon from insufficient oxidation of the coating. This analysis demonstrates that the composition of the SiO _x barrier layer applies to the polyethylene terephthalate tube according to the invention.

VA Table 4 shows the layer thickness of the SiO _x specimen determined using the TEM described in the following method. A specimen for focused ion beam (FIB) cross-section observation was prepared by coating the specimen with a sputter layer of platinum (layer thickness 50-100 nm) using the K575X Emitech coating system. The coated specimen was placed in the FEI FIB200 FIB system. An additional platinum layer was FIB deposited by injecting an organometallic gas while rastering a 30 kV gallium ion beam into the region of interest. The area of interest for each specimen was chosen to be half the length of the tube. A thin section with a length of about 15 μm (“micrometer”), a width of 2 μm, and a depth of 15 μm was extracted from the mold surface using the original in-situ FIB liftout method. The cross section was attached to a 200 mesh copper TEM grid using FIB deposited platinum. One to two windows of each section size approximately 8 μm wide were thinned into a watermark using a FEI FIB gallium ion beam.

              V.C. Cross-sectional image analysis of the prepared specimens was performed using a transmission electron microscope (TEM). The image data was digitally recorded.

The specimen grid was transferred to a Hitachi HF2000 transmission electron microscope. The transferred electronic image was acquired at an appropriate magnification. The related equipment settings used for image acquisition are as follows.

Example 5:
Plasma uniformity
A COC syringe barrel manufactured according to VA “Protocol for Molding a COC Syringe Barrel” was processed using a “Protocol for coating the inside of a COC syringe barrel with SiO _x ” with the following modifications. Three different modes of plasma generation were tested for coating a syringe barrel (eg 250) with a SiO _x film. In VA mode 1, a hollow cathode plasma ignition was generated in the gas inlet 310, the restriction region 292, and the processing vessel lumen 304, and normal / non-hollow cathode plasma was generated in the remaining portion of the vessel lumen 300. .

              In V.A. mode 2, hollow cathode plasma ignition was generated in restricted region 292 and process vessel lumen 304, and normal / non-hollow cathode plasma was generated in the vessel lumen 300 and the remainder of gas inlet 310.

              In V.A. mode 3, normal / non-hollow cathode plasma was generated throughout the vessel lumen 300 and the gas inlet 310. This was achieved by gradually increasing the power to quench the hollow cathode ignition. The conditions used to achieve these modes are shown in Table 6.

After VA, the syringe barrel 250 was exposed to ruthenium oxide staining. The dyeing was produced from sodium hypochlorite bleach and ruthenium ^(III) chloride hydrate. 0.2 g of ruthenium ^(III) chloride hydrate was placed in a vial. 10 ml of bleach was added and mixed well until the ruthenium (III) chloride hydrate was dissolved.

              Each syringe barrel was sealed with a plastic luer seal, and three drops of the staining mixture were added to each syringe barrel. The syringe barrel was sealed with aluminum tape and left for 30-40 minutes. For each series of syringe barrels to be tested, at least one uncoated syringe barrel was stained. The syringe barrel was stored with the restricted area 292 facing upward.

Based on the VA staining method, the following conclusions can be drawn:
VA1. Within 0.25 hours of exposure, the staining began to adhere to the uncoated (or undercoated) areas.

VA2. The restricted area 292 was covered with SiO _x by igniting in the restricted area 292.

              V.A.3. Tests conducted without hollow cathode plasma ignition in either the gas inlet 310 or the restricted area 292 produced the best syringe barrel. Only the restrictive opening 294 was stained, probably due to leakage of the staining.

              V.A.4. Staining is a good qualitative tool for guiding uniform work.

Based on all the above VA, we concluded that:
VA1. Under the test conditions, hollow cathode plasma in either the gas inlet 310 or the restricted region 292 inhibits the uniformity of the coating.

              V.A.2. Best uniformity was obtained when performed without hollow cathode plasma ignition in either the gas inlet 310 or the restricted region 292.

Example 6:
Interference fringes from reflection measurements-desk top example
VI.A. UV-visible source (Ocean Optics DH2000-BAL Deuterium Tungsten 200-1000nm), fiber optic reflection probe (emitter / collector complex Ocean Optics QR400-7 SR / BX with probe range of about 3mm), small detector ( Ocean Optics HR4000CG UV-NIR spectrometer) and software that converts the spectrometer signal into a transmission graph on a laptop computer, using a non-coated PET tube Becton Dickinson (Franklin Lakes, NJ, USA), product number 366703 13x75mm (No addition), with no interference fringes observed, using the probe in the longitudinal direction along the inner circumference of the tube and along the inner wall of the tube (radially from the tube centerline and thus perpendicular to the coated surface) Scan with a probe that emits and collects light. The Becton Dickinson product number 366703 13x75 mm (no additional) SiO _x plasma BD 366703 tube is _{then coated to a layer thickness of 20 nm with} the SiO _{2 coating} described in the protocol for coating the inside of the tube with SiO _{x .} The tube is scanned in the same manner as the uncoated tube. Obvious interference fringes were observed in the cladding, and certain wavelengths were enhanced in the periodic pattern and others were canceled, indicating the presence of coating on the PET.

Example 7:
Enhanced light transmission by integrating integrating sphere detection
VI.A. The equipment used was an Xenon light source (Ocean Optics HL-2000-HP-FHSA-20W halogen lamp source (185-2000nm)), integrating sphere detector machined to house the PET tube inside ( Ocean Optics ISP-80-8-I), and HR2000 + ES sensitivity-enhanced UV.VIS with optical transmission source and optical receiver optical fiber source (QP600-2-UV-VIS-600um Premium Optical FIBER, UV / VIS, 2m) Spectrometer and signal conversion software (SPECTRASUITE-Cross-platform Spectroscopy Operating SOFTWARE). An uncoated PET tube produced according to the protocol for molding a PET tube was inserted into a TEFZEL tube grip (pack) and inserted into the integrating sphere. The absorbance (615 nm) was set to zero using the Spectrasuite software in absorption mode. A SiO _x coated tube manufactured according to the “Protocol for molding PET tube” and coated according to the “Protocol for coating the inside of a tube with SiO _x ” (except when modified in Table 6) is mounted on the pack. And inserted into an integrating sphere, and the absorbance was recorded at a wavelength of 615 nm. The data is displayed in Table 16.

With respect to the SiO _x- coated tube, an increase in the absorbance was observed compared to the uncoated material, and the absorbance increased as the number of coatings was increased. The detection time was less than 1 second.

               VI.A. The spectroscopy should not be considered limited by the collection mode (eg reflection, transmission, absorption), the frequency or type of radiation applied, or other parameters.

Example 8:
Gas emission measurement on PET
This FIG. 30, adapted from FIG. 15 of US Pat. No. 6,584,828, is used to form a “PET tube that has been pre-filled using a sealing portion 360 at the upstream end of a micro flow technology measuring box (usually 362). In an example of measuring outgassing through the inside of a wall 346 of a PET tube 358 made according to the `` Protocol '' through a SiO <sub>x</sub> barrier coating 348 applied according to the `` Protocol for coating the inside of a tube with SiO _x '' FIG. 4 is a schematic diagram of the test setup used.

              VI.B. Vacuum pump 364 with commercially available measuring box 362 (leakage test equipment model ME2 mounted Intelligent Gas Leak System, 2nd generation IMFS sensor (all range 10μ / min), absolute pressure sensor range: 0 to 10 Torr, Flow measurement uncertainty: +/- 5% of measured value, Leak-Tek program for automatic data acquisition (with PC) and trace / plot of time-specific leakage flow in the range to be calibrated. (Provided by Inc.)). Further, in order to determine the mass flow rate of the vapor released from the wall into the container 358, the gas was sucked from the inside of the PET container 358 through the measurement box 362 in the direction of the arrow.

              VI.B. It was interpreted that the measurement box 362 schematically shown and described herein operates as follows. However, this information may deviate to some extent from the actual operation of the device. The box 362 has a conical path 368 that runs in the direction in which gas discharge flows. The pressure was applied at two transverse inner diameters 370 and 372 arranged longitudinally along the path 368 and fed in turn to the chambers 374 and 376 (partially shaped by the diaphragms 378 and 380). . The pressure accumulated in each chamber 374 and 376 deflects each diaphragm 378 and 380. The deflection is measured in an appropriate manner, such as measuring the variation in capacitance between the conductive surfaces of the diaphragms 378 and 380 and the adjacent conductive surfaces 382 and 384, and the like. By optionally providing a bypass 386 to bypass the measurement box 362 until the desired vacuum level in the test run is achieved, the initial pump down can be accelerated.

              VI.B. The PET wall 350 of the container used in this test had a thickness of about 1 mm, and the coating material 348 had a layer thickness of about 20 nm (nanometers). Therefore, the thickness ratio of the wall 350 to the covering material 348 was about 50,000: 1.

              VI.B. In order to determine the flow rate through the measuring box 362 including the container sealing part 360, 15 glass containers having substantially the same size and structure as the container 358 are continuously placed on the container sealing part 360. And pumped down to an internal pressure of 1 Torr, after which capacitance data was collected for the measurement box 362 and converted to a “gas out” flow rate. The test was performed twice for each container. After the first run, the vacuum was released with nitrogen and the vessel was given a recovery time to equilibrate before proceeding to the second run. At least most of this measurement is a measure of the leakage of the container and its relationship with the measuring box 362, as glass containers emit little gas and are considered essentially impermeable to their walls. It can be said. Also, accurate outgassing or permeation (if any) is hardly reflected. The results are shown in Table 7.

              The line group of the plot 390 in FIG. 31 shows the “gas release” flow rate of individual tubes corresponding to the second execution data in Table 7 (the unit is also microgram / minute). The flow rate is due to leakage because the flow rate in the plot does not increase substantially over time and is significantly lower than other flow rates.

              The lineage of VI.B. Table 8 and plot 392 in Figure 31 shows similar data for uncoated tubes made according to the protocol for forming PET tubes.

              VI.B. This data shows an increased flow rate for uncoated tubes. The increase is due to the discharge flow rate of the gas confined inside the container wall. There are some differences between the containers, indicating a slight difference between the containers and / or the sensitivity of the test to the method of loading the test apparatus.

Lines 394 and 396 in the plots of Table 9 and Fig. 31 show that the interior of the PET tube is made of SiO _x on the inside of the wall 346 of the PET tube made according to the protocol for molding a PET tube. Similar data is shown for the SiO _x barrier coating 348 coated according to the “Protocol for Coating”.

Since the flow rate in this test is consistently lower compared to VI.B. uncoated PET tubes, the SiO _x coating material functions as a barrier layer that limits gas release from the PET container wall. An example SiO _x coated injection molded PET tube is shown by curve family 394. (It is confirmed that the SiO _x coating itself hardly emits gas.) The separation between the curves 394 shown corresponding to each container distinguishes the slightly different barrier properties of the SiO _x coating on various tubes. It is shown that this test has sufficient accuracy. The spread of the family 394 is mainly due to the gas tightness differences in the SiO _x coating, and the difference in gas release or loading integrity in the PET container wall (representing the tighter curve family 392) In contrast to Two curves 396 corresponding to Specimen 2 and Specimen 4 are the outer layer, as shown below, and the disparity from the other data indicates that the SiO _x coating of these tubes was poor. I think. This shows that different treatment / damaged specimens can be extracted very clearly by this test.

              VI.B. Referring to Tables 8 and 9 above and FIG. 32, the data were statistically analyzed to obtain the average and first and third standard deviation values above and below the average. The values are plotted in FIG.

              VI.B. This statistical analysis first shows that specimens 2 and 4 in Table 9 representing coated PET tubes are clear outer layers, which are more than +3 standard deviations away from the average. However, the outer layers are shown to have some blocking effectiveness because their flow rate is still far (lower) from the flow rate of the uncoated PET tube.

              VI.B. This statistical analysis is also used to quickly and accurately analyze the barrier effectiveness of nanometer layer thickness barrier coatings, and to distinguish between coated and uncoated tubes (this coating layer thickness). It is believed that it cannot be distinguished using human perception). According to Figure 32, a coated PET container (shown in the top group of bars) that outgases three standard deviations above the mean is uncoated at a level that outgasses three standard deviations below the mean. Outgassing is less than PET containers (indicated at the bottom group of bars) In this data, there is no duplication of data reaching a certainty level exceeding 6σ (six sigma).

VI.B. Based on the success of this test, the presence or absence of the SiO _x coating material on these PET containers is considerably shorter than that of this example, especially because statistics are generated from a large number of specimens. It is conceivable that it can be detected by this test. This is evident, for example, from a lineage of smooth and well-divided plots where T = 12 seconds for a sample of 15 containers, and the test period following the origin about T = 11 seconds is about 1 second. Indicates.

VI.B. Based on this data, the barrier effectiveness of a SiO _x- coated PET container that is close to or equivalent to that of glass can be achieved by optimizing the SiO _x coating material. .

Example 9:
Wetting tension-plasma coated PET tube example
VII.A.1.a.ii. The wet tension measurement method is an improvement of the method described in ASTM D 2578. Wetting tension is a specific measurement of surface hydrophobicity or hydrophilicity. The method uses a standard wetting tension solution (called a dyne solution) to determine how close the solution is to the wet state of the plastic membrane surface in 2 seconds. This is the wetting tension of the film.

              VII.A.1.a.ii. The procedure used is different from that of ASTM D 2578, the substrate is not a flat plastic membrane, but is manufactured according to the “Protocol for Molding PET Tubes” (except for controls) It is a tube coated according to the “Protocol for coating the inside of a tube with hydrophobicity”. A silicon-coated glass syringe (Becton Dickinson Hypak® PRTC glass, prefillable syringe with luer end) (1 mL) was also tested. The results of this test are listed in Table 10.

Surprisingly, the plasma coating of uncoated PET tubes (40 dynes) is higher (more hydrophilic) using the same hexamethyldisiloxane (HMDSO) feed gas by changing the plasma treatment conditions. Of) or lower (more hydrophobic) energy surfaces. A thin film (approximately 20-40 nanometers) SiO _x coating (not shown in the table) made according to the protocol for coating the interior of the tube with SiO _x provides wettability similar to a hydrophilic bulk glass substrate . Thin film (less than about 100 nanometers) hydrophobic coating made according to the protocol for coating tube interior with hydrophobic coating provides non-wetting properties similar to hydrophobic silicon fluids (data not shown in the table) ).

Example 10:
Vacuum maintenance study of tubes via accelerated aging
VII.A.3 Accelerated aging allows rapid evaluation of products with long shelf life. The accelerated aging of blood tubes with respect to vacuum maintenance is described in US Pat. No. 5,792,940, column 1, lines 11-49.

VII.A.3 Three types of polyethylene terephthalate (PET) 13x75mm (wall thickness 0.85mm) mold tubes were tested:
Hemogard (R) system Becton Dickinson product number 366703 13x75mm (no additional) tube closed with a colorless guard and colorless guard (shelf life 545 days or 18 months) [commercial product control], protocol for molding PET tubes PET tube closed with similar Hemogard® system red stop and colorless guard [internal control], and according to the protocol for molding the PET tube
Injection molded PET 13x75mm tube [invention specimen] coated according to the protocol for coating with, and closed with a similar Hemogard® system red stop and colorless guard.

