KR20120060781A - Pecvd coating using an organosilicon precursor - Google Patents

Abstract

A method of coating a substrate surface by PECVD is provided that includes generating a plasma from a gaseous reactant comprising an organosilicon precursor and optionally O 2. The lubricity, hydrophobicity and / or barrier of the coating is set by setting the ratio of O 2 to organosilicon precursors in the gas reactant and / or setting the power used to generate the plasma. In particular, a lubricity coating made by the method is provided. In addition, there is provided the use of the container coated by the method and the compound or composition contained or contained within the coated container from the mechanical and / or chemical effects of the uncoated container material surface.

Description

PECVD coating using organosilicon precursor {PECVD COATING USING AN ORGANOSILICON PRECURSOR}

The present invention relates to the technical field of making coated containers for storing biologically active compounds or blood. In particular, the present invention relates to a container processing system for coating and inspection of a container, which is a container processing system for coating of a container, and to a portable container support for a container processing system, and to plasma enhancement for coating the inner surface of the container. Relates to a chemical vapor deposition apparatus, to a method for coating the inner surface of a container, to a method for coating and inspecting a container, to a method for processing a container, to a use of a container processing system, and to a computer readable medium , Program components.

A method of coating a substrate surface by PECVD is provided that includes generating a plasma from a gaseous reactant comprising an organosilicon precursor and optionally oxygen (O ₂ ). The lubricity, hydrophobicity and / or barrier of the coating is set by setting the ratio of O ₂ to organosilicon precursors in the gas reactant and / or setting the power used to generate the plasma. In particular, a lubricity coating made by the method is provided. In addition, there is provided the use of the container coated by the method and the compound or composition contained or contained within the coated container from the mechanical and / or chemical effects of the uncoated container material surface.

The present disclosure also relates to improved methods for the treatment of a plurality of identical containers, for example used for venipuncture and other medical sample collection, pharmaceutical agent storage and delivery, and other purposes. Such containers are used in large quantities for these purposes, must be relatively economical to manufacture and highly reliable in storage and use.

For example, vacuumed blood collection tubes are used to draw blood from a patient for medical analysis. The tubes are sold in a vacuum. The patient's blood is inserted into a patient's blood vessel by inserting one end of a hypodermic needle into both vessels and penetrating the closure of the vacuum blood collection tube to the other end of the needle using both sides into the interior of the tube. It will work. Due to the vacuum in the vacuumed blood collection tube, blood is drawn through a needle through the vacuumed blood collection tube (or more precisely, the blood pressure of the patient pushes the blood), thereby increasing the pressure in the tube to allow blood to flow. To reduce the pressure difference. Typically, blood flow continues until the tube is removed from the needle or the pressure differential is too small to support the flow.

Vacuum blood collection tubes must have a substantial shelf life prior to use to facilitate efficient and convenient dispensing and storage of the tubes. For example, a shelf life of one year is preferred, and increasingly longer shelf lives, such as 18 months, 24 months or 36 months, are also desirable in some cases. Preferably, while supplying very few (optimally none) of defective tubes, the tubes remain sufficiently vacuumed to the extent necessary to draw at least enough blood for analysis (common criteria) The tube maintains at least 90% of the volume originally sucked).

Defective tubes are likely to cause the bleeding specialist using the tubes to fail to draw enough blood. The bleeding physician then needs to obtain and use one or more other tubes to obtain a sufficient blood sample.

As another example, prefilled syringes are commonly prepared and sold such that the syringe does not need to be filled prior to use. In other instances, the syringe may be prefilled with saline, dye for injection or a pharmaceutically active agent.

Typically, the prefilled syringe is capped at the distal end using a cap and closed at the proximal end by the pulled plunger of the syringe. The prefilled syringe may be packaged in sterile packaging before use. To use the prefilled syringe, the package and cap are removed, optionally a hypodermic needle or other conduit is attached to the distal end of the barrel and the delivery or syringe is moved to the use position The plunger is advanced in the barrel to inject the contents of the barrel (such as inserting a hypodermic needle into the patient's blood vessel or into the device for rinsing with the contents of the syringe).

One important consideration in making prefilled syringes is that the contents of the syringe have a substantial lifespan, which is important to separate it from the barrel wall containing the material filling the syringe, preferably during its lifetime. The filling contents will avoid filtering the material or vice versa.

Since many of these containers are expensive and used in large quantities, it will be useful for certain applications to reliably obtain the required shelf life without increasing the manufacturing costs to forbidden levels. In addition, from glass containers that can be broken for a particular use and are expensive to manufacture, they are rarely broken in normal use (though they do not form sharp pieces in the residue of the container, as in glass tubes). It is also preferable to change it. Glass containers are preferred because the glass is more gas tight and inert to prefilled contents than untreated plastics. In addition, since it has been used traditionally, it is easily accepted since glass is known to be relatively harmless when it comes into contact with a medical sample or pharmaceutical preparation.

Another consideration when considering syringes is to allow the plunger to move at a constant speed and constant force when compressed into the barrel. For this purpose, lubricious coatings are preferred for either or both of the barrel and plunger.

A non-limiting list of possible related patents includes US Pat. Nos. 6,068,884 and 4,844,986 and the United States. Published applications 20060046006 and 20040267194.

It is an object of the present invention to produce improved coating containers.

In the following, methods and apparatuses manufactured according to the methods are described, which methods can be performed by a vessel processing system described further below and the apparatuses can be manufactured by this system.

The present invention provides a method of coating a surface, such as the inner surface of a container, with a coating made by PECVD from an organosilicon precursor. The present invention also provides the resulting coatings, containers coated with the coatings and the use of such coatings as, for example, lubricity coatings, hydrophobic coatings or barrier coatings. In addition, there are provided apparatuses and some devices for carrying out the invention. The present invention also provides a test method for the coating, in particular a method using degassing of volatile species by the coated surface for the test.

PECVD coating method

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

A surface, for example an inner vessel surface, is provided, such as a reaction mixture comprising an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas.

The surface is in contact with the reaction mixture. Plasma is formed in the reaction mixture. Preferably, the plasma is a non-hollow cathode plasma, or in another representation of the same conditions, the plasma is substantially free of hollow cathode plasma. The coating is deposited on at least a portion of the surface, for example on a portion of the vessel wall.

The method is performed as follows.

A precursor is provided. Preferably, the precursor is an organosilicon compound (also referred to below as an "organosilicon precursor"), more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyl trimethoxy Silanes, groups consisting of aza analogs of any of these precursors (eg, linear siloxanexazan, monocyclic siloxanexazan, polycyclic siloxanexazan, polysilsesquioxazan) and combinations of any two or more of these precursors Organosilicon compounds selected from. The precursor is applied to the substrate under conditions effective to form a coating by PECVD. Thus, the precursor is polymerized, crosslinked, partially or wholly oxidized, or any combination thereof.

In one aspect of the invention, the coating is a lubricity coating, ie, forms a surface with lower frictional resistance than an uncoated substrate.

In another aspect of the invention, the coating is, for example, a passivation coating such as, for example, a hydrophobic coating, which results in less precipitation of the components of the composition in contact with the coated surface. Such hydrophobic coatings are characterized by lower wet tension than uncoated.

In addition, the lubricity coatings of the present invention may be passivation coatings and vice versa.

In another aspect of the invention, the coating is a barrier coating such as, for example, a SiO _x coating. Typically, the barrier is for gas or liquid, preferably for water vapor, oxygen and / or air. The barrier film may also be used to create and / or maintain a vacuum inside a container coated with the barrier coating, such as inside a blood collection tube.

In addition, the method of the present invention may include the application of one or more other coatings made by PECVD from an organosilicon precursor. Another optional additional step is to work up the SiO _x coating with a process gas consisting essentially of oxygen and essentially free of volatile silicone compounds.

Lubricity coating

In one particular aspect, the present invention provides a lubricity coating.

Advantageously, this coating is made using the above PECVD method and the precursors described above.

For example, the present invention provides a method of setting the lubricity of a coating on a substrate surface, comprising the following steps:

(a) providing a gaseous reactant comprising an organosilicon precursor and optionally O 2 near the substrate surface; And

(b) generating a plasma from the gaseous reactant to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),

The lubricity of the coating is set by setting the ratio of O 2 to the organosilicon precursor in the gas reactant and / or setting the power used to generate the plasma.

Preferred precursors for such lubricity coatings are monocyclic siloxanes such as octamethylcyclotetrasiloxane (OMCTS).

This allows the coated surface to have lower frictional resistance than the uncoated substrate. For example, where the coated surface is the interior of a syringe barrel and / or syringe plunger, the lubricity coating is lower than the breakout force or plunger activation force, or the corresponding force required in the absence of the lubricity coating. It is effective in providing both strengths.

The article coated with the lubricity coating may comprise a container portion or container cap, such as a syringe plunger or a container cap, having the coating on a wall, preferably an inner wall, with a lubricity coating, such as a syringe barrel, or a container in contact with the surface. It may be a container having.

In one aspect, the lubricity coating is, for example, w is 1, x is 1 as w, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from about 2 to about 9 And preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to 9 having the formula Si _w O _x C _y H _z .

Passivation, for example hydrophobic coating

Passivation coatings according to the invention are, for example, hydrophobic coatings.

Preferred precursors for such passivation, for example hydrophobic coatings, are linear siloxanes such as hexamethyldisiloxane (HMDSO).

The passivation coating according to the present invention prevents or reduces the mechanical and / or chemical effects of the uncoated surface on the compound or composition contained in the container. For example, precipitation and / or coagulation or platelet activation of a compound or component of the composition in contact with the surface is prevented or reduced, e.g., blood coagulation or platelet activation or precipitation of insulin or of an uncoated surface by an aqueous fluid. Wetting is prevented.

One particular aspect of the invention is, for example, 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 a surface with a hydrophobic coating having the formula Si _w O _x C _y H _z of 6-9.

The article coated with the passivation coating can be a container having a coating on the wall, preferably an inner wall, such as a tube or a container in contact with the surface, or a container having a container cap, such as a container cap.

Coating of container

When the container is coated by the method using PECVD, the coating method includes several steps. A container having an open end, a closed end and an inner surface is provided. At least one gaseous reactant is introduced into the vessel. Plasma is formed in the vessel under conditions effective to form a reaction product of the reactant, ie a coating, on the inner surface of the vessel.

Preferably, the method is carried out by seating the open end of the vessel on a vessel holder as described herein and effecting a sealed communication between the vessel holder and the interior of the vessel. In this preferred aspect, the gaseous reactant is introduced into the vessel through the vessel holder. In a particularly preferred aspect of the invention, a plasma enhanced chemical vapor deposition (PECVD) apparatus comprising a vessel holder, an inner electrode, an outer electrode and a power supply is used for the coating method according to the invention.

The vessel holder has a port for receiving the vessel in a seated position for processing. The inner electrode is positioned to be received in a container seated on a container support. The outer electrode has an inner portion positioned to receive a vessel seated on the vessel holder. The power supply supplies alternating current to the inner and / or outer electrodes to form a plasma in the vessel seated on the vessel holder. Typically, the power supply supplies alternating current to the outer electrode while the inner electrode is grounded. In this embodiment, the vessel defines a plasma reaction chamber.

In one particular aspect of the invention, the PECVD apparatus described in the preceding paragraph does not necessarily include a vacuum source for delivering gas to or from the interior of a vessel seated on the port to define a closed chamber. A gas drain.

In another particular aspect of the invention, the PECVD apparatus comprises a vessel holder, a first gripper, a seat of the vessel support, a reactant feeder, a plasma generator and a vessel discharge device.

The vessel holder is configured to rest on the open end of the vessel. The first gripper is configured to selectively support and release the closed end of the container and to transport the container near the container support while holding the closed end of the container. The vessel holder has a seat configured to achieve sealed communication between the vessel holder and the inner space of the first vessel.

The reactant feeder is operably connected to introduce at least one gaseous reactant within the first vessel through the vessel holder. The plasma generator is configured to form a plasma in the first vessel under conditions effective to form a reaction product of a reactant on the inner surface of the first vessel.

The vessel dispensing device is provided to detach the first vessel from the vessel holder. The gripper, which is the first gripper or another gripper, is configured to transfer the first vessel in the axial direction from the vessel holder and to discharge the first vessel.

In one particular aspect of the invention, the method is for coating the inner surface of the limited opening of the container, eg, generally a tubular container, by PECVD. The container includes an outer surface, an inner surface defining a lumen, a larger opening with an inner diameter, and a limited opening with an inner diameter defined by the inner surface and smaller than the larger opening inner diameter. There is provided a treatment vessel having a lumen and a treatment vessel opening. The processing vessel opening is connected with the limited opening of the vessel to allow communication between the lumen of the vessel being processed and the processing vessel lumen through the restricted opening. At least a partial vacuum is drawn in the lumen of the vessel to be treated and in the vessel lumen being processed. PECVD reactant flows through the first opening, through the lumen of the vessel to be subsequently processed, and then through the restricted opening to the vessel lumen being processed. Plasma is generated in the vicinity of the restricted opening under conditions effective to deposit a coating of the PECVD reaction product on the inner surface of the restricted opening.

Coated Containers and Container Parts

The present invention provides a coating by the method described above, a surface coated with the coating and a container coated with, for example, the coating.

The surface coated with the coating, such as the vessel wall or part thereof, may be a glass or polymer, preferably a thermoplastic polymer, more preferably a polymer selected from the group consisting of polycarbonates, olefin polymers, cyclic olefin copolymers and polyesters. Can be. For example, it is a cyclic olefin copolymer, polyethylene terephthalate or polypropylene.

In one particular aspect of the invention, the vessel wall has an inner polymer layer surrounded by at least one outer polymer layer. The polymers may be the same or different. For example, the other polymer layer, which is one of the polymer layers of the cyclic olefin copolymer (COC) resin (eg, defining a water vapor barrier), is a layer of polyester resin. Such a container can be made by a process of introducing COC and polyester resin layers into an injection mold through concentric injection nozzles.

The coated container of the present invention is hollow and can be vacuum or (pre) filled with a compound or composition.

One particular aspect of the invention is a container having a passivation coating, for example the hydrophobic coating described above.

Another particular aspect of the present invention is a surface having the lubricity coating described above. It may be a lube coating on a wall, preferably an inner wall, such as a syringe barrel, or a container part or container cap having such coating on a container in contact with the surface, such as a container having a syringe plunger or a container cap.

One particular aspect of the invention is a syringe comprising a plunger, a syringe barrel and a lubricity coating as defined above on one or both of these syringe parts, preferably on the inner wall of the syringe barrel. The syringe barrel includes a barrel having an inner surface to slidably receive the plunger. The lubricity coating may be provided on the inner surface of the syringe barrel or on the plunger surface in contact with the barrel or on both surfaces. The lubricity coating is effective to reduce breakout force or plunger activation force sufficient to move the plunger within the barrel.

Another particular aspect of the invention is a syringe barrel coated with a lubricity coating as defined in the preceding paragraph.

In one particular aspect of the coated syringe barrel, the syringe barrel includes a barrel having an inner surface defining the lumen and slidably receiving the plunger. The syringe barrel is advantageously made of thermoplastic material. A lubricity coating is applied to the barrel inner surface, plunger or both by plasma enhanced chemical vapor deposition (PECVD). The solute retainer is applied to the lumen on the lubricity coating in an amount effective to reduce filtration of the lubricity coating, the thermoplastic or both by surface treatment. The lubricity coating and solute retainer are constructed and present in relative amounts effective to provide a breakout force or plunger activation force, or both lower than the corresponding force required in the absence of the lubricity coating and solute retainer.

Another aspect of the invention is a syringe comprising a plunger, a syringe barrel and inner and outer coatings. The barrel has an inner surface and an outer surface to slidably receive the plunger. Lubricating coating is on the internal surface, x may be added to the barrier coating of from about 1.5 to about 2.9 of SiO _X is provided on the inner surface of the barrel. For example, a barrier coating of a resin or other SiO _x coating is provided on the outer surface of the barrel.

Another aspect of the invention is a syringe comprising a plunger, a syringe barrel and a luer fitting. The syringe barrel has an interior surface slidably receiving the plunger. The luer fitting includes a luer taper having an inner passage defined by the inner surface. The luer fitting is formed of components separate from the syringe barrel and is joined to the syringe barrel by a coupling. The inner passage of the luer taper has a barrier coating of SiO _{X with} x of about 1.5 to about 2.9.

Another aspect of the invention is a plunger for a syringe, comprising a piston and a push rod. The piston has a front and side and rear portions configured to movably seat within a generally cylindrical syringe barrel. The plunger has a lubricity coating according to the invention on its side. The push rod is configured to engage the trailing portion of the piston and to advance the piston in a syringe barrel. The plunger may further comprise a SiO _x coating.

Another aspect of the invention is a container having only one opening, ie a container for collecting or storing a compound or composition. In one particular aspect such a container is a tube, such as a sample collection tube, such as a blood collection tube. The tube may be closed with a closure, such as a cap or stopper. Such a cap or stopper may comprise a lubricity coating according to the invention on the surface in contact with the tube and / or may comprise a passivation coating according to the invention on the surface in contact with the lumen of the tube. In one particular aspect, such stopper or a portion thereof may be made of an elastic material.

Such a stopper can be manufactured as follows: The stopper is located in a substantially vacuum chamber. A reaction mixture is provided which comprises an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas. Plasma is formed in the reaction mixture in contact with the stopper. A coating is deposited on at least a portion of the stopper.

Another aspect of the invention is a container having a barrier coating according to the invention. The container is generally tubular and can be made of thermoplastic material. The container has an inlet and a lumen at least partially bounded by the wall. The wall has an interior surface that interfaces with the lumen. In one preferred aspect, at least one essentially continuous barrier coating, made of SiO _x as defined above, is applied on the inner surface of the wall. The barrier coating is effective to maintain at least 90%, optionally 95%, of the original vacuum level during the shelf life of at least 24 months in the container. A closure is provided that covers the inlet of the vessel and separates the lumen of the vessel from the ambient air.

In addition, the above PECVD fabrication coatings and PECVD coating methods using the organosilicon precursors described herein are useful for coating barrier conduits, hydrophobic coatings, lubricity coatings, or conduits or cuvettes to form one or more of them. Cuvettes are small tubes of round or rectangular cross-section, sealed at one end, made of polymer, glass or fused quartz (for ultraviolet) and designed to support spectroscopic samples. The best cuvettes are as transparent as possible without impurities that can affect the spectroscopic reading. Like a test tube, a cuvette may have a cap that is open to the atmosphere or sealable. The PECVD-coated coatings of the present invention are very thin, transparent and optically glossy, so that they may not interfere with the optical testing of cuvettes or their contents.

(Preliminary) Filled Coating Container

One specific aspect of the present invention is a coated container as described above, which is used to prefill or be filled with a compound or composition in its lumen. The compound composition may be as follows.

(i) a biologically active compound or composition, preferably a medicament, more preferably insulin or a composition comprising insulin; or

(ii) biological fluids, preferably body fluids, more preferably blood or blood fractions (eg blood cells); or

(iii) Compounds for preventing blood coagulation or platelet activation in blood collection tubes, such as compounds or compositions for direct mixing with other compounds or compositions in the container, such as citrate or citrate-containing compositions.

In general, coated containers of the present invention are particularly useful for collecting or storing compounds or compositions that are sensitive to the mechanical and / or chemical effects of uncoated container material surfaces, and preferably the composition upon contact with the inner surface of the container. It is particularly useful to prevent or reduce precipitation and / or coagulation or platelet activation of a compound or component of the compound.

For example, a cell preparation tube having a wall provided with the hydrophobic coating of the present invention and containing a water soluble sodium citrate reagent is suitable for collecting blood and preventing or reducing blood aggregation. The water soluble sodium citrate reagent is provided to the lumen of the tube in an amount effective to inhibit coagulation of blood introduced into the tube.

One particular aspect of the invention is a container or blood containing container for collecting / receiving blood. The container has a wall; The wall has an interior surface defining a lumen. The inner surface of the wall at least partially has the hydrophobic coating of the present invention. The coating may be as thin as a single molecule or as thick as about 1000 nm. The blood collected or stored in the container is preferably viable to return to the patient's vasculature disposed within the lumen in contact with the coating. The coating is effective in reducing coagulation or platelet activation of blood exposed to the inner surface compared to uncoated walls of the same type.

Another aspect of the invention is an insulin containing vessel comprising a wall having an inner surface defining a lumen. The inner surface at least partially has the hydrophobic coating of the present invention. The coating can be from monomolecular thickness to about 1000 nm thick on the inner surface. Insulin or a composition comprising insulin is provided in the lumen in contact with the coating. Optionally, the coating is effective to reduce precipitation formation from insulin in contact with the inner surface, compared to the same surface without the coating.

Accordingly, the present invention provides the following examples regarding coating methods, coated products and the use of such products:

(1) a method of setting the lubricity of a coating on a substrate surface, comprising the following steps

(a) providing a gaseous reactant comprising an organosilicon precursor and optionally O 2 near the substrate surface; And

(b) generating a plasma from the gaseous reactant to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),

The lubricity of the coating is set by setting the ratio of O 2 to the organosilicon precursor in the gas reactant and / or setting the power used to generate the plasma.

(2) a method of making a hydrophobic coating on a substrate, comprising the following steps:

(a) providing a gaseous reactant comprising an organosilicon precursor and optionally O 2 near the substrate surface; And

(b) generating a plasma from the gaseous reactant to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),

The hydrophobic nature of the coating is set by setting the ratio of O 2 and organosilicon precursors in the gas reactant and / or setting the power used to generate the plasma.

(3) The method of (1) or (2), wherein the coating produces a coating characterized by a formula wherein the atomic ratio C: O is increased and / or the atomic ratio Si: O is reduced compared to that of the organosilicon precursor.

(4) The process according to any one of (1) to (3), wherein the oxygen (O2) is from 0: 1 to 5: 1, optionally 0: 1 in volume-volume ratio to the gas reactant. To 1: 1, optionally 0: 1 to 0.5: 1, alternatively 0: 1 to 0.1: 1, preferably at least essentially free of oxygen in the gaseous reactant.

(5) The process according to any one of (1) to (4), wherein the gaseous reactant comprises less than 1 volume percent O 2, in particular less than 0.5 volume percent O 2, most preferably free of O 2 Characterized in that the method.

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

(7) The process according to any one of (1) to (6), wherein the substrate is 0.5 to 50 mL, preferably 1 to 10 mL, more preferably 0.5 to 5 mL, most preferably 1 The inner wall of the vessel having a lumen having a pore volume of from 3 mL to 3 mL.

(8) The method of any one of (1) to (7).

(i) the plasma is between 0.1 and 25 W, preferably between 1 and 22 W, more preferably between 3 and 17 W, even more preferably powered electrodes sufficient to form a coating on the substrate surface Is produced using electrodes powered from 5 to 14 W, most preferably 7 to 11 W, in particular 8 W; And / or

(ii) the ratio of the power to the plasma volume is 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.

(9) A method of making a coating on a substrate surface, comprising the following steps:

(a) providing a gaseous reactant comprising an organosilicon precursor and optionally O 2 near the substrate surface; And

(b) generating a non-porous cathode plasma from the gas reactant under reduced pressure to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),

The physical and chemical properties of the coating are set by setting the ratio of O 2 and organosilicon precursors in the gas reactant and / or by setting the power used to generate the plasma.

(10) For example, the present invention provides a method of setting the lubricity of a coating on a substrate surface, comprising the following steps:

(a) providing a gaseous reactant comprising an organosilicon precursor and O 2 near the substrate surface; And

(b) generating a non-porous cathode plasma from the gas reactant under reduced pressure to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),

The barrier of the coating is set by setting the ratio of O 2 and organosilicon precursors in the gas reactant and / or setting the power used to generate the plasma.

(11) the method under paragraph (10);

(i) the plasma comprises electrodes supplied with sufficient power to form a coating on the substrate surface, preferably 8 to 500 W, preferably 20 to 400 W, more preferably 35 to 350 W, more More preferably between 44 and 300 W, most preferably between 44 and 70 W powered electrodes; And / or

(ii) the ratio of the power to the plasma volume is 5 W / ml or less, 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.

(12) The process according to (10) or (11), wherein O2 is a volume: volume ratio of 1: 1 to 100: 1 relative to the gas reactant, preferably in a ratio of 5: Furnace 1 to 30: 1, more preferably 10: 1 to 20: 1, more preferably 15: 1.

(13) The process according to any one of items (1) to (12), wherein the organosilicon precursor is a linear siloxane, a monocyclic siloxane, a polycyclic siloxane, a polysesquioxane, a linear silazane, or a monocylate. A process characterized in that it is selected from the group consisting of click silazanes, polycyclic silazanes, polysilsesquiazanes, alkyl trimethoxysiloxanes and combinations of two or more of these compounds, preferably linear or monocyclic siloxanes to be.

(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 process according to any one of (1) to (15), wherein the PECVD is 6 sccm or less, preferably 2.5 sccm or less, more preferably 1.5 sccm, most preferably 1.25 sccm or less. And at a flow rate of the organosilicon precursor.

(17) The polymer according to any one of (1) to (16), wherein the substrate is a polymer selected from the group consisting of polycarbonates, olefin polymers, cyclic olefin copolymers and polyesters, preferably between A click olefin copolymer, polyethylene terephthalate or polypropylene.

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

(19) The process according to any one of (1) to (18), wherein the plasma is at a radio frequency, preferably 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferred. Preferably using electrodes powered at a frequency of 10 to 15 MHz and most preferably 13.56 MHz.

(20) The process according to any one of (1) to (19), wherein the plasma is produced under reduced pressure and the reduced pressure is less than 300 mTorr, preferably less than 200 mTorr, more preferably less than 100 mTorr. How to feature.

(21) The process 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. How to.

(22) The method according to any one of (1) to (21), wherein the resulting coating has a thickness in the range of 1 to 100 nm, preferably 20 to 50 nm.

(23) A coating obtainable by the method of any one of the preceding claims.

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

(25) The coating according to (24), wherein the atomic ratio of carbon to oxygen is increased relative to the organosilicon precursor and / or the atomic ratio of oxygen to silicon is reduced compared to the organosilicon precursor.

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

(27) The method according to any one of (24) to (26), wherein the coating

(i) has a lower frictional resistance than the uncoated surface, preferably the frictional resistance is at least 25%, more preferably at least 45%, even more preferably at least 60 compared to the uncoated surface It is characterized by a decrease by%.

(28) The method according to any one of (24) to (27), wherein the coating

(i) a lower wet tension than the uncoated surface, preferably a wet tension of 20 to 72 dyne / cm, more preferably a wet tension of 30 to 60 dyne / cm, more preferably 30 to 40 dyne / have a wet tension of cm, preferably 34 dyne / cm;

(iv) more hydrophobic than the uncoated surface.

(29) A container coated on at least a portion of its inner surface with a coating according to any one of (23) to (28), preferably a container as follows:

(i) sample collection tubes, in particular blood collection tubes; or

(ii) vials; or

(iii) a syringe or syringe portion, in particular a syringe barrel or syringe plunger; or

(iv) pipes; or

(v) cuvette.

(30) The method of (29), wherein x further comprises at least one layer of SiO x from 1.5 to 2.9,

(i) the coating is located between the SiOx layer and the substrate surface or vice versa,

(ii) the coating is located between two SiOx layers or vice versa,

(iii) a coated container, wherein the layers of SiOx and the coating are a gradient functional composite of SiwOxCyHz to SiOx or vice versa.

(31) The process according to any one of items (29) to (30), comprising on its outer surface at least one other layer, preferably another barrier made of plastic or SiOx, wherein x is from 1.5 to Coated container, characterized in that 2.9.

(32) The compound or composition according to any one of items (29) to (31), wherein the compound or composition is preferably a biologically active compound or composition or biological fluid, more preferably (i) citric acid A coated container comprising a salt or citric acid containing composition, (ii) a medicament, in particular an insulin or insulin containing composition or (iii) blood or blood cells.

(33) The process according to any one of items (29) to (32), wherein the precursor is a siloxane, more preferably a monocyclic siloxane, even more preferably octamethylcyclotetrasiloxane. A coated container, which is a syringe barrel made according to the method of claim 1, wherein the gas reactant is substantially free of any O 2 gas in step (a) and moves the plunger through the coated barrel. A coated container, characterized in that it is reduced by at least 25%, more preferably at least 45%, even more preferably at least 60% compared to an uncoated syringe barrel.

(34) Use of a coating having the formula SiwOxCyHz wherein w is 1, x is 0.5 to 2.4, y is 0.6 to 3, and z is 2 to 9.

(i) lubricity coatings having lower frictional resistance than uncoated surfaces; And / or

(ii) The use of a coating, characterized in that the hydrophobic coating is more hydrophobic than the uncoated surface.

(35) The use according to (34), wherein the coating is a coating as defined in any one of (24) to (28).

(36) The method according to (34) or (35), wherein the coating is compared with the uncoated surface and / or the surface coated according to the method of (1) using HMDSO as a precursor. Use to prevent or reduce precipitation of compounds or components of the composition in contact with the coating, in particular to prevent or reduce insulin precipitation or blood coagulation.

In addition, there is provided the use of the container coated by the method and the compound or composition contained or contained within the coated container from the mechanical and / or chemical effects of the uncoated container material surface.

(38) The use according to (37), wherein the compound or composition is as follows.

(i) a biologically active compound or composition, preferably a medicament, more preferably a composition comprising insulin or insulin, wherein insulin precipitation is reduced or prevented; or

(ii) a biological fluid, preferably a body fluid, more preferably a blood or blood fraction in which blood clotting and / or platelet activation is reduced or prevented.

(39) a medicament or diagnostic agent contained in the coated container; And / or subcutaneous needles, needles that are both ends or other delivery numbers; And / or a coated container according to the invention, which may further comprise instructions.

The invention further provides the following embodiments:

I. Vessel processing system with multiple treatment stations and multiple vessel supports

According to one aspect of the present invention, there is provided a container processing system for coating a container, the system comprising a first processing station, a second processing station, a container support and a conveyor arrangement. The first processing station is configured to perform a first treatment, for example an inspection or coating of the inner surface of the vessel. The second processing station is configured to perform a second processing, which is based from the first processing station and is, for example, inspection or coating of the inner surface of the container. The vessel holder receives an opening of the vessel for processing (inspecting and / or coating and / or inspecting) the inner surface of the seated vessel via the vessel port at the first and second processing stations. And a container port configured to seat. The conveyor arrangement transfers the vessel holder and the seated vessel from the first processing station to a second processing station for a second treatment of the inner surface of the seated vessel at the second processing station after the first treatment. Tailored to

As used herein, containers include sample tubes for collecting or storing blood, urine or other samples, syringes for storing or delivering a biologically active compound or composition, vials for storing a biological material or biologically active compound or composition Or any type of container including, but not limited to, cuvettes carrying biological material or biologically active compound or composition and cuvettes supporting biological material or biologically active compound or composition. It is broadly defined as.

The vessels described below are all processed using one of the processing systems or apparatus described below. That is, the features described below for an apparatus or processing system may also be performed as method steps and may affect the container so processed.

Cuvettes are small tubes of round or rectangular cross-section, sealed at one end, made of plastic, glass or fused quartz (for ultraviolet) and designed to support spectroscopic samples. The best cuvettes are as transparent as possible without impurities that can affect the spectroscopic reading. Like a test tube, a cuvette may have a cap that is open to the atmosphere or sealable.

The term “inside of the container” refers to a hollow space inside the container that can be used to store blood or, according to another exemplary embodiment, to store a biologically active compound or composition.

The term treatment may include a series of coating and inspection steps, such as coating is performed after a coating step and / or an inspection step or, for example, an initial inspection step, followed by a second or even third or fourth inspection. Can be. The second, third and fourth checks may be performed simultaneously.

According to an exemplary embodiment of the present invention, the vessel holder includes a vacuum duct for recovering gas from the interior space of the seated vessel, wherein the vessel holder does not require any other vacuum chamber to process the vessel. Is adapted to maintain a vacuum inside the container. That is, the vessel holder forms a vacuum chamber that is adapted to provide a vacuum in the interior space of the vessel with the seated vessel. This vacuum is important for certain processing steps such as plasma enhanced chemical vapor deposition (PECVD) or other chemical vapor deposition steps. In addition, the vacuum inside the vessel may be important for performing a particular inspection of the vessel wall, for example by measuring the degassing rate of the wall or the electrical conductivity of the wall, such as coating of the inner surface of the vessel wall. Can be.

According to another exemplary embodiment of the present invention, the first treatment is performed in 30 seconds or less. In addition, the second processing is performed in 30 seconds or less.

Thus, there is provided a container processing system for container coating, which enables rapid production of a container.

According to another exemplary embodiment of the present invention, the first treatment and / or the second treatment comprises performing coating of the inner space after examining the inner space of the container.

According to another exemplary embodiment of the present invention, the vessel holder includes a gas input port for delivering gas to the interior of the vessel.

According to another exemplary embodiment of the invention, the system is adapted to automatically reprocess the container when a coating defect is detected. For example, the vessel processing system and in particular the vessel holder may comprise an array of different detectors, for example optical detectors, pressure probes, gas detectors, electrodes for electrical measurement, and the like. .

Further, according to another embodiment of the present invention, the processing system, for example one or more of the processing stations, includes one or more grippers for transporting the container to the container support and / or removing the container from the container support. do.

According to another exemplary embodiment of the present invention, the vessel holder includes a gas input port for delivering gas to the interior of the vessel.

According to another exemplary embodiment of the present invention, the container processing system is adapted to automatically reprocess the container when a coating defect is detected.

The gas delivered to the interior space of the vessel may be useful for PECVD coating the interior space of the vessel.

According to another exemplary embodiment of the invention, the first treatment and / or the second treatment comprises coating the interior space of the container.

According to another exemplary embodiment of the invention, the first and / or second processing station comprises a PECVD apparatus for coating the interior space of the vessel.

According to another exemplary embodiment of the invention, the system further comprises an external electrode surrounding at least an upper portion of the seated container.

According to another exemplary embodiment of the present invention, there is provided an electrically conducting probe for providing a counter electrode in the container.

According to another exemplary embodiment of the present invention, the first treatment and / or the second treatment comprises inspecting the inner surface of the container for defects.

According to another exemplary embodiment of the present invention, the system is inserted into the container through the container photo of the first and / or second processing station for inspecting the interior space of the container for defects. It further comprises a first detector adapted to be.

According to another exemplary embodiment of the present invention, the vessel processing system further includes a second detector located outside the vessel for inspecting the inner surface of the vessel for defects.

According to another exemplary embodiment of the invention, the first detector and / or the second detector is mounted in the container.

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

According to another aspect of the invention, a container treatment system described above and below comprises a syringe for storing a biologically active compound or composition, a vial for storing a biologically active compound or composition, a biologically active compound or Uses are described for use in conduits for transferring compositions or for pipettes for pipetting biologically active compounds or compositions.

In addition, the container processing system may be configured for inspection of the container, in particular, to perform a first inspection of the container to determine whether there is a defect, to apply a first coating on the inner surface of the container, and then to determine whether there is a defect It can be tailored to perform a second inspection of the inner surface of the coated container to find out. In addition, the system can be tailored to evaluate data obtained while performing different tests, the second test and the data evaluation taking less than 30 seconds.

According to another aspect of the present invention, a first inspection of the container to determine whether there is a defect, the application of the first coating on the inner surface of the container, and a second inspection of the inner surface of the coated container to determine whether there is a defect 10. A container processing system for coating and inspecting a vessel comprising a processing station arrangement configured to evaluate data obtained during the inspection and during the inspection, wherein the second inspection and data evaluation is less than 30 seconds. A container handling system for inspection is provided.

In addition, application of the first coating may be referred to as a first or second treatment, and performing a second inspection of the inner surface of the coated container may be referred to as a second treatment.

According to another exemplary embodiment of the invention, the treatment station arrangement is a first treatment station for performing the first inspection, the application of the first coating to the inner surface of the seated vessel and the second inspection. A first processing station to perform. The processing station arrangement also has a container having a container port configured to receive and seat an opening of the container for inspecting and applying a first coating of an interior surface of the seated container through the container port at the first processing station. It includes a support.

According to another exemplary embodiment of the invention, the treatment station arrangement is spaced apart from the first treatment station, performing the second inspection and applying a second coating and performing a third inspection after the second coating. And further comprising a second processing station configured to. In addition, the treatment system may be applied to the second treatment station for application of the second coating from the first treatment station to the inner surface of the seated vessel at the second treatment station after applying the first coating. And a conveyor arrangement for transporting the vessel holder and the seated vessel. The vessel port of the vessel holder is configured to receive and seat an opening of the vessel that coats and inspects the interior surface of the seated vessel via the vessel port at the first and second processing stations.

According to another exemplary embodiment of the invention, the vessel holder comprises a vacuum duct for recovering gas from the interior space of the seated vessel, wherein the vessel holder does not require any other vacuum chamber to coat and inspect the vessel. To maintain a vacuum inside the seated vessel.

According to another exemplary embodiment of the present invention, each test is performed in 30 seconds or less.

According to another exemplary embodiment of the present invention, the container processing system is adapted to automatically reprocess the container when a coating defect is detected.

According to another exemplary embodiment of the invention, the first processing station and / or the second processing station comprises a PECVD apparatus for coating application of the inner surface of the vessel.

According to another exemplary embodiment of the invention, the coating is a barrier coating, wherein the system is adapted to confirm the presence of a barrier.

According to another exemplary embodiment of the invention, the second coating is a lubricity coating, wherein the system is adapted to check for the presence of the lubricity coating (ie, lubricity layer).

According to another exemplary embodiment of the invention, the first coating is a barrier coating, wherein the system is adapted to confirm the presence of the barrier and lubricity coating.

According to another exemplary embodiment of the invention, the system is adapted to confirm the presence of the barrier layer and the lubricity layer with at least six-sigma level of certainty.

According to another exemplary embodiment of the present invention, the first inspection and / or the second inspection includes measuring the degassing rate of the gas from the coated container, performing optical monitoring of the application of the coating, At least one of measuring optical parameters of an inner surface of the coated container, and measuring electrical properties of the coated container.

The measurement data can then be analyzed by the processor.

According to another exemplary embodiment of the invention, the processing system comprises a first detector for measuring the degassing rate and / or a second detector for measuring the diffusion rate and / or a third detector for measuring the optical parameters and / or And a fourth detector for measuring electrical parameters.

According to another exemplary embodiment of the invention, the first coating and / or the second coating is less than 100 nm thick.

According to another exemplary embodiment of the invention, the container processing system further comprises a processor obtained during the inspection.

One aspect of the present invention is a vessel processing system comprising a first processing station, a second processing station, a plurality of vessel supports and a conveyor. The first processing station is adapted to process a container having an opening and a wall defining an inner surface. The second processing station is spaced from the first processing station and is adapted to process a wall having an opening and a wall defining an interior surface.

At least some, optionally all, of the vessel holder includes a vessel port configured to receive and seat an opening of the vessel for processing an interior surface of the seated vessel through the vessel port in the first treatment. . The conveyor is configured for transferring a series of the vessel holders and seated vessels from a first processing station to a second processing station for treatment of the inner surface of the seated vessel at the second processing station.

II. Container support

II.A.  Vessel supports that do not quote a specific containment

A portable container support of the container processing system, wherein the inner surface of the container is coated and inspected for defects and the container is transferred from the first processing station of the container processing system to the second processing station and the container support Is configured to seat the opening of the vessel and a vessel holder for treating the interior surface of the seated vessel via the vessel port at the first and second processing stations may be adapted to support the vessel.

According to another exemplary embodiment of the present invention, the portable vessel holder includes a second port for receiving an external gas supply or outlet and a duct for passing gas between the opening and the opening of the vessel seated on the vessel port and the second port. It further includes.

According to another exemplary embodiment of the present invention, the portable container support weighs less than 2.25 kg.

According to another exemplary embodiment of the present invention, the vessel holder includes a vacuum duct and an external vacuum port for recovering gas through the vessel port from the interior of the seated vessel, wherein the vessel holder is adapted to treat the vessel. It is adapted to maintain a vacuum inside the seated vessel so that no other vacuum chamber is required.

According to another exemplary embodiment of the present invention, the vessel holder includes a vacuum duct and an external vacuum port for recovering gas through the vessel port from the interior of the seated vessel, wherein the vessel holder is adapted to treat the vessel. It is adapted to maintain a vacuum inside the seated vessel so that no other vacuum chamber is required.

According to another exemplary embodiment of the present invention, the external vacuum port also incorporates a gas input port contained in the vacuum port for delivering gas into the seated vessel.

According to another exemplary embodiment of the invention, the treatment of the container comprises coating an inner surface of the seated container.

According to another exemplary embodiment of the present invention, the vessel holder is essentially made of thermoplastic material.

According to another exemplary embodiment of the present invention, the portable vessel holder has a cylindrical inner surface for receiving the cylindrical wall of the vessel, a first annular groove coaxially within the cylindrical inner surface and the first annular groove. And a first O-ring disposed within and providing a seal between the seated vessel in the vessel holder.

According to another exemplary embodiment of the present invention, the portable vessel holder further comprises a radially extending junction adjacent to a round cylindrical inner surface on which the open end of the seated vessel can be supported.

According to another exemplary embodiment of the present invention, the portable vessel holder further comprises a second annular groove coaxial with and within the cylindrical inner surface and axially spaced apart from the first annular groove. The vessel holder further comprises a second O-ring disposed in the second annular groove providing a seal between the seated vessel in the vessel holder.

According to another exemplary embodiment of the invention, the vessel holder further comprises a first detector for inspecting the interior space of the vessel through the inspection vessel port of the interior surface of the seated vessel to determine if there is a defect.

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

According to another exemplary embodiment of the invention, the container processing system for coating of the container comprises the container support described above and below.

According to another exemplary embodiment of the invention, the portable vessel holder comprises a vessel port, a second port, a duct and a movable housing. The container port is configured to seat a container opening which is in communication with each other. The second port is configured to receive an external gas supply or outlet. And pass one or more gases between the vessel opening seated on the vessel port and the second port. The vessel port, the second port and the duct are substantially rigidly attached to the movable housing. Optionally, the portable vessel holder weighs less than five pounds.

Another aspect of the invention is a portable vessel support comprising a vessel port, a vacuum duct, a vacuum port and a movable housing. The container port is configured to receive a container opening that is in sealed communication with each other. The vacuum duct is configured to recover gas from a vessel seated on the vessel port. The vacuum port is configured to communicate between the vacuum duct and an external vacuum source. The vacuum source may be a pump or gas cylinder or ballast tank at a lower pressure than the vacuum duct. The vessel port, vacuum duct and vacuum port are substantially rigidly attached to the movable housing. Optionally, the portable vessel holder weighs less than five pounds.

II.B. A vessel holder comprising a sealing arrangement.

Another aspect of the invention is a vessel holder for receiving an open end of a container having a substantially cylindrical wall adjacent its open end. The vessel holder may have an approximately cylindrical inner surface (eg, a round cylindrical inner surface), an annular groove and an O-ring. Containers designated as having round or circular openings or cross sections throughout this specification are illustrative only and will be understood as not limiting the scope of the disclosure or claims. If the vessel has, for example, an opening or cross section that is not generally circular where the vessel is a cuvette, the "round" cylindrical surface of the vessel holder may not be circular, as otherwise specifically required. Except, it may be sealed using a non-circular sealing component such as a gasket or seal shaped to seal the non-circular cross section. In addition, the "cylindrical" does not require a circular cross-section cylinder, and includes other cross-sectional shapes such as, for example, rounded corners.

The general cylindrical inner surface is sized to receive the vessel cylindrical wall.

The annular groove is disposed coaxially within the substantially cylindrical inner surface. The first annular groove has an opening in the substantially cylindrical inner surface and a bottom wall radially spaced from the substantially cylindrical inner surface.

The O-ring is disposed in the first annular groove. For the first annular groove, the O-ring is sized to extend radially outwardly through the opening and to be pressed radially outward by a container received by the approximately cylindrical inner surface. This arrangement forms a seal between the container and the first annular groove.

According to another aspect of the present invention, a method of coating and inspecting a container is provided, wherein a first inspection of the inner surface of the container to determine whether there is a defect is performed after the coating is applied to the inner surface of the container. Thereafter, a second inspection of the inner surface of the coated container is performed to see if there is a defect, and then evaluation of the data obtained during the first and second inspections is performed, and the second inspection and the data evaluation are It takes less than 30 seconds.

According to another aspect of the present invention, there is provided a container processing method wherein an opening of the container is seated on a container port of a container support after an inner surface of the container is coated through the container port. The coating is then inspected for defects in the coating through the container port. After doing this, the container is transferred from the first processing station to the second processing station, and the seated container is supported during coating, inspection and transport by the container support.

III. Container transfer method-processing of vessels seated on container supports

III.A. Transporting the vessel holder to the processing station

Another aspect of the present invention is a container processing method. A first processing station and a second processing station spaced from the first processing station are provided for vessel processing. A container having a wall defining an opening and an inner surface is provided. A vessel holder is provided that includes a vessel port. The opening of the container rests on the container port. The inner surface of the seated vessel is processed through the vessel port at the first processing station. The vessel holder and seated vessel are transported from the first processing station to the second processing station. The inner surface of the seated vessel is processed through the vessel port at the second processing station.

III.B. Transporting the processing apparatus to the vessel holder or vice versa.

Another aspect of the invention is a container processing method comprising some portions. The first processing device and the second processing device are provided for container processing. A container having a wall defining an opening and an inner surface is provided. A vessel holder is provided that includes a vessel port. The opening of the container rests on the container port.

The first processing device is operatively engaged with the vessel holder or moved in the opposite state. The inner surface of the seated vessel is processed through the vessel port using the first processing device.

The second processing device is then operatively engaged with the vessel holder or moved to the opposite state. The inner surface of the seated vessel through the vessel port using the second processing device.

III.C. Using a gripper to reciprocate the tube to a processing station

Another aspect of the invention is a method of plasma enhanced chemical vapor deposition (PECVD) processing of a first vessel, comprising some steps. A first container having an open end, a closed end and an inner surface is provided. At least the first gripper is configured to selectively grasp and release the closed end of the first container. The closed end of the first vessel is gripped using the first gripper and is transferred to the vicinity of the vessel holder configured to seat with the first end of the first vessel using the first gripper. The first gripper is then used to axially advance the first vessel and seat its open end on the vessel holder to achieve sealed communication between the vessel holder and the interior of the first vessel.

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

Thereafter, the first vessel is detached from the vessel holder and, using the first gripper or another gripper, the first vessel is axially transferred from the vessel holder. The first vessel is then released from the gripper used to axially transfer from the vessel holder.

IV. PECVD Equipment for Container Manufacturing

IV.A. PECVD apparatus including vessel holder, internal electrode, vessel as reaction chamber

According to another aspect of the invention, a plasma enhanced chemical vapor deposition (PECVD) apparatus is provided that coats an interior surface of a vessel. The PECVD apparatus may be part of the vessel processing system, the vessel configured to receive and seat a first opening of the vessel for treating the interior surface of the vessel seated through the vessel port, such as the supports described above and below. A vessel holder comprising a port. The PECVD apparatus also includes an inner electrode arranged in the inner space of the seated vessel and an outer electrode having an inner portion for receiving the seated vessel. A power supply is also provided for generating a plasma in the vessel, wherein the seated vessel and the vessel holder are adapted to define a plasma reaction chamber.

According to another exemplary embodiment of the invention, the PECVD apparatus further comprises a vacuum source for evacuating the interior space of the seated vessel, wherein the vessel port and the seated vessel are adapted to define a vacuum chamber.

According to another exemplary embodiment of the present invention, the PECVD apparatus further comprises a gas supply for supplying the reaction gas from the reactant gas source to the interior space of the vessel.

According to another exemplary embodiment of the invention, the gas supplier is located at the distal portion of the inner electrode.

According to another exemplary embodiment of the invention, the inner electrode is a probe having a distal region positioned to extend concentrically to the seated vessel.

According to another exemplary embodiment of the invention, the outer electrode has a cylindrical section and extends concentrically around the seated vessel.

According to another exemplary embodiment of the present invention, the PECVD apparatus selectively supports and discharges the closed end of the container and grips the grip end of the container to transfer the container to the vicinity of the container support. It further includes.

According to another exemplary embodiment of the present invention, the PECVD apparatus is adapted to form a plasma in an interior space of a container substantially free of hollow cathode plasma.

According to another exemplary embodiment of the present invention, the PECVD apparatus further comprises a detector for inspecting the inner space of the container through the inspection container port of the inner surface of the container to determine whether there is a defect.

According to another exemplary embodiment of the present invention, the PECVD apparatus has a processing vessel opening for connecting with a second limited opening of the vessel, wherein reactant gas flows from the interior space of the vessel into the processing vessel. It further comprises a processing container characterized in that.

According to another exemplary embodiment of the invention, the distal end of the inner electrode is located less than one half of the distance from the first larger opening of the seated vessel to the second limited opening.

According to another exemplary embodiment of the present invention, the distal end of the inner electrode is located outside the first larger opening of the seated vessel.

Also provided is a method of coating an interior surface of a container, receiving and seating an opening of the container on a container port of a container support for treating the interior surface of the seated container. The inner electrode is then arranged in the inner space of the seated vessel after the gas supply is located at the distal portion of the inner electrode. The seated vessel is also housed in an inner portion of the outer electrode. The seated vessel within the vessel holder is adapted to define a plasma reaction chamber.

In particular, a vacuum chamber may be defined by the vessel port and gas is withdrawn from the interior space of the seated vessel such that no external vacuum chamber is required for coating.

In another step, a plasma is formed in the interior space of the seated vessel and a coating material is deposited on the interior surface of the seated vessel.

According to another exemplary embodiment of the present invention, a processing vessel opening is connected with a limited opening of the vessel to allow reactant gas to flow from the interior space of the vessel to the processing vessel.

According to another aspect of the invention, a container treatment system described above and below comprises a syringe for storing a biologically active compound or composition, a vial for storing a biologically active compound or composition, a biologically active compound or Use to fabricate a conduit for conveying the composition or a cuvette for supporting a biologically active compound or composition.

Another aspect of the invention is a PECVD apparatus comprising a vessel holder, an inner electrode, an outer electrode and a power supply.

The vessel holder has a port for receiving the vessel in a seated position for processing. The inner electrode is positioned to be received in a container seated on a container support. The outer electrode has an inner portion positioned to receive a vessel seated on the vessel holder. The power supply supplies alternating current to the inner and outer electrodes to form a plasma in the vessel seated on the vessel holder. The vessel defines a plasma reaction chamber.

Another aspect of the invention is the PECVD apparatus described in the preceding paragraph, which does not necessarily include a vacuum source for delivering gas to or from the interior of a vessel seated on the port to define a closed chamber. PECVD apparatus comprising a gas exhaust port.

IV.B. PECVD apparatus using a gripper to reciprocate the tube to the coating station

Another aspect of the invention is an apparatus for PECVD processing of a first vessel having an open end, a closed end and an interior space. The apparatus includes a vessel holder, a first gripper, a sheet to be vessel supported, a reactant feeder, a plasma generator and a vessel discharge device.

The vessel holder is configured to rest on the open end of the vessel. The first gripper is configured to selectively support and release the closed end of the container and to transport the container near the container support while holding the closed end of the container. The vessel holder has a seat configured to achieve sealed communication between the vessel holder and the inner space of the first vessel.

The reactant feeder is operably connected to introduce at least one gaseous reactant within the first vessel through the vessel holder. The plasma generator is configured to form a plasma in the first vessel under conditions effective to form a reaction product of a reactant on the inner surface of the first vessel.

The vessel dispensing device is provided to detach the first vessel from the vessel holder. The gripper, which is the first gripper or another gripper, is configured to transfer the first vessel in the axial direction from the vessel holder and to discharge the first vessel.

V. PECVD methods

According to another aspect of the present invention, there is provided a method of coating (and / or inspecting) an inner surface of a container for receiving and seating an opening of the container on a container support for treating the inner surface of the seated container. The term treatment can refer to a coating step or some coating steps or even a series of coating and inspection steps.

In addition, a first treatment of the inner surface of the seated vessel is performed through a vessel port of the vessel holder at a first treatment station. Thereafter, the vessel holder and the seated vessel are transported to a second processing station after the first processing at the first processing station. Then, at the second processing station, a second treatment of the inner surface of the seated vessel is performed through the vessel port of the vessel holder.

V.A. SiO with plasma substantially free of hollow cathode plasma _x  PECVD to apply barrier coatings

Another aspect of the invention is a method of applying a barrier coating of SiO _x on a surface, preferably on the interior of a container, wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about It is a two-person, barrier coating application method. The method includes some steps.

For example, as a reaction mixture comprising an organosilicon compound gas, optionally an oxidizing gas and optionally a plasma forming gas comprising a hydrocarbon gas, a surface, such as a vessel wall, is provided.

Plasma is formed in the reaction mixture that is substantially free of cathode hollow plasma. The vessel wall is in contact with the reaction mixture and a coating of SiO _x is deposited on at least a portion of the vessel wall.

V.B. PECVD to coat the limited opening of the vessel (syringe capillary)

Another aspect of the present invention is a method of coating the inner surface of a limited opening of a generally tubular container treated by PECVD. The method includes these steps.

Typically a tubular container is provided and processed. The container includes an outer surface, an inner surface defining a lumen, a larger opening with an inner diameter, and a limited opening with an inner diameter defined by the inner surface and smaller than the larger opening inner diameter.

There is provided a treatment vessel having a lumen and a treatment vessel opening. The processing vessel opening is connected with the limited opening of the vessel to allow communication between the lumen of the vessel being processed and the processing vessel lumen through the restricted opening.

At least a partial vacuum is drawn in the lumen of the vessel to be treated and in the vessel lumen being processed. PECVD reactant flows through the first opening, through the lumen of the vessel to be subsequently processed, and then through the restricted opening to the vessel lumen being processed. Plasma is generated in the vicinity of the restricted opening under conditions effective to deposit a coating of the PECVD reaction product on the inner surface of the restricted opening.

V.C. How to apply a lubricity coating

Another aspect of the invention is a method of applying a lubricity coating on a substrate. The method is performed as follows.

A precursor is provided. The precursor is preferably an organosilicon compound, more preferably a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, or a combination of two or more of these precursors. Other precursors, such as organometallic precursors including Group III and Group IV metals of the periodic table, are also contemplated. The precursor is applied to the substrate under conditions effective to form a coating. The coating is polymerized, crosslinked or both to form a lubricious surface having a lower "plunger active force" or "breakout force" than the untreated substrate, as defined herein.

VI. Container inspection

VI.A. Container handling including precoating and postcoating inspection

Another aspect of the invention is a container processing method for treating a container having an opening and a wall defining an interior surface. The method examines the inner surface of the vessel provided for defects; Applying a coating to the inner surface of the container after inspecting the provided container; And by inspecting the coating for defects.

Another aspect of the present invention is a container treatment in which a barrier coating is applied to the container after inspecting the molded container, and the inner surface of the container is inspected for defects after the barrier coating is applied. Way.

V.I.B. Vessel inspection, for example, performed by detecting degassing of the vessel wall through a barrier

Another aspect of the invention is a method of inspecting a coating ("degassing method") by measuring volatile species degassed by the coated article. The method can be used to inspect the product of a coating process in which a coating is applied to the surface of a substrate to form a coated surface. In particular, the method can be used as an in-line process control for the coating process to distinguish and remove coated products or damaged coating products that do not meet certain criteria.

In general, the "volatile species" is a gas or vapor under test conditions, preferably selected from the group consisting of air, nitrogen, oxygen, water vapor, volatile coating components, volatile substrate components and combinations thereof, more preferably Preferably air, nitrogen, oxygen, water vapor or a combination thereof. The method can be used to measure only one or more volatile species, preferably a plurality of various volatile species measured in step (c), and more preferably substantially all volatile species released from the test subject are subjected to step (c Is measured.

The degassing method comprises the following steps:

(a) providing the product for inspection;

(c) measuring the release of at least one volatile species from the test object into the gas space adjacent the coated surface; And

(d) comparing the results of step (c) with the results of step (c) for at least one reference object measured under the same test conditions, and / or the physical and / or chemical Measuring properties.

In the degassing method, the physical and / or chemical properties of the coating to be measured are selected from the group consisting of a barrier effect, a wet tension and a composition thereof, and are preferably characterized as a barrier effect.

Advantageously, step (c) is carried out by measuring the mass flow rate or volume flow rate of at least one volatile species in the gas space adjacent to the coated surface.

Preferably, the reference object (i) comprises an uncoated substrate; Or (ii) a substrate coated with a reference coating. This is, for example, compared to a coating having known properties, for example, whether the degassing method is used to determine the presence or absence of a coating (the reference object can then be an uncoated substrate) or to characterize the coating. Depends on whether or not. In order to determine the identity of the coating as a specific coating, a reference coating may also be a common choice.

In addition, the degassing method provides atmospheric pressure in the gas space adjacent to the coated surface such that a pressure differential is provided through the coated surface and a higher mass flow rate or volume flow rate of the volatile species can be achieved than without the pressure differential. Step (b) may be included as an additional step between step (a) and step (c). In this case, the volatile species will migrate in the direction of the lower side of the pressure differential. If the coated object is a vessel, the pressure differential between the vessel lumen and the outside is set to measure the degassing state of the volatile species from the coated vessel wall. The pressure differential can be provided, for example, by at least partially vacuuming the gas space in the vessel. In this case, volatile species degassed into the lumen of the vessel can be measured.

If a vacuum is applied to produce a pressure differential, the measurement can be performed using a measuring cell sandwiched between the coated surface of the substrate and the vacuum source.

In one aspect, the test object is preferably capable of adsorbing or absorbing the volatile species on or within the volatile species of step (a), preferably into the material of the test object, preferably air, nitrogen , Volatile species selected from the group consisting of oxygen, water vapor and combinations thereof. Subsequent release of the volatile species from the test subject is then measured in step (c). Since different materials (eg, the coating and the substrate, etc.) have different adsorption and absorption characteristics, this can simplify the presence of the coating and the determination of the characteristics.

The substrate is a polymeric compound, preferably polyesters, polyolefins, cyclic olefin copolymers, polycarbonates or combinations thereof.

In the context of the present invention, the coating characterized by the degassing method is, for example, a coating typically prepared by PECVD from the organosilicon precursors described herein. In certain aspects of the invention (i) the coating is a barrier coating, preferably an SiO _x film wherein x is from about 1.5 to about 2.9; And / or (ii) the coating is a coating that modifies the lubricity and / or surface tension of the coated substrate, preferably 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, a film of _{Si w O x C y H z} .

If the coating process whose product is inspected by the degassing method is a PECVD coating carried out under vacuum conditions, subsequent degassing measurements can be performed without breaking the vacuum used for PECVD.

The volatile species measured can be a volatile species released from the coating, a volatile species released from the substrate, or a combination of both. In one aspect, the volatile species is a volatile species released from the coating, preferably a volatile coating component, and wherein the inspection is performed to determine the presence, properties and / or composition of the coating. In another aspect, the volatile species is a volatile species released from the substrate and the inspection is performed to determine the presence of the coating and / or the blocking effect of the coating.

The degassing method of the present invention is particularly suitable for measuring the presence and characteristics of the coating on the vessel wall. Thus, the coated substrate may be a container having a wall at least partially coated on its inner or outer surface during the coating process. For example, the coating is provided on the interior surface of the vessel wall.

Conditions effective for distinguishing the presence of the coating and / or measuring 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 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 order to increase the difference with respect to the discharge rate and / or the type of volatile species measured between the reference object and the test object, the discharge rate of the volatile species is varied by changing the ambient pressure and / or temperature and / or humidity. Can be.

In one particular aspect, the gas removal is measured using a microcantilever measurement technique. For example, the measurement can be made by performing the following.

(i) (a) providing at least one microcantilever having the property of being moved or changed to a different shape, when degassed material is present;

(b) exposing the microcantilever to the degassed material under conditions effective to cause the microcantilever to move or change in a different shape; And

(c) preferably reflects an energy incident beam, for example a laser beam, from a portion of the microcantilever that changes shape before and after exposing the microcantilever to the degassing, at a point spaced from the cantilever Measure the deflection of the reflected beam; Or detecting a movement or a different shape as follows

(ii) (a) providing at least one microcantilever that resonates at different frequencies, if degassed material is present;

(b) exposing the microcantilever to the degassed material under conditions effective to resonate the microcantilever at different frequencies; And (c) detecting different resonance frequencies using the harmonic vibration sensor.

