KR102157254B1 - A blood collection vessel - Google Patents

Abstract

Coating 　 process 　 products 　 inspection method 　 is provided. Measure the emission of at least one volatile species into the gas space adjacent to the coated surface from the coated surface, and compare the result with the result measured under the same test conditions and with at least one standard subject. Thereby, it is possible to determine the presence or absence of the coating and/or the physical and/or chemical properties of the coating. This 　 method is useful for 　 arbitrary 　 coated 　 products, for example 　, and 　 inspecting 　 containers. In particular, 　 for 　 for 　 for 　 for 　 for 　 for 　 for the 　 　 coating made of 　 organic silicon 　 precursor 　, especially for the 　 barrier 　 coating 　 is also launched.

Description

Blood collection container {A BLOOD COLLECTION VESSEL}

US Provisional Application No. 61/177,984, filed on May 13th, 2009 　; 61/222,727, filed 　 on July 2, 2009 　; 61/213,904 filed 　 on July 24 　 2009; 61/234,505, filed 　 on August 17, 2009 　; 61/261,321, filed 　 on January 14, 2009 　;　61/263,289 filed 　 on January 20, 2009 　; 61/285,813, filed 　 on February 11, 2009 　;　61/298,159 filed 　 on January 25th, 2001; 61/299,888, filed 　 on January 29, 2010 　;　61/318,197, filed on March 26th, 2001;　61/333,625, filed 　 on May 11, 2001 　; And 　61/413,334, filed 　 on January 12, 2001; And all of the 　US Ser.No.12/779,007 　 filed 　 on May 12 in 2001 　 are included in this original by reference in its entirety.

In addition, the following 　European patent applications are also included in 　by reference: 　EP10162755.2, filed on May 12th, 2010 　;　 filed on May 12, 2001 　 EP10162760.2;　EP10162756.0, filed on May 12th in 2001;　EP10162758.6, published on May 12th, 2001;　 filed on May 12, 2001 　 EP10162761.0; And 　EP10162757.8, filed 　 on 2010 　 May 12. This European patent application are described (Method of test for testing an in particular, the coating method and coating), a general device which can be used for carrying out the invention, the container, the precursor, the coating and method that does not otherwise stated herein, ． These are 　also 　siox 　prevention 　 coating 　 and 　 lubrication 　 coating 　, and 　 this is 　 referenced in the original 　.

　Applied 　PCT/US11/36097 degrees 　Additional 　 for reference 　 　 here 　 this 　 invention 　 ways 　 sea 　 inspected 　 received 　 and is specially coated 　 　

Throughout this 　 specification 　, refer to 　EP2251671 A2 　 (corresponds to 　 mentioned 　EP 10162758.6 　 above 　 also 　 this 　 for invention 　 is in the 　 position of the elected application) In these cases, the 　 general 　 gas removal 　 method 　 is described and exemplified 　 which follows the 　 basic 　 of the present 　 invention, and therefore 　 the contents 　 are included in this original as reference 　.

Field of invention

The present invention relates to the technical field of the manufacture of coated containers for storing biologically active compounds or blood. In particular, the present invention relates to a container treatment system for coating and inspection of a container, which is a container treatment system for the coating of containers, to a portable container holder for the container treatment system, and plasma-enhanced for coating the inner surface of the container. It relates to chemical vapor deposition apparatus, relates to a method of coating the inner surface of a vessel, relates to a method of coating and inspection of a vessel, relates to a method of handling vessels, relates to the use of a vessel handling system, relates to a computer readable medium. , It relates to program components.

Coating 　 process 　 products 　 inspection method 　 is provided. Measure the emission of at least one volatile species into the gas space adjacent to the coated surface from the coated surface, and compare the result with the result measured under the same test conditions and with at least one standard subject. Thereby, it is possible to determine the presence or absence of the coating and/or the physical and/or chemical properties of the coating. This 　 method is useful for 　 arbitrary 　 coated 　 products, for example 　, and 　 inspecting 　 containers. In particular, 　 for 　 for 　 for 　 for 　 for 　 for 　 for the 　 　 coating made of 　 organic silicon 　 precursor 　, especially for the 　 barrier 　 coating 　 is also launched.

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

Evacuated blood collection tubes are used to draw blood from the patient for medical analysis. The tubes are sold in a vacuum. The patient's blood is inserted into the blood vessel of the patient by inserting one end of the hypodermic needle using both sides into the blood vessel of the patient, and piercing the closure of the vacuumed blood collection tube with the other end of the needle using both of the above and into the inside of the tube. It works. Blood is collected through a needle through the vacuumed blood collection tube due to the vacuum in the vacuumed blood collection tube (or more precisely, the patient's blood pressure pushes the blood), increasing the pressure in the tube so that the blood flows. 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 flow.

Vacuum blood collection tubes should have a substantial shelf life that facilitates efficient and convenient distribution and storage of the tubes prior to use. For example, a shelf life of 1 year is preferred, and progressively longer shelf lives, such as 18 months, 24 months or 36 months, are also desirable in some cases. Preferably, the tube remains sufficiently evacuated to the extent necessary to draw at least enough blood for analysis during its entire shelf life, with little (optimally no) supply of defective tubes (common standard). The silver 　 above 　 tube keeps 　 at least 　 90% of the original 　 inhaled 　 volume).

A defective tube is likely to fail to draw enough blood by a hematologist using the tube. The hematologist needs to obtain and use one or more other tubes in order to obtain a sufficient blood sample.

Prefilled syringes are commonly prepared and sold so that the syringe does not need to be filled prior to use. For example, the syringe may be prefilled with saline solution, a dye for injection, or a pharmaceutically active agent.

Typically, the pre-filled syringe is capped at the distal end using a cap, and closed at the proximal end by the pulled plunger of the syringe. The pre-filled syringe may be packaged in sterile packaging prior to use. To use the prefilled syringe, the packaging and cap are removed, optionally a hypodermic needle or other delivery conduit is attached to the distal end of the barrel, and the delivery water or syringe is moved to the use position. (Such as inserting a hypodermic needle into a patient's blood vessel or inserting it into a device to rinse with the contents of the syringe), the plunger advances within the barrel to inject the contents of the barrel.

One important consideration in making prefilled syringes is that the contents of the syringe preferably have a substantial lifespan, where it is important to separate the contents of the syringe from the barrel wall containing the material filling the syringe during the lifespan, so that the reserve from the barrel. It will avoid filtering the material with the filled contents or vice versa.

Another consideration when considering syringes is to allow the plunger to move at a constant speed and force when compressed into the barrel. For this purpose, lubricity coatings, such as the lubricity coatings described in the above cited application, are preferred.

Since many of these containers are expensive and used in large quantities, it would be useful for certain applications to reliably obtain the required shelf life without increasing manufacturing costs to prohibitive levels.

For decades, most parenteral treatments have been delivered to end users in Type 1 medical grade borosilicate glass containers such as vials or prefilled syringes. The surface of borosilicate 　glass has been 　relatively 　 strong, 　 impermeable 　 inactive 　 surface has been 　 appropriately 　 for pharmaceuticals in the 　 part. However, as well as advanced delivery systems such as automatic injector expensive, complex, and there is a drawback of glass, including physical and chemical contamination that may be due to damage to the metal and found, among other issues in recent advent of sensitive biological materials. In addition, 　glass has 　can be leached 　 during 　and 　 contains 　 several 　 components that can cause 　 damage 　 to storage 　 material 　More 　in detail 　 borosilicate 　 container has many 　 disadvantages 　:

ㆍ Glass is made from sand containing a heterogeneous mixture of various components (silicon, oxygen, boron, aluminum, sodium, calcium) with traces of other alkali and alkaline earth metals. Type 1 borosilicate glass is composed of approximately 76% SiO2, 100.5% B2O3, 5% Al ₂ O ₃ , 7% Na ₂ O and 1.5% CaO, and is often made up of trace amounts such as iron, magnesium, zinc and copper. Contains metal. The heterogeneous nature of borosilicate glass creates non-uniform surface chemistry at the molecular level. The glass-forming process used to make glass containers exposes a portion of the container to temperatures as high as 120°C. Under these high temperatures, alkali ions migrate to the localized surface to form oxides. The presence of ions extracted from the borosilicate glass apparatus can be involved in the degradation, aggregation and denaturation of some biologics. Many proteins and other biologics are not sufficiently stable in glass vials or syringes and must be lyophilized (freeze dried).

ㆍ In glass 　 syringes, 　silicone 　 oil is 　 usually used 　 as lubricating oil so that the plunger 　 can slide 　 in the barrel 　. Silicones and oils have been associated with sedimentation of proteins and solutions, such as insulin and some other biologics. In addition, 　silicone 　 oil 　 coating is 　often 　 uneven, causing 　injectors 　 defects in the market.

ㆍ Glass 　 containers are 　 manufacturing, 　 filling, 　 shipping 　 and 　 during use 　 breaks 　 or 　 deteriorates 　 easy, 　 means that 　 glass 　 fine particles 　 enter the chemicals 　 meaning 　The existence of glass and fine particles has led to several warnings and product recalls.

ㆍ Glass 　 formation 　 process does not calculate 　 some 　 new 　 automatic 　 injector 　 and 　 delivery 　 system 　 required 　 strict dimensional tolerances.

ㆍAs a result, 　some 　 companies switched 　 to plastic 　 containers 　 provided 　 large 　 dimensions 　 tolerances 　 and 　 less than glass 　 damaged 　 impermeability 　 is insufficient.

ㆍPlastic is 　for 　 　 better than glass 　, but 　 dimension 　 tolerance 　 and 　 surface 　 uniformity, 　 1st 　 pharmaceutical 　 packaging 　 use of plastic 　 is limited to the following 　 disadvantages 　

ㆍSurface 　 Characteristics: Suitable for preliminary 　 syringes 　 and 　 vials 　 plastics 　 generally 　 hydrophobic 　 surface 　 denoting 　 common 　 devices 　 　 contained 　 biological stability 　

ㆍ Gas (oxygen) 　 Permeability: Plastics 　 small 　 molecules 　 gas are 　 devices 　 into (out) 　 permeate 　.　The permeability of plastic 　 to gas 　 is 　 remarkably larger than 　 than glass 　 in several 　 cases (like epiteprine 　 　 oxygen 　 sensitivity 　 drugs and 　), 　 plastic is not acceptable 　

ㆍ Water vapor transmission: Plastics 　 to a degree higher 　 than glass 　 to pass water vapor into the apparatus 　. This is 　solid (lyophilized) 　drugs 　can be harmful in the expiration date. Alternatively, the 　liquid 　 product could 　 lose moisture 　 in a very 　 dry environment.

ㆍ Filtrate and 　 extract: The plastic 　 container contains 　filtered 　 or can be 　 extracted with chemicals 　 organic 　 compounds. These 　compounds 　can contaminate/contaminate the 　drugs 　 or reduce the 　negative 　 effects on the 　stability of the drugs.

Obviously, 　plastic 　 and 　glass 　 container 　 each 　 pharmacy 　 primary 　 in packaging 　 some 　 benefits 　 but none 　 all 　 drugs, 　 leaky drugs 　 other 　 optimal treatment Therefore, there is a need for 　approaching 　 and 　 solutes 　 prevention 　 properties 　 plastics 　 containers, especially 　 plastics 　 syringes that approach the 　 properties of glass. In addition, there is a requirement for 　injector 　 contents and 　 compatible 　 can 　 　 sufficient 　 lubrication 　 and 　 lubrication 　 has coating 　 plastic 　 syringe 　.

　 　 mentioned above 　 application 　 　 described in one 　 　 organic silicon 　 using the precursor 　 　 　 　 　 coating 　 or 　 　 　 　 　 　 　 　 　However, in order to 　 economical 　 production 　 　 coating 　 inspection 　 possible 　 　 inspection method 　 is also required.

Non-limiting lists of possible related patents include US Pat. Nos. 6,068,884 and 4,844,986 and the United States. Published applications 20060046006 and 20040267194.

This invention provides a method of inspecting 　surfaces, especially 　coated 　surfaces and 　specifically 　organic silicon 　 made from 　precursors 　coated 　 plastics 　 by coating 　. The inspection is carried out by detecting 　inspection 　　 gas removal from the object, 　 especially 　 coated 　 surface 　 gas removal 　.　Invention of the main 　 application provides 　a method of 　inspecting the 　container 　by detecting 　through the 　coated 　 barrier 　 on the container 　 wall 　This 　invention is 　also 　including 　coating 　containing 　inspection 　, and the inspection is carried out by 　 in accordance with the 　invention 　 gas 　 removal 　 method. In a special 　sun, 　this 　invention is 　including 　 step 　 and 　 inspection 　 step 　 including 　 step 　 inspection 　 step is carried out 　 gas removal 　 method

The 　 gas 　 removal 　 method of this 　 invention should be 　 inspected 　 material 　 property 　 quickly 　 accurate 　 judged 　 　. For example, the 　gas 　 removal 　 method is 　 prevention 　 coating and the same 　 coatings 　 plastic 　 existing on the substrate 　 quickly and 　 accurate 　 judgment 　.

This 　invention is 　also 　referred 　 and/or 　 mentioned 　 method 　 to perform the steps 　 configured 　 devices (for example, 　 containers 　 processing 　 systems 　 containers 　 processing 　 stations) Examples of such 　processing stations (20, 　30, 　55001-1-5,504) are depicted in 　for example 　 also 　1　 and 　59-61.

The present invention also stores a computer program for surface inspection adapted to perform the method steps mentioned above or below when executed by a processor of a device, such as a container handling system, and adapted to command a processor to control the device. It is about the computer-readable medium in which it is located.

This 　invention is 　also 　a program for surface inspection, adapted 　 or a computer program for surface inspection 　 adapted to perform the method steps mentioned above or below, when executed by a processor of a device, such as a container handling system It is about 　.

Therefore, a processor can be equipped to carry out the exemplary embodiments of the method of the invention. Computers and programs can be written in any arbitrary or appropriate program and language, and stored in a computer-readable medium, such as a computer-readable medium. In addition, the 　computer　program can be used as the 　video 　 processing 　 means or 　 processor 　 or 　 arbitrary 　 appropriate 　 computer 　 can be downloaded 　 　 can be used 　 world wide 　 web (Ｗｏｒｌｄｗｉｄｅ〷)

The aspect of the present invention consists of a first material by measuring volatile species degassed by a coated product, and a coating or barrier film on a substrate or other object having a surface-for example, a syringe or blood collection tube. A method and system for inspecting a SiOx coating on a cyclic olefin copolymer ("COC") thermoplastic molded substrate as an object made of the first material. Here, the volatile species originate from the material to be tested or from the filler material, for example, carbon dioxide, nitrogen, argon, xenon, krypton, carbon number 　 1 　 to 　 4 　 low grade 　 hydrocarbons (e.g. 　 ethylene, 　 ethane, 　 or methane), lower hydrocarbon ether having a carbon number of lower halogenated hydrocarbons of 1 to 4 (for example, ethane as methyl chloride, methylene chloride, fluoride, methyl or trifluoromethyl), or 1 to 4 carbon atoms (e.g., diethyl ether or dimethyl ether, or ethyl-methyl-ether It originates from a filler containing ）, which is brought into contact with the inspection object before the degassed volatile species are measured ("Degassing Method"). 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. The 　 method is performed under conditions effective to distinguish the presence or absence of the prevention film, for example, 　. For example, 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, "volatile species" are gases or vapors under test conditions, inert 　 gas, 　 carbon dioxide, 　 hydrocarbons, 　 halogenated 　 hydrocarbons, 　 ether, 　 air, 　 nitrogen, 　 oxygen, 　 water vapor, 　 　 　 　 　 　 　 　 　 　 and coating components There are 　to be selected 　 　 from the 　 group consisting of the 　 combination, and 　 is optionally air, nitrogen, oxygen, water vapor, or a combination thereof. Volatile 　 species can be filled 　 in 　 inspection 　 subject 　 before 　 inspection 　, and not filled 　 in substances (for example, volatile 　 substrate 　 constituents 　 or 　 residuals of the coating 　 also exist 　) The method can be used to measure only one or more volatile species, but optionally a plurality of different volatile species are measured, and optionally, substantially all volatile species released from the test object are measured.

This 　invention 　other 　solar 　 example 　 　 knowing 　 existence of the barrier 　 as the inspection method of the object 　 the above 　 method is 　 filling 　 material 　 having 　 inspection 　 containing the object 　 filling In this 　 method, 　at least 　 is a 　 object made of a part 　 the first material 　, and the above 　 has a surface (in the first 　 sun, 　 the barrier is 　 as a barrier 　 the surface is the same as the surface 　 formed 　 with the object) It has a 　 at least 　 part 　 barrier. Optionally, 　the first substance 　dissolved, 　absorbed 　adsorbed 　filled 　substance 　 is provided, and the 　object comes into contact with the 　filled 　material. Degassing is measured from at least a portion of the surface. The 　 method is performed under conditions effective to determine the existence or non-existence of the prevention film, for example.