              VII.A.3 The BD commercial product control was used as delivered. The internal controls and invention samples were evacuated and capped with the stop member system to provide the desired partial pressure (vacuum) in the tube after sealing. All specimens were placed in a 3 gallon (3.8 L) 304 SS wide-mouth pressure vessel (Sterlitech # 740340). The pressure vessel was pressurized to 48 psi (3.3 atm, 2482 mm.Hg). Water volume aspiration fluctuation determination: (a) remove 3-5 specimens at increasing time intervals, (b) permit the suction of water from the 1 liter plastic bottle reservoir through the 20 gauge blood collection adapter, and (C) Measurement was performed by measuring the mass fluctuation before and after water suction.

              VII.A.3 The results are shown in Table 11.

              VII.A.3 Calculate the normalized mean decay rate by dividing the variation in mass by the number of days of pressurization and the initial mass suction [mass variation / (days x initial mass)]. Calculate the promotion time (month) to 10% loss. Both data are listed in Table 12.

VII.A.3 The data shows that both the commercial control and the uncoated internal control have the same vacuum loss rate. Surprisingly, incorporating the SiO _x coating on the PET inner wall improves the vacuum maintenance due to the 2.1 factor.

Example 11:
Lubricious coating
VII.B.1.a. The following components were used in this study:
Commercially available (BD Hypak (R) PRTC) glass prefillable syringe with Luer-lok (R) end (ca 1 mL)
A COC syringe barrel made according to the protocol for molding the COC syringe barrel;
Commercial plastic syringe plunger taken from Becton Dickinson product number 306507, with elastomeric end (obtained as a saline prefilled syringe);
Saline (taken from pre-filled syringe with Becton-Dickinson product number 306507);
Dillon test stand with Advanced Force gauge (model AFG-50N) Syringe gripping member and discharge pipe jig (assembled to attach to the Dillon test stand)

              VII.B.1.a. The following procedure was used in this study:

              VII.B.1.a. The jig was placed on the Dillon test bench. The movement of the platform probe was adjusted to 6 inches / minute (2.5 mm / second), and upper and lower stop positions were set. The stop position was confirmed using an empty syringe barrel. The commercially available saline-filled syringe was labeled, the plunger was removed, and the saline was drained through the open end of the syringe barrel (for reuse). Spare plungers were obtained in the same way for use with the COC and glass barrel.

              VII.B.1.a. Insert syringe plungers into the COC syringe barrel and equalize the second horizontal mold point of each plunger with the syringe barrel edge (about 10 mm from the end). A separate syringe and needle assembly was used to fill the test syringe with 2-3 ml of saline via the capillary end. At that time, the end of the capillary was positioned at the top. Tap the side of the syringe to remove the larger bubbles along the plunger / fluid interface and the wall, and carefully expel the bubbles from the syringe while maintaining the plunger in its vertical orientation. It was.

              VII.B.1.a. Each filled syringe barrel / plunger assembly was placed in the syringe jig. The test was started by pressing the down switch on the test stand, and the movable hammer was advanced toward the plunger. When the movable hammer is within 5mm of contact with the top of the plunger, press the data button on the Dillon module repeatedly until the plunger comes into contact with the syringe barrel front wall before the initial contact with the syringe plunger. The force during the period of pressing each data button until it stopped was recorded.

              VII.B.1.a. All benchmarks and coated syringe barrels were repeated 5 times (using a new plunger and barrel each time).

              VII.B.1.a. COC syringe barrel made according to “Protocol for molding COC syringe barrel” and OMCTS lubrication coating according to “Protocol for coating the inside of COC syringe barrel with OMCTS lubricity coating” Coated with material, filled with physiological saline after assembly, and tested as described above in this example for a lubricious coating. The polypropylene chamber used in accordance with the “Protocol for Coating COC Syringe Barrel Interior with OMCTS Lubricant Coating” passes through the syringe barrel of the OMCTS vapor (and oxygen, if added-see Table 13) and the Inflow into the polypropylene chamber through the syringe capillary was made possible (however, a lubricious coating may not be necessary for the capillary portion of the syringe in this case). Several different coating conditions were tested as shown in Table 13 above. All depositions were performed on COC syringe barrels from the same production batch.

              The coated specimen was then tested using the plunger slide force test according to the protocol of this example, and the results in Table 13 were obtained in British and metric force units. The data clearly shows that the plunger sliding force of COC and coated COC syringe is lowest when low power and anoxic. Note that when oxygen is added at low power (6W) (low power is the preferred condition), the plunger slide force increased from 1.09 pounds, 0.49 kg (power = 11 W) to 2.27 pounds, 1.03 kg I want to be. This indicates that the addition of oxygen may not be desirable to achieve the lowest plunger sliding force.

              VII.B.1.a. Also, the best plunger sliding force (power = 11W, plunger sliding force = 1.09 pounds, 0.49Kg) is the current industry standard for silicon coated glass (plunger sliding force = 0.58 pounds, 0.26 Note also that it is very close to Kg) and at the same time avoids the problems of glass syringes such as possible breakage and more expensive manufacturing processes. Utilizing additional optimization, it is expected to achieve values equivalent / better than current glasses with silicon performance.

VII.B.1.a. The specimen was created by coating the COC syringe barrel according to the “Protocol for coating the inside of the COC syringe barrel with OMCTS lubricity coating material”. An alternative embodiment of the technology described herein may apply the lubrication layer onto another thin film coating, such as SiO _x , for example, coated according to the “Protocol for Coating the Inside of a COC Syringe Barrel with SiO _x ”.

Example 12:
Improved syringe barrel lubricity coating
VII.B.1.a. The force required to release 0.9 percent saline payload from the syringe through the capillary opening using a plastic plunger was determined for the syringe coated on the inner wall.

              VII.B.1.a. Three types of COC syringe barrels manufactured according to the “Protocol for Molding COC Syringe Barrels” were tested: one with no inner coating [uncoated control] and another with It has a hexamethyldisiloxane (HMDSO) -based plasma coating inner wall coating coated according to “Protocol for coating the inside of a COC syringe barrel with HMDSO” [HMDSO control], and the third type is “COC syringe barrel inside” Having an octamethylcyclotetrasiloxane-based plasma coating inner wall coating applied according to the “Protocol for Coating with OMCTS Lubricating Coating” [OMCTS-Invention Sample]. A new plastic plunger with an elastomeric end, taken from BD Product Becton-Dickinson product number 306507, was used in all examples. Saline from product number 306507 was also used.

              VII.B.1.a. The plasma coating method and the syringe barrel inner wall coating apparatus are described in another experimental section of this application. Specific coating parameters for HMDSO-based and OMCTS-based coatings include: "Protocol for coating the inside of a COC syringe barrel with HMDSO coating", "Protocol for coating the inside of a COC syringe barrel with OMCTS lubricious coating", and It is described in Table 14.

              VII.B.1.a. The plunger was inserted approximately 10 mm into the syringe barrel, after which the experimental syringe was filled vertically through an open syringe capillary with a separate saline syringe / needle system. When the experimental syringe is filled into the capillary opening, the syringe is tapped lightly to remove bubbles adhering to the inner wall and discharged upward through the capillary opening.

              VII.B.1.a. Place the pre-filled experimental syringe barrel / plunger assembly vertically in a self-made hollow metal jig and support the syringe assembly with the jig at the finger flange. The jig has a discharge tube at the bottom and is mounted on a Dillon test bench with an Advanced Force gauge (model AFG-50N). The test bench has a hammer that moves vertically downward at a speed of 6 inches (152 mm) per minute. The hammer comes into contact with the extended plunger and drains the saline solution from the capillary. Once the plunger contacts the syringe barrel / capillary interface, the experiment is stopped.

              VII.B.1.a. During the downward movement of the hammer / distraction plunger, the resistance applied to the hammer is recorded in an electronic spreadsheet as measured on the force gauge. From the spreadsheet data, the maximum force for each experiment is identified.

              VII.B.1.a.Table 14 shows, for each example, the average maximum force from the repeatedly coated COC syringe barrel and the maximum force average of the coated syringe barrel divided by the maximum force average of the uncoated syringe barrel. Describe the normalized maximum force to judge.

VII.B.1.a. All OMCTS inner wall plasma coated COC syringe barrels (Inventive Samples C, E, F, G, H) are much more than uncoated COC syringe barrels (Uncoated Control Samples A and D) The data shows that it showed low plunger sliding force and, surprisingly, also showed much lower plunger sliding force than the HMDSO-based inner wall plasma coated COC syringe barrel (HMDSO control specimen B). Further surprisingly, the plunger sliding force is kept very low by the OMCTS-based coating material on the silicon oxide film (SiO _x ) gas barrier coating material (Invention Sample F). The best plunger sliding force was Example C (power = 8, plunger sliding force = 1.1 pounds, 0.5 kg). This is very close to the current industry standard for silicon-coated glass (plunger sliding force = 0.58 pounds, 0.26 kg), while avoiding glass syringe problems such as possible breakage and more expensive manufacturing processes. Utilizing additional optimization, it is expected to achieve values equivalent / better than current glasses with silicon performance.

Example 13:
Manufacture of COC syringe barrels with external coating-a desktop example
VII.B.1.c. A COC syringe barrel made according to the protocol for molding a COC syringe barrel is sealed at both ends with a disposable closure. The lidded COC syringe barrel is immersed in a solution bath of Daran® 8100 Saran latex (Owensboro specialty plastic). The latex contains 5 percent isopropyl alcohol, reducing the surface tension of the composition to 32 dynes / cm. The latex composition completely wets the outside of the COC syringe barrel. After draining for 30 seconds, the coated COC syringe barrel is placed in each forced air oven at 275 ° F (135 ° C) for 25 seconds (latex coalescence) and 122 ° F (50 ° C) for 4 hours (finish cure). Be exposed on a heating schedule. The resulting PvDC film has a layer thickness of 1/10 mil (2.5 microns). Measure the COC syringe barrel and the PvDC-COC laminated COC syringe barrel for OTR and WVTR using MOCON brand Oxtran 2/21 oxygen permeability measuring device and Permatran- W 3/31 water vapor permeability measuring device in order. .

              VII.B.1.c. Estimated OTR and WVTR values are listed in Table 15, and the expected improvement in blockage (BIF) for the laminate is 4.3 (OTR-BIF) and 3.0 (WVTR-BIF), respectively. there is a possibility.

Example 15:
Atomic composition of PECVD-coated OMCTS and HMDSO coatings
VII.B.4. Manufactured according to “Protocol for Molding COC Syringe Barrel” and coated with OMCTS (according to “Protocol for Coating COC Syringe Barrel Interior with OMCTS Lubricant Coating”) or “ Prepare a COC syringe barrel specimen coated with HMDSO according to “Protocol for coating the inside of COC syringe barrel with HMDSO coating material”. The atomic composition of the coating from OMCTS or HMDSO was characterized using X-ray photoelectron spectroscopy (XPS).

              VII.B.4. Quantify the XPS data using the associated sensitivity factor and a model that is assumed to be a uniform layer. The analysis volume is the product of the analysis range (spot size or aperture size) and the information depth. Photoelectrons are generated within the X-ray penetration depth (typically in microns), but only the photoelectrons that fall within the top three photoemission escape depths are detected. The escape depth is about 5 to 35 mm and the analysis depth is 50 to 100 mm or less. In general, 95% of the signal originates at this depth.

VII.B.4. The following analytical parameters were used:
Equipment: PHI Quantum 2000
X-ray source: Monochromatic lens Alkα 1486.6eV
Detection angle + 23 °
Injection angle 45 °
Analysis range 600μm
Charge compensation C1s 284.8 eV
Ion gun conditions Ar +, 1 keV, 2 x 2 mm raster Sputtering rate 15.6 Å / min (equivalent to SiO ₂ )

              VII.B.4. Table 17 shows the atomic concentrations of the detected elements. XPS does not detect hydrogen or helium. Arbitrary values are normalized to 100 percent using the detection element. The detection limit is about 0.05 to 1.0 atomic percent.

VII.B.4.b. From the results of the coating composition in Table 17 and the calculated monomer precursor element percentage at the beginning, the carbon atom percentage of the HMDSO-based coating is compared with the HMDSO monomer carbon atom percentage at the beginning. Surprisingly, the OMCTS-based coating carbon atom percent increased (from 34.8% to 48.4%) and increased compared to the OMCTS monomer carbon atom percent, while decreasing (from 54.1% to 44.4%) Min 39 atomic% was calculated as follows:
100% [(48.4 / 34.8)-1] = 39 at.%.

                In addition, the silicon atom percentage of the HMDSO-based coating material is almost unchanged (21.8% to 22.2%) compared to the HMDSO monomer silicon atom percentage at the start, while surprisingly, the OMCTS-based coating silicon atom The percent was significantly reduced (from 42.0% to 23.6%) compared to the OMCTS monomer silicon atomic percent, with a decrease of 44 atomic percent. For both carbon and silicon variations, the coating action of the OMCTS monomer has a different trend than that observed with common precursor monomers (eg HMDSO). See, for example, Hans J. Griesser, Ronald C. Chatelier, Chris Martin, Zoran R. Vasic, Thomas R. Gengenbach, George Jessup J. Biomed. Mater. (Appl Biomater) 53: 235-243, 2000.

Example 16:
Volatile components from plasma coatings (“gas release”)
VII.B.4. Created according to “Protocol for Molding a COC Syringe Barrel” and coated with OMCTS (according to “Protocol for Coating the Inside of a COC Syringe Barrel with OMCTS Lubricant Coating”) or “ Prepare a COC syringe barrel specimen coated with HMDSO according to “Protocol for coating the inside of COC syringe barrel with HMDSO coating material”. Gas emission gas chromatography / mass spectrometry (GC / MS) analysis was used to measure the volatile components released from OMCTS or HMDSO coatings.

VII.B.4. The syringe barrel specimen (four COC syringe barrels cut in half vertically) is placed in the 1 1/2 inch (37 mm) diameter chamber of the dynamic headspace sampling system (CDS 8400 automatic sampler). Installed in one. Prior to specimen analysis, the system blank was analyzed. The specimen was analyzed on an Agilent 7890A gas chromatograph / Agilent 5975 mass spectrometer using the following parameters to obtain the data listed in Table 18:
GC column: 30m X 0.25mm DB-5MS (J & W Scientific),
0.25μm membrane thickness Flow rate: 1.0 ml / min, constant flow mode Detector: Mass selective detector (MSD)
Injection mode: Split injection (split ratio 10: 1)
Outgassing conditions: 1 1/2 inch (37mm) chamber, 3 hours, 85 ° C,
Purge at a flow rate of 60 ml / min. Furnace temperature: Start at 40 ° C (5 minutes) and heat to 300 ° C at 10 ° C / min.
Hold at 300 ° C for 5 minutes.

The outgassing results from Table 18 clearly showed a compositional distinction between the HMDSO-based and OMCTS-based lubricity coatings tested. The HMDSO-based composition outgassed trimethylsilanol [(Me) ₃ SiOH], but no outgassing of polymeric oligomers containing repetitive-(Me) ₂ SiO- moieties was measured. On the other hand, for the OMCTS-based composition, outgassing of trimethylsilanol [(Me) ₃ SiOH] was not measured, but polymer oligomers containing repetitive-(Me) ₂ SiO- moieties were outgassed. This test may help to distinguish between HMDSO and OMCTS coatings.