Also contemplated are devices that perform the gas removal method, for example, devices including the microcantilever described above.

Using the degassing method of the present invention, for example, a barrier film on a material which removes vapor is inspected, which has several steps. A sample of material is provided that removes the gas and has at least one partially barrier film. In one particular aspect of the invention, a pressure differential is provided over the barrier so that at least some of the degassing material is on the high pressure side of the barrier. The degassed gas passing through the barrier is measured. If there is a pressure differential, the measurement is optionally performed on the lower pressure side of the barrier.

VII. PECVD Processed Containers

VII.A.1.a.i. Hydrophobic Coatings Deposited from Organosilicon Precursors

Another aspect of the invention is, for example, a hydrophobic coating deposited from an organosilicon precursor in a container having a hydrophobic coating on the inner wall. The coating is of the type made in the following steps.

Organometallic compounds, preferably organosilicon compounds, more preferably linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, alkyl trimethoxysilanes, linear silazanes, monocyclic silazanes A precursor is provided, which is an organometallic compound which is a compound selected from the group consisting of polycyclic silazanes, polysilsesquiazanes or combinations of any two or more of these precursors. In addition, organometallic compounds comprising metals of Group III or Group IV can be considered as precursors.

The precursor is applied to the substrate under conditions effective to form a coating. The coating is polymerized, crosslinked or both to form a hydrophobic surface with a higher contact angle than the substrates not treated herein.

The resulting coating may have a formula: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 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 9 Si _w O _x C _y H _z .

Numerical values of w, x, y and z as used throughout this specification should be understood as proportions in the empirical formula (eg, for coating) rather than a limitation on the number of atoms in one molecule. For example, octamethylcyclotetrasiloxane having a molecular formula of Si ₄ O ₄ C ₈ H ₂₄ is obtained by dividing each of w, x, y and z in the molecular formula by the maximum common factor of 4 Replaces.] Can be described empirically: Si ₁ O ₁ C ₂ H ₆ . Also, the numerical values of w, x, y and z are not limited to integers. For example, (acyclic) octamethyltrisiloxane, the molecular formula of 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 tube with walls coated with hydrophobic coating deposited from organosilicon precursor

Another aspect of the invention is a cell preparation tube having a wall provided with a hydrophobic coating and containing a water soluble sodium citrate reagent.

The wall is made of a thermoplastic material having a surface that defines the lumen.

The hydrophobic coating is provided on the inner surface of the tube. The hydrophobic coating is an organometallic compound, preferably an organosilicon compound, more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silazane, mono It is made by providing an organometallic compound which is a compound selected from the group consisting of cyclic silazanes, polycyclic silazanes, polysilsesquiazanes or combinations of any two or more of these precursors. PECVD is used to form a coating on the inner surface. The resulting coating can have the following structure: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 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 9 Si _w O _x C _y H _z .

The water soluble sodium citrate reagent is provided to the lumen of the tube in an amount effective to inhibit coagulation of blood introduced into the tube.

VII.A.1.c. SiO _x  Barrier-coated double walled plastic containers-COC, PET, SiO _x  Layers

Another aspect of the invention is a container having a wall that at least partially surrounds the lumen. The wall has an inner polymer layer surrounded by an outer polymer layer. One of the polymer layers is a layer that is at least 0.1 mm thick of cyclic olefin copolymer (COC) resin defining a water vapor barrier. One of the polymer layers is a layer that is at least 0.1 mm thick of polyester resin.

The wall is an oxygen barrier film of Si _x , wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2, comprising an oxygen barrier film having a thickness of about 10 to about 500 Angstroms. .

VII.A.1.d. How to make double wall plastic containers-COC, PET, SiO _x  Layers

Another aspect of the invention is a method of making a container having a wall having an inner polymer layer surrounded by an outer polymer layer, one layer made of COC and the other layer made of polyester. The vessel is manufactured by a process comprising introducing COC and polyester resin layers into an injection mold through concentric injection nozzles.

Another optional step is to apply an amorphous carbon coating to the vessel by PECVD as an inner coating and an outer coating or an interlayer coating positioned between the coatings.

An optional additional step is to apply SiO _x blocking film to the inside of the vessel wall as SiO _x is defined as before. Another optional additional step is to work up the SiO _x film with a process gas consisting essentially of oxygen and essentially free of volatile silicon compounds.

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

VII.A.1.e. Barrier coating made of glass

Another aspect of the invention is a container comprising a container, a barrier coating and a closure. The vessel is generally tubular and made of thermoplastic material. The vessel has a lumen at least partially bounded by a wall having an inlet and an inner surface interfacing with the lumen. On the inner surface of the wall there is at least one essentially continuous barrier coating made of glass. The closure covers the inlet and separates the lumen of the vessel from the ambient air.

One related aspect of the present invention is the container described in the preceding paragraph, wherein the barrier coating is made of soda lime glass or borosilicate glass or other types of glass.

VII.A.2. Stoppers

VII.A.2.a. How to apply a lubricity coating to a stopper in a vacuum chamber

Another aspect of the invention is a method of applying a coating, for example a lubricity coating as defined above, on an elastic stopper. For example, the stopper is located in a substantially vacuum chamber. A reaction mixture is provided which comprises a plasma forming gas such as an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas. Plasma is formed in the reaction mixture in contact with the stopper. Lubricity coating, such as w is 1, wherein x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, preferably w is 1 and x is about 0.5 1 to 1, y is about 2 to about 3, and z is 6 to 9, a coating of Si _w O _x C _y H _z is deposited on at least a portion of the stopper.

VII.A.2.b. Applying a group III or IV element and a coating of carbon onto the stopper by PECVD

Another aspect of the invention is a method of applying a coating of a composition comprising carbon and one or more elements of group III or group IV on an elastic stopper. In order to carry out the method, the stopper is placed in a vacuumed chamber.

A reaction mixture is provided in the deposition chamber that includes a plasma forming gas having a gas source of Group III elements (eg Al), Group IV elements (eg Si, Sn) or a combination of two or more thereof. Optionally, the reaction mixture comprises an oxidizing gas and optionally a gaseous compound having one or more C—H bonds. A plasma is formed in the mixture and the stopper is in contact with the reaction mixture. A coating of a group III element or compound, a group IV element or compound or a combination of two or more thereof is deposited on at least a portion of the stopper.

VII.A.3. Stoppered plastic container with barrier coating effective to maintain 95% vacuum for 24 months

Another aspect of the invention is a container comprising a container, a barrier coating and a closure. The vessel is generally tubular and made of thermoplastic material. The container has an inlet and a lumen at least partially bounded by the wall. The wall has an interior surface that interfaces with the lumen. At least one essentially continuous barrier coating is applied on the inner surface of the wall. The barrier coating is effective to maintain at least 90%, optionally 95%, of the original vacuum level during the shelf life of at least 24 months in the container. A closure is provided that covers the inlet of the vessel and separates the lumen of the vessel from the ambient air.

VII.B.1.a Syringe with barrel coated with lubricious coating deposited from organometallic precursor

Another aspect of the invention is a container having a lubricity coating made from an organosilicon precursor. In addition, other organometallic precursors as defined herein may be considered.

 The coating may be of the type produced by the following process.

Organometallic precursors, preferably organosilicon precursors, more preferably linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, linear silazanes, monocyclic silazanes, polycyclic silazanes A precursor is provided that is, polysilsesquiazane or any combination of two or more of these precursors.

The precursor is applied to the substrate under conditions effective to form a coating. The coating is polymerized, crosslinked, or both, to form a lubricious surface with lower plunger activation force or breakout force than the untreated substrate.

Another aspect of the invention is a syringe comprising a plunger, a syringe barrel and a lubricious layer. The syringe barrel has an interior surface slidably receiving the plunger. The lubricity layer comprises a coating of a Si _w O _x C _y H _z lubricity layer provided on the inner surface of the syringe barrel and fabricated from an organosilicon precursor as defined herein. The lubricity layer is less than 1000 nm thick and is effective in reducing the breakout force or plunger force required to move the plunger within the barrel.

Another aspect of the invention is a lubricity coating on the inner wall of the syringe barrel. The coating is produced from a PECVD process using the following materials and conditions. Cyclic precursors selected from monocyclic siloxanes, polycyclic siloxanes, or a combination of two or more thereof are employed. At least essentially no oxygen is added to the process. Sufficient plasma generating power input is provided to induce coating formation. The materials and conditions employed herein are effective to reduce the syringe plunger actuation force or breakout force traveling through the syringe barrel by at least about 25% relative to the uncoated syringe barrel.

The resulting coating can have the following formula: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 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 9 Si _w O _x C _y H _z .

VII .B.1.a.i. Lubricity  coating: SiO _x Membrane, Lubricity  Layer, surface treatment.

Another aspect of the invention is a syringe comprising a barrel defining a lumen and slidably receiving a plunger. The syringe barrel can be made of a thermoplastic based material. A lubricity coating is applied to the barrel inner surface, plunger or both, for example by PECVD. The lubricity coating can be made from an organosilicon precursor and can be less than 1000 nm thick. Surface treatment is carried out on the lubricity coating in an amount effective to reduce the lubricity coating, the thermoplastic base material, or both, to be filtered into lumens, ie to form a solute retainer on the surface. The lubricity coating and solute retainer are constructed and present in relative amounts effective to provide a breakout force or plunger activation force, or both lower than the corresponding force required in the absence of the lubricity coating and solute retainer.

VII.B.1.b SiO _X  Syringes with a barrel with a coated inside and a barrier coated outside

Another aspect of the invention is a syringe comprising a plunger, a barrel and inner and outer barrier coatings. The wall is made of a thermoplastic based material defining a lumen. The barrel has an inner surface and an outer surface to slidably receive the plunger. In this formula, a barrier coating of SiO _x is provided on the inner surface of the barrel, wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2. A barrier coating of resin is provided on the outer surface of the barrel.

VII.B.1.c SiO _x  Method of making a syringe having a barrel with a coated inside and a barrier coated outside

Another aspect of the invention is a method of making a syringe comprising a plunger, a barrel and inner and outer barrier coatings. A barrel is provided having an inner surface and an outer surface for slidably receiving the plunger. Wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2, a barrier coating of SiO _x is provided on the inner surface of the barrel by PECVD. A barrier coating of resin is provided on the outer surface of the barrel. The plunger and barrel are assembled to provide a syringe.

VII.B.2 Plungers

VII.B.2.a Using the piston face coated with the barrier film

Another aspect of the invention is a plunger for a syringe, comprising a piston and a push rod. The piston has a front and side and rear portions configured to movably seat within a generally cylindrical syringe barrel. The front face has a barrier coating. The push rod is configured to engage the back portion and to advance the piston in the syringe barrel.

VII.B.2.b. With lubricating coating in contact with the sides

Another aspect of the invention is a plunger for a syringe, comprising a piston, a lubricity coating and a push rod. The piston has a front side, a substantially cylindrical side and a rear portion. The side is configured to movably seat within the syringe barrel. The lubricity coating is in contact with the side. The push rod is configured to engage the trailing portion of the piston and to advance the piston in a syringe barrel.

VII.B.3. Two part syringe and luer fitting

Another aspect of the invention is a syringe comprising a plunger, a syringe barrel and a luer fitting. The syringe barrel has an interior surface slidably receiving the plunger. The luer fitting includes a luer taper having an inner passage defined by the inner surface. The luer fitting is formed of components separate from the syringe barrel and is joined to the syringe barrel by a coupling. The inner passage of the luer taper has a barrier coating of SiO _x in which x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2.

VII.B.4. Lubricatable Coatings Fabricated by In Situ Polymerized Organosilicon Precursors

VII.B.4.a. Product and Lubricity by Process

Another aspect of the invention is a lubricity coating made from an organosilicon precursor. This coating is from the type produced by the following process.

Organometallic precursors, preferably organosilicon precursors, preferably linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, linear silazanes, monocyclic silazanes, polycyclic silazanes, A precursor selected from polysilsesquiazane or any combination of two or more of these precursors is provided. The precursor is applied to the substrate under conditions effective to form a coating. The coating is polymerized, crosslinked, or both, to form a lubricious surface with lower plunger activation force or breakout force than the untreated substrate.

The resulting coating can have the following structure: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 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 9 Si _w O _x C _y H _z .

VII.B.4.b. Product and Analytical Properties by Process

Another aspect of the invention is an organometallic precursor, preferably an organosilicon precursor, more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, linear silazane, monocyclic sila A lubricity coating deposited by PECVD from a glass, polycyclic silazane, polysilsesquiazane or any combination of two or more of these precursors. The coating has a density between 1.25 and 1.65 g / cm ³ as measured by X-ray reflectance (XRR).

Also, it includes metals of group III such as boron, aluminum, gallium, indium, thallium, scandium, yttrium or lanthanum or silicon, germanium, tin, lead, titanium, zirconium, harp, thorium or any combination of two or more thereof. The use of organometallic precursors may also be considered. In addition, other volatile organic compounds may also be considered. However, organosilicon compounds are preferred for carrying out the present invention.

Another aspect of the invention is an organometallic precursor, preferably an organosilicon precursor, more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, linear silazane, monocyclic sila A lubricity coating deposited by PECVD from a feed gas comprising a glass, polycyclic silazane, polysilsesquiazane or any combination of two or more of these precursors. In addition, the use of precursors comprising metals of Group III or Group IV can also be considered.

The coating has, as a degassing component, one or more oligomers comprising repeating-(Me) ₂ SiO- moieties as measured by a gas chromatography / mass spectrometer. Optionally, the coating meets the limitations of any one of Examples VII.B.4.a or VII.B.4.b.

Another aspect of the invention is an organometallic precursor, preferably an organosilicon precursor, more preferably linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, linear silazane, monocyclic sila A lubricity coating deposited by PECVD from a feed gas comprising a glass, polycyclic silazane, polysilsesquiazane or any combination of two or more of these precursors. The coating has an atomic concentration normalized to 100% carbon, oxygen and silicon, less than 50% carbon and more than 25% silicon, as measured by X-ray photoelectron spectroscopy (XPS). Optionally, the coating meets the limitations of any one of Examples VII.B.4.a or VII.B.4.b.

Also contemplated are the use of organometallic precursors comprising metals of Group III or Group IV.

Another aspect of the invention is a feed gas comprising an organosilicon precursor, preferably a monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane or any combination of two or more of these precursors Is a lubricity coating deposited by PECVD. The coating is normalized to 100% of carbon, oxygen and silicon, as measured by X-ray photoelectron spectroscopy (XPS), and atomic concentration of carbon above the atomic concentration of carbon in the atomic formula for the feed gas. Has Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

Another aspect of the invention is a feed gas comprising an organosilicon precursor, preferably a monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane or any combination of two or more of these precursors Is a lubricity coating deposited by PECVD. The coating is normalized to 100% of carbon, oxygen and silicon, as measured by X-ray photoelectron spectroscopy (XPS), and the atomic concentration of silicon is less than the atomic concentration of silicon in the atomic formula for the feed gas. Have Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

VII.C.1. A container containing viable blood having a coating deposited from an organosilicon precursor

Another aspect of the invention is a blood containing vessel. The container has a wall; The wall has an interior surface defining a lumen. The inner surface of the wall is at least one partially hydrophobic coating described above, preferably a hydrophobic coating of Si _w O _x C _y H _z , preferably w is 1, wherein x is from about 0.5 to about 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 is 6 to About 9, having a hydrophobic coating. The coating may be as thin as a single molecule or as thick as about 1000 nm. The container contains viable blood that can return to the patient's vasculature placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.2. Coatings Deposited from Organosilicon Precursors Reduce Coagulation or Platelet Activation on the Vessel Wall

Another aspect of the invention is a container with walls. The wall has an inner surface defining a lumen and is at least one partial passivation, for example a hydrophobic coating made from an organosilicon precursor by PECVD, preferably a coating of Si _w O _x C _y H _z , preferably , w is 1, wherein x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, more preferably w is 1, x is from about 0.5 to 1 and , y is about 2 to about 3, and z is 6 to about 9, has a hydrophobic coating. The thickness of the coating is from monomolecular thickness to about 1000 nm thick on the inner surface. The coating is effective in reducing platelet activation of plasma treated with sodium citrate additive and exposed to the inner surface compared to uncoated walls of the same type. The coating is effective in reducing the coagulation of blood exposed to the inner surface, compared to uncoated walls of the same type.

VII.C.3. A container containing viable blood and having a coating of group III or group IV metal elements

Another aspect of the invention is a blood containing vessel having a wall having an inner surface defining a lumen. The inner surface has at least a partial coating of a composition comprising carbon, one or more Group III metals, one or more Group IV metals, or a combination of two or more thereof. The thickness of the coating is from above the monomolecular thickness up to about 1000 nm on the inner surface. The container contains viable blood that can return to the patient's vasculature disposed within the lumen in contact with the coating.

VII.C.4 Coating of Group III or IV Elements Reduces Coagulation or Platelet Activation of Blood in the Vessel

Optionally, in the vessel of the preceding paragraph, the coating of group III or IV elements is effective to reduce the coagulation or platelet activation of blood exposed to the inner surface of the vessel wall.

VII.D.1. A container containing insulin, having a coating deposited from an organosilicon precursor

Another aspect of the invention is an insulin containing vessel comprising a wall having an inner surface defining a lumen. The inner surface is at least partly a passivation coating made from an organosilicon precursor by PECVD, preferably a coating of Si _w O _x C _y H _z , preferably w is 1, where x is from about 0.5 to about 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 is 6 to About 9, having a passivation coating. The coating may be monomolecular thickness to about 1000 nm thick on the inner surface. Insulin is placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.D.2. Coatings Deposited from Organosilicon Precursors Reduce Insulin Precipitation in Containers

Alternatively, as compared in the vessel of the previous paragraph, with the same surface coating of Si _w O _x C _y H _z is not a coating of Si _w O _x C _y H _z, in reducing the precipitation from the insulin in contact with the inside surface effective.

VII.D.3. A container containing insulin, having a coating of Group III or Group IV elements

Another aspect of the invention is an insulin containing vessel comprising a wall having an inner surface defining a lumen. The inner surface has at least a partial coating of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof. The coating can be from monomolecular thickness to about 1000 nm thick on the inner surface. Insulin is provided in the lumen that is in contact with the coating.

VII.C.4 Coating of Group III or IV Elements Reduces Coagulation or Platelet Activation of Blood in the Vessel

Optionally, in the container of the preceding paragraph, the coating of the composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof may be compared with the interior surface, compared to the same surface without said coating. It is effective in reducing the formation of precipitates from contacting insulin.

VII.E. Cuvette

In addition, the PECVD coating methods and the like described herein are useful for coating barrier coatings, hydrophobic coatings, lubricity coatings or cuvettes to form one or more of these. Cuvettes are small tubes of round or rectangular cross-section, sealed at one end, made of plastic, glass or fused quartz (for ultraviolet) and designed to support spectroscopic samples. The best cuvettes are as transparent as possible without impurities that can affect the spectroscopic reading. Like test tubes or sample collection tubes, the cuvette may have a cap that is open to the atmosphere or sealable. The PECVD-coated coatings of the present invention are very thin, transparent and optically glossy, so that they may not interfere with the optical testing of cuvettes or their contents.

VII.F. Vials

In addition, the PECVD coating methods and the like described herein are useful for coating a vial for forming a coating, eg, a barrier coating or a hydrophobic coating, or a combination of one of these coatings. Vials are, in particular, small containers or bottles used to store medicaments such as liquids, powders or lyophilized powders. They can also be sample containers for use in autosampler devices, for example in analytical chromatography. The vial may have a tube shape or a bottle shape with a neck. The bottles are mainly flat, unlike test tubes or sample collection tubes, which have a mainly round bottom. The vial can be made, for example, of plastic (eg polypropylene, COC, COP).

Computer-readable media and program components

Also provided is a computer-readable medium having stored thereon a computer program for coating and / or inspection of a container which, when executed by a processor of the container processing system, causes the process to perform the above-mentioned or the method steps mentioned above. do.

Also provided is a program component for coating and / or inspection of a container which, when executed by a processor of the container processing system, allows the process to carry out the above-mentioned or the method steps mentioned above.

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

1 is a schematic diagram illustrating a vessel processing system according to one embodiment of the present disclosure.
2 is a simplified cross-sectional view of the vessel holder at a coating station according to one embodiment of the present disclosure.
3 is a view similar to FIG. 2 according to another embodiment of the present disclosure.
4 is a schematic plan view of another embodiment of the vessel holder.
5 is a schematic plan view of another embodiment of the vessel holder.
FIG. 6 is a view similar to FIG. 2 of the container inspection apparatus. FIG.
FIG. 7 is a view similar to FIG. 2 of another container inspection apparatus. FIG.
8 is a cross-sectional view taken along the section line AA of FIG. 2.
9 is another embodiment of the structure shown in FIG.
FIG. 10 is a view similar to FIG. 2 with a vessel holder in a coating station according to another embodiment of the present disclosure employing a CCD detector.
FIG. 11 is a detailed view similar to FIG. 10 of the light source and detector being inverted compared to the corresponding parts of FIG. 6.
12 is a view similar to FIG. 2 of the vessel holder in a coating station according to another embodiment of the present disclosure, employing microwave energy to generate a plasma.
FIG. 13 is a view similar to FIG. 2 of the vessel holder in a coating station according to another embodiment of the present disclosure, wherein the vessel may be seated on the vessel support at the process station.
14 is a view similar to FIG. 2 of the vessel holder in a coating station according to another embodiment of the present disclosure, in which the electrode may be configured as a coil.
FIG. 15 is a view similar to FIG. 2 of the vessel holder in a coating station according to another embodiment of the present disclosure, employing a tube transport for reciprocating the vessel at the coating station.
FIG. 16 is a schematic diagram showing the operation of a vessel transport system as shown in FIG. 15 to locate and support a vessel at a process station.
FIG. 17 is a schematic view showing a mold and a mold cavity for forming a container according to one aspect of the present disclosure. FIG.
FIG. 18 is a schematic view showing the mold cavity of FIG. 17 provided with a container coating apparatus according to one aspect of the present disclosure.
FIG. 19 is a view similar to FIG. 17, provided with another container coating apparatus according to one aspect of the present disclosure.
20 is an exploded longitudinal cross-sectional view of a syringe and cap adapted for use with a prefilled syringe.
FIG. 21 is a view generally similar to FIG. 2 showing a capped syringe barrel and vessel holder in a coating station according to one aspect of the present disclosure.
FIG. 22 is a view generally similar to FIG. 21 showing an uncapped syringe barrel and vessel holder in another coating station in another embodiment of the present invention.
23 is a perspective view of a blood collection tube assembly having a closure according to another embodiment of the present invention.
24 is a fragmentary cross sectional view of the blood collection tube and closure assembly of FIG. 23.
25 is an isolated cross section of the elastic insert of the closure of FIGS. 23 and 24.
FIG. 26 is a view similar to FIG. 22 of another embodiment of the present invention for processing syringe barrels and other containers.
FIG. 27 is an enlarged detailed view of the processing vessel of FIG. 26.
28 is a schematic view of another processing container.
29 is a schematic showing degassing of a material through a coating.
FIG. 30 is a simplified cross-sectional view showing a test set-up that allows the measurement of degassing and degassing from the vessel into the interior of the vessel using a measuring cell interposed between the vessel and the vacuum source.
FIG. 31 is a plot of degassing mass flow rate measured on the test setup of FIG. 30 for a number of vessels.
FIG. 32 is a bar graph showing statistical analysis of the endpoint data shown in FIG. 31.
33 is a longitudinal cross section showing a combination of a syringe barrel and a gas containing volume according to another embodiment of the present invention.
34 is a view similar to FIG. 34 of another embodiment of the present invention including an electrode extension.
FIG. 35 is a view taken from section line 35-35 of FIG. 34 showing the distal gas supply openings and extension electrode of FIG. 34.
36 is a perspective view of a double wall blood collection tube assembly according to another embodiment of the present invention.
37 is a view similar to FIG. 22 showing another embodiment.
FIG. 38 is a view similar to FIG. 22 showing yet another embodiment.
39 is a view similar to FIG. 22 showing yet another embodiment.
40 is a view similar to FIG. 22 showing yet another embodiment.
41 is a top view of the embodiment of FIG. 40.
FIG. 42 is another sealing arrangement usable with the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 33 and 37-41, for example to seat a container on a container support; A fragmentary detail longitudinal cross section of. FIG. 42 also shows other syringe barrel structures usable with the embodiments of FIGS. 2, 3, 6-10, 12-22, 26-28, 33-34, and 37-41, for example.
FIG. 43 is another enlarged detail view of the sealing arrangement shown in FIG. 42.
44 is for use with embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37-43, 46-49, and 52-54, for example. A view similar to FIG. 2 of another possible gas delivery tube / inner electrode.
45 illustrates a container usable with embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26, 28, 33-35, and 37-44, for example. Another structure for the support.
46 is a schematic cross-sectional view of a series of gas delivery tubes and a mechanism for inserting and removing the gas delivery tubes into the vessel holder, showing the gas delivery tube in a fully advanced position.
FIG. 47 is a view similar to FIG. 46 showing a gas delivery tube in an intermediate position.
FIG. 48 is a view similar to FIG. 46 showing the gas delivery tube in the retracted position. The series of gas delivery tubes of FIGS. 46-48 and the internal electrode drive 530, for example, FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33 Usable with the embodiments of -35, 37-45, 49 and 52-54. The mechanisms of FIGS. 46-48 are, for example, probes of the container inspection apparatus of FIGS. 6 and 7, as well as FIGS. 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, Usable with the gas delivery tube embodiments of 33-35, 37-45, 49, and 52-54.
FIG. 49 shows the FIG. 16 processed containers of the vessel inspection apparatus and a mechanism for delivering the cleaning reactor to the PECVD coating apparatus. FIG. The mechanism of FIG. 49 can be used with the container inspection apparatus of FIGS. 1, 9, 15, and 16, for example.
FIG. 50 is an exploded view of the two part syringe barrel and luer lock fitting. The syringe barrel can be used with the container handling and inspection apparatus of FIGS. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.
FIG. 51 is an assembly view of the two part syringe barrel and luer lock fitting of FIG. 50.
FIG. 52 is a view similar to FIG. 42 showing the syringe barrel being processed, with no flanges or flanger stops 440. The syringe barrel can be used with the container handling and inspection apparatus of FIGS. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.
53 is a schematic view of an assembly for processing containers. The assembly is usable with the devices of FIGS. 1-3, 8-9, 12-16, 18-22, 26-28, 33-35, and 37-49.
FIG. 54 is a schematic diagram of the embodiment of FIG. 53.
FIG. 55 is a schematic diagram similar to FIG. 2 of an embodiment of the present invention including a plasma screen.
FIG. 56 is a simplified cross-sectional view of a series of gas delivery tubes having a mechanism for inserting and removing unique gas supplies and gas delivery tubes into a vessel holder.
57 is a plot of the degassing mass flow rate measured in Example 19. FIG.
FIG. 58 shows a linear rack similar to FIG. 4.
59 is a simplified illustration of a vessel processing system in accordance with an exemplary embodiment of the present invention.
60 is a simplified illustration of a vessel processing system in accordance with an exemplary embodiment of the present invention.
61 illustrates a processing station of a vessel processing system according to an exemplary embodiment of the present invention.
62 illustrates a portable container support according to an exemplary embodiment of the present invention.

The invention will be described in more detail with reference to the accompanying drawings, in which some embodiments are shown. However, the invention may be embodied in many other forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are examples of the invention, having the full scope indicated by the language used in the claims. Like numbers refer to like elements throughout the specification.

In the context of the present invention, the following definitions and abbreviations are used:

RF is a radio frequency; sccm is the standard cubic centimeter per minute.

The term "at least" in the context of the present invention means "equal to or exceeding" an integer following the term. The word "comprising" does not exclude other components or steps, and the indefinite article "a" or "an" does not exclude a plural unless otherwise indicated.

"First" and "second" or similar reference, such as a processing station or processing apparatus, refers to the smallest number of processing stations or apparatuses present, but does not necessarily refer to the order or total number of processing stations and apparatuses. These terms do not limit the number of processing stations or the specific processing performed at individual stations.

For the purposes of the present invention, an "organosilicon precursor" is a tetravalent silicon atom connected to an oxygen atom and an organic carbon atom (an organic carbon atom that is a carbon atom bonded to at least one hydrogen atom).

It is a compound having at least one bond. Volatile organosilicon precursors defined as precursors that can be supplied with water vapor in a PECVD apparatus are preferred organosilicon precursors. Preferably, the organosilicon precursor is a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silazane, monocyclic silazane, polycyclic silazane, Polysilsesquiazane, selected from the group consisting of a combination of two or more of these precursors.

In the context of the present invention, "essentially oxygen free" or (synonymously) "substantially oxygen free" is added to the gaseous reactant in some embodiments. This means that some remaining atmospheric oxygen may be present in the reaction space, and residual oxygen that is supplied in a previous step and not completely consumed may be present in the reaction space, defined as essentially free of oxygen therein. In particular, if the gaseous reactant is less than 1% by volume of O ₂ , more preferably 0.5% by volume O ₂ , and even more preferably the gaseous reactant is free of O ₂ , then essentially no oxygen is present in the gaseous reactant, If no oxygen is added to the gaseous reactants or no oxygen is present during the PECVD, then this is also in the "essentially free of oxygen" range.

A "container" in the context of the present invention may be any type 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 "equal to or exceeding" an integer following the term. Thus, in the context of the present invention the container has one or more openings. One or two openings are preferred, such as openings in a sample tube (one opening) or syringe barrel (two openings). If the container has two openings, they can be the same or different sizes. If there are more than one opening, one opening can be used for the gas inlet for the PECVD coating method according to the invention, while the remaining openings are capped or open. The container according to the invention comprises a sample tube for collecting or storing biological fluids such as, for example, blood or urine, a syringe for storing or delivering a biologically active compound or composition, such as a pharmaceutical or pharmaceutical composition (or parts thereof, eg For example, a syringe barrel), eg, a vial containing a biological material or biologically active compound or composition, such as a pipe, such as a conduit for transporting a biological material or biologically active compound or composition, or a biological material or biologically It may be a cuvette supporting fluids, such as supporting an active compound or composition.

The container may be of any type, with a container having a substantially cylindrical wall adjacent to at least one of its open ends. In general, the inner wall of the container is cylindrical in shape, such as in a sample tube or syringe barrel. Particular preference is given to sample tubes and syringes or parts thereof (eg syringe barrels).

By "hydrophobic coating" in the context of the present invention is meant lowering the wetting tension of the surface coated with the coating, as compared to the corresponding surface without the coating. Thus, hydrophobicity is a function of both the uncoated substrate and the coating. The same applies to other contexts in which the term "hydrophobic" is used as appropriately modified. The term "hydrophilic" means the opposite, ie, the wet tension is increased relative to the reference sample. Particular hydrophobic coatings in the context of the present invention are Si _w O _x C _y H _z wherein w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from 2 to about 9. Or a coating having the formula.

"Wet tension" is a specific measure of the hydrophobicity or hydrophilicity of a surface. Preferred wet tension measurement methods in the context of the present invention are ASTM D 2578 or a variation of the method described in ASTM D 2578. This method uses standard wet tension solutions (called dyne solutions) to determine the closest solution to wet the plastic film surface for exactly 2 seconds. This is the wet tension of the film. The procedure used here is that the substrates are not flat plastic films, but tubes that are manufactured according to the protocol for forming PET tubes and coated according to the protocol for coating the inside of the tube with a hydrophobic coating (except for controls), It is a variation from ASTM D 2578 (see Example 9).

A "lubricating coating" according to the invention is a coating having a lower frictional resistance than an uncoated surface. That is, the frictional resistance of the coated surface is reduced compared to the uncoated reference surface. "Frictional resistance" can be static frictional resistance and / or kinetic frictional resistance. One of the preferred embodiments of the invention is a syringe part, such as a syringe barrel or plunger, coated with a lubricity coating. In this preferred embodiment, the appropriate static frictional resistance in the context of the present invention is the breakout force defined herein, and the appropriate kinetic frictional resistance in the context of the present invention is the plunger active force defined herein. For example, the plunger force defined and measured herein is used to determine the presence and lubricity characteristics of a lubricity coating in the context of the present invention when the coating is applied to any syringe or syringe part, such as the inner wall of a syringe barrel. It is suitable. Breakout force is applied to a prefilled syringe, i.e. a syringe that can be stored after a coating and stored for a period of time, such as months or even years, before the plunger has to be moved again (which must be "broken out"). It is particularly suitable for the evaluation of the coating effect.

In the context of the present invention, the "plunger force" is the force required to maintain movement of the plunger within the syringe barrel during aspiration or dispensing. This can be advantageously measured using the ISO 7886-1: 1993 test described herein and known in the art. Synonymous with "plunger active force" often used in the industry is "plunger force" or "pushing force".

A "breakout force" in the context of the present invention is the first force required to move the plunger in a syringe, for example in a prefilled syringe.

The "plunger actuation force" and "breakout force" as well as their measuring methods are described in more detail later in this description.

"Slidably" means that the plunger slides in the syringe barrel.

In the context of the present invention, "substantially robust" means that the assembled members (ports, ducts and housings, described further below) are not significantly displaced with respect to any one of the assembled members relative to the others. That is, it can be moved to one unit by operating the housing. Specifically, none of the members are connected by a hose or the like which allows substantial relative movement between the parts in normal use. Providing a substantially solid relationship of these parts ensures that the position of the vessel seated on the vessel holder is known and accurate as the positions of these components fixed to the housing.

In the following, an apparatus for carrying out the invention will be described first, followed by the coating methods, coatings and coated containers and uses according to the invention.

I. Vessel processing system with multiple treatment stations and multiple vessel supports

I. A vessel processing system is considered that includes a first processing station, a second processing station, a plurality of vessel supports and a conveyor. The first processing station is adapted to process a container having an opening and a wall defining an inner surface. The second processing station is spaced from the first processing station and is adapted to process a wall having an opening and a wall defining an interior surface.

I. At least some, optionally all of the vessel ports of the vessel holder have a vessel port configured to receive and seat an opening of the vessel for treating the inner surface of the seated vessel through the vessel port in the first treatment. Include. The conveyor is configured for transferring a series of the vessel holders and seated vessels from a first processing station to a second processing station for treatment of the inner surface of the seated vessel at the second processing station.

I. Referring first to FIG. 1, a vessel processing system, generally indicated at 20, is shown. The vessel processing system may include processing stations that are considered more broadly as processing devices. The vessel processing system 20 of the illustrated embodiment includes an injection molding machine 22 (which may be considered a processing station or apparatus), additional processing stations or apparatuses 24, 26, 28, 30, 32, and 34. And output 36 (which may be considered a processing station or apparatus). At a minimum, the system 20 has at least a first processing station, eg, a station 28, and a second processing station, eg, 30, 32, or 34.

I. In the illustrated embodiment, one of the processing stations 22-36 may be a first processing station, any other processing station may be a second processing station, or the like.

I. The embodiment shown in FIG. 1 may include the following eight processing stations or devices: 22, 24, 26, 28, 30, 32, 34 and 36. The exemplary vessel processing system 20 Injection molding machine 22, post-molding inspection station 24, pre-coating inspection station 26, coating station 28, post-coating inspection station 30, optical source delivery station for measuring the thickness of the coating ( 32) an optical source delivery station 34 and an output station 36 that inspect the coating for defects.

I. The system 20 may include a delivery mechanism 72 for moving the containers from the injection molding machine 22 to the container support 38. The delivery mechanism 72 finds, moves, picks up, delivers, orients, seats and ejects, for example, the containers 80 to remove them from the container forming machine 22 and 38. It can be composed of a robot arm for installing them on the vessel holders such as.

I. In addition, the system may employ a delivery mechanism at processing station 74 that removes the vessel from one or more vessel supports, such as 66, after processing the inner surface of the seated vessel, such as 80. May be included (FIG. 1). Thus, the vessels 80 are movable from the vessel holder 66 to packaging, storage or other suitable area or process step, indicated generally at 36. The delivery mechanism 72 finds, moves, picks up, delivers, orients, seats and ejects, for example, the containers 80 to remove them from the container supports 38 and the station ( In 36) it may consist of a robotic arm that installs them on other equipment.

I. The processing stations or apparatuses 32, 34, and 36 shown in FIG. 1 are coated and inspected system 20 after the individual vessels 80 have been removed from the vessel supports, such as 64. Optionally perform one or more of the appropriate steps below. Some non-limiting examples of the functions of the stations or devices 32, 34 and 36 include the following steps:

Placing the processed and inspected containers on a conveyor to move to another processing device;

Adding chemicals to the containers;

Capping the containers;

Placing the containers in appropriate processing racks;

Packaging the containers; And

Sterilizing the packaged containers

I. Also, as shown in FIG. 1, the vessel processing system 20 may include a plurality of vessel supports (or “pucks” that resemble a hockey puck in some embodiments) and generally end, each of 38 to 68. FIG. Containers such as one or more vessel supports 38 to 68 and, thus, 80, which are designated as bandless 70, may be transferred to the processing stations 22, 24, 26, 28, 30, 32, 34 and 36. It may include a conveyor for reciprocating to.

I. The processing station or device 22 may be a device for forming the containers 80. One device 22 contemplated may be an injection molding machine. Another contemplated apparatus 22 may be a blow molding machine. Also contemplated are vacuum forming machines, draw molding machines, cutting or milling machines, glass draw molding machines or other types of container forming machines for drawing glass or other drawable materials. Optionally, the container forming station 22 can be omitted since it can obtain containers already formed.

II. Container support

II.A. Portable container supports 38 to 68 are provided to support and move a container having an opening while the container is being processed. The container includes a container port, a second port, a duct and a movable housing.

II.A. The container port is configured to seat a container opening which is in communication with each other. The second port is configured to receive an external gas supply or outlet. And pass one or more gases between the vessel opening seated on the vessel port and the second port. The vessel port, the second port and the duct are substantially rigidly attached to the movable housing. Optionally, the portable vessel holder weighs less than five pounds. The advantage of the lightweight container support is that it can be more easily transported from one processing station to another.

II.A. In certain embodiments of the vessel holder, the duct is specifically a vacuum duct and the second port is specifically a vacuum port. The vacuum duct is configured to recover gas from a vessel seated on the vessel port. The vacuum port is configured to communicate between the vacuum duct and an external vacuum source. The vessel port, vacuum duct and vacuum port are substantially rigidly attached to the movable housing.

II.A. The vessel holders of Examples II.A and II.A.1. Are shown, for example, in FIG. The vessel holder 50 has a vessel port 82 configured to receive and seat an opening in the vessel 80. The inner surface of the seated vessel 80 may be processed through the vessel port 82. The vessel holder 50 may include a duct, for example a vacuum duct 94, to recover gas from the vessel seated on the vessel port 92. The vessel holder may comprise a second port, for example a vacuum port 96, that communicates between the vacuum duct 94 and an external vacuum source such as the vacuum pump 98. The vessel port 92 and the vacuum port 96 are for example O-ring support seals between the inner or outer cylindrical wall of the vessel port 82 and the inner or outer cylindrical wall of the vessel 80. And having sealing components, 100 and 102, respectively, to receive and form a seal with the vessel 80 or an external vacuum source 98 while enabling communication through the port. In addition, gaskets or other sealing schemes may be used.

II.A. The vessel holder such as 50 may be made of any material, for example thermoplastics and / or electrically nonconductive materials. In addition, the vessel holder, such as 50, is made partially or mainly of an electrically conductive material, in particular in the passages defined by the vessel port 92, the vacuum duct 94 and the vacuum port 96. This can counteract non-conductive materials. Examples of materials suitable for the vessel holder 50 are as follows: polyacetals such as Delrin® acetal materials sold by E. I. Dupont De Nemours, Wilmington, Delaware; Polytetrafluoroethylene (PTFE), for example Teflon® PTFE sold by E. I. Dupont De Nemours, Wilmington, Delaware; Ultra high molecular weight polyethylene (UHMWPE); High density polyethylene (HDPE); Or other substances known or newly discovered in the industry.

II.A. In addition, FIG. 2 may have a ring 116 that centers the vessel 80 when the vessel holder, for example 50, approaches or seats the port 92.

Array of vessel supports

II.A. Another approach to processing, inspecting and / or moving parts through the production system may be to use an array of vessel supports. The arrays can be composed of individual pucks or can be solid arrays on which devices are loaded. The array may allow one or more devices, optionally many devices, to be tested, moved or processed / coated simultaneously. The array can be, for example, one-dimensional or two-dimensional, similar to a tub or tray, grouped together to form a linear rack.

II.A. 4, 5, and 58 illustrate three array approaches. FIG. 4 shows a solid array 120 on which the apparatus or containers 80 are loaded. In this case, the devices or containers 80 may move through the production process as a solid array, even though they may be moved through the production process and to individual container supports. The single vessel holder 120 has a plurality of vessel ports, such as 122, for moving an array of seated vessels, such as 80, moving as a unit. In this embodiment, a plurality of individual vacuum ports, such as 96, may be provided to receive an array of vacuum sources 98. In addition, a single vacuum port may be provided connected to all vessel ports such as 96. In addition, a plurality of gas input probes, such as 108, may be provided to the array. Arrays of gas input probes or vacuum sources can be mounted and moved as a unit to process multiple vessels such as 80 simultaneously. In addition, a plurality of vessel ports, such as 122, may be processed more than one line at a time, or individually at a processing station. The number of devices in the array may relate to the number of devices molded in a single step or other tests or steps that may enable efficiency during operation. When processing / coating an array, the electrodes may be coupled together (to form one large electrode) or may be separate electrodes with their power air. All of the above approaches may still be applicable (in terms of electrode geometry, frequency, etc.).

II.A. In FIG. 5, individual puck or vessel supports (covered above) are brought together into an array by enclosing them in an outer frame 130. This arrangement provides the advantages of the solid array of FIG. 4 if desired, and also allows the array to be dismantled for other processing steps in which the containers 80 are processed in other arrays or alone.

II.A. FIG. 58 shows a linear rack similar to FIG. 4. If a linear rack is used, in addition to those described above, another option is to transport the rack in a single file format through a processing station to process the containers in series.

II.B. Vessel Support with O-Ring Array

II.B. 42 and 43 are alternatives, usable with the vessel holder embodiments of FIGS. 2, 3, 6, 7, 19, 12, 13, 16, 18, 19, 30 and 43, respectively, for seating the vessel on the vessel support. A fragmentary detail longitudinal cross section and detail view of the vessel holder 450 provided in a conventional sealing arrangement. Referring to FIG. 42, the syringe barrel 438 seated on the vessel, eg, the vessel holder 450, is generally annular (and commonly chamfered or rounded) as well as a generally cylindrical sidewall 454. ) Has a back opening 442 defined by lip 452. Medical fluid collection tubes commonly have the same type of lip 452, but lack a flange 440, and can instead be seated on the vessel holder 450.

II.B. In the illustrated embodiment, the vessel holder 450 includes a substantially cylindrical inner surface 456 that serves as a guide surface in the illustrated embodiment to receive the approximately cylindrical sidewall 454 of the syringe barrel 438. do. The wall is also defined by a generally annular joint 458 to which the annular lip 452 joins when the syringe barrel 438 rests on the vessel holder 450. A generally annular pocket or groove 460 formed in the inner surface 456 is provided to carry a sealing component, for example an O-ring 462. The radial depth of the pocket 460 is smaller than the radial cross section of the sealing component, for example O-ring 462 (shown in FIG. 42), and preferably has an inner diameter of the O-ring 462. Slightly smaller than the outer diameter of the annular lip 452.

II.B. These relative dimensions are approximately at least the outer wall 464 of the pocket 460 and the syringe barrel 438, as shown in FIG. 42, when a container such as 438 is seated as shown in FIG. 42. The radial cross section of the O-ring 462 is horizontally compressed between the cylindrical sidewalls 454. This compression flattens the bearing surfaces of the O-ring 462 to form a seal between at least the outer wall 464 of the pocket 460 and the approximately cylindrical sidewall 454 of the syringe barrel 438. Done.

II.B. The pocket 460 optionally separates the top and bottom walls 468 and 466 apart by the corresponding radial cross-sectional diameter of the O-ring 462 in relation to the values of the O-ring 462. It can be fabricated to form two or more seals between the bottom and top walls 466 and 468 and the side wall 454. When the O-ring 462 is squeezed between the outer wall 464 and the approximately cylindrical sidewall 454 of the pocket 460, the restoring force expands up and down as shown in FIG. And engage and flatten against the top and bottom walls 466 and 464. Optionally, the O-ring 462 tends to deform both vertically and horizontally to form a generally rounded cross section into a rectangle. The annular lip 452 seated at the junction 458 will also restrict the flow of PECVD process reactants and other gases introduced through or adjacent to the back opening 442.

II.B. As a result of this optional configuration, as shown in FIG. 43, only a gap in the lower right corner of the O-ring 462 is outside of the O-rings and introduced into the interior of the container 438. Or are exposed to process gases, plasma, etc. generated therein. This structure protects the O-ring 462 and adjacent surfaces (as the outer surface of the sidewall 438) from unwanted accumulation of PECVD deposits and attack by activated species in the plasma. In addition, the container 438 is different from the elastic surfaces provided by the butt seat of the annular lip 452 directly with respect to the O-ring, as shown in some of the other figures. The hard surface of 458 is more aggressively positioned. In addition, the forces acting on respective portions around the major circumference of the O-ring 462 are more evenly distributed as the vessel 438 is tightened for any substantial rocking. do.

II.B. The pocket 460 can also be formed with the bottom wall 466 over the junction 458 shown in FIG. 43. In another embodiment, one or more axially spaced pockets 460 may be provided to provide a double or higher level seal and to further tighten the container 438 for locking when seated against the splice 458. Can be.

II.B. 45 illustrates a container usable with embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26, 28, 33-35, and 37-44, for example. Another structure for the support 482. The vessel holder 482 includes an upper portion 484 and a base 486 joined together at a joint 488. A sealing component, for example an O-ring 490 (the right side of which is cut off so that the pocket holding it) is described between the upper portion 484 and the base 486 at the joint 488. Is captured in. In the illustrated embodiment, the O-ring 490 is received in the annular pocket 492 and positioned in the O-ring when the upper portion 484 is connected to the base 486.

II.B. In this embodiment, the O-ring 490 is captured and, in the case where the upper portion 484 and the base 486 are connected, in this case radially extending by screws 498 and 500 It bears against the radially extending wall 496 that partially defines surface 494 and pocket 492. Thus, the O-ring 490 seats between the upper portion 484 and the base 486. In addition, an O-ring 490 captured between the upper portion 484 and the base 486 accommodates the vessel 80 (which has been removed for clarity when other features are shown in this figure). A first O-ring seal of the container port 502 is formed around the opening of the container 80, similar to the O-ring sealing arrangement around the container rear opening 442 in FIG. 42.

II.B. In this embodiment, although not essential, the vessel port 502 has both the first O-ring 490 seal and the second axially spaced O-ring 504 seal, each of the vessels. It has an inner diameter such as 506 that is sized to receive an outer diameter (similar to sidewall 454 in FIG. 43) of a container such as 80 for sealing between the container such as port 502 and 80. The space between the o-rings 490 and 504 provides support for a vessel such as 80 at two axially spaced points so that a vessel such as 80 is attached to the o-rings 490 and 504. Or against the container port 502. In this embodiment, although not necessarily, a radially extending junction surface 494 is positioned near the O-ring 490 and 506 seals and surrounds the vacuum duct 508.

III. Container transfer method-processing of vessels seated on container supports

III.A. Transporting the vessel holder to the processing station

III.A. 1, 2 and 10 show how to treat the vessel 80. The method can be performed as follows.

III.A. A container 80 may be provided having an opening 82 and a wall 86 defining an inner surface 88. In one embodiment, the container 80 may be formed in a mold such as 22 and then removed from it. Optionally, within 60 seconds or within 30 seconds, or within 25 seconds, or within 20 seconds, or within 15 seconds, or within 10 seconds, or within 5 seconds, or 3 seconds after removing the container from the mold. Or, as soon as the container 80 can be moved within 1 second or without causing it to distort during processing of the container 80 (assuming it is made at high temperature and gradually cooled therefrom), the container opening 82 ) May be seated on the vessel port 92. Quickly moving the vessel 80 from the mold 22 to the vessel port 92 reduces dust or other impurities that may reach the surface 88 and reduces the barrier coating or other type of coating ( 90) to prevent or prevent adhesion. In addition, the faster the vacuum is drawn on the container 80 after the container 80 has been fabricated, the lower the chance that fine particle impurities will adhere to the inner surface 88.

III.A. A vessel support, such as 50, that includes vessel port 92 may be provided. An opening 82 of the vessel 80 may be seated on the vessel port 92. Prior to, during, or after seating the opening 82 of the vessel 80 on the vessel port 92, the vessel holder (eg, FIG. 6), such as 40, is transferred and In conjunction with the bearing surfaces 220-240 above, it may be positioned on the vessel holder 40 relative to a processing device or station, such as 24.

III.A. As shown by the station 24 shown in FIG. 6, one, one or more or all of the processing stations, such as 24 to 34, may be provided with the seated container 80 in a processing station or apparatus such as 24. One or more bearing surfaces 220, 222, 224, 226, 228, 230, 232, 234, 236 to allow the support of one or more vessel supports, such as 40, in a predetermined position during processing of the inner surface 88. Bearing surface, such as, 238, or 240). Such bearing surfaces may be part of a stationary or moving structure, such as for example tracks or guides that guide and position a vessel support such as 40 while the vessel is being processed. For example, the downwardly facing bearing surfaces 222 and 224 are located on the vessel holder 40 such that the probe 108 is inserted into the vessel holder 40 when the probe 108 is inserted into the vessel holder 40. Acts as a reaction surface to prevent it from moving upwards. The reaction surface 236 is positioned on the vessel holder while the vacuum source 98 (FIG. 2) is seated on the vacuum port 96 and prevents the vessel holder 40 from moving to the left. The bearing surfaces 220, 226, 228, 232, 238 and 240 are similarly positioned on the vessel holder 40 to prevent horizontal movement during processing. The bearing surfaces 230 and 240 are similarly located on the vessel holder such as 40 to prevent them from moving out of position vertically. Thus, the first bearing surface, the second bearing surface, the third bearing surface, etc. may be provided at each of the processing stations, such as 24 to 34.

III.A. The inner surface 88 of the seated vessel 80 is processed through the vessel port 92 at the first treatment station, which may be, for example, a barrier application or another type of coating station 28 shown in FIG. Can be. The vessel holder 50 and the seated vessel 80 are transported from the first processing station 28 to the second processing station, for example the processing station 32. The inner surface 88 of the seated vessel 80 may be processed through the vessel port 92 at the second processing station, such as 32.

III.A. One of the methods includes removing the vessel 80 from a vessel holder such as 66 after treating the inner surface 88 of the seated vessel 80 at the second processing station or apparatus. It may further include.

III.A. One of the methods may further comprise, after the removing step, providing a wall 86 defining a second container 80 having an opening 82 and an inner surface 88. Openings 82 of the second vessel, such as 80, may be seated on vessel ports 92 of other vessel supports, such as 38. The inner surface of the seated vessel 80 may be processed through the vessel port 92 at the first processing station or apparatus, such as 24. The vessel holder such as 38 and seated second vessel 80 may be transported from the first processing station or apparatus 24 to the second processing station such as 26. The seated second vessel 80 may be processed through the vessel port 92 by the second processing station or device 26.

III.B. Transporting the processing apparatus to the vessel holder or vice versa.

III.B. Further, the processing stations can be more broadly processing apparatuses, the vessel supports can be delivered relative to the processing apparatuses, and the processing apparatuses can be moved relative to the vessel supports, or Some may be provided for a given system. In another arrangement, the vessel holders can be moved to one or more stations, and one or more processing devices can be disposed at or near at least one of the stations. Thus, there is not always a one-to-one correspondence between the processing devices and the processing stations.

III.B. Container handling methods that include some portions are contemplated. A first processing device such as probe 108 (FIG. 2) and a second processing device such as light source 170 (FIG. 10) are provided for processing containers such as 80. A container 80 is provided having a wall 86 and an opening 82 defining an interior surface 88. A vessel holder 50 is provided that includes a vessel port 92. The opening 82 of the vessel 80 rests on the vessel port 92.

III.B. The first processing device, such as the probe 108, may be operatively engaged with the vessel holder 50 and moved to or vice versa. The inner surface 88 of the seated vessel 80 is processed through the vessel port 92 using the first processing device or probe 108.

III.B. A second processing device (FIG. 10), such as 170, may be operatively engaged with the vessel holder 50 and moved to or vice versa. The inner surface 88 of the seated vessel 80 is processed through the vessel port 92 using a second processing device such as a light source 170.

III.B. Optionally, any number of other processing steps may be provided. For example, a third processing device 34 may be provided for processing the containers 80. The third processing device 34 may be operatively engaged with the vessel holder 50 and moved to or vice versa. The inner surface of the seated vessel 80 may be processed through the vessel port 92 using the third processing device 34.

III.B. In another method of treating the container, a container 80 may be provided having an opening 82 and a wall 86 defining an inner surface 88. A vessel support, such as 50, that includes vessel port 92 may be provided. An opening 82 of the vessel 80 may be seated on the vessel port 92. The inner surface 88 of the seated vessel 80 may be processed through the vessel port 92 at the first processing station, which may be, for example, a blocking or other type of coating apparatus 28 shown in FIG. Can be. The vessel holder 50 and the seated vessel 80 are transported from the first processing unit 28 to the second processing unit, for example the processing unit 34 shown in FIGS. 1 and 10. The inner surface 88 of the seated vessel 80 may then be processed through the vessel port 92 by a second processing device such as 34.

III.C. Using a gripper to reciprocate the tube to the coating station

III.C. Another embodiment is a method of PECVD processing of a first vessel comprising some steps. A first container having an open end, a closed end and an inner surface is provided. At least the first gripper is configured to selectively grasp and release the closed end of the first container. The closed end of the first vessel is gripped using the first gripper and is transferred to the vicinity of the vessel holder configured to seat with the first end of the first vessel using the first gripper. The first gripper is then used to axially advance the first vessel and seat its open end on the vessel holder to achieve sealed communication between the vessel holder and the interior of the first vessel.

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

III.C. Thereafter, the first vessel is detached from the vessel holder and, using the first gripper or another gripper, the first vessel is axially transferred from the vessel holder. The first vessel is then released from the gripper used to axially transfer from the vessel holder.

III.C. 16 and 49, a tandem conveyor 538 can be used to support and transport a plurality of grippers, such as 204, through the apparatus and process as described herein. The grippers 204 are operably connected with the tandem conveyor 538 and continuously transport a series of at least two vessels 80 to the vicinity of the vessel holder 48 and as described herein. As well as other steps of the cleaning method.

IV. PECVD Equipment for Container Manufacturing

IV.A. PECVD apparatus including vessel holder, internal electrode, vessel as reaction chamber

IV.A. Another embodiment is a PECVD apparatus that includes a vessel holder, an inner electrode, an outer electrode, and a power supply. The vessel seated on the vessel holder defines a plasma reaction chamber, which may optionally be a vacuum chamber. Optionally, a vacuum source, reactant gas source, gas supply, or a combination of two or more thereof may be supplied. Optionally, to define a closed chamber, a gas vent is provided that does not necessarily include a vacuum source to deliver gas into or from the interior of the vessel seated on the port.

IV.A. The PECVD apparatus can be used for atmospheric PECVD when the plasma reaction chamber does not need to function as a vacuum chamber.

IV.A. In the embodiment shown in FIG. 2, the vessel holder 50 includes a gas input port 104 for delivering gas to a vessel seated on the vessel port. The gas input port 104 may comprise at least one O-ring 106, which may seat against the cylindrical probe 108 when the probe 108 is inserted through the gas input port 104. It has a sliding seal provided by two O-rings in series or three O-rings in series. The probe 108 may be a gas input water extending from the distal end 110 to the gas delivery port. The distal end 110 of the illustrated embodiment may be deeply inserted into a vessel 80 providing one or more PECVD reactants and other process gases.

IV.A. Optionally, in the embodiment shown in FIG. 2, or more generally in FIGS. 1-5, 8, 9, 12-16, 18, 19, 21, 22, 26-28, 33-35, 37-49 Or any of the disclosed embodiments, such as the embodiments of 52-55, and as specifically disclosed in FIG. 55, the plasma screen 610 may be a plasma formed within the vessel 80. 610 may be provided to limit the volume above. The plasma screen 610 is a conductive, porous material, some examples of which are a porous plate made of a ceramic or metal (eg, brass) or other conductive material coated with steel wool, a porous sintered metal or a conductive material or Disk. One example is center-to-center holes, with center holes sized to pass through the gas inlet 108 and 0.02 inches (0.5 mm) spaced 0.04 inches (1 mm) apart, the holes being the surface area of the disk. It is a pair of metal disks, with holes that provide, as part, a 22% open area.

IV.A. In particular, for embodiments in which the probe 108 functions as a counter electrode, the plasma screen 610 may be provided at or near the opening 82 of the tube, syringe barrel or other vessel 80 being processed. It may be in intimate contact with the gas inlet 108. In addition, the plasma screen 610 having a common potential with the gas inlet 108 may be grounded. The plasma screen 610 is the vessel holder 50 and, for example, the vacuum duct 94, the gas input port 104, the vicinity of the O-ring 106, the vacuum port 96, The plasma is reduced or eliminated in the O-ring 102 and other devices adjacent to the gas inlet 108. At the same time, the porosity of the plasma screen allows gases, air, etc., to flow out of the vessel 80 and into the vacuum port 96 and downstream apparatus.

IV.A. In the coating station 28 shown in FIG. 3, the vessel holder 112 delivers gas (via the probe 108) to the vessel 80 seated on the vessel port 92 and each vessel port. And a composite gas input port and vacuum port 96 in communication with the vessel port 92, which draw gas (via the vacuum source 98) from the vessel seated on 92. In this embodiment, the gas input probe 108 and the vacuum source 98 may be provided as a composite probe. The two probes can be advanced as a unit or separately if desired. This arrangement eliminates the need for a third seal 106 and allows the use of support seals throughout. The support seal clearly seats the vessel 80 and the vacuum source 98 by, for example, extracting a vacuum in the vessel 80 and applying an axial force to deform the O-rings, To close any gaps left due to the presence of any debris on the sealing surface on the opposite side of the ring. In the embodiment of FIG. 3, the axial forces exerted on the vessel holder 112 by the vessel 80 and the vacuum source 98 are directed opposite, and the vessel 80 and the vessel holder 112 are moved. Support it together and keep the respective supporting seals.

IV.A. FIG. 13 is a view similar to FIG. 2 of the vessel holder 48 in a coating station according to another embodiment of the present disclosure, in which the vessel 80 may be seated on the vessel holder 48 at the process station. to be. 2 of the vessel holders 48 in the coating station according to another embodiment of the present disclosure, in which the vessel 80 may be seated on the vessel holder 48 at the processing station. Or a block that first sits on a vessel holder such as 48 before the seated vessel 80 is moved to another device by the system 20 or may be used to treat a vessel 80 that does not move with it. Other types of coating stations 28 may be used.

IV.A. FIG. 13 shows a cylindrical electrode 160 suitable for frequencies of 50 Hz to 1 GHz as an alternative to the U-shaped electrodes of FIGS. 2 and 9. The vessel holder (or electrode) may be moved into place prior to activation by moving the electrode down or by moving the vessel holder up. In addition, the movement of the vessel holder and the electrode in a vertical plane may result in an electrode 160 having a structure such as a shell (two cylinders which can come together from opposite sides when ready for processing / coating in place). Can be prevented by making. IV.A. Optionally, in coating station 28, vacuum source 98 is a continuous process in which the tube is moved through a coating station, such as 28, while the vacuum is drawn and gas is introduced through probe 108. It generates a seal having a puck or vessel holder 50 that can be held during movement of the vessel holder. In addition, the puck or vessel holder 50 is moved to a stop position, where the probe 108 is pushed into the device so that the pump or vacuum source 98 is coupled and activated at the vacuum port 96 A stop process that generates a vacuum can be used. Once the probe 108 is in place and a vacuum occurs, the external fixed electrode 160 and the interior of the tube or vessel 80 are independent of the puck or vessel holder 50 and the tube or other vessel 80. In the plasma can be established.