The filling 　 material can 　 improve the 　 sensitivity of the 　 gas removal 　 method. In particular, it is possible to simplify the distinction between 　two 　inspection 　, 　for example 　 once 　 coated 　 once 　 uncoated 　 substrate quality 　. Filling 　 substances 　 different 　 quantity 　 each other 　 by different 　 substances 　 constrained 　 degassing 　 　 2 　 substances 　 　 distinction 　 possible 　 can also 　.

The distinction between uncoated 　 plastic 　 products and 　SIOS-coated 　 plastics 　 products 　 will be removed 　 later 　 measured 　 can 　 gas 　 absorbed 　 depends on the capacity of the 　 product.　Solubility of 　 in plastics 　 is an important 　 factor 　 determines the amount of 　 in plastic 　 　 exists 　 　 　 is therefore 　 appropriate 　 uncoated 　 non-coated 　 products special 　 specific products 　 specific 　 provided 　In the sun of the present invention, it is advantageous to increase the amount of gas that is absorbed or absorbed in the plastic by filling the plastic with a material. This can lead to a high content of 　 gas 　 removal 　 measurement 　 gas 　 removed 　 volatile species 　 can 　 can 　 improve reading 　 can.

In a particular aspect of the invention, an improved sensitivity of the degassing measurements using carbon dioxide flushed and / or carbon dioxide to a substrate (for example, carbon dioxide _gas), N 2, lower hydrocarbons, Ar, xenon, krypton, having from 1 to 4 carbon atoms (for example, Ethylene, ethane, or methane), lower halogenated hydrocarbons having 1 to 4 carbon atoms (eg methyl chloride, methylene chloride, methyl fluoride or trifluoroethane) or lower hydrocarbon ethers having 1 to 4 carbon atoms (eg diethyl ether or di It can be implemented by mixing methyl ether or ethyl-methyl-ether. The use of CO ₂ is particularly useful during testing of the COC substrate when the low solubility of nitrogen, water and oxygen.

In general, 　 this 　 in accordance with the invention 　 the gas removal method includes the following steps:

(a) providing the product for inspection;

(c) measuring the emission of at least one volatile species from the inspection object into a gas space adjacent to the surface of the object; And

(d) Compare the result of step (c) with the result of step (c) with respect to at least one reference object measured under the same test conditions, and coat the test 　 subject's 　 specific 　 substance 　 or 　 specific 　 component, 　 example 　 substrate quality 　Measuring the presence or absence of.

Typically, the degassing method for 　this 　invention 　coated 　inspection 　 includes the following steps:

(a) providing a product comprising a coating as an inspection object;

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

(d) Compare the result of step (c) with the result of step (c) for at least one reference object measured under the same test conditions, and the presence or absence of the coating and/or the physical properties of the coated 　 or 　And/or measuring chemical properties.

In the degassing method, the physical and/or chemical properties of the coating to be measured can be selected from the group consisting of a barrier effect, a wetting tension, and a composition thereof, and optionally 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.

Optionally, the reference object (i) is an uncoated substrate; Or (ii) a substrate coated with a reference coating. This is, for example, compared to a coating with known properties, for example, the degassing method determines the presence or absence of the coating (the reference object may be an uncoated substrate hereinafter) or compares it with a known 　 material 　 generally 　It depends on whether or not it is used to determine the properties of the material. In order to determine the identity of the coating as a specific coating, a reference coating may also be a conventional choice.

In addition, the gas removal method provides atmospheric pressure in the gas space adjacent to the coated surface so that a pressure difference is provided through the coated surface and a higher mass flow rate or volume flow rate of the volatile species than when there is no pressure difference can be realized. Step (b), which is a step of changing, may be included as an additional step between steps (a) and (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, a pressure differential between the vessel lumen and the outside is established to measure the outgassing state of the volatile species from the coated vessel wall. The pressure differential may be provided, for example, by at least partially evacuating the gas space in the vessel. In this 　 case, 　can be measured 　 the above 　 volatile 　 paper 　 being degassed into the 　 lumen of the container.

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

In another aspect, in order to enable adsorption or absorption of the volatile species in step (a), optionally onto or into the material of the test subject, the test object is optionally air, nitrogen, It can be contacted with a volatile species selected from the group consisting of oxygen, water vapor, carbon dioxide, inert 　 gas 　 and combinations thereof. Thereafter, the subsequent release of the volatile species from the test object is measured in step (c). Since different materials (eg, the coating and the substrate, etc.) have different adsorption and absorption characteristics, this can simplify the determination of the presence and characteristics of the coating.

The substrate may be a polymer compound, optionally polyester, polyolefin, cyclic olefin copolymer, polycarbonate, or a combination thereof. This 　invention 　gas 　 removal 　 method is especially interesting 　in the inspection of 　COC, 　polyethylene terephthalate 　 and 　polypropylene.

In the context of the present invention, the coating characterized by the degassing method can be any coating, but, for example, in the detailed 　 description, in the 　 paragraph 　 1 　 to 　 3 　 quoted 　 applications-that is, 　 the original 　 the invention is applied The following 　 for 　 here 　 clear 　 applications 　-　 and 　 is a coating prepared by PECVD, typically from the organosilicon precursors described in this specification. For example, 　coating is 　blocking film 　can 　, and 　optionally 　ｘ　1. 5　 to 　2. 9 in 　SiOx　 film. As another example, the coating can be hydrophobic makil with the features as defined by the features the lubricating coating, and / or in the definition section, or incorporated in applications such as those defined in the application in the section definition or reference.

When the coating process in which the product is inspected by the gas removal method is a PPD coating performed under vacuum conditions, the subsequent gas removal measurement can be performed without breaking the vacuum used for the PECVD.

The measured volatile species may be a volatile species released from the coating, a volatile species released from the substrate, or a combination thereof. In one aspect, the volatile species is a volatile species released from the coating and, optionally, a volatile coating component, wherein the test 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 test is performed to determine the presence of the coating and/or the barrier effect of the coating.

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

Conditions effective to distinguish the presence or absence of the coating and/or to measure 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. Test durations of less than, 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. .

For example, in order to increase the difference between the reference object and the test object with respect to the emission rate and/or the type of the measured volatile species, the emission rate of the volatile species is determined by the ambient pressure and/or temperature and/or humidity. Can be changed by changing.　The use of 　filling materials 　 in accordance with this invention 　 serves the same 　 purpose.

Measurements can be carried out using microflow techniques, for example.

In one 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 a property of moving or changing into a different shape when the degassed material is present;

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

(c) Optionally, reflecting an energy incident beam such as a laser beam from a portion of the microcantilever that changes shape before and after exposing the microcantilever to the degassing, and at a point spaced from the cantilever Measuring the deflection of the thus reflected beam; Or detecting a movement or a different shape as follows

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

(b) exposing the microcantilever to the outgassed material under conditions effective to cause the microcantilever to resonate at different frequencies; And

(c) measuring the different resonant frequencies, eg, using a harmonic vibration sensor.

Further, an apparatus for carrying out the above-described gas removal method is contemplated, for example an apparatus comprising the microcantilever described above.

Using the degassing method of the present invention, for example, a barrier film on a substance that removes vapor is inspected, the inspection method having several steps. A sample of material is provided which degassed and has at least one partially barrier film. In one aspect of the present invention, a pressure differential is provided across the barrier layer so that at least a portion of the material to be degassed is present on the high pressure side of the barrier layer. The outgassed gas passing through the barrier layer is measured. If there is a pressure differential, the measurement is typically performed on the lower pressure side of the barrier.

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

1 is a schematic diagram illustrating a container handling system according to an embodiment of the present disclosure.
2 is a simplified cross-sectional view of a vessel holder in a coating station according to one embodiment of the present disclosure.
20 is an unfolded longitudinal sectional view of a syringe and cap adapted for use as a prefilled syringe.
26 is a view similar to FIG. 22 of another embodiment of the present invention for handling syringe barrels and other containers.
Fig. 27 is an enlarged detail view of the processing container of Fig. 26;
29 is a schematic diagram showing the degassing of a material through coating.
Fig. 30 is a simplified cross-sectional view showing a test set-up for carrying out measurements of degassing and degassing from a vessel to the interior of the vessel, using a measuring cell interposed between a vessel and a vacuum source.
FIG. 31 is a plot of the outgassing mass flow rate measured on the test setup of FIG. 30 for multiple vessels.
32 is a bar graph showing statistical analysis of the endpoint data shown in FIG. 31.
36 is a perspective view of a double wall blood collection tube assembly according to another embodiment of the present invention.
Figure 4-5 is another structure for a vessel holder usable with the embodiments of Figures 1, 2 and 26, for example.
Figure 5 is a schematic diagram of an assembly for handling containers. The assembly can be used with the device of any of the preceding figures.
57 is a plot of the outgassing mass flow rate measured in Example 19 of EP2251671 A2.
Fig. 58 shows a linear rack (recv).
59 is a schematic diagram of a container handling system according to an exemplary embodiment of the present invention.
60 is a schematic diagram of a container handling system according to an exemplary embodiment of the present invention.
61 shows a processing station of a container processing system according to an exemplary embodiment of the present invention.
Figure 62 shows a portable container holder according to an exemplary embodiment of the present invention.
Figure 6 is a plot of the outgassing mass flow rate measured on the test setup of Figure 30 showing the data of Example 10 of EP2251671 A2.
The following reference characters are used in the drawing numbers:

The invention will now be described in more detail in particular with reference to the accompanying drawings, in which some embodiments are shown. However, the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments described herein. Rather, these embodiments are examples of the invention, having the full scope indicated by the language used in the claims. Similar numbers refer to corresponding similar elements throughout the specification.

Definition clause

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

RF is a radio frequency; The sccm is standard cubic centimeters per minute.

The term “at least” in the context of the present invention means “equal to or greater than” an integer following the term. The word "comprising" does not exclude other elements or steps, and the indefinite article "one" or "an" does not exclude the plural unless otherwise indicated. Whenever a parameter range is indicated, it is assumed that the parameter value is disclosed as the limit of the range and all values of the parameters within the range.

"First" and "second" or similar references, such as processing stations or processing devices, refer to the minimum number of processing stations or devices that exist, but do not necessarily indicate the order or total number of processing stations and devices. 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, the "organosilicon precursor" is a compound having at least one 　 linkage:

or

One 　Oxygen　Atom 　 and 　Organic 　 Carbon 　 (Organic 　 Carbon 　 Atom is 　 at least 　 　 Oxygen 　 is 　 bound 　 Carbon 　 Atom is 　 connected silicon 　 4 　A volatile organosilicon precursor, defined as a precursor that can be supplied as water vapor in a PECVD device, is an optional organosilicon precursor. Optionally, the organosilicon precursor is linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, alkyl trimethoxysilane, linear silazane, monocyclic silazane, polycyclic silazane, poly Silsesquiazane is selected from the group consisting of a combination of two or more of these precursors.

The amounts of supply of the PECVD precursor, gaseous reactant or process gas, and carrier gas are often expressed in the specification and claims as "standard volume". The standard volume of charge or a fixed amount of other gas is the volume occupied by a fixed amount of gas at standard temperature and pressure (regardless of the actual delivery temperature and pressure). Standard volumes may be measured using different units of volume and may still fall within the scope of this disclosure and claims. For example, the same fixed amount of gas can be expressed as the number of standard entrance centimeters, the number of standard cubic meters, or the number of standard cubic feet. Standard volumes may be defined using different standard temperatures and pressures, and may still fall within the scope of this disclosure and claims. For example, the standard temperature (as conventional) may be 0°C and the standard pressure may be 760 Torr, or the standard temperature may be 20°C and the standard pressure may be 1 Torr. However, no matter which standard is used in a given case, comparing the relative amounts of two or more different gases without specifying specific parameters, the same unit of volume, standard temperature and standard pressure will be used for each gas unless otherwise indicated. .

The feed rates of the corresponding PECVD precursor, gaseous reactant or process gas, and carrier gas are often expressed in the specification as standard volumes per unit time. For example, in the working examples, the flow rate is expressed in standard cubic centimeters per minute abbreviated as sccm. As with other parameters, other units of time, such as seconds or hours, may be used, but the matched parameter will be used when comparing two or more lyrics unless otherwise indicated.

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 coated substrate may be an inner wall of a container having a lumen. The present invention is not necessarily limited to a container of a specific volume, but a lumen having a void volume of 0.5 to 50 mL, optionally 1 to 10 mL, more preferably 0.5 to 5 mL, optionally 1 to 3 mL. Courage is considered. The substrate surface may be part or all of the inner surface of the container having at least one opening and an inner surface.

The term “at least” in the context of the present invention means “equal to or greater than” an integer following the term. Thus, a container in the context of the present invention has one or more openings. One or two openings are preferred, such as openings in a sample tube (one opening) or a syringe barrel (two openings). If the container has two openings, they can be of the same or different sizes. If there is more than one opening, one opening can be used for the gas inlet for the PPD coating method according to the invention, while the other openings are capped or opened. The container according to the present invention includes, for example, a sample tube for collecting or storing biological fluids such as blood or urine, a syringe for storing or delivering a biologically active compound or composition, such as a medicament or pharmaceutical composition (or parts thereof, e.g. For example, a syringe barrel), such as a vial storing a biological material or a biologically active compound or composition, such as a pipe such as a biological material or a conduit carrying a biologically active compound or composition, or a biological material or biologically It may be a cuvette that supports fluids, such as supporting an active compound or composition.

The container can be of any type, with a container having a substantially cylindrical wall adjacent at least one of its open ends is preferred. In general, the inner wall of the vessel is cylindrical in shape, for example in a sample tube or syringe barrel. Sample tubes and syringes or parts thereof (eg syringe barrels) are contemplated.

"Hydrophobic membrane" in the context of the present invention means lowering the wetting tension of a surface coated with said coating compared to a corresponding surface which is not coated with said coating. Thus, hydrophobicity is a function of both the uncoated substrate and the coating. The same is appropriately modified and applies in other contexts where the term "hydrophobic" is used. The term "hydrophilic" means vice versa, ie the wetting tension is increased relative to the reference sample. This hydrophobic film is mainly defined by its hydrophobicity, and the process conditions to provide hydrophobicity and optionally the experimental composition or the summation formula SiwOxCyHz. It can have a composition according to.

In general, it has an atomic ratio of SiwOxCy, where w is 1, x is about 0.5 to about 2.4, y is about 0.6 to about 3, preferably w is 1, and x is about 0.5 to 1.5, y is 0.9 to 2.0, more preferably w is 1, x is 0.7 to 1.2, and y is 0.9 to 2.0. The atomic ratio can be determined by X-ray photoelectron spectroscopy (XPS). Considering the hydrogen atom, the coating is thus in one aspect, for example, w is 1, x is 1 as w, x is about 0.5 to about 2.4, y is about 0.6 to about 3, and z is about 2 To about 9 SiwOxCyHz. Typically, the atomic ratio is Si 100:O 80-110: C 100-150 in certain coatings of the present invention. Specifically, the atomic ratio may be Si 100: O 92-107: C 116-133, and this coating thus contains carbon and oxygen and 36% to 41% carbon normalized to 100% silicon.

These values of w, x, y and z can be applied to the empirical formula SiwOxCyHz throughout this specification. The values of w, x, y, and z used throughout this specification are to be understood as relative ratios or empirical formulas (eg, for coatings) rather than limitations on the number of atoms in a molecule. For example, octamethylcyclotetrasiloxane having a molecular composition of Si ₄ O ₄ C ₈ H ₂₄ can be described by the following empirical formula obtained by dividing each of w, x, y and z in the molecular formula with the maximum common factor of 4. There is: Si ₁ O ₁ C ₂ H ₆ . Further, the numerical values of w, x, y, and z are not limited to integers. For example, the molecular composition of Si ₃ O ₂ C ₈ H ₂₄ (acyclic) octamethyltrisiloxane may be reduced to Si ₁ O _0.67 C _2.67 H ₈ .

"Wet tension" is a specific measure of the hydrophobicity or hydrophilicity of a surface. An optional wetting tension measurement method in the context of the present invention is ASTM D 2578, or a variation of the method described in ASTM D 2578. This method uses standard wetting tension solutions (called dyne solutions) to determine the closest solution to wet the plastic film surface for exactly 2 seconds. This is the wetting tension of the film. The procedure used here is that the substrates are not flat plastic films, in that they are tubes made according to the protocol for forming PET tubes and coated according to the protocol for coating the inside of the tube with a hydrophobic film (excluding controls), It is modified from ASTM D 2578 (see Example 9 of EP2251671 A2).

A "lubricating film" according to the invention is a coating that has a lower frictional resistance than an uncoated surface. That is, it reduces the frictional resistance of the coated surface compared to the uncoated reference surface. The present lubricating film is primarily defined by a lower frictional resistance than an uncoated surface and may have a composition according to the experimental composition or the summation formula SiwOxCyHz and the process conditions providing lower frictional resistance than the uncoated surface. In general, it has an atomic ratio of SiwOxCy, where w is 1, x is about 0.5 to about 2.4, y is about 0.6 to about 3, preferably w is 1, and x is about 0.5 to 1.5, y is 0.9 to 2.0, more preferably w is 1, x is 0.7 to 1.2, and y is 0.9 to 2.0. The atomic ratio can be determined by X-ray photoelectron spectroscopy (XPS). Considering the hydrogen atom, the coating is thus in one aspect, for example, w is 1, x is 1 as w, x is about 0.5 to about 2.4, y is about 0.6 to about 3, and z is about 2 To about 9 SiwOxCyHz. Typically, the atomic ratio is Si 100:O 80-110: C 100-150 in certain coatings of the present invention. Specifically, the atomic ratio may be Si 100: O 92-107: C 116-133, and this coating thus contains carbon and oxygen and 36% to 41% carbon normalized to 100% silicon.