Without limiting the invention according to the scope / accuracy of the following theory, this result shows that for each acyclic chemical structure of HMDSO in which each silicon atom is bonded to three methyl groups, only two methyl groups are This can be explained by taking into account the cyclic chemical structure of OMCTS bonded to the silicon atom. OMCTS is believed to react with the ring opening to form diradicals with repetitive-(Me) ₂ SiO- moieties that are already oligomeric and congealable to form polymeric oligomers. On the other hand, HMDSO reacts to the cleavage of a certain O-Si bond, and a fragment containing a single O-Si bond re-condensed as (Me) ₃ SiOH and O-re-coagulated as [(Me) ₃ Si] ₂ It is thought that other fragments that do not contain the Si bond are left.

              The cyclic nature of the OMCTS is believed to result in ring opening and condensation of the ring opening portion due to outgassing of higher molecular weight MW oligomers (26 ng / test). In contrast, based on the relatively low molecular weight of the fragments from HMDSO, it is believed that HMDSO-based coverings do not yield any polymeric oligomers.

Example 17:
Density determination of plasma coating materials using X-ray reflectivity (XRR)
Sapphire demonstration specimens (0.5 x 0.5 x 0.1 cm) were adhered to individual PET tube inner walls made according to the protocol for molding PET tubes. The PET tube containing the sapphire indication was coated with OMCTS or HMDSO (both in accordance with the “Procedure for Coating the Inside of a COC Syringe Barrel with an OMCTS Lubricant Coating”, all using twice as much power) ). The coated sapphire specimen was then removed and X-ray reflectivity (XRR) data was acquired with a PANalytical X'Pert diffractometer equipped with a parabolic multilayer incident beam monochromatic spectrometer and a parallel plate diffracted beam collimator. The coating density was determined from the critical angle measurement result using a two-layer Si _w O _x C _y H _z model. This model is believed to provide the best approach to isolating true Si _w O _x C _y H _z coatings. The results are shown in Table 19.

              From Table 17 showing the results of Example 15, the composition of OMCTS is lower in oxygen (28%) and higher in carbon (48.4%) compared to HMDSO, so both atomic mass ratings and valences (oxygen) = 2, carbon = 4) suggests that OMCTS should have a lower density. Surprisingly, the XRR density results show the opposite observation that the OMCTS density is higher than the HMDSO density.

              Without limiting the present invention according to the scope / accuracy of the following theory, it is believed that there are fundamental differences in the reaction mechanisms in the composition of each of the HMDSO and OMCTS coatings. HMDSO fragments can easily nucleate or react to form dense nanoparticles, and then deposit on the surface and react further on the surface. In contrast, OMCTS has a very low possibility of forming high-density vapor phase nanoparticles. OMCTS reactive species are very likely to condense on the surface in a form very similar to the original OMCTS monomer, producing an overall low density coating.

Example 18:
Layer thickness uniformity of PECVD coating
Manufactured according to the “Protocol for Molding the COC Syringe Barrel” and coated with SiO _x according to the “Protocol for Coating the COC Syringe Barrel Interior with SiO _x ” or “OMCTS Lubricating Coating Inside the COC Syringe Barrel” Samples of multiple COC syringe barrels coated with an OMCTS-based lubricity coating according to "Protocol for" were prepared. Also prepared according to the “Protocol for Molding PET Tubes”, and according to the “Protocol for coating the inside of a tube with SiO _x ”, specimens of multiple PET tubes coated or not coated with SiO _x are also prepared. Then, an accelerated aging test was conducted. Using transmission electron microscopy (TEM), the layer thickness of the PECVD coating material of the specimen was measured. The TEM procedure of Example 4 above was used. The method and apparatus described by the protocol for coating SiOx and lubricity used in this example provided a uniform coating as shown in Table 20.

Example 19
Gas emission measurement on COC
The COC tube was made according to the protocol for forming the VI.B.COC tube. A portion of the tube was coated with a SiOx internal barrier coating according to the “Protocol for Coating Tube Interior with SiO _x ” and other COC tubes were not coated. A commercial glass blood collection Becton Dickinson 13 x 75 mm tube with similar dimensions was also prepared as described above. The tube was stored for about 15 minutes in a room containing ambient air with a relative humidity of 45% and a temperature of 70 ° F. (21 ° C.), and the following tests were conducted at the same ambient relative humidity. The tube was tested for gas release and then tested for ATC microfluidic measurement procedure and the device of Example 8 (leakage test instrument model ME2 onboard Intelligent Gas Leak System, 2nd generation IMFS sensor (full range 10μ / min)) , Absolute pressure sensor range: 0 to 0 Torr, flow measurement uncertainty: +/- 5% of measured value, for automatic data acquisition (by PC) and trace / plot of time specific leakage flow rate in the range to be calibrated Leak-Tek program). In this case, each tube is subjected to a bulk vapor degassing procedure at a pressure of 1 mm Hg for 22 seconds, pressurized with nitrogen gas for 2 seconds (to 760 mm Hg), and then the nitrogen gas is pumped down to a pressure of about 1 mm Hg. The microfluidic measurement procedure was performed for 1 minute.

The results are shown in FIG. 57, which is similar to FIG. 31 generated in Example 8. In FIG. 57, the plot for the uncoated COC tube is at 630, the plot for the SiOx coated COC tube is at 632, and the plot for the glass tube used as a control is at 634. In addition, the gas release measurement starts in about 4 seconds, and after several seconds, the plot 630 of the uncoated COC tube and the plot 632 of the SiOx-coated COC tube are clearly differentiated, and again, the immediate insulation of the blocking and uncoated tubes again. The distinction was shown. A constant distance interval of uncoated COC (greater than 2 micrograms in 60 seconds) and a corresponding distance interval of SiO _x coated COC (less than 1.6 micrograms in 60 seconds) was achieved.

Example 20:
Lubricious coating
VII.B.1.a. COC syringe barrel made according to “Protocol for molding COC syringe barrel” and OMCTS lubrication coating according to “Protocol for coating the inside of COC syringe barrel with OMCTS lubricity coating” Covered with material. The results are shown in Table 21. The result showed an increasing tendency of the power level, and the lubricity of the coating material was improved when oxygen was 8-14 watts. Further experiments on power and flow rate may further enhance lubricity.

Example 21:
Lubricating dressings-hypothetical examples
An injection molded cyclic olefin copolymer (COC) plastic syringe barrel is made according to the protocol for molding the COC syringe barrel. Some are not coated (“control”), others are coated with a PECVD lubricating film (“lubricated syringe”) according to the “Protocol for coating the inside of a COC syringe barrel with an OMCTS lubricious coating”. The lubrication syringe and control are tested to force the plunger to begin moving within the barrel (starting force) and to maintain the plunger moving within the barrel (plunger Slide force) is measured using a Genesis Packaging automatic syringe force tester, model AST.

              This test is a modified version of the ISO 7886-1: 1993 test. The following procedure is used for each test. Remove from the syringe assembly a commercially available plastic syringe plunger with an elastomeric end, taken from Becton Dickinson product number 306507 (obtained as a saline prefilled syringe). The elastomer end is dried with clean, dry compressed air. The elastomer end and plastic plunger are then inserted into the COC plastic syringe barrel to be tested to position the plunger and further utilize the bottom of the syringe barrel. If necessary, the filled syringe is adjusted to achieve the test target state. For example, when the test object is for detecting the action of the lubricant coating material on the starting force of the syringe after being stored for 3 months, the syringe is stored for 3 months to achieve a desired state.

              The syringe is installed in the Genesis Packaging automatic syringe force tester. The test is calibrated from the beginning of the test according to the manufacturer's specifications. The input variables of the tester are speed = 100 mm / min, range = 10,000. Press the start button of the tester. At the completion of the test, the starting force (to initiate movement of the plunger within the barrel) and the plunger sliding force (to maintain movement) are measured and compared with the control syringe. The force was found to be substantially low.

              FIG. 59 shows a container processing system 20 according to an exemplary embodiment of the present invention. The container processing system 20 comprises a first processing station 5501 and a second processing station 5502, among others. Examples of such processing stations are depicted, for example, in reference number displays 24, 26, 28, 30, 32 and 34 in FIG.

              The first container processing system 5501 includes a container holder 38 that holds a loaded container 80. Although a blood tube 80 is depicted in FIG. 59, the container may be a syringe body, a vial, a catheter, or a pipette, for example. The container may be made of glass or plastic, for example. In the case of a plastic container, the first processing station may also comprise a mold for molding the plastic container.

              First processing at the first processing station (the processing includes mold of the container, first inspection for detecting defects of the container, coating of the inner surface of the container, and defect detection of the container, particularly the inner coating material) The container holder 38 is transported to the second container processing station 5502 together with the container 82. This transfer is performed by the conveyor equipment 70, 72, 74. For example, in order to move the container / holder complex to the next processing station 5502, one gripping part or a plurality of gripping parts for gripping the container holder 38 and / or the container 80 may be prepared. Alternatively, the container may be moved without the grip portion. However, if the gripping part is adapted, it can be transported by the conveyor equipment, so it may be advantageous to move the gripping part and the container together.

              FIG. 60 shows a container processing system 20 according to another exemplary embodiment of the present invention. Again, two container processing stations 5501 and 5502 are provided. In addition, additional container processing stations 5503, 5504 are deployed in succession to allow the containers to be processed, ie inspected and / or coated.

              The container can be moved from stock to the processing station 5504 on the left. Alternatively, the container can be molded at the first processing station 5504. In either case, a first container process such as molding, inspection and / or coating (which may then be followed by a second inspection) is performed at the processing station 5504. The container is then moved to the next processing station 5501 via the conveyor equipment 70, 72, 74. Generally, the container moves with the container holder. The second process is performed at the second process station 5501, and then the container and the gripper are moved to the next process station 5502 for performing the third process. The container is then (again with the gripper) moved to the fourth processing station 5503 for the fourth processing and then transported for storage.

              Before and after each coating procedure or mold procedure or other procedure that treats the container, an inspection of the entire container, a portion of the container, and particularly the inner surface of the container may be performed. The result of each inspection is transmitted to the central processing unit 5505 via the data bus 5507. Each processing station is connected to the data bus 5507. The processor 5505 (which may be adapted to the central control coordinator configuration) processes the test data, analyzes the data, and determines whether the last processing procedure was successful.

              If it is determined that the last processing procedure was unsuccessful, for example, because the dressing has holes, or the dressing surface is standard or not smooth enough, the container is placed in the next processing station. Removed from the manufacturing process (conveyor sections 7001, 7002, 7003, 7004) without progress or returned for reprocessing.

              The processor 5505 connects to a user interface 5506 for entering control / adjustment parameters.

              FIG. 61 shows a container processing station 5501 according to an exemplary embodiment of the present invention. The station includes a PECVD apparatus 5701 for coating the inner surface of the container. Further, a plurality of detectors 5702 to 5707 for container inspection are prepared. Such detectors may be, for example, electrodes that perform electrical measurements, optical detectors, CCD cameras, gas detectors, or pressure detectors.

              FIG. 62 shows an electrode having a plurality of detectors 5702, 5703, 5704 and gas inlet ports 108, 110 along with a container holder 38 as described in an exemplary embodiment of the invention.

              The electrode and the detector 5702 may be adapted to move into the lumen of the container 80 when the container is loaded in the gripping portion 38.

              For example, using an optical detector 5703, 5704 placed outside the loaded container 80, or even using an optical detector 5705 placed in the lumen of the container 80, particularly during the coating procedure. In addition, the optical inspection may be performed.

              The detector may consist of a color filter, and different wavelengths can be detected during the coating process. The processor 5505 analyzes the optical data to determine whether the coating was successful or has not reached a predetermined certainty level. If it is determined that the dressing was probably unsuccessful, each container is isolated from the processing system or reprocessed.

              While the invention has been illustrated and described in detail in the drawings and foregoing description, such illustration and description are to be considered illustrative or exemplary and not restrictive. The present invention is not limited to the disclosed embodiments. Other variations of the disclosed embodiments may be understood and brought about by those skilled in the art and practice of the claimed invention from studying the drawings, the disclosure, and the appended claims. In the claims, the term “consisting of” can include other elements or procedures, and the singular substance can be plural. The mere fact that certain measurements are recited in mutually different dependent claims does not indicate that a combination of these measurements cannot be used to benefit. Any reference signs in the claims should not be construed as limiting the scope.

              In the following list, exemplary embodiments of the present invention are described, for example, with reference to FIGS. It should be noted that although the term “claims” is used in the list below, the list below refers to exemplary embodiments, not claims.

I. Container processing system with multiple processing stations and multiple container holders
1. Container handling system 20 consists of:
The first processing station 5501, 24, 26, 28, 30 configured to process a container having a wall defining an opening and an inner surface;
The second processing station 5502, 24, 26, 28, 30 set apart from the first processing station and configured to process a container having a wall defining an opening and an inner surface;
A number of container holders 38 each including a container port 92 configured to receive and load the container opening for processing the inner surface of the loaded container via the container port at a first processing station; and
Conveyors 70, 72, carrying a series of the container holders and loaded containers from the first processing station to the second processing station for processing the inner surface of the loaded containers via the container port at the second processing station. 74.

      2. Further comprising a third processing station 5503 that is set apart from the first processing station and the second processing station and configured to process a container having a wall defining an opening and an inner surface. (See FIG. 60 for the embodiment).

      3. The conveyor transports a series of the container holders and loaded containers from the second processing station to the third processing station for processing the inner surface of the loaded containers via the container port at the third processing station. The invention of claim 2, set as follows.

      4. The invention of any one of claims 1 to 3, wherein the one or more container holders further comprise a vacuum duct for aspirating gas from a container already loaded on the one or more container ports.

      5. The invention of any one of claims 1-4, wherein the one or more container holders further comprise a vacuum port passing between the vacuum duct and an external vacuum source.

      6. The invention of any of claims 1-5, wherein the one or more vacuum ports further comprise an O-ring for receiving and forming a seal against an external vacuum source.

      7. The invention of any of claims 1-6, wherein the one or more container holders further comprise a gas inlet port for transporting gas to a container preloaded on the one or more container ports.

      8. Synthesizing one or more container holders further to one or more container ports, each carrying gas to / from gas to a container already loaded on one or more container ports The invention according to any one of claims 1 to 7, comprising a gas suction port and a vacuum port.

      9. The invention of any one of claims 1 to 8, wherein the material of the one or more container holders is a thermoplastic material.

      10. The invention of any one of claims 1 to 9, wherein the one or more container ports further comprise a sealing element for receiving and molding a seal against the container opening.

      10a. The invention of claim 10, wherein the sealing element is an O-ring.

      11. The invention of any of claims 1-10a, wherein the processing station is configured to inspect the inner surface of the container for defect detection.

      12. The invention of any one of claims 1 to 11, wherein the processing station is set to apply a coating on the inner surface of the container.

      13. The invention of any one of claims 1 to 12, wherein the processing station is configured to inspect the dressing for defect detection.

      14. The invention of any of claims 176-13, wherein the processing station is configured to measure atmospheric pressure loss through the vessel wall.