IV.A. 53 illustrates, for example, the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21, 22, 26-28, 30, 33-35, 37-44, and 52; Other optional details of the coating station 28 available are shown. The coating station 28 may also have a main vacuum valve 574 in the vacuum line 576 leading to the pressure sensor 152. Manual bypass valve 578 is provided in bypass line 580. Exhaust valve 582 controls the flow at exhaust port 404.

IV.A. The flow rate from the PECVD gas source 144 is controlled by the main reactant 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 liquid reservoir 588. The contents of the reservoir 588 are withdrawn through the organosilicon capillary line 590 provided to a suitable length to provide the desired flow rate. The flow rate of the organosilicon vapor is controlled by the organosilicon shutoff valve 592. The pressure may be, for example, a pressure source 616, such as compressed air, connected to the space portion 614 by pressure line 618 to establish repeatable organosilicon liquid delivery that does not depend on (and varies within) atmospheric pressure. Pressure in the range of 0 to 15 psi (0 to 78 cm. Hg) is applied to the space portion 614 of the liquid reservoir 588. The reservoir 588 is sealed and the capillary connection 620 allows only the pure organosilicon liquid (not the gas compressed from the space portion 614) to the capillary tube 590 at the bottom of the reservoir 588. To flow through. The organosilicon liquid may optionally be heated above ambient temperature if it is necessary or desired to evaporate the organosilicon liquid to form organosilicon vapors. Oxygen is provided from an oxygen tank 594 via an oxygen supply line 596 controlled by mass flow controller 598 and provided with an oxygen shutoff valve 600.

IV.A. In the embodiment of FIG. 7, the station or device 26 is fitted with a vacuum source 98 fitted to seat on the vacuum port 96, a side channel 134 connected to the probe 108, or both (shown). As shown). In the illustrated embodiment, the side channel 134 includes a shutoff valve 136 that regulates the flow rate between the probe port 138 and the vacuum port 140. In the illustrated embodiment, the selector valve 136 has at least two states: the ports 138 and 140 are connected so that two parallel passages for gas flow (thus increasing the pumping speed) Vacuum condition) or disconnected states of the ports 138 and 140). Optionally, the selector valve 136 may have a third port, such as a PECVD gas input port 142, for introducing PECVD reaction and process gases from the gas source 144. This means allows the same vacuum supply and probe 108 to be used for both leak or penetration testing and blocking or other types of coating application.

IV.A. In the illustrated embodiments, a vacuum line such as 146 to the vacuum source 98 may also include a shutoff valve 148. The shutoff valves 136 and 148 can be closed when the probe 108 and the vacuum source 98 are not connected to a vessel support such as 44, so that the side channel 134 and the vacuum line ( If 146 is moved from one vessel holder 44 to another, it does not need to be evacuated from the vessel 80 on the sides of the valves 136 and 148. Axial movement of the probe 108 independent of the position of the vacuum line 146 relative to the port 96 to facilitate removal of the probe 108 from the gas input port 104 axially. Flexible line 150 may be provided to enable the.

IV.A. FIG. 7 also shows any embodiment—exhaust 404 to ambient air controlled by valve 406 and other optional features available. The valve 406 discharges the vessel 80 from the vessel holder 44, or discharges the vessel holder 44 at the vacuum port 96 from the vacuum source 98, or optionally both. In all cases, the valve 406 may be opened to break the vacuum quickly after processing the vessel 80.

IV.A. In the illustrated embodiment (also referring to FIG. 7), the probe 108 may also be connected to a pressure gauge 152 and in communication with the interior 154 of the vessel 80, within the vessel 80. Allow pressure to be measured.

IV.A. In the apparatus of FIG. 1, the vessel coating station 28 applies a SiO _x barrier coating or other type of coating 90 on the inner surface 88 of the vessel 80, for example, as shown in FIG. 2. It may be a PECVD apparatus described further below, operating under conditions suitable for depositing

IV.A. In particular, with reference to FIGS. 1 and 2, the processing station 28 provides an electrode 160 supplied by a radio frequency power supply 162 that provides an electric field for generating plasma in the vessel 80 during processing. It may include. In this embodiment, the probe 108 is electrically conductive and grounded to provide a counter electrode within the vessel 80. Also, in some embodiments, the external electrode 160 may be grounded and the probe 108 may be directly connected to the power supply 162.

IV.A. In the embodiment of FIG. 2, the external electrode 160 may be generally cylindrical as shown in FIGS. 2 and 8 or FIGS. 2 and 9 (FIGS. 8 and 9 are cross-sectional views taken along section line AA of FIG. 2. It may be a generally U-shaped long channel, as shown in another embodiment). Each illustrated embodiment has one or more sidewalls, such as 164 and 166, and optionally, a top 168, all of which are disposed close to the vessel 80.

IV.A., IV.B. 12-19 show other variations of the vessel coating station or device 28 as described above. One or more of these variants may replace the vessel coating station or device 28 shown in FIGS.

IV.A. 12 shows another electrode system that may be used (in the same manner as described above using the same vessel holder and gas inlet) at frequencies above 1 GHz. At these frequencies, electrical energy from the power supply can be conducted into the interior of the tube through one or more waveguides that are connected to a cavity that absorbs energy or resonates energy. Resonating the energy allows it to couple with the gas. Since the vessel 80 interacts with a cavity that changes its resonance point to generate a plasma for coating and / or treatment, other cavities may be provided for use with vessels such as other frequencies and 80. have.

IV.A. 12 may include a microwave power supply 190 that directs microwaves through the wavelength guide 192 into a microwave cavity 194 at least partially surrounding the vessel within the vessel 80 from which plasma may be generated. . The microwave cavity 194 may be tuned to absorb microwaves and couple with the plasma-generating gas, with respect to the frequency of the microwaves and partial pressures and selection of gases. In FIG. 13, as well as any of the illustrated embodiments, the vessel 80 and the cavity 194 (or an electrode, detector, or other enclosing structure) to avoid aggression or damaging the vessel 80. There may be a small gap 196 between. In addition, in FIG. 13, the microwave cavity 194 has a flat end wall 198 such that the gap 196 is not uniform in width, particularly on the opposite side of the circular edge of the end wall 198. Optionally, the distal end 198 may be curved to provide a substantially uniform gap 196.IV.A.2. 44 is for use with embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37-43, 46-49, and 52-54, for example. A view similar to FIG. 2 of another possible gas delivery tube / inner electrode. As shown in FIG. 44, the distal portion 472 of the inner electrode 470 includes an elongated porous sidewall 474 that encloses an inner passage 476 within the inner electrode. The inner passage 476 is connected to the gas supply 144 by a proximal portion 478 of the inner electrode 470 extending out of the vessel 80. In addition, the distal end 480 of the internal electrode 470 may optionally be porous. Due to the porosity of the porous sidewall 474 and the porous distal end 480, if present, at least a portion of the reactant gas supplied from the gas supplier 144 exits and reacts laterally from the passage 476. Material gas is supplied to adjacent portions of the inner surface 88 of the vessel 80. In this embodiment, the porous portion of the porous sidewall 474 extends less than, although only a portion of the length of the inner electrode 470 is missing, the inner electrode 470 in the container 80. It will extend over the entire length of. As indicated elsewhere herein, the inner electrode 470 may be longer or shorter than that shown in FIG. 44 with respect to the length of the vessel 80, and the porous portion may be continuous or discontinuous. Can be.

IV.A. The outer diameter of the inner electrode 470 may be at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95% of the inner diameter adjacent to the side of the container. With respect to the inner diameter of the container 80, in particular, if the electrode 470 is concentric with the container 80, if the inner electrode 470 having a larger diameter is employed, the inner electrode 470 By reducing the distance between the outside of and the adjacent inner surface 88 of the vessel 80, it confines the plasma into a narrower region, whereby the plasma may be more uniform therein. In addition, employing an inner electrode 470 with a larger diameter, along the length of the inner electrode 88, very close to the initial reaction point, as opposed to flowing from a single point as compared to the formed inner surface 88 As fresh gases are introduced into the plasma at closely spaced points, the reactant gas and / or carrier gas are distributed more uniformly along the inner surface 80.

IV.A. In one contemplated arrangement, shown in solid lines, power supply 162 has one power connection to electrode 200, which may be at any point along electrode 200, and the probe 108 May be grounded. In such a configuration, a capacitive load may be used to generate the plasma in the vessel 80. In another contemplated arrangement, shown by an imaginary line (without the connections shown in solid lines), the individual ends of the coil 200 may be referred to herein as the “electrode” for convenience. Connected to the field. In such a configuration, an inductive load can be used to generate the plasma in the vessel 80. In addition, a combination of inductive and capacitive loads may also be used in other embodiments.

IV.A. 46-48 show an array of two or more gas delivery tubes 510 and 512 (also shown in FIG. 2), such as 108, which are also internal electrodes. The array can be linear or rotary. The rotary array allows the electrodes to be reused periodically.

IV.A. 46-48 also show internal electrodes for inserting and removing the gas delivery tubes / inner electrodes 108, 510, and 512 from and into one or more vessel supports, such as 50 or 48. An extender and retractor 514 is shown. These features are an optional means for using gas delivery tubes.

IV.A. In the illustrated embodiment, referring to FIGS. 46 to 48 as well as to FIG. 53, the internal electrodes 108, 510, and 512 are separated by shutoff valves 522, 524 and flexible hoses 516, 518, and 520, respectively. 526 is connected to a common gas supplier 144. (The flexible hoses were shortened by omitting the loose parts in FIGS. 46-48). Referring briefly to FIG. 56, the flexible hoses 516, 518, and 520 may alternately be connected to independent gas sources 144. Mechanism 514 is provided to extend and contract internal electrodes, such as 108. The inner electrode extender and retractor are configured to move the inner electrode between a fully advanced position, an intermediate position and a reduced position relative to the vessel holder.

IV.A. 46 and 56, the inner electrode 108 extends into the operating position within the vessel holder 50 and the vessel 80, and the shutoff valve 522 is open. In addition, internal electrodes 510 and 512 that do not operate in FIG. 46 are collapsed and their shutoff valves 524 and 526 are closed. In the illustrated embodiment, one or more of the non-operating internal electrodes 510 and 512 are disposed within the electrode cleaning device or station 528. One or more electrodes can be cleaned and optionally the others can be replaced in the station 528. The cleaning operations may include, but are not limited to, chemical reactions or solvent treatments that remove deposits, milling or physically removed deposits that physically remove deposits.

IV.A. In FIG. 47, the working internal electrode 108 shrinks outside the vessel 80 such that its distal end remains within the vessel holder 50 and the valve 522 is closed while the inoperative Internal electrodes 510 and 512 are the same as before. In this condition, the vessel 80 can be removed and a new vessel seated on the vessel holder 50 without risk of touching the electrode 108 while the vessels 80 are removed and replaced. Can be. After the vessel 80 has been removed, the inner electrode 108 may be advanced to the positions of FIGS. 46 and 56 and the shutoff valve 522 may be opened again using the same inner electrode 108 as before. Coating of the vessel 80 may begin. Thus, in an arrangement in which a series of the vessels 80 are seated on and removed from the vessel holder 50, at the station where the vessel 80 is installed or the internal electrode 108 is in use As it is removed from the vessel holder 50, the internal electrode 108 may extend and partially shrink several times.

IV.A. In FIG. 48, the vessel holder 50 and its vessel 80 have been replaced with a new vessel holder 48 and another vessel 80. Referring to FIG. 1, in this type of embodiment, each vessel 80 remains on its vessel support, such as 50 or 48 and an internal electrode such as 108 has its vessel support a coating station. As the name is inserted into each container.

IV.A. In addition, in FIG. 48, the inner electrodes 108, 510 and 512 are all fully collapsed, and the array of inner electrodes 108, 510 and 512 is compared with the respective positions of FIG. Moved to the right relative to the support 48 and the electrode cleaning station, the inner electrode 108 is out of its position and the inner electrode 510 is moved to the position relative to the vessel holder 48.

IV.A. It will be appreciated that the movement of the array of inner electrodes may be independent of the movement of the vessel holders. They can be moved together or separately to simultaneously or independently switch to a new vessel holder and / or a new internal electrode.

IV.A. 46-48 show an array of two or more gas delivery tubes 510 and 512 (also shown in FIG. 2), such as 108, which are also internal electrodes. The array can be linear or rotary. The rotary array allows the electrodes to be reused periodically.

IV.A. In addition, 46-48 are internal electrodes that insert and remove the gas delivery tubes / inner electrodes 108, 510, and 512 from and into one or more vessel supports, such as 50 or 48. An extender and retractor 514 is shown. These features are an optional means for using gas delivery tubes.

IV.A. In the illustrated embodiment, referring to FIGS. 46 to 48 as well as to FIG. 53, the internal electrodes 108, 510, and 512 are separated by shutoff valves 522, 524 and flexible hoses 516, 518, and 520, respectively. 526 is connected to a common gas supplier 144. (The flexible hoses were shortened by omitting the loose parts in FIGS. 46-48). Mechanism 514 is provided to extend and contract internal electrodes, such as 108. The inner electrode extender and retractor are configured to move the inner electrode between a fully advanced position, an intermediate position and a reduced position relative to the vessel holder.

IV.A. 46 and 56, the inner electrode 108 extends into the operating position within the vessel holder 50 and the vessel 80, and the shutoff valve 522 is open. 46 and 56, the internal electrodes 510 and 512 that are not working are reduced and their shutoff valves 524 and 526 are closed. In the illustrated embodiment, the inoperative internal electrodes 510 and 512 are disposed in an electrode cleaning device or station 528. Some electrodes can be cleaned and optionally others can be replaced in the station 528. The cleaning operations may include, but are not limited to, chemical reactions or solvent treatments that remove deposits, milling or physically removed deposits that physically remove deposits.

IV.A. In FIG. 47, the working internal electrode 108 shrinks outside the vessel 80 such that its distal end remains within the vessel holder 50 and the valve 522 is closed while the inoperative Internal electrodes 510 and 512 are the same as before. In this condition, the vessel 80 can be removed and a new vessel seated on the vessel holder 50 without risk of touching the electrode 108 while the vessels 80 are removed and replaced. Can be. After the vessel 80 has been removed, the inner electrode 108 may be advanced to the positions of FIGS. 46 and 56 and the shutoff valve 522 may be opened again using the same inner electrode 108 as before. Coating of the vessel 80 may begin. Thus, in an arrangement in which a series of the vessels 80 are seated on and removed from the vessel holder 50, at the station where the vessel 80 is installed or the internal electrode 108 is in use As it is removed from the vessel holder 50, the internal electrode 108 may extend and partially shrink several times.

IV.A. In FIG. 48, the vessel holder 50 and its vessel 80 have been replaced with a new vessel holder 48 and another vessel 80. Referring to FIG. 1, in this type of embodiment, each vessel 80 remains on its vessel support, such as 50 or 48 and an internal electrode such as 108 has its vessel support a coating station. As the name is inserted into each container.

IV.A. In addition, in FIG. 48, the inner electrodes 108, 510 and 512 are all fully collapsed, and the array of inner electrodes 108, 510 and 512 is compared with the respective positions of FIG. Moved to the right relative to the support 48 and the electrode cleaning station, the inner electrode 108 is out of its position and the inner electrode 510 is moved to the position relative to the vessel holder 48.

IV.A. It will be appreciated that the movement of the array of inner electrodes may be independent of the movement of the vessel holders. They can be moved together or separately to simultaneously or independently switch to a new vessel holder and / or a new internal electrode.

IV.A. An array of two or more inner electrodes 108, 510 and 512 is useful, in which the individual combined gas delivery tubes / inner electrodes 108, 510 and 512 are in some cases polymerized reactant gases or This is because some other types of deposits tend to accumulate as they are used to coat a series of containers, such as 80. The deposits can accumulate to a point where the coating speed or the resulting uniformity is compromised, which may be undesirable. In order to maintain a uniform process, the internal electrodes can be suspended, replaced or cleaned periodically, and new or cleaned electrodes can be used. For example, going from FIG. 46 to FIG. 48, the inner electrode 108 is a new or readjusted inner electrode that easily extends to the vessel holder 48 and the vessel 80 to apply an inner coating to the new vessel. Replaced with (510).

IV.A. Accordingly, the internal electrode drive 530 moves the first internal electrode 108 from the extended position to the reduced position, replaces the first internal electrode 108 with the second internal electrode 510, and replaces the second internal electrode 108. It is operable in connection with the internal electrode extender and retractor 514 to advance the internal electrode 510 to an extended position (similar to FIGS. 46 and 56 except for replacement of the electrode).

IV.A. The series of gas delivery tubes of FIGS. 46-48 and the internal electrode drive 530, for example, FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33 Usable with the embodiments of -35, 37-45, 49 and 52-54. Extension and Reduction Mechanisms 514 The mechanisms of FIGS. 46-48 are described, for example, as well as the probes of the container inspection apparatus of FIGS. 6 and 7, as well as FIGS. It is usable with the gas delivery tube embodiments of 21-22, 26-28, 33-35, 37-45, 49, and 52-54.

IV.A The electrode 160 shown in FIG. 2 may be shaped like a “U” channel towards the page in length, with the puck or vessel holder 50 activated (powered during the processing / coating process. Can be moved through the electrode. Since external and internal electrodes are used, such a device may use a frequency between 50 Hz and 1 GHz applied from the power supply 162 to the U channel electrode 160. The probe 108 may be grounded to complete the electrical circuit, allowing current to flow through the low pressure gas (es) in the interior of the vessel 80. The current generates a plasma to enable selective treatment and / or coating of the inner surface 88 of the device.

IV.A The electrode of FIG. 2 may also be powered by a pulsed power supply. The pulsing allows for the depletion of the reactant gases and then for the removal of by-products before the activation and (re) depletion of the gases occur. Pulsed power systems are typically characterized by a duty cycle that measures the amount of time an electric field (and thus plasma) is present. The power-on time is relative to the power-off time. For example, a 10% duty cycle may correspond to a 10% power on time of a cycle where power is off for 90% of the time. In a particular embodiment, the power may be on for 0.1 second and off for 1 second. Pulsed power systems reduce the effective power supply for a given power supply 162 because off-time results in an increase in processing time. If the system is pulsed, the resulting coating can be very pure (no byproducts or contaminants). Another consequence of pulsed systems is the possibility to achieve atomic layer deposition (ALD). In this case, the duty cycle can be adjusted so that the power-on time is achieved with a single layer deposition of the desired material. In this way, a single atomic layer is considered to be deposited in each cycle. This approach can produce very pure and very structural coatings (although at the temperatures required for deposition on the polymer surface, the temperature is preferably kept low (<100 ° C.) and low temperature coatings can be amorphous). have.

IV.A. Another coating station employing a microwave cavity instead of an external electrode is disclosed in FIG. 12. The energy applied can be, for example, a microwave frequency of 2.45 GHz.

IV.B. PECVD apparatus using a gripper to reciprocate the tube to the coating station

IV.B. Another embodiment is an apparatus for PECVD processing of a container that employs a gripper as described above. 15 and 16 show an apparatus generally indicated at 202 during PECVD processing of a first vessel 80 having an open end 82, a closed end 84 and an inner surface defined by the surface 88. Shows. This embodiment includes a vessel holder 48, at least a first gripper 204 (in this embodiment, for example, a suction cup), defined by the vessel port 92 on the vessel holder 48. A seat, reactant feeder 144, plasma generator presented by electrodes 108 and 160, a vessel discharge device that may be an exhaust valve such as 534 and the same gripper 204 or second gripper (optional And a second gripper 204.

IV.B. As shown by any of the grippers, the first gripper 204 is configured to selectively support and release the closed end 84 of the container 80. The first gripper 204 can transport the container near the container support 48 while holding the closed end 84 of the container. In the illustrated embodiment, the transfer function is facilitated by a tandem conveyor 538 to which the grippers 204 are attached in series.

IV.B. The vessel holder 48 has been described above in connection with other embodiments and is configured to seat on the open end 82 of the vessel 80. The seat defined by the container port 92 has been described above in connection with other embodiments, wherein the container support is any one of the container support 48 and the first container, in this case the containers 80. It is configured to be sealed communication between the internal space of the. The reactant feeder 144 has been described above in connection with other embodiments and is operatively connected to introduce at least one gaseous reactant within the first vessel 80 through the vessel holder 48. have. The plasma generator defined by the electrodes 108 and 160 has been described above in connection with other embodiments, the first being under conditions effective to form a reaction product of the reactant on the inner surface of the first vessel. And to form a plasma in the vessel.

IV.B. Other means, such as introducing reactant gas, carrier gas, or expensive gas, such as compressed nitrogen or air, within the vessel discharge device 534 or the seated vessel 80 may be provided from the vessel holder 48. 1 may be used to detach the container 80.

IV.B. The grippers are configured to discharge the first vessel by axially transferring the first vessel 80 from the vessel holder 48 and then discharging suction between the gripper 48 and the vessel end 84. It is.

IV.B. 15 and 16 also illustrate a method of PECVD processing of a first vessel comprising some steps. A first container 80 is provided having an open end 82, a closed end 84, and an inner surface 88. At least a first gripper 204 is provided that is configured to selectively support and release the closed end 84 of the first vessel 80. The closed end 84 of the first vessel 80 is gripped using the first gripper 204, whereby it is conveyed to the vicinity of the vessel holder 48, which is configured to seat at the open end of the first vessel. . In the embodiment of FIG. 16, two vessel supports 48 are provided, allowing the vessels 80 to advance and settle on the vessel supports 48 two at a time to double the effective production rate. Let's do it. The first gripper 204 then advances the first vessel 80 axially and seats the open end 82 on the vessel holder 48, such that the vessel holder 48 and the first portion are secured. Sealed communication is used between the interior of the container. Next, at least one gas reactant is optionally introduced into the first vessel through the vessel holder, as described for the previous embodiments.

IV.B. Continuing, optionally, plasma is formed in the first vessel under conditions effective to form a reaction product of the reactant on the inner surface of the first vessel, as described for the previous embodiments. The first vessel is detached from the vessel holder, as described for the previous embodiments. As described for the previous embodiments, the first gripper or another gripper is optionally used to transfer the first vessel in the axial direction from the vessel holder. Thereafter, the first vessel is optionally released from the gripper used to axially transport it from the vessel holder, as described for the previous embodiments.

IV.B. Other optional steps that may be performed in accordance with the method include a reaction vessel different from the first vessel, providing a reaction vessel having an open end and an interior space, seating the open end of the reaction vessel on a vessel support. And establishing a sealed communication between the vessel holder and the inner space of the reaction vessel. PECVD reactant passages may be provided in the interior space. Plasma may be generated in the interior space of the reaction vessel under conditions effective to remove at least a portion of the deposit of the PECVD reaction product from the reactant water. These reaction conditions have been described in connection with the examples described above. Thereafter, the reaction vessel is detached from the vessel holder and transferred from the vessel holder.

IV.B. Other optional steps that may be performed in accordance with any embodiment of the method include the following steps:

Providing at least a second gripper;

Operatively connecting at least first and second grippers to a tandem conveyor;

Providing a second container having an open end, a closed end, and an inner surface;

Providing a gripper configured to selectively support and release the closed end of the second container;

Using the gripper to hold the closed end of the second container;

Using the gripper to transfer the second vessel to a vicinity of a vessel holder configured to seat at the open end of the second vessel;

Using the gripper, advancing the second vessel axially and seating its open end on the vessel holder to achieve sealed communication between the vessel holder and the interior of the second vessel;

Introducing at least one gaseous reactant into the second vessel through the vessel holder;

Forming a plasma in the second vessel under conditions effective to form a reaction product of a reactant on the inner surface of the second vessel;

Detaching the second vessel from the vessel holder; And

Axially transferring the second vessel from the vessel holder using the second gripper or another gripper; And

Discharging said second vessel from said gripper used for axially conveying from said vessel holder.

IV.B. 16 is an example of using a suction cup type device holding the end of a sample collection tube (in this example) that can move through a production line / system. The specific example shown here is one possible step of the coating / treatment (of many possible steps as described above and below). The tube can move to a coating step / area and the tube can be lowered into the vessel holder and (in this example) a cylindrical electrode. The vessel holder, sample collection tube and suction cup can then move together to the next stage where the electrode is powered and treatment / coating takes place. Any of the above types of electrodes can be used in this example.

IV.B. Thus, FIGS. 15 and 16 employ a vessel transporter, generally indicated at 202, to reciprocate the vessel 80 to the coating station 28 in a coating station 28 similar to FIG. 13. The container transporter 202 may be provided with a grip 204, which may be a suction cup in the transporter 202 shown. In addition, an adhesive pad, an active vacuum source (using a pump that draws air out of the grip, to actively create a vacuum) or other means may be employed as the grip. The vessel transporter 202 can be used, for example, to lower the vessel 80 to a seated position in a vessel port 92 that places the vessel 80 for coating. The vessel transporter 202 may also be used to lift the vessel 80 from the vessel port 92 after processing at the station 28 may be completed. The vessel transporter 202 may also be used to seat the vessel 80 before the vessel 80 and the vessel transporter 48 are advanced together to the station. The vessel transporter may also be used to direct the vessel 80 against the sheet on the vessel port 92. Also, although FIG. 15 can be oriented to show the vessel 80 rising vertically from above, the vessel transporter 202 is below the vessel 80 and has an inverted orientation that supports it from below. May be considered or inverted orientation.

IV.B. 16 not only transfers the containers 80 horizontally from one station to the next station but also (or instead) transfers the containers 80 such as suction cup 204 to a station such as 28 or An embodiment of a method of vertically delivering away from this is shown. The containers 80 may be raised and transported in any orientation. Thus, 16 presents a method of PECVD processing of a first vessel 80 comprising some steps.

IV.B. In the embodiment of FIG. 13, the external electrode 160 may be generally cylindrical with open ends and may be stationary. The container 80 may be advanced through the external electrode 160 until the opening 82 is seated on the container port 96. In this embodiment, the probe 108 is optionally permanently molded or otherwise a gas input port, as opposed to a wiping seal that allows relative movement between the port 104 and the probe 108. 104 can be fixed.

IV.B. 14 shows another alternative for coupling electrical energy to a plasma of 50 Hz to 1 GHz. It may consist of a coil that can be lowered into position or a vessel support that can be raised to position (using the device). The coiled electrodes are called inductive coupling devices and can impart a magnetic component into the interior of the device from which the plasma can be generated.

IV.B. Probe 108 may be used as discussed in FIGS. 2 and 13. The vessel holder or other sides of the vessel holder 48 covered above can remain the same.

IV.B. For example, as shown in FIG. 49, a reaction vessel 532 different from the first vessel 80 may be provided having an open end 540 and an interior space defined by the interior surface 542. Can be. Like the vessels 80, the reaction vessel 532 has an open end 540 on the vessel holder 48 and seals between the vessel holder 48 and the interior space 542 of the reaction vessel. There may be established communication.

IV.B. FIG. 49 illustrates a mechanism for delivering the processed vessel 80 and the cleaning reactor 532 of the vessel inspection apparatus to the PECVD coating apparatus. In this embodiment, the inner electrode 108 can optionally be cleaned without removing it from the vessel holder 48.

IV.B. FIG. 49 illustrates that the reaction vessel may be located within the interior space 542 of the reaction vessel 532 when seated on the vessel holder 48 instead of the vessel 80 provided for coating as described above. It shows that the PECVD reactant channel 108 described above is located. FIG. 49 shows the reactant channel 108 in this configuration, although the channel 108 has an outer portion as well as an inner distal end. This is suitable for this purpose and satisfies this claim if the reactant channel 108 extends at least partially into the vessel 80 or 532.

IV.B. As shown, the mechanism of 49 is usable with at least the embodiments of FIGS. 1 and 15-16, for example. In addition, the cleaning reactor 532 may be provided as a simple vessel to be seated and transported in a vessel support such as 48 in another embodiment. In this configuration, the cleaning reactor 532 is at least of FIGS. 1-3, 8, 9, 12-15, 18, 19, 21, 22, 26-28, 33-35, 37-48 and 52-54. Can be used with the device.

IV.B. The plasma generator defined by the electrodes 108 and 160 generates a plasma in the interior space of the reaction vessel 532 under conditions effective to remove at least a portion of the deposit of a PECVD reaction product from the reactant channel 108. It can be configured to form. The internal electrode and gas source 108 may be a conductive tube, for example a metallic tube, and the reaction vessel 532 may be with other materials that can withstand more heat than ceramic, quartz, glass or thermoplastic vessels. It is contemplated that it may be made of any suitable, preferably heat-resistant material as such. In addition, the material of the reaction vessel 532 may preferably be a plasma that is chemical or resistant to the conditions used in the reaction vessel to remove deposits of reaction products. Optionally, the reaction vessel 532 may be made of an electrically conductive material and itself acts as a special-purpose external electrode for the purpose of removing deposits from the reactant channel 108. As another alternative, the reaction vessel 532 may be comprised of a cap seated on the outer electrode 160, in which case the outer electrode 160 is preferably seated on the vessel holder 48. This will define a closed cleaning reaction chamber.

IV.B. Reaction conditions effective to remove at least a portion of the deposit of the PECVD reaction product from the reactant channel 108 include the introduction of a substantial portion of the oxidizing reactant, such as oxygen or ozone (either independently or by a plasma device), coatings. Higher power levels than those used for deposition, longer cycle times than those used for deposition of coatings, or other means known to remove undesired types of deposits found on the reaction channel 108. Is considered. For another example, mechanical milling can also be used to remove unwanted deposits. Alternatively, solvents or other agents can forcibly remove obstructions through the reactant channel 108. These conditions may be more severe than the containers 80 to be coated can withstand because the reaction vessel 532 need not be suitable for normal use of the vessel 80. However, optionally, vessel 80 may be used as the reaction vessel, and if the deposit removal conditions are too severe, vessel 80 employed as the reaction vessel may be discarded in other embodiments.

V. PECVD methods to fabricate containers

V.1 Precursors for PECVD Coatings

Precursors for PECVD coatings of the present invention are broadly defined as organometallic precursors. Organic silicon precursors encompass compounds of Group III and / or Group IV metal elements of the periodic table having organic residues, such as hydrocarbon, aminocarbon or oxycarbon residues, for all purposes herein. Is defined. Organometallic compounds defined as shown include any precursor having organic moieties bonded directly to silicon or other Group III / IV metal atoms, or optionally through oxygen or nitrogen atoms. Corresponding elements of group III of the periodic table are boron, aluminum, gallium, indium, thallium, scandium, yttrium and lanthanum, with aluminum and boron being preferred. The corresponding elements of group IV of the periodic table are silicon, germanium, tin, lead, titanium, zirconium, hafnium and thorium, with silicon and tin being preferred. In addition, other volatile organic compounds may also be considered. However, organosilicon compounds are preferred for carrying out the present invention.

An "organosilicon precursor" is preferably an organosilicon precursor, broadly defined as a compound having at least one of the following linkages throughout:

or

The first structure directly above is a tetravalent silicon atom connected to one oxygen atom and an organic carbon atom (the organic carbon atom being a carbon atom bonded to at least one oxygen atom). The second structure directly above is a tetravalent silicon atom linked to one —NH— bond and an organic carbon atom (the organic carbon atom is a carbon atom bonded to at least one oxygen atom). Preferably, the organosilicon precursors are linear siloxanes, monocyclic siloxanes, polycyclic siloxanes, polysilsesquioxanes, linear silazanes, monocyclic silazanes, polycyclic silazanes, polysilsesquiazanes and Selected from the group consisting of a combination of two or more of these precursors. Also, although not the two formulas just above, alkyl trimethoxysilane is considered as a precursor.

When an oxygen-containing precursor (eg, siloxane) is used, a representative expected empirical formula obtainable from PECVD under conditions that form a hydrophobic or lubricity coating is Si _w O _x C _y H _z , where w is 1, where x is about 0.5 to about 1, y is about 2 to about 3, and z is 6 to 9, while a representative expected experimental composition obtainable from PECVD under the conditions of forming a barrier coating is SiO _x , Wherein x is from about 1.5 to about 2.9. If a nitrogen-containing precursor (eg silazane) is used, the expected composition is Si _{w *} N _{x *} C _{y *} H _{z *} . That is, in Si _w O _x C _y H _z according to the invention, oxygen (O) is replaced with nitrogen (N) and the indices are set to a higher valence of N compared to oxygen O (3 instead of 2) . The latter will generally follow the ratio of w, x, y and z to the corresponding aza counterparts in the siloxane. In one particular aspect of the invention, Si _{w *} N _{x *} C _{y *} H _{z *} is defined as w *, y * and z * as in the siloxane counterparts, but there is an optional variation in the number of hydrogens. have.

One type of precursor starting material having the empirical formula is a linear siloxane, for example a material having the formula:

Each R is independently selected from alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkane and the like, n is 1, 2, 3, 4, or It is more than that, Preferably it is two or more. Some examples of linear siloxanes considered

Hexamethyldisiloxane (HMDSO),

Octamethyltrisiloxane,

Decamethyltetrasiloxane,

Dodecamethylpentasiloxane,

Or combinations of two or more thereof. In addition, similar silazanes in which -NH- is replaced by an oxygen atom are useful for making similar coatings. Some examples of linear silazanes contemplated are octamethyltrisilazane, decamethyltetrasilazane or combinations of two or more thereof.

V.C. Another type of precursor starting material is a linear siloxane, for example a material having the following structure:

Wherein R is defined as a linear structure and “a” is 3 to about 10 or similar monocyclic silazanes. Some examples of hetero- and unsubstituted monocyclic siloxanes and silazanes contemplated 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, -trifluoroprop) cyclosiloxane,

The following cycloorganosilazanes are also contemplated,

Octamethylcyclotetrasilazane,

1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane hexamethylcyclotrisilazane,

Octamethylcyclotetrasilazane,

Decamethylcyclopentasilazane,

Dodecamethylcyclohexasilazane or any combination of two or more thereof

Another type of VC precursor starting material is polycyclic siloxane, for example, a material having one of the following structural formulas:

Wherein Y may be oxygen or nitrogen, E is silicon, Z is a hydrogen atom or an alkyl such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkane and the like Phosphorus is an organic substituent. When each Y is oxygen, the respective structures going from left to right are silatran, silquasilatran and silproatran. When Y is nitrogen, the respective structures are azasilatran, azasilquacyatran and azaylproatran.

Another type of VC polycyclic siloxane precursor starting material is the polysilsesquioxane of the empirical formula and the following structural formula of RSiO _1.5 :

Each R is a hydrogen atom or an organic substituent that is alkyl, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkane and the like. Two commercially available materials of this kind are SST-eM01 poly (methylsilsesquioxane), wherein each R is methyl, and SST-3MH1.1 poly (methyl, 90% of the R groups are methyl and 10% are hydrogen atoms. Hydridosilsesquioxane). This material can be used, for example, in a 10% solution of tetrahydrofuran. Also contemplated are combinations of two or more of these. Other examples of precursors contemplated are SST-eM01 poly (M) which may be methylsilatran, methylazasilatran, CAS a 2288-13-3, wherein each Y is oxygen and Z is methyl, each R may be optionally methyl Methylsilsesquioxane), SST-3MH1.1 poly (methyl-hydridosilsesquioxane), wherein 90% of the R groups are methyl and 10% are hydrogen atoms, or a combination of two or more thereof.

V.C. In addition, similar polysilsesquiazanes in which -NH- is substituted with an oxygen atom are useful for making similar coatings. Examples of polysilsesquiazanes contemplated 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 )to be. Also contemplated are combinations of two or more of these.

 V.C. One precursor specifically contemplated for the lubricity coating according to the invention is a monocyclic siloxane which is for example octamethylcyclotetrasiloxane.

One precursor specifically contemplated for the hydrophobic coating according to the invention is a monocyclic siloxane which is for example octamethylcyclotetrasiloxane.

One precursor specially contemplated for the barrier coating according to the invention is linear siloxane, for example HMDSO.

V.C. In any of the coating methods according to the invention, the applying step can optionally be carried out by evaporating the precursor and providing it near the substrate. For example, OMCTS evaporates primarily by heating it to about 50 ° C. before applying it to a PECVD apparatus.

V.2 Common PECVD Methods

In the context of the present invention, the following PECVD method is generally applied, comprising the following steps:

(a) providing a gaseous reactant comprising a precursor, preferably an organosilicon precursor, and optionally O ₂ as defined herein near the substrate surface; And

(b) generating a plasma from the gaseous reactant to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD).

In the method, the coating characteristics are advantageously set by one or more of the following conditions: plasma characteristics, pressure at which the plasma is applied, power source applied to generate the plasma, presence and relative amount of O ₂ in the gas reactant, plasma volume and Organosilicon precursors. Preferably, the coating properties are set by the presence and relative amount of O ₂ in the gas reactant and / or the power source applied to generate the plasma.

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

In another preferred aspect, the plasma is produced at reduced pressure (relative to ambient or atmospheric pressure). Preferably, the reduced pressure is less than 300 mTorr, more preferably less than 200 mTorr, even more preferably less than 100 mTorr.

Preferably, the PECVD is carried out by applying a gas reactant comprising a precursor together with electrodes powered at the microwave or radio frequency and preferably at radio frequency. Further, preferred radio frequencies for carrying out embodiments of the present invention will be referred to as " RF frequencies. &Quot; Typical radio frequency ranges for carrying out the invention are from 10 kHz to less than 300 MHz, more preferably from 1 to 50 MHz, even more preferably from 10 to 15 MHz. The frequency of 13.56 MHz is most preferred, which is a government approved frequency for performing PECVD operations.

There are several advantages of using an RF power source for microwave sources: The heating of the substrate / vessel is lower because the RF operates a lower power source. Since the center of the invention is to give a plasma coating on plastic substrates, lower processing temperatures are desirable to prevent melting / distortion of the substrate. To avoid overheating of the substrate when using microwave PECVD, microwave PECVD is applied to short bursts by pulsed power. Power pulsing increases the cycle time for the coating, which is undesirable in the present invention. In addition, higher microwave frequencies may cause offgassing of volatiles such as residual moisture, oligomers and other materials in the plastic substrate. Such degassing can interfere with the PECVD coating. A major concern in using microwaves for PECVD is that the coating is peeled off the substrate. Peeling occurs because microwaves change the surface of the substrate before depositing the coating layer. In order to reduce the likelihood of delamination, interfacial coating layers for microwave PECVD have been developed to achieve a good bond between the coating and the substrate. In RF PECVD, an interface coating layer without the risk of peeling is not required. Finally, the lubricity and hydrophobic coatings according to the invention are advantageously applied using lower power. RF power supplies operate at lower power supplies and provide better control over PECVD processes than microwave power. Nevertheless, although not preferred, microwave power supplies are available under appropriate process conditions.

In addition, for all the PECVD methods described herein, there is a specific correlation between the power source (watts) used to generate the plasma and the volume of lumens from which the plasma is generated. Typically, the lumen is the lumen of the container coated according to the invention. The RF power source must be scaled to the volume of the vessel if the same electrode system is employed. Once all other parameters of the PECVD coating method, except for the composition of the gaseous reactants, for example the ratio of precursor to O ₂ , and the power source, are established, they are typically used when the shape of the vessel is maintained and its volume changes only. Does not change In this case, the power source will be directly proportional to the volume. Thus, starting from the power-to-volume ratios provided in this description, it is easy to find a power source that must be applied to achieve the same or similar coating in containers of the same shape but different sizes. The effect of the container shape on the applied power source is shown as the results of the embodiments for the tubes as compared to the embodiment for the syringe barrels.

For any of the coatings of the present invention, a plasma is generated using electrodes powered with sufficient power to form a coating on the substrate surface. For lubricating coatings or hydrophobic coatings in the method according to one embodiment of the invention, the plasma is preferably (i) 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, for example 8 W powered electrodes and / or (ii) the ratio of power to plasma volume is 10 W / ml, preferably Is produced using electrodes that are between 5 W / ml and 0.1 W / ml, more preferably between 4 W / ml and 0.1 W / ml and most preferably between 2 W / ml and 0.2 W / ml. For barrier coatings or SiOx coatings, the plasma is preferably (i) 8 to 500 W, preferably 20 to 400 W, more preferably 35 to 350 W, even more preferably 44 to 300 W, most Preferably using 44-70 W powered electrodes and / or (ii) a ratio of power to plasma volume of at least 5 W / ml, preferably 6 W / ml to 150 W / ml, more preferably It is produced using electrodes that are 7 W / ml to 100 W / ml, most preferably 7 W / ml to 20 W / ml.

In addition, the vessel shape may affect the choice of gas inlet used for PECVD coating. In certain aspects, the syringe may be coated with an open tube inlet, and the tube may be coated with a gas inlet having small holes extending into the tube.

In addition, the power source (watts) used for PECVD affects the coating properties. Typically, increasing the power source will increase the barrier properties of the coating and decreasing the power source will increase the lubricity and hydrophobicity of the coating. For example, for a coating on the inner wall of a syringe barrel having a volume of about 3 ml, a power of less than 30 W leads to a coating that is overwhelmingly barrier coating, while a power of more than 30 W is overwhelmingly a lubricant coating. Will lead to a coating (see Examples).

Another parameter that determines the coatability is the ratio of O ₂ (or other oxidant) to the precursor (eg organosilicon precursor) in the gas reactant used to generate the plasma. Typically, increasing the O ₂ content in the gaseous reactants increases the barrier properties of the coating and decreasing the O ₂ content increases the lubricity and hydrophobicity of the coating. Therefore, the PECVD coating method of the present invention can be used to set the lubricity, the hydrophobicity of the coating and the barrier of the coating produced by the method.

If a lubricity coating is desired, O ₂ is preferably in the volume-volume ratio for the gas reactant, preferably 0: 1 to 5: 1, more preferably 0: 1 to 1: 1, even more preferably 0: 1. To 0.5: 1, or even more preferably 0: 1 to 0.1: 1. Most advantageously, essentially no oxygen is present in the gaseous reactants. Thus, the gaseous reactant comprises less than 1% by volume of O ₂ , in particular less than 0.5% by volume of O ₂ , most preferably free of O ₂ . The same applies to hydrophobic coatings.

Alternatively, if a barrier or SiO _x coating is desired, O ₂ is preferably compared to the silicon-containing precursor, preferably with a volume: volume ratio of 1: 1 to 100: 1, preferably 5: 1 for the gas reactant. To 30: 1, more preferably 10: 1 to 20: 1, more preferably 15: 1.

V.A. SiO with plasma substantially free of hollow cathode plasma _x  PECVD to apply barrier coatings

A VA specific example is a method of applying a barrier coating of SiO _x as defined herein (unless otherwise specified) as a coating comprising silicon, oxygen and optionally other elements, wherein silicon atoms in X, the ratio of oxygen to these, is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2. These other definitions of _x apply to the use of the term SiO _x herein. The barrier coating is applied to the interior of a container, such as a sample collection tube, syringe barrel or other type of container. The method includes some steps.

V.A. For example, a vessel wall is provided as a reaction mixture comprising an organosilicon compound gas, optionally an oxidizing gas and optionally a plasma forming gas comprising a hydrocarbon gas.

VA plasma is formed in the reaction mixture substantially free of cathode hollow plasma. The vessel wall is in contact with the reaction mixture and a coating of SiO _x is deposited on at least a portion of the vessel wall.

In certain embodiments, the creation of a uniform plasma throughout the portion of the container being coated is desirable because it can be seen that in certain instances it produces a SiO _x coating that provides a better barrier to oxygen. Uniform plasma is a regular that does not include a substantial amount of hollow cathode plasma (which is represented by a higher intensity local area that has a higher emission intensity than regular plasma and impedes the more uniform intensity of the regular plasma). Means plasma.

V.A. The hollow cathode effect is created by a pair of conductive surfaces facing each other with the same cathode potential for a common cathode. If spacing occurs (depending on pressure and gas type) to overlap the space charge sheaths, the electrons oscillate between the reflection potentials of the opposite wall sheaths as the electrons are accelerated by the potential gradient across the sheath region. It starts hitting, causing a lot of collisions. The electrons are trapped in the space charge sheath overlap leading to very high ionization and high ion density plasmas. This phenomenon is described as the hollow cathode effect. Those skilled in the art can vary processing conditions such as power levels and supply rates or pressures of gases to form a uniform plasma throughout or to form plasma comprising varying degrees of hollow cathode plasma.

V.A. For example, in another method, using the apparatus of FIG. 12 described above, microwave energy can be used to generate a plasma in a PECVD process. However, the processing conditions will be different as the microwave energy applied to the thermoplastic container excites (vibrates) the water molecules. Because there is a small amount of water in all plastic materials, the microwaves will heat the plastic. As the plastic heats up, the large motive force generated by the vacuum inside the device against the atmospheric pressure outside the device freely collects or easily desorbs the materials on the inner surface 88 where they become volatile or easily bonded to the surface. will be. The easily bonded materials will then form an interface that can prevent subsequent coatings (deposited from the plasma) from adhering to the plastic inner surface 88 of the device.

VA As one way of preventing this coating prevention effect from occurring, the coating can be deposited at a very low power source (5-20 watts at 2.45 GHz in the above example) to create a cap to which subsequent coatings can be attached. This leads to a two-step coating process (and two coating layers). In this example, the initial gas flow rates (for the capping layer) may vary with 2 sccm (“standard square centimeters per minute”) HMDSO and 20 sccm oxygen with a process power of 5-20 watts for approximately 2-10 seconds. The gases can then be adjusted to the flow rates in the above example and the power supply level is increased to, for example, 35 to 50 W, where x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2 SiO _x coatings may be deposited. Note that in certain embodiments the capping layer may provide little or no functionality except that the materials do not migrate to the vessel inner surface 88 during the higher power SiO _x coating deposition. do it. Also note that the lower frequencies do not excite (vibrate) molecular species, so that the movement of easily desorbed materials in the device walls is usually not a problem at lower frequencies.

V.A. As another method of preventing the above-described coating prevention effect, the container 80 may be dried to remove moisture that has penetrated before applying microwave energy. Dehydration or drying of the vessel 80 may be performed by heating the vessel 80, for example using an electric heater or forced air heating. In addition, dehydration or drying of the vessel 80 may be performed by exposing a gas in contact with the interior of the vessel 80 or the interior of the vessel 80 to a desiccant. In addition, other means of drying the vessel, such as vacuum drying, may also be used. Such means may be performed in one or more stations or devices shown or by a separate station or device.

V.A. In addition, the coating prevention effect described above may be solved by the selection or treatment of the resin in which the containers 80 are molded in order to minimize the moisture content of the resin.

V.B. PECVD to coat the limited opening of the vessel (syringe capillary)

V.B. 26 and 27 show a method for coating the inner surface 292 of the restricted opening 294 of the generally tubular container 250 that is treated, for example, by the limited chemical opening 294 of the syringe barrel 250 by PECVD. And a device generally represented by 290. The process described above is modified by connecting the restricted opening 294 to the processing vessel 296 and optionally by applying certain other modifications.

V.B. The generally tubular vessel 250 to be processed is defined by an outer surface 298, an inner or inner surface 254 defining a lumen, a larger opening 302 with an inner diameter, and an inner surface 292. And a limited opening 294 having an inner diameter smaller than the inner diameter of the larger opening 302.

V.B. The processing vessel 296 has a lumen 304 and a processing vessel opening 306 which is optionally the only opening, although in other embodiments a second opening may be provided that is optionally closed during processing. The processing vessel opening 306 is connected between the lumen 300 of the vessel 250 and the processing vessel lumen through the restricted opening 294 in connection with the restricted opening 294 of the vessel 250 being processed. Communication is established.

V.B. At least a partial vacuum is drawn within the lumen 300 of the vessel 250 to be processed and the lumen 304 of the processing vessel 296. PECVD reactant passes through the first opening 302, through the lumen 300 of the vessel 250 to be subsequently processed, and then through the restricted opening 294, the gas source 144 (see FIG. 7). From the lumen 304 of the processing vessel 296.

V.B. In other embodiments in which a plurality of distal apertures may be provided adjacent the distal end 314 and in communication with the inner passage 310, the PECVD reactant may include the inner passage 310, the proximal end 312, and the distal end. A generally tubular inner electrode 308 having a 314 and a distal opening 316 can be introduced through the larger opening 302 of the vessel 250. The distal end of the electrode 308 may be located adjacent or in the larger opening 302 of the vessel 250 being processed. Reactant gas may be supplied into the lumen 300 of the vessel 250 being silver treated through the distal opening 316 of the electrode 308. The reactant will then flow through the limited opening 294 into the lumen 304 to the extent that the PECVD reactant is provided at a higher pressure than the first vacuum made prior to introducing the PECVD reactant.

V.B. Plasma is generated in the vicinity of the restricted opening 294 under conditions effective to deposit a coating of the PECVD reaction product on the inner surface of the restricted opening 294. In the embodiment shown in FIG. 26, the plasma is generated by providing RF energy to a generally U-shaped outer electrode 160 and grounding the inner electrode 308. In addition, the supply and ground connections to the electrodes may also change, although the vessel 250 and thus the inner electrode 308, which are processed due to this reversal, also pass through the U-shaped outer electrode while the plasma is generated. Even if you can introduce complexity if you move.

V.B. The plasma 318 generated in the vessel 250 during at least some processing may include hollow cathode plasma generated inside the confined opening 294 and / or the processing vessel lumen 304. The generation of hollow cathode plasma 318 may contribute to the ability to successfully apply a barrier coating in the limited opening 294, although the present invention is limited by the accuracy or applicability of this theory of operation. Thus, in one contemplated mode of operation, the process is hollow under conditions that produce a uniform plasma throughout the vessel 250 and the gas inlet and, for example, in part adjacent the confined opening 294. It can be carried out under conditions that produce a cathode plasma.

V.B. The treatment is described herein and shown in the figures, wherein the plasma 318 is preferably operated under conditions that extend substantially throughout the syringe lumen 300 and the restricted opening 294. In addition, the plasma 318 extends substantially through the syringe lumen 300, the restricted opening 294, and the entire lumen 304 of the processing vessel 296. This assumes that a uniform coating of the interior 254 of the vessel 250 is desired. In other embodiments, non-uniform plasma may be desired.

V.B. The plasma 318 has a substantially uniform color throughout the syringe lumen 300 and the restricted opening 294 during processing, preferably the syringe lumen 300, the restricted opening 294 and the It is generally desirable to have a substantially uniform idea throughout the lumen 304 of the processing vessel 296. Preferably, the plasma is substantially stable throughout the syringe lumen 300 and the restricted opening 294, and preferably throughout the lumen 304 of the processing vessel 296.

V.B. The order of the steps in this method is not considered to be decisive.

V.B. In the embodiment of FIGS. 26 and 27, the restricted opening 294 has a first fitting 332 and the processing vessel opening 306 is seated with the first fitting 332 to lumen the processing vessel 296. It has a second fitting 334 adapted to communicate between 304 and the lumen 300 of the vessel 250 being processed.

V.B. In the embodiment of FIGS. 26 and 27, the restricted opening 294 has a first fitting 332 and the processing vessel opening 306 is seated with the first fitting 332 to lumen the processing vessel 296. It has a second fitting 334 adapted to communicate between 304 and the lumen 300 of the vessel 250 being processed. As one of the fittings, in this case the male luer lock fitting 332 generally comprises a locking ring 336 with an annular first joint 338, while in axial contact with the threaded inner surface, The other fitting 334 includes a generally annular second junction 340 facing axially opposite the first junction 338 when the fittings 332 and 334 are engaged.

V.B. In the illustrated embodiment, for example, a seal, which is an O-ring 342, may be located between the first and second fittings 332 and 334. For example, an annular thread can be engaged between the first and second junctions 338 and 340. The female luer fitting 334 also engages the threaded inner surface of the locking ring 336 to secure the O-rings 342 between the first and second fittings 332 and 334. And (344). Optionally, the communication formed between the lumen 300 of the vessel 250 to be processed and the processing vessel 304 lumen through the restricted opening 294 is at least substantially leak free.

V.B. As another option, either or both of the luer lock fittings 332 and 334 can be made of an electrically conductive material such as, for example, stainless steel. This structural material forming or adjacent to the confined openings 294 may contribute to the formation of plasma in the confining openings 294.

V.B. The preferred volume of lumen 304 of the treatment vessel 296 is a small volume that will not divert a significant amount of reactant flow rate from the product surfaces desired to be coated (pressure differential across the limited opening 294). Trade-off between large volumes to support the total reactant gas flow rate through the limited opening 294 prior to filling the lumen 304 sufficiently to reduce the flow rate to an undesirable value. It is considered to be (trade-off). In one embodiment, the contemplated volume of the lumen 304 is less than three times the volume of the lumen 300 of the vessel 250 being processed or two of the volume of the lumen 300 of the vessel 250 being processed. Less than twice or less than the volume of the lumen 300 of the vessel 250 to be processed or less than 50% of the volume of the lumen 300 of the vessel 250 to be processed or the lumen 300 of the vessel 250 to be processed Less than 25% of the volume. Also, other effective relationships of the volumes of each lumen are considered.

V.B. The inventors have found that in certain embodiments the uniformity of the coating can be improved by repositioning the distal end of the electrode 308 with respect to the vessel 250 such that the vessel ( It has been found that it does not penetrate the lumen 300 of 250). For example, although in some embodiments the distal opening 316 may be located adjacent to the constrained opening 294, in other embodiments the distal opening 316 may supply reactant gas. May be located less than 7/8 of the distance from the larger opening 302 of the vessel to be processed to the limited opening 294, optionally less than 3/4 of the distance, and optionally less than half. Further, the distal opening 316 is less than 40%, less than 30%, less than 20%, less than 15% of the distance from the larger opening of the vessel being treated to the restricted opening 294 during the supply of reactant gas. , Less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, or less than 1%.

V.B. Further, the distal end of the electrode 308 is located slightly inside or outside of the larger opening 302 of the vessel 250 that is in communication with the interior of the vessel 250 and that is processed during the supply of the reactant gas. Or at the same height. The positioning of the distal portion 316 relative to the vessel 250 to be processed can be optimized at specific locations and other conditions of the treatment by testing it at various locations. One particular location of the electrode 308 contemplated for processing the syringe barrels 250 penetrates about a quarter inch (about 6 mm) into the vessel lumen 300 on the larger opening 302. Position with distal end 314.

V.B. The inventors are contemplated to function properly as an electrode by placing at least the distal end 314 of the electrode 308 in the container 250, although this is not a requirement. Surprisingly, the plasma 318 generated in the vessel 250 can be more uniform, so that the electrode 308 less penetrates into the lumen 300 unlike previously employed, so that the limited opening 294 Through the treatment vessel lumen 304. Using other arrangements, such as processing a closed end container, the distal end 314 of the electrode 308 is usually located closer to the closed end of the container than this inlet.

V.B. Also, as shown for the example of FIG. 33, the distal end 314 of the electrode 308 extends beyond or beyond the restricted opening 294, for example, the processing vessel lumen. It can be located within 304. Various means may optionally be provided, such as forming the processing vessel 296 to enhance gas flow through the restricted opening 294.

V.B. As another alternative, shown in FIGS. 34 and 35, the composite internal electrode and gas supplier tube 398 is optionally located near distal gas supply openings, such as 400, and located near the larger opening 302. May have an extension electrode 402 extending the distal portion of the distal gas supply openings 400, extending to the distal end adjacent the restricted opening 294 and optionally further extending to the processing vessel 324. have. This structure is considered to facilitate the formation of a plasma in the interior surface 292 adjacent to the restricted opening 294.

V.B. In another contemplated embodiment, as in FIG. 26, the internal electrode 308 moves during the process, for example initially extending to the process vessel lumen 304 and then towards the nearer as the process proceeds. It can be gradually withdrawn. This means is particularly contemplated if the container 250 is long under selected processing conditions and facilitates more uniform treatment of the inner surface 254 due to the movement of the inner electrode. Using such means, processing conditions such as gas supply rate, vacuum discharge rate, electrical energy applied to the external electrode 160, rate of drawing the internal electrode 308 or other factors may be processed in the process. Can be altered as the other parts of the vessel being processed.

V.B. As in other processes described herein, the larger opening of the generally tubular container 250 to be treated may be such that the larger opening 302 of the container 250 to be treated may be the port (of the container support 320). It can be easily positioned on the vessel holder 320 by seating on 322. The inner electrode 308 may then be located in the vessel 250 seated on the vessel holder 320 prior to drawing at least a partial vacuum in the lumen 300 of the vessel 250 being processed. have.

V.B. In another embodiment shown in FIG. 28, as shown in FIG. 26, a first opening 306 fixed to the vessel 250 to be processed and a communication with the vacuum port 330 in the vessel holder 320 are provided. A processing vessel 324 in the form of a canal with a second opening 328 can be provided. In this embodiment, the PECVD process gases flow into the vessel 250, then through the restricted opening 294 into the processing vessel 324, and then back through the vacuum port 330. Can be. Optionally, the vessel 250 may be evacuated through both openings 294 and 302 prior to adding PECVD reactants.

VB also introduces a reaction material from the source 144 through the opening at the rear end 256 of the barrel 250 and draws through the opening at the tip 260 of the barrel. By deriving a vacuum using the circle 98, in this formula x is about 1.5 to about 2.9, or about 1.5 to about 2.6, or about 2, an internal coating of SiO _x , an uncapped with PECVD coating or other type of uncapped A syringe barrel 250 may be provided. For example, the vacuum source 98 may be connected via a second fitting 266 seated on the tip 260 of the syringe barrel 250. Using this means, the reactants can flow in one direction (although the direction is not important, but upwards as shown in FIG. 22), and the feed gas from the gas exhausted in the syringe barrel 250 There is no need to deliver the reactants through the probe to separate it. Also, in other arrangements, the leading and trailing ends 260 and 256 of the syringe barrel 250 may be reversed relative to the coating apparatus. The probe 108 may simply act as an electrode, and in this embodiment may be tubular or solid rods. As before, the separation between the inner surface 254 and the probe 108 may be uniform over at least most of the length of the syringe barrel 250.

V.B. FIG. 22 shows another embodiment where the fitting 266 is independent of the plate electrodes 414 and 416 and is not attached thereto. The fitting 266 may have a luer lock fitting that is adapted to be secured to the corresponding fitting of the syringe barrel 250. This embodiment allows the vacuum channel 418 to move onto the electrode 416 while the vessel holder 420 and the attached vessel 250 move between the electrodes 414 and 416 during the coating step. Yes.

V.B. FIG. 38 shows another embodiment, FIG. 22 shows that the tip 260 of the syringe barrel 250 is open and the syringe barrel 250 is opened by a vacuum chamber 422 seated on the vessel holder 424. Another enclosed embodiment is shown. In one embodiment, the pressures P1 in the syringe barrel 250 and the vacuum chamber 422 are approximately equal, and the vacuum in the vacuum chamber 422 is optionally the tip 260 of the syringe barrel 250. Derived through. When process gases flow into the syringe barrel 250, they are applied to the syringe barrel 250 until a normal composition is provided in the syringe barrel 250 at the time that the electrode 160 receives current to form a coating. It flows through the tip 260 of the). Due to the larger volume of the vacuum chamber 422 relative to the syringe barrel 250 and the position of the counter electrode 426 within the syringe barrel 250, process gases passing through the tip 260 are introduced into the vacuum chamber. It is contemplated that substantially no deposits will be formed on the walls of 422.

V.B. FIG. 39 shows yet another embodiment. FIG. 22 shows an electrode with the backside flange of the syringe barrel 250 fixed to a vessel holder, a pair of plate electrodes designated as a cylindrical electrode or 160 and a vacuum source 98. Another embodiment is shown clamped between assemblies 430. The volume indicated entirely at 432 surrounded by the outside of the syringe barrel 250 is in this embodiment to minimize the interior of the syringe barrel 250 operating the pumping and PECVD processes required to evacuate the volume 432. It is a relatively reduced scale.

V.B. FIG. 40 shows another embodiment, FIGS. 22 and 41 are top views showing another embodiment as an alternative to FIG. 38 in which the ratio of pressure P1 / P2 is maintained at a desired level by providing a pressure balancing valve 434. to be. P1 may be at a lower vacuum, ie higher pressure, than P2 during the PECVD process, so it is believed that waste process gases and by-products will be exhausted through the tip 260 of the syringe barrel 250. In addition, the provision of an individual vacuum chamber channel 436 acting as the vacuum chamber 422 allows for the use of an individual vacuum pump to more quickly produce a larger closed volume 432 of vacuum.