"Friction resistance" may be static friction resistance and/or kinetic friction resistance. One of the alternative embodiments of the present invention is a syringe component, such as a syringe barrel or plunger, coated with a lubricating membrane. In this contemplated embodiment, a suitable static frictional resistance in the context of the present invention is a breakout force as defined herein, and a suitable kinetic frictional resistance in the context of the present invention is a plunger action force as defined herein. For example, the plunger actuation force as defined and measured herein is suitable for determining the presence and lubrication characteristics of a lubricating membrane in the context of the present invention when a coating is applied to any syringe or syringe part, such as the inner wall of a syringe barrel. Do. The breakout force is applied to a prefilled syringe, ie a syringe that is filled after coating and can be stored for a period of time, such as months or even years, before the plunger is moved again (which has to be "broken out"). It is particularly suitable for evaluating the effect of the coating to be applied.

"Slideable" means that the plunger, closure, 　 or 　 other 　 removable part 　 in the syringe 　 barrel or other 　 container 　.

In the context of the present invention, "substantially rigid" means that the assembled members (ports, ducts and housings, further described below) are not displaced significantly relative to the other. , It means that it can be moved as a unit by manipulating the housing. Specifically, none of the members are connected by hoses or the like that allow substantial relative motion between the parts during normal use. Providing a substantially rigid relationship between these parts makes the position of the container seated on the container holder as known and accurate as the positions of these parts fixed to the housing.

In the following, the apparatus for carrying out the present invention will be described first, followed by the coating methods, coated and coated containers and the gas removal method according to the present invention will be described in more detail.

I. Vessel processing system with multiple processing stations and multiple vessel holders

I. A vessel processing system is contemplated comprising a first processing station, a second processing station, a plurality of vessel holders and a conveyor. The first processing station is adapted to process a vessel having an opening and a wall defining an interior surface. The second processing station is spaced apart from the first processing station and is adapted to process a vessel having an opening and a wall defining an interior surface.

I. At least a part of the vessel holder, and optionally all of the vessel ports, are configured such that the vessel port is configured such that the vessel port is configured to cover the inner vessel surface and the vessel port is configured through the above vessel container port through the above vessel container port. Include. The conveyor is configured for transferring the series of 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 from the second processing station.

I. Referring first to Fig. 1, there is shown a vessel handling system, generally designated 20. 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 comprises an injection molding machine 22 (which may be considered a processing station or apparatus), additional processing stations or devices 24, 26, 28, 30, 32, and 34. And an output 36 (which may be considered a processing station or device). At a minimum, the system 20 has at least a first processing station, eg 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, and the like.

I. The embodiment shown in FIG. 1 may include the following 8 processing stations or devices: 22, 24, 26, 28, 30, 32, 34, and 36. The exemplary vessel processing system 20 Silver 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), it includes an optical source delivery station 34 and an output station 36 for inspecting the coating for defects.

I. The system 20 may include a transfer mechanism 72 to move containers from the injection molding machine 22 to the container holder 38. The delivery mechanism 72, for example, finds, moves, picks up, transfers, orients, seats and ejects the vessels 80 to remove them from the vessel forming machine 22 (38). It may be composed of a robot arm to install them on the vessel holders such as.

I. In addition, the system 20 may, after processing the inner surface of the seated vessel such as 80, at a processing station 74 that removes the vessel from one or more vessel holders such as 66. It may include a delivery mechanism (Fig. 1) Thus, the containers 80 are movable from the container holder 66 to packaging, storage or other suitable area or processing step, generally denoted 36. The The delivery mechanism 74, for example, finds, moves, picks up, transfers, orients, seats and ejects the vessels 80 to remove them from the vessel holders 38 and remove them from the station 36 ) Can be configured with a robotic arm to install them on other equipment.

I. The processing stations or devices 32, 34 and 36 shown in FIG. 1 are applied to the coating and inspection system 20 after the individual containers 80 are removed from the container holders such as 64. ), optionally performing one or more appropriate steps. Some non-limiting examples of the functions of the processing stations or devices 32, 34 and 36 include:

• placing the treated and inspected containers (80) on a conveyor and moving them to another processing unit;

ㆍ adding chemicals to the containers;

• capping the containers;

• locating the vessels in suitable processing racks;

-Packing the containers; And

ㆍ sterilizing the packaged containers

I. Also, as shown in Fig. 1, the vessel handling system 20 has a plurality of vessel holders (or “pucks”, each 38 to 68, as they resemble a hockey puck in some embodiments) and generally end. One or more vessel holders 38 to 68 and thus vessels such as 80, denoted by a band 70 without a band 70, are placed at the processing stations 22, 24, 26, 28, 30, 32, 34 and 36. It may include a conveyor for reciprocating transport to and from.

I. The processing station or device 22 may be a device forming the vessels 80. One device 22 contemplated could be an injection molding machine. Another contemplated device 22 may be a blow molding machine. Also contemplated are vacuum molding machines, draw molding machines, cutting or milling machines, glass draw molding machines or other types of container forming machines that draw glass or other draw moldable materials. Optionally, the vessel forming station 22 can be omitted since it can obtain vessels that have already been formed.

II. Vessel holder

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

II.A. The container ports are configured to seat container openings in communication with each other. The second port is configured to receive an external 　 gas 　 supplier 　 or 　 discharge port. It is configured to pass one or more gases 　 between the 　 container 　 opening 　 seated on the 　 container 　 port and the 　 top 　 agent 　 2 　 port 　. The vessel port, the second port and the duct are substantially rigidly attached to the movable housing. Optionally, the above 　portable container 　 support weighs less than 　5 pounds. The advantage of the lightweight vessel holder 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 the container seated on the container 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 in Figure 2, for example. The vessel holder 50 has a vessel port 82 configured to receive and seat an opening of the vessel 80. The inner surface of the seated container 80 may be processed through the 　 container 　 port 82 　. The container support 50 may include a duct, for example, a vacuum duct 94, for recovering 　 gas from the 　 container 80 mounted on the 　 container 　 port 92. The vessel holder may include a second port, for example, a vacuum port 96 communicating 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 between the inner or outer cylindrical wall of the vessel port 82 and the inner or outer cylindrical wall of the vessel 80, for example, O-ring support seals. , It has the sealing elements (100) and (102), respectively, it is possible to receive and form a seal with the container 80 or the external vacuum source 98 while allowing communication through the port. In addition, gaskets or other sealing methods may also be used.

II.A. The vessel holder, such as 50, can be made of any material, for example a thermoplastic material and/or an electrically non-conductive material. In addition, a vessel holder such as 50 is partially or mainly made of an electrically conductive material, and in particular, in the passages defined by the vessel port 92, the vacuum duct 94 and the vacuum port 96. It can fight against non-conductive materials. Examples of suitable materials for the vessel holder 50 are as follows: polyacetal, for example Delrin® acetal material sold by E. I. DuPont de Nemours, Wilmington, Delaware; Polytetrafluoroethylene (PTFE), for example Teflon® PTFE sold by the E. I. DuPont de Nemours company, 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, 2 may have a ring 116 that centers the vessel 80 when the vessel holder, eg 50, approaches or seats the port 92.

　Array of vessel holders

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

II.A. 4, 5 and 58 show three array approaches. Fig. 4 shows a solid array 120 in which the devices or containers 80 are loaded. In this case, the devices or vessels 80 can move through the production process as a solid array, although they can be moved through the production process and moved to individual vessel holders. 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 the array 98 of vacuum sources. Also, a single vacuum port may be provided connected to all vessel ports, such as 96. Further, a plurality of gas input probes such as 108 may be provided in the array. Arrays of gas input probes or vacuum sources can be mounted and moved as a unit to simultaneously process multiple vessels, such as 80. Further, a plurality of vessel ports such as 122 may be processed individually or more than one row at a time at the processing station. The number of devices in the array may be related to the number of devices being 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 individual electrodes with their own power air. All of the above approaches may still be applicable (in terms of electrode geometry, frequency, etc.).

II.A. In Figure 5, individual pucks or vessel holders (discussed above) are brought together into the array by enclosing them with an outer frame 130. This arrangement provides the advantages of the solid array of Figure 4, if desired, and also allows the array to be disassembled for other processing steps in which the vessels 80 are processed in other arrays or alone.

II.A. Figure 58 shows a 　linear 　rack (recｋ) similar to 　degree 4 and 　. If a linear rack is used, in addition to those described above, another option is to transport the rack in the form of a single file through a processing station to process the containers serially.

II.B. Vessel holder with O-ring arrangement

II.B. 42 and 43 are usable with the embodiments of the container holders of Figs. 2, 3, 6, 7, 19, 12, 13, 16, 18, 19, 30, and 43 for mounting the container on the container support object, respectively, 　 alternative It is a fragmentary detailed longitudinal cross-section and detailed view of the 　 container support 450 provided with a special 　 sealing 　 arrangement. Referring to Figure 42, the container, for example, the syringe barrel 438 seated on the container holder 450 is generally annular (and commonly rounded or rounded) as well as a generally cylindrical side wall 454. ) Has a rear opening 442 defined by a lip 452. Medical bodily fluid collection tubes have the same type of lip 452 in common, but do not have a flange 440 and can instead be seated on the vessel holder 450.

II.B. In the illustrated embodiment, the vessel holder 450 includes an approximately cylindrical inner surface 456 that serves as a guide surface in the illustrated embodiment and accommodates the approximately cylindrical sidewall 454 of the syringe barrel 438. do. Further, the wall is defined by a generally annular joint 458 to which the annular lip 452 joins when the syringe barrel 438 is seated on the vessel holder 450. A generally annular pocket or groove 460 formed in the inner surface 456 is provided to bear 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), preferably the inner diameter of the O-ring 462 It is slightly smaller than the outer diameter of the annular lip 452.

II.B. These relative dimensions are at least approximately 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. The radial cross section of the O-ring 462 between the cylindrical side walls 454 is horizontally compressed. This compression flattens the bearing surfaces of the O-ring 462, forming a seal between at least the outer wall 464 of the pocket 460 and the approximately cylindrical side wall 454 of the syringe barrel 438. Is done.

II.B. The pocket 460 is optionally spaced apart from the upper and lower walls 468 and 466 by a corresponding radial cross-sectional diameter of the O-ring 462, with respect to the values of the O-ring 462. It may be manufactured to form two or more threads between the lower and upper walls 466 and 468 and the side walls 454. When the O-ring 462 is compressed between the outer wall 464 and the substantially cylindrical side wall 454 of the pocket 460, it expands up and down as shown in FIG. 43 due to its restoring force. , Engaging and flattening the top and bottom walls 466 and 464. Optionally, the O-ring 462 tends to deform vertically and horizontally to make a normally round cross section square. In addition, the annular lip 452 seated on the junction 458 will limit the flow of PECVD process reactants and other gases introduced through the rear opening 442 or adjacent thereto.

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

II.B. In addition, the pocket 460 may be formed together with the bottom wall 466 on 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 of seal and further tighten the vessel 438 against locking when seated against the abutment 458. I can.

II.B. Figure 45 is a different structure for the container 482 that can be used in conjunction with the examples of other drawings, for example, 　 and other 　 drawings. The vessel holder 482 includes an upper portion 484 and a base 486 joined together at a joint 488. A sealing component, e.g., an O-ring 490 (the right side of which is cut off so that the pocket supporting it is described) is between the upper portion 484 and the base 486 at the joint 488. Is captured in. In the illustrated embodiment, when the upper portion 484 is connected to the base 486, the O-ring 490 is accommodated in the annular pocket 492 and is positioned on the O-ring.

II.B. In this embodiment, the O-ring 490 is captured, and when the upper portion 484 and the base 486 are connected, in this case a joint extending radially by screws 498 and 500 It bears against a surface 494 and the radially extending wall 496 that partially defines the pocket 492. Accordingly, the O-ring 490 is seated between the upper portion 484 and the base 486. In addition, the O-ring 490 captured between the upper portion 484 and the base 486 accommodates the vessel 80 (removed for clarity in this figure when other features are shown) and , Forming a first O-ring seal of the vessel port 502 around the vessel 80 opening, similar to the O-ring sealing arrangement around the vessel 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 which It has an inner diameter, such as 506, sized to accommodate the outer diameter of the container, such as 80 (similar to the side wall 454 in FIG. 43) for sealing between the container such as port 502 and 80. The space between the O-rings 490 and 504 provides support for a container such as 80 at two axially spaced points, so that a container such as 80 can be applied to the O-rings 490 and 504. ) Or the container port 502 to prevent distortion. In this embodiment, although not required, a radially extending abutment surface 494 is located close to the O-rings 490 and 506 seals and surrounds the vacuum duct 508.

III. Container transfer method-handling a container seated on a container holder

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

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

III.A. A vessel 80 may be provided having an opening 82 and a wall 86 defining an interior surface 88. As an example, the container 80 may be formed in a mold such as 22 and then removed therefrom. 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 within 3 seconds after removing the container from the mold , Or within 1 second or as soon as the container 80 can be moved without distorting it during processing of the container 80 (assuming that it is manufactured at a high temperature and is gradually cooled therefrom), the container opening 82 ) May be seated on the vessel port 92. When the container 80 is moved quickly from the mold 22 to the container port 92, dust or other impurities that may reach the surface 88 are reduced and the barrier coating or other type of coating ( 90) will block or prevent adhesion. In addition, the faster the vacuum is pulled out on the container 80 after the container 80 is manufactured, the lower the likelihood of fine particle impurities adhering to the inner surface 88.

III.A. A vessel holder such as 50 including vessel ports 92 may be provided. The opening 82 of the container 80 may be seated on the container port 92. Prior to, during or after seating the opening 82 of the vessel 80 on the vessel port 92, the vessel holder, such as 40, is transferred to one or more of the bearing surfaces 220- In engagement with 240, it may be positioned on the vessel holder 40 with respect to a processing device or station such as 24.

III.A. One, two or more, or all of the processing stations may have one or more vessel holders such as 40 at a predetermined location while processing the inner surface 88 of the seated vessel 80 at a processing station or apparatus such as 24. It may include one or more bearing surfaces to support. These bearing surfaces may be part of a stationary or moving structure such as, for example, tracks or guides that guide and position a vessel holder 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, so that when the probe 108 is inserted into the vessel holder 40, the vessel holder 40 Acts as a reaction surface so that it cannot move 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 located on the vessel holder 40 to prevent horizontal movement during processing. The bearing surfaces 230 and 234 are similarly positioned on the vessel holder such as 40 to prevent vertically out-of-position movement. Thus, a first bearing surface, a second bearing surface, a third bearing surface, or more can be provided at each processing station.

III.A. The inner surface 88 of the seated vessel 80 is to be processed through the above 　 control 　 1 　 treatment 　 station 　 above 　 container 　 port 92, which could be, for example, a blocking or other type of coating device 28 shown in FIG. I can. 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 container 80 may be processed through the 　 above 　 container 　 port 92 at the above 　 manufacturing 　 2 　 treatment station such as 32.

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

III.A. One of the methods may further comprise, after the removing step, providing a second container 80 having an opening 82 and a wall 86 defining an inner surface 88. The opening 82 of the second vessel, such as 80, can be seated on the vessel port 92 of another vessel holder, such as 38. The inner surface of the seated container 80 may be treated through the 　 above 　 container 　 port 92 in the above 　 manufacture 　 1 　 treatment 　 station or device such as (24). The vessel holder such as 38 and a 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 container 80 may be processed through the container port 92 by the 　 control 　 2 　 processing 　 station or device 26.

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

III.B. Further, the processing stations may be more broadly processing devices, the vessel holders can be transferred relative to the processing apparatuses, the processing apparatuses can be moved relative to the vessel holders, or each arrangement of Some may be provided for a given system. In another arrangement, the vessel holders may be moved to one or more stations, and one or more processing devices may 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 processing stations.

III.B. A method of handling a container comprising some parts is contemplated. The first treatment device such as the probe 108 (FIG. 2) and the second treatment device such as the light source 170 may be provided in the container such as (80). A vessel 80 is provided having an opening 82 and a wall 86 defining an inner surface 88. A vessel holder 50 comprising a vessel port 92 is provided. The opening 82 of the vessel 80 is seated on the vessel port 92.

III.B. The first processing device, such as the probe 108, may move operatively in engagement with the vessel holder 50 or vice versa. The inner surface 88 of the seated container 80 is processed through the 　 manufacture 　 1 　 treatment 　 device or the 　 the container 　 port 92 using the probe 108.

III.B. Thereafter, the second processing device is operatively engaged with the vessel holder 50 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 different processing steps may be provided. For example, a third processing device 34 may be provided for processing the vessels 80. The third processing device 34 may move in operative engagement with the vessel holder 50 or vice versa. The inner surface of the seated container 80 may be treated through the 　 container 　 port 92 using the third processing device 34.