      15. The invention of any of claims 1-14, wherein the processing station comprises a support surface for supporting one or more container holders in place and processing the inner surface of the loaded container at the processing station.

      16. One of the preceding claims, wherein another processing station comprises a second support surface for supporting one or more container holders in place and processing the loaded container inner surface at the other processing station. Invention.

      17. Another processing station comprises a third support surface that supports one or more container holders in place and processes the loaded container inner surface via one or more container ports at the other processing station; The invention according to any one of claims 1 to 16.

      18. The invention according to any one of claims 1 to 17, further comprising a third processing station for container processing that is installed apart from the first and second processing stations.

      19. The invention of claim 18 further comprising a fourth processing station for container processing located remotely from the first, second and third processing stations.

      20. The invention of claim 19, further comprising a fifth processing station for container processing located remotely from said first, second, third and fourth processing stations.

      21. The invention of claim 20, further comprising a sixth processing station for container processing disposed remotely from the first, second, third, fourth and fifth processing stations.

      22. The invention of any of claims 1-21, further comprising a conveyor for transporting the one or more container holders and loaded containers from the second processing station to the third processing station.

      23. The invention of claim 22, further comprising a conveyor for transporting the one or more container holders and loaded containers from the third processing station to the fourth processing station.

      24. The invention of claim 23, further comprising a conveyor for transporting the one or more container holders and loaded containers from the fourth processing station to the fifth processing station.

      25. The invention of claim 24, further comprising a conveyor for transporting the one or more container holders and loaded containers from the fifth processing station to the sixth processing station.

      26. The invention according to any one of claims 1 to 25, further comprising a coating device for forming a coating material inside the container via one or more container ports at the processing station.

      27. The invention of any of claims 1-26, wherein the processing station comprises a PECVD apparatus.

28. The invention of claim 27, wherein the PECVD apparatus comprises:
An internal electrode positioned to be received in a fluid passage with the interior of the container loaded on the container holder;
An external electrode having an internal portion positioned to receive a loaded container on a container holder;
A power supply device for generating a plasma in a container already loaded in the container holder by causing an electric current to be exchanged with the internal and external electrodes;
A vacuum source for evacuating the interior of the container defining the vacuum chamber;
A reactive gas source; and
A gas supply device for supplying reactive gas from a reactive gas source to a container already loaded in the container holder.

      29. The invention of claim 28, wherein the internal electrode extends into the container.

      30. The invention of claim 28, wherein the internal electrode is located outside the container.

      31. The invention of claim 28 or 30, wherein the internal electrode is located inside the container.

      32. The invention of claim 28, wherein the internal electrode is a probe having a distal portion positioned to extend normally concentrically into a container loaded in the container holder.

      33. The invention of claim 28 or 32, wherein the gas supply device is located at a distal portion of the internal electrode.

      34. The method of claim 28, 32 or 33, further comprising a reactive gas source and path in the internal electrode for conveying the reactive gas from the reactive gas source to a distal portion of the internal electrode. The described invention.

      35. Further, the distal portion of the internal electrode comprises an elongated porous sidewall that encloses the pathway within the internal electrode for releasing at least a portion of the reactive gas laterally from the pathway. Invention.

      36. The invention of claim 35, wherein the outer diameter of the inner electrode is at least 50% of the inner diameter of the container adjacent in the lateral direction.

      37. The invention of claim 35, wherein the outer diameter of the inner electrode is at least 60% of the inner diameter of the container adjacent in the lateral direction.

      38. The invention of claim 35, wherein the outer diameter of the inner electrode is at least 70% of the inner diameter of the container adjacent in the lateral direction.

      39. The invention of claim 35, wherein the outer diameter of the inner electrode is at least 80% of the inner diameter of the container adjacent in the lateral direction.

      40. The invention of claim 35, wherein the outer diameter of the inner electrode is at least 90% of the inner diameter of the container adjacent in the lateral direction.

      41. The invention of claim 35, wherein the outer diameter of the inner electrode is at least 95% of the inner diameter of the container adjacent in the lateral direction.

      42. The invention of any one of claims 28 to 34, further comprising a carrier gas source and a path in the internal electrode for conveying the carrier gas from the carrier gas source to a distal portion of the internal electrode.

      43. The invention of any one of claims 28 to 42, further comprising an internal electrode distracter and storage for inserting and removing the internal electrode into / from the container holder.

      44. The invention of any of claims 28-43, further comprising an array of at least two internal electrodes, wherein the internal electrode distracter and storage are configured to insert / remove the internal electrode array into / from the container holder. .

      45. The invention of claim 44, wherein the internal electrode distracter and storage are configured to move the internal electrode between an advanced position, an intermediate position, and a stored position for the container holder.

      46. Further, the internal electrode drive is operable by using both the internal electrode distracter and the storage device. The first internal electrode is removed from the extended position to the storage position, and the first internal electrode is used instead of the second internal electrode. 46. The invention of claim 44 or 45, wherein the second internal electrode can be advanced to a distraction position.

      47. The invention of claim 28, 32, 33, 34, or 42, wherein the external electrode is generally cylindrical and is positioned to extend generally concentrically around a container loaded in the container holder.

      48. The invention of any one of claims 28 to 47, wherein the external electrode comprises an end cover.

      49. The invention of claim 48, wherein the gap defined between the end cap and the distal end of the container loaded in the container holder is essentially uniform.

      50. The invention of any of claims 28-49, wherein the gap defined between the external electrode and the container loaded in the container holder is essentially uniform.

      51. The device of any of claims 1-50, further comprising a detector configured to be inserted into the vessel via one or more vessel ports at a processing station for detecting conditions on the inner surface of the vessel. invention.

      52. The invention of any one of claims 1 to 51, further comprising a detector located at a processing station outside the vessel.

      53. The invention of any of claims 1-52, further comprising an energy source located at the processing station that directs energy inwardly through the vessel wall and the vessel inner surface for detection by a detector.

      54. Further comprising an energy source located at a processing station that directs energy relative to the container wall, reflects the energy from at least one coating on the wall surface and the wall surface. Any of the inventions.

      55. The invention of any of claims 1-54, further comprising an energy source located at a processing station that directs energy outwardly through the vessel wall and the vessel inner surface for detection by a detector.

      56. The invention of any one of claims 1 to 55, comprising an energy source configured to be inserted into the container via the container opening.

      57. The invention of any one of claims 51 to 56, wherein the detector is configured to detect the condition of the container inner surface at a number of dense points on the container inner surface.

      58. The invention of any of claims 51-57, wherein the detector is positioned to receive energy from an energy source.

      59. The invention of any one of claims 1 to 58, comprising a removal device located at the processing station for removing the container from one or more container holders after treatment of the inner surface of the loaded container at the second processing station. .

II. Container holder
II.A.
60. A portable container holder for gripping and transporting a container having an opening during the container processing, the container holder comprising:
A container port configured to load container openings in a mutually passable manner;
A second port configured to accept or discharge outside air supply;
A duct for venting one or more gases between a container opening loaded on the container port and the second port;
A transportable housing in which the container port, the second port, and the duct are mounted in a substantially fixed state;
A portable container holder that weighs less than 5 pounds.

II.B.
61. A portable container holder for gripping and transporting a container having an opening during the container processing, the container holder comprising:
A container port configured to receive the container opening in a sealed and mutually passable manner;
A vacuum duct that draws gas from inside the container already loaded onto the container port via the container port;
The vacuum port set to allow passage between the vacuum duct and an external vacuum source;
A transportable housing in which the vessel port, vacuum duct, and vacuum port are mounted in a substantially fixed state;
A portable container holder that weighs less than 5 pounds.

      62. The invention of claim 61, wherein the container port comprises a sealing element for receiving and molding a seal against the container opening.

      62a. The invention of claim 61, wherein the sealing element is an O-ring.

      63. The invention of any of claims 61-62a, wherein the vacuum port has an O-ring for receiving and molding a seal against an external vacuum source.

      64. The invention according to any one of claims 61 to 63, wherein the gas suction port has an O-ring for receiving and molding a sealing portion with respect to the gas suction portion.

      65. Any of claims 61-64, wherein the vacuum port is further configured to function as a gas inlet port leading to the container port for conveying gas to a container loaded on the container port. The invention.

      66. The invention of any one of claims 61 to 65, wherein the raw material of the casing is a thermoplastic material.

      67. The gas intake port according to any one of claims 61 to 66, further comprising a gas suction port that is substantially fixedly attached to the transportable housing and configured to transport gas to a container already loaded on the container port. invention.

II.C. Container holder including hermetically sealed equipment.
68. A container holder for receiving the open end of a container having a substantially cylindrical wall adjacent to the open end, comprising:
An inner surface, usually cylindrical, that is sized to receive the cylindrical wall of the container;
A first grooved nail groove inside and generally coaxially with the inner surface of the cylindrical shape, and an opening on the inner surface that is usually cylindrical and a lower wall that radially diverges from the inner surface that is usually cylindrical. Grooved nail grooves; and
Associated with the first grooved nail groove is a size that normally extends radially through the opening and is pressed radially outward by a container received by the inner surface, which is typically cylindrical, and the first A first sealing element attached to the first grooved nail groove, forming a sealing portion between the grooved nail groove bottom wall.

      68a. The container holder of claim 68, wherein said sealing element is an O-ring.

      69. The container holder of claim 68, further comprising a radially extending abutting portion adjacent to the generally cylindrical inner surface to which the container open end can abut.

      70. Further, when the first O-ring is pushed radially outward by the container, comprising the first upper and lower side walls attached between the opening and the bottom wall of the first grooved nail groove 70. The container holder of claim 68 or 69, wherein the first side wall is positioned to abut against the first O-ring.

      71. The container holder according to any of claims 68 to 70, wherein a cross-sectional diameter of the first O-ring when not stressed is larger than a radial depth of the first normal grooved nail groove.

72. The container holder of any of claims 68-71, further comprising:
Inside the cylindrical inner surface and in the coaxial direction, it is a two-grooved nail groove that is axially separated from the first grooved nail groove, and an opening on the inner surface that is usually cylindrical and a normal cylinder shape A second grooved nail groove having a bottom wall radially deviating from the inner surface; and
Associated with the second grooved nail groove, is a size that normally extends radially through the opening, and is pressed radially outward by a container received by the inner surface, usually cylindrical, and grooved with the container A second O-ring attached to the second grooved nail groove, forming a sealing part between the bottom wall of the nail groove.

      73. Further, when the second O-ring is pushed radially outward by the container, comprising the first upper and lower side walls attached between the opening and the bottom wall of the second grooved nail groove 75. The container holder of claim 72, wherein the second side wall is positioned to abut against the second O-ring.

      74. The container holder according to any of claims 72 to 73, wherein a cross-sectional diameter of the second O-ring when not stressed is larger than a radial depth of the first normal grooved nail groove.

      75. The method of claims 69-74, further comprising a vacuum source in the abutment positioned to draw a vacuum in a container loaded on the container holder having an opening opposite the abutment. Any container holder:

      76. The method of any one of claims 69-75, further comprising a process gas source located in the abutment positioned to communicate with the interior of the container loaded on the container holder having an opening opposite the abutment. A container holder.

III. Container Transport Method-Processing of Containers Loaded in Container Holder
III.A. Transport of container holder to processing station
77. A method of treating a container, the method comprising:
Providing a first processing station for container processing;
Providing a second processing station away from the first processing station for container processing;
Providing a container having a wall defining an opening and an inner surface;
Providing a container holder comprising a container port;
Loading the container opening onto the container port;
Treatment of the inner surface of the loaded container via the container port at the first treatment station;
Transport of the container holder and loaded container from the first processing station to the second processing station; and
Treatment of the inner surface of the loaded container via the container port at the second processing station.

      78. The invention of claim 77, wherein the container is generally tubular.

      79. The invention of claim 77 or 78, wherein the opening is located at one of the ends of the container.

      80. The invention of any one of claims 77 to 79, wherein the material of the container is a thermoplastic material.

      81. The invention of any one of claims 77-80, wherein the material of the container is polyethylene terephthalate.

      82. The invention of any one of claims 77-80, wherein the material of the container is a polyolefin.

      83. The invention of any one of claims 77-80, wherein the material of the container is polypropylene.

      84. The invention of any one of claims 77 to 83, wherein the material of the container is glass.

      85. The invention of any one of claims 77 to 84, wherein the material of the container is borosilicate glass.

      86. The invention of any one of claims 77 to 85, wherein the material of the container is soda lime glass.

      87. The invention of any one of claims 77 to 86, wherein the material of the container is quartz glass.

      88. The invention of any one of claims 77-87, wherein the container has a strength to withstand substantially all internal new vacuum that does not substantially deform upon exposure to an external pressure of 760 Torr.

      89. The invention of any one of claims 77-88, wherein the container is made by injection molding.

      90. The invention of any one of claims 77-88, wherein the container is made by blow molding.

      91. The invention of any one of claims 77-90, wherein the container is created by a tube end closure.

      92. The invention of any one of claims 77 to 91, wherein the container holder further comprises a vacuum duct for aspirating gas from a container already loaded onto the container port.

      93. The invention of claim 92, wherein the container holder further comprises a vacuum port passing between the vacuum duct and an external vacuum source.

      94. The invention of claim 93, wherein said vacuum port has an O-ring for receiving and molding a seal against an external vacuum source.

      95. The invention of any one of claims 77-94, wherein the container holder further comprises a gas inlet port for conveying gas to a container preloaded on the container port.

      96. The container holder comprises a synthetic gas inlet port and a vacuum port for communicating with and / or sucking gas into and out of the container loaded on the container port, respectively. Any invention of 77-95.

      97. The invention of any one of claims 77 to 96, wherein the material of the container holder is a thermoplastic material.

      98. The invention of any one of claims 77-97, wherein the container holder comprises a top and a bottom joined together at a joint.

      99. The invention of claim 98, further comprising an O-ring constrained between the top and bottom of the joint to seal the joint.

      100. The invention of any one of claims 77-99, wherein the O-ring constrained between the top and bottom also receives the container and forms a seal around the container opening.

      101. The container port has first and second axially offset o-rings, each having an inner diameter sized to receive the container outer diameter, sealing between the container port and the container. Any invention of ~ 100.

      102. The invention of any one of claims 77-101, wherein the container port has a radially extending abutment surface located proximal to the O-ring and around the vacuum duct.

      103. The invention of any one of claims 77-102, wherein the processing station is configured to inspect the inner surface of the container for defect detection.

      104. The invention of any of claims 77-103, wherein the processing station is set to apply a coating to the interior surface of the container.

      105. The invention of any of claims 77-104, wherein the processing station is configured to apply a barrier film or other type of coating to the interior surface of the container.

      106. The invention of any one of claims 77-105, wherein the processing station is configured to inspect the dressing for defect detection.

      107. The invention of any of claims 77-106, wherein the processing station is configured to inspect the barrier coating for defect detection.

      108. The invention of any of claims 77-107, wherein the processing station is configured to measure atmospheric pressure loss through the vessel wall.

      109. The invention of any one of claims 77-108, wherein the processing station comprises a support surface for supporting the container holder in place and processing the inner surface of the loaded container at the processing station.

      110. The invention of claim 109, wherein the container holder is transported and engaged with the support surface after the container opening is loaded onto the container port.