V.B. 41 is a top view of the embodiment of FIG. 40. 40 also shows electrode 160 removed from FIG.

V.C. How to apply a lubricity coating

V.C. Another embodiment is a method of applying a lubricity coating derived from an organosilicon precursor. The term “lubricating coating” or similar term is generally defined as a coating that reduces the frictional resistance of a coated surface against an uncoated surface. If the coated object is a syringe (or syringe part, such as a syringe barrel) or any other item that generally includes a plunger or movable part that is in sliding contact with the coated surface, the frictional resistance is two major aspects. -Has breakout force and plunger force.

The plunger sliding force test is a special test of the sliding friction coefficient of the plunger in a syringe, in which the normal force associated with the sliding friction coefficient generally measured on a flat surface is caused to slide the tube or the tube with the plunger or other sliding component. To explain the fact that it is processed by standardizing the pit between different containers. The parallel force associated primarily with the sliding friction coefficient measured is comparable to the measured plunger sliding force as described herein. Plunger sliding force can be measured, for example, as provided in the ISO 7886-1: 1993 test.

The plunger sliding force test can also be tailored to measure other types of frictional resistance, for example friction holding the stopper in a tube, by appropriate variations on the device and procedure. In one embodiment, the plunger can be replaced by a closure and the withdrawing force to remove or insert the closure can be measured in correspondence with the plunger sliding force.

In addition, instead of the plunger sliding force, the breakout force can be measured. The breakout force is the force required to start a stationary plunger moving within the syringe barrel or the comparable force required to detach and start the seated stop closure. The breakout force is measured by applying force to the plunger starting at zero or a low value and increasing until the plunger starts to move. The breakout force tends to increase with storage of the syringe after the prefilled syringe plunger pushes out the intervening lubricant or attaches to the barrel due to decomposition of the lubricant between the plunger and the barrel. The breakout force is required to overcome “sticktion”, which is a term used in the industry for attachment between the plunger and the barrel that is overcome to spur the plunger out and allow the plunger to start moving. It's power.

V.C. Optionally a sliding configuration such as a stopper in the piston or sample tube in the syringe or insertion or removal of the stopper or in some machines due to some installations that coat all or part of the container with a lubricity coating, such as on surfaces that are in sliding contact with other parts. Facilitate the passage of elements. The container may be made of glass or polyester, for example, polymeric materials such as polyethylene terephthalate (PET), cyclic olefin copolymers (COC), olefins such as polypropylene or other materials. Applying a lubricity coating by PECVD avoids or reduces the need to coat the vessel wall or closure with an organosilicon being sprayed, immersed or applied, or other lubricants typically applied in much larger amounts than those deposited by the PECVD process. Can be.

V.C. In any one of the above embodiments, a plasma, optionally a non-hollow-cathode plasma, may optionally be formed near the substrate.

V.C. In any one of the embodiments V.C., the precursor may optionally be provided in the substantial absence of oxygen. V.C. In any one of the embodiments V.C., the precursor may optionally be provided in the substantially absence of a carrier gas. V.C. In any one of the embodiments V.C., the precursor may optionally be provided in the substantial absence of nitrogen. V.C. In any one of the embodiments V.C., the precursor may optionally be provided at less than 1 Torr absolute pressure.

V.C. In any one of the embodiments, the precursor may optionally be provided near the plasma emission.

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

V.C. The TEM may be performed as follows, for example. Samples can be prepared in two ways for focused ion beam (FIB) cross-section cutting. Samples may be first coated with a thin film of carbon (50-100 nm thick) and then coated with a platinum sputtering layer (50-100 nm thick) using a K575X Emitech coating system, or the samples may be coated with protective sputtering. It can be coated directly with a Pt layer. The coated samples can be placed in a FEI FIB200 FIB system. The platinum additional layer can be FIB deposited by injecting an organometallic gas while scanning a 30 kV gallium ion beam over the region of interest. The region of interest for each sample can be selected to be one half below the length of the syringe barrel. Thin sections measured approximately 15 μm in length (“micrometer”), 2 μm in width and 15 μm in depth can be extracted from the die surface using a proprietary in-situ FIB lift-out technique. The cross sections can be attached to a 200 mesh copper TEM grid using FIB-deposited platinum. One or two windows in each section, measuring about 8 μm wide, can be thinned to electronic transparency using the gallium ion beam of the FEI FIB.

Cross-sectional image analysis of VC prepared samples can be performed using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) or both. All image data can be recorded digitally. For the STEM image, a grid with thin foils can be transferred to a Hitachi HD2300 dedicated STEM. Scanned and transmitted electron images can be obtained with appropriate magnification in atomic number contrast mode (ZC) and transferred electron mode (TE). The following tool settings can be used.

For VC TEM analysis, sample grids can be transferred to Hitachi HF2000 transmission electron microscope. The transmitted electronic images can be obtained with appropriate magnification. Appropriate tool settings used during image acquisition may be those given below.

V.C. In any one of the embodiments VC, the substrate is glass or a polymer, such as a polycarbonate polymer, an olefin polymer, a cyclic olefin copolymer, a polypropylene polymer, a polyester polymer, a polyethylene terephthalate polymer or any of these It may comprise a combination of two or more.

V.C. In any one of the embodiments VC, PECVD optionally comprises an RF frequency as defined above, eg, 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to This may be done by powering a gaseous reactant comprising the precursor using electrodes powered at a frequency of 15 MHz and most preferably 13.56 MHz.

V.C. In any one of the embodiments V.C, the plasma may be generated by energizing a gaseous reactant comprising the precursor using electrodes supplied with sufficient power to form a lubricity coating. Optionally, the plasma is 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, in particular 8 It is produced by energizing a gaseous reactant comprising the precursor using powered electrodes of W. The ratio of power to plasma volume may be 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. These power levels are suitable for applying lubricating coatings to syringes and sample tubes and containers of similar shape having a void volume of 1 to 3 mL in which PECVD plasma is generated. It is contemplated that the power applied for larger or smaller objects will increase or decrease as the process scales with respect to the size of the substrate.

V.C. Optionally, one product contemplated as a product may be a syringe with a barrel treated by the method of V.C., any one or more of the embodiments.

V.D. Liquid-coatings

VD Other examples of blocking or other types of suitable coatings that may be used in conjunction with PECVD applied coatings or other PECVD treatments as disclosed herein may be direct or Si _w O _x C _y H _z , SiO _x , lubricity coatings or both. Liquid barrier, lubricant, surface energy tailoring, or other type of coating 90 applied to the interior surface of the container, prepared by using one or more intervening PECVD-applied coatings.

V.D. Optionally, a suitable liquid barrier or other type of coatings 90 may, for example, apply a liquid monomer or other polymerizable or curable material to the interior surface of the vessel 80 and cure the liquid monomer, It may be applied by polymerization or crosslinking to form a solid polymer. In addition, a suitable liquid barrier or other type of coatings 90 may be provided by applying a solvent-dispersed polymer to the surface 88 and removing the solvent.

V.D. Any of the above methods may include forming a coating 90 on the interior 88 of the vessel 80 via the vessel port 92 at a processing station or device 28. One example of this is, for example, applying a liquid coating of a curable monomer, prepolymer, or polymer dispersion to the inner surface 88 of the vessel 80 and curing it to bring the contents of the vessel 80 to its inner surface. Forming a physical film that physically separates from (88). The prior art describes polymer coating techniques as suitable for coating plastic blood collection tubes. For example, acrylic and polyvinylidene chloride (PVdC) coating materials and coating methods described in US Pat. No. 6,165,566, which are incorporated herein by reference, may optionally be used.

V.D. In addition, any of the above methods may include forming a coating on the outer wall of the vessel 80. Optionally, the coating may be a barrier coating, optionally an oxygen barrier coating or optionally a moisture barrier coating. One example of a suitable coating is polyvinylidene chloride, which functions as both a moisture barrier and an oxygen barrier. Optionally, the barrier coating may be applied as an aqueous coating. Optionally, the coating can be immersed in the container and sprayed onto the container or applied by other means. Also contemplated are containers with the outer barrier coating described above.

VI. Container inspection

VI. One station or device shown in FIG. 1 is designed to measure air pressure loss or mass flow rate or volume flow rate through the vessel wall or to inspect the interior surface of the vessel 80 for defects, such as degassing the vessel wall. A processing station or apparatus 30 that can be configured. The device 30 is in the illustrated embodiment, because a barrier or other type of coating is applied by the station or device 28 before it reaches the station or device 30, so that the device 30 can be applied to the device 30. It may operate similarly to device 26, except that the vessel may be required to pass the inspection due to the better performance provided (less leakage or penetration under given process conditions). In one embodiment, the inspection of the coated vessel 80 may be comparable to the inspection of the same vessel 80 at the device or station 26. Less leakage or penetration in the station or device 30 is to function to a minimum.

VI. The identity of the vessel 80, measured at two different stations or by two different apparatuses, is a bar code, other marks or radio frequency identification (RFID) apparatus for each of the vessel supports 38 to 68. Or by identifying individual identification features such as markers and matching the identity of the containers measured at two or more different points around the endless conveyor shown in FIG. Since the vessel holders can be reused, immediately after a new vessel 80 is seated on the vessel holder 40, they store other data because they reach the location of the vessel holder 40 in the computer database or in FIG. Registered in the structure and can be removed from the data register at or near the end of the process, for example after they have reached or reached the position of the vessel holder 66 of FIG. Is removed by the transfer mechanism 74.

VI. The processing station or device 32 may be configured, for example, to inspect a container with a barrier or other type of coating applied to the container to see if it is defective. In the illustrated embodiment, the station or device 32 measures the optical source transmission of the coating as a measure of the thickness of the coating. If properly applied, the barrier or other type of coating may make the container 80 more transparent because it provides a more uniform surface even if additional material is applied.

VI. In addition, energy waves bounced into the interior of the coating 90 (interfering with the atmosphere within the interior of the vessel 154) and energy waves bounced the inner surface 88 of the vessel 80 (the coating 90 Other measures of measuring the thickness of the coating are also contemplated, such as using interference measurements to measure the difference in travel distance between outside). As is known, the difference in travel distance can be measured directly by measuring the arrival time of each wave with high precision for test conditions or indirectly by measuring what wavelength of incident energy is reinforced or cancelled. Can be.

VI. Another measurement technique that can be performed to check the integrity of the coating is ellipsometer measurement on the device. In this case, a polarizing laser beam can be projected from inside or outside of the vessel 80. In the case of a laser beam projected from the inside, the laser beam can be directed diagonally to the surface and then the transmitted or reflected beam can be measured. The change in beam polarization can be measured. Since coating or treatment on the device surface affects (changes) the polarization of the laser beam, the change in polarization may be the desired result. The change in polarization is a direct result of the presence of a coating or treatment on the surface and the amount of change is related to the amount of treatment or coating.

VI. If a polarized beam is projected from the outside of the device, the detector may be located inside to measure the transmitted component (and polarization as measured above) of the beam. In addition, a detector may be placed outside the device at a position that may correspond to the reflection point of the beam from the interface between the treatment / coating. The polarization change (s) can then be measured as described above.

VI. In addition to measuring optical properties and / or leak rates as described above, other probes and / or devices can be inserted into the interior of the device and measurements can be made using the detection device. This apparatus is not limited by the measurement technique or method. Other test methods may be utilized that employ mechanical, electrical or magnetic properties or any other physical, optical or chemical property.

VI. During the plasma process setup, it can optionally be used to record the plasma emission spectrum (wavelength and intensity profile) corresponding to the unique chemical symbol of the plasma environment using an optical detection system. This characteristic emission spectrum provides confirmation that the coating has been applied and processed. The system can also provide real-time precision measurements and data preservation tools for each component being processed.

VI. Any of the above methods may include inspecting the interior surface 88 of the vessel 80 for defects at a processing station such as 24, 26, 30, 32 or 34. The inspection inserts the detection probe 172 through the vessel port 92 into the vessel 80 and uses the probe 172 to remove the vessel interior surface 88 or the barrier or other type of coating 90. Inspection can be performed at the stations 24, 32 and 34 by detecting the condition. As shown in FIG. 11, inspection may be performed by radiating energy inwards through the vessel wall 86 and the vessel inner surface 88 and detecting the energy with the probe 172. In addition, inspection may be performed by reflecting radiation from the vessel inner surface 88 and detecting energy using a detector located within the vessel 80. In addition, inspection can be performed by detecting the condition of the container interior surface 88 at numerous closely spaced locations on the container interior surface.

VI. In any of the above methods, if the vessel is first vacuumed and its walls are exposed to the ambient atmosphere, the barrier or other type of coating 90 may cause the pressure in the vessel to be reduced to 20 Performing the inspection step at a sufficient number of positions throughout the vessel inner surface 88 to determine that it is effective to prevent it from increasing above%.

VI. Either of the above methods is 30 seconds or less per container, or 25 seconds or less per container, or 20 seconds or less per container, or 15 seconds or less per container, or 10 seconds or less per container, or 5 seconds or less per container, or container And performing the inspection step within an elapsed time of 4 seconds or less per hour, 3 seconds per container, or 2 seconds per container, or 1 second or less. This illustrates, for example, a device for measuring the effectiveness of a barrier or other type of coated vessel wall or for charge coupled devices, which may include one measurement for the entire vessel 80, as shown in FIG. It may be possible by inspecting a large number or even all of the inspected points being inspected, such as using it as the detector 172 which can be shown or replaced in 6, 10 and 11. The latter step can be used to detect the barrier or other type of coating at numerous closely spaced locations on the vessel inner surface 88 in a very short overall time.

VI. In any embodiment of the method, the multipoint vessel inspection, if necessary, collects data using the charge coupled device 172 while the vessel 80 moves downstream, and the vessel 80 that has just been inspected. Can be made easier by transporting and processing the collected data immediately afterwards. If the defect in the vessel 80 is later identified as being due to data processing, the defective vessel 80 may be moved off line at a point downstream of a detection station such as 34 (FIG. 10).

VI. In any of the above embodiments, the inspecting step is performed when the vessel is first evacuated and its wall 86 is exposed to the ambient atmosphere, the initial vacuum level (ie, pressure versus ambient) within the vessel 80. Initial decrease) to at least 20%, optionally 15%, optionally 10%, optionally 5%, optionally 2% or more of the ambient atmospheric pressure for a life of at least 12 months or at least 18 months or at least 2 years. The inspection step may be performed at a sufficient number of positions throughout the vessel 80 inner surface 88 to determine that it is effective to prevent a reduction.

VI. The initial vacuum level may be a high vacuum, ie, a residual pressure of less than 10 Torr, or a lower vacuum, such as a positive pressure of less than 20 Torr (ie, extra pressure for a full vacuum), or a positive pressure of less than 50 Torr, or less than 100 Torr. , Or less than 150 Torr, or less than 200 Torr, or less than 250 Torr, or less than 300 Torr, or less than 350 Torr, or less than 380 Torr. For example, the initial vacuum level of vacuumed blood collection tubes is in many cases determined by the type of test tube used, and therefore the type and appropriate amount of reagents added to the tube at the time of manufacture. The initial vacuum level is commonly set to draw the correct volume of blood to combine with the reagent fill in the tube.

VI. In any of the above embodiments, the blocking or other type of coating 90 inspecting step may be performed when the container is first vacuumed and its walls are exposed to the ambient atmosphere. Sufficient number of positions throughout the vessel interior surface 88 to determine that pressure within this vessel is effective to prevent an increase in pressure over 15% or above 10% of the ambient atmospheric pressure for at least one year of life. Can be performed in the field.

VI.A. Container handling including precoating and postcoating inspection

VI.A. Yet another embodiment is a container processing method for processing a molded plastic container having an opening and a wall defining an interior surface. The method includes inspecting just before coating to check whether the inner surface of the container has been molded or for defects; Applying a coating to the inner surface of the container after inspecting that the container is molded; And by inspecting the coating for defects.

VI.A. Another embodiment is a container processing method in which a barrier coating is applied to the container after inspecting that the container is molded, and the inner surface of the container is inspected for defects after the barrier coating is applied. .

VI.A. In one embodiment, the station or device 26 (which can function as a station or device 28 for applying a coating) can be used as follows for testing an air pressure vessel. With either or both of the valves 136 and 148 open, the vessel 80 may be evacuated to a very low pressure, optionally less than 1 Torr, to a desired degree, preferably less than 10 Torr. . The first open of either of the valves 136 and 148 is then closed, separating the vacuum interior 154 of the vessel 80 and the pressure gauge 152 from the ambient conditions and the vacuum source 98. Whether due to ingress of gas through the vessel wall or degassing from the material on the wall and / or coating on the vessel wall, a pressure change is then sensed over the measurement time and the vessel (44) on the vessel holder 44. 80) can be used to calculate the rate of inlet gas into the environment. For this purpose, degassing is optionally defined as the gas or water vapor adsorbed or occluded in at least partial vacuum withdrawn from the vessel wall.

VI.A. Another optional variant may be to provide ambient gas at a pressure higher than atmospheric pressure. This can increase the rate of gas delivery through a barrier or other type of layer, thereby providing a measurable difference in less time than a lower ambient pressure is provided. Gas can also be introduced into the vessel 80 at a pressure higher than atmospheric pressure to further increase the rate of delivery through the wall 86 again.

VI.A. Optionally, inspection of the vessel at the station or by the device 26 can be altered by providing a test gas, such as helium, on the upstream side with respect to the substrate in or outside the vessel 80 and detecting it on the downstream side. . In addition, low molecular weight gases such as hydrogen or low cost available gases such as oxygen or nitrogen may be used as test gases.

VI.A. Helium is a test gas that, as it passes through an unsafe barrier or other type of coating or leak seal, can increase leak or penetration detection rates much faster than normal ambient gases such as nitrogen and oxygen in normal air. Is considered. Helium is (1) inert, to some extent not adsorbed by the substrate, (2) not easily ionized, and the molecules are very dense due to the high level of attraction between the electrons and the nucleus, and (3) nitrogen It has a molecular weight of 4 as opposed to (molecular weight 28) and oxygen (molecular weight 32), which makes the molecules more dense and easily passes through the porous substrate or gap, thus allowing high transfer rates through many solid substrates or small gaps. Have Due to these factors, helium will migrate through the barrier with a given permeability much faster than many other gases. In addition, since the atmosphere contains only a very small amount of helium in nature, the additional presence of helium, in particular, is detected outside the vessel 80 to introduce helium into the vessel 80 and to measure leakage and penetration. If so, it may be relatively easy to detect. Helium may be detected by the pressure drop upstream of the substrate or by other means such as spectroscopic analysis of the downstream gas passing through the substrate.

VI.A. An example of atmospheric pressure vessel inspection by measuring oxygen concentration from O ₂ fluorescence detection is as follows.

VI.A. Excitation source (Ocean Optics USB-LS-450 pulse blue LED), fiber assembly (Ocean Optics QBIF6000-VIS-NIR), spectrometer (USB4000-FL fluorescence spectrometer), oxygen sense probe (Ocean Optics FOXY-R) and vacuum source A vacuum supply via a connected adapter (such as the VFT-1000-VIS-275) is used. Vacuum may be applied to remove ambient air, and if the vessel is at a defined pressure, the amount of oxygen leaked or penetrated to refill the vessel from ambient air may be measured using a detection system. Coated tubes replace the uncoated tubes and allow for O ₂ concentration measurements. The coated tube differs from the uncoated sample due to a differential O ₂ surface absorption (SiO _x surface to uncoated PET or glass surface) on the phase coated tube and / or a change in the rate of O ₂ diffusion from the surface. The atmospheric oxygen content will be shown reproducibly. The detection time can be less than 1 second.

VI.A. Such atmospheric methods should not be considered limited to the specific gas detected (helium detection or other gases may be considered) or the specific device or arrangement.

VI.A. In addition, the processing station or device 34 may be configured to inspect for barriers or other types of coatings to determine for defects. 1 and 10, in 1 and 10, the treatment station or apparatus 34 is in turn blocked at the barrier or other type of coating 90 at numerous closely spaced locations. At least a portion or substantially the entire barrier or other optical inspection performed with the intention of scanning or separately measuring the properties of the other type of coating 90. The numerous closely spaced locations are in all cases or on average on at least a portion of the surface, for example, about 1 micron, or about 2 microns, or about 3 microns, or about 4 microns, or about 5 microns, or It may be spaced about 6 microns or about 7 microns, so that some or all small portions of the barrier or other type of coating 90 are measured separately. In one embodiment, scanning each small area of the coating separately finds individual pinholes or other defects and localizes the pinhole defects from more common defects, such as a large area with a too thin or porous coating. It may be useful to distinguish effects.

VI.A. Inspection by the station or device 34 may include radiation or light source 170 or any other suitable radio frequency, microwave, infrared, visible, ultraviolet, x-ray, or electron beam source, for example, container port 92. Can be performed by inserting into the vessel 80 and detecting the state of the vessel interior surface, for example the barrier coating 90, and using a detector to detect radiation delivered from the radiation source.

VI.A. The vessel holder system can also be used to test the device. For example, the probe 108 of FIG. 2, with the gas delivery port 110, can be replaced by the light source 170 (FIG. 10). The light source 170 can irradiate the inside of the tube and then measure the transmission or other properties to complete subsequent testing outside of the tube. The light source 170 may extend into the tube in the same manner as the probe 108 is pushed into the puck or vessel holder 62, although vacuum and seals are not necessarily required. The light source 170 may be an optical fiber source, a laser, a point source (such as an LED), or any other radiation source. The source may radiate at one or more frequencies ranging from far infrared (100 nm) to far infrared (100 microns) and all frequencies there between. There is no limitation as to the source that can be used.

VI.A. As a specific example, see FIG. 10. In FIG. 10, the tube or vessel 80 is located within the puck or vessel support 62 and a light source 170 behind the probe 108 has been inserted into the tube. In this case, the light source 170 may be a blue LED source having sufficient intensity received by the detector 172 surrounding the outside of the container 80. The light source 170 may be, for example, a three-dimensional charge-coupled-device (CCD) that includes an array of pixels such as 174 on its inner surface 176. Pixels such as 174 receive and detect illumination that is radiated through a blocking or other type of coating 90 and vessel wall 86. In this embodiment, the detector 172 has a larger inner diameter for the vessel 80 than the separation of the electrode 164 and the vessel 80 of FIG. 2, and the cylinder adjacent the closed end 84 instead of the semicircular top portion. Has a mold top part. The outer detector 172 may have a smaller radial gap from the vessel 80 and a more uniformly sized gap in the upper portion adjacent the closed end 84. This can be done, for example, by providing a center of curvature with respect to the top of the closed end 84 and the detector 172 when the container 80 is sealed. Such a change may provide a more uniform inspection of the curved closed end 84 of the container 80, although any change is considered appropriate.

VI.A. Before lighting the light source, the CCD is measured and the value obtained thereby is stored as background (which can be subtracted from subsequent measurements). Thereafter, the light source 170 is turned on and measured using a CCD. This measurement is then carried out by taking the total light transmission (and compared with the uncoated tube to determine the average coating thickness) and the defect density (take individual photoelectron numbers on each component of the CCD and compare them to the threshold— If the number of optoelectronics is lower then this can be used to calculate that no sufficient light is transmitted). Low light transmission can be the result of no coating at all or coating too thin-this is a defect in the coating on the tube. By measuring the number of adjacent components with a low number of optoelectronics, the defect size can be estimated. By combining the size and number of defects, the quality of the tube can be solved, or other properties can be measured that can be specific to the frequency of radiation from the light source 170.

VI.A. In the embodiment of FIG. 10, energy can be radiated out through the vessel inner surface, such as through the coating 90 and the vessel wall 86, to be detected using a detector 172 located outside the vessel. Can be. Various types of detectors 172 may be used.

VI.A. The incident radiation coming from the light source 170 delivered through the barrier or other type of coating 90 and the vessel wall 80 is relative to the lower angle of incidence (compared to the baseline perpendicular to the vessel wall 80 at a given point). Because it can be larger, pixels such as 174 normalizing through the container wall 86 may be able to receive some of the light that passes through a given portion of the blocking or other type of coating, even though one or more pixels may Will receive more radiation than adjacent pixels, and light passing through more than a given portion of the blocking or other type of coating 90 and vessel wall 80 may be received by a particular pixel, such as 174. will be.

VI.A. In order to detect radiation that penetrates through the blocking or other type of coating 90 and certain portions of the container wall 86, the resolution of the pixels, such as 174, is increased by placing the CCD to increase the resolution of the pixels, such as 174. The array is very close to the vessel wall 86 and closely conforms to its contours. In addition, the resolution can be increased by selecting a smaller or essentially point light source, as shown schematically in FIG. 6, to illuminate the interior of the vessel 80. Also, using smaller pixels will improve the resolution of the array of pixels in the CCD.

VI.A. In FIG. 6, the point light source 132 (laser or LED) is located at the end of the rod or probe. ("Point source" refers to coherent light transmitted by light or laser that emits from a small volume of source resembling a mathematical point, such as can be produced by small LEDs or diffusion tips for optical fiber radiation in all directions. Light emitted by the same small-section beam.) The point light source 132 is stationary or, for example, while blocking or other types of coating 90 and the features of the container wall 80 are measured. It may be movable as it can move on axis. If so, the point light source 132 can be moved up and down inside the device (tube) 80. In a manner similar to that described above, the inner surface 88 of the vessel 80 can be scanned and subsequent measurements can be made by the external detector device 134 to measure the integrity of the coating. The advantage of this approach is that similar focused light sources can be used that are linearly polarized or have a specific orientation.

VI.A. The location of the point light source 132 can be represented exponentially in the pixels as shown at 174 so that the illumination of the detectors can be measured when the detector is perpendicular to a particular portion of the coating 90. . In the embodiment of FIG. 10, a cylindrical detector 172 having a curved end that matches the curve (if any) of the closed end 84 of the container 80 may be used to detect features of the cylindrical container 80. Can be.

VI.A. With reference to FIG. 10, the inspection station or device 24 or 34 may be altered by reversing the positions of the light beam or other radiation source 170 and detector 172 such that light may pass through the vessel wall 86 through the vessel (86). It should be noted that copying from outside to inside. If this means is selected, in one embodiment a uniform source of incident or other radiation may be provided by inserting the container into the opening 182 through the wall 184 of the integrated spherical light source 186. Since an integrated spherical light source will disperse light or radiation from sources 170 outside of the container 80 and inside the integrated circle, light penetrating through respective points of the wall 86 of the container 80. Will be relatively uniform. This tends to reduce the distortion caused by structures with respect to portions of the wall 86 having different shapes.

VI.A. In the embodiment of FIG. 11, the detector 172 may appear to be in close compliance with the blocking or other type of coating 90 or interior surface of the container 80. Since the detector 172 may be on the same side of the vessel wall 86 as the barrier or other type of coating 80, this proximity is in this embodiment such that the detector 172 is preferably blocked. Or a resolution of pixels such as 174, although it may be accurately positioned relative to another type of coating 90 to avoid damaging either of the coating or CCD array by rubbing against one another against the other. Tends to increase. In addition, placing the detector 172 immediately adjacent to the coating 90 may occur after light or other radiation passes through the blocking or other type of coating 90 in the embodiment of FIG. 10. The effect of refraction by the vessel wall 86 can be reduced, such that the detected signal can be differentially refracted depending on the local shape of the vessel 80 and the angle of incidence of light or other radiation.

VI.A. In addition, other barrier or other types of coating inspection techniques and devices may be used. For example, fluorescence measurements can be used to characterize the treatment / coating on the device. Using the same device described in FIGS. 10 and 6, the light source 132 or 170 (or other radiation) capable of interacting with the dopant in the polymeric material of the wall 86 and / or the polymeric material of the wall 86. Circle) can be selected. When coupled with a detection system, it can be used to characterize various properties including defects, thicknesses and other performance factors.

VI.A. Another test example is the use of x-rays to characterize the treatment / coating and / or the polymer itself. 10 or 6, the light source can be replaced with an x-radiant and the external detector can be of a type for measuring x-ray intensity. Elemental analysis of the barrier or other type of coating can be performed using this technique.

VI.A. After shaping the device 80 as in the station 22 above, some potential problems may arise that can render any subsequent treatment or coating incomplete and useless. If the devices are inspected prior to coating for these problems, the devices can be coated with a highly optimized, optionally up to 6-sigma control process to ensure the desired result (or results).

VI.A. Some potential problems that can interfere with treatment and coating include (depending on the nature of the coated item being produced):

VI.A. 1. High density particulate contamination defects (e.g., at least 10 micrometers each with the largest size) or larger particulate contamination (e.g., at least 10 micrometers each, with the largest size) at a lower density.

VI.A. 2. Chemical or other surface contamination (eg silicone mold release or oil).

VI.A. 3. High surface roughness, characterized by large numbers / bulges of sharp peaks and valleys, can also be characterized by quantifying the average roughness Ra below 100 nm.

VI.A. 4. Any defects in the device, such as holes, that prevent the creation of vacuum.

VI.A. 5. Any defect on the surface of the device to be used to create the seal (eg open end of the sample collection tube).

VI.A. 6. Large wall thickness nonuniformity that can interfere or change the power coupling through the thickness during processing or coating.

VI.A. 7. Other defects that would render the barrier or other type of coating useless.

VI.A. In order for the treatment / coating operation to be successful using parameters in the processing / coating operation, the device may be preliminarily checked for the presence of one or more of the potential problems or other problems. Earlier, an apparatus for supporting a puck or vessel holder, such as apparatus 38-68, and moving it through a production process involving various tests and processing / coating operations has been disclosed. Some tests that can be performed can be performed to ensure that the device has a surface suitable for processing / coating. These include:

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

VI.A. 2. Digital Inspection-For example, using a digital camera capable of measuring a specific length and shape (eg, how "round", flat or precisely shaped the open end of the sample collection tube is with respect to the reference).

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

VI.A. 4. Sound velocity (supersonic) test of the device.

VI.A. 5. X-ray analysis.

VI.A. 6. Electrical conductivity of the device (plastic tube material and SiO _x have different electrical resistances—for example, as bulk material, on the order of 1020 Ohm-cm for quartz and about 1014 Ohm-cm for polyethylene terephthalate). size).

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

VI.A. 8. Degassing of the vessel wall, which can be measured under a post-coating test to optionally measure the degassing baseline, as described below.

VI.A. The test can be performed at station 24 as shown in FIG. 6. In this figure, the device (eg, sample collection tube 80 may be left in place and light source 132 (or other source) may be located on the device and the appropriate detector 134 located outside of the device). It can be inserted into the instrument to measure the desired result.

VI.A. In the case of vacuum leak detection, the vessel holder and the device can be coupled to a vacuum pump and measuring device inserted into the tube. In addition, testing may be performed as described elsewhere herein.

VI.A. The processing station or device 24 may be a visual inspection station, one or more of the interior surface 88 of the vessel, its exterior surface 118 or the interior of the vessel wall 86 between its surfaces 88 and 118. Can be configured to check for defects. In particular, if the container is transparent or translucent to the type of radiation and wavelength used for inspection, inspection of the outer surface 118, the inner surface 88 or the container wall 86 may be performed from outside the container 80. Can be performed. If necessary, inspection of the inner surface 88 may be facilitated by providing an optical fiber probe inserted into the vessel 80 through the vessel port 92, so that the situation inside the vessel 80 may be It can obtain from the container 80 outside. For example, an endoscope or bosco may be used in such an environment.

VI.A. Another means shown in FIG. 6 is to be able to insert the light source 132 into the container 80. Light transmitted through the vessel wall 86 and artifacts of the vessel 80 exposed by the light can be detected from outside the vessel 80 using a detector measuring device 134. Such a station or device 24 may be visible, for example, unaligned containers 80 or visually distorted, impurity or other that are not properly seated on the container port 96 within the wall 86. It can be used to detect and correct or remove defective containers 80. In addition, visual inspection of the container 80 may be performed by an operator who observes the container 80 in place of or in addition to the mechanical inspection.

VI.A. The processing station or device 26 shown in more detail in FIG. 7 may optionally be configured to inspect the inner surface 88 of the vessel 80 for defects, for example, barrels or other types. It can be configured to measure the gas pressure loss through the vessel wall 86, which can be performed before the coating of. This test compresses or vacuums the interior of the vessel 80 and isolates the interior 154 of the vessel 80 so that the pressure remains constant without leaking around the chamber or seeping gas through the vessel wall and this problem. By measuring the hourly pressure change that accumulates from them, it can be done by creating a pressure difference between the two sides of the barrier coating 90. This measurement not only reveals any gas entering through the vessel wall 86 but also enables the leakage chamber to be measured between the inlet 82 of the vessel and the O-ring or other chamber 100, which It may indicate that there is a problem in the alignment of the container 80 or the function of the seal 100. In either case, poorly seated tubes can be calibrated or tubes drawn from the processing line prevent dilution of process gases by air drawn through the malfunctioning chamber and attempts to achieve or maintain an appropriate processing vacuum level. This saves time in prevention.

VI.A. The systems can be integrated into a fabrication and inspection method comprising a plurality of steps.

VI.A. As described above, 1 shows a simplified arrangement of the steps of one possible method, although the invention is limited to a single concept or approach. Initially, the container 80 is visually inspected at the station or by the device 24, which may include measuring the size of the container 80. If any defects are found, the device or vessel 80 is rejected and the puck or vessel holder, such as 38, is inspected, recycled or removed to see if there are any defects.

VI.A. Next, the leak rate or other characteristics of the assembly of the vessel holder 38 and the seated vessel 80 are tested at the station 26 and stored for comparison after coating. The puck or vessel holder 38 then moves, for example, to the coating step 28. The device or vessel 80 is coated with, for example, SiO _x or other barrier or other type of coating at a power supply frequency of 13.56 MHz. Once coated, the vessel holder is retested for its leak rate or other characteristics (which can be performed as a second test in a double or similar station, such as test station 26 or 30-using a dual station). To increase system throughput).

VI.A. The coating measurement can be compared to the uncoated measurement. If the ratio of these values exceeds a predetermined required level that indicates acceptable overall coating performance, the vessel holder and the device continue to move. Optical test station 32, for example, will follow with a blue light source and an external integrated spherical detector to measure the total light transmitted through the tube. The value may be required to exceed the preset limit at which the device is recycled or recycled for further coating. Next (for devices that are not rejected), a second optical test station 34 can be used. In this case, a point light source can be inserted into the interior of the tube or vessel 80 and slowly pulled out during measurement with a tubular CCD detector array outside the vessel. The data is then analyzed by computer to determine the defect density distribution. Based on the measurements, the device is approved or rejected for final packaging.

VI.A. The data may optionally be recorded and plotted (eg, electronically) using statistical process control techniques to ensure maximum 6-sigma quality.

VI.B. Vessel inspection performed by detecting degassing of the vessel wall through the barrier

VI.B. Another embodiment is a method of inspecting a barrier or other type of layer on a vaporizing material that has several steps. A sample of material is provided that removes the gas and has at least one partially barrier film. Optionally, a pressure differential can be provided across the barrier so that at least a portion of the degassing material is on the high pressure side of the barrier. In another option, the degassed gas can be allowed to diffuse without providing a pressure differential. Degassed gas is measured. If a pressure differential is provided across the barrier, the degassing can be measured on the high or low pressure side of the barrier.

 VI.B. In addition, measuring the effectiveness of the inner coating (applied above) can be made by measuring the diffusion rate of specific species or adsorbed materials in the walls of the device (prior to coating). Compared to uncoated (untreated) tubes, this type of measurement can provide a barrier to the coating or treatment or a direct measurement of other types of properties or the presence of the coating or treatment. In addition to or instead of a barrier film, the coating or treatment detected may be a lubricity layer, a hydrophobic layer, a decorative coating, or other types of layers that increase or decrease the outgassing of the substrate.

VI.B. As a specific example using the vessel holder of FIG. 2 and referring back to FIG. 7, the device or vessel 80 can be inserted into a puck or vessel holder 44 (also moved from other operations such as coating / treatment). The test can be performed on a seated vessel 80 that is moved from a puck or vessel holder, such as (44). Once the vessel holder is moved to the blocking test area, the measuring tube or probe 108 can be inserted into it (although similar to gas tubes for coating, even if the measuring tube does not need to extend inside the tube). have. Valves 136 and 148 can both be open and the interior of the tube can be vacuumed (vacuum created).

VI.B. Once the desired measured pressure is reached, the valves 136 and 148 can be closed and the pressure gauge 152 can begin to measure pressure. By measuring the time at which a certain pressure (higher than the starting pressure) is reached or by measuring the reached pressure measured after a given time, it is connected to the valves 1 and 2 but connected to the tube, vessel holder, pump channel and internal volume. The rate of rise (or leak-rate) of all the other parts separated by this can be measured. Then, if this value is compared to an uncoated tube, the ratio of the two measurements (coated tube value divided by uncoated tube value) allows to measure the rate of leakage through the coated surface of the tube. This measurement technique is connected to the vessel holder, pump channel and internal volume but minimizes the internal volume of all other components separated by valves 1 and 2 (except tubes / devices), thereby allowing gas infiltration or degassing from these surfaces. May be required to minimize the impact of

VI.B. In this disclosure, a distinction is made between "penetration", "leakage" and "surface diffusion" or "degassing".

As used herein with reference to a container, “penetration” refers to the passage of material through a wall 346 or other obstacle, from the outside of the container to the interior or vice versa along the path 350 of FIG. 29. Means that.

Degassing may include, for example, coating 348 (if any) absorbed or adsorbed material, such as gas molecules 354 or 357 or 359, outward from the interior of wall 346 or coating 348 of FIG. It means moving to the vessel 358 (to the right in FIG. 29). Degassing may also mean that a material, such as 354 or 357, exits the wall 346 and moves to the left as shown in FIG. 29 and moves out of the vessel 357 as shown. . Degassing may also refer to the removal of adsorbed material from the surface of the item, such as, for example, gas molecules 355 from the exposed surface of the vessel coating 90.

Leakage means the passage of material through the closure and the wall of the closed container with the closure, thereby moving the material around the obstacle presented by the wall 346 and the coating 348 rather than through or off the surface of the obstacle.

VI.B. Penetration refers to the rate of gas movement through materials that are free of gaps / defects and are not related to leakage or degassing. Referring to FIG. 29, in showing the vessel wall or another substrate 346 with the barrier coating 348, the penetration is a gas through the substrate 346 and the coating 348 all along the path 350 through both layers. Is to traverse. Infiltration is considered thermodynamically a relatively slow process.

VI.B. Penetration measurements are very slow because the penetration gas must pass completely through the unbroken wall of the plastic item. In the case of vacuumed blood collection tubes, measurement of the penetration of gas through the wall is commonly used as a direct indication of the tendency of the vessel to lose vacuum over time, but usually to the extreme requiring a test period of six days. The slow measurement is not fast enough to support the on-line coating test. Such tests are generally used for off-line testing of samples of containers.

VI.B. Also, penetration testing is not a very sensitive measure of the barrier effectiveness of thin coatings on thick substrates. Since all gas flow is through both the coating and the substrate, any change in flow through the thick substrate will introduce a change on its own, not due to the barrier effectiveness of the coating.

VI.B. The inventors have found a much faster and potentially more sensitive method of measuring the degassing of air or other gases or volatile components that have been quickly separated from the vessel wall through the coating-measuring the barrier properties of the coating. The gas or volatile constituents may in fact be any substance that can be degassed or selected from one or more specific substances to be detected. The components are oxygen, nitrogen, air, carbon dioxide, water vapor, helium, alcohols, ketones, hydrocarbons, coating precursors, substrate components, by-products of coating preparation such as volatile organosilicones, by-products of coated substrate preparation But may include, but are not limited to, other components or mixtures or combinations of either of which are present by chance or introduced by spikes of the substrate.

Surface diffusion and degassing are synonymous. Each term refers to some motif, such as extracting a vacuum (which produces air movement indicated by the arrows in FIG. 29) within a vessel that is first adsorbed or absorbed by the wall 346 and has a wall, such as the wall of the vessel. It refers to a fluid that passes through the adjacent space by the force to force the fluid to move into the interior of the container outside the wall. Degassing or diffusion is considered a relatively rapid process with mobility. For a wall 346 that is substantially resistant to penetration along the path 350, degassing may cause molecules, such as 354, closest to the interface 356 between the wall 346 and the barrier 348. It seems to drive out quickly. This differential degassing is carried out by mass molecules such as 354 near the interface 356 shown as degassing and masses such as 358 further away from the interface 356 and not shown as degassing. By other molecules of.

VI.B. Thus, another method is contemplated for inspecting the barrier on the vapor degassing material, including several steps. A sample of material is provided that degass the gas and has at least one partially barrier film. A pressure differential is provided across the barrier so that at least a portion of the degassing material is initially on the high pressure side of the barrier. The degassed gas transported to the low pressure side of the barrier during the test is measured to determine the presence of the barrier or how effective it is as a barrier.

VI.B. In this method, the gas outgassing may comprise a polymeric compound, a thermoplastic compound or one or more compounds having both properties. The gas outgassing material may include a polyester such as polyethylene terephthalate, for example. The gas outgassing material may comprise polyolefins, two examples being polypropylene, cyclic olefins or combinations thereof. The material that outgasses the gas is a complex of two different materials, at least one of which can outgas the vapor. One example is a bilayer structure of polypropylene and polyethylene terephthalate. Another example is the bilayer structure of cyclic olefin copolymer and polyethylene terephthalate. These materials and complexes are exemplary; Any suitable material or combination of materials may be used.

VI.B. Optionally, the gas outgassing material is provided in the form of a container having an outer surface and an inner surface, the inner surface having a wall surrounding the lumen. In this embodiment, the barrier film is optionally provided on the vessel wall and optionally on the inner surface of the vessel wall. The barrier film may also be provided on an outer surface of the vessel wall. Optionally, the gas outgassing material may be provided in the form of a film.

VI.B. The barrier can be a full or partial coating of any of the barriers currently described. The barrier film is less than 500 nm thick, or less than 300 nm thick, or less than 100 nm thick, or less than 80 nm thick, or less than 60 nm thick, or less than 50 nm thick, or less than 40 nm thick, or less than 30 nm thick, It may be less than 20 nm thick, or less than 10 nm thick, or less than 5 nm thick.

VI.B. In the case of coated walls, we have found that diffusion / degassing can be used to measure coating integrity. Optionally, a pressure differential may be provided across the barrier by at least partially vacuuming the lumen or interior space of the vessel. This can be done, for example, by connecting the lumen to a vacuum source through a duct to at least partially vacuum the lumen. For example, an uncoated PET wall 346 of a container exposed to ambient air may gaseous a number of oxygen and other gas molecules such as 354 from its interior surface for some time after the vacuum is drawn. Will be removed. If the same PET wall is coated on the interior with barrier coating 348, the barrier coating will stop, delay or reduce this outgassing. This is true for example with the SiO _x barrier coating 348 which degass less than the plastic surface. By measuring the differential of degassing between the coated and uncoated PET walls, the blocking effect of the coating 348 on the degassed material can be quickly measured.

VI.B. If the barrier coating 348 is incomplete due to known or theoretical pores, cracks, gaps or insufficient thickness or density or areas of the composition, the PET wall is preferentially degassed through this imperfection, thereby degassing it. Will increase the total amount. The primary source of gas collected is not from the outside of the item, but from dissolved gas or vaporizable components on the (bottom) surface of the plastic item next to the coating. The amount of degassing off the baseline level (e.g., the amount passed or discharged by the standard coating with incomplete or average and acceptable degree of incompleteness attainable with no or minimal imperfections) Can be measured in various ways to measure.

VI.B. The measurement can be performed, for example, by providing a degassing measurement cell in communication between the lumen and the vacuum source.

VI.B. The measurement cell may perform one of different measurement techniques. One example of a suitable measurement technique is the micro-flow technique. For example, the mass flow rate of the degassed material can be measured. The measurement can be performed in a molecular flow mode of operation. Exemplary measurements include the measurement of the volume of degassed gas through a barrier per time interval.

VI.B. The outgassed gas on the low pressure side of the barrier can be measured under conditions effective to distinguish the presence of the barrier. Optionally, the conditions effective for distinguishing the presence of the barrier film 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 less than 10 seconds, or 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.

VI.B. Optionally, the measurement of the absence of the barrier film can be identified with at least a six-sigma level of certainty within any one of the identified time intervals.

VI.B. Optionally, the degassed gas on the low pressure side of the barrier is measured under conditions effective to measure the barrier enhancement factor (BIF) of the barrier compared to the same material without the barrier. BIF, for example, provides two groups with identical vessels, adds a barrier to one vessel group, and provides barrier properties (such as degassing rate per minute or other suitable measure) on vessels with the barrier. The test can be performed by performing the same test on containers lacking a barrier and taking the ratio of the properties of the barrier-free material to the barrier-free material. For example, if the rate of degassing through the barrier is one third of the rate of degassing without barrier, the barrier has a BIF of three.

VI.B. Optionally, when there is more than one type of gas, such as both nitrogen and oxygen in the case of degassed air, degassing of a plurality of different gases can be measured. Optionally, degassing of substantially all or all of the degassed gases can be measured. Alternatively, the degassing of substantially all or all of the degassed gases can be measured simultaneously using physical measurements such as the combined mass flow rate of all gases.

VI.B. The measurement of the number or partial pressure of individual gas species degassed from the sample (such as oxygen or helium) can be performed faster than the atmospheric test, but the test rate is reduced such that only a portion of the degassing is the measured species. do. For example, if oxygen and nitrogen are degassed from the PET wall at a ratio of about 4: 1 in the atmosphere, but only oxygen degassing is measured, then a test that measures all species degassed from the vessel wall is an equally sensitive test. It needs to be done about five times (converted to the number of molecules detected to obtain sufficient statistical query results).

VI.B. For a given sensitivity level, it is believed that the method of accounting for the volume of all species degassed from the surface will provide the desired confidence level much more quickly than tests that measure the degassing of specific species such as oxygen atoms. As a result, degassing data with practical utility can be generated for in-line measurements. Optionally, such in-line measurements can be performed on all manufactured containers, thereby reducing the number of unusual or discrete defects and potentially eliminating them (at least at the time of measurement).

VI.B. In actual measurements, the factor that changes the apparent outgassing amount is a leak that exits an unsafe seal, such as a seal of a vessel seated on a vacuum receptor as the vacuum is drawn in the outgassing test. Leakage may be caused by fluid that bypasses the solid wall of the item, such as between a blood tube and its closure, between a syringe plunger and a syringe barrel, between a container and its cap or between the container inlet and the container inlet (unsafe or incorrectly seated). Refers to the fluid flowing between the yarns). The word “leakage” mainly refers to the movement of gas / gas through openings in plastic items.

VI.B. Leakage and (if required, if necessary) permeation can be factored into the basic level of degassing, so that acceptable test results indicate that the container is properly seated in the vacuum acceptor yarn (the seated surface is not damaged and is properly formed and positioned). The vessel walls do not support unacceptable levels of penetration (the vessel walls are not damaged and formed properly) and ensure that the coating has sufficient barrier integrity.

VI.B. Degassing can be variously measured by atmospheric pressure measurement (measures the pressure change in the vessel at a given time after the initial vacuum is drawn) or by measuring the partial pressure or flow rate of degassed gas from the sample. Equipment for measuring mass flow rates in molecular flow mode of operation is available. An example of this type of commercially available equipment employing Micro-Flow Technology is available from ATC, Indianapolis, Indiana. For further description of such known equipment, see US Pat. Nos. 5861546, 6308556, 6584828 and EP1356260, incorporated herein by reference. Also shown is an example of a degassing measurement that very quickly and reliably distinguishes barrier coated polyethylene terephthalate (PET) tubes from uncoated tubes.

VI.B. For containers made of polyethylene terephthalate (PET), the microflow rates are different for SiO _x coated and uncoated surfaces. For example, in Working Example 8 herein, as shown in Figure 31, the microflow rate for PET after the test was run for 30 seconds was 8 or It was above. This rate for uncoated PET was much higher than the measured rate for SiO _x -coated PET, which was less than 6 micrograms after the test was run for 30 seconds, as shown again in FIG. 31.

VI.B. One possible explanation for this difference in flow rate is that uncoated PET contains approximately 0.7 percent equilibrium moisture; This high moisture content is considered to lead to the observed high microflow rate. Using SiO _x -coated PET plastics, SiO _x coatings can have higher levels of surface moisture than uncoated PET surfaces. However, under test conditions, barrier coatings are considered to prevent moisture from further desorbing from the bulk PET plastic, resulting in lower microflow rates. It is expected that the microflow rate of oxygen or nitrogen from the uncoated PET plastics versus SiO _x coated PET is also distinguishable.

VI.B. Modifications of the above test for PET tubes may be appropriate when using other materials. For example, polyolefin plastics tend to have little moisture content. An example of a polyolefin having a low moisture content is the TOPAS® cyclic olefin copolymer (COC), which has an equilibrium moisture content (0.01 percent) and a much lower moisture penetration rate than that for PET. In the case of COC, the uncoated COC plastic may have a microflow rate similar or even lower than that of the SiO _x coated COC plastic. This is likely due to the higher surface moisture content of the SiO _x -coating and the lower equilibrium bulk moisture content and lower penetration rate of the uncoated COC plastic surface. This makes it more difficult to distinguish between uncoated and coated COC items.

The present invention shows that exposing the surface of a COC article to be tested (uncoated and coated) to moisture results in improved and consistent microflow separation between the uncoated plastic and the SiO _x coated COC plastic. This is illustrated in Example 19 and FIG. 57 of the present specification. The moisture exposure may be a simple exposure to a relative humidity ranging from 35% to 100%, such as in a controlled relative humidity room or directly to a mild (humidifier) or cold (vaporizer) moisture source, with the latter being more preferred.

VI.B. While the validity and scope of the present invention is not limited by the accuracy of this theory, moisture doping or spiking of the uncoated COC plastics may result in moisture or other degassing of the already saturated SiO _x -coated COC surface. It seems to increase the possible content. This can also be done by exposing the coated and uncoated tubes to other gases including oxygen, nitrogen, or other mixtures such as, for example, air.

VI.B Thus, before measuring the degassed gas, the barrier can be contacted with water, for example water vapor. Water vapor can be provided, for example, by contacting the barrier with air at a relative humidity of 35% to 100%, or 40% to 100%, or 40% to 50%. Instead of or in addition to water, the barrier film may be contacted with oxygen, nitrogen or a mixture of oxygen and nitrogen, for example ambient air. The contact time can be 10 seconds to 1 hour, or 1 minute to 30 minutes, or 5 minutes to 25 minutes, or 10 minutes to 20 minutes.

In addition, the degassing wall 346 inflows the left side of the wall 346 into the wall 346 as shown in FIG. 11 and then either the left or the right side as shown in FIG. 29. It may be spiked or supplemented from the side opposite to the blocking layer 348 by exposing it to a degassing material as one. After gas inflow and spiking of the wall from the left or other material, such as 346, measuring the degassing of the spiked material from the right (or vice versa) determines the wall when the gas presented through the coating is measured. In contrast to the material traveling through the entire path 350, the spiked material is distinguished from the penetration measurement because it is present in the wall 346 when degassing is measured. Gas inflow can occur over time as one embodiment before the coating 348 is applied and as another embodiment after the coating 348 is applied and before being tested for outgassing.

VI.B. Another possible way to increase the separation of microflow reactions between uncoated plastics and SiO _x coated plastics is to change the measurement pressure and / or temperature. Increasing the pressure or decreasing the temperature when measuring outgassing can result in more relative bonding of water molecules in the SiO _x coated COC than in the uncoated COC. Thus, the degassed gas may be 0.1 Torr to 100 Torr, or 0.2 Torr to 50 Torr, or 0.5 Torr to 40 Torr, or 1 Torr to 30 Torr, or 5 Torr to 100 Torr, or 10 Torr to 80 Torr, or 15 It can be measured at a pressure of Torr to 50 Torr. The degassed gas may be measured at a temperature of 0 ° C to 50 ° C, or 0 ° C to 21 ° C, or 5 ° C to 20 ° C.

VI.B. In any embodiment of the present disclosure, another method contemplated for measuring outgassing is to employ a microcantilever measurement technique. Such techniques are thought to enable the determination of less mass differences in degassing, potentially in the sizes of 10 ^-12 g. (Picograms) to 10 ^-15 g. (Femtograms). This less mass detection allows for the difference between coated and uncoated surfaces as well as other coatings in one second, optionally less than 0.1 second, optionally microseconds.

VI.B. In some cases, microcantilever (MCL) sensors may bend, move, or change shape due to outgassing or absorption of molecules to correspond to the presence of a given material. In some cases, microcantilever (MCL) sensors may respond due to shifting at the resonant frequency. In other cases, the MCL sensors may change in both these ways or in other ways. They can be operated in different environments, such as a gaseous environment, liquid or vacuum. In the gas, the microcantilever sensors can be operated as an artificial nose, whereby the bending pattern of the microfabricated array of eight polymer-coated silicon cantilevers is characteristic of steam, unlike solvents, flavors and beverages. Also contemplated are the use of any other type of electronic nose, operated by any technique.

Some MCL electronic designs, including piezoresistive, piezoelectric and capacitive approaches, are applied and are considered to measure the motion, shape change or frequency change of the MCLs upon exposure to chemicals.

VI.B. One specific example of measuring outgassing can be performed as follows. If degassed material is present, at least one microcantilever is provided that has the property of movement or change in different shapes. The microcantilever is exposed to the degassed material under conditions effective to cause the microcantilever to move or change in a different shape. Then, the movement or different shape is detected.

VI.B. For example, reflecting an energy incident beam from a portion of the microcantilever that moves or changes its shape before and after exposing the microcantilever to the degassing, and deflects the reflected beam at a point away from the cantilever. By measuring, movement or different shapes can be detected. Preferably, the shape is measured at a point away from the cantilever because the amount of deflection of the beam under a given condition is proportional to the distance of the measurement point from the reflection point of the beam.

VI.B. Some suitable examples of energy incident beams are photon beams, electron beams, or a combination of two or more thereof. In addition, two or more other beams may be reflected from the MCL along different incident and / or reflected paths to determine movement or shape change from one or more viewpoints. One type of specifically contemplated energy incident beam is the beam of coherent photons, such as a laser beam. Photons described herein are implicitly defined to include wave energy as well as particle or photon energy per se.

VI.B. Another example of measurement takes advantage of the properties of specific MCLs of change at the resonance frequency when encountering an environmental material in an amount effective to effect the change at the resonance frequency. This type of measurement can be performed as follows. If degassed material is present, at least one microcantilever is provided which resonates at different frequencies. The microcantilever can be exposed to the degassed material under conditions effective to resonate the microcantilever at different frequencies. Thereafter, different resonant frequencies are detected by any suitable means.

VI.B. In one example, different resonance frequencies may be detected by inputting energy into the microcantilever to induce resonance before and after exposing the microcantilever to outgassing. Differences between the resonance frequencies of the MCL are measured before and after exposure to degassing. In addition, instead of measuring the difference in the resonant frequency, an MCL may be provided which is known to have a particular resonant frequency in the presence of a sufficient concentration or amount of degassed material. The equilibrium frequency, which signals the presence of a different resonance frequency or a sufficient amount of degassed material, is detected using a harmonic vibration sensor.

As an example of MCL technology for measuring outgassing, the MCL device can be integrated into a quartz vacuum tube connected to a vessel and a vacuum pump. Harmonic vibration sensors using commercially available piezoresistive cantilevers, Wheatstone bridge circuits, positive feedback controllers, excitable piezoelectric elements, and phase locked loop (PLL) demodulators can be constructed. for example,

Hayato Sone, Yoshinori Fujinuma and Sumio Hosaka Picogram Mass Sensor Using Resonance Frequency Shift of Cantilever , Jpn. J. Appl. Phys. 43 (2004) 3648;

Hayato Sone, Ayumi Ikeuchi, Takashi Izumi1, Haruki Okano2 and Sumio Hosaka Femtogram Mass Biosensor Using Self-Sensing Cantilever for Allergy Check, Jpn. 43 (2006) 2301).

To prepare the MCL for detection, one side of the microcantilever may be coated with gelatin. 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 that desorbs from the vacuum coated vessel surface binds with gelatin, causing the cantilever to bend and its resonance frequency to change, as measured by laser deflection from the surface of the cantilever. Changes in the mass of uncoated versus coated containers can change in seconds and are considered to be highly reproducible. The items cited above in connection with the cantilever technology are incorporated herein by reference to disclose specific MCLs and equipment arrangements that can be used to detect and quantify desected species.

Other coatings for moisture detection (phosphate) or oxygen detection may be applied to the MCLs in lieu of or in addition to the gelatin coating described above.

VI.B. It is also contemplated that any of the degassing test setups currently under consideration can be combined with a SiO _x coating station. In such an arrangement, the measurement cell 362 may be as shown above, using the main vacuum channel for PECVD, such as bypass 386. In one embodiment, the measurement cell, generally indicated at 362 in FIG. 30, includes (50) wherein the bypass channel 386 consists of a main vacuum duct 94 and the measurement cell 362 is a side channel. It can be integrated into the same vessel support.

VI.B. This combination of the measuring cell 362 and the vessel holder 50 optionally allows degassing measurements to be performed without breaking the vacuum used for PECVD. Optionally, the vacuum pump for PECVD will be short (preferably pumped down to less than 1 Torr and pumped down), preferably for pumping some or all of the remaining reactant gases remaining after the coating step. Prior to doing so have a small amount of air, nitrogen oxygen or other gas spills or other options to dilute the process gases). This will facilitate the combined processes of coating the container and testing the coating for presence and barrier levels.

VI.B. In addition, after reviewing this specification, it will be appreciated that degassing measurement and all other described barrier measurement techniques can be used for many purposes other than or in addition to measuring barrier effectiveness. In one example, testing may be made on uncoated or coated containers to determine the degree of degassing of the container walls. This test may be made, for example, if an uncoated polymer is needed to degas less than a certain amount.

VI.B. For another example, these degassing measurements and all other described barrier measurement techniques are barrier coated or coated as an in-line test that measures a change in degassing of the film as a stationary test or as the film crosses the measurement cell. Can be used for films that are not. The test can be used to determine the continuity or barrier effectiveness of other types of coatings such as aluminum coatings or EVOH barrier coatings or layers of packaging films.

VI.B. These degassing measurements and all other described barrier measurement techniques are applied to the sides of the vessel wall, film, etc., as opposed to the measuring cell, such as the barrier membrane, which is applied to the exterior of the vessel wall and tested for outgassing into the interior of the vessel wall. It can be used to measure the effectiveness of the barrier. In this case, there will be a flow differential for penetration through the substrate film or wall after penetration through the barrier coating. This measurement would be particularly useful when the substrate film or wall, such as a very thin or porous film or wall, is permeable.

VI.B. These degassing measurements and all other described barrier measurement techniques can be used to determine the effectiveness of a barrier, which is an inner layer of a vessel wall, film, etc., where the measurement cell is a layer or layer farther from the measurement cell than the barrier. In addition to degassing through their barrier, any degassing through the layer adjacent to the measurement cell will be detected.

VI.B. These degassing measurements and all other described barrier measurement techniques, if the barrier is not present on any part of the material, determine the degree of degassing of the partially barrier coated material as a percentage of the expected degassing amount, Can be used to measure the percentage of coverage of the pattern of blocking material on the material to be removed.

VI.B. One test technique that can be used to increase the test rate for degassing a container, which can be used with any degassing test embodiment herein, is to insert a plunger or closure into the container to It is to reduce the void volume of the vessel by reducing the void volume. Reduced void volume allows the vessel to pump down more quickly to a given vacuum level, reducing test intervals.

VI.B. Many other applications for the presently described degassing assays and all other described barrier measurement techniques will become apparent after review by the skilled person in reviewing this specification.