III.B. In another method of handling the vessel, a vessel 80 may be provided having an opening 82 and a wall 86 defining an inner surface 88. A vessel holder such as 50 including vessel ports 92 may be provided. The opening 82 of the container 80 may be seated on the container port 92. The inner surface 88 of the seated vessel 80 is to be processed through the above 　 control 　 1 　 treatment 　 station 　 above 　 container 　 port 92, which could be, for example, a blocking or other type of coating device 28 shown in FIG. I can. The vessel holder 50 and the seated vessel 80 are transported from the first processing device 28 to the second processing device, for example, the processing device 34 shown in FIGS. 1 and 10. The inner surface 88 of the seated vessel 80 can then be processed through the vessel port 92 by a second processing device such as 34.

IV. PECVD device for container manufacturing

IV.A. PECVD device including a vessel holder, an internal electrode, and a vessel as a reaction chamber

IV.A. Another embodiment is a PVC apparatus comprising a container support, an inner electrode, an outer electrode and a power supply, configured to perform an exhaust gas test. The vessel seated on the vessel holder defines a plasma reaction chamber, which may optionally be a vacuum chamber. Optionally, a vacuum source, a reactant gas source, a gas supply, or a combination of two or more of them may be supplied. Optionally, in order to define a closed chamber, a gas exhaust port that does not necessarily include a vacuum source is provided to deliver gas into or from the interior of the vessel seated on the port.

IV.A. The PECVD device can be used for atmospheric pressure PPD in cases where 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 is at least one O-ring 106, which can be seated against the cylindrical probe 108 when the probe 108 is inserted through the gas input port 104, or It has a sliding seal provided by two O-rings connected in series or three O-rings connected 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 inserted deeply into a vessel 80 that provides one or more PVD reactants and other process gases.

IV.A. In the embodiment shown in FIG. 2, 　 selectively or 　 　 more generally in the disclosed embodiments, the plasma screen 610 limits the plasma formed in the vessel 80 to a volume above the plasma screen 610 in general. Can be provided to The plasma screen 610 is a conductive, porous material, some examples of which are steel wool, porous sintered metal or ceramic material coated with a conductive material, or a porous plate made of metal (for example, brass) or other conductive material It's a disk. One example is center-to-center holes, which have center holes sized to pass through the gas inlet 108 and which are 0.02 inch (0.5 mm) spaced 0.04 inch (1 mm), the holes being of the surface area of the disk. It is a pair of metal disks, with holes providing 22% open area as part.

IV.A. For example, for embodiments in which the probe 108 functions as a counter electrode, the plasma screen 610 is at or near the opening 82 of the tube, syringe barrel or other vessel 80 to be processed. In the gas inlet 108 can be in close contact. Also, optionally, the plasma screen 610 having a potential common to the gas inlet 108 may be grounded. The plasma screen 610 includes 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, Reduces or eliminates plasma 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 to the vacuum port 96 and the downstream device.

IV.A. FIG. 53 shows, for example, the embodiments of FIGS. 1, 2, 26-27 and 30 and other optional details of a coating station 28 usable. In addition, the coating station 28 may have a main vacuum valve 574 in the vacuum line 576 leading to the pressure sensor 152. A manual bypass valve 578 is provided in the bypass line 580. The exhaust valve 582 controls the flow.

IV.A. The flow rate from the PPD gas source 144 is controlled by the main reactant gas valve 584, which regulates the flow rate through the main reactant supply line 586. One component of the gas source 144 is an organosilicon liquid storage tank 588. The contents of the storage tank 588 are recovered through an organosilicon capillary line 590 provided with an appropriate length to provide a desired flow rate. The flow rate of the organosilicon vapor is controlled by the organosilicon shutoff valve 592. The pressure is, for example, a pressure source 616 such as compressed air connected to the space portion 614 by a pressure line 618 to establish a repeatable organosilicon liquid delivery that is independent of (and fluctuates within) atmospheric pressure. A 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 storage tank 588 is sealed and the capillary connection 620 connects the capillary tube 590 to only pure organic silicon liquid (not the gas compressed from the space portion 614) at the bottom of the storage tank 588. Let it flow through. The organosilicon liquid may be optionally heated to an ambient temperature or higher if it is necessary or desired to form organosilicon vapor by evaporating the organosilicon liquid. Oxygen is provided from an oxygen tank 594 provided with an oxygen shutoff valve 600 through an oxygen supply line 596 controlled by a mass flow controller 598.

IV.A. In the apparatus of Fig. 1, the container coating station 28 deposits SiOx blocking 　 coating 　 or other 　 type 　 coating (90) on the inner surface 88 of the vessel 80, for example, as shown in Fig. 2 It can be a 　EPCVD 　 device that is 　 operated under suitable 　 conditions and explained further below.

IV.A. In particular, referring to 　degree 　 1 　 and 　 2 　, 　 　 processing 　 station (28) during 　 processing 　 in the 　 　 container (80) 　 generating plasma 　 and supplying 　 electric field 　 2 　 6 6 You can include In this 　 embodiment, the 　above probe (1008) is 　electrically 　conductive and 　 is grounded, so in the 　above 　 container (80) 　 provides a 　 counter electrode 　. In addition, in the 　random 　 embodiment, 　the above 　 external 　 electrode (160) is 　 grounded 　 can be 　 and the above 　 probe (108) is 　 directly connected to the 　 power supply 　 (162) 　 　

IV.A. In the embodiment of Fig. 2, the 　external 　 electrode (160) is like the 　 bar and 　 shown in the 　 degree 　 2 　 　 generally 　 cylinder type 　 can 　 or 　 or 　 also 　 2 in 　 or the long 　 2 　 generally like the same number of channels. Each 　shown embodiment has one or more 　 sidewalls, such as 　(164) 　 and 　(166), and 　optionally, has a 　 top (168), and 　0　 all of which are 　 above.

IV.A The electrode 160 shown in FIG. 2 may be shaped like a "U" channel toward the page with its length, and the puck or container holder 50 is activated during the processing/coating process (power supply ) Can be moved through the electrode. Because external and internal electrodes are used, this device can use frequencies between 50 Hz and 1 GHz, applied from power supply 162 to the U channel electrode 160. The probe 108 is grounded to complete the electrical circuit, allowing current to flow through the low pressure gas(s) inside the vessel 80. The current creates a plasma to enable selective treatment and/or coating of the inner surface 88 of the device.

IV.A Also, the electrode of Fig. 2 may be powered by a pulsed power supply. Due to the pulsing, it is possible to deplete the reaction gases, and then to activate the gases and to remove by-products before (re) depletion occurs. 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 duty cycle of 10% may correspond to a power-on time of 10% of a cycle in which power is turned off for 90% of the time. In a specific embodiment, the power may be on for 0.1 second and off for 1 second. The pulsed power system reduces 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 by-products or contaminants). Another result of pulsed systems is the possibility to achieve atomic layer deposition (ALD). In this case, the duty cycle can be adjusted such that the power-on time is achieved so that a single layer of a material is deposited. In this way, a single atomic layer is considered to be deposited in each cycle. This approach can yield very pure and highly structured coatings (although at the temperature required for deposition on the polymer surface, even if the temperature is optionally kept low (<100°C) and the low temperature coatings can be amorphous). have.

Other coating stations employ microwave cavities instead of external electrodes. The applied energy may be, for example, a microwave frequency of 2.45 GHz. However, in the context of this invention, the radio frequency is preferred.

V. 　PECVD methods of making containers

Ｖ．1　PLECVD　for coating 　precursors

The 　PECVD　coating 　precursor of this 　invention is 　organic metal 　precursor 　 is broadly defined. Organosilicon precursors for all purposes herein to encompass the compounds of the organic moiety, e.g., hydrocarbon, amino-carbonyl (aminocarbon) or aryloxy carbonyl (oxycarbon) of the periodic table group III and / or Group IV metal element, having a moiety Is defined. Like the presented 　, 　organic metals 　 defined 　 or 　 other 　 III/IV 　 metals 　 directly 　 bound or 　 selectively 　 oxygen 　 or 　 containing all groups of atoms 　 　 　The elements of 　III of the periodic table are 　boron, 　aluminum, 　gallium, 　indium, 　thalium, 　scandium, yttrium and lanthanum, and aluminum 　 and boron are preferred. The elements of the 　IV group of the periodic table are 　silicon, 　germanium, 　tin, 　lead, 　titanium, 　zirconium, hafnium 　 and thorium, 　silicon 　 and 　 straightforward. In addition, other volatile organic compounds may also be considered. However, organosilicon compounds are preferred for carrying out the present invention.

"Organic silicon precursor" is a 　 specification 　 overall 　 connections 　 having at least one 　 compound 　 extensively 　 defined, 　 organic silicon 　preferred:

or

The structure is 　one 　 oxygen atom 　 and 　 organic 　 carbon 　 atom (organic 　 carbon 　 atom is 　 at least 　 one 　 oxygen 　 4　 atoms are connected to a single 　 oxygen 　 atom) The structure is 　 in one 　-ＮＨ-　 and 　 organic 　 carbon 　 (organic 　 carbon 　 atom is 　 at least 　 one 　 oxygen 　 connected to a single atom 　 　 　 connected to a silicon 　 4 atoms) Optionally, the organosilicon precursor is linear siloxane, monocyclic siloxane, polycyclic siloxane, polysilsesquioxane, linear silazane, monocyclic silazane, polycyclic silazane, polysilsesquiazane, and It is selected from the group consisting of a combination of two or more of these precursors. Also, 　above 　 above 　 two 　 formulas 　 albeit not 　, 　alkyl 　 trimethoxysilane is considered as a 　 precursor. When an oxygen-containing precursor (e.g., siloxane) is used, a representative expected composition obtainable from the PPD under conditions that form a hydrophobic or lubricating coating is a SiwOxCyHz as defined in the Definitions section, while SiwOxCyHz, whereas a barrier coating is used. A representative expected experimental composition obtainable from PECVD under forming conditions is SiOx, where x is from about 1.5 to about 2.9. When a nitrogen-containing precursor (eg, silazane) is used, the expected composition is Siw*Nx*Cy*Hz*. That is, for SiwOxCyHz as defined in the definition clause, oxygen (O) is replaced by 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 in the siloxane to the corresponding indices in its aza counterpart. In a specific aspect of the present invention, Siw*Nx*Cy*Hz* is w*, y*, and z* are defined identically to 　ｗ, ｘ, and 　ｚ　 and 　 in siloxane counterparts, but in the number of hydrogen 　 atoms. Optionally there is a deviation.

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

Each R is independently selected from alkyl, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkane, etc., and n is 1, 2, 3, 4, or More than that, and optionally 2 or more. Some examples of linear siloxanes considered are

ㆍ Hexamethyldisiloxane (HMDSO),

ㆍ Octamethyltrisiloxane,

ㆍ decamethyltetrasiloxane,

ㆍ dodecamethylpentasiloxane,

Or combinations of two or more thereof. Further, similar silazanes in which -NH- is substituted with an oxygen atom in the above structure are useful for making similar coatings. Some examples of linear silazane 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 with the following structural formula:

Here, R is defined as a linear structure and “a” is 3 to about 10 or similar monocyclic silazanes. Some examples of contemplated hetero-substituted and unsubstituted monocyclic siloxanes and silazanes include the following.

ㆍ 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)methyl]cyclotrisiloxane

ㆍ 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane,

ㆍ pentamethylcyclopentasiloxane,

ㆍ pentavinylpentamethylcyclopentasiloxane,

ㆍ hexamethylcyclotrisiloxane,

ㆍ hexaphenylcyclotrisiloxane,

ㆍ Octamethylcyclotetrasiloxane (OMCTS),

ㆍ Octaphenylcyclotetrasiloxane,

ㆍ Decamethylcyclopentasiloxane

ㆍ dodecamethylcyclohexasiloxane,

ㆍ methyl(3,3,3,-trifluoroprople)cyclosiloxane,

ㆍ Octamethylcyclotetrasilazane,

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

ㆍ Octamethylcyclotetrasilazane,

ㆍ decamethylcyclopentasilazane,

Cyclo organosilazane, such as dodecamethylcyclohexasilazane or any combinations of two or more thereof, are also contemplated.

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

Here, Y may be oxygen or nitrogen, E is silicon, and Z is a hydrogen atom or alkyl such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkane, etc. It is a phosphorus organic substituent. When each Y is oxygen, the respective structures going from left to right are silatran, silquasilatran and silproatran. When Y is nitrogen, each of the structures is azasilatran, azasilquasiatran and azasilproatran.

V.C. Another type of polycyclic siloxane precursor starting material is the empirical formula of RSiO1.5 and the polysilsesquioxane of the following structural formula:

Each R is a hydrogen atom or an organic substituent which is, for example, an alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne and the like. Two commercially available materials of this kind are SST-eM01 poly(methylsilsesquioxane), where each R is methyl, and SST-3MH1.1 poly(methyl), where 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. In addition, combinations of two or more of these are also contemplated. Each of Y is oxygen and Z is methyl, with CAS No. 2288-13-3, methylsilatran, methylazasilatran, poly(methylsilsesquioxane), where each R may be optionally methyl (e.g. SST-eM01 poly(methylsilsesquioxane)), poly(methyl-hydridosilsesquioxane) in which 90% of R groups are methyl and 10% are hydrogen atoms (for example, SST-3MH1.1 poly(methyl) -Hydridosilsesquioxane)) or a combination of two or more thereof.

V.C. In addition, similar polysilsesquiazanes in which -NH- is substituted with an oxygen atom in the above structure are useful for making similar coatings. Examples of contemplated polysilsesquiazanes are poly(methylsilsesquiazane) in which each R is methyl and poly(methyl-hydridosilsesquiazane in which 90% of R groups are methyl and 10% are hydrogen atoms. )to be. In addition, combinations of two or more of these are also contemplated.

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

One precursor specifically contemplated for the hydrophobic layer according to the invention is monocyclic siloxane, for example octamethylcyclotetrasiloxane.

One precursor specifically contemplated for the barrier coating according to the invention is a 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 is mainly evaporated by heating it to about 50° C. prior to applying it to a PECVD device.

V.2 General PEVD method

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

(a) providing a gas comprising a precursor as defined herein, optionally a carrier gas, optionally O ₂ and optionally a hydrocarbon; And

(b) forming a coating on the surface of the substrate by plasma-enhanced chemical vapor deposition (PECVD) by generating plasma from the process 　 gas,

In this 　 specification, 　above 　 plasma 　 coating 　 technology is based on 　 plasma 　 reinforcement 　 chemical 　 vapor deposition (PECVD). The 　equipment 　 and 　 method suitable for performing the above 　PLECVD coating 　 is 　EP10162755.2 filed on 　2010　 on May 12th;　 filed on May 12, 2001 　 EP10162760.2;　EP10162756.0, filed on May 12th in 2001;　EP10162758.6, published on May 12th, 2001;　 filed on May 12, 2001 　 EP10162761.0; And in 　 EP10162757.8 filed 　 on May 12, 2001 　. The 　 device 　 and 　 PECVD methods described here 　 are suitable for 　 carrying out the original 　 invention 　 and thus 　 by reference 　 　 here 　 integrated.

An exemplary 　 preferred embodiment of the PECVD technology will be described in the next 　 section.

The process is 　in a container 　 (mＴｏｒｒ　 range-atmospheric pressure 　７60　Ｔｏｒｒ) 　 utilizes silicon 　 containing oxygen and 　 can be combined with 　 vapor.

For example, 　13. 　 is applied to generate 　 plasma between 　 generated 　 in 　 　 　 (radio frequency 　 range) 　 electric field 　 external 　 electrode and 　 internal 　 ground 　 gas In the 　 power and 　 pressure used for 　 coating the container 　, the 　 plasma process, the 　 electrons in the 　 process 　 is the driving force behind the chemical reaction 　 　 meaning 　 electrons 　 collision 　 deionization is also induced by ionization. Particularly, 　plasma is 　 of silicon-containing 　materials (for example, 　hexamethyldisiloxane (HMDSO) or 　octamethylcyclotretrasiloxane (OMCPS) and 　 other 　 vaporization of 　 on the surface of oxidized silicon 　Or, it causes a 　SiwOxCyHz coating 　to induce a chemical reaction. Such a 　 coating is 　 in a 　 thickness 　 in a 　 unit of 20 nanometers 　 or more 　 is a typical 　 embodiment. ＨＭＤＳＯ is composed of 　Si-O-Si　 backbone (ｂａｃｋｂｏｎｅ) with 　 six (6) 　methyl 　 groups attached to 　 silicon 　 atoms. The process breaks the 　Si-C　 bond and 　 reacts with oxygen (on the 　 surface of the tube 　 or 　 syringe) to produce 　 silicon dioxide. Because the coating is 　atomic 　 basis 　 grows 　, it has a 　20 to 30 nanometers 　 thickness 　 compact 　 conformal 　 coating (cｏｎｆｏｒｍａｌ　 cｏａｔｉｎｇ) has excellent characteristics 　 　 　 　Gas, 　moisture, 　 and 　 small 　 organic 　 molecules 　 as 　 physical 　 blocking 　 silicon 　 oxides 　 function, 　 commercial 　 than glass 　 higher 　 has a high purity. OMCTS makes 　coating with 　 lubricity 　 or 　 non-stickiness 　. Their 　 average 　 thickness is 　 generally 　 thickness of SiOx barrier coating, 　 for example 　 average 　 30 to 　 100 nm 　 greater than 　.