      111. The invention of any one of claims 77-110, wherein another processing station comprises a second support surface for supporting the container holder in place and processing the inner surface of the loaded container at another processing station.

      112. The invention of claim 110, wherein after the container opening is loaded onto the container port, the container holder is transported and engaged with the second support surface.

      113. Any of claims 77-112, wherein another processing station comprises a third support surface that supports the container holder in place and processes the inner surface of the loaded container via a container port at another processing station. Invention.

      114. The invention of claim 113, wherein after the container opening is loaded onto the container port, the container holder is transported and engaged with the third support surface.

115. The invention of any one of claims 77-114, further comprising:
Providing a third processing station for processing containers disposed remotely from the first and second processing stations;
Transport of the container holder and loaded containers from the second processing station to the third processing station; and
Processing of the inner surface of the loaded container via the container port at the third processing station.

      116. The invention of any one of claims 77-115, further comprising loading the container opening onto the container port at a processing station:

      117. The invention of any one of claims 77 to 116, further comprising forming a coating on the inner surface of the container via the container port at the processing station.

      118. The invention of any one of claims 77 to 117, wherein the processing at the processing station comprises an inspection of the inner surface of the container for defect detection.

      119. The invention of claim 118, wherein the inspection is performed by inserting a detection probe into the container via the container port and detecting the condition of the inner surface of the container using the probe.

      120. The invention of claim 119, further comprising radiation of energy inwardly through the container wall and the inner surface of the container, and detection of the energy by the probe.

      121. The invention of claim 119 or 120, further comprising detecting the condition of the inner surface of the container at a number of dense points on the inner surface of the container.

      122. Perform an inspection by inserting the radiation source into the container via the container port and detecting the radiation from the radiation source using a detector to detect the condition of the inner surface of the container; The invention according to any one of claims 118 to 121.

      123. The invention according to any one of claims 118 to 122, further comprising radiation of energy to the outside through the container wall and the container inner surface, and detection of the energy by a detector located outside the container.

      124. The invention of any one of claims 120 to 123, further comprising reflection of the radiation from the inner surface of the container and detection of the energy by a detector located inside the container.

      125. The invention of any one of claims 118 to 124, further comprising detecting the state of the inner surface of the container at a number of dense points on the inner surface of the container.

      126. The invention of any one of claims 77-125, wherein the treatment at the treatment station comprises applying a coating to the inner surface of the container.

      127. The invention of any one of claims 77 to 126, wherein the treatment at the treatment station comprises applying a barrier coating to the inner surface of the container.

      128. The invention of any one of claims 77-127, wherein the treatment at the treatment station comprises applying a fluid barrier coating to the inner surface of the container.

      129. The invention of any one of claims 77 to 128, wherein the processing at the processing station comprises a defect detection inspection of the coating material on the inner surface of the container.

      130. The invention of any one of claims 77-129, wherein the processing at the processing station comprises a defect detection inspection of the barrier coating on the inner surface of the container.

      131. The invention according to any one of claims 77 to 130, wherein the processing at the processing station comprises defect detection inspection of a coating material applied as a fluid on the inner surface of the container.

      132. The invention of any one of claims 126 to 131, comprising insertion of a detection probe into the container via the container port, and detection of the state of the covering material using the probe.

      133. The invention of any one of claims 127 to 132, further comprising radiation of energy inward through the vessel wall and detection of the energy by the probe.

      134. The invention according to any one of claims 127 to 133, further comprising detecting the state of the covering material at a number of dense points on the inner surface of the container.

      135. If the dressing is initially evacuated and its walls are exposed to ambient air, the pressure in the container will increase by more than 20% of ambient atmospheric pressure during the shelf life of one year. 135. The invention of any of claims 129 to 134, comprising performing an inspection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent.

      136. The invention of any of claims 129-135, wherein the inspection procedure is performed within an elapsed time of 30 seconds or less per container.

      137. The invention of any of claims 129-135, wherein the inspection procedure is performed within an elapsed time of 25 seconds or less per container.

      138. The invention of any one of claims 129-135, wherein the inspection procedure is performed within an elapsed time of 20 seconds or less per container.

      139. The invention of any of claims 129-135, wherein the inspection procedure is performed within an elapsed time of 15 seconds or less per container.

      140. The invention of any of claims 129-135, wherein the inspection procedure is performed within an elapsed time of 10 seconds or less per container.

      141. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 5 seconds or less per container.

      142. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 3 seconds or less per container.

      143. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 2 seconds or less per container.

      144. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 1 second or less per container.

      145. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 30 seconds or less per container.

      146. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 25 seconds or less per container.

      147. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 20 seconds or less per container.

      148. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 15 seconds or less per container.

      149. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 10 seconds or less per container.

      150. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 8 seconds or less per container.

      151. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 7 seconds or less per container.

      152. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 6 seconds or less per container.

      153. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 5 seconds or less per container.

      154. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 4 seconds or less per container.

      155. The invention of any of claims 129-135, wherein the coating and inspection procedure is performed within an elapsed time of 3 seconds or less per container.

      156. When the container is initially evacuated and its walls are exposed to ambient air, the pressure in the container increases by more than 20% of ambient atmospheric pressure during a shelf life of at least 18 months. 135. The invention of any one of claims 129 to 135, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent the occurrence.

      157. When the container is initially evacuated and its walls are exposed to ambient air, the pressure in the container increases by more than 20% of ambient atmospheric pressure during a shelf life of at least 2 years. 135. The invention of any one of claims 129 to 135, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent the occurrence.

      158. If the vessel is initially evacuated and its walls are exposed to ambient air, the pressure in the vessel will increase by more than 15% of ambient atmospheric pressure during the 1-year shelf life. 135. The invention of any of claims 129-135, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent.

      159. If the vessel is initially evacuated and its walls are exposed to ambient air, the pressure in the vessel will increase by more than 10% of ambient atmospheric pressure during the 1-year shelf life. 135. The invention of any of claims 129-135, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent.

      160. Perform an inspection by inserting the radiation source into the container via the container port, and detecting the radiation from the radiation source using a detector to detect the condition of the dressing; The invention according to any one of claims 129 to 159.

      161. The invention of any one of claims 129-160, further comprising the outward emission of energy through the covering and the container wall and the detection of the energy by a detector located outside the container.

      162. The invention of any one of claims 129 to 161, further comprising reflection of the radiation from the covering and the container wall and detection of the energy by a detector located inside the container.

      163. The invention according to any one of claims 129 to 162, further comprising detecting the state of the covering material at a number of dense points on the inner surface of the container.

      164. The invention according to any one of claims 129 to 163, wherein the defect detection inspection of the covering material on the inner surface of the container is performed by measuring the air pressure blocking effectiveness of the barrier film-coated container wall.

      165. Further, the invention according to any one of claims 117 to 164, wherein permeation of atmospheric gas through the inner surface of the container into the container is reduced compared to the coating material.

      166. The invention of any one of claims 117 to 165, further wherein contact of the contents of the container with the inner surface is reduced from the dressing.

      167. The coating of claims 117-166, wherein the dressing comprises SiOx (x in the formula is about 1.5 to about 1.5, alternatively about 1.5 to about 2.6, alternatively about 2), elemental carbon, or a composite thereof. Any invention.

      168. The invention of any one of claims 77-167, further comprising removal of the container from the container holder after treatment of the inner surface of the loaded container at the second processing station.

      169. The invention of claim 168, further comprising:

Providing a second container having a wall defining an opening and an inner surface after the removal procedure;
Loading the second container opening onto the container port.

      170. The invention of any one of claims 168-169, further comprising processing the inner surface of the loaded second container via the container port at the first processing station.

      171. The invention of any one of claims 168-170, further comprising transporting the container holder and the loaded second container from the first processing station to the second processing station.

      172. The invention of any of claims 168-171, further comprising processing of the loaded second container via a container port at the second processing station.

      173. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 60 seconds after removal of the container from the mold. The invention of any one of claims 77-172.

      174. Further comprising forming the container in a mold, removing the container from the mold, and loading the container opening into the container port within 30 seconds after removal of the container from the mold, The invention of any one of claims 77-173.

      175. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 25 seconds after removal of the container from the mold. The invention of any one of claims 77-174.

      176. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 20 seconds after removal of the container from the mold. The invention of any one of claims 77-175.

      177. Further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 15 seconds after removal of the container from the mold. The invention of any one of claims 77-176.

      178. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 10 seconds after removal of the container from the mold. The invention of any one of claims 77-177.

      179. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 5 seconds after removal of the container from the mold. The invention of any one of claims 77-178.

      180. Further comprising: molding the container in the mold; removing the container from the mold; and loading the container opening into the container port within 3 seconds after removal of the container from the mold. The invention of any one of claims 77-179.

      181. further comprising forming the container in a mold, removing the container from the mold, and loading the container opening into the container port within 1 second after removal of the container from the mold, The invention of any one of claims 77-180.

III.B. Transport of processing equipment to the container holder or vice versa.
182. A method of treating a container, the method comprising:
Providing first processing equipment for container processing;
Providing second processing equipment for container processing;
Providing a container having a wall defining an opening and an inner surface;
Providing a container holder comprising a container port;
Loading the container opening onto the container port;
Movement of the first processing device for operative engagement with the container holder, or vice versa;
Treatment of the inner surface of the loaded container via the container port using the first processing equipment;
Movement of the second processing device for operative engagement with the container holder, or vice versa;
Treatment of the inner surface of the loaded container via the container port using the second processing equipment;

183. The invention of claim 182, further comprising:
Provision of third processing equipment for container processing;
Movement of the third processing device for operative engagement with the container holder, or vice versa;
Treatment of the inner surface of the loaded container via the container port using the third processing equipment;

      184. The invention of claim 182 or 183, wherein the container is generally tubular.

      185. The invention of any one of claims 182-184, wherein the opening is located at one of the ends of the container.

      186. The invention of any one of claims 182-185, wherein the material of the container is a thermoplastic material.

      187. The invention of any one of claims 182-186, wherein the material of the container is polyethylene terephthalate.

      188. The invention of any one of claims 182-187, wherein the material of the container is a polyolefin.

      189. The invention of any one of claims 182-186, wherein the material of the container is polypropylene.

      190. The invention of any of claims 182-189, wherein the container is strong enough to withstand substantially all internal new vacuum that does not substantially deform upon exposure to an external pressure of 760 Torr.

      191. The invention of any one of claims 182-190, wherein the container is made by injection molding.

      192. The invention of any one of claims 182-191, wherein the container is made by blow molding.

      193. The invention of any one of claims 182 to 192, wherein the container holder further comprises a vacuum duct for aspirating gas from a container preloaded on the container port.

      194. The invention of claim 193, wherein the vessel holder further comprises a vacuum port passing between the vacuum duct and an external vacuum source.

      195. The invention of claim 194, wherein said vacuum port has an O-ring for receiving and molding a seal against an external vacuum source.

      196. The invention of any one of claims 182-195, wherein the container holder further comprises a gas inlet port for transporting gas to a container preloaded on the container port.

      197. The container holder comprises a synthetic gas inlet port and a vacuum port for communicating with and / or sucking gas into and out of the container loaded on the container port, respectively. The invention of any one of 182 to 196.

      198. The invention of any one of claims 182-197, wherein the container holder material is a thermoplastic material.

      199. The invention of any one of claims 182 to 198, wherein the container port has an O-ring for receiving and molding a seal against the container opening.

      200. The invention of any one of claims 182-199, wherein the processing equipment is configured to inspect the inner surface of the container for defect detection.

      201. The invention of any one of claims 182 to 200, wherein the processing equipment is configured to apply a coating to the inner surface of the container.

      202. The invention of any of claims 181-201, wherein the processing equipment is configured to inspect the dressing for defect detection.

      203. The invention of any one of claims 182-202, wherein the processing equipment is configured to measure atmospheric pressure loss through the vessel wall.

      204. The invention according to any one of claims 182 to 203, wherein the processing device comprises a support surface for supporting the container holder in a predetermined position and processing the inner surface of the loaded container by the processing device.

      205. The invention of claim 204, wherein after the container opening is loaded onto the container port, the container holder is transported and engaged with the support surface.

      206. The invention of any one of claims 182 to 205, wherein another processing device comprises a second support surface that supports the container holder in place and processes the inner surface of the loaded container with the other processing device.

      207. The invention of claim 206, wherein after loading the container opening onto the container port, the container holder is transported and engaged with the second support surface.

      208. Any one of claims 182 to 207, wherein another processing device comprises a third support surface that supports the container holder in place and processes the inner surface of the loaded container via the container port by another processing device. Invention.

      209. The invention of claim 208, wherein after loading the container opening onto the container port, the container holder is transported and engaged with a third support surface.

210. The invention of any one of claims 182-109, further comprising:
Providing a third processing device for processing a container installed away from the first and second processing devices;
Transport of the container holder and loaded container from the second processing device to the third processing device; and
Treatment of the inner surface of the loaded container via the container port by a third processing device;

      211. The invention of any one of claims 182 to 210, further comprising loading the container opening on the container port in a processing device:

      212. The invention of any one of claims 181-211, further comprising molding of a coating material on the inner surface of the container via the container port of the processing equipment.

      213. The invention of any one of claims 182 to 212, wherein the processing in the processing equipment comprises inspection of the inner surface of the container for defect detection.

      214. The invention of claim 213, wherein the inspection is performed by inserting a detection probe into the container via the container port and detecting the condition of the inner surface of the container using the probe.

      215. The invention of claim 214, further comprising radiation of energy inward through the container wall and the inner surface of the container, and detection of the energy by the probe.

      216. The invention of claim 214 or 215, further comprising detecting the condition of the container inner surface at a number of dense points on the container inner surface.

      217. Perform inspection by inserting the radiation source into the container via the container port and detecting the radiation from the radiation source using a detector to detect the condition of the inner surface of the container; The invention according to any one of claims 213 to 216.

      218. The invention of any one of claims 213 to 217, further comprising radiation of energy outward through the container wall and the container inner surface and detection of the energy by a detector located outside the container.

      219. The invention of any one of claims 215 to 216, further comprising reflection of the radiation from the inner surface of the container and detection of the energy by a detector located within the container.

      220. The invention of any one of claims 213 to 219, further comprising detecting the state of the inner surface of the container at a number of dense points on the inner surface of the container.

      221. The invention according to any one of claims 182-120, wherein the treatment in the treatment equipment comprises applying a coating material to the inner surface of the container.

      222. The invention according to any one of claims 182 to 221, wherein the treatment in the treatment equipment comprises application of a coating material applied as a fluid to the inner surface of the container.

      223. The invention according to any one of claims 182 to 222, wherein the processing in the processing equipment comprises a defect detection inspection of the coating material on the inner surface of the container.

      224. The invention of any one of claims 221 to 223, comprising insertion of a detection probe into the container via the container port, and detection of the state of the covering material using the probe.

      225. The invention of any one of claims 221-224, further comprising radiation of energy inward through the vessel wall and detection of the energy by the probe.

      226. The invention of any one of claims 221 to 225, further comprising detecting the state of the covering material at a number of dense points on the inner surface of the container.

      227. If the vessel is initially evacuated and its walls are exposed to ambient air, the pressure in the vessel will increase by more than 20% of ambient atmospheric pressure during the 1-year shelf life. 132. The invention of any one of claims 223-131, comprising performing an inspection procedure at a sufficient point across the inner surface of the container to determine that it is effective to prevent.