VII. PECVD Processed Containers

VII. At least 2 nm, or 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 Can be a SiO _x coating applied to a thickness of at least 200 nm, or 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 ( For example, containers with barrier coating 90 (shown in FIG. 2) are considered. The coating may be up to 1000 nm, or 900 nm, or about 800 nm, or about 700 nm, or about 600 nm, or about 500 nm, or about 400 nm, or about 300 nm, or about 200 nm, or about 100 nm. Or about 90 nm, or at least about 80 nm, or about 70 nm, or about 60 nm, or about 50 nm, or about 40 nm, or about 30 nm, or about 20 nm, or about 10 nm, or about 5 nm Degree of thickness. In addition to the specific thickness range consisting of any of the minimum thicknesses indicated above, any one or more of the maximum thicknesses indicated above are explicitly contemplated. The thickness of the SiO _x or other coating can be measured, for example, by transmission electron microscopy (TEM) and its composition can be measured by X-ray photoelectron spectroscopy (XPS).

VII. It is contemplated that the choice of material that will not penetrate the coating and the properties of the applied SiO _x coating can affect the barrier efficacy. For example, two examples of materials commonly intended to not penetrate are oxygen and water / water vapor. Commonly, materials are better barriers to one than the rest. This is believed to be partly because oxygen is permeated through the coating by a mechanism other than that of water.

VII. Oxygen permeation is affected by the physical characteristics of the coating such as thickness, the presence of cracks and other physical details of the coating. On the other hand, moisture permeation is generally believed to be affected by chemical factors that are more than physical factors, such as the material from which the coating is made. In addition, the inventors consider that at least one of these chemical factors is a substantial concentration of OH moieties in the coating, which will further increase the rate of water penetration through the barrier membrane. Since SiO _x coatings often include OH moieties, physically normal coatings containing a high proportion of OH moieties have better barrier to oxygen than water. Physically normal carbon-based barriers, such as amorphous carbon or diamond-like carbon (DLC), typically have better barriers to water than those of SiO _x , which typically has a higher concentration of OH moieties. Because it is low.

VII. However, other factors lead to preference for SiO _x coatings such as oxygen barrier efficacy and close chemical similarities to glass and quartz. Glass and quartz are two materials that have long been known to present very high barriers to oxygen and water permeation, as well as substantial inertness to many materials commonly contained in containers (when used as base material for containers). Thus, it is generally desirable to optimize aqueous barrier properties such as the water vapor transmission rate (WVTR) of SiO _x coatings rather than selecting different or different types of coatings to act as a water barrier.

VII. Some methods considered to improve the WVTR of the SiO _x coating are as follows.

VII. The concentration ratio of organic moieties (carbon and oxygen 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 gases (by increasing the oxygen feed rate or lowering the feed rate of one or more other components). The lower incidence of OH moieties is believed to be due to an increase in the reaction of oxygen supply and hydrogen at the silicon source to produce more volatile moisture at the PECVD outlet and to reduce the concentration of OH moieties trapped or incorporated in the coating.

VII. Higher energy can be applied in the PECVD process by raising the plasma generated power level, applying the power for a longer time, or both. Since the increase in energy applied tends to distort the vessel being treated, it must be handled with care so that the tube absorbs the plasma generated power when used to coat plastic tubes or other devices. This is because RF power is preferred in the context of the present application. Employs energy in a series of two or more pulses separated by a cooling time, cools the vessels while applying energy, applies the coating in a short time (thus making the coating thinner), and applies to the base material selected for coating The distortion of the medical devices can be reduced or eliminated by selecting the frequency of the applied coating that is absorbed by the minimum and / or by applying one or more coatings with the time between each energy application step. For example, high power pulsing may be used with a duty cycle that runs for 1 millisecond and shuts down for 99 milliseconds while continuing to supply the process gas. Then, as the flow continues between the pulses, the process gas is a refrigerant. Another alternative is to re-adjust the power applicator by adding magnets to limit the plasma, and the effective power application (in practice, the power gradually subtracts the coating, as opposed to the hydraulic power leading to heating or unwanted coating). To increase. This means the application of more coating formation energy per total watt-hour of applied energy. See, for example, US Pat. No. 5,904,952.

VII. Oxygen post-treatment of the coating can be used to remove OH moieties from the previously deposited coating. It is also believed that this treatment removes residual volatile organosilicon compounds or silicon or oxidizes the coating to form another SiO _x .

VII. The plastic base material tube can be preheated.

VII. Volatile sources of other silicon, such as hexamethyldisilazane (HMDZ), can be used as part or all of the silicon supply. Since these compounds do not have oxygen moieties in the feed gas, it is contemplated that changing the feed gas to HMDZ will solve the problem. It is contemplated that the source of one of the OH moieties in the HMDSO-source coating is the hydrogenation of at least some of the oxygen atoms present in the unreacted HMDSO.

VII. Composite coatings such as carbon-based coatings mixed with SiO _x can be used. This can be done, for example, by changing the reaction conditions or by adding substituted or unsubstituted hydrocarbons, such as alkanes, alkenes or alkane, as well as organosilicon compounds to the feed gas. See, for example, US Pat. No. 5,904,952, which refers to the relevant part: including low hydrocarbons such as propylene, for example, to provide a carbon moiety, most of the properties of the deposited films (except light transmission) The binding analysis with the improvement of the properties indicates that the film is silicon dioxide in nature. However, the use of methane, methanol or acetylene results in films that are silicon in nature. Inclusion of traces of gaseous nitrogen in the gas stream provides nitrogen moieties in the deposited films, increases the deposition rate, improves transmission and reflection optical properties on glass and changes the refractive index in response to changes in the amount of N ₂ . . Adding nitric oxide to the gas stream increases deposition rate and improves optical properties, but tends to reduce film hardness.

VII. The diamond-like carbon (DLC) coating can be formed as the first or only coating deposited. This can be done, for example, by changing the reaction conditions or by supplying methane, hydrogen and helium to the PECVD process. Since these reaction feeds do not have oxygen, OH moieties cannot be formed. As an example, the SiO _x coating may be applied on the inside of the tube or syringe barrel and the outer DLC coating may be applied on the outer surface of the tube or syringe barrel. Alternatively, SiO _x and DLC coatings can both be applied as a single layer or multiple layers of inner tube or syringe barrel coating.

VII. Referring to FIG. 2, a barrier or other type of coating 90 reduces the permeation of atmospheric gases through the interior surface 88 into the vessel 80. In addition, a barrier or other type of coating 90 reduces the contact of the interior surface 88 with the contents of the container 80. The barrier or other type of coating may include, for example, SiO _x , amorphous (eg diamond-like) carbon or a combination thereof.

VII. Any coating described herein can be used to coat a surface that is, for example, a plastic surface. It can also be used, for example, as a barrier against gas or liquid, preferably as a barrier against water vapor, oxygen and / or air. In addition, the coated surface can be used to prevent or reduce the mechanical and / or chemical effects that may have on the compound or composition if the surface is not coated. For example, it can prevent or reduce precipitation of compounds or compositions, such as insulin precipitation or blood coagulation or platelet activation.

VII.A. Vacuumed Blood Collection Containers

VII.A.1. Tubes

VII.A.I. Referring to FIG. 2, more details of the containers, such as 80, are shown. The depicted vessel 80 may be generally tubular with an opening 82 at one end of the vessel as opposed to the closed end 84. The vessel 80 also has a wall 86 that defines an interior surface 88. One example of the container 80 is a medical sample tube, such as a vacuumed blood collection tube, as is commonly used by a hematologist who receives a venipuncture sample of a patient's blood for use in a medical laboratory.

VII.A.1. The container 80 may be made of, for example, a thermoplastic material. Some examples of suitable thermoplastics are polyethylene terephthalates or polyolefins such as polypropylene or cyclic polyolefin polymers.

VII.A.1. The container 80 may be manufactured by any suitable method or other suitable means such as injection molding, blow molding, machining, tubing stock, or the like. PECVD can be used to form a coating on the inner surface of SiO _x .

VII.A.1. If intended for use as a vacuumed blood collection tube, the vessel 80 is preferably sufficient to withstand substantially the entire internal vacuum without substantially deformation when exposed to an external or atmospheric pressure of 760 Torr and other coating process conditions. Can be strong. In the thermoplastic container 80, a container 80 made of suitable materials having a suitable size and a glass transition temperature higher than the processing temperature of the coating process, for example a cylinder with sufficient wall thickness for its diameter and material This property can be provided by providing a mold wall 86.

VII.A.1. Medical containers or containers, such as sample collection tubes and syringes, are injection molded, allowing relatively small and relatively thick walls to be vacuumed without being squeezed by ambient atmospheric pressure. Thus, they are stronger than carbonated beverage bottles or other large or thin walled plastic containers. Since sample collection tubes designed for use as a vacuumed container are made to withstand full vacuum during storage, they can be used as vacuum chambers.

VII.A.1. Aligning the vessel with its own vacuum chambers may eliminate the need to place the vessels in a vacuum chamber for PECVD processing, which is typically performed at very low pressures. Using the vessel as its own vacuum chamber allows for faster processing times and simplified equipment configuration (because no loading and unloading of parts from the individual vacuum chamber is required). In addition, for certain embodiments, the device is supported (for alignment to gas tubes and other devices), the device is sealed (so that the vessel holder can be attached to a vacuum pump to create a vacuum) and subsequent formation. A vessel support is contemplated to move the device between processing steps.

VII.A.1. The vessel 80 used as a vacuumed blood collection tube is intended to not leak significant volumes of air or other atmospheric gas into the tube (by bypassing the closure) or to penetrate through the wall 86 for its lifetime. It must be able to withstand the external atmospheric pressure while internally vacuumed at a reduced pressure useful for the intended use. If the molded container 80 cannot meet this requirement, it can be treated by coating the inner surface 88 with a barrier or other type of coating 90. It is desirable to treat and / or coat the inner surface of such devices (such as sample collection tubes and syringe barrels) to provide various properties and / or to mimic existing glass articles that will provide better advantages over existing polymer devices. . It is also desirable to measure various properties of the devices before and / or after treatment or coating.

VII.A.1.a. Coatings Deposited from Organosilicon Precursors Prepared by In Situ Polymerization of Organosilicon Precursors

VII.A.1.a. Applying any one of the precursors described above on or near a substrate having a thickness of 1 to 5000 nm, optionally 10 to 1000 nm, optionally 10 to 200 nm, optionally 20 to 100 nm, and in a PECVD process A process for applying a lubricating coating on the interior of a barrel of a substrate, such as a syringe, is envisioned, comprising providing a lubricating surface by crosslinking or polymerizing the coating (or both). In addition, the coating applied by this process is considered new.

VII.A.1.a. As applied by PECVD, w is 1, where 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 and x is about 0.5 To _w , y is about 2 to about 3, and z is 6 to about 9, the coating of Si _w O _x C _y H _z further has utility as a hydrophobic coating. Coatings of this kind are considered hydrophobic, whether or not they function as lubricity coatings. Compared with the coated or uncoated surface, the coating or treatment is defined as “hydrophobic” if the wet tension of the surface is lowered. Thus, hydrophobicity is a function of both the uncoated substrate and the treatment.

The degree of hydrophobicity of the coating can be varied by changing its composition, properties or deposition method. For example, coatings of SiOx with little or no hydrocarbon content are more hydrophilic than coatings of Si _w O _x C _y H _z with substituent values as defined herein. Generally speaking, the higher the CH _x (eg, CH, CH ₂ or CH ₃ ) moiety content of the coating, either by weight, volume or molar ratio relative to the silicon content, the higher the hydrophobicity of the coating.

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 Hydrophobic coatings having a 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 can be very thin. The coating may be up to 1000 nm, or 900 nm, or about 800 nm, or about 700 nm, or about 600 nm, or about 500 nm, or about 400 nm, or about 300 nm, or about 200 nm, or about 100 nm. Or about 90 nm, or at least about 80 nm, or about 70 nm, or about 60 nm, or about 50 nm, or about 40 nm, or about 30 nm, or about 20 nm, or about 10 nm, or about 5 nm Degree of thickness. In addition to the specific thickness range consisting of any of the minimum thicknesses indicated above, any one or more of the maximum thicknesses indicated above are explicitly contemplated.

VII.A.1.a. One utility with such hydrophobic coatings is to separate the thermoplastic tube walls made of, for example, polyethylene terephthalate (PET) from blood collected in the tubes. The hydrophobic coating can be applied on top of a hydrophilic SiO _x coating on the inner surface of the tube. The SiO _x coating improves the barrier properties of the thermoplastic tube and the hydrophobic coating changes the surface energy of the tube tube and the blood contact surface. Hydrophobic coatings can be made by providing a precursor selected from the precursors identified herein. For example, the hydrophobic coating precursor may comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS).

VII.A.1.a. Another use for hydrophobic coatings is to make glass cell manufacturing tubes. The tube has a hydrophobic coating on the wall defining the lumen, the inner surface of the glass wall and contains the citrate reagent. Hydrophobic coatings can be made by providing a precursor selected from those precursors identified elsewhere herein. In another example, the hydrophobic coating precursor may comprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane (OMCTS). Another source material for hydrophobic coatings is that R is a hydrogen atom or an organic substituent such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkane, epoxide, etc.

R-Si (OCH ₃ ) ₃

Alkyl trimethoxysilane. Also contemplated are combinations of two or more of these.

VII.A.1.a. Using the alkyl trimethoxysilane precursors described above, a combination of acid or base catalysis and heating can condense the precursors (by removing ROH by-products) and optionally cross-link them, which may be further crosslinked through other methods. Polymers may be formed. Specific examples are given by Shimojima et. al. J. Mater. Chem., 2007, 17, 658-663.

VII.A.1.a. Coating of Si _w O _x C _y H _z may be achieved by applying a SiO _x blocking coating to the inner surface 88 of the vessel 80 to provide a lubricious surface, especially if the surface coating is a liquid organosiloxane compound at the end of the coating process. After application, it may be applied as a subsequent coating.

VII.A.1.a. Optionally, after a coating of Si _w O _x C _y H _z is applied, it may be post-cured after the PECVD process. Heat as described in UV-initiated (free radicals or cations), electron-beam (E-beam) and development of novel cycloaliphatic siloxanes for thermal and UV-curable applications (Ruby Chakraborty Paper, Can 2008) Including radiation curing approaches can be used.

VII.A.1.a. Another approach to providing a lubricity coating is to use a silicone demolding agent when injection molding a lubricated thermoplastic container. For example, it is contemplated that any of the above release agents and latent monomers that cause in-situ heat lubricity coating formation during the molding process can be used. Alternatively, the aforementioned monomers can be doped with traditional release agents to achieve the same result.

VII.A.1.a. In particular, a lubricity coating is contemplated for the inner surface of the syringe barrel, as described further below. The lubricating inner surface of the syringe barrel may push out the lubricant interposed between the plunger force or the prefilled syringe plunger required to advance the plunger in the barrel during operation of the syringe or, for example, disassemble the lubricant between the plunger and the barrel. After being attached to the barrel, it is possible to reduce the breakout force required to move the plunger. As described elsewhere herein, w is 1, wherein x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, and z is from 2 to about 9 Si _w O _x C _y H _z A coating of may also be applied to the inner surface 88 of the vessel 80 to enhance the adhesion of subsequent coatings of SiO _x .

VII.A.1.a. Thus, the coating 90 has a layer of SiO _x and w is 1, where x is from about 0.5 to 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z is from 6 to about 9 may comprise a layer of Si _w O _x C _y H _z . A layer of Si _w O _x C _y H _z may be deposited between the layer of SiO _x and the inner surface of the container. In addition, a layer of SiO _x may be deposited between the layer of Si _w O _x C _y H _z and the inner surface of the container. In addition, three or more layers may be used alternately or progressively between these two coating compositions. The layer of SiO _x may be deposited adjacent or away from the layer of Si _w O _x C _y H _z , with at least one intervening layer of different material. The layer of SiO _x may be deposited adjacent to the interior surface of the vessel. In addition, a layer of Si _w O _x C _y H _z may be deposited adjacent to the interior surface of the vessel.

VII.A.1.a. For adjacent layers of SiO _x and Si _w O _x C _y H _z , another means contemplated herein is w is 1, where x is from about 0.5 to 2.4, y is from 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 6 to about 9 Si _w O _x C _y H _z to SiO _x It is an inclined functional composite. Functionally gradient composite material is between that of the separating layer of Si _w O _x C _y H _z and SiO _x has a transition or interface between the intermediate composition between the separated layers of Si _w O _x C _y H _z and SiO _x or those Continuously or stepwise change from a composition of Si _w O _x C _y H _{z to} a composition more similar to SiO _x , experiencing coatings in the normal direction or in separate layers of Si _w O _x C _y Hz with an intermediate distinguishing layer of intermediate composition It may be a single layer.

VII.A.1.a. In the gradient complex, the gradient may go in either direction. For example, the composition Si _w O _x C _y H _z can be applied directly to the substrate and gradually change from the composition to the surface of SiO _x . Alternatively, the composition of SiO _x can be applied directly to the substrate and gradually change to a composition from the surface of Si _w O _x C _y H _z . Gradient coatings are particularly contemplated if a coating of one composition is better to attach to the coating than the other, so that a better-adhesive composition is applied directly to the substrate, for example. The longer distances of the gradient coating may be less compatible with the substrate than the adjacent portions of the gradient coating, which gradually changes the properties of the coating at any point, so that adjacent points at nearly the same depth of the coating have approximately the same composition. It is contemplated that portions that are physically broader at substantially different depths may have more diverse characteristics. In addition, the coating portions that form a better barrier against the material transfer or from the substrate may be used to prevent contamination of the farther coating portions that form a barrier of lesser quality with a material that is restrained or impeded by the barrier. It is contemplated that the substrate can be opposed directly.

VII.A.1.a. Instead of being gradientd, the coating can optionally have a sharp transition between one layer and the next without a substantial gradient of the composition. Such coatings can be prepared, for example, by providing gases that produce a layer from a non-plasma state to a steady state flow, and then powering the system with a short plasma discharge to form a coating on the substrate. When attempting to apply a subsequent coating, the gases for the previous coating are removed with little or no gradual transition at the interface and the gases for the next coating activate the plasma and again on the surface of the substrate or its outermost previous coating. It is applied in a steady-state state before forming.

VII.A.1.b. Citrate blood tube with walls coated with hydrophobic coating deposited from organosilicon precursor

VII.A.1.b. Another example is a cell preparation tube having a wall provided with a hydrophobic coating on an inner surface and containing a water soluble sodium citrate reagent. In addition, the hydrophobic coating can be applied on top of a hydrophilic SiO _x coating on the inner surface of the tube. The SiO _x coating improves the barrier properties of the thermoplastic tube and the hydrophobic coating changes the surface energy of the tube tube and the blood contact surface.

VII.A.1.b. The wall is made of a thermoplastic material having a surface that defines the lumen.

VII.A.1.b. The blood collection tube according to example VII.A.1.b acts as an oxygen barrier membrane, as described herein, and extends the life of the vacuumed blood collection tube made of thermoplastic material. It may have a first layer of SiO _{x on} the surface. w is 1, wherein x is from about 0.5 to 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, preferably w is 1, x is from about 0.5 to 1, y is A second layer of Si _w O _x C _y H _z wherein from about 2 to about 3 and z is 6 to about 9 can be applied on the barrier film on the inner surface of the tube to provide a hydrophobic surface. The coating is effective in reducing platelet activation of plasma treated with sodium citrate additive and exposed to the inner surface compared to uncoated walls of the same type.

VII.A.1.b. PECVD is used to form a coating on the inner surface having the following structure: Si _w O _x C _y H _z . Unlike conventional citrate blood collection tubes, blood collection tubes with a hydrophobic layer of Si _w O _x C _y H _z are baked onto silicon on the vessel wall, as conventionally applied to render the surface of the tube hydrophobic. Does not require a coated coating.

VII.A.1.b. For example, both layers can be applied using the same precursor and different PECVD reaction conditions such as HMDSO or OMCTS.

VII.A.1.b. The sodium citrate anticoagulant reagent is then provided in the tube and vacuumed and sealed with a closure to produce a vacuumed blood collection tube. Components and preparations of such reagents are known to those skilled in the art. The water soluble sodium citrate reagent is provided to the lumen of the tube in an amount effective to inhibit coagulation of blood introduced into the tube.

VII.A.1.c. SiO _x  Barrier-coated double walled plastic containers-COC, PET, SiO _x  Layers

VII.A.1.c. Another embodiment is a container having a wall that at least partially surrounds the lumen. The wall has an inner polymer layer surrounded by an outer polymer layer. One of the polymer layers is a layer that is at least 0.1 mm thick of cyclic olefin copolymer (COC) resin defining a water vapor barrier. One of the polymer layers is a layer that is at least 0.1 mm thick of polyester resin.

VII.A.1.c. The wall comprises an oxygen barrier film of SiO _x having a thickness of about 10 to about 500 angstroms.

VII.A.1.c. In one embodiment shown in FIG. 36, the vessel 80 may be a double wall vessel having an inner wall 408 and an outer wall 410, each made of the same or different materials. One particular embodiment of this type is one wall formed of a cyclic olefin copolymer (COC) and a polyethylene terephthalate (PET) with an SiO _x coating as previously described for the inner surface 412. It can be fabricated from other walls molded from polyester. If desired, tie coatings or layers may be inserted between the inner and outer walls to facilitate adhesion therebetween. The advantage of this wall structure is that walls with different properties can be combined to form a composite with the individual properties of each wall.

VII.A.1.c. As an example, the inner wall 408 may be made of PET coated on the inner surface 412 with a SiO _x blocking film, and the outer wall 410 may be made of COC. As shown elsewhere herein, PET coated with SiO _x is an excellent oxygen barrier, while COC is an excellent barrier to water vapor, providing a low water vapor transmission rate (WVTR). Such composite vessels may have good barrier properties for both oxygen and water vapor. This structure is contemplated, for example, on a vacuumed medical sample collection tube containing a water soluble reagent as manufactured and having a substantial lifespan, so that the tube may be exposed to water vapor through its composite wall while maintaining its lifespan. It must have a barrier that prevents it from being delivered to the interior or from delivering oxygen or other gases to the interior.

VII.A.1.c. As another example, the inner wall 408 may be made of COC coated on the inner surface 412 with an SiO _x blocking film, and the outer wall 410 may be made of PET. This structure is contemplated for prefilled syringes containing, for example, aqueous sterile fluid. The SiO _x barrier will prevent oxygen from entering the syringe through the wall. The COC inner wall prevents the inflow or outflow of other materials, such as water, to prevent water in the aqueous sterile fluid from being filtered out of the wall material by the syringe. In addition, the COC inner wall is contemplated as preventing water from the aqueous sterile fluid from passing out of the syringe (undesirably concentrating the aqueous sterile fluid) and unsterilized water or other fluid outside the syringe. Will be introduced into the syringe and will prevent the contents from becoming sterile. In addition, the COC inner wall is considered to be useful for reducing the breaking force or friction of the plunger against the inner wall of the syringe.

VII.A.1.d. How to make double wall plastic containers-COC, PET, SiO _x  Layers

VII.A.1.d. Another embodiment is a method of making a container having a wall having an inner polymer layer surrounded by an outer polymer layer, one layer made of COC and another layer made of polyester. The vessel is manufactured by a process comprising introducing COC and polyester resin layers into an injection mold through concentric injection nozzles.

VII.A.1.d. Another optional step is to apply an amorphous carbon coating to the vessel by PECVD as an inner coating and an outer coating or an interlayer coating positioned between the coatings.

VII.A.1.d. An optional additional step is to apply SiO _x blocking film to the inside of the vessel wall as SiO _x is defined as before. Another optional additional step is to work up the SiO _x film with a process gas consisting essentially of oxygen and essentially free of volatile silicon compounds.

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

VII.A.1.d. The container 80 shown in FIG. 36 is for example injection molded of the inner wall in the first forming cavity and then moved the inner and shaped inner walls from the first forming cavity to the second larger forming cavity. It can be fabricated outwardly by shaping the outer wall with respect to the inner wall in the second forming cavity. Optionally, a tie layer may be provided on the outer surface of the molded inner wall prior to overmolding the outer wall onto the tie layer.

VII.A.1.d. In addition, the container 80 shown in FIG. 36 inserts a first core into a molding cavity, for example, injection molding an outer wall into the molding cavity, and then moves the first center from the molded first wall. After removal and insertion of a smaller second center, it can be fabricated outwardly by injection molding the inner wall against the outer wall still remaining in the forming cavity. Optionally, a tie layer may be provided on the inner surface of the molded outer wall prior to overforming the inner wall onto the tie layer.

VII.A.1.d. In addition, the container 80 shown in FIG. 36 can be manufactured with two shot molds. This can be done, for example, by injection molding the material for the inner wall from the inner nozzle and the material for the outer wall from the outer nozzles of concentric circles. Optionally, the tie layer may be provided from a third concentric nozzle disposed between the inner and outermost nozzles. The nozzles can supply respective wall materials simultaneously. One useful means is to start feeding the outer wall material through the outer nozzle just before feeding the inner wall material through the inner nozzle. If there is an intermediate concentric nozzle, the flow sequence may begin with the outer nozzle and continue with the intermediate nozzle and then with the inner nozzle. In addition, the supply start sequence can work outward from the inner nozzle, in the reverse order compared to the preceding description.

VII.A.1.e. Barrier coating made of glass

VII.A.1.e. Another embodiment is a container comprising a container, a barrier coating and a closure. The vessel is generally tubular and made of thermoplastic material. The vessel has a lumen at least partially bounded by a wall having an inlet and an inner surface interfacing with the lumen. On the inner surface of the wall there is at least one essentially continuous barrier coating made of glass. The closure covers the inlet and separates the lumen of the vessel from the ambient air.

VII.A.1.e. In addition, the container 80 may be made of any type of glass used in medical or laboratory applications such as soda lime glass, borosilicate glass or other glass formulations. It is also contemplated that other containers of any shape or size, made of any material, will be used in the system 20. One function of coating the glass container is to reduce the influx of ions into the glass, either deliberately or as impurities, for example sodium, calcium, etc., from the glass to the contents of the container, such as reagents or blood, in a vacuumed blood collection tube. It can be done. Other functions of coating all or part of the glass container, such as on surfaces that are in sliding contact with other parts, provide lubricity to the coating, for example by inserting or removing the stopper or by sliding the sliding component such as a piston in the syringe. Facilitate traffic Another reason for coating a glass container is to prevent an increase in the rate of coagulation of blood, such as reagents or blood, of the intended sample for the container sticking to or contacting the wall of the container.

VII.A.1.e.i. One related embodiment is the container described in the preceding paragraph, wherein the barrier coating is made of soda lime glass or borosilicate glass or other types of glass.

VII.A.2. Stoppers

VII.A.2. 23-25 illustrate a container 268, which may be a vacuumed blood collection tube, with a closure 270 that separates lumen 274 from the surrounding environment. The closure 270 has an inner-facing surface 272 exposed to the lumen 274 of the vessel 268 and a wall-contacting surface 276 in contact with the inner surface 278 of the vessel wall 280. Include. In the illustrated embodiment, the closure 270 is an assembly of the stopper 282 and the shield 284.

VII.A.2.a. How to apply a lubricity coating to a stopper in a vacuum chamber

VII.A.2.a. Another embodiment is a method of applying a coating onto an elastic stopper, such as 282. The stopper 282 separated from the vessel 268 is located in a substantially vacuum chamber. A reaction mixture is provided which comprises a plasma forming gas such as an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas. Plasma is formed in the reaction mixture in contact with the stopper. w is 1, wherein x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 2 to about 9, preferably w is 1, x is from about 0.5 to 1, y Is about 2 to about 3, and z is 6 to about 9, a coating of Si _w O _x C _y H _z is deposited on at least a portion of the stopper.

VII.A.2.a. In the illustrated embodiment, the wall-contacting surface 276 of the closure 270 is coated with a lubricity coating 286.

VII.A.2.a. In some embodiments, the coating of Si _w O _x C _y H _z is equal to the metal ion component of the stopper or one or more components of the vessel wall are effective to reduce permeation to the vessel lumen. Certain elastic compositions of the type useful for fabricating the stopper 282 include trace amounts of one or more metal ions. These ions must sometimes not move to lumen 274 or be in contact with the container contents in substantial amounts, especially if the sample container 268 is used to collect a sample for trace metal analysis. Coatings comprising relatively little amount of organic content with low or zero y and z are considered to be particularly useful herein as metal ion barriers. For silica as a metal ion barrier, for example, Anupama Mallikarjunan, Jasbir Juneja, Guangrong Yang, Shyam P. Murarka, and Toh-Ming Lu, The Effect of Interfacial Chemistry on Metal Ion Penetration, all of which are incorporated herein by reference. into Polymeric Films, Mat. Res. Soc. Symp. Proc., Vol. 734, pp. B9.60.1 to B9.60.6 (Materials Research Society, 2003); See US Pat. Nos. 5,578,103 and 6200658 and European Patent Application EP0697378A2. However, it is contemplated that some organic content may be useful for providing a more elastic coating and for attaching the coating to the elastic surface of the stopper 282.

VII.A.2.a. In some embodiments, the coating of Si _w O _x C _y H _z has a first or inner layer 288 interfering with the elastomeric stopper 282 and one or more components of the stopper 282 to the vessel lumen It may be a composite made of a material having first and second layers effective to reduce the permeation of. The second layer 286 may interfere with the interior wall 280 of the vessel and the stopper 282 and the vessel of the vessel when the stopper 282 is seated on or in the vessel 268. It is effective to reduce friction between inner walls 280. Such complexes are described elsewhere in connection with syringe coatings herein.

VII.A.2.a. The first and second layers 288 and 286 are also defined by a coating of thickened properties, where the values of y and z are greater in the first layer than in the second layer.

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

VII.A.2.a. Certain advantages are contemplated for much thicker (more than one micron) conventional spray applied silicone lubricants versus plasma applied lubricity layers. Plasma coatings have a lower migration potential to move into the blood than sprayed or micron-coated silicones, which have a much smaller amount of plasma coated material, which is applied more closely to the coated surface and more in place Because it can be combined well.

VII.A.2.a. As applied by PECVD, nanocoatings are considered to provide lower resistance to sliding of adjacent surfaces or flow of adjacent fluids than micron coatings because plasma coatings tend to provide smoother surfaces.

VII.A.2.a. Another embodiment is a method of applying a coating of Si _w O _x C _y H _z on an elastic stopper. The stopper can be used, for example, to close the container described above. The method includes some steps. The stopper is provided in a substantially vacuum chamber. A reaction mixture is provided which comprises a plasma forming gas such as an organosilicon compound gas, optionally an oxidizing gas and optionally a hydrocarbon gas. Plasma is formed in the reaction mixture. The stopper is in contact with the reaction mixture and deposits a coating of Si _w O _x C _y H _z on at least a portion of the stopper.

VII.A.2.a. In carrying out this method, it is contemplated that in order to obtain a larger number of y and z, the reaction mixture may comprise a hydrocarbon gas, as further described above and below. Optionally, if lower values of y and z or higher values of x are considered, the reaction mixture may include oxygen. Also, in particular, the reaction mixture may be essentially free of oxidizing gas in order to reduce oxidation and increase the values of y and z.

VII.A.2.a. In implementing a method of coating certain embodiments of a stopper, such as stopper 282, it is considered unnecessary to project the reaction mixture onto recesses of the stopper. For example, the wall-contacting and inner facing surfaces 276 and 272 of the stopper 282 are convex in nature so that a plurality of stoppers such as 282 can be found and processed in a single substantially vacuum reaction chamber. It is easily processed by a batch process. In addition, in some embodiments, the coatings 286 and 288 are oxygen or water as barrier coatings on the inner surface 280 of the container 268 because the material of the stopper 282 can perform this function considerably. It is not considered necessary to suggest that the barrier against is strong.

VII.A.2.a. Many variations of the stopper and stopper coating processes are contemplated. The stopper 282 may be in contact with the plasma. In addition, plasma is formed upstream of the stopper 282 to produce a plasma product, which may be in contact with the stopper 282. The plasma may be formed by exciting the reaction mixture with electromagnetic energy and / or microwave energy.

VII.A.2.a. Changes in the reaction mixture are contemplated. The plasma forming gas may comprise an inert gas. The inert gas can be, for example, argon or helium, or other gases described in this disclosure. The organosilicon compound gas may be or include any one of HMDSO, OMCTS, other organosilicon compounds mentioned in the present disclosure, or a combination of two or more thereof. The oxidizing gas can be oxygen or other gases mentioned in this disclosure or a combination of two or more of them. The hydrocarbon gas can be, for example, methane, methanol, ethane, ethylene, ethanol, propane, propylene, propanol, acetylene or combinations of two or more thereof.

VII.A.2.b. Applying a group III or IV element and a coating of carbon onto the stopper by PECVD

VII.A.2.b. Another embodiment is a method of applying a coating of a composition comprising carbon and one or more elements of Group III or Group IV on an elastic stopper. In order to carry out the method, the stopper is placed in a vacuumed chamber.

VII.A.2.b. A reaction mixture is provided in the deposition chamber comprising a plasma forming gas having a gas source of Group III elements, Group IV elements, or a combination of two or more thereof. Optionally, the reaction mixture comprises an oxidizing gas and optionally a gaseous compound having one or more C—H bonds. A plasma is formed in the mixture and the stopper is in contact with the reaction mixture. A coating of a group III element or compound, a group IV element or compound or a combination of two or more thereof is deposited on at least a portion of the stopper.

VII.A.3. Stoppered plastic container with barrier coating effective to maintain 95% vacuum for 24 months

VII.A.3. Another embodiment is a container comprising a container, a barrier coating and a closure. The vessel is generally tubular and made of thermoplastic material. The container has an inlet and a lumen at least partially bounded by the wall. The wall has an interior surface that interfaces with the lumen. At least one essentially continuous barrier coating is applied on the inner surface of the wall. Barrier coatings are effective in providing substantial life. A closure is provided that covers the inlet of the vessel and separates the lumen of the vessel from the ambient air.

VII.A.3. 23-25, a vessel 268 is shown, such as a vacuumed blood collection tube or other vessel.

VII.A.3. In this embodiment, the container is a generally tubular container having at least one essentially continuous barrier coating and closure. The vessel has a lumen at least partially bounded by a wall having an inlet and an inner surface interfacing with the lumen. The barrier coating is deposited on the inner surface of the wall and provides at least 95%, or at least 90% of the initial vacuum level of the container for a shelf life of at least 24 months, optionally at least 30 months, and optionally at least 36 months. It is effective to maintain. The closure covers the inlet of the vessel and separates the lumen of the vessel from the ambient air.

VII.A.3. Closures, for example closure 270 or other types of closures shown in the figures, are provided to maintain a partial vacuum and / or include a sample and to limit or prevent exposure of the sample to oxygen or contaminants. 23 to 25 are based on the drawings in US Pat. No. 6,602,206, but the present findings are not limited to that or other specific types of closures.

VII.A.3. The closure 270 has an inner-facing surface 272 exposed to the lumen 274 of the vessel 268 and a wall-contacting surface 276 in contact with the inner surface 278 of the vessel wall 280. Include. In the illustrated embodiment, the closure 270 is an assembly of the stopper 282 and the shield 284.

VII.A.3. In the illustrated embodiment, the stopper 282 defines the wall-contacting surface 276 and the inner surface 278, while the vessel 268 is open and air enters in and out to equalize the pressure difference. Due to the pressure difference in and out of the vessel 268, the shield is usually or entirely outside of the stopper vessel 268 and maintains and provides a grip for the stopper 282, and the closure 270 is provided. The self removing is not exposed to any contents discharged from the container 268.

VII.A.3. It is also contemplated that the coatings on the vessel wall 280 and the wall contact surface 276 of the stopper can be adjusted. The stopper may be coated with a lubricious silicone layer, for example the container wall 280 made of PET or glass may be coated with a harder SiO _x layer or the bottommost SiO _x layer and a lubricity overcoat.

VII.B. Syringes

VII.B. The foregoing description usually covers applying a barrier coating to a tube that is permanently closed at one end, such as a blood collection tube or more generally a sample receiving tube 80. The device is not limited to such a device.

VII.B. Another example of a suitable container, shown in FIGS. 20-22, is a syringe barrel 250 for a medical syringe 252. Such syringes 252 are sometimes pre-filled with saline, pharmaceutical preparations or the like for use in medical technology. In addition, the prefilled syringes 252 may be configured to prevent the contents of the prefilled syringe 252 from coming into contact with the plastic of the syringe, for example, the plastic of the syringe barrel 250 during storage. 254 is believed to benefit from a SiO _x barrier or other type of coating. A barrier or other type of coating can be used to avoid discoloring components of the plastic through the inner surface 254 into the contents of the barrel.

VII.B. In general, the shaped syringe barrel 250 includes a rear end 256 which receives the plunger 258 and a shear which receives tubing for the purpose of dispensing the contents of a subcutaneous injection, nozzle or syringe or receiving material into the syringe 252 ( 260 may be open on both sides. However, the front end 260 may optionally be capped and the plunger 258 may optionally be in place before the prefill syringe 252 is used to close the barrel 250 at both ends. have. The cap may have the syringe barrel 250 until the cap 262 is removed and (optionally) a subcutaneous injection or other delivery channel is fitted on the shear 260 to make the syringe 252 ready for use. Or for handling the assembled syringe or to hold it in place during storage of the prefilled syringe 252.

VII.B.1. Assemblies

VII.B.1. 42 is also usable with the embodiments of FIGS. 2, 3, 6-10, 12-22, 26-28, 33-34, and 37-41, for example the vessel holder 450 of the figure. And other syringe barrel structures suitable for use with the present invention.

VII.B.1. 50 is an exploded view and FIG. 51 is an assembled view of the syringe. The syringe barrel can be treated with the container handling and inspection apparatus of FIGS. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.

VII.B.1. The installation of the cap 262 causes the barrel 250 to be a closed end container in which the SiO _x blocking layer or other type of coating can be provided on the inner surface 254 in the device shown previously, optionally A coating is provided on the interior 264 of the cap and connects the interface between the interior of the cap 264 and the barrel tip 260. A suitable device adapted for this use is shown, for example, in FIG. 21 and is similar to FIG. 2 except for replacing the container 80 of FIG. With a capped syringe barrel 250. VII.B.

VII.B.1 degree. 52 is a view similar to FIG. 42 showing the syringe barrel being processed, with no flanges or flanger stops 440. The syringe barrel can be used with the container handling and inspection apparatus of FIGS. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.

VII.B.1.a. Syringe with barrel coated with lubricious coating coated from organosilicon precursor

VII.B.1.a. Another embodiment is a container having a lubricity coating of Si _w O _x C _y H _z , a type made by the following process.

VII.B.1.a. A precursor is provided as defined above.

VII.B.1.a. The precursor is applied to the substrate under conditions effective to form a coating. The coating is polymerized, crosslinked, or both, to form a lubricious surface with lower plunger activation force or breakout force than the untreated substrate.

VII.B.1.a. For each of the VII or sub-parts of any of the embodiments, an optionally applying step is performed by evaporating the precursor and providing it near the substrate.

VII.B.1.a. Any one of the above embodiments VII.A.1.a.i, optionally plasma, and optionally non-hollow-cathode plasma, is formed near the substrate. Optionally, the precursor is provided in the substantial absence of oxygen. Optionally, the precursor is provided in the substantial absence of carrier gas. Optionally, the precursor is provided in the substantial absence of nitrogen. Optionally, the precursor is provided at an absolute pressure of less than 1 Torr. Optionally, the precursor is optionally provided near the plasma emission. Optionally, the reaction product of the precursor is applied to the substrate in a thickness of 1 to 5000 nm, or 10 to 1000 nm or 10 to 200 nm or 20 to 100 nm thick. Optionally, the substrate comprises glass. Optionally, the substrate is a polymer, optionally a polycarbonate polymer, optionally an olefin polymer, optionally a cyclic olefin copolymer, optionally a polypropylene polymer, optionally a polyester polymer, optionally polyethylene terephthalate Polymers.

Optionally, the plasma is for example an RF frequency as defined above, for example less than 10 kHz to 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz and most preferred. It is preferably produced by energizing a gaseous reactant comprising the precursor using electrodes powered at a frequency of 13.56 MHz.

Optionally, the plasma is 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, in particular 8 It is produced by energizing a gaseous reactant comprising the precursor using powered electrodes of W. The ratio of power to plasma volume may be 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. These power levels are suitable for applying lubricating coatings to syringes and sample tubes and containers of similar shape having a void volume of 1 to 3 mL in which PECVD plasma is generated. It is contemplated that the power applied for larger or smaller objects will increase or decrease as the process scales with respect to the size of the substrate.

VII.B.1.a Another embodiment is a lubricity coating on the inner wall of a syringe barrel. The coating is produced from a PECVD process using the following materials and conditions. As defined elsewhere herein for lubricity coatings, cyclic precursors selected from monocyclic siloxanes, polycyclic siloxanes, or a combination of two or more thereof are preferably employed. One example of a suitable cyclic precursor includes octamethylcyclotetrasiloxane (OMCTS), optionally mixed with other precursor materials in any ratio. Optionally, the cyclic precursor is essentially composed of octamethycyclotetrasiloxane (OMCTS), which thereby provides the basic and novel properties of the resulting lubricity coating, ie the plunger activity or breakout force of the coated surface. It means that it can exist in an amount that does not change, such as a decrease.

VII.B.1.a At least essentially no oxygen is added to the process. Residual atmospheric oxygen may be present in the syringe barrel, and residual oxygen supplied in the previous stage and not completely consumed may be present in the syringe barrel, defined as essentially oxygen free here. If no oxygen is added to the process, it is also in the "essentially oxygen free" range.

VII.B.1.a Sufficient Plasma Generating Power Input, For example, any power level successfully used or described herein in one or more of the examples herein is provided to induce coating formation. .

VII.B.1.a The materials and conditions employed herein may comprise at least about 25%, or at least 45%, or at least 60, of the syringe barrel uncoated syringe plunger force or breakout force moving through the syringe barrel. It is effective to reduce by more than%, or 60%. Plunger active or brake force reduction ranges of 20 to 95 percent, or 30 to 80 percent, or 40 to 75 percent, or 60 to 70 percent are contemplated.

VII.B.1.a. Another embodiment is a container having a hydrophobic coating on the inner wall with the following structure: w, x, y and z are Si _w O _x C _y H _z as defined above. The coating is prepared as described for lubricant coatings of similar composition, but under conditions effective to form a hydrophobic surface with a higher contact angle than the untreated substrate.

VII.B.1.a. For any of the above embodiments VII.A.1.a.ii, the substrate optionally comprises glass or polymer. Optionally the glass is 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 embodiment is a syringe comprising a plunger, a syringe barrel and a lubricious layer. The syringe barrel has an interior surface slidably receiving the plunger. The lubricity layer is provided on the inner surface of the syringe barrel and includes a coating of Si _w O _x C _y H _z lubricity layer. The lubricity layer is less than 1000 nm thick and is effective in reducing the breakout force or plunger force required to move the plunger within the barrel. In addition, the decrease in the plunger force is expressed as a decrease in the sliding coefficient of sliding of the plunger or a decrease in the plunger force in the barrel; These terms are considered to have the same meaning herein.

VII.B.1.a. The syringe 544 of FIGS. 50-51 includes a plunger 546 and a syringe barrel 548. The syringe barrel 548 has an inner surface 552 that slidably receives the plunger 546. In addition, the inner surface 552 of the syringe barrel 548 includes a lubricant coating 554 coating of Si _w O _x C _y H _z . The lubricity layer is less than 1000 nm thick, optionally less than 500 nm thick, optionally less than 200 nm thick, optionally less than 100 nm thick, optionally less than 50 nm thick, and overcomes adhesion of the plunger after storage It is effective to reduce the plunger force required to move the plunger in the barrel after the breakout force or plunger force required to loosen. Lubricity coatings are characterized as having plunger active or breakout forces on uncoated surfaces.

VII.B.1.a. Any of the precursors of any type may be used alone or in combination of two or more of them to provide a lubricity coating.

VII.B.1.a. In addition to utilizing vacuum processes, low temperature atmospheric (non-vacuum) plasma processes may also be utilized to induce molecular ionization and deposition via precursor monomer vapor delivery in a non-oxidizing atmosphere such as helium or argon. Thermal CVD can also be considered to be through flash pyrolysis deposition.

VII.B.1.a. The approaches are similar to vacuum PECVD in that surface coating and crosslinking mechanisms can occur simultaneously.

VII.B.1.a. Another means contemplated for any coating or coatings described herein is a coating that is not uniformly applied throughout the interior 88 of the container. For example, different or different coatings may be selectively applied to the cylindrical portion inside the container, or vice versa, as compared to the semicircular portion inside the container at the closed end 84. This means is particularly contemplated for the syringe barrel or sample collection tube described below, provided that a lubricating surface is provided on some or all of the cylindrical portion of the barrel with the plunger piston or the closure sliding, but not elsewhere.

VII.B.1.a. Optionally, the precursor may be provided in the presence, substantially presence or absence of oxygen, in the presence, substantially presence or absence of nitrogen, or in the presence, substantially presence or absence of a carrier gas. In one embodiment contemplated, the precursor is transferred to the substrate and via PECVD to apply and cure the coating.

VII.B.1.a. Optionally, the precursor may be provided at an absolute pressure of less than 1 Torr.

VII.B.1.a. Optionally, the precursor may be provided near the plasma emission.

VII.B.1.a. Optionally, the reaction product of the precursor may be applied to the substrate in a 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 embodiments, the substrate may be a glass or polymer, such as a polycarbonate polymer, an olefin polymer (eg cyclic olefin copolymer or polypropylene polymer), or a polyester polymer (eg, Polyethylene terephthalate polymer).

VII.B.1.a. In any of the above embodiments, the plasma is generated by energizing a gaseous reactant containing the precursor using electrodes powered at an RF frequency, as defined herein.

VII.B.1.a. In any of the above embodiments, the plasma is generated by energizing a gaseous reactant containing the precursor using electrodes supplied with sufficient power to produce a lubricity coating. Optionally, the plasma is 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, in particular 8 It is produced by energizing a gaseous reactant comprising the precursor using powered electrodes of W. The ratio of power to plasma volume may be 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. These power levels are suitable for applying lubricating coatings to syringes and sample tubes and containers of similar shape having a void volume of 1 to 3 mL in which PECVD plasma is generated. It is contemplated that the power applied for larger or smaller objects will increase or decrease as the process scales with respect to the size of the substrate.

VII.B.1.a. The coating can be cured by polymerizing, crosslinking or performing both of the coatings to form a lubricious surface with lower plunger activity or breakout force than the untreated substrate. Curing may occur during an application process such as PECVD or may be performed or at least completed by other treatments.

VII.B.1.a. Although plasma deposition has been used herein to demonstrate coating characteristics, other deposition methods can be used as long as the chemical composition of the starting material is preserved as much as possible while still desorbing the solid film attached to the base substrate.

VII.B.1.a. For example, the coating material may be applied onto a syringe barrel (from liquid state) by spraying the coating or immersing the substrate into a coating in which the coating is a pure precursor or a solvent-diluted precursor (allowing mechanical deposition of thinner coatings). Can be. Preferably, the coating may be crosslinked using thermal energy, UV energy, electron beam energy, plasma energy or any combination thereof.

VII.B.1.a. It is also contemplated to apply the silicon precursor onto the surface as described above and then perform a separate curing process. Application and curing conditions may be similar to those used for atmospheric plasma curing of pre-coated polyfluoroalkyl ethers, a process performed under the TriboGlide® brand. Further details of this process can be found at http://www.triboglide.com/process.htm.

VII.B.1.a. In such a process, the part of the part to be coated may optionally be pre-treated with an atmospheric plasma. This pretreatment cleans and activates the surface to accommodate the lubricant sprayed in the next step.

VII.B.1.a. In the case of any of the precursors or polymerized precursors, the lubricating fluid is then sprayed onto the surface to be treated. For example, IVEK precision dispensing techniques can be used to accurately spray fluids and produce a uniform coating.

VII.B.1.a. The coating is then bonded or crosslinked to the part, again using an atmospheric plasma field. All this immobilizes the coating and improves the performance of the lubricant.

  VII.B.1.a. Optionally, atmospheric plasma can be generated from ambient air in the vessel, in which case no gas supply and vacuum extraction equipment are required. Preferably, however, the vessel is at least substantially closed during the generation of the plasma to minimize power requirements and prevent contact of the plasma with surfaces or materials outside the vessel.

VII.B.1.a.i. Lubricity Coating: SiO _x Blocking, lubricious layer, surface treatment.

Surface treatment

VII.B.1.a.i. Another embodiment is a syringe with an inner surface that includes a barrel defining a lumen and that slidably receives the plunger, ie, receives the plunger in sliding contact with the inner surface.

VII.B.1.a.i. The syringe barrel can be made of a thermoplastic based material.

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

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

VII.B.1.a.i. For example, the lubricity coating can be applied by PECVD in any embodiment. The lubricity coating is deposited from an organosilicon precursor and is less than 1000 nm thick.

VII.B.1.a.i. Surface treatment is carried out on the lubricity coating in an amount effective to reduce the lubrication coating, the thermoplastic base material, or both, to be filtered or extractable. Thus, the treated surface can act as a solute retainer. Such surface treatment may be a skin coating such as at least 1 nm thick and less than 100 nm, or less than 50 nm thick, or less than 40 nm thick, or less than 30 nm thick, or less than 20 nm thick, or less than 10 nm thick, or 5 Skin coatings that are less than nm thick, or less than 3 nm thick, or less than 2 nm thick, or less than 1 nm thick, or less than 0.5 nm thick can be obtained.

As used herein, “filtration” refers to a material that has transferred from a substrate, such as a container wall, into the contents of a container, such as a syringe. Typically, the filterables are measured by storing the container with the intended contents and then analyzing the contents to determine what material is filtered from the container wall into the intended contents. “Extraction” refers to a material that is removed from a substrate by introducing a solvent or dispersion medium other than the intended contents of the container to determine what material can be removed from the substrate to the extraction medium in the test conditions.

VII.B.1.ai The surface treatment to be a solute retainer may optionally be a SiO _x or Si _w O _x C _y H _z coating, respectively, as previously defined herein. In one embodiment, the surface treatment may be applied by PECVD deposition of SiO _x or Si _w O _x C _y H _z . Optionally, the surface treatment is applied using higher power or strong oxidation conditions, or both, than that used to produce the lubricity layer, providing a stronger, thinner, continuous solute retainer 539. can do. Surface treatment is less than 100 nm deep, optionally less than 20 nm deep, optionally less than 10 nm deep, optionally less than 5 nm deep, optionally less than 3 nm deep, optionally less than 1 nm deep in lubricity coatings. Alternatively less than 0.5 nm deep, optionally between 0.1 and 50 nm deep.

VII.B.1.ai The solute retainers, including the substrate, are contemplated to provide as low solute filtration performance as necessary for the base lubricity and other layers. This retainer may be composed of large solute molecules and oligomers (eg, siloxane monomers such as HMDSO, OMCTS, fragments thereof, and mobile phase oligomers derived from lubricants such as, for example, "filterable retainers"). It needs to be a solute retainer for, and not a gas (O ₂ / N ₂ / CO ₂ / vapor) barrier. However, the solute retainer may also be a gas barrier (eg, SiOx coating according to the present invention). Vacuum or atmospheric pressure-based PECVD processes can produce good filterable retainers without gas barrier performance. The leachable barrier membrane is thin enough so that during the syringe plunger movement the plunger easily penetrates the “solute retainer” and exposes the sliding plunger nipple just below the lubricity coating, resulting in lower plunger activity or breakout force than the untreated substrate. It forms a lubricious surface having a.

VII.B.1.ai In another embodiment, the surface treatment may be performed by oxidizing the surface of the previously applied lubricity layer by exposing the surface to oxygen in a plasma environment. Plasma environments that form the SiO _x coatings described herein can be used. In addition, atmospheric plasma conditions may be employed in an oxygen rich environment.

VII.B.1.a.i. Although formed, the lubricity layer and solute retainer may optionally be cured simultaneously. In another embodiment, the lubricity layer is at least partially cured, optionally fully cured, and surface treatment may be provided and applied after curing, and the solute retainer may be cured.

VII.B.1.a.i. The lubricity coating and solute retainer are constructed and present in a relative amount effective to provide breakout force, plunger activation force, or both lower than the corresponding force required in the absence of the lubricity coating and surface treatment. That is, the thickness and composition of the solute retainer reduces the filtration of material from the lubricity layer to the contents of the syringe while the lubricity coating below lubricates the plunger. The solute retainer is easily released and is considered thin enough to lubricate the plunger while the lubricity layer still functions when the plunger is moved.

VII.B.1.ai In one embodiment contemplated, lubricity and surface treatment can be applied on the barrel inner surface. In other embodiments contemplated, lubricity and surface treatment can be applied on the plunger. In another embodiment contemplated, lubricity and surface treatment can be applied on the barrel inner surface and plunger. In any of these embodiments, an optional SiO _x blocking layer may be present or absent on the interior of the syringe barrel.

VII.B.1.ai One embodiment contemplated is a triple layer, which is a configuration applied to the inner surface of a multilayer, such as a syringe barrel. Layer 1 may be a SiO _x gas barrier layer made by PECVD of HMDSO, OMCTS or both at oxidation atmospheric pressure. Such atmosphere can be provided, for example, by supplying HMDSO and oxygen gas to the PECVD coating apparatus described herein. Layer 2 may be a lubricity layer with OMCTS applied in a non-oxidizing atmosphere. Such a non-oxidizing atmosphere can be provided, for example, by supplying HMDSO to the PECVD coating apparatus described herein, optionally with substantially or completely free of oxygen. Subsequent solute retainers may be formed as solute retainers using oxygen and higher power sources using OMCTS and / or HMDSO, by treatment to form a thin film of SiO _x or Si _w O _x C _y H _z .

VII.B.1.a.i. It is contemplated that certain such multilayer coatings have at least some of one or more of the following optional advantages. The solute retainer may define internal silicone and prevent it from moving to or within the contents of the syringe, resulting in less silicone particles in the deliverable contents of the syringe and for interaction between the lubricity coating and the contents of the syringe. As opportunities are reduced, they can solve the reported difficulties in handling silicon. They can also solve the problem of moving the lubricity layer away from the lubrication point, thus improving the interface between the syringe barrel and the plunger. For example, the brake free force can be reduced and the attraction to the moving plunger can be reduced or, optionally, both.

VII.B.1.a.i. If the solute retainer breaks, the solute retainer may subsequently adhere to the lubricity coating and syringe barrel to prevent particles from entraining the deliverable contents of the syringe.

VII.B.1.ai In addition, these particular coatings will provide fabrication advantages, especially if barrier coatings, lubricity coatings and surface treatments are applied to the same device, for example the illustrated PECVD device. Optionally, the SiO _x barrier coating, lubricity coating and surface treatment can all be applied in one PECVD apparatus to significantly reduce the amount of handling required.

Other advantages can be obtained by using the same precursors and changing the process to form barrier coatings, lubricity coatings and solute retainers. For example, a SiO _x gas barrier film may be applied using an OMCTS precursor under high power / high O ₂ conditions, followed by an OMCTS precursor with substantially or completely free of low power and / or oxygen. The lubricating film can be applied and the surface treatment can be completed using an OMCTS precursor under medium power and oxygen.

VII.B.1.b SiO _X  Syringes with a barrel with a coated inside and a barrier coated outside

VII.B.1.b. Another embodiment shown in FIG. 50 is a syringe 544 that includes a plunger 546, a barrel 548 and inner and outer barrier coatings 554 and 602. The barrel 548 may be made of a thermoplastic based material defining the lumen 604. The barrel 548 may have an inner surface 552 and an outer surface 606 that slidably receive the plunger. A barrier coating 554 of SiO _x , wherein x is from about 1.5 to about 2.9, may be provided on the inner surface 552 of the barrel 548. A barrier coating 602 of resin may be provided on the outer surface 606 of the barrel 548.

VII.B.1.b. In certain embodiments, the thermoplastic base material is optionally a polyolefin, such as a polypropylene or cyclic olefin copolymer (eg, a material sold under the TOPAS® tradename), a polyester such as polyethylene tere Phthalates, polycarbonates such as bisphenol A polycarbonate thermoplastics or other materials. Composite syringe barrels are contemplated having either one of these materials as the outer layer and the same or different one of these materials as the inner layer. In addition, any of the composite syringe barrels or material combinations of sample tubes described elsewhere herein can be used.

VII.B.1.b. In certain embodiments, the resin can optionally include polyvinylidene chloride in the form of a homopolymer or copolymer. For example, PvDC homopolymers (common name: Saran) or copolymers described in US Pat. No. 6,165,566, incorporated herein by reference, may be employed. Optionally, the resin can be applied on the outer surface of the barrel in the form of a latex or other dispersion.

VII.B.1.b. In some embodiments, the syringe barrel 548 may optionally include a lubricity coating disposed between the plunger and the barrier coating of SiO _x . Suitable lubricity coatings are described herein.

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

VII.B.1.b. In some embodiments, the syringe barrel 548 has a surface that handles the lubricity coating in an amount effective to reduce surface filtering of the lubricity coating, components of the thermoplastic based material, or both, into the lumen 604. Treatment may be included.

VII.B.1.b SiO _X  Method of making a syringe having a barrel with a coated inside and a barrier coated outside

VII.B.1.c. Yet another embodiment is a method of making a syringe as described in any of the embodiments of Part VII.B.1.b, which includes a plunger, a barrel and inner and outer barrier coatings. A barrel is provided having an inner surface and an outer surface for slidably receiving the plunger. A barrier coating of SiO _x is provided on the inner surface of the barrel by PECVD. A barrier coating of resin is provided on the outer surface of the barrel. The plunger and barrel are assembled to provide a syringe.

VII.B.1.c. For effective coating (homogeneous wetting) of plastic articles with water soluble latex, it is contemplated that matching the surface tension of the latex to the plastic substrate is useful. This may for example reduce the surface tension of the latex (surfactants or solvents) and / or several approaches to independently or in combination with corona pretreatment of plastic articles and / or chemical priming of plastic articles. It can be performed by.

VII.B.1.c. Optionally, the resin can be dip coated onto the outer surface of the barrel and latex coated onto the outer surface of the barrel or applied through both to provide plastic based articles that provide improved gas and vapor barrier performance. can do. Polyvinylidene chloride plastic laminate articles can be fabricated that provide improved gas barrier performance versus unlaminated plastic articles.

VII.B.1.c. In some embodiments, the resin can optionally be heat cured. The resin can optionally be cured by removing water. The resin may be thermally cured, the resin may be exposed to a partial vacuum or low humidity environment, the resin may be catalytically cured or water may be removed by other means.

VII.B.1.c. An effective thermal cure schedule is considered to finally dry and allow PvDC crystallization to provide blocking performance. The primary curing may of course be carried out at high temperatures, for example 180 to 310 ° F. (82 to 154 ° C.), depending on the heat resistance of the thermoplastic based material. The barrier performance after the primary cure may optionally be about 85% of the final barrier performance reached after the final cure.

VII.B.1.c. Final curing may be performed for a long time (such as two weeks) at a temperature ranging from ambient temperature, such as about 65-75 ° F. (18-24 ° C.), to a high temperature, such as 122 ° F. (50 ° C.), for a short time, such as four hours. Can be.

VII.B.1.c. In addition to good barrier performance, PvDC-plastic laminate articles are contemplated to optionally provide one or more desirable properties such as colorless transparency, good gloss, wear resistance, printability and mechanical deformation resistance.

VII.B.2 Plungers

VII.B.2.a Using the piston face coated with the barrier film

VII.B.2.a. Another embodiment is a plunger for a syringe comprising a piston and a push rod. The piston has a front and side and rear portions configured to movably seat within a generally cylindrical syringe barrel. The front face has a barrier coating. The push rod is configured to engage the back portion and to advance the piston in the syringe barrel.

VII.B.2.b. With lubricating coating in contact with the sides

VII.B.2.b. Yet another embodiment is a plunger for a syringe that includes a piston, a lubricity coating and a push rod. The piston has a front side, a substantially cylindrical side and a rear portion. The side is configured to movably seat within the syringe barrel. The lubricity coating is in contact with the side. The push rod is configured to engage the trailing portion of the piston and to advance the piston in a syringe barrel.

VII.B.3. Two part syringe and luer fitting

VII.B.3. Another embodiment is a syringe including a plunger, syringe barrel and luer fitting. The syringe includes a barrel having an inner surface slidably receiving the plunger. The luer fitting includes a luer taper having an inner passage defined by the inner surface. The luer fitting is formed of components separate from the syringe barrel and is joined to the syringe barrel by a coupling. The inner passage of the luer taper has a barrier coating of SiO _x .