The above 　 technique is 　 unique in several 　 points of view.

(A) The 　 process is 　uses a hard 　 container as a vacuum chamber. PECVD uses 　Secondary 　Vacuum 　with 　 parts 　 mounted and 　 coated 　 like the conventional 　. Using the container as a vacuum chamber significantly simplifies the process and equipment and reduces the cycle/processing time and manufacturing cost and funding. This 　approach 　 also makes the scale 　 　 　 to satisfy the demand 　 throughput 　 required 　 required 　 multiple 　 or 　 tubes 　 duplication and 　 　 simplifies the problem

(Ｂ) 　 radio frequency 　 excitation 　 parts 　 small 　 heating furnace 　 ionized 　 gas 　 so that energy is given In general, 　 　 used in 　 　 parts 　 groups 　 in itself 　 water 　 　 gives considerable energy 　 　 microwave 　 excitation 　 energy and 　 different from the 　 radio frequency 　 or no polymer 　Controlled 　heat 　 absorption 　 is important in order to prevent 　 from increasing 　 the temperature 　 due to the 　 access to the 　 plastic 　 glass transition temperature 　 dimensional 　 bonding property 　 loss.

(C) Single layer 　 Gas 　 Blocking 　 Coating-The new 　 technology can 　 directly 　 form a single layer of silicon dioxide 　 on the 　 inner surface of the part. Most 　 other 　 blocking 　 technologies (thin films) require at least 　 two layers 　.

(Ｄ) Barrier property-Lubricity 　 Coating 　 Combination-New 　 technology utilizes a combination of SiOx / SiwOxCyHz coating 　 to provide 　 multiple performance 　 contributions (blocking/lubricating).

In the preferred 　 embodiment 　 plasma 　 deposition 　 technology utilizes 　 simple 　 manufacturing 　 composition. The system is based on the coating and the puck used for the movement of the tubes outside the ophthalmic and the outside of the station and the syringes. The device-puck interface (degree 　6) is 　once 　 coating/characteristics 　 conditions are established in 　 pilot 　 stage 　 go to mass production 　 step 　 simply 　 the same 　 process is increased 　 because the same 　 process is not possible because 　 is not necessary 　 　The puck is made of a polymer material (eg Delrin®) to provide an electrically insulated floor. The container (for example, the same 　 tube as in Fig. 6) is 　O-ring (installed in the puck 　 group 　 itself) 　 sealing 　 having the largest 　 opening 　 is installed in the puck 　 between the parts and the puck provided 　Then, the atmosphere (some 　 water vapor 　 mainly 　 nitrogen and 　 oxygen) is removed (depressurized), and the process 　 gas is injected 　. The puck is 　Ｏ-ring 　 added to the seal, and some puck has some oxidized gas and reacted 　Provides a vacuum 　 pump and 　 connected 　 means, 　 gas 　 inlet 　 precisely matched 　 　 and 　 puck and 　 gas 　 inlet 　 provides a vacuum 　

For SiO ₂ deposition, HMDSO and oxygen gas enter the vessel through a grounded gas inlet that extends to the component. At this time, the puck and container move to the electrode area. The electrode is made of a conductive material (eg copper) and provides a tunnel through which the component passes. The electrodes are supported independently without making physical contact with the container or puck. The RF impedance matching network and power supply are directly connected to the electrodes. The power supply provides energy (at 133.6MHW) to the impedance matched network. The RF matching network acts to match the impedance output of the power supply to the complex (capacitive and inductive) impedance of the ionized gas. The matching network delivers maximum power transfer to the ionized gas ensuring the deposition of silicon dioxide.

Once the 　 container is 　 coated (because 　 puck 　 moves 　 through the stopped 　 electrode 　 channel 　 　 　), the gas 　 stops, and the atmosphere (or 　 pure nitrogen) enters the atmosphere (or 　 pure nitrogen) 　 swells/container At this time, the container will be removed from the puck and moved to the next process station.

The above 　 describes 　 clearly 　 means of coating 　 containers 　 having only one 　 opening 　. The syringes require an additional step before and after being mounted on the puck. The syringes have an opening at the end (one to connect to the needle and one to attach the plunger to the plunger), so the end of the needle must be sealed and must be sealed before coating. The above 　 process is 　 reaction 　 gas enters 　 plastic 　 part 　 inside 　, electric current flows 　 inside 　 of the 　 gas 　 flows 　, and 　 part 　 generates 　 plasma 　 inside 　Plasma (　 or 　OMCTS　 and 　ionized 　 composition of oxygen 　 gas) is to induce 　deposition and 　chemical reaction of the 　plasma coating.

In this method, the coating characteristic is advantageously set by one or more of the following conditions: the plasma characteristic, the pressure applied to the plasma, the power applied to generate the plasma, the presence and relative amount of O ₂ in the gaseous reactant, the plasma volume and Organosilicon precursor. Optionally, the coating properties are set by the presence and relative amount of O ₂ in the gaseous reactant and/or the power applied to generate the plasma.

In all embodiments of the present invention, the plasma is a non-hollow-cathode plasma in an optional aspect when the SiOx? coating is ready?.

In another preferred aspect, the plasma is generated at reduced pressure (compared to ambient or atmospheric pressure). Optionally, the decompression is less than 300 mTorr, alternatively less than 200 mTorr, more alternatively less than 100 mTorr.

Optionally, the PECVD is performed by applying an electric current to a gaseous reactant containing a precursor together with electrodes powered at a microwave or radio frequency and optionally at a radio frequency. Further, the preferred radio frequency for carrying out the embodiments of the present invention will be referred to as "RF frequency". A typical radio frequency range for carrying out the present invention is 10 kHz to less than 300 MHz, alternatively 1 to 50 MHz, and more alternatively 10 to 15 MHz. A frequency of 13.56 MHz is most preferred, which is a government-approved frequency for performing PECVD work.

There are several advantages of using an RF power source for a microwave source: Because the RF operates a lower power source, the heating of the substrate/vessel is lower. Since the focus of the present invention is to provide a plasma coating on plastic substrates, a lower processing temperature is desirable to prevent melting/distortion of the substrate. In order to prevent the substrate from overheating when using microwave PECVD, Pycrowave PEVD pulses power and is applied in short bursts. Power pulsing increases the cycle time for coating, which is not desirable in the present invention. In addition, the higher the microwave frequency is, the more volatile substances such as residual moisture, oligomers, and other substances may be offgassed from the plastic substrate. This degassing can interfere with the PPD coating. This will change the content and composition of the volatile compound in the coated substrate, and thus may interfere with the degassing measurement of the present invention. A major concern in using microwaves for PECVD is the peeling of the coating from the substrate. Peeling occurs because microwaves change the surface of the substrate prior to depositing the coating layer. In order to reduce the likelihood of peeling occurring, interfacial coating layers for microwave PVD have been developed in order to achieve good bonding between the coating and the substrate. In the RF PECVD, an interfacial coating layer without risk of delamination is not required. Finally, the lubricity layer and the hydrophobic layer according to the invention are advantageously applied using lower power. The RF power supply operates from a lower power supply and provides better control over the PECVD process than the microwave power supply. Nevertheless, although not desirable, microwave power sources can be used under appropriate process conditions.

In addition, for all the PVD methods described herein, there is a specific correlation between the power source used (watts) to generate the plasma and the volume of the lumen in which the plasma is generated. Typically, the lumen is the lumen of a 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 the composition of the gaseous reactant, e.g., the ratio of precursor to O ₂ and all other parameters of the PECVD coating method except the power source, are set, they are typically used if the shape of the vessel is maintained and only its volume changes. 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 should be applied to achieve the same or similar coating in containers of the same shape but different sizes. The effect of the vessel shape on the applied power source is shown as the results of the examples for tubes compared to the examples for syringe barrels.

For any coating of the present invention, the plasma is generated using electrodes powered with sufficient power to form the coating on the substrate surface. Lubricity 　 Coating 　 or 　 Hydrophobic 　 About coating, 　 This 　 In the 　 Example of the invention 　 Follow the method

Plasma is optionally (i) 0.1 to 25 W, alternatively 1 to 22 W, selectively 　 1 to 　 10 W, more selectively 　 1 to 5 W, alternatively 　 2 　 to 　 4 Ｗ, 　 for example 　 3 W, optionally　3 to 　17W, more 　optionally 　5 to 14 W, for example 　6　 or 　7.5W, 　optionally 7 to 11 W, for example, 8 W of power supplied electrodes are used and/or (ii ) The ratio of power to plasma volume is 10 W/ml, alternatively 6 W/ml to 0.1 W/ml, alternatively 5 W/ml to 0.1 W/ml, alternatively 4 W/ml to 0.1 W/ml , Alternatively from 3 W/ml to 0.2 W/ml, alternatively from 　2 W/ml to 0.2 W/ml 　 using electrodes smaller than 　.

Low 　 power 　 level is 　 lubricity 　 coating 　 preparation 　 the most 　 advantage 　 (for example, 　2 to 3. 5Ｗ 　 power 　 level and 　 given power in the example)

For blocking 　 coating 　 or 　 SiOx, the plasma is

(i) 8 to 500 W, alternatively 20 to 400 W, alternatively 35 to 350 W, more selectively 44 to 300 W, alternatively generated using electrodes supplied with power of 44 to 70 W Become/or;

(ii) The ratio of the power to the plasma volume is 5 W/ml or less, optionally 6 W/ml to 150 W/ml, optionally 7 W/ml to 100 W/ml, optionally 7 W/ml to 20 W/ml.

In addition, the shape of the vessel can influence the selection of the gas inlet used for the PPD coating. In a particular aspect, the syringe may be coated with an open tube inlet, and the tube may be coated with a gas inlet having small apertures extending into the tube.

In addition, the power (watt) 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 with a volume of about 3 ml, a power of less than 30 W leads to a coating that is predominantly a lubricity coating, while a power source above 30 W is an overwhelming barrier coating. It will lead to coating (see examples). This is also seen in the 　ＥＰ　2　251　4555　A2, and the 　clear 　 reference 　here 　 was made.

Another parameter that determines coatability is the ratio of O ₂ (or other oxidizing agent) to precursor (eg, organosilicon precursor) in the gaseous reactant used to create the plasma. Typically, when the O ₂ ratio in the gaseous reactant increases, the barrier property of the coating increases, and when the O ₂ ratio decreases, the lubricity and hydrophobicity of the coating increase.

If a lubricity layer is desired, O ₂ is optionally 0:1 to 5:1, alternatively 0:1 to 1:1, alternatively 0:1 to 0.5:1, or More selectively from 0:1 to 0.1:1. In relation to the organosilicon precursor, some O ₂ is preferably present in a range of 0.1:1 to 0.5:1, more selectively 0.05:1 to 0.4:1, and particularly 0.1:1 to 0.2:1. In relation to the organosilicon precursor, the presence of about 5% to 35% (v/v in sccm), especially about 10% to 20%, and the presence of O ₂ in a volume of the ratio as given in the example, is particularly useful for obtaining a lubricity coating. proper.

The same method applies for the hydrophobic layer. Alternatively, if a barrier or SiOx coating is desired, O ₂ is optionally a volume:volume ratio of 1:1 to 100:1, alternatively 5:1 to 30:1 for the gaseous reactant for the silicon-containing precursor. , Optionally in a ratio of 10:1 to 20:1, more optionally 15:1.

V.A. PPD for applying SiOx barrier coating using plasma substantially free of hollow cathode plasma

V.A. A specific embodiment is a method of applying a barrier coating of SiOx as defined herein (unless specified otherwise) as a coating comprising silicon, oxygen and optionally other elements, in which silicon atoms are The ratio of oxygen to x is from about 1.5 to about 2.9, or from about 1.5 to about 2.6, or from about 2, the barrier coating application method. These other definitions of x apply to the use of the term SiOx 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 several steps.

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

V.A. Plasma is formed in the reaction mixture substantially free of hollow cathode plasma. The vessel wall is contacted with the reaction mixture and a coating of SiOx is deposited on at least a portion of the vessel wall.

V.A. In certain embodiments, the creation of a uniform plasma throughout the portion of the vessel being coated is considered, as it can be seen to produce a SiOx coating that provides better barrier to oxygen in certain instances. A uniform plasma is a regular plasma that does not contain a substantial amount of hollow cathode plasma (represented by a localized region of higher intensity that has a higher emission intensity than a regular plasma and blocks 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 at the same cathode potential for a common cathode. If spacing occurs (depending on the pressure and gas type) and the space charge sheaths overlap, electrons fluctuate between the reflected potentials of the opposite wall sheaths as the electrons are accelerated by a potential gradient across the sheath region. Start hitting, and the majority collide. The electrons are trapped in space charge sheath overlap leading to very high ionization and high ion density plasmas. This phenomenon is described as the hollow cathode effect. One of ordinary skill in the art can change processing conditions such as power level and supply rate or pressure of gases to form a plasma uniform throughout or to form a plasma including a hollow cathode plasma of varying degrees.

V.A. Plasma is 　generally 　 using 　 RF 　 energy 　 for the reasons mentioned above. In the other 　 method, but the 　 somewhat 　 general method, microwave energy can be used to generate the plasma in the PECVD process. However, the processing conditions will be different as the microwave energy applied to the thermoplastic vessel excites (vibrates) the water molecules. Since there is a small amount of water in all plastic materials, microwaves will heat the plastic. As the plastic heats up, the large motive force created by the vacuum inside the device against the atmospheric pressure outside the device freely collects or easily desorbs materials on the interior surface 88, where they become volatile or easily bond to the surface. will be. The readily bonded materials will then form an interface that can prevent subsequent coatings (deposited from plasma) from adhering to the plastic interior surface 88 of the device.

V.A. As one way to prevent this anti-coating effect from occurring, the coating can be deposited at a very low power source (5 to 20 watts at 2.45 GHz in this example) creating a cap on 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 to 2 sccm (“standard square centimeters per minute”) HMDSO and 20 sccm oxygen with a process power of 5 to 20 watts for approximately 2 to 10 seconds. Then, the gases can be adjusted to the flow rates in the example above and the power level is increased to 20 to 50 W, where x is about 1.5 to about 2.9, or about 1.5 to about 2.6, or about 2 SiOx coating. Can be deposited. Note that in certain embodiments the capping layer may provide little or no functionality, except to prevent materials from moving to the vessel interior surface 88 during the deposition of the higher power SiOx coating. . Also note that, since lower frequencies do not excite (vibrate) molecular species, the movement of readily desorbed materials in the device walls is typically not a problem at lower frequencies.

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

V.A. In addition, the above-described coating preventing effect can be solved by selecting or treating a resin in which the containers 80 are molded in order to minimize the moisture content of the resin.

V.B. PECVD coating a limited opening in a container (syringe capillary)

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

V.B. The generally tubular vessel 250 to be treated has an outer surface 298, an inner or inner surface 254 defining a lumen 300, a larger opening 302 having an inner diameter, and an inner surface 292. And a restricted 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 that is optionally the only opening, although in other embodiments may be provided with a second opening that is selectively closed during processing. The processing vessel opening 306 is connected to the limited opening 294 of the vessel 250 to be processed, and between the lumen 300 of the vessel 250 to be processed and the processing vessel lumen through the restricted opening 294. Communication is established.

V.B. At least partial vacuum is drawn within the lumen 300 of the vessel 250 to be processed and the lumen 304 of the processing vessel 296. The PECVD reactant is transferred from the gas source 144 through the first opening 302, through the lumen 300 of the container 250 to be processed thereafter, and then through the restricted opening 294. 296) of the lumen 304.

V.B. In another embodiment, a plurality of distal openings may be provided adjacent to the distal end 314 and communicated with the inner passage 310, the PECVD reactant is an inner passage 310, a proximal end 312, and a distal end. A generally tubular inner electrode 308 having 314 and a distal opening 316 may be provided to be introduced through the larger opening 302 of the vessel 250. The distal end of the electrode 308 may be positioned adjacent to or within the larger opening 302 of the vessel 250 being processed. The reactant gas may be supplied into the lumen 300 of the vessel 250 to be silver treated through the distal opening 316 of the electrode 308. The reactant will then flow into the lumen 304 through the limited opening 294 to the extent that the PPD reactant is provided at a pressure higher than the vacuum initially achieved prior to the introduction of the PPD reactant.

V.B. Plasma 318 is created in the vicinity of the restricted opening 294 under conditions effective to deposit a coating of the PPD reaction product on the inner surface 292 of the restricted opening 294. In the embodiment shown in Fig. 26, the plasma is generated by providing RF energy to the U-shaped external electrode 160 and grounding the internal electrode 308 in general. In addition, the supply and ground connections to the electrodes may also be changed, although the vessel 250 and thus the internal electrode 308 processed due to this reversal are also processed through the U-shaped external 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 while at least partially being processed may include the hollow cathode plasma generated inside the limited opening 294 and/or the processing vessel lumen 304. The creation of the hollow cathode plasma 318 may contribute to the ability to successfully apply a barrier coating in the limited opening 294, even though the invention is limited by the accuracy or applicability of this theory of operation. Thus, in one contemplated mode of operation, the treatment is hollow under conditions that create a uniform plasma throughout the vessel 250 and the gas inlet and, for example, partially adjacent to the restricted opening 294. It can be carried out under conditions of generating a cathode plasma.