      228. The invention of any one of claims 223-227, wherein the inspection procedure is performed within an elapsed time of 30 seconds or less per container.

      229. The invention of any one of claims 223-227, wherein the inspection procedure is performed within an elapsed time of 25 seconds or less per container.

      230. The invention of any one of claims 223-227, wherein the inspection procedure is performed within an elapsed time of 20 seconds or less per container.

      231. The invention of any one of claims 223-227, wherein the inspection procedure is performed within an elapsed time of 15 seconds or less per container.

      232. The invention of any one of claims 223-227, wherein the inspection procedure is performed within an elapsed time of 10 seconds or less per container.

      233. The invention of any one of claims 223-227, wherein the coating and inspection procedure is performed within an elapsed time of 30 seconds or less per container.

      234. The invention of any of claims 223-227, wherein the coating and inspection procedure is performed within an elapsed time of 25 seconds or less per container.

      235. The invention of any of claims 223-227, wherein the coating and inspection procedure is performed within an elapsed time of 20 seconds or less per container.

      236. The invention of any one of claims 223-227, wherein the coating and inspection procedure is performed within an elapsed time of 15 seconds or less per container.

      237. The invention of any one of claims 223-227, wherein the coating and inspection procedures are performed within an elapsed time of 10 seconds or less per container.

      238. When the container is initially evacuated and its walls are exposed to ambient air, the pressure in the container increases by more than 20% of ambient atmospheric pressure during a shelf life of at least 18 months. 227. The invention of any one of claims 223 to 227, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent the occurrence of the problem.

      239. If the barrier coating is initially evacuated and its walls are exposed to ambient air, the pressure in the container will exceed 20% of ambient atmospheric pressure for a shelf life of at least 2 years. 224. The invention of any one of claims 223-227, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent an increase.

      240. When the barrier coating is initially evacuated and its walls are exposed to ambient air, the pressure in the container increases by more than 15% of ambient atmospheric pressure during the 1-year shelf life 227. The invention of any one of claims 223-227, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent it from occurring.

      241. When the barrier coating is initially evacuated and its walls are exposed to ambient air, the pressure in the container increases by more than 10% of ambient atmospheric pressure during the 1-year shelf life 227. The invention of any one of claims 223-227, comprising performing a detection procedure at a sufficient point throughout the inner surface of the container to determine that it is effective to prevent it from occurring.

      242. Perform an inspection by inserting the radiation source into the container via the container port, and detecting the radiation from the radiation source using a detector to detect the condition of the dressing; The invention of any one of claims 223-241.

      243. The invention of any one of claims 223 to 242, further comprising radiating energy outward through the dressing and the container wall and detecting the energy by a detector located outside the container.

      244. The invention according to any one of claims 223 to 243, further comprising reflection of the radiation from the covering and the container wall, and detection of the energy by a detector located inside the container.

      245. The invention of any one of claims 223 to 244, further comprising detecting the state of the covering material at a number of dense points on the inner surface of the container.

      246. The invention according to any one of claims 223 to 245, wherein the defect detection inspection of the covering material on the inner surface of the container is performed by measuring the effectiveness of blocking air pressure of the wall of the covering container.

      247. The invention according to any one of claims 212 to 246, wherein permeation of atmospheric gas through the inner surface of the container into the container is reduced as compared with the coating material.

      248. The invention of any one of claims 212 to 247, further wherein contact of the contents of the container with the inner surface is reduced over the dressing.

      249. The coating material is SiOx (x in this formula is about 1.5 to about 2.9, or about 1.5 to about 2.6, or about 2), elemental carbon, fluorine-based material, SiwOxCyHz (w is 1, x about 0.5 to about 249. The invention of any of claims 212-248, comprising 2.4, y from about 0.6 to about 3, z from 2 to about 9), or a complex thereof.

      250. The invention of any one of claims 182-149, further comprising removal of the container from the container holder after the inner surface treatment of the loaded container by the second processing equipment.

251. The invention of claim 250, further comprising:
Providing a second container having a wall defining an opening and an inner surface after the removal procedure;
Loading the second container opening onto the container port.

      252. The invention of any one of claims 250-251, further comprising processing the inner surface of the loaded second container via the container port by the first processing device.

      253. The invention of any one of claims 250 to 252, further comprising transporting the container holder and the loaded second container from the first processing device to the second processing device.

      254. The invention of any one of claims 250 to 253, further comprising processing of the loaded second container via a container port by a second processing device.

      255. Further comprising: molding the container in the mold; removing the container from the mold; and loading the container opening into the container port within 60 seconds after removal of the container from the mold. The invention according to any one of claims 182 to 254.

      256. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 30 seconds after removal of the container from the mold. The invention according to any one of claims 182 to 255.

      257. Further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 25 seconds after removal of the container from the mold. The invention according to any one of claims 182 to 256.

      258. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 20 seconds after removal of the container from the mold. The invention of any one of claims 182-157.

      259. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 15 seconds after removal of the container from the mold. The invention of any one of claims 182-158.

      260. Further comprising: molding the container in the mold; removing the container from the mold; and loading the container opening into the container port within 10 seconds after removal of the container from the mold. The invention of any one of claims 182-159.

      261. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 5 seconds after removal of the container from the mold. The invention according to any one of claims 182 to 260.

      262. Further comprising molding the container in the mold, removing the container from the mold, and loading the container opening into the container port within 3 seconds after removal of the container from the mold, The invention according to any one of claims 182 to 261.

      263. further comprising: molding the container in a mold; removing the container from the mold; and loading the container opening into the container port within 1 second after removal of the container from the mold. The invention according to any one of claims 182 to 262.

III.C. Use of grips to transport tubes to / from the coating station
264. Method of PECVD treatment of the first vessel, which consists of:
Providing a first container having an open end, a closed end, and an inner surface;
At least one first gripper configured to selectively grip and release the closed end of the first container;
Gripping the closed end of the first container having the first gripping portion;
Transport of the first container to the vicinity of the container holder set to load the first container opening end using the first gripping portion;
Advancement of the first container in the axial direction using the first gripping part, loading of the open end onto the container holder, establishment of a passing seal between the container holder and the interior of the first container;
Introduction of at least one gaseous reactant into the first container through the container holder;
Generation of plasma in the first container under conditions effective to shape a reaction product of the reactant on the inner surface of the first container;
Unloading the first container from the container holder; and
Transporting the first container axially away from the container holder using the first gripping part or other gripping part; and
Release of the first container from the grip used to move away from the container holder in the axial direction.

265. The invention of claim 264, further comprising:
Providing a reaction vessel having a different reaction vessel than the first vessel, an open end and a lumen;
Loading the open end of the reaction vessel onto the vessel holder, establishing a passage seal between the vessel holder and the lumen of the reaction vessel;
Providing a PECVD reactant conduit within the lumen;
Generation of plasma within the reaction vessel lumen under conditions effective to remove at least a portion of the deposition of the PECVD reaction product from the reactant conduit;
Unloading the reaction vessel from the vessel holder; and
Transport the reaction vessel away from the vessel holder.

266. The invention of claim 264 or 265, further comprising:
Providing at least one second grip;
An operable connection of at least a first and a second gripper to a series of conveyors;
Providing a second container having an open end, a closed end, and an inner surface;
Providing a gripper configured to selectively grip and release the closed end of the second container;
Gripping the closed end of the second container having the gripping portion;
Transporting the second container to the vicinity of the container holder set to load the second container opening end using the gripping part;
Advancing the second container in the axial direction using the gripping portion, loading the open end onto the container holder, establishing a passage seal between the container holder and the interior of the second container;
Introduction of at least one gaseous reactant into the second container through the container holder;
Generation of plasma in the second container under conditions effective to shape a reaction product of the reactant on the inner surface of the second container;
Unloading the second container from the container holder; and
Transport of the second container in the axial direction away from the container holder using the second gripping part or other gripping part; and
Release of the second container from the grip used to move it axially away from the container holder.

IV. PECVD equipment for container production
IV.A. PECVD equipment including vessel holder, internal electrode, and vessel as reaction chamber
267. PECVD equipment consisting of:
A container holder having a port for receiving the container in a loading position for processing;
An internal electrode positioned to be received in a container loaded on the container holder;
An external electrode having an internal portion positioned to receive the loaded container on the container holder; and
A power supply device for generating a plasma in a vessel preloaded in the vessel holder, which is the vessel defining the plasma reaction chamber, with alternating current to at least one internal and external electrode;

      268. The invention of claim 267, wherein the internal electrode is a probe having a distal portion positioned to extend normally concentrically into a container loaded in the container holder.

      268a. The invention of claim 267 or 268, further comprising a reactive gas source and a gas supply device for supplying the reactive gas from the reactive gas source to a container loaded in the container holder.

      269. The invention of claim 268a, wherein the gas supply device is located distal to the internal electrode.

      270. The invention of claim 268a or 269, further comprising a path in the internal electrode for conveying the reactive gas from a reactive gas source to a distal portion of the internal electrode.

      271. The invention of any one of claims 267 to 270, further comprising a carrier gas source and path within the internal electrode for delivering carrier gas from the carrier gas source to a distal portion of the internal electrode.

      272. The invention of any one of claims 267 to 271 wherein the external electrode is generally cylindrical and is positioned to extend generally concentrically around a container already loaded in the container holder.

      273. The invention of any one of claims 267 to 272, wherein the external electrode comprises an end lid.

      274. The invention of claim 273, wherein the gap defined between the end cap and the distal end of the container loaded in the container holder is essentially uniform.

      275. The invention of any of claims 267-274, wherein the gap defined between the external electrode and the container loaded in the container holder is essentially uniform.

      276. The coatings of claim 117-167, comprising a SiOx layer and a SiwOxCyHz layer (where w is 1, x is about 0.5 to about 2.4, y is about 0.6 to about 3, and z is about 2 to about 9). Or any invention of 212-168.

      278. The invention of claim 276 or 277, wherein the SiwOxCyHz layer is deposited on a SiOx layer deposited on the inner surface of the vessel.

      279. The invention of claim 276 or 277, wherein the SiOx layer is deposited between the SiwOxCyHz layer and the vessel inner surface.

      280. The invention of any of claims 276-279, wherein the SiOx layer is deposited adjacent to the SiwOxCyHz layer.

      281. The invention of any of claims 276-280, wherein the SiOx layer is deposited adjacent to the inner surface of the vessel.

      282. The invention of any of claims 276-280, wherein the SiwOxCyHz layer is deposited adjacent to the inner surface of the vessel.

      283. The invention of any one of claims 280-282, wherein the SiOx layer and the SiwOxCyHz layer are stepwise composites of SiwOxCyHz to SiOx.

      284. The invention of any one of claims 267 to 283, wherein the container further comprises a closure.

      285. The invention of claim 284, wherein the closure comprises an interior facing surface exposed to the container lumen.

      286. The invention of claim 284 or 285, wherein the closure comprises a wall contacting surface that contacts the inner surface of the container wall.

      287. The invention of any one of claims 284-286, wherein the closure portion comprises a stop member.

      288. The invention of claim 287, wherein the closure is a shield that holds a stop member.

      289. The invention of claim 287 or 288, wherein the stop member comprises a wall contacting surface that contacts the inner surface of the container wall.

      290. The invention of any of claims 284-289, wherein the stop member comprises an internally facing surface that is exposed to the container lumen.

      290a. The invention of any of claims 267-290, further comprising a vacuum source for removing gas from a loaded container on the container holder, which is a loaded container defining a vacuum chamber.

      291. The invention of any one of claims 284-290a, wherein a portion of the container wall that contacts the wall contacting surface of the closure is coated with a SiwOxCyHz lubricious coating.

      301. The invention of any of claims 284-300, wherein the SiwOxCyHz coating is applied by PECVD.

      302. The invention of any one of claims 291 to 301, wherein the SiwOxCyHz coating material has a layer thickness of 0.5 to 5000 nm.

      303. The invention of any one of claims 291 to 301, wherein the SiwOxCyHz coating material has a layer thickness of 100 to 5000 nm.

      304. The invention of any one of claims 291 to 301, wherein the SiwOxCyHz coating material has a layer thickness of 200 to 5000 nm.

      305. The invention of any one of claims 291 to 301, wherein the SiwOxCyHz coating material has a layer thickness of 500 to 5000 nm.

      306. The invention of any one of claims 291 to 301, wherein the SiwOxCyHz coating material has a layer thickness of 1000 to 5000 nm.

      307. The invention of any one of claims 291 to 301, wherein the SiwOxCyHz coating material has a layer thickness of 2000 to 5000 nm.

      308. The invention of any one of claims 291 to 301, wherein the SiwOxCyHz coating material has a layer thickness of 3000 to 5000 nm.

      309. The invention of any one of claims 291-301, wherein the SiwOxCyHz coating material has a layer thickness of 4000-10000 nm.

310. PECVD equipment consisting of:
A container holder having a port for receiving the container in a loading position for processing;
An internal electrode positioned to be received in a container loaded on the container holder;
An external electrode having an internal portion positioned to receive a loaded container on a container holder;
A power supply device for generating a plasma in a container already loaded in the container holder by causing an electric current to be exchanged with the internal and external electrodes;
A gas exhaust line that defines a closed chamber by transferring gas into and out of the container already loaded into the port;
A reactive gas source; and
A gas supply device for supplying reactive gas from a reactive gas source to a container already loaded in the container holder.

IV.B. PECVD equipment using grips to transport tubes to / from the coating station
311. An apparatus for PECVD processing of a first container having an open end, a closed end, and a lumen, comprising:
A container holder set to load the open end of the container;
A first gripper configured to selectively grip and release the closed end of the container and transport the container to the vicinity of the container holder while gripping the closed end of the container;
A loading section on the container holder, the loading section set to establish a passing seal between the container holder and the lumen of the first container;
A reactant supply device operably connected to introduce at least one gaseous reactant through the vessel holder into the first vessel;
A plasma generator configured to generate a plasma in the first container under conditions effective to form a reaction product of the reactant on the inner surface of the first container;
A container release machine for unloading the first container from the container holder; and
A gripping part, which is a first gripping part or other gripping part, configured to transport the first container away from the container holder in the axial direction and then release the loading of the first container.

312. The invention of claim 311 further comprising:
A reaction vessel different from the first vessel, the reaction vessel having an open end and a lumen and set to load the open end on the vessel holder, and between the vessel holder and the lumen of the reaction vessel Establishing a passage seal; and
A PECVD reactant conduit positioned at a location within the reaction vessel lumen when the reaction vessel is preloaded on the vessel holder;
The plasma generator is configured to generate a plasma within the reaction vessel lumen under conditions effective to remove at least a portion of the PECVD reaction product deposit from the reactant conduit.

313. The invention of claim 311 or 312 further comprising:
A series of conveyors set up to transport multiple grips;
A second gripper configured to selectively grip and release the closed end of the container and transport the container to the vicinity of the container holder while gripping the closed end of the container;
Operably connected to the series of conveyors, continuously conveying a series of at least two containers to the vicinity of the container holder, loading the container open end on the container holder, the container holder and the second First and second gripping portions that are set to establish a passing seal between the interior of the container, transport the container in the axial direction away from the container holder, and release the container from the gripping portion.