VII.B.3. 50-51, syringe 544 optionally includes a luer fitting 556 that includes a luer taper 558 for receiving a cannula installed on an auxiliary luer taper (not shown, conventional). It may include. The luer taper 558 has an interior passageway 560 defined by the interior surface 562. The luer fitting 556 is optionally formed from components separate from the syringe barrel 548 and bonded to the syringe barrel 548 by a coupling 564. As shown in FIGS. 50 and 51, in this case the coupling 564 is clamped together with the male part 566 and the female part 568 together to secure the luer fitting to the barrel 548 in at least substantially leak-proof manner. Has The inner surface 562 of the luer taper may include a barrier coating 570 of SiO _x . The barrier coating can be less than 100 nm thick and is effective in reducing the ingress of oxygen into the inner passages of the luer fitting. The barrier coating may be applied before the luer fitting is connected to the syringe barrel. In addition, the syringe of FIGS. 50-51 has an optional locking ring 572 threaded therein to lock the secondary luer taper of the cannula on the taper 558.

VII.B.4. Lubricant Compositions—Lubricable coatings deposited from organosilicon precursors made by in situ polymerization of organosilicon precursors

VII.B.4.a. Product and Lubricity by Process

VII.B.4.a. Another embodiment is a lubricity coating. This coating may be of the type produced by the following process.

VII.B.4.a. Any of the precursors mentioned herein may be used alone or in combination. The precursor is applied to the substrate under conditions effective to form a coating. The coating is polymerized, crosslinked, or both, to form a lubricious surface with lower plunger activation force or breakout force than the 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 form a coating. The coating is polymerized, crosslinked, or both, to form a lubricious surface with lower plunger activation force or breakout force than the untreated substrate.

VII.B.4.b. Product and Analytical Properties by Process

VII.B.4.b. Another aspect of the invention is an organometallic precursor, preferably an organosilicon precursor, preferably linear siloxane, linear silazane, monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane Or a lubricity coating deposited by PECVD from a feed gas comprising any combination of two or more of these. The coating is between 1.25 and 1.65 g / cm ³ , optionally 1.35 to 1.55 g / cm ³ , optionally 1.4 to 1.5 g / cm ³ , optionally 1.44 as measured by X-ray reflectance (XRR). At a density between 1.48 g / cm ³ .

VII.B.4.b. Another aspect of the invention is an organometallic precursor, preferably an organosilicon precursor, preferably linear siloxane, linear silazane, monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane Or a lubricity coating deposited by PECVD from a feed gas comprising any combination of two or more of these. The coating has, as a degassing component, one or more oligomers comprising repeating-(Me) ₂ SiO- moieties as measured by a gas chromatography / mass spectrometer. Optionally, the coating meets the limitations of any one of Examples VII.B.4.a or VII.B.4.b. Optionally, the coating degassing component measured by gas chromatography / mass spectrometer is substantially free of trimethylsilanol.

VII.B.4.b. Optionally, the coating degassing component can be at least 10 ng / test of oligomers comprising repeating-(Me) ₂ SiO- moieties as measured by a gas chromatography / mass spectrometer using the following test conditions have:

GC column: 30 m X 0.25 mm DB-5MS (J & W Scientific),

0.25 μm film thickness

Flow rate: 1.0 ml / min, uniform flow mode

Detector: mass selection detector (MSD)

Scan Mode: Split Scan (10: 1 Split Ratio)

Degassing conditions: 1½ "(37mm) chamber, purge at 85 ° C. for 3 hours,

Flow rate 60 ml / min

Oven temperature: 40 ° C. (5 minutes) to 300 ° C. at a rate of 10 ° C./min;

Hold at 300 ° C. for 5 minutes.

VII.B.4.b. Optionally, the outgassing component may comprise at least 20 ng / test of oligomers comprising repeating-(Me) ₂ SiO- moieties.

VII.B.4.b. Optionally, the feed gas may be monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane or any combination of two or more thereof, such as monocyclic siloxane, monocyclic sila Glass or any combination of two or more thereof.

VII.B.4.b. The lubricity coating of any embodiment may have a thickness between 1 and 500 nm, alternatively 20 and 200 nm, alternatively 20 and 100 nm, optionally 30 and 100 nm, measured by transmission electron microscopy (TEM). Can be.

VII.B.4.b. Another aspect of the invention is a lubricity coating deposited by PECVD from a feed gas comprising monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane or any combination of two or more thereof. The coating is normalized to 100% of carbon, oxygen and silicon, as measured by X-ray photoelectron spectroscopy (XPS), and atomic concentration of carbon above the atomic concentration of carbon in the atomic formula for the feed gas. Has Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

VII.B.4.b. Optionally, the atomic concentration of carbon (calculated based on XPS conditions in Example 15) is from 1 to 80 atomic percent, or from 10 to 70 atomic percent, or from 20 to 60 atomic percent, or from 30 to 50 atomic percent, or Increase by 35 to 45 atomic percent, or 37 to 41 atomic percent.

VII.B.4.b. Another aspect of the invention is a lubricity coating deposited by PECVD from a feed gas comprising monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane or any combination of two or more thereof. The coating is normalized to 100% of carbon, oxygen and silicon, as measured by X-ray photoelectron spectroscopy (XPS), and the atomic concentration of silicon is less than the atomic concentration of silicon in the atomic formula for the feed gas. Have Optionally, the coating meets the limitations of Example VII.B.4.a or VII.B.4.b.

VII.B.4.b. Optionally, the atomic concentration of silicon (calculated based on XPS conditions in Example 15) is 1 to 80 atomic percent, or 10 to 70 atomic percent, or 20 to 60 atomic percent, or 30 to 55 atomic percent, or 40 to 50 atomic percent, or 42 to 46 atomic percent.

VII.B.4.b. In addition, lubricating coatings having a combination of any two or more of the properties recited in Section VII.B.4 are explicitly contemplated.

VII.C. Courage general

VII.C. Coated containers or containers described herein and prepared according to the methods described herein can be used for the receipt and / or storage and / or delivery of a compound or composition. The compound or composition is, for example, air-sensitive, oxygen-sensitive, humidity sensitive and / or mechanically sensitive. It may be a biologically active compound or composition, such as a drug such as insulin or a composition comprising insulin. In another aspect, it may be a biological fluid, preferably a body fluid such as blood or a blood fraction. In certain aspects of the invention, the compound or composition requires a product to be injected, such as, for example, blood (transfusion from donor to recipient or reintroduction of blood from patient back to the patient) or insulin. It is a product administered to a subject.

VII.C. In addition, a coated container or container, described herein and prepared according to the methods described herein, is used to protect a compound or composition contained in its interior space from mechanical and / or chemical effects of the surface of an uncoated container material. Can be used. For example, it can be used to prevent or reduce precipitation and / or coagulation or platelet activation of the compound or components of the composition, such as insulin precipitation or blood coagulation or platelet activation.

VII.C. It may also be used, for example, to prevent or reduce the entry of one or more compounds from the environment surrounding the container into the interior space of the container to protect the compound or composition contained therein from the environment outside of the container. Such environmental compounds may be gases or liquids, for example atmospheric gases or liquids comprising oxygen, air and / or water vapor.

VII.C. In addition, the coated container as described herein can be stored in a vacuum and in a vacuum. For example, the coating allows for better vacuum retention compared to the corresponding uncoated vessel. In one aspect of this embodiment, the coated container is a blood collection tube. The tube may also contain an agent that prevents blood coagulation or platelet activation, such as for example EDTA or heparin.

VII.C. Any one of the foregoing embodiments is for example about 1 cm to about 200 cm, 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 to 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 It can be made by providing a container with and treating it with a probe electrode as described below. In particular, for longer lengths in this range, it is contemplated that relative motion between the probe and the vessel may be useful during coating formation. This can be done, for example, by moving the vessel relative to the probe or by moving the probe relative to the vessel.

VII.C. In such embodiments, it is contemplated that the coating may be thinner or less complete than would be preferred for the barrier coating, because in some embodiments the container does not require high barrier integrity of the vacuumed blood collection tube. do.

VII.C. An optional feature of any of the preceding embodiments has a central axis.

VII.C. In an optional feature of any one of the preceding embodiments, the vessel wall is at least substantially straight over a span of radius of curvature in the central axis about 100 times the outer diameter of the vessel without breaking the wall. It is flexible enough to bend at least once at &lt; RTI ID = 0.0 &gt;

VII.C. In an optional feature of any one of the preceding embodiments, the radius of curvature at the central axis is about 90 times, or about 80 times, or about 70 times, or about 60 times, or about 50 times, the outer diameter of the vessel, or About 40 times, or about 30 times, or about 20 times, or about 10 times, or about 9 times, or about 8 times, or about 7 times, or about 6 times, or about 5 times, or about 4 times, or About three times, or about two times, or about the outer diameter of the container.

VII.C. As an optional feature of any of the preceding embodiments, the vessel wall may be a fluid-contacting surface made of a flexible material.

VII.C. As an optional feature of any of the preceding embodiments, the vessel lumen can be a fluid flow passage of the pump.

VII.C. As an optional feature of any of the preceding embodiments, the container may be a blood bag adapted to maintain blood in good condition for medical use.

VII.C., VII.D. As an optional feature of any of the preceding embodiments, the polymeric material may be, in two examples, a silicone elastomer or thermoplastic polyurethane or any material suitable for contact with blood or insulin.

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. In an optional feature of any one of the preceding embodiments, the container is a tube.

VII.C. As an optional feature of any one of the preceding embodiments, the lumen has at least two open ends.

VII.C.1. A container containing viable blood having a coating deposited from an organosilicon precursor

VII.C.1. Another embodiment is a blood containing container. Some non-limiting examples of such containers include a blood transfusion bag, a blood sample collection container in which the sample is collected, a tubing of the heart-lung machine, a blood collection bag with a flexible wall, or a patient's blood collection during surgery and the blood collected from the patient. Tubing used to reintroduce the vessel's vasculature. If the container comprises a pump for a blood pump, a particularly suitable pump is a centrifugal pump or a peristaltic pump. The container has a wall; The wall has an interior surface defining a lumen. The inner surface of the wall is preferably w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3, z is from 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 has at least a partial coating of Si _w O _x C _y H _z of 6 to 9. The coating may be as thin as a single molecule or as thick as about 1000 nm. The container contains viable blood that can return to the patient's vasculature placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.1. One embodiment is a blood containing vessel that includes a wall and has an inner surface defining a lumen. The inner surface has at least a partial coating of Si _w O _x C _y H _z . In addition, the coating may comprise or essentially consist of SiO _x where x comprises SiO _x as defined herein. The thickness of the coating is in the range of monomolecular thickness to about 1000 nm thickness on the inner surface. The container contains viable blood that can return to the patient's vasculature placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.C.2. Coatings Deposited from Organosilicon Precursors Reduce Coagulation or Platelet Activation of Blood in Vessels

VII.C.2. Another embodiment is a container having a wall. The wall has an inner surface defining a lumen and preferably w, x, y and z are as defined above: w is 1, x is from about 0.5 to about 2.4, y is from about 0.6 to about 3 , z is from 2 to about 9, more preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, z is from 6 to about 9 Si _w O _x C _y H _z Has at least a partial coating of. The thickness of the coating is from monomolecular thickness to about 1000 nm thick on the inner surface. The coating is effective to reduce clotting or platelet activation of blood exposed to the inner surface, compared to walls of the same type not coated with Si _w O _x C _y H _z .

VII.C.2. Compared to the properties in contact with the unmodified polymer or the SiO _x surface due to the mixing of the Si _w O _x C _y H _z coating, it is believed that the blood will reduce the adhesion or clot formation tendency. This property reduces the required blood concentration of heparin in patients undergoing a type of surgery that requires blood to be removed from the patient and subsequently returned to the patient when using the heart-lung machine during cardiac surgery. It is contemplated to reduce or potentially eliminate this need for treatment with heparin. It is contemplated that this will reduce the complications of surgery involving the passage of blood through such containers by reducing the bleeding complications resulting from the use of heparin.

VII.C.2. Another embodiment is a blood containing container having a wall and having an inner surface defining a lumen. The inner surface has a thickness of the coating of monomolecular thickness to about 1000 nm on the inner surface, wherein the coating is at least a portion of Si _w O _x C _y H _z effective to reduce coagulation or platelet activation of blood exposed to the inner surface. Has a general coating.

VII.C.3. A container containing viable blood and having a coating of group III or group IV elements

VII.C.3. Another embodiment is a blood containing vessel having a wall having an inner surface defining a lumen. The inner surface has at least a partial coating of a composition comprising one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof. The thickness of the coating is from above the monomolecular thickness up to about 1000 nm on the inner surface. The container contains viable blood that can return to the patient's vasculature disposed within the lumen in contact with the coating.

VII.C.4 Coating of Group III or IV Elements Reduces Coagulation or Platelet Activation of Blood in the Vessel

VII.C.4. Optionally, in the vessel of the preceding paragraph, the coating of group III or IV elements is effective to reduce the coagulation or platelet activation of blood exposed to the inner surface of the vessel wall.

VII.D. Pharmaceutical Delivery Containers

VII.D. As described herein, a coated container or container can be used to prevent or reduce the compound or composition contained within the container from escaping into the environment surrounding the container.

Also contemplated are other uses of the coatings and containers described herein that are apparent from either of the description and claims.

VII.D.1. A container containing insulin, having a coating deposited from an organosilicon precursor

VII.D.1. Another embodiment is an insulin containing vessel including a wall having an interior surface defining a lumen. The inner surface is preferably as defined above with w, x, y and z: w is 1, x is from about 0.5 to 2.4, y is from about 0.6 to about 3, z is from 2 to about 9 , More preferably w is 1, x is from about 0.5 to 1, y is from about 2 to about 3, and z is from 6 to about 9 having at least a partial coating of Si _w O _x C _y H _z . The coating may be monomolecular thickness to about 1000 nm thick on the inner surface. Insulin is placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.D.1. Another embodiment is an insulin containing vessel having a wall and having an inner surface defining a lumen. The inner surface has at least a partial coating of Si _w O _x C _y H _z whose thickness of the coating is from monomolecular thickness to about 1000 nm thick on the inner surface. Insulin, eg, FDA approved pharmaceutical insulin for use in humans, is placed in the lumen in contact with the Si _w O _x C _y H _z coating.

VII.D.1. Compared with the properties in contact with the unmodified polymer surface, the mixing of Si _w O _x C _y H _z coatings is thought to reduce the tendency of the insulin to adhere or coagulate in the delivery tube of the insulin pump. . This property is contemplated to reduce or potentially eliminate the need to filter insulin through the delivery tube to remove solid precipitates.

VII.D.2. Coatings Deposited from Organosilicon Precursors Reduce Insulin Precipitation in Containers

VII.D.2. Alternatively, as compared in the vessel of the previous paragraph, with the same surface coating of Si _w O _x C _y H _z is not a coating of Si _w O _x C _y H _z, in reducing the precipitation from the insulin in contact with the inside surface effective.

VII.D.2. Another embodiment is a container having an interior surface that includes a wall and defines a lumen. The inner surface comprises at least a partial coating of Si _w O _x C _y H _z . The thickness of the coating is in the range of monomolecular thickness to about 1000 nm thickness on the inner surface. The coating is effective to reduce precipitation formation from insulin in contact with the inner surface.

VII.D.3. A container containing insulin, having a coating of Group III or Group IV elements

VII.D.3. Another embodiment is an insulin containing vessel including a wall having an interior surface defining a lumen. The inner surface has at least a partial coating of a composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof. The coating can be from monomolecular thickness to about 1000 nm thick on the inner surface. Insulin is provided in the lumen that is in contact with the coating.

VII.C.4 Coating of Group III or IV Elements Reduces Coagulation or Platelet Activation of Blood in the Vessel

VII.D.4. Optionally, in the container of the preceding paragraph, the coating of the composition comprising carbon, one or more Group III elements, one or more Group IV elements, or a combination of two or more thereof may be compared with the interior surface, compared to the same surface without said coating. It is effective in reducing the formation of precipitates from contacting insulin.

Work example

Example 0 Basic Protocols for Forming and Coating Tube and Syringe Barrels

The vessels tested in the examples below were formed and coated according to the following exemplary protocols, except as otherwise indicated in the individual examples. Specific parameter values, such as power and process gas flow, given in the basic protocols below are typical values. If the parameter values have changed compared to these conventional values, this will be indicated in subsequent work examples. The same applies to the type and composition of the process gas.

Protocol for forming a COC tube (eg, used in Examples 1, 19)

Cyclic olefin copolymer (COC) tubes ("COC tubes") of the type and size commonly used as vacuum blood collection tubes have the following dimensions, Topas, available from Hoechst AG, Frankfurt am Main, Germany Injection molded from 8007-04 cyclic olefin copolymer (COC) resin: 75 mm long, 13 mm outer diameter and 0.85 mm wall thickness, each with a volume of about 7.25 cm ³ and a closed and rounded end.

Protocol for forming PET tube (eg used in Examples 2, 4, 8, 9, 10)

Polyethylene terephthalate (PET) tubes ("PET tubes") of the type commonly used as vacuum blood collection tubes are injection molded in the same mold used in the protocol for forming COC tubes having the following dimensions: length 75 mm, outer diameter 13 mm and 0.85 mm wall thickness, each with a volume of about 7.25 cm ³ and a closed, rounded end.

SiO inside the tube _x Protocol for coating with (eg used in Examples 1, 2, 4, 8, 9, 10, 18, 19)

As shown in FIG. 2, an apparatus with the sealing mechanism of FIG. 45, which is a specifically contemplated embodiment, was used. The vessel holder 50 is E.I. Wilmington Delaware. Made from Delrin® acetal resin available from du Pont de Neumours, it has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The vessel holder 50 was housed in a Delrin® structure that allowed the device to move in and out of the electrode 160.

Electrode 160 has a Delrin® shield and is made of copper. The Delrin® shield is uniform around the outside of the copper electrode 160. Electrode 160 was measured approximately 3 inches (76 mm) high (inside) and approximately 0.75 inches (19 mm) wide.

The tube used as the vessel 80 is a vessel holder 50 using Viton® O-rings 490, 504 (trade name of Dupont Performance Elastomers LLC, Wilton, Delaware, USA) around the outside of the tube. Inserted into the base seal (FIG. 45). The tube 80 was carefully moved to the sealing position on an extended (stopped) 1 / 8-inch (3-mm.) Diameter brass probe or counter electrode 108 and pushed against the copper plasma screen.

The copper plasma screen 610 is a perforated copper foil material (K & S Engineering, Chicago, Illinois, part # LXMUW5 copper mesh) cut to fit the outer diameter of the tube, extending radially to serve as a stop for tube insertion. And held in place by the junction surface 494 (see FIG. 45). The two pieces of copper mesh fit snugly around the brass probe or counter electrode 108 to ensure good electrical contact.

The brass probe or counter electrode 108 extended approximately 70 mm into the interior of the tube and had an array of # 80 wires (diameter = 0.0135 inch or 0.343 mm). The brass probe or counter electrode 108 extended through the Swagelok® fitting (available from Swagelok, Solon Ohio, USA) at the bottom of the vessel holder 50 and extended through the vessel holder 50 base structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

Gas delivery port 110 is twelve holes in the probe or counter electrode 108 along the length of the tube (three on each of four sides 90 degrees from each other) and is blocking the end of gas delivery port 110. Two holes in the cab. The gas delivery port 110 was connected to a stainless steel assembly consisting of Swagelok® fittings incorporating a manual ball valve for discharge, a thermocouple pressure gauge and a bypass valve connected to a vacuum pumping line. In addition, process gases, oxygen, and hexamethyldisiloxane (HMDSO) were connected to the gas delivery port 110 to flow through the gas delivery port 110 (under process pressure) into the interior of the tube.

The gas system uses an Aalborg® GFC17 mass flow meter (Part # EW-32661-34, Cole, Barrington, Ill.) To allow oxygen to be controlled and flowed into the process at 90 sccm (or in certain flows reported for specific examples). -Parmer Instrument) and 49.5 in. (1.26 m) polyether ether ketone ("PEEK") capillaries (outer diameter, "OD" 1 / 16-inch (1.5-mm.), Inner diameter, "ID" 0.004 inches ( 0.1 mm)). PEEK capillary ends were inserted into liquid hexamethyldisiloxane ("HMDSO", Alfa Aesar® Part No. L16970, NMR grade available from Johnson Matthey PLC, London). Liquid HMDSO was aspirated through the capillary due to the lower pressure in the tube during the process. The HMDSO was then vaporized with steam at the outlet of the capillary as it entered the low pressure region.

To avoid condensation of the liquid HMDSO past this point, the gas stream (containing oxygen) was diverted to the pumping line if it did not flow into the interior of the treatment tube via a Swagelok® three-way valve. Once the tube was installed, the vacuum pump valve was opened into the vessel holder 50 and the interior of the tube.

Alcatel rotary vacuum pumps and blowers included a vacuum pump system. The pumping system allowed the interior of the tube to be reduced to a pressure of less than 200 mTorr while the process gases were flowing at the indicated speed.

Once the basic vacuum level was reached, the vessel holder 50 assembly was moved to the electrode 160 assembly. The gas stream (oxygen and HMDSO vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the tube was approximately 300 mTorr as measured by a capacitive manometer (MKS) installed in the pumping line near the valve that regulates the vacuum. In addition to the tube pressure, the pressure within the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 8 Torr.

Once the gas flowed into the tube, the RF power supply was operated at a fixed power level. The ENI ACG-6 600 Watt RF power supply was used (at 13.56 MHz) at a fixed power level of approximately 50 Watts. The output power was calibrated in this and all the following protocols and examples using a Bird Corporation Model 43 RF Watt Meter connected to the RF output of the power supply while the coating device was running. The following relationship was found between the dial setting for the power supply and the output power: RF power output = 55 x dial setting. In the priority applications for this application, factor 100 was used, which was inaccurate. The RF power supply was connected to the COMDEL CPMX1000 auto matching, which matches the complex impedance of the plasma (generated in the tube) with the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 50 watts (or a specific amount reported for the specific example) and the reflected power was 0 watts so that the applied power was delivered to the interior of the tube. The RF power supply was controlled by a laboratory timer and power for a time set to 5 seconds (or a specific time period reported for a particular embodiment). Once the RF power source was initiated, a uniform plasma was established inside the tube. The plasma was held for a total of 5 seconds until the RF power was terminated by a timer. The plasma produced a silicon oxide coating approximately 20 nm thick (or the specific thickness reported in the specific examples) on the inside of the tube surface.

After coating, the gas flow returned back to the vacuum line and the vacuum valve was closed. The exhaust valve then opened, returning the interior of the tube to atmospheric pressure (approximately 760 Torr). The tube was then carefully removed from the vessel holder 50 assembly (after moving the vessel holder 50 assembly from the electrode 160 assembly).

Protocol for coating the inside of the tube with a hydrophobic coating (eg used in Example 9)

As shown in FIG. 2, an apparatus with the sealing mechanism of FIG. 45, which is a specifically contemplated embodiment, was used. The vessel holder 50 is E.I. Wilmington Delaware. Made from Delrin® acetal resin available from du Pont de Neumours, it has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The vessel holder 50 was housed in a Delrin® structure that allowed the device to move in and out of the electrode 160.

Electrode 160 has a Delrin® shield and is made of copper. The Delrin® shield is uniform around the outside of the copper electrode 160. Electrode 160 was measured approximately 3 inches (76 mm) high (inside) and approximately 0.75 inches (19 mm) wide.

The tube used as the vessel 80 is a vessel holder (50) using Viton® O-rings 490, 504 (Viton® is a trademark of Dupont Performance Elastomers LLC, Wilmington, USA) around the outside of the tube. ) Was inserted into the base seal (FIG. 45). The tube 80 was carefully moved to the sealing position on an extended (stopped) 1 / 8-inch (3-mm.) Diameter brass probe or counter electrode 108 and pushed against the copper plasma screen.

The copper plasma screen 610 is a perforated copper foil material (K & S Engineering, Chicago, Illinois, part # LXMUW5 copper mesh) cut to fit the outer diameter of the tube, extending radially to serve as a stop for tube insertion. And held in place by the junction surface 494 (see FIG. 45). The two pieces of copper mesh fit snugly around the brass probe or counter electrode 108 to ensure good electrical contact.

The brass probe or counter electrode 108 extended approximately 70 mm into the interior of the tube and had an array of # 80 wires (diameter = 0.0135 inch or 0.343 mm). The brass probe or counter electrode 108 extended through the Swagelok® fitting (available from Swagelok, Solon Ohio, USA) at the bottom of the vessel holder 50 and extended through the vessel holder 50 base structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

Gas delivery port 110 is twelve holes in the probe or counter electrode 108 along the length of the tube (three on each of four sides 90 degrees from each other) and is blocking the end of gas delivery port 110. Two holes in the cab. The gas delivery port 110 was connected to a stainless steel assembly consisting of Swagelok® fittings incorporating a manual ball valve for discharge, a thermocouple pressure gauge and a bypass valve connected to a vacuum pumping line. In addition, process gases, oxygen, and hexamethyldisiloxane (HMDSO) were connected to the gas delivery port 110 to flow through the gas delivery port 110 (under process pressure) into the interior of the tube.

The gas system uses an Aalborg® GFC17 mass flow meter (Part # EW-32661-34, Cole, Barrington, Ill.) To allow oxygen to be controlled and flowed into the process at 60 sccm (or in certain flows reported for specific examples). -Parmer Instrument) and 49.5 in. (1.26 m) polyether ether ketone ("PEEK") capillaries (outer diameter, "OD" 1 / 16-inch (1.5-mm.), Inner diameter, "ID" 0.004 inches ( 0.1 mm)). PEEK capillary ends were inserted into liquid hexamethyldisiloxane ("HMDSO", Alfa Aesar® Part No. L16970, NMR grade available from Johnson Matthey PLC, London). Liquid HMDSO was aspirated through the capillary due to the lower pressure in the tube during the process. The HMDSO was then vaporized with steam at the outlet of the capillary as it entered the low pressure region.

To avoid condensation of the liquid HMDSO past this point, the gas stream (containing oxygen) was diverted to the pumping line if it did not flow into the interior of the treatment tube via a Swagelok® three-way valve. Once the tube was installed, the vacuum pump valve was opened into the vessel holder 50 and the interior of the tube.

Alcatel rotary vacuum pumps and blowers included a vacuum pump system. The pumping system allowed the interior of the tube to be reduced to a pressure of less than 200 mTorr while the process gases were flowing at the indicated speed.

Once the basic vacuum level was reached, the vessel holder 50 assembly was moved to the electrode 160 assembly. The gas stream (oxygen and HMDSO vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the tube was approximately 270 mTorr as measured by a capacitive manometer (MKS) installed in the pumping line near the valve that regulates the vacuum. In addition to the tube pressure, the pressure within the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 8 Torr.

Once the gas flowed into the tube, the RF power supply was operated at a fixed power level. The ENI ACG-6 600 Watt RF power supply was used (at 13.56 MHz) at a fixed power level of approximately 39 Watts. The RF power supply was connected to the COMDEL CPMX1000 auto matching, which matches the complex impedance of the plasma (generated in the tube) with the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 39 watts (or a specific amount reported for the specific example) and the reflected power was 0 watts so that the applied power was delivered to the interior of the tube. The RF power supply was controlled by a laboratory timer and power for a time set to 7 seconds (or a specific time period reported for a particular embodiment). Once the RF power source was initiated, a uniform plasma was established inside the tube. The plasma was held for a total of seven seconds until the RF power was terminated by a timer. The plasma produced a silicon oxide coating approximately 20 nm thick (or the specific thickness reported in the specific examples) on the inside of the tube surface.

After coating, the gas flow returned back to the vacuum line and the vacuum valve was closed. The exhaust valve then opened, returning the interior of the tube to atmospheric pressure (approximately 760 Torr). The tube was then carefully removed from the vessel holder 50 assembly (after moving the vessel holder 50 assembly from the electrode 160 assembly).

Protocol for forming COC syringe barrels (eg, used in Examples 3, 5, 11-18, 20)

Syringe barrels (“COC syringe barrels”), CV Holdings Part 11447, each with a 2.8 mL total volume (except luer fitting) and a nominal 1 mL delivery volume or plunger variation of the Luer adapter type, Hoechst AG, Frankfurt am Main, Germany Injection molded from Topas® 8007-04 cyclic olefin copolymer (COC) resin, available from USA, having the following values: approximately 51 mm in total length, 8.6 mm inner syringe barrel diameter and 1.27 mm wall in cylindrical area Thickness, integrated 9.5 mm long needle capillary luer adapter molded at one end and two finger flanges formed at the other end.

SiO inside the COC syringe barrel _x Protocol for coating with (eg used in Examples 3, 5, 18)

Injection molded COC syringe barrels were internally coated with SiO _x . As shown in FIG. 2, the device with the sealing mechanism of FIG. 45, which is a specifically contemplated embodiment, was modified to maintain a COC syringe barrel with a bonded seal at the bottom of the COC syringe barrel. In addition, a stainless steel luer fitting and a polypropylene cap sealing the ends of the COC syringe barrel (shown in FIG. 26) were made to allow the interior of the COC syringe barrel to be evacuated.

The vessel holder 50 It is made from Delrin® and has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The vessel holder 50 was housed in a Delrin® structure that allowed the device to move in and out of the electrode 160.

Electrode 160 has a Delrin® shield and is made of copper. The Delrin® shield is uniform around the outside of the copper electrode 160. Electrode 160 was measured approximately 3 inches (76 mm) high (inside) and approximately 0.75 inches (19 mm) wide. The COC syringe barrel was base sealed with Viton® O-rings and inserted into the vessel holder 50.

The COC syringe barrel was carefully moved to the sealing position on an extended (stopped) 1 / 8-inch (3-mm.) Diameter brass probe or counter electrode 108 and pushed against the copper plasma screen. The copper plasma screen is a perforated copper foil material (K & S Engineering, part # LXMUW5 copper mesh) cut to fit the outer diameter of the COC syringe barrel and held in place by a joint surface 494 acting as a stop for COC syringe barrel insertion. It was. The two pieces of copper mesh fit snugly around the brass probe or counter electrode 108 to ensure good electrical contact.

The brass probe or counter electrode 108 extended approximately 20 mm into the interior of the COC syringe barrel and was open at its distal end. The brass probe or counter electrode 108 extended through the Swagelok® fitting at the bottom of the vessel holder 50 and through the vessel holder 50 basic structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

The gas delivery port 110 was connected to a stainless steel assembly consisting of Swagelok® fittings incorporating a manual ball valve for discharge, a thermocouple pressure gauge and a bypass valve connected to a vacuum pumping line. In addition, process gases, oxygen, and hexamethyldisiloxane (HMDSO) were connected to the gas delivery port 110 to flow through the gas delivery port 110 (under process pressure) into the interior of the COC syringe barrel.

The gas system has an Aalborg® GFC17 mass flow meter (Cole-Parmer Part # EW-32661-34) and 49.5 inches in length for controllable flow of oxygen into the process at 90 sccm (or in certain flows reported for specific examples). (1.26 m) of PEEK capillary (OD 1 / 16-inch (3-mm.) ID 0.004 inch (0.1 mm)). The PEEK capillary ends were inserted into liquid hexamethyldisiloxane (Alfa Aesar® Part No. L16970, NMR grade). Liquid HMDSO was aspirated through the capillary due to the lower pressure in the COC syringe barrel during the process. The HMDSO was then vaporized with steam at the outlet of the capillary as it entered the low pressure region.

In order to avoid condensation of the liquid HMDSO past this point, the gas stream (containing oxygen) was diverted to the pumping line if it did not flow through the Swagelok® 3-way valve into the interior of the treatment COC syringe barrel.

Once the COC syringe barrel was installed, the vacuum pump valve was opened into the vessel holder 50 and the interior of the COC syringe barrel. Alcatel rotary vacuum pumps and blowers included a vacuum pump system. The pumping system allowed the interior of the COC syringe barrel to be reduced to a pressure of less than 150 mTorr while the process gases were flowing at the indicated rate. Lower pumping pressures can be achieved using a COC syringe barrel against the tube because the COC syringe barrel has a much smaller internal volume.

Once the basic vacuum level was reached, the vessel holder 50 assembly was moved to the electrode 160 assembly. The gas stream (oxygen and HMDSO vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the COC syringe barrel was approximately 200 mTorr as measured by a capacitive manometer (MKS) installed in the pumping line near the valve that regulates the vacuum. In addition to the COC syringe barrel pressure, the pressure within the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 8 Torr.

Once the gas flowed into the interior of the COC syringe barrel, the RF power supply was operated at a fixed power level. The ENI ACG-6 600 Watt RF power supply was used (at 13.56 MHz) at a fixed power level of approximately 39 Watts. The RF power supply was connected to a COMDEL CPMX1000 automatch that matches the complex impedance of the plasma (generated in the COC syringe barrel) with the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 30 watts (or any number reported in the example) and the reflected power was 0 watts so that power was delivered to the interior of the COC syringe barrel. The RF power supply was controlled by a laboratory timer and power for a time set to 5 seconds (or a specific time period reported for a particular embodiment).

Once the RF power was initiated, a uniform plasma was established inside the COC syringe barrel. The plasma was held for a total of 5 seconds (or other coating time indicated in certain embodiments) until the RF power was terminated by a timer. The plasma produced a silicon oxide coating approximately 20 nm thick (or the specific thickness reported in the specific examples) on the interior of the COC syringe barrel surface.

After coating, the gas flow returned back to the vacuum line and the vacuum valve was closed. The exhaust valve then opened, returning the interior of the COC syringe barrel to atmospheric pressure (approximately 760 Torr). The COC syringe barrel was then carefully removed from the vessel holder 50 assembly (after moving the vessel holder 50 assembly from the electrode 160 assembly).

Protocol for coating the inside of a COC syringe barrel with an OMCTS lubricity coating (eg, used in Examples 11, 12, 15-18, 20)

The COC syringe barrels identified above were internally coated with a lubricity coating. As shown in FIG. 2, the device with the sealing mechanism of FIG. 45, which is a specifically contemplated embodiment, was modified to maintain a COC syringe barrel with a bonded seal at the bottom of the COC syringe barrel. In addition, a stainless steel luer fitting and a polypropylene cap sealing the ends of the COC syringe barrel (shown in FIG. 26) were made to allow the interior of the COC syringe barrel to be evacuated. Installing a Buna-N O-ring on the luer fitting enabled a vacuum tight seal, allowing the interior of the COC syringe barrel to be vacuumed.

The vessel holder 50 It is made from Delrin® and has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The vessel holder 50 was housed in a Delrin® structure that allowed the device to move in and out of the electrode 160.

Electrode 160 has a Delrin® shield and is made of copper. The Delrin® shield is uniform around the outside of the copper electrode 160. Electrode 160 was measured approximately 3 inches (76 mm) high (inside) and approximately 0.75 inches (19 mm) wide. The COC syringe barrel was base sealed with Viton® O-rings near the bottom of the finger flanges and the lip of the COC syringe barrel and inserted into the vessel holder 50.

The COC syringe barrel was carefully moved to the sealing position on an extended (stopped) 1 / 8-inch (3-mm.) Diameter brass probe or counter electrode 108 and pushed against the copper plasma screen. The copper plasma screen is a perforated copper foil material (K & S Engineering, part # LXMUW5 copper mesh) cut to fit the outer diameter of the COC syringe barrel and held in place by a joint surface 494 acting as a stop for COC syringe barrel insertion. It was. The two pieces of copper mesh fit snugly around the brass probe or counter electrode 108 to ensure good electrical contact.

The probe or counter electrode 108 extends approximately 20 mm into the interior of the COC syringe barrel (unless otherwise indicated) and is open at its distal end. The brass probe or counter electrode 108 extended through the Swagelok® fitting at the bottom of the vessel holder 50 and through the vessel holder 50 basic structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

The gas delivery port 110 was connected to a stainless steel assembly consisting of Swagelok® fittings incorporating a manual ball valve for discharge, a thermocouple pressure gauge and a bypass valve connected to a vacuum pumping line. In addition, a gas that allows the process gas, octamethylcyclotetrasiloxane (OMCTS) (or the specific process gas reported for a particular embodiment), to flow into the interior of the COC syringe barrel through the gas delivery port 110 (under process pressure). A gas system is connected to the delivery port 110.

The gas system consisted of a commercially available Horiba VC1310 / SEF8420 OMCTS 10SC 4CR heated mass flow vaporization system that heats the OMCTS to about 100 ° C. The Horiba system connects to liquid octamethylcyclotetrasiloxane (Alfa Aesar® Part No. A12540, 98%) via a 1 / 8-inch (3-mm) outer diameter PFA tube with an inner diameter of 1/16 inch (1.5 mm) It became. OMCTS flow rate was set to 1.25 sccm (or specific organosilicon precursor flow reported for specific examples). In order to avoid condensation of the vaporized HMDSO stream past this point, the gas stream was diverted to a pumping line if it did not flow through the Swagelok® 3-way valve into the interior of the processing COC syringe barrel.

Once the COC syringe barrel was installed, the vacuum pump valve was opened into the vessel holder 50 and the interior of the COC syringe barrel. Alcatel rotary vacuum pumps and blowers included a vacuum pump system. The pumping system allowed the interior of the COC syringe barrel to be reduced to a pressure of less than 100 mTorr while the process gases were flowing at the indicated rate. In this case, because the overall process gas flow rate is lower, a lower pressure could be obtained compared to the tube and previous COC syringe barrel embodiments.

Once the basic vacuum level was reached, the vessel holder 50 assembly was moved to the electrode 160 assembly. A gas stream (OMCTS vapor) flowed into the brass gas delivery port 110 (by adjusting a three-way valve from the pumping line to the gas delivery port 110). The pressure inside the COC syringe barrel was approximately 140 mTorr as measured by a capacitive manometer (MKS) installed in the pumping line near the valve that regulates the vacuum. In addition to the COC syringe barrel pressure, the pressure within the gas delivery port 110 and the gas system was also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 6 Torr.

Once the gas flowed into the interior of the COC syringe barrel, the RF power supply was turned on to a fixed power level. The ENI ACG-6 600 Watt RF power supply was used (at 13.56 MHz) at a fixed power level of approximately 7.5 watts (or other power levels indicated in certain embodiments). The RF power supply was connected to a COMDEL CPMX1000 automatch that matches the complex impedance of the plasma (generated in the COC syringe barrel) with the 50 ohm output impedance of the ENI ACG-6 RF power supply. The forward power was 30 watts and the reflected power was 0 watts so that 7.5 watts of power (or other power level delivered in the given example) was delivered to the interior of the COC syringe barrel. The RF power supply was controlled by a laboratory timer and power for a time set to 10 seconds (or a different time designated in certain embodiments).

Once the RF power was initiated, a uniform plasma was established inside the COC syringe barrel. The plasma was maintained for the entire coating time until the RF power was terminated by a timer. The plasma produced a lubricious coating on the interior of the COC syringe barrel surface.

After coating, the gas flow returned back to the vacuum line and the vacuum valve was closed. The exhaust valve then opened, returning the interior of the COC syringe barrel to atmospheric pressure (approximately 760 Torr). The COC syringe barrel was then carefully removed from the vessel holder 50 assembly (after moving the vessel holder 50 assembly from the electrode 160 assembly).

Protocol for coating the inside of a COC syringe barrel with a HMDSO coating (eg, used in Examples 12, 15, 16, 17)

In addition, a protocol for coating the interior of a COC syringe barrel with an OMCTS lubricity coating was used to apply the HMDSO coating except for replacing OMCTS with HMDSO.

Example 1

V. In the following tests, hexamethyldisiloxane (HMDSO) was used as the organosilicon (“O-Si”) feed to the PECVD apparatus of FIG. 2 to form a cyclic olefin as described in the protocol for forming COC tubes. A SiO _x coating was applied on the inner surface of the copolymer (COC) tube. The deposition conditions are summarized in Table 1 and the protocol for coating the inside of the tube with SiO _x . The control was of the same type as the tube without barrier coating applied. The coated and uncoated tubes were then tested for oxygen transmission rate (OTR) and its water vapor transmission rate (WVTR).

V. Referring to Table 1, the uncoated COC tube had an OTR of 0.215 cc / tube / day. Tubes A and B that had undergone PECVD for 14 seconds had an OTR of 0.0235 cc / tube / day on average. These results show that the SiO _x coating provided oxygen transfer BIF for the uncoated tube of 9.1. That is, the SiO _x barrier coating reduced oxygen transfer through the tube to less than one-ninth of the value without the coating.

V. Tube (C) which had undergone PECVD for 7 seconds had an OTR of 0.026. This result shows that the SiO _x coating provided OTR BIF for the uncoated tube of 8.3. That is, the SiO _x barrier coating applied within 7 seconds reduced oxygen transfer through the tube to less than one eighth of the value in the absence of the coating.

V. Also, the relative WVTRs of the same barrier coatings on COC tubes were measured. The uncoated COC tube had a WVTR of 0.27 mg / tube / day. Tubes A and B that had undergone PECVD for 14 seconds had an OTR of 0.10 mg / tube / day on average. Tube (C) which had undergone PECVD for 7 seconds had a WVTR of 0.10 mg / tube / day. This result shows that the SiO _x coating provided a water vapor transmission barrier enhancement factor (WVTR BIF) for the uncoated tube of about 2.7. This was surprising because the uncoated COC tube already had a very low WVTR.

Example 2

V. A series of PET tubes, made according to the protocol for forming PET tubes, were coated with SiO _x according to the protocol for coating the inside of the tube with SiO _x under the conditions reported in Table 2. Controls were made according to the protocol for forming PET tubes but remained uncoated. OTR and WVTR samples of the tubes were prepared by epoxy sealing the open ends of each tube with an aluminum adapter.

In individual tests using coated PET tubes of the same type, mechanical scratches of various lengths were induced using steel needles through the inner coating and OTR BIF was tested. Controls were coated tubes of the same type with no scratches left or uncoated. OTR BIF was reduced while still improving on uncoated tubes (Table 2A).

V. The tubes were tested for OTR as follows. Each sample / adapter assembly was fitted on a MOCON® Oxtran 2/21 oxygen permeable instrument. Samples were allowed to equilibrate to the permeation rate steady state (1 to 3 days) under the following test conditions:

Test gas: oxygen

Test gas concentration: 100%

Test gas humidity: 0% relative humidity

Test gas pressure: 760 mmHg

Test temperature: 23.0 ° C (73.4 ° F)

Carrier gas: 98% nitrogen, 2% oxygen

Carrier Gas Humidity: 0% Relative Humidity

V. OTR is reported as the average of two measurements in Table 2.

V. The tubes were tested as follows for the WVTR. The sample / adapter assembly was fitted on a MOCON® Permatran-W 3/31 water vapor permeable instrument. Samples were allowed to equilibrate to the permeation rate steady state (1 to 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 as the average of two measurements in Table 2.

Example 3

A series of syringe barrels were made according to the protocol for forming COC syringe barrels. The syringe barrels were _not barriers coated with SiO _x or under the conditions reported in the protocol for coating the COC syringe barrel interior with modified SiO _x as indicated in Table 3.

OTR and WVTR samples of the syringe barrels were prepared by epoxy sealing the open end of each syringe barrel with an aluminum adapter. In addition, the syringe barrel capillary ends were sealed with epoxy. Syringe-adapter assemblies were again tested for OTR or WVTR in the same manner as PET tube samples, using a MOCON® Oxtran 2/21 oxygen permeable instrument and a MOCON® Permatran-W 3/31 water vapor permeable instrument. The results are reported in Table 3.

Example 4

Composition measurement of plasma coatings using x-ray photoelectron spectroscopy (XPS) / electron spectroscopy for chemical analysis (ESCA) surface analysis

PET tubes made according to the protocol for forming VA PET tubes and coated according to the protocol for coating the inside of the tube with SiO _x were cut in half to expose the inner tube surface, which was then X-ray photoelectron spectroscopy (XPS). ).

V.A. XPS data was quantified using a model with relative sensitivity factors and a single layer. The analysis volume is the product of the analysis area (spot size or aperture size) and the depth of information. Optoelectronics are produced within the X-ray penetration depth (typically several microns), but only optoelectronics within the three top electron escape depths are detected. The escape depth is on the order of 15 to 35 mm 3, which leads to an analysis depth of about 50 to 100 mm 3. Typically, 95% of the signal comes from this depth.

V.A. Table 5 provides the atomic ratios of the components detected. The analysis parameters used for the XPS are as follows:

Tool: PHI Quantum 2000

X-ray Source: Solid Color Alka 1486.6 eV

Reception angle + 23 °

Takeoff angle 45 °

600 μm analysis area

Charge Correction C1s 284.8 eV

Ion Gun Conditions Ar +, 1 keV, 2 x 2 mm Raster

Sputter Speed 15.6Å / min (SiO ₂ Equivalent)

V.A. XPS does not detect oxygen or helium. The values given are normalized to Si = 1 for the experimental number (last row) and 0 = 1 for the uncoated polyethylene terephthalate calculations and examples using the detected components. Detection limits are approximately 0.05 to 1.0 electron percent. Also, given values are normalized to 100% Si + O + C atoms.

The VA invention has a Si / O ratio of 2.4, indicating an SiO _x composition with some residual carbon due to incomplete oxidation of the coating. This analysis shows the composition of the SiO _x barrier film applied to the polyethylene terephthalate tube according to the present invention.

VA Table 4 shows the thickness of SiO _x samples measured using TEM according to the following method. Samples were prepared for focused ion beam (FIB) by coating the samples with a sputtered layer of platinum (50-100 nm thick) using the K575X Emitec coating system. The coated samples were placed in a FEI FIB200 FIB system. Platinum additional films were deposited by FIB by injecting organometallic gas while scanning a 30 kV gallium ion beam over the region of interest. The region of interest for each sample was chosen to be less than half the length of the tube. Thin sections measured approximately 15 μm in length (“micrometer”), 2 μm in width, and 15 μm in depth were extracted from the die surface using a proprietary in-situ FIB lift-out technique. . The sections were attached to a 200 mesh copper TEM grid using FIB-deposited platinum. One or two windows in each section, measuring about 8 μm wide, were thinned to electronic transparency using the gallium ion beam of the FEI FIB.

V.C. Cross-sectional image analysis of the prepared samples was performed using transmission electron microscopy (TEM). Imaging data was recorded digitally.

Sample grids were transferred to a Hitachi HF2000 transmission electron microscope. The transmitted electronic images were obtained with appropriate magnification. Appropriate tool settings used during image acquisition are given below.

Example  5

Plasma uniformity

COC syringe barrels made according to the protocol for forming VA COC syringe barrels are processed using a protocol for coating the inside of the COC syringe barrel with SiO _x and Transformed. Three different plasma generation modes were tested for coating syringe barrels such as 250 with SiO _x films. In VA mode 1, hollow cathode plasma ignition was generated within the gas inlet 310, the confined region 292 and the processing vessel lumen 304, and a conventional or non-hollow-cathode plasma was generated from the rest of the vessel lumen 300. Generated in part.

V.A. In mode 2, the hollow cathode plasma ignition was generated in the confined region 292 and the processing vessel lumen 304, and a conventional or non-hollow-cathode plasma was generated in the vessel lumen 300 and the rest of the gas inlet 310. Generated from

V.A. In mode 3, conventional or non-hollow-cathode plasma was generated at the retention vessel lumen 300 and the gas inlet 310. This was done by quenching the hollow cathode ignition at full power up. Table 6 shows the conditions used to achieve these modes.

V.A. The syringe barrels 250 were then exposed to ruthenium oxide staining techniques. Staining was made from sodium hypochlorite bleach and Ru (III) chloride hydrate. 0.2 g of Ru (III) chloride hydrate was placed in a vial. 10 ml of bleach was added and thoroughly mixed until the Ru (III) chloride hydrate was dissolved.

V.A. Each syringe barrel was sealed with a plastic luer seal and three drops of dye mixture were added to each syringe barrel. The syringe barrels were then sealed with aluminum tape and left for 30-40 minutes. In each set of syringe barrels tested, at least one uncoated syringe barrel was stained. The syringe barrels were stored with the restricted area 292 facing up.

V.A. Based on the staining the following conclusions were drawn:

V.A. 1. The staining started to attack the uncoated (or insufficiently coated) areas with exposure within 0.25 hours.

VA 2. An SiO _x coating of the confined region 292 was achieved due to ignition in the confined region 292.

V.A. 3. The best syringe barrels were produced by testing conducted without hollow cathode plasma ignition either at gas inlet 310 or confined area 292. Perhaps only a limited opening 294 was dyed due to stain leakage.

V.A. 4. Dyeing is a good qualitative tool for inducing uniformity work.

V.A. Based on all of the above, we concluded that:

V.A. 1. Under test conditions, the hollow cathode plasma at either the gas inlet 310 or the restricted region 292 had a poor coating uniformity.

V.A. 2. The highest uniformity was achieved without hollow cathode plasma ignition either in the gas inlet 310 or in the restricted region 292.

Example 6

Interference Patterns from Reflectance Measurement—Prophetic Example

VI.A. UV-Visible Light Source (Ocean Optic DH2000-BAL Deuterium Tungsten 200-1000nm), Fiber Optic Reflective Probe (Emitter / Collector Ocean Optic Combination QR400-7 SR / BX with Approx. 3mm Probe Area), Compact Detector (Ocean Optic HR4000CG Using software to convert spectrometer signals to transmittance / wavelength graphs on UV-NIR spectrometers) and laptop computers, uncoated PET tube Becton Dickinson (NJ, USA) product number 366703 13x75 mm (without additives) Scanned using the probe (using a probe perpendicular to the coated surface, emitting and collecting light radially from the centerline of the tube) both in the longitudinal direction around the inner circumference of the tube and along the inner wall of the tube. No possible interference pattern was observed. Then, Beckton Dickinson Product No. 366703 13x75 mm (no additives) SiO _x plasma-coated BD 366703 tube was coated with a 20 nanometer thick SiO ₂ coating, as described in the protocol for coating the inside of the tube with SiO _x . This tube is scanned in a similar manner as the uncoated tube. Certain wavelengths are observed for the coated tube with a distinct interference pattern that is reinforced and the others canceled out in the periodic pattern, indicating the presence of the coating on the PET tube.

Example 7

Enhanced light transmission from integrating constraint detection

VI.A. The equipment used was a Xenon light source (Ocean Optics HL-2000-HP-FHSA-20W output halogen lamp source (185-2000 nm)), an integral restraint detector (Ocean) processed to receive the PET tube therein HR2000 + ES enhanced sensitivity UV with optical ISP-80-8-I) and light transmission and light receptor fiber optical sources (QP600-2-UV-VIS-600um premium optical fiber, UV / VIS, 2m). VIS spectrometer and signal conversion software (SPECTRASUITE-cross-platform spectroscopy operating software). Uncoated PET tubes made according to the protocol for forming PET tubes were inserted onto a TEFZEL tube support (puck) and inserted into an interlacing constraint. Using the Spectrasuite software in absorbance mode, the absorbance was set to zero (at 615 nm). SiO _x coated tube manufactured in accordance with a protocol for forming the PET tube is coated according to the protocol (except for changes it from the table 16) for coating the inner tube with SiO _x is provided on the subsequent puck (puck), the The absorbance was recorded at a wavelength of 615 nm inserted into the tegating constraint. Data is recorded in Table 16.

Using the SiO _x coated tubes, an increase in absorbance for the uncoated article was observed; An increase in coating time resulted in an increase in absorbance. Measurement took less than 1 second.

 VI.A. These spectroscopic methods should not be considered as limited by the mode of acquisition (eg reflectance vs. transmittance vs. absorbance), frequency or type of radiation applied or other parameters.

Example 8

Degassing Measurement on PET

VI.B. 30, currently employed from FIG. 15 of U.S. Patent No. 6,584,828, is in accordance with the protocol for forming a PET tube seated using a seal 360 on the upstream end of a micro-flow technology measurement cell, generally designated as 362. Test set-up used in the working example of measuring outgassing via SiO _x barrier coating 348 applied according to a protocol for coating the inside of the tube with SiO _x on the inside of the wall of the fabricated PET tube 358. Schematic diagram.

VI.B. The vacuum pump 364 has a flow measurement uncertainty of +/- 5% reading in the second generation IMGS sensor, (10 μ / min full range), absolute pressure sensor range: 0 to 10 Torr, calibrated range (PC Downstream of a commercially available measurement cell 362 (an intelligent gas leak system with leak test tool model ME2) employing a Leak-Tek program for automated data acquisition and a signal / plot of leak flow versus time Connected at the end. The equipment is supplied by ATC and guides the gas from the interior of the PET container 358 in the direction of the arrow through a measuring cell 362 for measuring the mass flow rate of vapor degassed from the walls into the container 358. Consists of.

VI.B. The measurement cell 362 shown and described briefly herein is understood to operate substantially as follows, although this information may deviate slightly from the operation of the actual equipment used. The cell 362 has a conical passage 368 to which the degassed flow is directed. Pressure is initiated in two lateral holes 370 and 372 longitudinally spaced along the passage 368 and partially supplied to chambers 374 and 376 formed by diaphragms 378 and 380. . Pressures accumulated in the respective chambers 374 and 376 deflect the respective diaphragms 378 and 380. This deflection is appropriately measured by measuring the change in capacitance between the conductive surfaces of the diaphragms 378 and 380 and nearby conductive surfaces such as 382 and 384. Bypass 386 may optionally be provided to accelerate the initial pump-down by bypassing the measurement cell 362 until the desired vacuum level for performing the test is reached.

VI.B. The PET walls 350 of the containers used in this test were about 1 mm thick and the coating 348 was about 20 nm (nanometer) thick. Thus, the wall 350 to coating 348 thickness ratio was about 50,000: 1.

VI.B. In order to measure the flow rate through the measuring cell 362 including the vessel chamber 360, fifteen glass vessels substantially the same in size and structure as the vessel 358 were pumped down to an internal pressure of 1 Torr. 360) was subsequently settled, and the capacitive data was then collected using the measuring cell 362 and converted to a "gas removal" flow rate. The test was performed twice for each vessel. After the first run, the vacuum was released using nitrogen and the vessel was allowed to reach equilibrium before proceeding to the second run during the recovery time. Since the glass vessel is considered to be almost degassing and infiltration through its walls is impossible, this measurement is understood to be at least overwhelmingly an indication of the amount of leakage and connection of the vessel within the measuring cell 362, If degassing or infiltration is present, it is rarely reflected. The results are in Table 7.

VI.B. The plot of plots 390 in FIG. 31 shows the “gas removal” flow rate expressed in micrograms per minute of the individual tubes corresponding to the second run data of Table 7 mentioned above. Since the flow rates for the plots do not increase substantially over time and are much lower than the other flow rates shown, the flow rate is due to leakage.

VI.B. The group of plots 392 in Table 8 and FIG. 31 shows similar data for uncoated tubes made according to the protocol for PET tube formation.

VI.B. This data for uncoated tubes shows much higher flow rates: the increase is due to the outgassing flow of gases on or in the interior region of the vessel wall. There is some spread between the containers, showing the sensitivity of the test to small differences between the containers and / or showing how the containers are seated on the test apparatus.

VI.B. The groups of plots 394 and 396 in Table 9 and FIG. 31 according to the protocol for coating the PET tube interior with SiO _x on the interior of the wall 346 of the PET tube fabricated according to the protocol for PET tube formation. Similar data is shown for the applied SiO _x barrier coating 348.

VI.B. Because of this example SiO _x coating, injection group (family) of curves 394 for a shaped PET tube was consistently in this test than for PET tubes that flow is not coated more low, the SiO _x It shows that the coating acts as a barrier to limit outgassing from the PET container walls. (The SiO _x coating itself is considered to be nearly degassed.) The separation between the curves 394 for each of the containers indicates that the test has a slightly different blocking effect of SiO _x on which the coatings are applied to different tubes. It is sensitive enough to distinguish between them. This spread in the group 394 is largely due to a change in gas tightness between the SiO _x coatings, which means a change in the degassing between the PET container walls or a change in the seating integrity (more With group 392 of hermetic curves). The two curves for Samples 2 and 4 are shown below and differing from the other data is considered to show that the SiO _x coatings of these tubes are defective. This shows that the current test can very clearly separate samples that are being treated differently or damaged.

VI.B. Referring to the aforementioned Tables 8 and 9 and FIG. 32, the data was statistically analyzed to find the median and values of the first and third standard deviations above and the median (mean) below. These values are plotted in FIG. 32.

VI.B. Firstly, this statistical analysis shows that the samples 2 and 4 of Table 9 presenting coated PET tubes are obvious outliers that are more than +3 standard deviations from the median. However, these separators appear to have a constant barrier effectiveness since their flow rate is still clearly distinct (much lower) from the flow rates of uncoated PET tubes.

VI.B. In addition, this statistical analysis very quickly and accurately analyzes the blocking effectiveness of nano-thickness barrier coatings and distinguishes coated tubes from uncoated tubes (which are currently considered indistinguishable using human sensation in coating thickness). Demonstrate the power of degassing measurements. Referring to FIG. 32, a coated PET container showing a degassing level with a mean of 3 standard deviations above the mean, shown in the upper bar group, is not coated with a degassing level with a mean of 3 standard deviations below the mean, shown in the lower bar group. Less degassing than non-PET containers. This data shows no overlap to the data with certainty levels beyond 6σ (sigma).

VI.B. Based on the success of this test, the absence of SiO _x coatings on these PET containers can be detected in shorter tests than this example, especially as statistics are generated for a larger number of samples. It is considered. This is evident from, for example, groups of clearly separated plots that are flat even at a time of T = 12 seconds for samples of 15 containers, showing a test duration of about 1 second, originating at T = 11 seconds.

VI.B. Also, based on this data, it is contemplated that barrier effectiveness for SiO _x coated PET containers approaching the barrier effectiveness equivalent to glass or glass can be obtained by optimizing the SiO _x coating.

Example 9

Wet Tension-Plasma Coated PET Tube Examples

VII.A.1.a.ii. The wet tension measurement method is a variation of the method described in ASTM D 2578. Wet tension is a specific measure of the hydrophobicity or hydrophilicity of a surface. This method uses standard wet tension solutions (called dyne solutions) to determine the closest solution to wet the plastic film surface for exactly 2 seconds. This is the wet tension of the film.

VII.A.1.a.ii. The procedure used here is that the substrates are not flat plastic films, but tubes that are manufactured according to the protocol for forming PET tubes and coated according to the protocol for coating the inside of the tube with a hydrophobic coating (except for controls), It is a variation from ASTM D 2578. In addition, a silicone coated glass syringe (Becton Dickinson Hypak® PRTC glass prefillable syringe with Luer-lok® tip) (1 mL) was also tested. The results of this test are listed in Table 10.

Surprisingly, plasma coating (40 dynes / cm) of uncoated PET tubes modified the plasma process conditions, thereby using higher (more hydrophilic) or lower (more hydrophobic) using the same hexamethyldisiloxane (HMDSO) feed gas. Energy surfaces). Thin (approximately 20-40 nanometers) SiO _x coatings (data not shown in the tables) made according to the protocol for coating the inside of the tube with SiO _x provide similar wettability as hydrophobic bulk glass substrates. Thin (about 100 nanometers) hydrophobic coatings (data not shown in the tables) made according to the protocol for coating the inside of the tube with a hydrophobic coating provide similar wettability as hydrophobic silicone fluids.

Example 10

Study of vacuum retention of tubes through accelerated aging

VII.A.3 Acceleration of aging will provide a faster evaluation of long life products. Acceleration of aging of blood tubes for vacuum retention is described in US Pat. No. 5,792,940, column 1, lines 11-49.

VII.A.3 Three types of polyethylene terephthalate (PET) 13x75 mm (0.85 mm thick walls) molded tubes were tested:

Becton Dickinson product number 366703 13x75 mm (without additives) tube (lifetime 545 days or 18 months) sealed with Hemogard® system red stopper and colorless guard [commercial control];

PET tubes made according to the protocol for forming PET tubes sealed with the same type of Hemogard® system red stopper and colorless guard [internal control]; And

Injection molded PET made according to the protocol for forming PET tubes, coated according to the protocol for coating the inside of the tube with SiO _x , and sealed with the same type of Hemogard® system red stopper and colorless guard [invented specimen] 13x75 mm tubes.