V.B. The treatment is preferably operated under conditions that extend substantially throughout the syringe lumen 300 and the restricted opening 294, as described herein and shown in the figures. Further, the plasma 318 extends substantially throughout the syringe lumen 300, the restricted opening 294 and the lumen 304 of the processing vessel 296. This assumes that a uniform coating of the interior 254 of the container 250 is desired. In other embodiments, a 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, and optionally the syringe lumen 300, the restricted opening 294, and the It is generally desirable to have a substantially uniform color 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 optionally throughout the lumen 304 of the processing vessel 296.

V.B. The order of steps in this method is not considered critical.

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 provide a lumen of the processing vessel 296. It has a second fitting 334 fitted to establish communication between 304 and the lumen 300 of the vessel 250 being processed.

V.B. In the examples of Figs. 26 and 27, the first fitting and the second fitting are 　respectively 　 above 　 restricted 　 openings (29 4) and 　 tops 　 treatments 　 containers 　 openings 　 　 defining 　 structure 　 integrated with 　 　 3 male locks Fitting (34) is done. As one of the above fittings, the male Luer lock fitting 332 in this case comprises a locking ring 336 having a generally annular first abutment 338 while axially abutting the threaded inner surface, the remaining Another fitting 334 includes a generally annular second abutment 340, axially facing the first abutment 338 when the fittings 332 and 334 are engaged.

V.B. In the illustrated embodiment, for example, the O-ring 342 may be positioned between the first and second fittings 332 and 334. For example, an annular seal may be engaged between the first and second joints 338 and 340. In addition, the female luer fitting 334 meshes with the threaded inner surface of the locking ring 336 to fix the O-ring 342 between the first and second fittings 332 and 334 Including 344. Optionally, the communication formed between the lumen 300 of the vessel 250 to be processed and the lumen 304 of the processing vessel 296 through the restricted opening 294 is at least substantially leak-proof.

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 stainless steel, for example. This structural material forming or adjacent to the restricted opening 294 may contribute to the formation of a plasma in the restricted opening 294.

V.B. The desired volume of the lumen 304 of the processing vessel 296 is a small volume that will not divert a significant amount of the reactant flow rate from the product surfaces desired to be coated (the pressure difference across the restricted opening 294). A trade-off between large volumes that will support the overall reactant gas flow rate through the restricted opening 294 prior to filling the lumen 304 sufficiently to reduce the flow rate to an undesirable value. It is thought to be (trade-off). In one embodiment, the considered volume of the lumen 304 is less than three times the volume of the lumen 300 of the vessel 250 being processed or 2 times the volume of the lumen 300 of the vessel 250 being processed. Less than twice the volume of the lumen 300 of the vessel 250 being processed or less than 50% of the volume of the lumen 300 of the vessel 250 being processed or the lumen 300 of the vessel 250 being processed Is less than 25% of the volume. In addition, other effective relationships of the volumes of the respective lumens are also considered.

V.B. The present inventors 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, so that the vessel ( It was found that it does not penetrate to the lumen 300 of 250). For example, although in certain embodiments the distal opening 316 may be located adjacent to the restricted opening 294, in other embodiments the distal opening 316 supplies reactant gas. It may be located less than 7/8, alternatively less than 3/4, alternatively less than half of the distance from the larger opening 302 of the vessel being processed during to the restricted opening 294. 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 processed while supplying the reactant gas to the restricted opening 294. , Less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, or less than 1%.

V.B. In addition, the distal end of the electrode 308 communicates with the interior of the container 250 and is located slightly inside or outside the larger opening 302 of the container 250 that is processed while supplying the reactant gas. Or can be positioned at the same height. The positioning of the distal site 316 with respect to the vessel 250 being processed can be optimized for specific dimensions and other conditions of treatment by testing it at several locations. One particular location of the electrode 308 considered for processing the syringe barrels 250 is that it penetrates about a quarter inch (about 6 mm) into the vessel lumen 300 over the larger opening 302. It is a position with the distal end 314.

V.B. The inventors are contemplating to place at least the distal end 314 of the electrode 308 within the vessel 250 to function properly as an electrode, although not a requirement. Surprisingly, the plasma 318 generated in the vessel 250 may be more uniform, and unlike previously employed, the electrode 308 penetrates less into the lumen 300, and the limited opening 294 It may extend through the processing vessel lumen 304. Using other arrangements, such as handling a closed end container, the distal end 314 of the electrode 308 is usually positioned 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 is at or beyond the restricted opening 294, e.g., the processing vessel lumen. 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, the composite inner electrode and gas feeder tube 398 is located at distal gas supply openings such as 400 and optionally the restricted opening 294, optionally located near the larger opening 302. It may have an extension electrode 402 extending the distal portion of the distal gas supply openings 400, extending to an adjacent distal end and optionally further extending to the processing vessel 324. It is contemplated that this structure facilitates the formation of a plasma within the inner surface 292 adjacent the confined opening 294.

V.B. In another contemplated embodiment, as shown in FIG. 26, the internal electrode 308 moves during processing, for example, initially extending into the processing vessel lumen 304, and then closer as the process proceeds. It can be withdrawn gradually. This means is a particularly considered means if the vessel 250 is of a longer length under selected processing conditions and facilitates a more uniform treatment of the inner surface 254 due to movement of the inner electrode. Using these means, processing conditions such as a gas supply rate, a vacuum discharge rate, electric energy applied to the external electrode 160, a rate of drawing out the internal electrode 308, or other factors are determined by the process. It can be changed as it fits into different parts of the container being processed.

V.B. As in the other processes described in this specification, the larger opening of the generally tubular vessel 250 to be processed connects the larger opening 302 of the vessel 250 to be processed to the port of the vessel holder 320 ( By seating on the 322), it can be easily positioned on the container holder 320. Thereafter, the internal electrode 308 may be positioned within the vessel 250 seated on the vessel holder 320 before drawing at least a partial vacuum within the lumen 300 of the vessel 250 to be processed. have.

V.C. How to apply a lubricating layer

V.C. Another 　 embodiment is a 　 application method of 　 derived 　 from organic silicon 　 precursors. This 　 method and 　 lubricating 　 coating 　 and 　 coated 　 products were also described in 　201 year 　 May 　11 　 filed 　 PCT / US11 / 359９７. The same 　 methods, 　coated 　 and 　 coated 　 product 　 and 　 to indicate the characteristics 　 above 　 for the application 　 clear reference 　 here 　 was made.

＂Lubricated 　 layer ＂　 or 　 iwa 　 similar terms 　 is defined as 　coating 　for 　 uncoated 　 surface 　 coated 　 surface If the coated object to a syringe if any other items which typically include a plunger or movable parts (or the syringe components, for example, a syringe barrel), or the coated surface of the slide contact, the two main aspects is the friction resistance of -Have breakout 　 force 　 and 　 plunger 　 active force.

A plunger sliding force test is a special test of the sliding coefficient of friction of the plunger in the syringe, which is the normal force associated with a general sliding friction coefficient measured in which the plunger or other sliding elements and the tube or the tube sliding over a flat surface It is to explain the fact that the 　 　 between different 　 containers 　 is 　 standardized 　 processed 　. Mainly, the 　measured 　sliding 　 friction 　 coefficient and the associated 　 parallel force are comparable to the measured 　 plunger 　 sliding 　 force 　 as described in the 　 specification 　. Plunger 　sliding 　 force 　For example, 　ISO　７８８6-1: ９９3　 in the test 　 can be measured 　 like the provided 　 bar and 　.

In addition, the 　above 　 plunger s sliding 　 force 　 test 　 device 　 and 　 procedures 　 　 suitable 　 variations 　 by 　 different 　 types 　 friction 　 resistance, 　 to fit the tube to fit the 　 　 to fit the test tube In one embodiment, the 　 above 　 plunger can be replaced 　 by 　 closure 　, and 　 removing or inserting the above 　 closure 　 extraction force (the number of sliding plungers to be measured) corresponds to the number of plungers to be measured. 　 　 　

In addition, instead of 　above 　 plunger 　sliding 　 force 　, 　 above 　 breakout 　 force 　 can be measured 　. Breakout 　 force 　 syringe 　 barrel 　 　 moving 　 stopped 　 plunger 　 start 　 required 　 force 　 or 　 settled 　 stop 　 clearer 　 desorption 　 required 　 necessary to start 　The above 　 breakout 　 is measured by applying 　 force to the 　 starting 　 plunger at the 　 0 　 or 　 low 　 value, and increases 　 until the 　 reminder 　 plunger starts 　. The 　 breakout 　 force tends to increase with storage of the syringe after the prefilled syringe plunger pushes away the intervening lubricant or is attached to the barrel due to decomposition of the lubricant between the plunger and the barrel. The breakout force is overcome to spur the plunger and is required to overcome “sticktion,” the term used in the industry for the attachment between the plunger and the barrel required to cause the plunger to start moving. It's strength.

V.C. Optionally, the insertion or removal of a stopper or a sliding configuration, such as a stopper in a piston or sample tube in a syringe, due to some equipment coating all or part of the container with a lubricating layer, such as on surfaces that slide in contact with other parts It facilitates the passage of elements. The container may be made of glass or polyester, for example a polymeric material such as polyethylene terephthalate (PET), a cyclic olefin copolymer (COC), an olefin such as polypropylene, or other materials. COC is particularly suitable for 　syringe 　 and 　syringe 　barrel 　. Application of a lubricating layer by PECVD avoids or reduces the need to coat the vessel walls or closures with other lubricants that are typically applied in much larger amounts than those deposited by spraying, dipping, or applying organosilicon or the PECVD process. I can.

V.C. In any one of the above embodiments V.C., the plasma may be formed near the substrate.

In any one of the embodiments V.C., the precursor may optionally be provided in the substantially absence of nitrogen.

V.C. In any of the embodiments V.C., the precursor may optionally be provided at less than 1 Torr absolute pressure.

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

V.C. In any one of the embodiments VC, the coating is optionally 1 to 5000 nm, or 10 to 1000 nm or 10 to 500 nm or 10 to 200 nm or 　 20 to 10 0 nm or 　 30 　 to 　 100 nm, or 30 nm or 　 to the substrate. It can be applied in a thickness of 50 nm　. The typical 　 thickness is 　30 to 1000 nm or 20 to 100 nm, and the very common 　 thickness is 80 to 150 nm　. These 　 ranges are 　 representing the average thickness 　, and there is a slight 　 roughness 　 　 lubrication 　 properties of the coating 　 reinforcement 　. Therefore, it is advantageous that 　 these 　 thickness 　 coating 　 overall 　 not uniform 　. However, 　 uniform 　 thickness 　 lubricity 　 coating is also considered 　.

At a single 　 measurement point, 　Absolute 　 thickness of the coating, 　Average 　From the thickness 　preferably 　+/- 50%, 　more 　preferably 　+/- 25% and 　more 　more 　+/with the maximum deviation of 15% 　There are 　 higher 　 or 　 lower than the range. However, 　 usually varies 　 in this 　 detailed 　 explanation 　 average 　 about thickness 　 given 　 thickness 　 range 　.

The thickness of this and other coatings can be measured, for example, by transmission electron microscopy (TEM).

V.C. The TEM can be performed, for example, as follows. Samples can be prepared in two ways to cut a focused ion beam (FIB) cross section. Samples may be first coated with a carbon thin film (50 to 100 nm thick) and then coated with a platinum sputtering layer (50 to 100 nm thick) using a K575X Emitech coating system, or the samples may be protected sputtered It can be directly coated with a Pt layer. The coated samples can be placed in the FEI FIB200 FIB system. The platinum 　 additional film can be deposited 　ＦIＢ　by injecting 　organometallic gas 　 during 　30ｋＶ　gallium 　 ion beam 　for the area of interest. The area of interest for each 　 sample can be selected as the 　 position below 　 1/2 　 of the syringe barrel 　 length. Thin sections measuring 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 in width can be thinned with electron transparency using the gallium ion beam of the FEI FIB.

V.C. Cross-sectional image analysis of the prepared samples may 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 STEM imaging, a grid with thin foils can be transferred to a Hitachi HD2300 dedicated STEM. The scanned and transmitted electron images may be obtained by appropriately magnifying in the atomic number contrast mode (ZC) and the transmitted electron mode (TE). The following tool settings are available.

V.C. For TEM analysis, sample grids can be transferred to a Hitachi HF2000 transmission electron microscope. The transmitted electronic images can be appropriately enlarged and obtained. The appropriate tool settings used during image acquisition may be those given below.

V.C. In any one of the embodiments VC, the substrate is a glass or polymer, e.g., 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 contain a combination of two or more.

V.C. In any one of the embodiments VC, PECVD is optionally an RF frequency as defined above, for example 10 kHz to less than 300 MHz, optionally 1 to 50 MHz, more selectively 10 to 15 MHz and Optionally, it may be performed by applying electric power to the gaseous reactant including the precursor using electrodes receiving power at a frequency of 13.56 MHz.

V.C. In any one of the embodiments V.C, the plasma may be generated by applying electric power to the gaseous reactant containing the precursor using electrodes supplied with sufficient power to form the lubricating layer. Plasma is selectively 0.1 to 25 W, selectively 1 to 22 W, selectively 　 1 to 　 10 W, more selectively 　 1 to 5 W, optionally 　 1 　 to 　 4 Ｗ, for example 　 1 to 　 3 W, selectively 　 3 to ７W, 　More 　Selectively 　5 to 14 W, for example 　6　 or 　７. 5W, 　Alternatively using electrodes supplied with 7 to 11 W, for example 8 W of electric power 　reacting 　 containing a precursor 　 gas It is generated by adding 　 energy 　. The ratio of power to plasma volume is 10 W/ml, optionally 6 W/ml to 0.1 W/ml, optionally 4 W/ml to 0.1 W/ml, optionally 3 W/ml to 0.2 W/ml, optionally less than 　2 W/ml to 0.2 W/ml 　. Low 　 power 　 level is 　 lubricity 　 coating 　 preparation 　 the most 　 advantage 　 (for example, 　2 to 3. 5Ｗ 　 power 　 level and 　 given power in the example) These power levels are suitable for applying lubricating coatings to syringes and sample tubes and vessels of similar shape with a void volume of 1 to 3 mL in which the PPD plasma is generated. It is believed that for larger or smaller objects the applied power will increase or decrease as the process scales with respect to the size of the substrate.

V.C. Examples 　 one 　 　 　 in C, 　 treatment 　 gas 　 one 　 preferred 　 combination is 　 　 gas as 　 oxygen and 　 carrier 　 gas 　 M as a carrier 　 gas 　 　 existed in other cyclones 〴 methyl 　 〴 do. Not tied to the 　accuracy of these 　theories 　, the inventors believe that 　 these 　 specific 　 combinations are effective 　 for the following 　 reasons.

V.C. It is believed that the OMCTS　 or 　other 　 cyclic 　 siloxane 　 molecules 　 offers 　 some advantages 　 to other 　 siloxanes 　 materials. Firstly, such a cyclic structure is such that the less dense coating to allow the molecules or selective ionization (as compared to the coating made from HMDSO) directly controlled through the application of the final structure of the coating with the chemical composition of the plasma power Be 　 be 　 　. Other 　organic silicon 　 molecules are 　 already 　 ionized (crushed), making 　to maintain the 　 original structure of the molecule 　 more difficult.

V.C. Because 　addition of argon 　gas 　 lubrication 　 improves performance 　 (see below 　 operation example 　), under the presence of argon 　 the 　 of molecules 　 additional 　 ionization 　 lubrication 　 is believed to contribute 　 to provide The 　Si-O-Si bond of the molecule has the 　high 　energy 　 followed by the 　Si-C　 bond, and the 　C-H　 bond is the 　the weakest. It appears that when a part of the C-H bond is broken, the lubricity is obtained. This allows 　connections (cross coupling) of 　 structures during 　growing 　. It is understood that the 　 addition of oxygen (with argon and 　) would 　 enhance these 　 processes. Small 　 amount 　 oxygen can 　 provide 　 C-O bonds 　 other 　 molecules 　 bind. The combination of adding oxygen and breaking the C-H bond at low pressure and power induces a solid chain and chemical structure while providing lubricity.

In the 　 specific 　 examples of this 　 invention, 　 lubricity is influenced by the 　 from the 　EPCV process 　 using the 　 precursor and 　 conditions 　 described in the original 　 and also the 　 lubricity 　 the roughness of the coating. Surprisingly, through the scanning electron microscope (SEM) and atomic force microscopy (AFM) in the context of the present invention, tough, continuous page that OMCTS plasma coating is smooth and provides a lower plunger force than continuous OMCTS plasma coating (May 2011 On the 11th day, in the filed 　PCT/US11/35697, the same 　Fi, 　Fm, similar to the 　 described 　 was found. This was explained by the example of the 　ＰＴ／ＵS１１／360９７ 　Ｏ　 to 　Ｖ filed in 　201 year 　 May 　11 day 　.