PECVD coating covering the restricted opening (syringe capillary) of the VB container
316. A method of coating the inner surface of a restricted opening of a container to be treated, which is usually tubular, with PECVD, the method comprising:
Providing a treated container that is generally tubular, including an outer surface, an inner surface defining a lumen, a large opening having an inner diameter, and a restrictive opening defined by the inner surface and having an inner diameter that is smaller than the inner diameter of the large opening;
Providing a processing vessel having a lumen and a processing vessel opening;
Connection of the treatment vessel opening to the restrictive opening of the treated vessel to establish a passage between the treatment vessel lumen and the treatment vessel lumen via the restrictive opening;
A vacuum of at least a portion of the lumen of the container to be processed and the lumen of the processing container;
The inflow of PECVD reactant through the first opening and then into the lumen of the vessel to be processed, the restrictive opening, the lumen of the processing vessel;
Plasma generation adjacent to the limiting opening under conditions effective to deposit a PECVD reaction product on the inner surface of the limiting opening.

      317. The method of claim 316, wherein said container to be treated is a syringe barrel.

      318. The restrictive opening has a first mounting portion, and the processing vessel opening has a second mounting portion adapted to be loaded into the first mounting portion, and is treated with the lumen of the processing vessel 321. The method of claim 316 or 317, establishing passage between the lumen of the container.

      319. The method of claim 318, wherein the first and second attachment portions are luer lock attachment portions.

      320. The method of claim 319, wherein the raw material of the at least one first and second attachment portion is a conductive material.

      321. The method of claim 299, 319, or 320, wherein the raw material of the at least one first and second attachment portion is a conductive material.

      322. The method of claim 299, 319, 320, or 299a2, wherein the raw material of the at least one first and second attachment portion is stainless steel.

      323. The method of claim 319, wherein the first and second luer lock attachment portions are a male portion and a female portion, respectively.

      324. The method of claim 299, 319, or 323, further comprising a sealing portion located between the first and second attachment portions.

      325. The method of claim 324, wherein the seal comprises an O-ring.

      326. One of the attachments consists of a locking collar defining a first abutment with a normal grooved nail that has a thread and is axially opposed, and the other attachment is engaged by the attachment 321. The method of claim 319, 323, 324, or 325, comprising an axially opposed normal grooved nail second abutment portion facing the first abutment portion.

      327. The method of claim 326, further comprising a grooved seal engaging between the first and second abutments.

      328. The method of any of claims 316-318, wherein the passage established between the lumen of the container being processed and the lumen of the process container via the restrictive opening is at least substantially leak resistant. .

329. The method of any of claims 316-328, wherein inflow of the PECV reactant through the large opening of the vessel to be treated is performed by:
Providing an internal electrode, usually tubular, having an internal pathway, a proximal end, a distal end, and a distal opening adjacent to and leading to the internal pathway;
Insertion of the distal end of the electrode adjacent to / into the large opening of the container to be treated; and
Reactive gas supply through the distal opening of the electrode to the lumen of the container to be treated.

      330. The method of claim 329, wherein the distal end of the electrode is located at less than half the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied.

      331. The method of claim 329, wherein the distal end of the electrode is located at less than 40% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      332. The method of claim 329, wherein the distal end of the electrode is located at less than 30% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      333. The method of claim 329, wherein the distal end of the electrode is located at less than 20% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      334. The method of claim 329, wherein the distal end of the electrode is located at less than 15% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      335. The method of claim 329, wherein the distal end of the electrode is located at less than 10% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      336. The method of claim 329, wherein the distal end of the electrode is located at less than 8% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      337. The method of claim 329, wherein the distal end of the electrode is located at less than 6% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      338. The method of claim 329, wherein the distal end of the electrode is located at less than 4% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      339. The method of claim 329, wherein the distal end of the electrode is located at less than 2% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      340. The method of claim 329, wherein the distal end of the electrode is located at less than 1% of the distance from the large opening of the container to be treated to the restrictive opening when the reactive gas is supplied. .

      341. The method of claim 329, wherein the distal end of the electrode is located within the large opening of the container to be treated upon supply of the reactive gas.

      342. The method of claim 329, wherein the distal end of the electrode is located outside the large opening of the container to be treated when the reactive gas is supplied.

      343. The method of any of claims 329-342, wherein the distal end of the electrode is located distal to the restrictive opening.

      344. The method of any of claims 329-343, wherein the electrode moves axially during deposition of the PECVD reaction product.

      345. The method of any of claims 316-344, wherein the plasma extends substantially across the syringe lumen and the restrictive opening.

      346. The method of any of claims 316-345, wherein the plasma extends across substantially the entire lumen of the syringe, the restrictive opening, and the processing vessel lumen.

      347. The method of any of claims 316-346, wherein the plasma has a substantially uniform color across the syringe lumen and the restrictive opening.

      348. The method of any of claims 316-347, wherein the plasma has a substantially uniform color across the syringe lumen, the restrictive opening, and the processing vessel lumen.

      349. The method of any of claims 316-348, wherein the plasma is substantially unchanged throughout the syringe lumen and the restrictive opening.

      350. The method of any of claims 316-349, wherein the plasma is substantially unchanged throughout the syringe lumen, the restrictive opening, and the processing vessel lumen.

      351. The method of any of claims 316-350, wherein the vessel opening of the processing vessel is the only opening.

      352. The method of any of claims 316-351, wherein the volume of the processing vessel lumen is less than three times the volume of the lumen 300 of the vessel 250 to be processed.

      353. The method of any of claims 316-352, wherein the volume of the processing vessel lumen is less than twice the volume of the vessel lumen to be processed.

      354. The method of any of claims 316-353, wherein the volume of the processing vessel lumen is less than the volume of the vessel lumen to be processed.

      355. The method of any of claims 316-354, wherein the volume of the processing vessel lumen is less than 50% of the volume of the vessel lumen to be processed.

      356. The method of any of claims 316-355, wherein the volume of the processing vessel lumen is less than 25% of the volume of the vessel lumen to be processed.

      357. The method further comprises loading the treated container large opening of the tubular container onto a container support prior to at least partially evacuating the lumen 300 of the treated container 250. Any method of 316-356.

      358. The method of claim 357, further comprising loading a large opening of the treated container onto a port of the container support.

      359. The method of claim 357 or 358, further comprising positioning an internal electrode into the treated container loaded on the container support.

      360. 357, 358, or 359 further comprising positioning of the treated container with respect to an external electrode having an internal portion positioned to receive the treated container being loaded on the container support. the method of.

      361. 357, 358, further comprising pressurization of a power supply that causes alternating current to flow to the external electrode for plasma generation in the treated container loaded on the container support 359, or 330 ways.

      362. The invention of claim 361, further comprising grounding of the internal electrode.

      363. The method of claim 357, 358, 359, 360, or 361, further comprising a vacuum source defining a vacuum chamber for evacuating the interior of the vessel to be processed.

      364. The invention of claim 363, further comprising providing a second vacuum chamber surrounding the container to be processed.

      365. The method of claim 364, wherein the interior of the container is maintained at a lower vacuum level than the second vacuum chamber.

      366. The method of claim 363, wherein the processing vessel is a conduit leading to a vacuum port in the vessel support.

      367. The method of any one of claims 357 to 366, further comprising a reactive gas source and a gas supply device that supplies the reactive gas from the reactive gas source to the vessel to be processed that is loaded on the vessel support. The invention.

VI. Container inspection
VI.A. Container handling including pre- and post-coating inspections
399. A container processing method for processing a molded plastic container having a wall defining an opening and an inner surface, the method comprising:
Inspection for detecting defects when molding the coating on the inner surface of the container;
Application of coating material to the inner surface of the container after the container inspection at the time of molding;
Inspection for detecting defects in the covering material.

400. A container processing method for processing a molded plastic container having a wall defining an opening and an inner surface, the method comprising:
Inspection for detecting defects when molding the coating on the inner surface of the container;
Applying a barrier coating to the container after inspection of the container at the time of molding; and
Inspection for detecting defects on the inner surface of the container after application of the barrier coating;

      401. The invention of claim 400, wherein the inner surface of the container during molding is inspected at a number of dense points on the inner surface of the container.

      402. The invention of claim 400 or 401, wherein the inner surface of the container after application of the barrier coating is inspected at a number of dense points on the inner surface of the container.

      403. A number of dense points on the inner surface of the container are inspected at / on the container at the time of molding, coated with the barrier coating, and re-inspected after application of the barrier coating. Invention of Item 400, 401, or 402.

VI.B. Container inspection by detecting container wall outgassing through barrier layer
404. A method for inspecting a barrier film on a material that outgases a vapor and consists of:
Providing an analyte outgassing and at least a portion of a substance that is a barrier layer; and
Measurement of the released gas.

      405. The method of claim 404, wherein the outgassing material comprises a polymeric compound.

      406. The method of claim 404 or 405, wherein the outgassing material comprises a thermoplastic compound.

      407. The method of any of claims 404-406, wherein the outgassing material comprises polyester.

      408. The method of any of claims 404-407, wherein the gas releasing material comprises polyethylene terephthalate.

      409. The method of any of claims 404-408, wherein the outgassing material comprises a polyolefin.

      410. The method of any of claims 404-409, wherein the outgassing material comprises polypropylene.

      411. The method of any of claims 404-410, wherein the gas releasing material comprises a cyclic olefin copolymer.

      411a. The method of any of claims 404-411, further comprising contacting the barrier layer with water prior to measuring the emitted gas.

      411b. The method of any of claims 404-411, further comprising contacting the barrier layer with water vapor prior to measuring the emitted gas.

      411c. The method of any of claims 404-411, further comprising contacting the atmosphere with a relative humidity of 35% to 100% of the barrier layer prior to measuring the emitted gas.

      411d. The method of any of claims 404-411, further comprising contacting the atmosphere with a relative humidity of 40% to 100% of the barrier layer prior to measuring the emitted gas.

      411e. The method of any of claims 404-411, further comprising contacting the atmosphere with a relative humidity of 40% to 50% of the barrier layer prior to measuring the emitted gas.

      411f. The method of any of claims 404-411, further comprising contacting the barrier layer with oxygen prior to measuring the emitted gas.

      411g. The method of any of claims 404-411, further comprising contacting the barrier layer with nitrogen prior to measuring the emitted gas.

      411h. The method of any of claims 411a-411g, wherein the contact time is from 10 seconds to 1 hour.

      411i. The method of any of claims 411a-411g, wherein the contact time is from 1 minute to 30 minutes.

      411j. The method of any of claims 411a-411g, wherein the contact time is from 5 minutes to 25 minutes.

      411k. The method of any of claims 411a-411g, wherein the contact time is from 10 minutes to 20 minutes.

      411l. The method of any of claims 404-411k, wherein the pressure measurement of the released gas is from 0.1 Torr to 100 Torr.

      411m. The method of any of claims 404-411k, wherein the pressure measurement of the released gas is from 0.2 Torr to 50 Torr.

      411n. The method of any of claims 404-411k, wherein the pressure measurement of the released gas is from 0.5 Torr to 40 Torr.

      411o. The method of any of claims 404-411k, wherein the pressure measurement of the released gas is 1 to 30 torr.

      411p. The method of any of claims 404-411k, wherein the pressure measurement of the released gas is 5 to 100 torr.

      411q. The method of any of claims 404-411k, wherein the pressure measurement of the released gas is from 10 Torr to 80 Torr.

      411r. The method of any of claims 404-411k, wherein the pressure measurement of the released gas is 15 to 50 torr.

      411s. The method of any of claims 404-411r, wherein the temperature measurement of the released gas is from 0C to 50C.

      411t. The method of any of claims 404-411r, wherein the measured temperature of the released gas is between 0 ° C and 21 ° C.

      411u. The method of any of claims 404-411r, wherein the temperature measurement of the emitted gas is 5 ° C to 20 ° C.

      412. The method of any of claims 404-411u, wherein the outgassing material is provided in the form of a container having a wall having an outer surface and an inner surface, the inner surface enclosing a lumen.

      413. The method of claim 412, wherein the barrier layer adheres to an inner surface of the container wall.

      414. The method of claim 412 or 413, wherein the pressure differential is provided in the barrier layer by at least partially evacuating the lumen.

      415. The method of any of claims 412-414, further comprising a connection with a vacuum source via a duct in the lumen to evacuate at least a portion of the lumen.

      416. The method of claim 415, further comprising providing an outgassing measurement box that passes between the lumen and the vacuum source.

      417. The method of any of claims 404-416, wherein the measurement is performed by determining the volume of outgassing material outgassing through the barrier layer at each time interval.

      418. The method of any of claims 404-417, wherein the measurement is performed using a micro flow technique.

      419. The method of any of claims 404-418, wherein the measurement is performed by measuring the mass flow rate of the outgassing material.

      420. The method of any of claims 404-419, wherein the measurement is performed in a molecular flow mode of operation.

      420a. The method of any of claims 404-420, wherein the measurement is performed as follows.

Providing at least one microcantilever having the property of moving or changing into a different shape in the presence of an outgassing material;
Exposure of the microcantilever to an outgassing material under conditions effective to move or change the microcantilever to a different shape; and
Detection of this movement or different shape.

      420b. Moving or different depending on the irradiation of the incident energy beam from the microcantilever shape change before and after exposure to the gas release of the microcantilever, and by measuring the deviation of the irradiated beam at a point away from the cantilever The method of claim 420a, wherein a shape is detected.

      420c. The method of claim 420b, wherein the energy incident light is selected from photon rays, electron rays, or a combination of two or more thereof.

      420d. The method of claim 420b, wherein the energy incident light is a photon light.

      420e. The method of claim 420b, wherein the energy-incident beam is a laser beam.

420f. The method of any of claims 404-420, wherein the measurement is performed as follows.
Providing at least one microcantilever that resonates at different frequencies in the presence of an outgassing material;
Exposure of the microcantilever to an outgassing material under conditions effective to resonate the microcantilever at different frequencies; and
Detection of different resonance frequencies.

      420 g. Before and after exposing the microcantilever to outgassing by inputting energy into the microcantilever to induce its resonance and before and after exposing the microcantilever to outgassing. 442. The method of claim 420f, wherein the different resonance frequencies are detected by determining a difference between.

      420h. The method of claim 420g, wherein said different resonant frequencies are detected using a harmonic vibration sensor.

      421. The method of claim 404, wherein the outgassing material is provided in the form of a membrane.

      422. The method of any of claims 404-421, wherein the barrier layer covers all or part of the surface of the outgassing material.

      425. The method of any of claims 404-424, wherein the barrier layer comprises SiOx (x is from about 1.5 to about 2.9).

      426. The method of any of claims 404-425, wherein the barrier layer consists essentially of SiOx, where x is from about 1.5 to about 2.9.