VII.A.3 BD Commercial Controls were used as received. The internal control and inventive samples were evacuated, capped with a stopper system and sealed to provide the desired partial pressure (vacuum) inside the tube. All samples were placed in a 3 gallon (3.8 L) 304 SS wide inlet pressure vessel (Sterlitech No. 740340). The pressure vessel was pressurized to 48 psi (3.3 atm, 2482 mm.Hg). (a) removing 3-5 samples at increasing time intervals, (b) allowing water to be aspirated from the 1 liter plastic bottle reservoir into the evacuated tubes via a 20 gauge blood collection adapter and (c) prior to water intake and The water volume intake change was then measured by measuring the mass change.

VII.A.3 The results are shown in Table 11.

VII.A.3 The normalized mean decay rate is calculated by dividing the time change in mass by the number of days of compression and the initial mass intake [mass change / (days x initial mass)]. In addition, the months accelerated to 10% loss are calculated. Both data are listed in Table 12.

VII.A.3 These data show that commercial and uncoated internal controls have the same vacuum loss rate and surprisingly improve vacuum retention time by factor 2.1 due to the incorporation of SiO _x coatings on the PET inner wall.

Example 11

Lubricity coating

VII.B.1.a. The following materials were used for this test:

Commercial (BD Hypak® PRTC) glass prefillable syringes with Luer-lok® tip (approx. 1 mL)

COC syringe barrels made according to a protocol for forming a COC syringe barrel;

Commercial plastic syringe plungers with elastomeric tips taken from Becton Dickinson Product No. 306507 (obtained as saline prefilled syringes);

Normal saline solution (taken from Beckton Dickinson Product No. 306507 prefilled syringes);

Dilon Test Stand (Advanced Force Gauge) (Model AFG-50N)

Syringe support and drain jig (made to fit the Dilon test stand)

VII.B.1.a. The following procedure was used for this test.

VII.B.1.a. The jig was mounted on a Dilon test stand. Platform probe movement was adjusted to 6 inches / minute (2.5 mm / second) and top and bottom stop positions were set. The stop positions were identified using syringes and barrels with empty contents. Commercial saline-filled syringes were labeled, plungers were removed and the saline solution was drained through the open ends of the syringe barrels for reuse. Extra plungers were obtained in the same way for use with COC and glass barrels.

VII.B.1.a. The syringe plungers were inserted into the COC syringe barrels so that the second horizontal forming point of each plunger was parallel to the syringe barrel lip (about 10 mm from the tip end). Using another syringe and needle assembly, the test syringes were filled with 2-3 milliliters of saline solution through the capillary end to the top of the capillary. The sides of the syringe were tapped to remove large air bubbles at the plunger / fluid interface and along the wall, and any air bubbles were carefully pushed out of the syringe while holding the plunger in the vertical direction.

VII.B.1.a. Each filled syringe barrel / plunger assembly was installed with a syringe jig. The test was started by pressing a switch on the test stand to move the moving metal hammer toward the plunger. If the moving metal hammer is within 5 mm of contact with the top of the plunger, tap the data button on the Dillon module repeatedly so that the plunger is in front of the syringe barrel before first contact with the syringe plunger when the data button is pressed down. The force was recorded until it stopped in contact with.

VII.B.1.a. All benchmark and coated syringe barrels were operated five times (using a new plunger and barrel for each iteration).

VII.B.1.a. COC syringe barrels made according to the protocol for forming a COC syringe barrel are coated with an OMCTS lubricity coating, assembled, filled with saline, and subjected to a lubricity coating according to the protocol for coating the inside of a COC syringe barrel with an OMCTS lubricity coating. In the examples it was tested as described above. Due to the polypropylene chamber used according to the protocol for coating the interior of the COC syringe barrel with an OMCTS lubricity coating, the OMCTS vapor (and oxygen, if added-see Table 13) flows through the syringe barrel and through the syringe capillary into the polypropylene chamber. (Lubricous coating may not be necessary in the capillary portion of the syringe in this case). Some different coating conditions were tested as shown in Table 13 above. All deposits were completed on COC syringe barrels from the same production batch.

The coated samples were then tested using the plunger active force according to the protocol of this example and the results are shown in Table 13 in British units and metric force units. The data clearly shows that low power and no oxygen provided the lowest plunger activity for COC and coated COC syringes. Note that when oxygen is added at lower power (6 W) (lower power is preferred), the plunger activation force increases from 1.09 lb, 0.49 kg (power = 11 W) to 2.27 lb., 1.03 kg. . This indicates that the addition of oxygen may not be desirable to achieve the lowest possible plunger activity.

VII.B.1.a. In addition, the highest plunger force (power = 11 W, plunger force = 1.09 lb, 0.49 kg) avoids glass syringe problems such as breakability and more expensive manufacturing processes, while the current industry standard for silicone coated glass Notice that it is close to (Activity = 0.58 lb, 0.26 kg). Further optimization is expected to achieve values above the value of current glass with silicon performance.

VII.B.1.a. Samples were prepared by coating the COC syringe barrels according to the protocol for coating the inside of the COC syringe barrel with an OMCTS lubricity coating. Another embodiment of the technology herein is to apply a lubricity layer onto another thin film coating such as, for example, SiO _x applied according to a protocol for coating the inside of a COC syringe barrel with SiO _x .

Example 12

Enhanced syringe barrel lubricity coating

VII.B.1.a. The force required to drain the 0.9 percent saline payload from the syringe through the capillary aperture using a plastic plunger was measured for the inner wall-coated syringes.

VII.B.1.a. Three types of COC syringe barrels were tested according to the protocol for forming COC syringe barrels: a first type without an inner coating [uncoated control], a protocol for coating the inside of a COC syringe barrel with an HMDSO coating. Octamethylcyclotetrasiloxane [OMCTS-concentrated] applied according to the protocol for coating the inside of the COC syringe barrel with an OMCTS lubricity coating with another type [HMDSO control] with a hexamethyldisiloxane (HMDSO) based plasma coated inner wall coating according to Eg a third type having a system plasma coated inner wall coating. New plastic plungers with elastomeric tips taken from BD product Becton Dickinson Product No. 306507 were tested for all examples. In addition, saline solution of the product number 306507 was also used.

VII.B.1.a. Plasma coating methods and apparatus for coating syringe barrel inner walls are described in other experimental sections of this application. Specific coating parameters for HMDSO-based and OMCTS-based coatings are listed in Table 14, Protocol for Coating COC Syringe Barrels with HMDSO Coating, Protocol for Coating COC Syringe Barrels with OMCTS Lubricating Coatings.

VII.B.1.a. The plunger is inserted about 10 millimeters into the syringe barrel and there is a vertical filling of the experimental syringe using a saline-filled syringe / needle system separated through an open syringe capillary. When the experimental syringe is filled into the capillary hole, the syringe is tapped so that air bubbles sticking to the inner walls are discharged through the capillary hole and rise.

VII.B.1.a. The filled experimental syringe barrel / plunger assembly is inserted vertically into a household hollow metal jig so that the syringe assembly is supported on the jig at the finger flanges. The jig has a drain tube at the bottom and is mounted on a Dilon test stand using an advanced force gauge (model AFG-50N). The test stand has a metal hammer that moves vertically downward at a speed of 6 inches (152 millimeters) per minute. The metal hammer is in contact with an extended plunger which discharges the saline solution through the capillary. Once the plunger contacts the syringe barrel / capillary interface, the experiment is stopped.

VII.B.1.a. While the metal hammer / extended plunger is moving downward, the resistive force imparted on the hammer as recorded on the force gauge is recorded on the electronic spreadsheet. The maximum force for each experiment is identified from the spreadsheet data.

VII.B.1.a. Table 14 lists the normalized maximum force measured for each example by dividing the maximum force average and the coated syringe barrel maximum force average from the repeatedly coated COC syringe barrels by the uncoated maximum force average.

VII.B.1.a. This data shows that all OMCTS-series inner wall plasma coated COC syringe barrels (invention C, E, F, G, H) are much better than uncoated COC syringe barrels (uncoated controls A and D). It shows low plunger activity and surprisingly much lower plunger activity than HMDSO-based inner wall plasma coated COC syringe barrels (HMDSO control B). More surprisingly, the OMCTS-based coating on a silicon oxide (SiO _x ) gas barrier coating keeps the plunger sliding force very low (central example F). The best plunger activity was Example C (power = 8, plunger activity = 1.1 lb, 0.5 kg). Note that this avoids glass syringe problems such as cleavability and more expensive manufacturing processes, while being very close to the current industry standard (activity = 0.58 lb, 0.26 kg) of silicone coated glass. Further optimization is expected to achieve values above the value of current glass with silicon performance.

Example 13

Fabrication of COC Syringe Barrels with External Coatings-Prophetic Example

VII.B.1.c. The COC syringe barrel, formed according to the protocol for forming the COC syringe barrel, is sealed using disposable closures at both ends. The capped COC syringe barrel was passed through a bath of Daran® 8100 Saran Latex (Owensboro Specialty Plastics). This latex contains 5 percent isopropyl alcohol to reduce the surface tension of the composition to 32 dyne / cm. The latex composition completely wets the outside of the COC syringe barrel. After draining for 30 seconds, the coated COC syringe barrel contains 275 ° F. (135 ° C.) (latex fusion) for 25 seconds and 122 ° F. (50 ° C.) (final curing) for 4 hours in each forced air oven. Is exposed to a heating schedule. The resulting PvDC film is 1/10 mil (2.5 microns) thick. COC syringe barrels and PvDC-COC laminates COC syringe barrels are measured for OTR and WVTR using the MOCON brand Oxtran 2/21 oxygen permeability instrument and the Permatran-W 3/31 water vapor permeability instrument.

VII.B.1.c. Expected OTR and WVTR values are listed in Table 15, which shows the expected blocking enhancement factor (BIF) for the laminate.

Example 15

Atomic Compositions of PECVD Applied OMCTS and HMDSO Coatings

VII.B.4. Made according to the protocol for forming the COC syringe barrel, and coated with HMDSO (according to the protocol for coating the inside of the COC syringe barrel with OMCTS lubricity coating) or with the HMDSO according to the protocol for coating the inside of the COC syringe barrel with HMDSO coating. Coated COC syringe barrel samples are provided. Atomic compositions of coatings derived from OMCTS or HMDSO were characterized using X-ray photoelectron spectroscopy (XPS).

VII.B.4. XPS data was quantified using a model with relative sensitivity factors and a single layer. The analysis volume is the product of the analysis area (spot size or aperture size) and the depth of information. Optoelectronics are produced within the X-ray penetration depth (typically several microns), but only optoelectronics within the three top electron escape depths are detected. The escape depth is on the order of 15 to 35 mm 3, which leads to an analysis depth of about 50 to 100 mm 3. Typically, 95% of the signal comes from this depth.

VII.B.4. The following analysis parameters were used:

Tool: PHI Quantum 2000

X-ray Source: Solid Color Alka 1486.6 eV

Reception angle + 23 °

Takeoff angle 45 °

Analysis area 600 μm

Charge Correction C1s 284.8 eV

Ion Gun Conditions Ar +, 1 keV, 2 x 2 mm Raster

Sputtering speed 15.6 kW / min (SiO ₂ equivalent)

VII.B.4. Table 17 provides atomic concentrations of the detected components. XPS does not detect oxygen or helium. Given values are normalized to 100 percent using the detected components. Detection limits are approximately 0.05 to 1.0 electron percent.

VII.B.4.b. From the coating composition results and calculated starting monomer precursor element percentages of Table 17, the carbon atom percentage of the HMDSO-based coating was reduced relative to the starting HMDSO monomer carbon atom percentage (decreased from 54.1% to 44.4%), surprisingly OMCTS-series The percentage of coated carbon atoms was increased relative to the percentage of OMCTS monomer carbon atoms (up from 34.8% to 48.4%), which is an increase of 39 atomic% calculated as follows:

100% [(48.4 / 34.8) -1] = 39 atomic%.

 In addition, the percentage of silicon atoms of the HMDSO-based coating is almost unchanged from the percentage of starting HMDSO monomer silicon atoms (from 21.8% to 22.2%), while the percentage of silicon atoms of the OMCTS-based coatings is significantly higher than that of the OMCTS monomer silicon atoms. Decreased (from 42.0% to 23.6%), which is a reduction of 44 atomic%. Using carbon and silicon variations, the OMCTS monomer to coating behavior does not go in the same direction as the behavior observed for ordinary precursor monomers (eg HMDSO). See, eg, Hans J. Griesser, Ronald C. Chatelier, Chris Martin, Zoran R. Vasic, Thomas R. Gengenbach, George Jessup J. Biomed. Mater. (Appl Biomaster) 53: 235-243, 2000.

Example 16

Volatile Components from Plasma Coatings

VII.B.4. Made according to the protocol for forming the COC syringe barrel, coated with OMCTS (according to the protocol for coating the inside of the COC syringe barrel with OMCTS lubricity coating) or according to the protocol for coating the inside of the COC syringe barrel with HMDSO coating) COC syringe barrel samples coated with HMDSO are provided. Degassing gas chromatography / mass spectrometry (GC / MS) analysis was used to determine the volatile components released from OMCTS or HMDSO coatings.

VII.B.4. Syringe barrel samples (four COC syringe barrels cut in half) were placed in one of the 1½ "(37 mm) diameter chambers of the dynamic headspace sampling system (CDS 8400 auto-sampler). Prior to sample analysis, the system blanks were analyzed The samples were analyzed on an Agilent 7890A gas chromatography / Agilent 5975 mass spectrometer, using the following parameters to generate the data described in Table 18:

GC column: 30 m X 0.25 mm DB-5MS (J & W Scientific),

0.25 μm film thickness

Flow rate: 1.0 ml / min, uniform flow mode

Detector: mass selection detector (MSD)

Scan Mode: Split Scan (10: 1 Split Ratio)

Degassing conditions: 1½ "(37mm) chamber, purged for 3 hours

85 ° C, flow rate 60 ml / min

Oven temperature: 40 ° C. (5 minutes) to 300 ° C. at a rate of 10 ° C./min;

At 300 ° C., hold for 5 minutes.

The degassing results in Table 18 clearly show the difference in composition between the HMDSO-based and OMCTS-based lubricity coatings tested. HMDSO based compositions degassed trimethylsilanol [(Me) ₃ SiOH], but did not degas more measured oligomers containing repeating-(Me) ₂ SiO- moieties, whereas OMCTS based compositions The measured trimethylsilanol [(Me) ₃ SiOH] was not degassed and more oligomers containing repeating-(Me) ₂ SiO- moieties were degassed. This test is considered to be useful for distinguishing HMDSO-based coatings from OMCTS-based coatings.

Without limiting the invention according to the scope or accuracy of the following theory, the result is that the acyclic structure of HMDSO in which each silicon atom is bonded to three methyl groups versus the methyl groups bonded to each silicon atom It is contemplated that this can be explained by considering the cyclic structure of only two OMCTS. OMCTS is considered to react by a ring-opening reaction that forms a double radical with repeating-(Me) ₂ SiO- moieties that are already oligomers, and can condense to form higher oligomers. HMDSO, on the other hand, decomposes at least one O-Si bond and recondenses it into [(Me) ₃ Si] ₂ and one fragment containing a single O-Si bond that recondenses to (Me) ₃ SiOH. It is considered to have a reaction that leaves other fragments that do not contain O-Si bonds.

The cyclic properties of the OMCTS are considered to lead to the ring opening and condensation of these ring-opened moieties which outgass the higher MW oligomers (26 ng / test). In contrast, HMDSO-based coatings are considered to not provide relatively low molecular weight fragments from HMDSO.

Example 17

Density Determination of Plasma Coatings Using X-Ray Reflectance (XRR)

Sapphire witness samples (0.5 × 0.5 × 0.1 cm) were adhered to the inner walls of the separated PET tubes made according to the protocol for the formation of PET tubes. Sapphire Witness-containing PET tubes (according to the protocol for coating the interior of the COC syringe barrel with an OMCTS lubricity coating, all escaping at twice the power source) were coated with OMCTS or HMDSO. The coated sapphire samples were then removed and X-ray reflectance (XRR) data were obtained on a PANalytical X＇Pert diffractometer equipped with a parabola multilayer incident beam monochromator and an equilibrium plate diffraction beam collimator. A two layer Si _w O _x C _y H _z model was used to determine the coating density from the critical angle measurement results. This model is considered to provide the best approach for separating true Si _w O _x C _y H _z coatings. The results are in Table 19.

From Table 17 showing the results of Example 15, the lower oxygen (28%) and higher carbon (48.4%) composition of OMCTS relative to HMDSO showed both atomic mass considerations and valence (oxygen = 2; carbon = 4) All would mean that OMCTS should have a lower density. Surprisingly, the XRR density results show that the opposite will be observed, ie the OMCTS density is higher than the HMDSO density.

Without limiting the invention to the scope or accuracy of the following theory, it is contemplated that there is a fundamental difference in reaction mechanisms in the formation of the respective HMDSO- and OMCTS-based coatings. HMDSO fragments aggregate and react very easily to form nanoparticles, which can then deposit on the surface and react more on the surface, while OMCTS is less likely to form dense gaseous nanoparticles. OMCTS reactive species are more likely to condense on the surface in a more similar form to the original OMCTS monomer, resulting in a less dense coating as a whole.

Example 18

Thickness Uniformity of PECVD Applied Coatings

Is produced in accordance with a protocol for forming the COC syringe barrels, each syringe barrel COC or COC syringe barrel inside the SiO _x in accordance with the protocol for coating the inside of a SiO _x in accordance with the protocol for coating the lubricant coating OMCTS OMCTS- series lubricity Samples of COC syringe barrels coated with a coating are provided. Moreover, it was provided with a sample of the PET tube is manufactured in accordance with a protocol for forming the PET tube, according to the protocol for coating each of the inner tube to the SiO _x coated with SiO _x is not coated which is subjected to the accelerated aging test. Transmission electron microscopy (TEM) was used to measure the thickness of the PECVD-applied coatings on the samples. The TEM procedure of Example 4 recorded above was used. The method and apparatus described by the SiOx and lubricity coating protocol used in this example showed a uniform coating as shown in Table 20.

Example 19

Degassing Measurement on COC

VI.B. COC tubes were fabricated according to the protocol for forming COC tubes. Some of the tubes were provided with an internal barrier coating of SiOx according to a protocol for coating the inside of the tube with SiO _x , and the remaining COC tubes were uncoated. In addition, commercial glass blood collection Becton Dickinson 13x75 mm tubes with similar dimensions were provided as above. The tubes were stored for about 15 minutes in a room containing ambient air at 45% relative humidity and 70 ° F. (21 ° C.) and the following tests were performed at the same ambient relative humidity. The tubes were subjected to the following ATC microflow measurement procedure and equipment of Example 8 (second generation IMFS sensor, (10 μ / min full range), absolute pressure sensor range: 0-10 Torr, +/- 5% in calibrated range Intelligent Gas Leakage Systems with Leak-Tek Program for Automatic Data Acquisition (using PC) and Leak Test Tool Model ME2 with Leak Flow vs. Time / Signal with Uncertainty of Flow Measurement of Readings Tested. In the present case, each tube undergoes a 22-second bulk moisture degassing step at a pressure of 1 mm Hg, and after being compressed (with 760 millimeters Hg) using nitrogen gas for 2 seconds, the nitrogen gas is pumped down. The microflow measurement step was performed for about 1 minute at 1 millimeter Hg pressure.

VI.B. The results are shown in FIG. 57 similar to FIG. 31 generated in Example 8. FIG. In FIG. 57, plots for uncoated COC tubes are at 630, plots for SiOx coated COC tubes are at 632, plots for glass tubes used as a control are 634. Is in. In addition, the outgassing measurement starts at about 4 seconds, after a few seconds the plots 630 for uncoated COC tubes and the plots 632 for SiOx blocking coated tubes are clearly branched, which is a blocking It shows a sharp difference between coated and uncoated tubes. Consistent separation of uncoated COC (> 2 micrograms at 60 seconds) versus SiO _x -coated COC (less than 1.6 micrometers at 60 seconds) was realized.

Example 20

Lubricity coating

VII.B.1.a. COC syringe barrels made according to the protocol for forming COC syringe barrels were coated with a lubricity coating according to the protocol for coating the inside of the COC syringe barrel with an OMCTS lubricity coating. The results are provided in Table 21. The results show that the tendency to increase the power level from 8 watts to 14 watts in the absence of oxygen improved the lubricity of the coating. Other experiments with power and flow rates can provide other lubricity improvements.

Example 21

Lubricatable Coatings-Hypothetical Examples

Injection molded cyclic olefin copolymer (COC) plastic syringe barrels are made according to the protocol for forming COC syringe barrels. Some are uncoated ("control") and others are PECVD lubricity coated ("lubricated syringe") according to the protocol for coating the interior of the COC syringe barrel with an OMCTS lubricity coating. The lubricated syringes and controls measured the force to initiate movement of the plunger in the barrel (breakout force) and the force (maintenance force) of the plunger in the barrel using the Genesis Packaging Automated Syringe Force Tester, Model AST. Is tested to do.

The test is a modified version of the ISO 7886-1: 1993 test. The following procedure is used for each test. A new plastic plunger with elastomeric tips taken from Becton Dickinson Product No. 306507 (obtained as saline prefilled syringes) is removed from the syringe assembly. The elastomeric tip is dried with clean dry compressed air. The elastomeric tip and plastic plunger are then inserted into the COC plastic syringe barrel, which is tested with the plunger located flush with the bottom of the syringe barrel. The filled syringes are then adjusted as needed to reach the state under test. For example, if the purpose of the test is to determine the effect of the lubricant coating on the breakout force of the syringes after storing the syringes for three months, the syringes are stored for three months to achieve the desired condition.

The syringe is installed with a Genesis Packaging Automated Syringe Force Tester. The tester is calibrated at the start of the test according to the manufacturer's specifications. The tester input variables are speed = 100 mm / min and range = 10,000. Press the start button of the tester. Upon completion of the test, the breakout force (which initiates movement of the plunger in the barrel) and the plunger force (which maintains movement) are measured and are substantially lower for lubricated syringes than for control syringes. Get to know.

59 illustrates a vessel processing system 20 according to an exemplary embodiment of the present invention. The vessel processing system 20 includes, in particular, a first processing station 5501 and a second processing station 5502. Embodiments for such processing stations are shown, for example, by reference numerals 24, 26, 28, 30, 32 and 34 in FIG. 1.

The first vessel processing system 5501 includes a vessel holder 38 that supports a seated vessel 80. Although FIG. 59 shows a blood tube 80, the container may be a syringe body, a vial, a conduit, such as a pipette. The container can be made of glass or plastic, for example. In the case of a plastic container, the first processing station may comprise a mold for molding the plastic container.

A first treatment at the first treatment station (the treatment is a first inspection of the container to see if it is molded, defective, a coating of the inner surface of the container and, in particular, a second of the container to see if the inner coating is defective). Afterwards), the vessel holder 38 is transferred with the vessel 82 to the second vessel processing station 5502. This transfer is performed by conveyor arrangements 70, 72, 74. For example, a gripper or some grippers may be provided to hold the vessel holder 38 and / or vessel 80 to move the vessel / support combination to the next processing station 5502. Also, only the container can be moved without the support. However, it may be advantageous to move the support with the container if the support is adapted to be transported by the conveyor arrangement.

60 illustrates a vessel processing system 20 according to another exemplary embodiment of the present invention. In addition, two vessel processing stations 5501, 5502 are provided. Also provided are other container processing stations 5503, 5504 arranged in series and in which the container is processed, ie inspected and / or coated.

The vessel may be moved from the stock to the left processing station 5504. The container may also be molded in a first processing station 5504. In either case, a first vessel treatment, such as molding, inspection, and / or coating, is performed at the processing station 5504, and then a second inspection may be performed. The vessel is then moved through the conveyor arrangements 70, 72, 74 to the next processing station 5501. Typically, the vessel is moved with the vessel holder. The second processing is performed at the second processing station 5501, after which the vessel and the support are moved to the next processing station 5502 where the third processing is performed. The vessel is then moved to the fourth processing station 5503 (again with the support) for the fourth treatment, which is then transferred to the conveyor to the reservoir.

Before and after each coating step or forming step or other step of manipulating the container, inspection of the entire container, part of the container and especially the inner surface of the container can be performed. The results of each check may be communicated to the central processing unit 5505 via the data bus 5507. Each processing station is connected to the data bus 5507. Processor 5505, which can be retrofitted in the form of a central control and control unit, processes the inspection data, analyzes the data and determines whether the final processing step is successful.

If the final processing step is determined to be unsuccessful, the container does not enter the next container processing station but is removed from the process (conveyor) because the coating contains, for example, holes or the coating surface is determined to be regular or not smooth enough. See sections 7001, 7002, 7003, 7004) and are moved back to the conveyor for reprocessing.

Processor 5505 is coupled to user interface 5506 for entering control or adjustment parameters.

61 illustrates a processing station 5501 of a vessel processing system according to an exemplary embodiment of the present invention. The station includes a PECVD apparatus 5701 that coats the interior surface of the vessel. In addition, several detectors 5702 to 5707 are provided for visual inspection. Such detectors can be, for example, electrodes for performing electronic measurements as optical detectors such as CCD cameras, gas detectors or pressure detectors.

FIG. 62 shows a vessel holder 38 according to an exemplary embodiment of the present invention, with an electrode with several detectors 5702, 5703, 5704 and gas input ports 108, 110.

The electrode and detector 5702 can be adapted to move into the interior space of the vessel 80 when the vessel is seated on the support 38.

For example, using optical detectors 5703, 5704 arranged outside the seated vessel 80 or even using an optical detector 5707 arranged inside the interior space of the vessel 80, in particular during the coating step Optical inspection can be performed.

The detectors may include color filters so that other wavelengths can be detected during the coating process. The processing unit 5505 analyzes the optical data and determines whether the coating is successful at a certain level of fidelity. If it is determined that the coating is probably unsuccessful, then each container is separated from the processing system or reprocessed.

While the present invention has been illustrated and described in detail in the drawings and the foregoing detailed description, such drawings and description are to be regarded as illustrative or illustrative, and not restrictive; The invention is not limited to the disclosed embodiments. Other variations to the disclosed embodiments can be understood and carried out by those skilled in the art, which practice the claimed invention from a study of the drawings, the disclosure, and the appended claims. In the claims, the word comprising does not exclude other components or steps, and the indefinite article "a" or "an" does not exclude a plural form. The fact that certain measures are cited in different dependent claims does not indicate that a combination of these measures cannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope.

Coated COC Tube OTR and WVTR Measurements Coating ID Power (watts) O-Si O-Si flow rate
(sccm) O ₂
flow
(sccm) Time (seconds) OTR
(cc /
tube.
Work) WVTR
(mg /
tube.
Work) number
coating 0.215 0. 27 A 50 HMDSO 6 90 14 0.023 0. 07 B 50 HMDSO 6 90 14 0.024 0. 10 C 50 HMDSO 6 90 7 0.026 0. 10

Coated PET Tube OTR and WVTR Measurements Coating ID Power (watts) O-Si O-Si flow (sccm) O ₂
Flow (sccm) Time (seconds) OTR
(cc /
tube.
Work) WVTR
(mg /
tube.
Work) Uncoated control 0.0078 3.65 SiO _x 50 HMDSO 6 90 3 0.0035 1.95

Coated COC COC Syringe Barrel OTR and WVTR Measurements Example syringe
coating O-Si
Composition power
(watt) O-Si
flux
(sccm) O ₂
flux
 (sccm) coating
time
(second) OTR
(cc /
Barrel.
Work) WVTR
(mg /
Barrel.
Work) BIF
(OTR) BIF
(WVTR) A Uncoated control 0.032 0.12 B SiO _x Inventive Example HMDSO ４４ 6 90 7 0.025 0.11 1.3 1.1 C SiO _x Inventive Example HMDSO ４４ 6 105 7 0.021 0.11 1.5 1.1 D SiO _x Inventive Example HMDSO 50 6 90 7 0.026 0.10 1.2 1.2 E SiO _x Inventive Example HMDSO 50 6 90 14 0.024 0.07 1.3 1.7 F SiO _x Inventive Example HMDSO ５２ 6 97.5 7 0.022 0.12 1.5 1.0 G SiO _x Inventive Example HMDSO 61 6 105 7 0.022 0.11 1.4 1.1 H SiO _x Inventive Example HMDSO 61 6 120 7 0.024 0.10 1.3 1.2 I SiO _x Inventive Example HMDZ ４４ 6 90 7 0.022 0.10 1.5 1.3 J SiO _x Inventive Example HMDZ 61 6 90 7 0.022 0.10 1.5 1.2 K SiO _x Inventive Example HMDZ 61 6 105 7 0.019 0.10 1.7 1.2

SIO detected by TEM _x  Coating thickness (nanometer) sample O-Si Thickness (nm) Power (watts) HMDSO flow rate (sccm) Oxygen flow rate (sccm) Inventive Example A HMDSO 25-50 39 6 60 Inventive Example B HMDSO 20 to 35 39 6 90

Atomic ratio of detected elements (parenthesis: percentage concentration, normalized to 100% of detected components) sample Plasma coating Si O C Uncoated PET Tube-Comparative Example - 0.08 (4.6) 1 (31.5) 2.7 (63.9) Polyethylene terephthalate (calculated) - 1 (28.6) 2.5 (71.4) Coated PET Tube-Invention SiO _x 1 (39.1) 2.4 (51.7) 0.57 (9.2)

Degree of hollow cathode plasma ignition sample power time Hollow cathode plasma ignition Dyeing results A 25 Watt 7 sec Not ignited at gas inlet 310, ignited at restricted portion 292 Good B 25 Watt 7 sec Ignition at gas inlet 310 and restricted portion 292 Bad C 8 Watt 9 sec Not ignited at gas inlet 310, ignited at restricted portion 292 Great D 30 Watts 5 sec Not ignited at gas inlet 310 or restricted portion 292 Very good

Flow rate using glass tubes Glass tube Task # 1 (μg / min) Task # 2 (μg / min) Average (μg / min) One 1.391 1.453 1.422 2 1.437 1.243 1.34 3 1.468 1.151 1.3095 4 1.473 1.019 1.246 5 1.408 0.994 1.201 6 1.328 0.981 1.1545 7 Broken Broken Broken 8 1.347 0.909 1.128 9 1.171 0.91 1.0405 10 1.321 0.946 1.1335 11 1.15 0.947 1.0485 12 1.36 1.012 1.186 13 1.379 0.932 1.1555 14 1.311 0.893 1.102 15 1.264 0.928 1.096 Average 1.343 1.023 1.183 maximum 1.473 1.453 1.422 at least 1.15 0.893 1.0405 maximum minimum 0.323 0.56 0.3815 Standard Deviation 0.097781 0.157895 0.1115087

Flow rate using glass tubes Uncoated
PET Task # 1 (μg / min) Task # 2 (μg / min) Average (μg / min) One 10.36 10.72 10.54 2 11.28 11.1 11.19 3 11.43 11.22 11.325 4 11.41 11.13 11.27 5 11.45 11.17 11.31 6 11.37 11.26 11.315 7 11.36 11.33 11.345 8 11.23 11.24 11.235 9 11.14 11.23 11.185 10 11.1 11.14 11.12 11 11.16 11.25 11.205 12 11.21 11.31 11.26 13 11.28 11.22 11.25 14 10.99 11.19 11.09 15 11.3 11.24 11.27 Average 11.205 11.183 11.194 maximum 11.45 11.33 11.345 at least 10.36 10.72 10.54 maximum minimum 1.09 0.61 0.805 Standard Deviation 0.267578 0.142862 0.195121

Flow Rate for SiOx Coated PET Tubes Coated
PET Task # 1 (μg / min) Task # 2 (μg / min) Average (μg / min) One 6.834 6.655 6.7445 2 9.682 9.513 Isolates 3 7.155 7.282 7.2185 4 8.846 8.777 Isolates 5 6.985 6.983 6.984 6 7.106 7.296 7.201 7 6.543 6.665 6.604 8 7.715 7.772 7.7435 9 6.848 6.863 6.8555 10 7.205 7.322 7.2635 11 7.61 7.608 7.609 12 7.67 7.527 7.5985 13 7.715 7.673 7.694 14 7.144 7.069 7.1065 15 7.33 7.24 7.285 Average 7.220 7.227 7.224 maximum 7.715 7.772 7.7435 at least 6.543 6.655 6.604 maximum minimum 1.172 1.117 1.1395 Standard Deviation 0.374267 0.366072 0.365902

Wet Tension Measurement of Coated and Uncoated Tubes Example Tube coating Wetting tension
(Dyne / cm) Reference Uncoated glass 72 Inventive Example PET tubes coated with SiO _X according to the SiO _X protocol 60 Comparative example Uncoated PET 40 Inventive Example PET tubes coated according to hydrophobic coating protocol 34 Comparative example Glass (+ silicone fluid) glass syringe, part number 30

Water Mass Draw (DRAW) (grams) Compression Time (Days) tube 0 27 46 81 108 125 152 231 BD PET (commercial control) 3.0 1.9 1.0 Uncoated PET (Internal Control) 4.0 3.1 2.7 SiO _x -coated PET (invention) 4.0 3.6 3.3

Calculated Normal Average Vacuum Reduction Rate and Time Taken for 10% Vacuum Loss tube Normalized average reduction rate (delta mL / first mL.day) 10% loss in months-accelerated BD PET
(Commercial control) 0.0038 0.9 Uncoated PET
(Internal control) 0.0038 0.9 SiOx-coated PET (invention) 0.0018 1.9

Syringe Barrel with Lubricating Coating, UK sample Power, (watt) O-Si flow, (sccm) O ₂  Flow, (sccm) Time (seconds) Average force, (lb.) Standard Deviation Glass with silicone No coating No coating No coating No coating 0.58 0.03 Uncoated COC No coating No coating No coating No coating 3.04 0.71 A 11 6 0 7 1.09 0.27 B 17 6 0 14 2.86 0.59 C 33 6 0 14 3.87 0.34 D 6 6 90 30 2.27 0.49 Uncoated COC - - - - 3.9 0.6 SiO _x on COC 4.0 1.2 E 11 1.25 0 5 2.0 0.5 F 11 2.5 0 5 2.1 0.7 G 11 5 0 5 2.6 0.6 H 11 2.5 0 10 1.4 0.1 I 22 5 0 5 3.1 0.7 J 22 2.5 0 10 3.3 1.4 K 22 5 0 5 3.1 0.4

Plunger Activity Measurement of HMDSO- and OMCTS-Based Plasma Coatings details Monomer Coating time
(Seconds) coating
Si-O flow rate (sccm) coating
power
(watt) maximum
power
(lb, kg.) Normalized
Max power Uncoated control 3.3, 1.5 1.0 HMDSO coating HMDSO 7 6 8 4.1, 1.9 1.2 OMCTS Lubricating Coating OMCTS 7 6 8 1.1, 0.5 0.3 Uncoated control 3.9, 1.8 1.0 OMCTS Lubricating Coating OMCTS 7 6 11 2.0, 0.9 0.5
Double layer coating
1 COC syringe barrel + SiO _x

2 OMCTS lubricity coating
14


7
6



6
50



8




2.5, 1.1




0.6
OMCTS Lubricating Coating
OMCTS
5
1.25
11
2, 0.9
0.5
OMCTS Lubricating Coating
OMCTS
10
1.25
11
1.4, 0.6
0.4

OTR and WVTR Measurements (Prophecy) sample OTR
(cc / barrel.day) WVTR
(Gram / barrel.day) COC Syringe-Comparative Example 4.3 X 3.0 Y PvDC-COC Laminated COC Syringe-Invention X Y

Optical absorption of SiOx coated PET tubes (normalized to uncoated PET tubes) sample Coating time Average Absorption (at 615 nm) copy Standard Deviation Reference (uncoated) - 0.002 to 0.014  4 Inventive A 3 sec 0.021 8 0.001 Invention B 2 x 3 seconds 0.027 10 0.002 Invention C 3 x 3 seconds 0.033 4 0.003

Atomic concentration (parentheses, normalized to 100% of detected components) sample Plasma coating Si O C HMDSO-Series Coated COC COC Syringe Barrel Si _w O _x C _y 0.76 (22.2) 1 (33.4) 3.7 (44.4) OMCTS-Series Coated COC Syringe Barrels Si _w O _x C _y 0.46 (23.6) 1 (28) 4.0 (48.4) HMDSO Monomer-Calculated Si ₂ OC ₆  2 (21.8) 1 (24.1) 6 (54.1) OMCTS monomer-calculated Si ₄ O ₄ C ₈ 1 (42) 1 (23.2) 2 (34.8)

Volatile Components from Syringe Degassing Coating monomer Me ₃ SiOH (ng / test) Higher Order SiOMe Oligomers (ng / test) Uncoated COC Syringe-Comparative Example Uncoated ND ND HMDSO-Series Coated COC Syringes-Comparative Example HMDSO 58 ND OMCTS-Series Coated COC Syringe Barrels-Invention OMCTS ND 26

Plasma Coating Density from XRR Measurement sample layer Density g / cm ³ HMDSO-Series Coated Sapphire- Comparative Example Si _w O _x C _y H _z 1.21 OMCTS-Series Coated Sapphire-Inventive Example Si _w O _x C _y H _z 1.46

Thickness of PECVD Coatings by TEM Sample ID TEM
Thickness I TEM
Thickness II TEM
Thickness III Protocol for forming a COC syringe barrel; _{Protocol for coating the} inside of a COC syringe barrel with SiO _x 164 nm 154 nm 167 nm Protocol for forming a COC syringe barrel; Protocol for coating COC syringe barrel interior with OMCTS lubricity coating 55 nm 48 nm 52 nm A protocol for forming a PET tube; SiO inside the tube
Protocol for coating with x 28 nm 26 nm 30 nm A protocol for forming a PET tube; Protocol for Coating SiOx Inside Tube
PET tube formation (uncoated) - - -

OMCTS Lubricity  Coating Performance (UK) sample Average Plunger Force (lbs) * Percentage force reduction (vs uncoated) Power (watts) OMCTS flow (sccm) Compare (no coating) 3.99  - - - Sample A 1.46 63% 14 0.75 Sample B 1.79 55% 11 1.25 Sample C 2.09 48% 8 1.75 Sample D 2.13 47% 14 1.75 Sample E 2.13 47% 11 1.25 Sample F 2.99 25% 8 0.75 * Average of 4 repetitions

The force measurement is the average of four samples.

For example, in the following list with reference to FIGS. 59-62, exemplary embodiments of the present invention are described. While the use of the term "claim" or "claims" is used in the following list, it should be noted that the following list refers to exemplary embodiments and does not refer to the claims.

I. Vessel processing system with multiple treatment stations and multiple vessel supports

1. In the container processing system 20,

A first processing station 5501, 24, 26, 28, 30 configured to process a vessel having an opening and a wall defining an interior surface;

A second processing station (5502, 24, 26, 28, 30) spaced to said first processing station and configured to process a container having a wall defining an opening and an interior surface;

As a plurality of vessel holders 38, each vessel holder has a vessel port 92 configured to receive and seat an opening in the vessel for processing the inner surface of the vessel seated through the vessel port at the first processing station. Container supports 38 including; And

Conveyors 70, 72 for transporting a series of vessel supports and seated vessels from the first processing station to the second processing station for processing the inner surface of the vessel seated through the vessel port at the second processing station; Container processing system 20, including;

2. The method of claim 1, further comprising a third processing station 5503 configured to process a container spaced from the first and second processing stations and having a wall defining an opening and an interior surface. invent.

3. The conveyor of claim 2, wherein the conveyor is mounted with a series of vessel supports and seated from the second processing station to a third processing station for processing the inner surface of the container seated through the container port at the third processing station. Invention, characterized in that configured to transport containers.

4. The invention of any one of the preceding clauses wherein the one or more vessel supports further comprise a vacuum duct for withdrawing gas from the vessel seated on the one or more vessel ports.

5. The invention of any one of paragraphs 1-4, wherein one or more vessel supports further comprise a vacuum port in communication between the vacuum duct and an external vacuum source.

6. The invention according to any one of items 1 to 5, characterized in that the one or more vacuum ports have an O-ring for receiving and forming a seal with respect to an external vacuum source.

7. The invention of any one of the preceding clauses, wherein the one or more vessel supports further comprise a gas inlet port for delivering gas to a vessel seated on the one or more vessel ports.

8. The method of any of clauses 1-7, wherein the one or more vessel supports communicate with one or more vessel ports, each delivering gas to and transferring gas from the vessel to a vessel seated on the one or more vessel ports. The invention further comprises a composite gas inlet port and a vacuum port for extracting.

9. The invention according to any one of items 1 to 8, characterized in that the one or more vessel supports are made of thermoplastic material.

10. The invention of any one of the preceding claims, wherein one or more vessel ports have a sealing component for receiving and forming a seal against the vessel opening.

10a. The invention of claim 10 wherein the sealing component is an O-ring.

11. The invention of any of the preceding claims, wherein the treatment station is configured to inspect the inner surface of the container for defects.

12. The invention according to any one of items 1 to 11, wherein the treatment station is configured to apply a coating to the inner surface of the container.

13. The invention of any of the preceding clauses, wherein the treatment station is configured to inspect the coating for defects.

14. The invention of any of paragraphs 176-13, wherein the processing station is configured to measure air pressure loss through the vessel wall.

15. The process of any of the preceding clauses, wherein the processing station comprises a bearing surface for supporting one or more vessel supports in a predetermined position while processing the inner surface of the vessel seated at the processing station. Invention characterized.

16. The process of any of clauses 1-15, wherein the other processing station has a second bearing surface for supporting one or more vessel supports at a predetermined position while processing the inner surface of the vessel seated at the other station. Invention, characterized in that it comprises.

17. The method of any of the preceding clauses, wherein the other processing station supports the one or more vessel supports in a predetermined position while processing the inner surface of the vessel seated through the one or more vessel ports at the other station. An invention comprising a third bearing surface for the invention.

18. The invention according to any one of the preceding claims, further comprising a third processing station spaced from the first and second processing stations for processing the containers.

19. The invention of claim 18, further comprising a fourth processing station spaced from the first, second and third processing stations for processing the containers.

20. The invention of claim 19, further comprising a fifth processing station spaced apart from the first, second, third and fourth processing stations for processing containers.

21. The invention of claim 20, further comprising a sixth processing station spaced from said first, second, third, fourth and fifth processing stations for processing containers.

22. The method of any one of the preceding claims, further comprising a conveyor for transporting one or more vessel supports and seated vessels from the second processing station to the third processing station. invent.

23. The invention of claim 22, further comprising a conveyor for transporting one or more vessel supports and seated vessels from the third processing station to the fourth processing station.

24. The invention of any one of the preceding claims, further comprising a conveyor for transporting one or more vessel supports and seated vessels from the fourth processing station to the fifth processing station. .

25. The invention according to any one of items 1 to 24, further comprising a conveyor for transporting one or more vessel supports and seated vessels from the fifth processing station to the sixth processing station. .

26. The invention of any one of the preceding claims, further comprising a coater for forming a coating on the interior of the vessel through the one or more vessel ports at the processing station.

27. The invention according to any one of items 1 to 26, wherein the processing station comprises a PECVD apparatus.

28. The apparatus of paragraph 27, wherein the PECVD apparatus is

An internal electrode positioned to be received in fluid communication with the interior of the vessel seated on the vessel support;

An outer electrode having an inner portion positioned to receive a vessel seated on the vessel holder;

A power supply for supplying alternating current to inner and outer electrodes forming a plasma in the vessel seated on the vessel support object;

A vessel defining a vacuum chamber, comprising: a vacuum source for evacuating an interior of the vessel;

Reactant gas source; And

And a gas supply for supplying reactant gas from the reactant gas source to a vessel seated on the vessel support object.

 29. The invention of claim 28 wherein the inner electrode extends into the container.

30. The invention of claim 28, wherein the inner electrode is located outside of the container.

31. The invention of paragraph 28 or 30, wherein the inner electrode is located within the vessel holder.

32. The invention of claim 28, wherein the inner electrode is a probe having a distal portion positioned to extend generally concentrically to a vessel seated on the vessel holder.

33. The invention of paragraph 28 or 32, wherein the gas supply is at a distal portion of the internal electrode.

34. The method of clause 28, 32 or 33, further comprising a reactant gas source within the inner electrode and a passage for delivering a reactant gas from the reactant gas source to the distal portion of the inner electrode. Invention characterized.

35. The method of clause 34, wherein the distal portion of the inner electrode includes an elongated porous sidewall surrounding the passageway to release at least a portion of the reactant gas from the keg to the side within the inner electrode. invent.

36. The invention of clause 35, wherein the outer diameter of the inner electrode is at least 50% of the inner diameter adjacent to the side of the container.

37. The invention of clause 35, wherein the outer diameter of the inner electrode is at least about 60% of the inner diameter adjacent to the side of the container.

38. The invention of clause 35, wherein the outer diameter of the inner electrode is at least about 70% of the inner diameter adjacent to the side of the container.

39. The invention of clause 35, wherein the outer diameter of the inner electrode is at least 80% of the inner diameter adjacent to the side of the container.

40. The invention of clause 35 wherein the outer diameter of the inner electrode is at least about 90% of the inner diameter adjacent to the side of the container.

41. The invention of clause 35 wherein the outer diameter of the inner electrode is at least about 95% of the inner diameter adjacent to the side of the vessel.

42. The method of any of paragraphs 28-34, further comprising a reactant carrier gas source in the inner electrode and a passage for delivering the carrier gas from the carrier gas source to the distal portion of the inner electrode. Invention characterized.

43. The invention of any of paragraphs 28 to 42, further comprising an internal electrode extender and a retractor for inserting and removing internal electrodes from the vessel holder.

44. The method of any of paragraphs 28-43, further comprising an array of at least two internal electrodes, wherein the internal electrode extenders and retractors are configured to insert and remove internal electrodes of the array from a vessel holder. Invention characterized in that.

45. The invention of clause 44, wherein the inner electrode extender and retractor are configured to move the inner electrode between a fully advanced position, an intermediate position and a reduced position with respect to the vessel holder.

46. The method of clause 44 or 45, wherein the first inner electrode is removed from its extended position to its reduced position, the first inner electrode is replaced with a second inner electrode and the second inner electrode is removed. And an internal electrode drive operable in connection with said internal electrode extender and retractor for advancing to an extended position.

47. The method of clause 28, 32, 33, 34 or 42, wherein the outer electrode is approximately cylindrical and positioned to extend generally concentrically around the vessel seated on the vessel holder. Invention characterized by the above-mentioned.

48. The invention of any one of claims 28 to 47 wherein the external electrode comprises an end cap.

49. The invention of claim 48, wherein a gap defined between the outer electrode and the distal end of the vessel seated on the vessel holder is essentially uniform.

50. The invention according to any of paragraphs 28 to 49, wherein the gap defined between the outer electrode and the vessel seated on the vessel holder is essentially uniform.

51. The apparatus of any of paragraphs 1-50, further comprising a detector configured to be inserted into the vessel through one or more vessel ports at a processing station for detecting a condition of the vessel interior surface. invent.

52. The invention of any of paragraphs 1-51, further comprising a detector located at a processing station outside the vessel.

53. The process of any of paragraphs 1-52, further comprising an energy source at the processing station for directing energy inwards through the vessel wall and the vessel inner surface for detection by a detector. Invention.

54. The method of any of paragraphs 1-53, further comprising an energy source at a processing station for directing energy opposite the vessel wall and for reflecting energy from the at least one coating on the wall surface and the wall surface. Invention, characterized in that it comprises.

55. The process of any of paragraphs 1-54, further comprising an energy source at the processing station for directing energy inwards through the vessel wall and the vessel interior surface for detection by a detector. Invention.

56. The invention of any of paragraphs 1-55, comprising an energy source configured to insert into the vessel through the vessel opening.

57. The invention of any of paragraphs 51-56, wherein the detector is configured to detect the condition of the container interior surface at numerous closely spaced locations on the container interior surface.

58. The invention of any of paragraphs 51-57, wherein the detector is positioned to receive energy from the energy source.

59. The picker of any of paragraphs 1-58, wherein the picker is at a processing station for removing the vessel from one or more vessel supports after treating the inner surface of the seated vessel at the second processing station. The invention characterized in that it further comprises a (picker).

II. Container support

II.A.

60. A portable container support for holding and delivering the container with an opening while the container is being processed,

A container port configured to seat a container opening in mutually communicating relationship;

A second port configured to receive an external gas supply or exhaust;

A duct for passing one or more gases between the vessel opening seated on the vessel port and the second port; And

A deliverable housing to which the vessel port, the second port and the duct are substantially firmly attached;

The portable container holder is characterized in that less than 5 pounds weight.

II.B.

61. A portable container holder for holding and delivering the container having an opening while the container is being processed,

A container port configured to receive a container opening in a sealed intercommunication relationship;

A vacuum duct for drawing gas through the vessel port from a vessel seated on the vessel port;

A vacuum port configured to communicate between the vessel duct and an external vacuum source; And

A deliverable housing to which the vessel port, the vacuum duct and the vacuum port are substantially firmly attached;

The portable container holder is characterized in that less than 5 pounds weight.

 62. The invention of clause 61, wherein the vessel port has a sealing component for receiving and forming a seal against the vessel opening.

62a. 62. The invention of claim 61, wherein the sealing component is an O-ring.

63. The invention of any of paragraphs 61-62a, wherein the vacuum port has an O-ring for receiving and forming a seal with respect to an external vacuum source.

64. The invention of any of paragraphs 61-63, wherein the inlet port has an O-ring for receiving and forming a seal with respect to the gas inlet.

65. The vessel of any of paragraphs 61-64, wherein the vessel port is further configured to function as a gas inlet port in communication with the vessel port for delivering gas to a vessel seated on the vessel port. Invention characterized.

66. The invention of any of paragraphs 61-65, wherein the housing is made of thermoplastic material.

67. The method of any of paragraphs 61-66, further comprising a gas inlet port substantially rigidly attached to the deliverable housing and configured to deliver gas to the vessel seated on the vessel port. Invention.

II.C. A vessel holder comprising a sealing arrangement.

68. A vessel holder for receiving an open end of a container having a substantially cylindrical wall adjacent the open end,

An approximately cylindrical interior surface sized to receive the vessel cylindrical wall;

A first annular groove coaxial within said substantially cylindrical inner surface, said first annular groove having an opening in said substantially cylindrical inner surface and a bottom wall radially spaced from said substantially cylindrical inner surface. A first annular groove; And

The container disposed in the first annular groove and in relation to the first annular groove, pressed radially outwardly by a vessel that normally extends radially through the opening and is received by the approximately cylindrical inner surface; And a first sealing component for forming a seal between the bottom wall of the first annular groove.

68a. 69. The vessel holder of claim 68 wherein the sealing component is an O-ring.

69. The vessel holder of clause 68, further comprising a radially extending joint adjacent an approximately cylindrical inner surface on which the open end of the vessel may be supported.

70. The method of clause 68 or 69, wherein the first upper and lower sidewalls are disposed between the opening and the bottom wall of the first annular groove, wherein the first sidewalls are provided by the container with the first o-ring. Further comprising first sidewalls positioned to support the first o-ring when pressed radially outward.

71. The container of any of paragraphs 68-70, wherein the first O-ring has a cross-sectional diameter that is greater than the radial depth of the first generally annular groove when not stressed. support fixture.

72. The method of any of paragraphs 68 to 71, wherein

A second annular groove coaxial in the substantially cylindrical inner surface and axially spaced apart from the first annular groove, the opening in the approximately cylindrical inner surface and a bottom wall radially spaced apart from the substantially cylindrical inner surface. Having a second annular groove; And

The container and the annular groove being disposed radially outwardly by the vessel disposed in the second annular groove and generally radially extending through the opening in relation to the second annular groove and received by the approximately cylindrical inner surface. And a second O-ring forming a seal between the bottom walls of the vessel.

73. The first upper and lower sidewalls of clause 72, wherein the first upper and lower sidewalls are disposed between the opening and the bottom wall of the second annular groove, the second sidewalls radially outwardly of the second o-ring by the container. Further comprising second sidewalls positioned to support the second O-ring when pressed.

74. The container of any of paragraphs 72-73, wherein the second O-ring has a cross-sectional diameter that is greater than the radial depth of the first generally annular groove when not stressed. support fixture.

75. The method of any of paragraphs 69 to 74, further comprising a vacuum source in the junction positioned to withdraw the vacuum in the vessel seated in the vessel holder having an opening opposite the junction. Vessel Support.

76. The process of any of paragraphs 69 to 75, further comprising a source of process gas in the junction positioned to communicate with the interior of the vessel seated in the vessel holder having an opening opposite the junction. Container support.

III. Container transfer method-processing of vessels seated on container supports

III.A. Transporting the vessel holder to the processing station

77. A method of treating a container,

Providing a first processing station for processing the vessel;

Providing a second processing station spaced from the first processing station for processing the containers;

Providing a container having an opening and a wall defining an interior surface;

Providing a vessel holder comprising a vessel port;

Seating the opening of the container on the container port;

Processing the inner surface of the seated vessel through the vessel port at the first processing station;

Transporting the vessel holder and seated vessel from the first processing station to the second processing station; And

Processing the interior surface of the seated vessel through the vessel port at the second processing station.

78. The invention of clause 77, wherein the vessel is generally tubular.

79. The invention of clause 77 or 78 wherein the opening is at one end of the container.

80. The invention of any of paragraphs 77-79, wherein the container is made of thermoplastic material.

81. The invention of any of paragraphs 77-80 wherein the container is made of polyethylene terephthalate.

82. The invention of any of paragraphs 77-80 wherein the vessel is made of polyolefin.

83. The invention of any of paragraphs 77-80, wherein the container is made of polypropylene.

84. The invention of any of paragraphs 77-83, wherein the container is made of glass.

85. The invention of any of paragraphs 77-84, wherein the container is made of borosilicate glass.

86. The invention according to any one of items 77 to 85, wherein the container is made of soda-lime glass.

87. The invention of any of paragraphs 77-86, wherein the vessel is made of quartz glass.

88. The invention of any of paragraphs 77-87, wherein the vessel is sufficiently strong to withstand substantially the entire internal vacuum without deformation when exposed to an external pressure of 760 Torr.

89. The invention of any of paragraphs 77-88, wherein the container is provided by injection molding it.

90. The invention according to any one of items 77 to 88, wherein the container is provided by blow molding it.

91. The invention of any of paragraphs 77-90, wherein the container is provided by closing the end of the tube.

92. The invention of any of paragraphs 77-91 wherein the vessel holder further comprises a vacuum duct for withdrawing gas from the vessel seated on the vessel port.

93. The invention of clause 92, wherein the vessel holder further comprises a vacuum port in communication between the vacuum duct and an external vacuum source.

94. The invention of clause 93 wherein the vacuum port has an O-ring to receive and form a seal relative to an external vacuum source.

95. The invention of any of paragraphs 77-94 wherein the vessel holder further comprises a gas inlet port for delivering gas to the vessel seated on the vessel port.

96. The complex gas according to any of paragraphs 77-95, wherein the vessel holder is in communication with the vessel port, each for delivering gas to and withdrawing gas from the vessel seated on the vessel port. An invention comprising an inlet port and a vacuum port.

97. The invention of any of paragraphs 77-96, wherein the vessel holder is made of thermoplastic material.

98. The invention of any of paragraphs 77-97, wherein the vessel holder comprises a base and an upper portion joined together at a joint.

99. The invention of claim 98, further comprising an O-ring entrapped between the upper portion and the base in the joint and for sealing the joint.

100. The invention of any of paragraphs 77-99, wherein the O-ring captured between the upper portion and the base receives the vessel and forms a seal around the vessel opening.

101. The container of any of paragraphs 77-100, wherein the container port comprises O-rings spaced apart on first and second axes, each of which is a container for sealing between the container port and the container. Invention, characterized in that having an inner diameter sized to accommodate the outer diameter of.

102. The invention of any of paragraphs 77-101 wherein the vessel port has a radially extending junction surface in the vicinity of the O-rings and surrounding the vacuum duct.

103. The invention of any of paragraphs 77-102, wherein the processing station is configured to inspect the interior surface of the container for defects.

104. The invention of any of paragraphs 77-103, wherein the processing station is configured to apply a coating to the interior surface of the vessel.

105. The invention of any of paragraphs 77-104, wherein the processing station is configured to apply a barrier or other type of coating to the interior surface of the vessel.

106. The invention of any of paragraphs 77-105, wherein the processing station is configured to inspect the coating for defects.

107. The invention of any of paragraphs 77-106, wherein the processing station is configured to inspect the barrier coating for defects.

108. The invention of any of paragraphs 77-107, wherein the processing station is configured to measure air pressure loss through the vessel wall.

109. The process of any of paragraphs 77-108, wherein the processing station includes a bearing surface for supporting the vessel holder at a predetermined position while processing the inner surface of the vessel seated at the processing station. Invention.

110. The invention of clause 109, wherein after the opening of the vessel is seated on the vessel port, the vessel holder is moved to engage the bearing surface.

111. The process of any of paragraphs 77-110, wherein the other processing station includes a second bearing surface for supporting the vessel holder at a predetermined position while processing the inner surface of the vessel seated at the other station. Invention characterized in that.

112. The invention of clause 110 wherein after the opening of the vessel rests on the vessel port, the vessel holder is moved to engage the bearing surface.

113. The vessel of any of clauses 77-112, wherein the other processing station is adapted to support the vessel holder in a predetermined position while processing the inner surface of the seated vessel through the vessel port at the other station. An invention comprising a third bearing surface.

114. The invention of clause 113, wherein after the opening of the vessel rests on the vessel port, the vessel holder is moved to engage the bearing surface.

115. The method of any of paragraphs 77-114, wherein

Providing a third processing station spaced from the first and second processing stations for processing containers;

Transporting the vessel holder and the seated vessel from the second processing station to the third processing station; And

Processing the inner surface of the seated vessel through the vessel port at the third processing station.

116. The invention of any of paragraphs 77-115, further comprising seating an opening of the vessel on the vessel port at a processing station.

117. The invention of any of paragraphs 77-116, further comprising forming a coating on the interior of the vessel through the vessel port at a processing station.

118. The invention of any of paragraphs 77-117, wherein said processing at the processing station includes inspecting the interior surface of the container for defects.

119. The invention of clause 118, wherein the inspection is performed by inserting a detection probe through the vessel port into the vessel and using the probe to detect a condition of the interior surface of the vessel.

120. The invention of clause 119, further comprising radiating energy inwardly through the vessel wall and the vessel inner surface and detecting the energy with the probe.

121. The invention of clauses 119 to 120, further comprising detecting the state of the vessel inner surface at numerous closely spaced locations on the vessel inner surface.

122. The method of any of clauses 118-121, wherein the inspection inserts a radiation source into the vessel through the vessel port and detects radiation from the radiation source using a detector to determine the condition of the interior surface of the vessel. The invention is carried out by detecting.

123. The invention of any of paragraphs 118-122, further comprising radiating energy outwardly through the vessel surface and detecting the energy with a detector located outside the vessel. .

124. The invention of any of paragraphs 120-123, further comprising detecting the energy with a detector located within the vessel that reflects the radiation from the vessel surface.

125. The invention of any of paragraphs 118-124, further comprising detecting the condition of the vessel inner surface at numerous closely spaced locations on the vessel inner surface.

126. The invention of any of paragraphs 77-125, wherein the treatment at the treatment station includes applying a coating to the interior surface of the vessel.

127. The invention of any of paragraphs 77-126, wherein the treatment at the treatment station comprises applying a barrier coating to the interior surface of the vessel.

128. The invention of any of paragraphs 77-127, wherein the treatment at the treatment station comprises applying a liquid barrier coating to the interior surface of the vessel.

129. The invention of any of paragraphs 77-128, wherein the treatment at the processing station includes inspecting a coating on the interior surface of the container for defects.

130. The invention of any of paragraphs 77-129 wherein the treatment at the treatment station includes inspecting a barrier coating on the interior surface of the container for defects.

131. The process of any of paragraphs 77-130, wherein the treatment at the processing station includes inspecting a coating applied with a liquid on the interior surface of the container to see if there is a defect. Invention.

132. The invention according to any one of claims 126 to 131, comprising inserting a detection probe through the vessel port into the vessel and using the probe to detect the state of the coating. .