Without being bound by theory, the inventors estimate that these special effects can be partly based on all of the mechanical effects of the following mechanical effects or are partially based on it: 　 　 　 　 　

(A), contacting the lower surface of the lubricating coating and the plunger (e.g., a solid plunger surface of the circular contact only the peaks of the rough coat), on the plunger moves the initial and / or in total, the whole lower contact and hence It causes friction. (b) Plunger 　 in motion, 　 plunger is 　 first 　 uneven, 　 coarse 　 coating 　 uncoated 　 valleys (ｖａｌｌｅｙｓ) 　 spreads 　 smoothly.

The roughness of the lubricating coating is increased by reducing the power (watts) applying the plasma and by the presence of O ₂ in the above amount. The roughness can be expressed as “RMS roughness” or “RMS” determined by AFM. The RMS is the standard deviation of the difference between the highest point and the lowest point in an AFM image (the deviation is expressed as “Ｚ”). It is calculated according to the following equation.

R _q = {Σ(Z ₁ -Z _avg ) ² /N} ^-2

Where Z _avg is the average Z value in the image; Z ₁ is the current value of Z; N is the number of points in the image.

In the specific 　 embodiment, the 　RMS　 range is 　usually 　７　 to 　20 nm, and preferably 　12 to 　20 nm. However, the 　the 　 lower 　RTMS could still 　induce 　 to satisfy 　 lubrication characteristics 　.

V.C. Optionally, one product contemplated as a product may be a syringe having a barrel processed by the method of V.C., which is any one or more of the examples. The above 　syringe is 　in accordance with the invention 　 only 　 lubricity 　 coating only 　 or 　 or 　 with lubricity 　 one 　 or more 　 other 　 coating, 　 examples 　 add 　 top 　 coating 　 with lubricating properties 　 　 or below 　

V.D. Liquid-coating coatings

V.D. Other examples of blocking or other types of blocking or other types of suitable coatings that may be used in conjunction with PECVD coated coatings or other PEVD treatments as disclosed herein are, for example, one or more intervening PDP coatings, either directly or as described in this specification. SiOx, in the definitions section 　as specified 　bars 　　characterized 　with a lubricity 　layer 　or 　groups 　 in the case, 　liquid blocking, lubricant, surface energy may be applied to the inner surface of a coating (90) of other types of coating (90) .

V.D. Also, optionally suitable liquid barrier or other types of coatings 90, for example, applying a liquid monomer or other polymerizable or curable material to the inner surface of the vessel 80, curing the liquid monomer, It can be polymerized or crosslinked to form a solid polymer and applied. Further, suitable liquid barrier or other types of coatings 90 may be provided by applying a solvent-dispersed polymer to the surface 88 and removing the solvent.

V.D. Either of the above methods may include forming a coating 90 on the interior 88 of the vessel 80 through the vessel port 92 at a processing station or apparatus 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 container 80 and curing it to make the contents of the container 80 It is a step of forming a film that is physically separated from (88). The prior art describes the polymer coating technique as suitable for coating plastic blood collection tubes. For example, acrylic and polyvinylidene chloride (PVdC) coating materials and coating methods described in U.S. Patent Nos. 6,156,566, which are incorporated herein by reference, may be selectively used.

V.D. In addition, any of the above methods may include forming a coating on the outer wall of the container 80. Optionally, the coating may be a barrier coating, optionally an oxygen barrier coating, or optionally a moisture barrier coating. An 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 a water-based coating. Optionally, the coating may be applied by immersing the container therein and spraying it onto the container or by other means. Also contemplated are containers having the outer barrier coating described above.

VI. Container inspection

VI. In the following, the 　 container 　 inspection by the 　 gas 　 removal 　 method of the present invention will be described in detail 　 than 　. However, 　 methods 　 containers, 　 examples 　 plastic 　 film 　 or 　 three-dimensional 　 objects other than 　 objects 　 other 　 products 　 also 　 suitable 　. These 　 other 　 products 　 are also included in the 　 scope of this 　 invention.

VI. One station or device shown in Figure 1 is to measure the air pressure loss or mass flow rate or volume flow rate through the vessel wall, or to inspect the inner surface of the vessel 80 for defects, such as degassing the vessel wall. It is a processing station or device 30 that can be configured. The device 30 is applied to the device 30 because in the embodiment shown, a barrier or other type of coating is applied by the station or device 28 prior to reaching the station or device 30. It can operate similarly to apparatus 26, except that the vessel may be required to pass inspection due to the better performance provided by it (less leakage or penetration occurs under given process conditions). In one embodiment, inspection of the coated vessel 80 may be compared to 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 as measured at two different stations or by two different devices is a bar code, different marks or radio frequency identification (RFID) device for each of the vessel holders 38 to 68. Or it can be confirmed by identifying individual identifying features such as a marker and matching the identity of the containers measured at two or more different points around the endless conveyor shown in FIG. 1. Since the vessel holders can be reused, immediately after a new vessel 80 is seated on the vessel holder 40, the position of the vessel holder 40 in FIG. 1 is reached, so they are stored in a computer database or other data. Registered in the structure, for example, they can be removed from the data register at the end or near the end of the process after they reach or have reached the position of the vessel holder 66 in FIG. 1, and the processed vessel 80 Is removed by means of a 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 for defects.

VI. The 　container 　inspection method in accordance with this 　invention 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 Including the step of performing the above inspection step (ie, measurement of 　gas　removed　volatile　substances) within an elapsed time of 4 seconds or less per container, 3 seconds or less per container, or 2 seconds or less per container, or 1 second or less per container can do. This may be possible, for example, by measuring the effectiveness of a barrier or other type of coated vessel wall.

VI. In any of the above embodiments, the inspection step is that when the vessel is initially vacuumed and its walls 86 are exposed to the surrounding atmosphere, a barrier or other type of coating 90 is applied within the vessel 80. At least 20%, alternatively 15%, alternatively 10%, alternatively at least 12 months or at least 18 months or at least 2 years of life at the initial vacuum level (i.e. The inspection step can be carried out at a sufficient number of locations throughout the inner surface 88 of the vessel 80 to determine that it is effective to prevent it from being reduced by more than 5%, optionally by 2% or more. .

VI. The initial vacuum level is a high vacuum, i.e. a residual pressure of less than 10 Torr, or a lower vacuum such as a positive pressure of less than 20 Torr (i.e., extra pressure for 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 evacuated blood collection tubes is in many cases determined by the type of test tube used, and thus the type and appropriate amount of reagents added to the tube during manufacture. The initial vacuum level is commonly set to draw the correct volume of blood in the tube for binding reagent filling.

VI. Optionally, the step of inspecting the barrier or other type of coating 90 is that when the vessel is initially vacuumed and its walls are exposed to the surrounding atmosphere, the barrier or other type of coating 90 is At a sufficient number of locations throughout the vessel inner surface 88 to determine that it is effective to prevent the pressure from increasing to more than 15% or more than 10% of the ambient atmospheric pressure for a lifetime of at least one year. I can.

Fig. 59 shows a 　 example of a 　 system of the invention (an example 　20) in accordance with the 　above and 　below 　 to carry out the described 　 inspection 　 method 　 to perform 　 applied 　 devices (that is, 　 one 　 or more 　 processing 　 stations). The treatment system 20 may be a container, a treatment system, and in particular, may include a first treatment station 5501, and may include a second treatment station 5502, and may or may not. Embodiments for such processing stations are shown by reference numerals 24, 26, 28, 30, 32 and 34 in FIG. 1, for example.

The first vessel processing station 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, for example a pipette or any other object having a side to be examined. The container may be made of glass or plastic, for example. In the case of a plastic container, the first processing station may include a mold for molding the plastic container.

The first treatment at the first treatment station (processing is the molding of the container, the first inspection of the container to see if it is defective, the coating of the inner surface of the container, and in particular, the second treatment of the container to see if the inner coating is defective). Inspection), the vessel holder 38 is transferred along with the vessel 82 to a second vessel processing station 5502. This transfer is carried out by means of a conveyor arrangement (70, 72, 74). For example, a gripper or some grippers may be provided to hold the vessel holder 38 and/or vessel 80 in order to move the vessel/support combination to the next processing station 5502. Also, only the container can be moved without a support. However, it may be advantageous to move the support with the container if the support is adapted to be transportable by means of a conveyor arrangement.

One or more 　processing 　 stations include 　 tubing around 　 on the 　 surface being inspected, for example 　 inside 　 　 in the container 　 　 　 　 supplying volatile substances. In addition, a gas detector may be provided to measure the emission of at least one volatile species from the inspection object into the gas space adjacent to the coated surface.

FIG. 60 shows a 　 container 　 processing system 20 according to 　 this 　 invention 　 another exemplary 　 embodiment. In addition, two vessel processing stations 5501 and 5502 are provided. Also provided are other vessel processing stations 5503, 5504 arranged in series and in which the vessel is processed, ie inspected and/or coated.

The vessel can be moved from the stock to the left processing station 5504. Additionally, the vessel may be molded within the first processing station 5504. In either case, a first vessel treatment, such as shaping, inspection and/or coating, may be performed at the processing station 5504, followed by a second inspection. The vessel is then moved to the next processing station 5501 via conveyor arrangements 70, 72, 74. Typically, the vessel is moved with the vessel holder. The second treatment is performed at the second treatment station 5501, after which the vessel and support are moved to the next treatment station 5502 where the third treatment is performed. Thereafter, the vessel is moved (again with the support) to a fourth processing station 5503 for a fourth processing, which is then conveyed to the storage by a conveyor.

Before and after each coating step or shaping step or other steps of manipulating the container, inspection of the entire container, part of the container and in particular the inner surface of the container can be carried out. The results of each inspection may be transmitted to the central processing unit 5505 through the data bus 5507. Each processing station is connected to the data bus 5507. The above-described 　program 　 can operate 　 in the 　processor (5505), and that 　, which can be converted into the form of a central control and control unit, controls the system 　and analyzes the inspection data and checks whether the final processing step is successful or not.　 to determine 　 checks 　 data can be processed 　 and can also be modified 　.

If the final processing step is determined to be unsuccessful, the vessel does not enter the next vessel 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 (conveyor Sections 7001, 7002, 7003, 7004) are moved back to the conveyor for reprocessing.

Processor 5505 can be coupled to user interface 5506 for entering control or regulation parameters.

61 shows a 　container 　 processing 　 system 　 processing 　 station 5501 in accordance with 　this 　invention 　exemplary 　 embodiment. The station includes a PPD device 5701 that coats the inner surface of the container. Also, several detectors 5702-5707 may be provided for visual inspection. Such detectors may be electrodes for carrying out electronic measurements, for example as optical detectors such as a CCD camera, a gas detector or a pressure detector.

FIG. 62 shows a container container 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 may be adapted to move into the inner space of the container 80 when the container is seated on the support 38.

For example, using optical detectors 5703 and 5704 arranged outside the seated vessel 80, or even using an optical detector 5705 arranged inside the inner space of the vessel 80, especially during the coating step. Optical inspection can be performed.

The detectors may include color filters so that different wavelengths can be detected during the coating process. The processing unit 5505 analyzes the optical data and determines whether the coating is successful with a certain level of fidelity. If it is determined that the coating is probably unsuccessful, each vessel is removed from the processing system or reprocessed.

VI.A. Container handling including pre-coating and post-coating inspection

VI.A. 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 checking whether the inner surface of the container is molded or immediately before coating to see if there is a defect; Applying a coating to the inner surface of the container after inspecting whether the container is molded; And it is performed by inspecting the coating to see if there are any defects.

VI.A. Another embodiment is a container treatment method in which a barrier coating is applied to the container after inspecting whether the container is molded, and the inner surface of the container is inspected to determine whether there is a defect after applying the barrier coating. .

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

VI.A. As helium passes through an unsafe barrier or other type of coating or leak chamber, it is a test gas that can increase the rate of leak or penetration detection much faster than normal ambient gases such as nitrogen and oxygen in normal air. Is considered. Helium has 　 high 　 pass 　 speeds 　 through many 　 spheres 　 substrates 　 or 　 small 　 cracks. Helium is (1) inert, to some extent not adsorbed by the substrate, (2) not easily ionized, so its molecules are very dense due to the high level of attraction between their electrons and the nucleus, and (3) nitrogen As opposed to (molecular weight 28) and oxygen (molecular weight 32), it has a molecular weight of 4, which makes the molecules more dense and allows them to easily pass through a porous substrate or gap, thus allowing a high transfer rate through many solid substrates or small gaps. Have. Due to these factors, helium will move through the barrier with a given permeability much faster than many other gases. In addition, since the atmosphere contains a very small amount of helium in nature, the presence of additional helium is particularly detected outside the vessel 80 to measure the leakage and penetration of helium introduced into the vessel 80. If so, it can 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. After molding the device 80 as in the station 22, several potential problems may arise that could render any subsequent processing or coating incomplete and useless. If the devices are inspected prior to coating for these problems, they are highly optimized and can optionally be coated with a maximum 6-sigma control process that will ensure the desired result (or results).

VI.A. Some of the potential problems that may interfere with processing and coating include (depending on the nature of the resulting coated article):

VI.A. 1. High density particulate contamination defects (eg, 10 micrometers or more each with the largest size) or larger particulate contamination of a smaller density (eg, 10 micrometers or more each with the largest size).

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

VI.A. 3. High surface roughness, characterized by a large number/volume of abrupt peaks and valleys. Also, it can be characterized by quantifying the average roughness Ra, which is less than 100 nm.

VI.A. 4. Any defect in the device, such as a hole that prevents a vacuum from being created.

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

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

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

VI.A. In order for the treatment/coating operation to be successful using the parameters in the treatment/coating operation, the device may be preliminarily inspected for the presence of one or more of the above potential problems or other problems. Previously, an apparatus was disclosed that supports a puck or vessel holder such as apparatus 38-68) and moves it through a production process including various tests and treatment/coating operations. Some tests that can be carried out can be carried out to ensure that the device has a suitable surface for treatment/coating. This includes the degassing of the vessel walls, which can be measured under post-coating inspection to optionally determine the degassing baseline, as described below.

VI.A. The test can be performed at the station 24 as shown in FIG. 2. In this figure, the device (e.g., the sample collection tube 80) is 　 in place 　 　 　 　 to measure the desired result 　 suitable 　 detector (134) can be positioned.

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

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

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

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. Thereafter, the puck or vessel holder 38 moves to a coating step 28, for example. The device or vessel 80 is coated with SiOx or another barrier film or other type of coating, for example at a power supply frequency of 13.56 MHz. Once coated, the vessel holder is retested for its leak rate or other characteristics (this can be done as a second test at a dual or similar station such as test station 26 or 30-using a dual station. Doing so can increase system throughput).

VI.A. The coating measurement can be compared to an uncoated measurement. If the ratio of these values exceeds a preset required level representing acceptable overall coating performance, the vessel holder and device continue to move. This value may be required to exceed a preset limit at which the device is rejected 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 inside of the tube or container 80 and slowly pulled out while the measurement is being made with the tubular CCD detector array from the outside of the container. Thereafter, the data is analyzed by a computer to measure the defect density distribution. Based on these measurements, the device is approved or rejected for final packaging.

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

VI.B. Container inspection performed by detecting the outgassing of the container wall through a barrier

Degassing 　By measurement 　For the barrier 　 　The method 　 to inspect the object was explained in the following 　. In this 　 method, a 　object (substrate) made of 　at least 　part of the first substance 　 is provided. The 　object has 　surface, and 　selectively has 　the first material has a 　at least 　 partial 　 blocking film between the 　surface 　. In the 　 extensive 　 sun of the disclosed 　 technology, 　 barriers are 　 in special cases, 　 containers have 　 barrier properties 　 coatings 　 have 　 or not 　 to determine 　 because 　 can be inspected 　. Optionally, a 　filling 　 substance that is 　dissolved, 　absorbed or 　adsorbed in the first substance is provided. When the 　object is 　, the filling 　 material is in contact with it. Now the degassing is measured from at least a portion of the surface. The 　 method is performed under conditions effective to determine the presence or absence of the prevention film.

The difference between “coated” and “uncoated” and “uncoated” (uncoated) can be made based on the angle of the flow rate and the initial gradient. This 　 flow rate 　 slope is 　 (a) directly 　 slope 　 calculation (delta 　 flow / delta 　 time) or 　 (ｂ) flow rate 　 contrast 　 time 　 curves 　 again 　 calculated 　 in order to solve the calculated 　The difference between the coated 　 item and 　 uncoated 　 item 　 is 　 there is a 　 difference 　 as long as they can be 　 re-produced 　 can be 　 original 　 invention 　 but it is good enough to see 　 　 0 　 but it's good enough. Seconds, 　 more 　 preferably 　 at least 　 0. 3 seconds 　 to 　 10 seconds, 　 even more 　 more 　 preferably 　 at least 　 1 second 　 to 5 seconds 　The 　 upper limit of the slope 　 difference is 　 number 　 minutes, for example 　 15 　 or 　 30 minutes 　 number 　. Normally, the 　 inclination 　 difference is 　 1 second 　 to 　 15 minutes, 　 more 　 usually 　 1 second 　 to 　 1 minute, 　 1 second 　 to 　 30 seconds 　 or 　 1 second 　 to 10 　.