      427. The method of any of claims 404-426, wherein the barrier layer has a thickness of less than 500 nm.

      428. The method of any of claims 404-427, wherein the barrier layer has a thickness of less than 300 nm.

      429. The method of any of claims 404-428, wherein the barrier layer has a layer thickness of less than 100 nm.

      430. The method of any of claims 404-429, wherein the barrier layer has a layer thickness of less than 80 nm.

      431. The method of any of claims 404-430, wherein the barrier layer has a layer thickness of less than 60 nm.

      432. The method of any of claims 404-431, wherein the barrier layer has a thickness of less than 50 nm.

      433. The method of any of claims 404-432, wherein the barrier layer has a thickness of less than 40 nm.

      434. The method of any of claims 404-433, wherein the barrier layer has a thickness of less than 30 nm.

      435. The method of any of claims 404-434, wherein the barrier layer has a thickness of less than 20 nm.

      436. The method of any of claims 404-435, wherein the barrier layer has a thickness of less than 10 nm.

      437. The method of any of claims 404-436, wherein the barrier layer has a layer thickness of less than 5 nm.

      438. The method of any of claims 404-437, wherein the measurement of the emitted gas is performed under conditions effective to determine the presence or absence of the barrier layer.

      439. The method of claim 438, wherein the test time less than 1 minute is included under conditions effective to determine the presence or absence of the barrier layer.

      440. The method of claim 438, wherein the test time less than 50 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      441. The method of claim 438, wherein the test time less than 40 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      442. The method of claim 438, wherein the test time less than 30 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      443. The method of claim 438, wherein the test time less than 20 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      444. The method of claim 438, wherein the test time less than 15 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      445. The method of claim 438, wherein the test time less than 10 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      446. The method of claim 438, wherein a test time less than 8 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      447. The method of claim 438, wherein a test time of less than 6 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      448. The method of claim 438, wherein the test time less than 4 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      449. The method of claim 438, wherein a test time of less than 3 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      450. The method of claim 438, wherein the test time less than 2 seconds is included under conditions effective to determine the presence or absence of the barrier layer.

      451. The method of claim 438, wherein the test time less than 1 second is included under conditions effective to determine the presence or absence of the barrier layer.

      452. The method according to any one of claims 438 to 451, wherein the measurement of the presence or absence of the barrier layer is confirmed with a certainty of at least a six sigma level.

      453. The method of any of claims 438-452, wherein the measurement has at least a Six Sigma level certainty.

      454. The measurement of the released gas on the low pressure side of the barrier layer is carried out under conditions effective to determine the barrier improvement (BIF) of the barrier layer and compared with the same material without the barrier layer, The method of any of claims 404-453.

      455. The method of any of claims 404-454, wherein outgassing of a number of different gases is measured.

      456. The method of any of claims 404-455, wherein the outgassing of substantially all of the outgassing is measured.

      457. The method of any of claims 404-456, wherein the outgassing of substantially all of the outgassing is measured simultaneously.

      458. The method of any of claims 404-457, wherein outgassing of substantially all of the outgassing is measured simultaneously.

The following reference signs are used in the drawings:

20 Container handling system
22 Injection molding machine
24 visual inspection station
26 Inspection station (before coating)
28 Inspection station
30 Inspection station (after coating)
32 Optical source transmission station (layer thickness)
34 Optical source transmission station (defect)
36 outputs
38 Container holder
40 Container holder
42 Container holder
44 Container holder
46 Container holder
48 Container holder
50 container holder
52 Container holder
54 Container holder
56 Container holder
58 Container holder
60 Container holder
62 Container holder
64 container holder
66 Container holder
68 Container holder
70 conveyor
72 Transport mechanism (ON)
74 Transport mechanism (off)
80 containers
82 opening
84 Closed end
86 walls
88 Inside
90 Barrier coating
92 Container port
94 Vacuum duct
96 Vacuum port
98 Vacuum source
100 (92) O-ring
102 (96) O-ring
104 Gas inlet port
106 (100) O-ring
108 Probe (counter electrode)
110 (108) gas supply ports
112 Container holder (Figure 3)
114 (50 or 112) enclosure
116 colors
118 (80's) exterior
120 Container holder (array)
122 Container port (Fig. 4, 58)
130 frames (Figure 5)
132 Light source
134 Side channel
136 Shut-off valve
138 Probe port
140 Vacuum port
142 PECVD gas inlet port
144 PECVD gas source
146 (98) vacuum lines
148 Shut-off valve
150 (134) flexure lines
152 Pressure gauge
154 Inside of container 80
160 electrodes
162 Power supply device
164 (160) sidewalls
166 (160) sidewalls
168 (160) closed end
170 Light source (Figure 10)
172 Detector
174 (172) pixels
176 (172) inner surface
182 (186) apertures
184 (186) walls
186 integrating sphere
190 Microwave power supply
192 Waveguide
194 Microwave cavity
196 gap
198 (194's) top edge
200 electrodes
202 pipe transfer
204 Suction cup
208 Mold core
210 Mold cavity
212 Mold cavity liner
220 Support surface (Fig. 2)
222 Support surface (Fig. 2)
224 Support surface (Fig. 2)
226 Support surface (Fig. 2)
228 Support surface (Fig. 2)
230 Support surface (Fig. 2)
232 Support surface (Fig. 2)
234 Support surface (Fig. 2)
236 Support surface (Fig. 2)
238 Support surface (Fig. 2)
240 Support surface (Fig. 2)
250 syringe barrel
252 syringe
254 (250) inside
256 (250) rear end
258 (252) Plunger
260 (250) front end
262 lid
264 (262) inside
266 Mounting part
268 containers
270 Closure
272 Internal surface
274 Lumen
276 Wall contact inner surface
278 (280) inside
280 container wall
282 Stopping member
284 Shield
286 Lubrication layer
288 Barrier layer
290 coating equipment, e.g. 250
292 (294) inside
294 (250) restrictive openings
296 Processing container
298 (250) exterior
300 (250) lumens
302 (250) large opening
304 Processing vessel lumen
306 Processing container opening
308 Internal electrode
310 (308) internal pathway
312 (308) proximal end
314 (308) distal end
316 (308) distal opening
318 Plasma
320 Container support
322 (320) ports
324 Processing vessel (conduit type)
326 (324) container opening
328 (324) second opening
330 (Accept 328) Vacuum port
332 1st mounting part (Male luer taper)
334 2nd mounting part (Female luer taper)
336 (332) lock collar
338 (332) first contact part
340 (332) second contact
342 O-ring
344 dog
346 walls
348 (on 346) dressing
350 transmission path
352 vacuum
354 gas molecules
355 gas molecules
356 interface (between 346 and 348)
357 gas molecules
358 PET container
359 gas molecules
360 Sealing part
362 measuring box
364 vacuum pump
366 Arrow Line
368 Conical Path
370 drilling machine
372 drilling machine
374 chamber
376 chamber
378 diaphragm
380 diaphragm
382 Conductive surface
384 conductive surface
386 Bypass
390 plot (glass tube)
392 plot (uncoated PET)
394 Main plot (SiO2 coating)
396 Outer layer (SiO2 coating)
398 Internal electrode and gas supply pipe
400 Distal opening
402 Protruding counter electrode
404 Vent (Figure 7)
406 valve
408 Inner wall (Fig. 36)
410 Exterior wall (Fig. 36)
412 Inside (Fig. 36)
414 Plate electrode (Fig. 37)
416 Plate electrode (Fig.37)
418 vacuum conduit
420 Container holder
422 Vacuum chamber
424 Container holder
426 Counter electrode
428 Container holder (Fig. 39)
430 electrode assembly
432 430 more enclosed capacity
434 Pressure proportional valve
436 Vacuum chamber conduit
438 Syringe barrel (Figure 42)
440 (438) flange
442 (438) rear opening
444 (438) barrel walls
450 Container holder (Figure 42)
452 Grooved nail rim
454 (438) regular cylindrical side walls
456 (450) normal cylindrical inner surface
458 abutment
460 Pocket
462 O-ring
464 (460) exterior walls
466 (460) bottom wall
468 (460) top wall
470 Internal electrode (Fig. 44)
472 (470) distal part
474 (472) porous sidewall
476 (472) internal pathways
478 (470) proximal
480 (470) distal end
482 Container holder body
484 (482) top
486 (482) base
488 (between 484 and 486) joint
490 O-ring
492 Slotted nail pocket
494 Surface of contact part extending radially
496 Radially extending walls
498 screw
500 screws
502 container port
504 2nd O-ring
506 (490) ID
508 (482) vacuum duct
510 Internal electrode
512 Internal electrode
514 Insertion and removal mechanism
516 Deflection hose
518 Deflection hose
520 deflection hose
522 valve
524 valves
526 valve
528 electrode purification station
530 Internal electrode drive
532 Purification reactor
534 Ventilation valve
536 Second grip
538 conveyor
539 Solute Holding Member
540 (532) open end
542 (532) lumen
544 syringe
546 Plunger
548 body
550 barrels
552 (550) inner surface
554 Coating material
556 Luer mount
558 Lure Taper
560 (558) internal pathways
562 Inside
564 coupling
566 (564) male part
568 (564) female part
570 barrier coating
572 lock collar
574 Main vacuum valve
576 vacuum line
578 Manual bypass valve
580 Bypass pipeline
582 Ventilation valve
584 Main reactive gas valve
586 Main reactant supply line
588 Organosilicon fluid reservoir
590 Organosilicon supply line (capillary)
592 Organosilicon shut-off valve
594 oxygen tank
596 Oxygen supply line
598 Mass flow controller
600 oxygen shut-off valve
602 Syringe external barrier coating
604 Lumen
606 barrel exterior
610 plasma shield
612 Plasma shield cavity
614 headspace
616 Pressure source
618 pressure line
620 Capillary connection
630 Uncoated COC plot
632 plot for SiOx coated COC
634 Plot for glass
5501 1st processing station
5502 Second processing station
5503 3rd treatment station
5504 4th treatment station
5505 processor
5506 user interface
5507 bus
5701 PECVD equipment
5702 First detector
5703 Second detector
5704 detector
5705 detector
5706 detector
5707 Detector
7001 Conveyor exit branch
7002 Conveyor exit branch
7003 Conveyor exit branch
7004 Conveyor exit branch

Claims (24)

A method for inspecting a coated product in which a coating material is applied to a substrate surface to form the coated surface is provided, which method comprises the following steps:
(a) Providing products as inspection objects,
(c) measuring at least one volatile species released from the test object into the air layer adjacent to the coated surface; and
(d) Comparison of the result of procedure (c) with at least one reference object under the same test conditions with the result of (c) above, and therefore the presence or absence of a coating and / or the physical properties of the coating Determination of chemical and / or chemical properties.   The method of claim 1, wherein the physical and / or chemical properties of the dressing are determined and selected from the group consisting of barrier properties, wetting tensions, and compositions, and are preferably barrier properties.   The method according to claim 1 or 2, wherein step (c) is carried out by measuring the mass flow or volume flow of at least one volatile species in the gas layer adjacent to the coated surface. The method according to any one of claims 1 to 3, which satisfies the following:
(i) the reference object is an uncoated substrate, or
(ii) The reference object is a substrate coated with a reference coating material. The method according to any one of claims 1 to 4, comprising the following steps as an additional step between steps (a) and (c):
(b) A change in air pressure in the gas layer adjacent to the coated surface such that a pressure difference is provided through the coated surface and a higher volatile species mass flow or volume flow without pressure differential can be achieved.   6. The method according to claim 5, wherein the pressure is measured using a measurement cell interposed between the coated surface of the substrate and a vacuum source.   The volatile species is a gas or vapor at the test conditions, preferably selected from the group consisting of air, nitrogen, oxygen, water vapor, volatile coating components, volatile substrate components, and complexes thereof, more preferably air. The method of any one of Claims 1-6 which is nitrogen, oxygen, water vapor | steam, or those composites.   The test object contacts in step (a) a volatile species, preferably a volatile species selected from the group consisting of air, nitrogen, oxygen, water vapor, and complexes thereof, and thus preferably on the material of the test object. 8. The method according to any one of claims 1 to 7, wherein absorption of the volatile species into / in is allowed and subsequent release of the volatile species from the test substance is measured in step (c). .   9. A number of different volatile species are measured in step (c), preferably substantially all volatile species released from the test substance are measured in step (c). the method of.   The method according to any one of claims 1 to 9, wherein the substrate is a polymer compound, preferably polyester, polyolefin, cyclic olefin copolymer, polycarbonate, or a composite thereof.   The method according to claim 1, wherein the coating material is a coating material prepared by PECVD from an organosilicon precursor. The method according to any one of claims 1 to 11, which satisfies the following:
(i) the coating is a barrier coating, preferably a SiO _x layer (x is about 1.5 to about 2.9), and / or
(ii) A coating that changes the lubricity and / or surface tension of the substrate coated with the coating material, preferably a Si _w O _x C _y H _z layer (w is 1, x is about 0.5 to 2). .4, y is about 0.6 to about 3, and z is 2 to about 9).   A volatile species is a volatile species released from the dressing, preferably a volatile dressing component, and performs a test to determine the presence, nature, and / or composition of the dressing. The method according to claim 1.   The method according to claim 1, wherein the volatile species are volatile species released from the substrate, and an inspection is performed to determine the presence or absence of a coating material and / or the barrier effect of the coating material.   The substrate is a container having a wall, and at least a part of the inner surface or the outer surface of the wall is coated during the coating process, and preferably the coating material is attached to the inner surface of the container wall. 2. The method according to item 1.   16. The method of claim 15, wherein a pressure differential is established inside and outside the container to measure volatile species gas emissions from the coated container wall.   17. A method according to claim 15 or 16, wherein the pressure difference is provided by at least partial evacuation within the vessel.   Effective conditions for determining the presence or absence of a coating and / or determining the physical and / or chemical properties of the coating are less than 1 hour, or less than 1 minute, or less than 50 seconds, or less than 40 seconds, Or less than 30 seconds, or less than 20 seconds, or less than 15 seconds, or less than 10 seconds, or less than 8 seconds, or less than 6 seconds, or less than 4 seconds, or less than 3 seconds, or less than 2 seconds, or less than 1 second The method according to claim 1, wherein a test period is included.   By changing the atmospheric pressure and / or temperature and / or humidity, the emission amount of the volatile species is changed, thus the reference object and the inspection object with respect to the emission amount and / or the type of volatile species to be measured. 19. A method according to any one of claims 1-18, wherein the difference between them is increased.   20. A method according to any one of the preceding claims, used as an in-line process control method for coating treatment to identify and remove coating products or damaged coatings that do not meet predetermined criteria.   21. A method according to any one of claims 1 to 20, wherein the coating is a PECVD coating performed under vacuum conditions and subsequent outgassing measurements are performed without breaking the vacuum used in the PECVD coating.   The method according to any one of claims 1 to 21, wherein the measurement is performed using a microcantilever measurement technique. The method according to claim 22, wherein the measurement is carried out by:
(i) (a) providing at least one microcantilever having the property of moving or changing into a different shape in the presence of a gas releasing material;
(b) exposure of the microcantilever to an outgassing material under conditions effective to move or change the microcantilever to a different shape; and
(c) preferably the movement of the microcantilever or the detection of a different shape by reflection of the incident energy beam from the shape change part of the microcantilever, e.g. before and after exposure of the microcantilever to the gas releasing material; and Measuring the deviation of the reflected beam at a point away from the cantilever, or
(ii) (a) providing at least one microcantilever that resonates at different frequencies in the presence of an outgassing material;
(b) exposure of the microcantilever to an outgassing material under conditions effective to resonate the microcantilever at different frequencies; and
(c) Detection of different resonance frequencies, for example using harmonic vibration sensors.   24. An apparatus for performing the method of any of claims 20-23.

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