133. The invention of any of paragraphs 127-132, further comprising radiating energy inwardly through the vessel wall and detecting the energy with the probe.

134. The invention of any one of paragraphs 127-133, further comprising detecting the state of the coating at numerous closely spaced locations on the interior surface of the container.

135. The process of any of clauses 129 to 134, wherein when the vessel is first evacuated and its walls are exposed to the ambient atmosphere, the coating is subjected to pressure in the vessel at ambient atmospheric pressure for a one year lifetime. And carrying out the inspection step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent an increase by more than 20%.

136. The invention of any of paragraphs 129-135, wherein said inspecting step is performed within an elapsed time of 30 seconds or less per container.

137. The invention of any of paragraphs 129-135, wherein said inspecting step is performed within an elapsed time of 25 seconds or less per container.

138. The invention of any of paragraphs 129-135, wherein said inspecting step is performed within an elapsed time of 20 seconds or less per container.

139. The invention of any of paragraphs 129-135, wherein said inspecting step is performed within an elapsed time of less than 15 seconds per container.

140. The invention of any of paragraphs 129 to 135, wherein said inspecting step is performed within an elapsed time of 10 seconds or less per container.

141. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 5 seconds or less per container.

142. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 3 seconds or less per container.

143. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of no more than 2 seconds per container.

144. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 1 second or less per container.

145. The invention of any of paragraphs 129-135, wherein said coating and inspecting step is performed within an elapsed time of no more than 30 seconds per container.

146. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 25 seconds or less per container.

147. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 20 seconds or less per container.

148. The invention of any of paragraphs 129-135, wherein said coating and inspecting step is performed within an elapsed time of no greater than 15 seconds per container.

149. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 10 seconds or less per container.

150. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of no more than 8 seconds per container.

151. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of no more than 7 seconds per container.

152. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of no more than 6 seconds per container.

153. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 5 seconds or less per container.

154. The invention of any of paragraphs 129-135, wherein said coating and inspecting step is performed within an elapsed time of 4 seconds or less per container.

155. The invention of any of paragraphs 129-135, wherein the coating and inspecting step is performed within an elapsed time of 3 seconds or less per container.

156. The method of any of paragraphs 129-135, wherein when the vessel is first vacuumed and its walls are exposed to the ambient atmosphere, the vessel increases to at least 20% of the ambient atmospheric pressure for a life of at least 18 months. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent it from becoming.

157. The method of any of paragraphs 129-135, wherein when the vessel is first evacuated and its walls are exposed to the ambient atmosphere, the vessel increases to at least 20% of the ambient atmospheric pressure for at least two years of life. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent it from becoming.

158. The method of any of clauses 129 to 135, wherein when the vessel is first evacuated and its walls are exposed to the ambient atmosphere, the vessel is increased to at least 15% of the ambient atmospheric pressure over the life of one year. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent it.

159. The method of any of clauses 129 to 135, wherein when the vessel is first evacuated and its walls are exposed to the ambient atmosphere, the vessel is increased to at least 10% of the ambient atmospheric pressure during its one-year lifetime. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent it.

160. The method of any one of paragraphs 129 to 159, wherein the inspection detects the condition of the container by inserting a radiation source into the container through the container port and using a detector to detect radiation from the radiation source. Invention characterized in that it is carried out.

161. The method of any one of paragraphs 129-160, further comprising radiating energy outwardly through the vessel and the vessel wall and detecting the energy with a detector located outside the vessel. Invention.

162. The invention of any of paragraphs 120-161, further comprising the step of reflecting the radiation from the coating and the vessel wall and detecting the energy with a detector located inside the vessel. .

163. The invention of any of paragraphs 129-162, further comprising detecting the state of the coating at numerous closely spaced locations on the interior surface of the container.

164. The method of any one of claims 129-163, wherein inspecting the coating on the interior surface of the container for defects is performed by measuring the air pressure blocking effectiveness of the barrier coated container wall. Invention characterized.

165. The invention of any one of claims 117-164, wherein the coating reduces the permeation of atmospheric gases through the interior surface of the vessel.

166. The invention of any one of claims 117-165, wherein the coating reduces the contact of the contents of the container with the inner surface.

167. The method of any of paragraphs 117-166, wherein the coating comprises SiO x, wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2. Invention.

168. The method of any of paragraphs 77-167, further comprising removing the container from the container support after treating the inner surface of the seated container at the second processing station. Invention.

169. The method of clause 168,

Providing a second container having a wall defining an opening and an interior surface after said removing step; And

And seating the opening of the second vessel on the vessel port.

170. The invention of any of paragraphs 168 to 169, further comprising treating the interior surface of the seated second vessel through the vessel port at the first processing station.

171. The invention of any of paragraphs 168-170, further comprising transporting the vessel holder and the seated vessel from the first processing station to the second processing station.

172. The invention of any one of paragraphs 168-171, further comprising processing the seated second vessel through the vessel port at the second processing station.

173. The container opening according to any one of items 77 to 172, wherein the container is formed in a mold, the container is removed from the mold, and the container opening is removed within 60 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

174. The container opening according to any one of items 77 to 173, wherein the container is formed within the mold, the container is removed from the mold, and the container opening is within 30 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

175. The container opening according to any one of items 77 to 174, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is within 25 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

176. The container opening according to any one of items 77 to 175, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 20 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

177. The container opening according to any one of items 77 to 176, wherein the container is formed within the mold, the container is removed from the mold, and the container opening is within 15 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

178. The container opening according to any one of items 77 to 177, wherein the container is formed in a mold, the container is removed from the mold, and the container opening is removed within 10 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

179. The container opening according to any one of items 77 to 178, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 5 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

180. The container opening according to any one of items 77 to 179, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 3 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

181. The container opening according to any one of items 77 to 180, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 1 second of removing the container from the mold. The invention further comprises the step of seating on the container port.

III.B. Transporting the processing apparatus to the vessel holder or vice versa.

182. A method of treating a container,

Providing a first processing station for processing containers;

Providing a second processing station for processing the containers;

Providing a container having an opening and a wall defining an interior surface;

Providing a vessel holder comprising a vessel port;

Seating the opening of the container on the container port;

Moving the first processing device operatively in engagement with the vessel holder or vice versa;

Treating the interior surface of the seated vessel through the vessel port using the first processing device;

Moving the second processing device operatively in engagement with the vessel holder or vice versa; And

Treating the interior surface of the seated vessel through the vessel port using the second processing device.

183. The method of paragraph 182,

Providing a third processing apparatus for processing containers;

Moving the third processing device operatively in engagement with the vessel holder or vice versa; And

Processing the inner surface of the seated vessel through the port using the third processing apparatus.

184. The invention of clause 182 or 183, wherein the vessel is generally tubular.

185. The invention of any one of paragraphs 182 to 184, wherein the opening is at one end of the container.

186. The invention of any one of paragraphs 182 to 185, wherein the container is made of thermoplastic material.

187. The invention of any of paragraphs 182 to 186, wherein the container is made of polyethylene terephthalate.

188. The invention according to any one of paragraphs 182 to 187, wherein the container is made of polyolefin.

189. The invention of any of paragraphs 182 to 186, wherein the container is made of polypropylene.

190. The invention of any of paragraphs 182-189 wherein the vessel is sufficiently strong to withstand substantially the entire internal vacuum without deformation when exposed to an external pressure of 760 Torr.

191. The invention of any of paragraphs 182 to 190, wherein the container is provided by injection molding it.

192. The invention according to any one of paragraphs 182 to 191, wherein the container is provided by blow molding it.

193. The invention of any of paragraphs 182 to 192, wherein the vessel holder further comprises a vacuum duct for withdrawing gas from the vessel seated on the vessel port.

194. The invention of 193, wherein the vessel holder further comprises a vacuum port in communication between the vacuum duct and an external vacuum source.

195. The invention of 194, wherein the vacuum port has an O-ring for receiving and forming a seal relative to an external vacuum source.

196. The invention of any of paragraphs 182-195, wherein the vessel holder further comprises a gas inlet port for delivering gas to the vessel seated on the vessel port.

197. The complex gas according to any one of paragraphs 182 to 196, wherein the vessel holder is in communication with the vessel port, each for delivering gas to and withdrawing gas from the vessel seated on the vessel port. An invention comprising an inlet port and a vacuum port.

198. The invention according to any one of paragraphs 182 to 197, wherein the vessel holder is made of thermoplastic material.

199. The invention according to any one of paragraphs 182 to 198, wherein the vessel port has an O-ring for receiving and forming a seal with respect to the vessel opening.

200. The invention of any of paragraphs 182 through 199, wherein the processing device is configured to inspect the interior surface of the container for defects.

201. The invention according to any one of paragraphs 182 to 200, wherein the processing device is configured to apply a coating to the inner surface of the container.

202. The invention of any of paragraphs 182 through 201, wherein the processing device is configured to inspect the coating for defects.

203. The invention of any of paragraphs 182-202, wherein the processing device is configured to measure air pressure loss through the vessel wall.

204. The process of any of paragraphs 182-203, wherein the processing apparatus includes a bearing surface for supporting the vessel holder at a predetermined position while treating the inner surface of the seated vessel with the processing apparatus. Invention characterized.

205. The invention of 204, wherein after placing the opening of the vessel on the vessel port, the vessel holder is moved to engage the bearing surface.

206. The method of any one of paragraphs 182 to 205, wherein the other processing device is adapted to provide a second bearing surface for supporting the container support at a predetermined position while treating the inner surface of the seated container with the processing device. Invention, characterized in that it comprises.

207. The invention of clause 206, wherein after placing the opening of the vessel on the vessel port, the vessel holder is moved to engage the bearing surface.

208. The apparatus of any of clauses 182-207, wherein the other processing apparatus supports the vessel holder at a predetermined position while treating the inner surface of the seated vessel through the vessel port with the other processing apparatus. An invention comprising a third bearing surface for the invention.

209. The invention of clause 208, wherein after placing the opening of the vessel on the vessel port, the vessel holder is moved to engage the bearing surface.

210. Paragraph 182 to 209, wherein

Providing a third processing station spaced from the first and second processing stations for processing containers;

Transporting the vessel holder and the seated vessel from the second processing apparatus to the third processing apparatus; And

Processing the inner surface of the seated vessel through the vessel port using the third processing apparatus.

211. The invention of any one of paragraphs 182 to 210 further comprising mounting an opening of the vessel on the vessel port at a processing station.

212. The invention according to any one of paragraphs 182 to 211, further comprising forming a coating on the interior of the vessel through the vessel port in a processing device.

213. The invention of any of paragraphs 182 through 212, wherein said processing at the processing station includes inspecting the interior surface of the container for defects.

214. The invention of clause 213, wherein the inspection is performed by inserting a detection probe through the vessel port into the vessel and using the probe to detect a condition of the interior surface of the vessel.

215. The invention of 214, further comprising radiating energy inwardly through the vessel wall and the vessel inner surface and detecting the energy with the probe.

216. The invention of clause 214 or 215, further comprising detecting the state of the vessel inner surface at numerous closely spaced locations on the vessel inner surface.

217. The method of any of paragraphs 213 to 216, wherein the inspection inserts a radiation source into the vessel through the vessel port and detects radiation from the radiation source using a detector to determine the condition of the interior surface of the vessel. The invention is carried out by detecting.

218. The invention according to any one of paragraphs 213 to 217, further comprising radiating energy outwardly through the vessel surface and detecting the energy with a detector located outside the vessel. .

219. The invention of any of paragraphs 215-216, further comprising detecting the energy with a detector located within the vessel that reflects the radiation from the vessel surface.

220. The invention of any of paragraphs 213 to 219, further comprising detecting a condition of the interior surface of the container at numerous closely spaced locations on the interior surface of the container.

221. The invention of any of paragraphs 182-220, wherein the processing at the processing device comprises applying a coating to an interior surface of the container.

222. The invention of any one of paragraphs 182 to 221, wherein the treatment at the processing device comprises applying a coating applied with a liquid to the interior surface of the container.

223. The invention of any one of paragraphs 182 to 222, wherein the treatment at the treatment station includes inspecting a coating on the interior surface of the container for defects.

224. The invention of any one of claims 221 to 223, comprising inserting a detection probe through the vessel port into the vessel and using the probe to detect the state of the coating. .

225. The invention of any one of paragraphs 221-224, further comprising radiating energy inwardly through the vessel wall and detecting the energy with the probe.

226. The invention of any of paragraphs 221-225, further comprising detecting the state of the coating at numerous closely spaced locations on the interior surface of the container.

227. The method of any of clauses 223 to 131, wherein when the vessel is first evacuated and its walls are exposed to the ambient atmosphere, the vessel is increased to at least 20% of the ambient atmospheric pressure over the life of one year. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent it.

228. The invention of any of paragraphs 223 to 227, wherein said inspecting step is performed within an elapsed time of 30 seconds or less per container.

229. The invention according to any one of paragraphs 223 to 227, wherein said inspecting step is performed within an elapsed time of 25 seconds or less per container.

230. The invention of any of paragraphs 223 to 227, wherein said inspecting step is performed within an elapsed time of 20 seconds or less per container.

231. The invention of any of paragraphs 223 to 227, wherein said inspecting step is performed within an elapsed time of no more than 15 seconds per container.

232. The invention according to any one of claims 223 to 227, wherein said inspecting step is performed within an elapsed time of 10 seconds or less per container.

233. The invention of any of paragraphs 223-227, wherein said coating and inspecting step is performed within an elapsed time of 30 seconds or less per container.

234. The invention of any of paragraphs 223-227, wherein said coating and inspecting step is performed within an elapsed time of 25 seconds or less per container.

235. The invention of any one of paragraphs 223 to 227, wherein said coating and inspecting step is performed within an elapsed time of 20 seconds or less per container.

236. The invention of any of paragraphs 223-227, wherein said coating and inspecting step is performed within an elapsed time of no more than 15 seconds per container.

237. The invention of any of paragraphs 223-227, wherein said coating and inspecting step is performed within an elapsed time of 10 seconds or less per container.

238. The method of any of clauses 223 to 227, wherein when the vessel is first evacuated and its walls exposed to the ambient atmosphere, the vessel increases to at least 20% of the ambient atmospheric pressure for a life of at least 18 months. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent it from becoming.

239. The method according to any one of items 223 to 227, wherein when the barrier coating is first vacuumed and its walls are exposed to the ambient atmosphere, at least 20% of the ambient atmospheric pressure for a life of at least two years. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent an increase.

240. The method of any of clauses 223 to 227, wherein when the barrier coating is first evacuated and its walls are exposed to the ambient atmosphere, the barrier coating is at least 15% of the ambient atmospheric pressure over its lifetime of one year. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent an increase.

241. The barrier coating according to any of clauses 223 to 227, wherein when the barrier coating is first vacuumed and its walls are exposed to the ambient atmosphere, the barrier coating is at least 10% of the ambient atmospheric pressure for a period of one year. And performing the detecting step at a sufficient number of positions throughout the vessel inner surface to determine that it is effective to prevent an increase.

242. The method according to any one of paragraphs 223 to 241, wherein the inspection detects the state of the coating by inserting a radiation source through the vessel port into the vessel and detecting radiation from the radiation source using a detector. Invention characterized in that it is carried out.

243. The method of any of paragraphs 223-242, further comprising radiating energy outwardly through the coating and the vessel wall and detecting the energy with a detector located outside the vessel. Invention.

244. The invention of any one of paragraphs 223 to 243, further comprising the step of reflecting said radiation from said coating and vessel wall and detecting said energy with a detector located inside said vessel. .

245. The invention of any of paragraphs 223-244, further comprising detecting the state of the coating at numerous closely spaced locations on the interior surface of the container.

246. The method of any of clauses 223 to 245, wherein inspecting the coating on the interior surface of the container for defects is performed by measuring the air pressure blocking effectiveness of the coated container wall. Invention.

247. The invention of any one of claims 212-246, wherein said coating reduces permeation of atmospheric gases through said interior surface into said vessel.

248. The invention of any of paragraphs 212-247, wherein the coating reduces the contact of the contents of the container with the inner surface.

249. The SiOx, elemental carbon, fluorine of any of clauses 212-248, wherein the coating wherein x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or about 2. The family of materials, w is 1, x is from about 0.5 to 2.4, y is from about 0.6 to about 3 and z is from 2 to about 9 SiwOxCyHz or a combination thereof.

250. The method of any of paragraphs 182 to 249, further comprising removing the container from the container support while treating the inner surface of the seated container using the second processing device. Invention.

251. The method of paragraph 250,

Providing a second container having a wall defining an opening and an interior surface after said removing step; And

And seating the opening of the second vessel on the vessel port.

252. The method of any of paragraphs 250-251, further comprising treating the interior surface of the seated second vessel through the vessel port using the first treatment device. invent.

253. The invention of any one of 250 to 252, further comprising transporting the vessel holder and the seated vessel from the first processing station to the second processing station.

254. The invention of any of paragraphs 250-253, further comprising processing the seated second vessel through the vessel port using the second processing device.

255. The container opening according to any one of items 182 to 254, wherein the container is formed in a mold, the container is removed from the mold, and the container opening is removed within 60 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

256. The container opening according to any one of paragraphs 182 to 255, wherein the container is formed within the mold, the container is removed from the mold, and the container opening is within 30 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

257. The container opening according to any one of items 182 to 256, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 25 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

258. The container opening according to any one of items 182 to 257, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 20 seconds after removing the container from the mold. The invention further comprises the step of seating on the container port.

259. The container opening according to any one of paragraphs 182 to 258, wherein the container is formed within the mold, the container is removed from the mold, and the container opening is within 15 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

260. The container opening according to any one of paragraphs 182 to 259, wherein the container is formed within the mold, the container is removed from the mold, and the container opening is removed within 10 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

261. The container opening according to any one of paragraphs 182 to 260, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 5 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

262. The container opening according to any one of paragraphs 182 to 261, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within 3 seconds of removing the container from the mold. The invention further comprises the step of seating on the container port.

263. The container opening according to any one of paragraphs 182 to 262, wherein the container is formed within a mold, the container is removed from the mold, and the container opening is removed within one second after removing the container from the mold. The invention further comprises the step of seating on the container port.

III.C. Using a gripper to reciprocate the tube to the coating station

264. The method of PECVD of a first vessel,

Providing a first container having an open end, a closed end, and an inner surface;

Providing at least a first gripper configured to selectively grasp and release the closed end of the first container;

Using the gripper to hold the closed end of the first container;

Using the first gripper to transfer the first vessel to a vicinity of a vessel holder configured to seat at the open end of the first vessel;

Using the first gripper, advancing the first container axially and seating its open end on the container support to ensure sealed communication between the container support and the interior of the first container;

Introducing at least one gaseous reactant into the first vessel through the vessel holder;

Forming a plasma in the first vessel under conditions effective to form a reaction product of a reactant on the inner surface of the first vessel;

Detaching the first vessel from the vessel holder; And

Axially transferring the first vessel from the vessel holder using the first gripper or another gripper; And

And evacuating said first vessel from said gripper used to transfer axially from said vessel holder.

265. The method of clause 264,

Providing a reaction vessel different from the first vessel, the reaction vessel having an open end and an inner space;

Seating an open end of the reaction vessel on the vessel support to establish a sealed communication between the vessel holder and the inner space of the reaction vessel;

Providing a PECVD reactant water in the interior space;

Forming a plasma in the interior space of the reaction vessel under conditions effective to remove at least a portion of the deposit of the PECVD reaction product from the reactant water;

Detaching the first vessel from the vessel holder; And

Inventing the reaction vessel from the vessel holder.

266. The invention according to paragraph 264 or 265, further comprising.

Providing at least a second gripper;

Operatively connecting at least first and second grippers to a tandem conveyor;

Providing a second container having an open end, a closed end, and an inner surface;

Providing a gripper configured to selectively support and release the closed end of the second container;

Using the gripper to hold the closed end of the second container;

Using the gripper to transfer the second vessel to a vicinity of a vessel holder configured to seat at the open end of the second vessel;

Using the gripper, advancing the second vessel axially and seating its open end on the vessel holder to achieve sealed communication between the vessel holder and the interior of the second vessel;

Introducing at least one gaseous reactant into the second vessel through the vessel holder;

Forming a plasma in the second vessel under conditions effective to form a reaction product of a reactant on the inner surface of the second vessel;

Detaching the second vessel from the vessel holder; And

Axially transferring the second vessel from the vessel holder using the second gripper or another gripper; And

Discharging said second vessel from said gripper used for axially conveying from said vessel holder.

IV. PECVD Equipment for Container Manufacturing

IV.A. PECVD apparatus including vessel holder, internal electrode, vessel as reaction chamber

267. A PECVD apparatus,

A vessel holder having a port for receiving the vessel in a seated position for processing;

An internal electrode positioned to be received in a container seated on the container support object;

An outer electrode having an inner portion positioned to receive a vessel seated on the vessel holder; And

And the power supply includes a power supply for supplying alternating current to at least one of the inner and outer electrodes to form a plasma in the vessel defining a plasma reaction chamber seated on the vessel holder.

268. The invention as recited in 267 wherein the inner electrode is a probe having a distal portion in a position generally extending concentrically to a vessel seated on the vessel holder.

268a. 268. The invention of claim 267 or 268, further comprising a reactant gas source and a gas supply for supplying reactant gas from the reactant gas source to a vessel seated on the vessel holder.

269. The invention of 268a, wherein the gas supply is at a distal portion of the internal electrode.

270. The invention of 268a or 269, further comprising a passage in the inner electrode for delivering a reactant gas from the reactant gas source to a distal portion of the inner electrode.

271. The method according to any one of items 267 to 270, further comprising a carrier gas source within the inner electrode and a passage for transferring carrier gas from the carrier gas source to the distal portion of the inner electrode. invent.

272. The invention of any one of paragraphs 267 to 271, wherein the external electrode is approximately cylindrical and positioned to extend generally concentrically around the vessel seated on the vessel holder.

273. The invention according to any one of paragraphs 267 to 272, wherein the external electrode comprises an end cap.

274. The invention of clause 273, wherein a gap defined between the end cap and the distal end of the vessel seated on the vessel holder is essentially uniform.

275. The invention according to any one of paragraphs 267 to 274, wherein the gap defined between the outer electrode and the vessel seated on the vessel holder is essentially uniform.

276. The method of any one of clauses 117-167 or 212-168, wherein the coating is wherein w is 1, wherein x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3 And z is a layer of SiOx and a layer of SiwOxCyHz, from about 2 to about 9.

278. The invention of 276 or 277 wherein the layer of SiwOxCyHz is deposited on a layer of SiOx deposited on the interior surface of the vessel.

279. The invention of clause 276 or 277, wherein the layer of SiO x is deposited between the layer of SiwO x CyZ and the inner surface of the vessel.

280. The invention according to any one of paragraphs 276 to 279, wherein the layer of SiO x is deposited in the vicinity of the layer of Si w O x Cy Hz.

281. The invention of any of paragraphs 276-280, wherein the layer of SiO x is deposited near an interior surface of the vessel.

282. The invention of any of paragraphs 276-280, wherein the layer of SiwOxCyHz is deposited near an interior surface of the vessel.

283. The invention according to any one of paragraphs 280 to 282, wherein the layers of SiOx and SiwOxCyHz are gradient functional composites of SiwOxCyHz to SiOx.

284. The invention of any of paragraphs 267 to 283, wherein the container further comprises a closure.

285. The invention of 284, wherein the closure comprises an inner-facing surface exposed to the lumen of the vessel.

286. The invention of clause 284 or 285 wherein the closure comprises a wall-contacting surface in contact with the interior surface of the vessel wall.

287. The invention according to any one of 284 to 286, wherein the closure comprises a stopper.

288. The invention of 287, wherein the closure comprises a shield having a stopper.

289. The invention of 287 or 288, wherein the stopper comprises a wall-contacting surface in contact with the interior surface of the vessel wall.

290. The invention of any one of paragraphs 284-289 wherein the stopper comprises an inner-facing surface exposed to the lumen of the vessel.

290a. 290. The invention of any one of claims 267-290, further comprising a vacuum source for removing gas from the vessel defining the vacuum chamber seated on the vessel support.

291. The invention of any one of paragraphs 284-290a, wherein a portion of the vessel wall in contact with the wall-contacting surface of the closure is coated with a lubricating coating of SiwOxCyHz.

 301. The invention of any of paragraphs 284-300, wherein the coating of SiwOxCyHz is applied by PECVD.

302. The invention of any one of 291 to 301, wherein the coating of SiwOxCyHz is between 0.5 and 5000 nm thick.

303. The invention of any of paragraphs 291-301, wherein the coating of SiwOxCyHz is between 100 and 5000 nm thick.

304. The invention of any of paragraphs 291-301 wherein the coating of SiwOxCyHz is between 200 and 5000 nm thick.

305. The invention according to any of paragraphs 291 to 301, wherein the coating of SiwOxCyHz is between 500 and 5000 nm thick.

306. The invention of any of paragraphs 291-301, wherein the coating of SiwOxCyHz is between 1000 and 5000 nm thick.

307. The invention according to any one of paragraphs 291 to 301, wherein the coating of SiwOxCyHz is between 2000 and 5000 nm thick.

308. The invention of any of paragraphs 291-301, wherein the coating of SiwOxCyHz is between 3000 and 5000 nm thick.

309. The invention of any of paragraphs 291-301, wherein the coating of SiwOxCyHz is between 4000 and 10,000 nm thick.

310. A PECVD apparatus, comprising: a vessel support having a port for receiving a vessel in a seated position for processing;

An internal electrode positioned to be received in a container seated on the container support object;

An outer electrode having an inner portion positioned to receive a vessel seated on the vessel holder;

A power supply for supplying alternating current to inner and outer electrodes forming a plasma in the vessel seated on the vessel support object;

A gas exhaust port for delivering gas to or from an inner wall of the vessel seated on the port to define a closed chamber;

Reactive gas source; And

And a gas supply for supplying a reactant gas from the reactant gas source to a vessel seated on the vessel support object.

IV.B. PECVD apparatus using a gripper to reciprocate the tube to the coating station

 311. An apparatus for PECVD processing of a first vessel having an open end, a closed end, and an inner space,

A vessel holder configured to rest on an open end of the vessel;

A first gripper configured to selectively support and release the closed end of the container and to convey the container near the container support while holding the closed end of the container;

The container holder is a seat of the container support, configured to be a sealed communication between the container support and the inner space of the first container;

A reactant feeder operably connected to introduce at least one gas reactant into the first vessel through the vessel holder;

A plasma generator configured to form a plasma in the first vessel under conditions effective to form a reaction product of a reactant on the inner surface of the first vessel;

A container ejector for detaching the first container from the container support; And

The gripper being the first gripper or another gripper comprises a gripper that is the first gripper or the other gripper, configured to transfer the first container axially from the vessel holder and to discharge the first container.

312. The method of clause 311,

A reaction vessel different from the first vessel, the reaction vessel having an open end and an inner space and configured to seat the open end of the reaction vessel on a container support and to achieve sealed communication between the vessel holder and the inner space of the reaction vessel; Vessel; And

Further comprising a PECVD reactant water positioned to settle in the interior space of the reaction vessel when the reaction vessel is seated on the vessel support,

And wherein the plasma generator may be configured to form a plasma in the interior space of the reaction vessel under conditions effective to remove at least a portion of the deposit of the PECVD reaction product from the reactant water.

313. The method of clause 311 or 312, wherein

A tandem conveyor configured to transport grippers; And

A second gripper configured to selectively support and release the closed end of the container, and to convey the container near the container support while holding the closed end of the container,

The first and second grippers are operably connected to the tandem conveyor and continuously transport a series of at least two vessels to the vicinity of the vessel holder, seating the open ends of the vessels to the vessel holder, and Invention in a sealed communication between the vessel holder and the interior of the second vessel, axially transporting the vessels from the vessel holder and releasing the vessels from the grippers.

V.B. PECVD to coat the limited opening of the vessel (syringe capillary)

316. A method of coating the inner surface of a restricted opening of a generally tubular vessel treated by PECVD,

Providing a generally tubular container comprising an outer surface, an inner surface defining a lumen, a larger opening with an inner diameter, and a restricted opening defined by the inner surface and having an inner diameter smaller than the larger opening inner diameter. step;

Providing a treatment vessel having a lumen and a treatment vessel opening;

Connecting the processing vessel opening with a restricted opening of the processing vessel to enable communication through the restricted opening between the lumen of the processing vessel and the processing vessel lumen;

Drawing at least a partial vacuum in the lumen of the vessel being processed and the vessel lumen being processed;

Flowing a PECVD reactant through the first opening, then through the lumen of the vessel to be processed, and then through the restricted opening to flow into the vessel lumen being processed; And

Generating a plasma in the vicinity of the restricted opening under conditions effective to deposit a coating of a PECVD reaction product on the inner surface of the restricted opening.

317. The method of clause 316, wherein the vessel to be treated is a syringe barrel.

318. The method of clauses 316 or 317, wherein the restricted opening has a first fitting and the processing vessel opening is seated in the first fitting to establish communication between the processing lumen of the processing vessel and the lumen of the processing vessel. And a second fitting adapted to achieve.

319. The method of clause 318, wherein the first and second fittings are luer lock fittings.

320. The method of 319, wherein at least one of the first and second fittings is made of an electrically conductive material.

321. The method of clause 299, 319 or 320, wherein at least one of the first and second fittings is made of an electrically conductive material.

322. The method of clauses 299, 319, 320 or 299a2, wherein at least one of the first and second fittings is made of stainless steel.

323. The method of 319, wherein each of the first and second fittings are male and female fittings.

324. The method of clause 299, 319 or 323, further comprising a seal positioned between the first fitting and the second fitting.

325. The method of 324, wherein the seal is an O-ring.

326. Locking according to clauses 319, 323, 324 or 325, wherein when the fittings are engaged one of the fittings has a thread and defines a generally annular first axially directed axially. Wherein the remaining fitting comprises an annular, generally annular second junction opposite the first junction, which includes an annulus.

327. The method of clause 326, further comprising an annular seal engaged between the first abutment and the second abutment.

328. The method of any of paragraphs 316-318, wherein the communication formed between the lumen of the vessel being treated and the vessel lumen being processed through the restricted opening is at least substantially leak free. .

329. The method according to any one of paragraphs 316 to 328, wherein

The flow of PECVD reactant through the larger opening of the vessel being processed provides and is in communication with the inner passageway generally providing a tubular inner electrode having an inner passageway, a proximal end, a distal end and a distal opening adjacent the distal end. ;

Inserting the distal end of the electrode into or around a larger opening of the vessel being processed; And

Supplying a reactant gas into the lumen of the vessel being processed through the distal opening of the electrode.

330. The method of clause 329, wherein the distal end of the electrode is located less than one half of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

331. The method of clause 329, wherein the distal end of the electrode is located less than 40% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

332. The method of claim 329, wherein the distal end of the electrode is located less than 30% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

333. The method of clause 329, wherein the distal end of the electrode is located less than 20% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

334. The method of clause 329, wherein the distal end of the electrode is located less than 15% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

335. The method of clause 329, wherein the distal end of the electrode is located less than 10% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

336. The method of clause 329, wherein the distal end of the electrode is located less than 8% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

337. The method of clause 329, wherein the distal end of the electrode is located less than 6% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

338. The method of clause 329, wherein the distal end of the electrode is located less than 4% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

339. The method of clause 329, wherein the distal end of the electrode is located less than 2% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

340. The method of clause 329, wherein the distal end of the electrode is located less than 1% of the distance from the larger opening of the treated vessel to the restricted opening while supplying the reactant gas.

341. The method of clause 329, wherein the distal end of the electrode is located in a larger opening of the vessel being treated while supplying the reactant gas.

342. The method of clause 329, wherein the distal end of the electrode is located outside the larger opening of the vessel being treated while supplying the reactant gas.

343. The method of any of paragraphs 329 to 342, wherein the distal end of the electrode is located distal to the restricted opening.

344. The method of any of paragraphs 329 to 343, wherein the electrode is moved axially during the deposition of the PECVD reaction product.

345. The method of any of paragraphs 316-344, wherein the plasma extends substantially through the syringe lumen and the restricted opening.

346. The method of any one of paragraphs 316-345, wherein the plasma extends substantially throughout the syringe lumen, the restricted opening, and the vessel lumen being processed.

347. The method of any of paragraphs 316-346, wherein the plasma has a substantially uniform color throughout the syringe lumen and the restricted opening.

348. The method of any of paragraphs 316-347, wherein the plasma has a substantially uniform color throughout the syringe lumen, the restricted opening, and the vessel lumen being processed.

349. The method of any of paragraphs 316-348, wherein the plasma is substantially stable throughout the syringe lumen and the restricted opening.

350. The method of any of paragraphs 316 through 349, wherein the plasma is substantially stable throughout the syringe lumen, the restricted opening, and the vessel lumen being processed.

351. The method of any of paragraphs 316-350, wherein the vessel opening of the vessel being processed is the only opening.

352. The method of any of paragraphs 316-351, wherein the volume of the vessel lumen being processed is less than three times the volume of the lumen (300) of the vessel being treated (250).

353. The method of any of paragraphs 316-352, wherein the volume of the vessel lumen being processed is less than twice the volume of the lumen of the vessel being treated.

354. The method of any of paragraphs 316-353, wherein the volume of the vessel lumen being processed is less than the volume of the lumen of the vessel being treated.

355. The method of any of paragraphs 316-354, wherein the volume of the vessel lumen being processed is less than 50% of the volume of the lumen (300) of the vessel being treated (250).

356. The method of any of paragraphs 316-355, wherein the volume of the vessel lumen being processed is less than 25% of the volume of the lumen (300) of the vessel being treated (250).

357. The generally tubular vessel of any of clauses 316-356, wherein the generally tubular vessel is processed on the vessel support prior to drawing at least a partial vacuum in the lumen 300 of the vessel 250 being treated. And seating a larger opening in the.

358. The method of 357, further comprising seating a larger opening in the vessel to be processed on the port of the vessel holder.

359. The method of paragraph 357 or 358, further comprising placing an internal electrode in the vessel to be treated and seating on the vessel support.

360. The method of clause 357, 358 or 359, further comprising positioning the treated container relative to an external electrode having an inner portion positioned to receive the processed container while seated on the container support. It further comprises a method.

361. Paragraphs 357, 358, 359 or 330, wherein the electric power is supplied to a power supply for supplying alternating current to the external power to form a plasma in the processed vessel seated on the vessel support object. The method further comprises the step of.

362. The method of paragraph 361, further comprising grounding the internal electrode.

363. The method of clauses 357, 358, 359, 360 or 361, further comprising providing a vacuum source for evacuating the interior of the treated vessel defining a vacuum chamber. How to.

364. The method of claim 363, further comprising providing a second vacuum chamber surrounding the vessel being processed.

365. The method of clause 364, wherein the interior of the vessel is maintained at a lower vacuum level than the second vacuum chamber.

366. The method of clause 363, wherein the vessel under treatment is a water column in communication with a vacuum port in the vessel holder.

367. The method according to any one of paragraphs 357 to 366, further comprising a reactant gas source and a gas supply for supplying a reactant gas from the reactant gas source to a vessel seated on the vessel support object. invent.

VI. Container inspection

VI.A. Container handling including precoating and postcoating inspection

399. A container processing method for processing a molded plastic container having an opening and a wall defining an interior surface thereof.

Inspecting the inner surface of the shaped container for defects;

Applying a coating to the inner surface of the container after the inspecting of the molded container; And

Inspecting the coating for defects.

400. A vessel processing method for processing a molded plastic vessel having an opening and a wall defining an interior surface.

Inspecting the inner surface of the shaped container for defects;

Applying a barrier coating to the container after the inspecting step of the molded container; And

Inspecting the interior surface of the container for defects after applying the barrier coating.

401. The invention of clause 400, wherein the interior surface of the shaped container is inspected at numerous closely spaced locations on the interior surface of the container.

402. The invention of clause 400 or 401, wherein after applying the barrier coating the inner surface of the vessel is inspected at numerous closely spaced locations on the vessel inner surface.

403. The method of clause 400, 401 or 402, wherein a number of closely spaced locations on the interior surface of the container are located and inspected on the molded container, coated with the barrier coating and after applying the barrier coating. Invention, characterized in that the re-examination.

V.I.B. Vessel inspection performed by detecting degassing of the vessel wall through the barrier

404. A method of inspecting a barrier membrane on a material that degass vapors,

Removing the gas and providing a sample of the material having at least one partially barrier film; And

Measuring the degassed gas.

405. The method of 404, wherein the gas removing material is a polymeric compound.

406. The method of clause 404 or 405, wherein the gas removing material comprises a thermoplastic compound.

407. The method of any of paragraphs 404-406, wherein the gas removing material comprises a polyester.

408. The method of any of paragraphs 404-407, wherein the gas removing material comprises polyethylene terephthalate.

409. The method of any of paragraphs 404-408, wherein the gas removing material comprises polyolefin.

410. The method of any of paragraphs 404-409, wherein the gas removing material comprises polypropylene.

411. The method of any of paragraphs 404-410, wherein the gas scavenging material comprises a cyclic olefin copolymer.

411a. 403. The method of any one of claims 404-411, further comprising contacting the barrier membrane with water prior to measuring the degassed gas.

411b. 403. The method of any one of claims 404-411, further comprising contacting the barrier membrane with water prior to measuring the degassed gas.

411c. 403. The method of any one of claims 404-411, further comprising contacting the barrier membrane with air at a relative humidity of 35% to 100% prior to measuring the degassed gas. Way.

411d. 403. The method of any one of claims 404-411, further comprising contacting the barrier membrane with air at a relative humidity of 40% to 100% prior to measuring the degassed gas. Way.

411e. 403. The method of any one of claims 404-411, further comprising contacting the barrier membrane with air at a relative humidity of 40% to 50% prior to measuring the degassed gas. Way.

411f. 403. The method of any one of claims 404-411, further comprising contacting the barrier membrane with oxygen prior to measuring the degassed gas.

411 g. 403. The method of any one of claims 404-411, further comprising contacting the barrier membrane with nitrogen prior to measuring the degassed gas.

411h. The method of any one of claims 411a to 411g, wherein the contact time is 10 seconds to 1 hour.

411i. The method of any one of claims 411a-411g, wherein the contact time is 1 minute to 30 minutes.

411j. The method of any one of claims 411a to 411g, wherein the contact time is between 5 minutes and 25 minutes.

411k. The method of any one of claims 411a-411g, wherein the contact time is 10 minutes to 20 minutes.

411l. 403. The method of any one of claims 404-411 k, wherein the degassed gas is measured at a pressure between 0.1 Torr and 100 Torr.

411 m. 403. The method of any one of claims 404-411 k, wherein the degassed gas is measured at a pressure between 0.2 Torr and 50 Torr.

411n. The method of any of claims 404-411k, wherein the degassed gas is measured at a pressure of 0.5 Torr to 40 Torr.

411o. The method of any one of claims 404-411k, wherein the degassed gas is measured at a pressure of 1 Torr to 30 Torr.

411p. 403. The method of any one of claims 404-411 k, wherein the degassed gas is measured at a pressure of 5 Torr to 100 Torr.

411q. 403. The method of any one of claims 404-411 k, wherein the degassed gas is measured at a pressure of 10 Torr to 80 Torr.

411r. The method of any one of claims 404-411k, wherein the degassed gas is measured at a pressure of 15 Torr to 50 Torr.

411s. 403. The method of any one of claims 404-411r, wherein the degassed gas is measured at a temperature between 0 ° C and 50 ° C.

411t. 403. The method of any one of claims 404-411r, wherein the degassed gas is measured at a temperature between 0 ° C and 21 ° C.

411 u. 403. The method of any one of claims 404-411r, wherein the degassed gas is measured at a temperature of 5 ° C to 20 ° C.

412. The method of any of clauses 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 surrounding the lumen.

413. The method of clause 412, wherein the barrier membrane is provided on an inner surface of the vessel wall.

414. The method of clause 412 or 413, wherein a pressure difference is provided across the barrier membrane by at least partially vacuuming the lumen.

415. The method of any of paragraphs 412-414, further comprising connecting the lumen through a duct to a vacuum source that at least partially evacuates the lumen.

416. The method of 415, further comprising providing a degassing measurement cell in communication with the lumen and the vacuum source.

417. The method of any of paragraphs 404-416, wherein the measurement is performed by measuring the volume of degassed material through the barrier membrane per time interval.

418. The method of any of paragraphs 404-417, wherein the measurement is performed using micro-flow technology.

419. The method according to any one of items 404 to 418, wherein the measurement is performed by measuring the mass flow rate of the degassed material.

420. The method of any one of clauses 404-419, wherein the measurement is performed in a molecular flow mode of operation.

420a. 420. The method of any of claims 404-420, wherein the measurement is

Providing at least one microcantilever having the property of being moved or changed to a different shape when degassed material is present;

Exposing the microcantilever to the degassed material under conditions effective to cause the microcantilever to move or change in a different shape; And

Characterized in that it is carried out by detecting a movement or a different shape.

420b. 420. The method of claim 420a, wherein the different shape reflects an energy incident beam from a portion of the microcantilever that changes shape before and after exposing the microcantilever to the outgassing, and is thus reflected at a point spaced from the cantilever And is detected by measuring the deflection of the beam.

420c. 420. The method of claim 420b, wherein the energy incident beam is selected from photon beams, electron beams, and combinations of two or more thereof.

420d. 420. The method of claim 420b, wherein the energy incident beam is a photon beam.

420e. 420. The method of claim 420b, wherein the energy incident beam is a laser beam.

420f. 420. The method of any of claims 404-420, wherein the measurement is

If at least one degassed material is present, providing at least one microcantilever that resonates at a different frequency;

Exposing the microcantilever to the degassed material under conditions effective to resonate the microcantilever at different frequencies; And

Detecting said different resonance frequency.

420g. 420f. The method of claim 420f, wherein the different resonant frequencies induce energy to the microcantilever to resonate before and after exposing the microcantilever to outgassing and between the resonant frequencies before and after exposing the microcantilever to outgassing. Detected by measuring the difference in

420h. 420g. The method of claim 420, wherein the different resonance frequencies are detected using a harmonic vibration sensor.

421. The method of 404, wherein the degassed material is provided in the form of a film.

422. The method of any of paragraphs 404-421, wherein the barrier membrane is all or part of a coating on the surface of the degassing material.

425. The method of any of paragraphs 404-424, wherein the barrier film comprises SiO x, wherein x is from about 1.5 to about 2.9.

426. The method of any of paragraphs 404-425, wherein the barrier film consists essentially of SiO x, wherein x is from about 1.5 to about 2.9.

427. The method according to any one of items 404 to 426, wherein the barrier film is less than 500 nm thick.

428. The method of any of paragraphs 404-427, wherein the barrier film is less than 300 nm thick.

429. The method according to any one of clauses 404 to 428, wherein the barrier film is less than 100 nm thick.

430. The method of any of paragraphs 404-429, wherein the barrier film is less than 80 nm thick.

431. The method of any of paragraphs 404-430, wherein the barrier film is less than 60 nm thick.

432. The method of any one of claims 404-431, wherein the barrier film is less than 50 nm thick.

433. The method according to any one of paragraphs 404 to 432, wherein the barrier film is less than 40 nm thick.

434. The method of any of paragraphs 404-433, wherein the barrier film is less than 30 nm thick.

435. The method according to any one of paragraphs 404 to 434, wherein the barrier film is less than 20 nm thick.

435. The method of any of paragraphs 404-435, wherein the barrier film is less than 10 nm thick.

437. The method of any one of paragraphs 404-436, wherein the barrier film is less than 5 nm thick.

438. The method of any of paragraphs 404-437, wherein the measurement of the degassed gas is performed under conditions effective to distinguish the presence of the barrier film.

439. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier membrane include a test duration of less than one minute.

440. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier film include a test duration of less than 50 seconds.

441. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier membrane include a test duration of less than 40 seconds.

442. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier membrane include a test duration of less than 30 seconds.

443. The method of clause 438, wherein the effective conditions for distinguishing the presence or absence of the barrier membrane include a test duration of less than 20 seconds.

444. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier film comprise a test duration of less than 15 seconds.

445. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier film include a test duration of less than 10 seconds.

446. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier film include a test duration of less than 8 seconds.

447. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier film comprise a test duration of less than 6 seconds.

448. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier film include a test duration of less than 4 seconds.

449. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier membrane comprise a test duration of less than 3 seconds.

450. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier membrane comprise a test duration of less than 2 seconds.

451. The method of clause 438, wherein the conditions effective for distinguishing the presence or absence of the barrier film include a test duration of less than one second.

452. The method according to any one of paragraphs 438 to 451, wherein the measurement of the absence of the barrier film is confirmed at at least a six-sigma level of the certainty.

453. The method of paragraphs 438 to 452, wherein the measurement is confirmed at at least a six-sigma level of the certainty.

454. The method of any of paragraphs 404-453, wherein the degassing gas measurement on the low pressure side of the barrier membrane is effective to determine the barrier enhancement factor of the barrier membrane compared to the same material without the barrier membrane. Characterized in that it is carried out under conditions.

455. The method of any one of claims 404-454, wherein degassing of the plurality of different gases is measured.

456. The method of any one of claims 404-455, wherein degassing of substantially all of the degassed gases is measured.

457. The method of any one of claims 404-456, wherein degassing of substantially all of the degassed gases is measured simultaneously.

458. The method of any one of claims 404-457, wherein degassing of substantially all of the degassed gases is measured simultaneously.

20 canister processing system
22 Injection Molding Machine
24 vision inspection station
26 Inspection Station (Pre-Coated)
28 coating stations
30 Inspection Station (Post-Coating)
32 Light Source Transmission Station (Thickness)
34 Light source transmission station (defective)
36 Output
38 Vessel Support
40 Vessel Support
42 Vessel Support
44 Vessel Support
46 Vessel Support
48 Vessel Support
50 Vessel Support
52 Container Support
54 Vessel Support
56 Vessel Support
58 Vessel Support
60 Vessel Support
62 Vessel Support
64 Vessel Support
66 Vessel Support
68 Vessel Support
70 conveyor
72 Delivery Mechanism (In Operation)
74 Delivery Mechanism (Discontinued)
80 containers
82 opening
84 occlusion
86 walls
88 inner surface
90 blocking coating
92 container port
94 vacuum duct
96 vacuum ports
98 vacuum source
100 O-ring (９2)
102 O-ring (９6)
104 gas input port
106 O-ring (100)
108 probe (relative electrode)
110 gas delivery port （10８）
112 Vessel Support (Fig. 3)
114 housings (50 or 12)
116 Rings (ｃｏｌｌａｒ)
118 Outer Surface （90 °）
120 Vessel Support (Array)
122 "Container Ports (FIGS. 4, 58)"
130 frames (Fig. 5)
132 light source
134 side channels
136 shutoff valve
138 probe port
140 vacuum port
142 PCD gas input port
144 pecd gas source
146 vacuum line (up to ９８)
148 shutoff valve
150 flexible lines
152 pressure gauge
154 Inner 90 of the container
160 electrodes
162 power supply
164 sidewalls (160)
166 sidewalls (160)
168 Occlusion Groups (160)
170 light source (Fig. 10)
172 detector
174 pixels (172)
176 Internal Surfaces
182 Aperture （1８６）
184 walls （１８６）
186 integrating sphere
190 microwave power supply
192 waveguide
194 microwave cavity
196 gap
198 Top (1９４)
200 electrodes
202 tube transport
204 Suction Cup
208 mold center
210 mold cavity
212 Mold Cavity Liner
220 bearing surface (FIG. 2)
222 bearing surface (FIG. 2)
224 bearing surface (FIG. 2)
226 bearing surface (FIG. 2)
228 bearing surface (FIG. 2)
230 bearing surface (FIG. 2)
232 bearing surface (FIG. 2)
234 bearing surface (FIG. 2)
236 bearing surface (FIG. 2)
238 bearing surface (FIG. 2)
240 bearing surface (FIG. 2)
250 syringe barrel
252 syringe
254 internal surface (250)
256 rear end (250)
258 plunger
260 leaflet (250)
262 caps
264 inner surface (262)
266 fitting
268 containers
270 closure
272 inner facing surface
274 lumens
276 Wall-Contact Surface
278 inner surface （20８）
280 vessel walls
282 stopper
284 shield
286 lubricity coating
288 barrier coating
290 coating apparatus, for example 250
292 Internal Surfaces (24)
294 limited opening (25)
296 processing vessel
298 outer surface (250)
300 lumens (250)
302 large opening (25)
304 processing vessel lumen
306 treatment vessel opening
308 internal electrodes
310 Internal passage （300３）
312 proximal
314 Distal Ends
316 distal opening (30 kW)
318 plasma
320 Vessel Support
322 ports (320)
324 Treatment Vessel (Waterworks Type)
326 Container Openings
328 Second Opening (of 244)
330 vacuum ports
332 First fitting (male luer taper)
334 2nd fitting (female luer taper)
336 Locking Hooks
338 First Connection (of 324)
340 Second Junction (of 324)
342 O-ring
344 Brackets (Ｄｏｇ)
346 walls
348 coating (363 phase)
350 penetration route
352 vacuum
354 gas molecules
355 gas molecules
356 interface (between 34 and 34)
357 gas molecules
358 PET container
359 gas molecules
360 sealed
362 measuring cell
364 vacuum pump
366 arrows
368 conical aisle
370 perforator
372 perforator
374 chamber
376 chamber
378 plates
380 plates
382 conductive surface
384 conductive surface
386 bypass
390 plots (glass tubes)
392 plots (PET not coated)
394 main plots (SiO ₂ coated)
396 isolates (SiO ₂ coated)
398 Internal Electrode and Gas Supply Tube
400 distal opening
402 extended counter electrode
404 outlet (FIG. 7)
406 valve
408 Interior Wall (FIG. 36)
410 exterior wall (FIG. 36)
412 inner surface (FIG. 36)
414 plate electrode (FIG. 37)
416 plate electrode (FIG. 37)
418 vacuum water
420 Vessel Support
422 vacuum chamber
424 Vessel Support
426 counter electrode
428 Vessel Support (FIG. 39)
430 electrode assembly
Volume surrounded by 432 430
434 pressure balancing valve
436 vacuum chamber water
438 syringe barrel (FIG. 42)
440 flange (438)
442 Backward Openings (438)
444 Barrel Wall （438）
450 container support (FIG. 42)
452 fantasy lip
454 approximately cylindrical sidewalls (438)
456 approximately cylindrical inner surface (450)
458 junctions
460 pockets
462 O-ring
464 Exterior Wall （460）
466 floor wall （460）
468 upper wall （460）
470 Internal Electrode (FIG. 44)
472 distal regions (470)
474 Porous Sidewalls (472)
476 Internal Passage (472)
478 proximal regions (470)
480 Distal Ends (470)
482 Vessel Support Body
484 Top Area (482)
486 bases (482)
488 joint (between 484 and 486)
490 O-ring
492 annular pockets
494 radially extending junction surfaces
496 radially extending walls
498 screw
500 screw
502 vessel port
504 2nd O-ring
506 inner diameter (490)
508 vacuum ducts (482)
510 internal electrodes
512 internal electrodes
514 Insertion and Removal Mechanism
516 flexible hose
518 flexible hose
520 flexible hose
522 valves
524 valves
526 valve
528 Electrode Cleaning Station
530 internal electrode drive
532 cleaning reactor
534 outlet valve
536 2nd Gripper
538 conveyor
539 solute retainers
540 Open Ends (532)
542 Internal Spaces (532)
544 Syringes
546 plunger
548 body
550 barrel
552 inner surface （550）
554 coating
556 lure fitting
558 luer taper
560 internal passageway (558)
562 inner surface
564 coupling
566 male part (564)
568 arm part (564)
570 barrier coating
572 locking collar
574 main vacuum valve
576 vacuum lines
578 manual bypass valve
580 bypass line
582 outlet valve
584 main reactant gas valve
586 main reactant supply lines
588 organosilicon liquid reservoir
590 Organosilicon Supply Line (Capillary Tube)
592 organosilicon shutoff valve
594 oxygen tank
596 oxygen supply line
598 flow controller
600 oxygen shutoff valve
602 syringe outer barrier coating
604 lumens
606 barrel outer surface
610 plasma screen
612 plasma screen cavity
614 space part
616 pressure source
618 pressure lines
620 capillary connection
Plots for 630 Uncoated COC
Plots for 632 SiOx Uncoated COC
Plots for 634 Glass
5501 first processing station
5502 second processing station
5503 third processing station
5504 fourth processing station
5505 processor
5506 user interface
5507 bus
5701 PCD device
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 Outlet Branch

Claims (28)

In the method for setting the lubricity of the coating on the substrate surface,
(a) providing a gaseous reactant comprising an organosilicon precursor and optionally oxygen (O ₂ ) near the substrate surface; And
(b) generating a plasma from the gaseous reactant to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),
The lubricity of the coating comprises the step of setting the ratio of oxygen (O ₂ ) and organosilicon precursors in the gaseous reactant and / or setting the power used to generate the plasma. A method of making a hydrophobic coating on a substrate surface,
(a) providing a gaseous reactant comprising an organosilicon precursor and optionally oxygen (O ₂ ) near the substrate surface; And
(b) generating a plasma from the gaseous reactant to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),
Wherein the hydrophobic character of the coating is set by setting the ratio of O ₂ and organosilicon precursors in the gaseous reactant and / or by setting the power used to generate the plasma. The process of claim 1, wherein the atomic ratio C: O is increased and / or the atomic ratio Si: O is reduced by comparison with the formula of the organosilicon precursor. The method of claim 1, wherein the oxygen (O ₂ ) is 0: 1 to 5: 1, optionally 0: 1 to 1: 1, optionally in volume-volume ratio to the gaseous reactant. Alternatively 0: 1 to 0.5: 1, optionally 0: 1 to 0.1: 1, preferably at least essentially free of oxygen in the gaseous reactant. Process according to any one of the preceding claims, characterized in that the gaseous reactant comprises less than 1% by volume of O ₂ , in particular less than 0.5% by volume of O ₂ , most preferably free of O ₂ . The method of claim 1, wherein the plasma is a non-hollow cathode plasma. The method of any one of the preceding claims,
(i) the plasma is between 0.1 and 25 W, preferably between 1 and 22 W, more preferably between 3 and 17 W, even more preferably powered electrodes sufficient to form a coating on the substrate surface Is produced using electrodes powered from 5 to 14 W, most preferably 7 to 11 W, in particular 8 W; And / or
(ii) the ratio of the power to the plasma volume is 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. In a method of making a coating on a substrate surface,
(a) providing a gaseous reactant comprising an organosilicon precursor and optionally O 2 near the substrate surface; And
(b) generating a non-porous cathode plasma from the gas reactant under reduced pressure to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),
Wherein the physical and chemical properties of the coating are set by setting a ratio of O 2 and organosilicon precursors in the gaseous reactant and / or setting the power used to generate the plasma. In a method of making a barrier coating on a substrate surface,
(a) providing a gaseous reactant comprising an organosilicon precursor and O 2 near the substrate surface; And
(b) generating a non-porous cathode plasma from the gas reactant under reduced pressure to form a coating on the substrate surface by plasma enhanced chemical vapor deposition (PECVD),
The barrier of the coating is set by setting the ratio of O 2 and organosilicon precursors in the gas reactant and / or setting the power used to generate the plasma. Method according to claim 9
(i) the plasma comprises electrodes supplied with sufficient power to form a coating on the substrate surface, preferably 8 to 500 W, preferably 20 to 400 W, more preferably 35 to 350 W, more More preferably between 44 and 300 W, most preferably between 44 and 70 W powered electrodes; And / or
(ii) the ratio of the power to the plasma volume is 5 W / ml or less, 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. The method according to claim 9 or 10, wherein the O ₂ has a volume: volume ratio of 1: 1 to 100: 1, preferably 5: 1 to 30: 1, relative to the silicon-containing precursor. More preferably 10: 1 to 20: 1, more preferably 15: 1. The method of claim 1, wherein the organosilicon precursor is a linear siloxane, monocyclic siloxane, polycyclic siloxane, polysesquioxane, linear silazane, monocyclic silazane, polycyclic silazane, poly Silsesquiazane, alkyl trimethoxysiloxane and combinations of two or more of these compounds,
Preferably a linear or monocyclic siloxane. Method according to claim 1 or 2, characterized in that the organosilicon precursor is a monocyclic siloxane, preferably OMCTS. 10. The process according to claim 2 or 9, wherein the organosilicon precursor is a linear siloxane, preferably HMDSO. The substrate of claim 1, wherein the substrate is a polymer selected from the group consisting of polycarbonates, olefin polymers, cyclic olefin copolymers and polyesters, preferably cyclic olefin copolymers, polyethylene terephthalates or polypropylenes. Method characterized in that. The plasma according to any one of the preceding claims, wherein the plasma is at radiofrequency, preferably 10 kHz to less than 300 MHz, more preferably 1 to 50 MHz, even more preferably 10 to 15 MHz and most preferably Generated using electrodes powered at a frequency of 13.56 MHz. A coating obtainable by the method of any one of the preceding claims. 18. The coating of claim 17, wherein the coating is a lubricious and / or hydrophobic coating. The coating of claim 18 wherein the atomic ratio of carbon to oxygen is increased relative to the organosilicon precursor and / or the atomic ratio of oxygen to silicon is reduced relative to the organosilicon precursor. The method of claim 18, wherein the coating is
(i) has a lower frictional resistance than the uncoated surface, preferably the frictional resistance is at least 25%, more preferably at least 45%, even more preferably at least 60 compared to the uncoated surface Coating reduced by%. The method according to any one of claims 18 to 20,
(i) a lower wet tension than the uncoated surface, preferably a wet tension of 20 to 72 dyne / cm, more preferably a wet tension of 30 to 60 dyne / cm, more preferably 30 to 40 dyne / have a wet tension of cm, preferably 34 dyne / cm;
(iv) a coating which is more hydrophobic than said uncoated surface. A container, preferably a container, coated on at least a portion of its inner surface with a coating according to claim 17.
(i) sample collection tubes, in particular blood collection tubes; or
(ii) vials; or
(iii) a syringe or syringe portion, in particular a syringe barrel or syringe plunger; or
(iv) pipes; or
(v) a container, characterized in that it is a cuvette. The method of claim 22, wherein x further comprises at least one SiO _x layer from 1.5 to 2.9,
(i) the coating is located between the SiOx layer and the substrate surface or vice versa,
(ii) the coating is located between two SiO _x layers or vice versa,
(iii) a coated container, characterized in that the SiO _x and layers of the coating are a gradient functional composite of Si _w O _x C _y H _z to SiO _x or vice versa. 24. The compound or composition according to any one of claims 22 to 23, wherein the lumen comprises a compound or composition, preferably a biologically active compound or composition or biological fluid, more preferably (i) citrate or citrate A coated container comprising a composition comprising, (ii) a medicament, in particular insulin or an insulin containing composition, or (iii) blood or blood cells. The method of any one of claims 22 to 24, wherein the precursor is a siloxane, more preferably a monocyclic siloxane, even more preferably octamethylcyclotetrasiloxane. A coated container, which is a syringe barrel made according to claim 1, wherein in step (a) the gaseous reactant is substantially free of any O ₂ gas and the force to move the plunger through the coated barrel is an uncoated syringe barrel. Coated container, characterized in that by at least 25%, more preferably at least 45%, even more preferably at least 60%. In the use of a coating having the formula Si _w O _x C _y H _z wherein w is 1, x is 0.5 to 2.4, y is 0.6 to 3, z is 2 to 9,
(i) lubricity coatings having lower frictional resistance than uncoated surfaces; And / or
(ii) the use of a coating, characterized in that it is used as a hydrophobic coating that is more hydrophobic than the uncoated surface. Precipitation and / or precipitation of compounds and composition components, preferably in contact with the inner surface of the container, to protect the compound or composition contained or contained in the coated container from the mechanical and / or chemical effects of the uncoated container material surface. Use of the coated container according to any one of claims 22 to 25 to prevent or reduce solidification. The method of claim 27, wherein the compound or composition is
(i) a biologically active compound or composition, preferably a medicament, more preferably a composition comprising insulin or insulin, wherein insulin precipitation is reduced or prevented; or
(ii) a biological fluid, preferably a bodily fluid, more preferably a blood or blood fraction in which blood clotting is reduced or prevented.

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