In this 　 detailed 　 explanation 　 degree 　 31 and 　 related 　 as described 　 bawa 　 　 six sigma 　 evaluation 　 about the examination 　 passed 　 or 　 failure 　 very helpful 　 　In the example, the number of sigma applied by the inventors was 6, and this is also the most desirable number to carry out the invention. Depending on the desired 　reliability　, the number of sigma 　 can vary from 　2　 to 　8, 　preferably 　3　to 　７, 　more　preferably 　4　 to 　７　 or 　5. Reliability 　 vs 　 sigma 　 is 　 trade 　 off 　: if 　 invention 　 carry out 　 more 　 long 　 inspection 　 time 　 allowed 　 can 　 if possible, 　 more 　 high 　

The measured volatile species may be a volatile species released from the coating, a volatile species released from the substrate, or a combination thereof. In one aspect, the volatile species is a volatile species released from the coating and, optionally, a volatile coating component, wherein the test 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 test is performed to determine the presence of the coating and/or the barrier effect of the coating. In particular, the 　 volatile 　 species are 　 atmosphere 　 composition, for example 　 nitrogen, 　 oxygen, 　 water, 　 dioxide 　 carbon, 　 arron, 　 helium, 　neon, 　 krypton, 　 or 　 air days 　

An example of a 　 film 　 or 　 container is a 　 suitable 　 object to be provided with a barrier 　. Some consideration is specified container is a syringe or syringe barrel, medical sample collection container, vial, ampoule, and / or smashing one end two different tube ends are open, such as blood or other medical sample collection tubes.

The above object is 　plastic, 　for example, 　thermoplastic 　walls 　can be 　can be. The first material, i.e. the material forming the plastic wall, for instance a thermoplastic material, for example, include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or polyethylene naphthalate or a combination or copolymer Which is basically 　 configured 　 or 　 configured 　 can. The first substance is 　for example 　olefin 　 polymer, 　 example 　 cyclic 　 olefin 　 copolymer (COC), 　 cyclic 　 olefin 　 polymer (COＰ), 　 polypropylene 　 homopolymer 　 or a combination of them or a copolymer 　 or a copolymer Basically, there are 　 configured 　 or 　 configured Other 　considered 　the first substances are 　polystyrene, 　polycarbonate, 　polyvinyl 　 chloride, nylon, 　 polyurethane, 　 epoxy 　 resin, 　 polyacrylonitrile (PAN), 　 polymethylpentene, ionomer (iono-based resin) Includes.

In another 　 embodiment, the 　 first material 　 contains a cyclic 　 olefin 　 copolymer 　 can be 　 cyclic 　 olefins 　 copolymers 　 basically 　 composed 　 can be 　 or composed of cyclic 　 resin 　 co-polymer In this 　 Example, 　"consisted" is not 　to complete the 　 molding 　 composition 　 pure 　 cyclic 　 　 mixed with 　 copolymer 　 other 　 materials 　 excluded. These 　 definitions of “constructed” apply 　originals 　 detailed 　 explanations 　 as a whole 　 all 　 materials 　. ＂Constructed 　 also 　consisted of 　 described 　resin 　 composition 　 at least 　 with one 　 layer and 　 with another 　 composition 　 different 　 layers 　 　 having 　 layers 　 does not exclude 　 materials

In another 　 embodiment, 　 the first substance 　 can contain 　 polyethylene 　 terephthalate 　 can be composed of 　 polyethylene 　 terephthalate 　 basically 　 can be composed 　 can be 　 or can be composed of polyethylene 　 terephthalate 　 composed of 　 water

The 　 special 　 combination of the first material (for example 　 with SiOx coating 　 the 　 material of the tube) and the volatile 　 constituents are 　COC and 　 carbon dioxide.

The 　 special 　 combination of the first substance (for example 　 with SiOx coating 　 the 　 material of the tube) and the volatile 　 constituents are 　 PEP and 　 water.

The 　more　preferred 　 combination of the first substance (for example 　, the 　 material of the tube 　 coated with SiOx coating) and the volatile composition are 　COC and 　 argon.

In another embodiment, the barrier film is made of SiOX with an x of about 1.5 to about 2.9, or includes or is made of other materials as described in this specification. The ＂blocking film 　 is 　 hydrophobic, 　 or 　 described in the specification 　 the same 　 with the other 　 layers 　 different 　 surface 　 properties 　 granting 　 different 　 different 　 primary 　 functions Any method for applying the blocking film described in this specification may be used.

Charged 　 substances 　 discharges 　 from the material 　 by providing gas 　 to the gas 　 promotes the measurement of 　 gas 　 removal 　 can be a substance. Some 　without 　considered 　examples are 　atmospheric 　constituents, for example 　nitrogen, 　oxygen, 　water, 　dioxide 　carbon, 　arron, 　helium, 　neon, 　krypton, 　 or water Includes 　filling 　materials 　 different 　 types 　 forming 　 blocking films 　 used 　 process 　 materials. For example, 　filling 　 material 　organic silicon 　 material, 　 for example 　 octamethylcyclotetrasiloxane, 　 hexamethyldisiloxane, 　 or 　 precursor or 　 process 　 material 　 other 　 in the specification 　 included 　 　The other 　 forms of 　 filling 　 material considered are 　 for example 　 　 coating 　 used in the 　 process 　 carrier 　 gas.

Barrier property 　 coating is 　filling 　before 　 contacting 　, 　 filling 　 material 　 contacting 　, during 　 filling 　 material contacting 　, 　 or 　 or both of the 　 or applied 　 　 at or above

The contact 　 step can be performed 　 in various 　 methods, such as 　 containing 　 charged 　 substance 　 volume 　 exposed object 　 　 　Contact can be carried out by 　 filling 　 containing 　 surrounding 　 air 　 exposing objects 　. One considered 　filling 　 substance 　 is 　 moisture 　 provided in 　 formation of air 　 hydration 　 water. Contact is 　For example, before gas 　 removal 　 measurement 　, 　 blocking film 　35% 　 to 　 100%, 　 selectively 　 40% 　 to 　 100%, 　 selectively 　 40 　 selectively, selectively 　 40 　 5% selectively, selectively 80%, 　Selectively 　At least 　80%, 　Selectively 　At least 　90%, 　Selectively 　At least 　85%, 　 Optionally 　10% of 　Relative 　Can be in contact with the 　 of humidity.

Filling 　substances 　contacting 　by 　 filling 　 containing 　 substances 　 exposing 　 to gas 　 or 　 filling 　 by 　 exposing 　 to liquids containing 　 substances. 　

Exemplary contact times are 0.1 second to one hour, alternatively from 1 second to 50 minutes, alternatively from 10 seconds to 40 minutes, alternatively from 1 minute to 30 minutes, alternatively from 5 minutes to 25 minutes, optionally from 10 minutes to It can be 20 minutes. However, the contact time can also be very short. One option to get a shorter time (for example shorter than 12 minutes in the example) is to increase the temperature while touching the object to the filling material. The rise in temperature can accelerate the diffusion of the contact material through the product being inspected, for example a plastic substrate. For example, the diffusion of CO ₂ through the walls of the PET bottle increased significantly when the temperature was raised to a temperature between 30 and 40°C.

The typical parameters and conditions for filling a CO ₂ were displayed in the main protocol for filling with CO _2. The parameters given in the basic protocol can be varied by +/-50% or less when performing filling. Similar conditions are suitable for carrying out filling with one of the other filling materials, if appropriately modified in consideration of other physicochemical properties of the other filling materials described herein.

In the gas removal measurement including the filling of the filling material and the article according to the present invention, the reinforced difference between the coated plastic articles, for example, the articles coated with a barrier layer compared to the uncoated ones, is determined by the continuous gas removal measurement ( It depends on the ability of the plastic article to absorb gas into the resin for micrograms/minute). This was illustrated in the example using argon, N ₂ or CO ₂ as the filling material. The solubility of gases in plastics is an important factor in determining the amount of gas that can be present in the plastic resin and is therefore a good estimate of the likelihood of a specific fill gas to provide a good distinction between uncoated versus coated products. While the experimental determination of the solubility of various gases in plastic resins is very limited, the difference between the gas solubility S and the Leonard-Jones gas temperature [=Gas potential energy constant divided by Boltzmann's constant (W) (epsilon)] The linear relationship (Eq. 1) is for glassy polymers with an accuracy of +/-0. 6, Van Amerongen, Michael and Bixler (DW Van Krevelen, Properties of Polymers, Elsevier, 3rd Ed., 1990, pp. 538-542, and their references).

In the table 　Ｈ 　 in the 　 list of gases (in the example 　 used 　 carbon dioxide, 　 argo 　 and 　 nitrogen 　 gas 　) of the gases 　 　 　 gas 　 temperature (epsilon / 　 calculated for the logarithmic and uncoated parameters), and 　 　The 　 average 　 ratio of the 　SiOx-coated ATC (micrograms/min) signal was shown. Compared to the calculated log S　　 carbon dioxide, 　 argon, 　 and 　the 　experimental 　AC ratio (degree 　5) is 　 more 　 high 　 gas 　 solubility 　 has gass 　 desirable 　 gas is less 　 desirable

In other words, the 　gass (from the table 　Ｈ 　 further 　 below) 　 gass 　 removed 　 measured 　 coated 　 not used 　 on substrate 　 compared 　 or provided more separated 　 coated 　

Table H. Gas 　 list, 　 Leonard-Jones 　 temperature, calculated 　log S (298) and uncoated/SiOx-coated ATC response.

The same 　principles 　 different 　 or 　 different 　 gas 　 absorbability 　 and 　 indicating adhesion 　 can be applied 　 to the difference 　 of different 　 materials.

Therefore, it is desirable to use 　in the 　in the 　 text of the invention 　 inspected 　 plastics 　 materials 　 good 　 has solubility 　 gas 　 filling 　.　To improve the sensitivity of the test, 　filling 　 material can be 　 supplemented 　 or replaced 　 in plastics 　 has a higher 　 solubility 　 in a 　 fill 　 material.

In the 　special 　sun of this 　invention, the 　filling 　 material is selected 　 for the indicated 　 materials in the 　 table 　Ｈ.

In another 　special 　sun, 　 is selected from a group of 　 gases having 　-7．5 or more, preferably 　-7 or more, and more preferably 　-6. 9 or more 　log S. In a specific 　 embodiment, 　filling 　 gas has a 　log S of 　-7. 5 　 to 　-4．5 people, preferably 　-6. 9　 to 　 -5. 1 　 range.

Measurements are performed by measuring the flow rate of gas removal from the surface and removal of gas from the surface, for example, at least partially from the vacuum, and the flow rate of the gas removal from the surface is measured by, for example, 　 at least 　 part of the 　 at least 　 from the surface 　. Any of the gas removal methods described herein are contemplated.

The degassed gas is 0.1 Torr to 100 Torr, optionally 0.2 Torr to 50 Torr, optionally 0.5 Torr to 40 Torr, optionally 1 Torr to 30 Torr, optionally 5 Torr to 100 Torr, optionally 10 Torr to 80 Torr. , Optionally with a pressure of 15 Torr to 50 Torr, 　for example 　 　 gas 　 removal 　 measurement 　 in 　 coated 　 from the coated 　 surface by 　 by 　 can be measured.

The outgassed gas may be measured at a temperature of -10°C to 150°C, optionally 0°C to 100°C, optionally 0°C to 50°C, optionally 0°C to 21°C, and optionally 5°C to 20°C. . Depending on the measured 　degassed 　gas and 　physical and chemical properties of the first substance (substrate), 　different 　temperatures 　also 　may be appropriate. Some of the materials, such as COC, do not heat up to the extent that they will cause deformation, but are also important, but at elevated temperatures they have higher permeability. For example, for the 　COC (with a glass transition temperature in the range of about 70℃ to about 180℃), it is kept below the glass transition temperature 　, and if the deformation is prevented, the gas will be removed 　 or the temperature will be more than 80℃. There is a number.

In one of the examples described in this specification, the first material optionally has an outer surface and an inner surface, and the inner surface is provided in the form of a container having a wall surrounding the lumen. Optionally, the blocking film may be provided on the inner surface of the vessel wall.

Optionally, a pressure differential may be provided across the barrier by at least partially evacuating the lumen 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.

The gas 　 removal 　 measurement 　 cell can be provided 　 by communicating between the lumen and the vacuum source 　.

Gas 　 removal can be measured 　 per time 　 interval 　 above 　 barrier properties 　 through 　 　 passing 　 gas 　 removal 　 by determining the volume of substances 　.

Gas 　 removal can be measured 　 using 　 fine 　 flow 　 technology.

Outgassing can be measured as the mass flow rate of the outgassed substance.

Gas 　 removal can be measured 　 in 　 molecular 　 flow 　 operation 　 mode.

The gas removal can be measured using the micro cantilever technology described in this specification.

Optionally, a pressure differential may be provided across the barrier layer such that at least a portion of the degassing material exists on the high pressure side of the barrier layer. In another option, the outgassed gas can be allowed to diffuse without providing a pressure difference. The outgassed gas is measured. If a pressure differential is provided across the barrier, the outgassing can be measured on the high or low pressure side of the barrier.

VI.B. Further, the measurement of the effectiveness of the inner coating (applied above) can be made by measuring the diffusion rate of specific species or adsorbed substances within the wall of the device (prior to coating). When compared to an uncoated (untreated) tube, this type of measurement can provide a direct measure of the blocking or other type of properties of the coating or treatment or the presence or absence of the coating or treatment. In addition to or instead of the barrier film, the coating or treatment detected may be a lubricating layer, a hydrophobic layer, a decorative coating, or other types of layers that increase or decrease the outgassing of the substrate to alter it.

VI.B. In this disclosure, a distinction is made between “penetration”, “leakage” and “surface diffusion” or “outgassing”.

As used herein with reference to a container, "penetration" refers to the traversing of a material through a wall 346 or other obstruction, from the outside of the container to the inside or vice versa along the path 350 of FIG. 29. Means that.

Degassing can be accomplished by absorbing or adsorbed substances such as gas molecules 354 or 357 or 359 outward from the inside of the wall 346 or coating 348 of FIG. 29, for example, the coating 348 (if present) and It means moving to the container 358 (to the right in Fig. 29). In addition, degassing may mean that a material such as 354 or 357 comes out of the wall 346 and moves to the left as shown in FIG. 29 and moves to the outside of the container 357 as shown. . In addition, degassing may mean removal of a substance adsorbed from the surface of an item, such as gas molecules 355 from the exposed surface of the container coating 90.

Leakage refers to the movement of material around the obstruction presented by the wall 346 and coating 348 rather than through or out of the surface of the obstruction, by passing between the closure and the wall of the container closed with the closure.

VI.B. Penetration refers to the rate of gas movement through a material that is free of gaps/defects and is not related to leakage or outgassing. VI.B. Penetration refers to the rate of gas movement through a material that is free of gaps/defects and is not related to leakage or outgassing. Infiltration is considered a relatively slow process, thermodynamic.

VI.B. The penetration measurement is very slow because the infiltrating gas has to pass completely through the unbroken wall of the plastic item. In the case of evacuated blood collection tubes, the measurement of the penetration of gas through the wall is usually used as a direct indication of the tendency of the vessel to lose vacuum over time, but to the extreme, usually requiring a test period of 6 days. It's a slow measurement, so it's not fast enough to support on-line coating inspection. Such tests are generally used for off-line testing of samples of containers.

VI.B. Also, the penetration test is not a very sensitive measurement of the barrier effectiveness of a thin coating on a thick substrate. Since all gas flow is through both the coating and the substrate, any change in the flow through the thick substrate will in itself introduce a change that is 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 barrier properties of a coating-measuring the outgassing of air or other gases or volatile constituents that have quickly separated from the vessel wall through the coating. The gaseous or volatile constituents may in fact be any substance that can be selected from or outgassing one or more specific substances to be detected. The components are oxygen, nitrogen, air, carbon dioxide, water vapor, helium, alcohols, ketones, hydrocarbons, halides 　 hydrocarbons, 　 ethers, 　 coating precursors, substrate components, by-products of coating manufacturing such as volatile organosilicons , By-products of the manufacture of the coated substrate, other constituents, or mixtures or combinations of any one of them, which are accidentally present or introduced by spike the substrate, but are not limited thereto.

Degassing provides a much faster measure (relative to penetration) of the presence and barrier properties of a coating such as (348). Degassing is a faster test since it does not have to go through the entire thickness of wall 346 in FIG. 29. Degassing may be in the wall 346 close to the barrier coating 348 or on the inner surface of the vessel (if there is no coating), so that it can traverse a very small portion of the thickness of the wall 346. Since the barrier coating is thousands of times thinner than the vessel wall, the degassing measurement eliminates practically any delay required for permeation testing by reducing the wall thickness through which the gas must pass before being detectable in the vessel. Reducing the distance you have to travel reduces the length of the movement.

Degassing can be made more sensitive and faster by filling the surface to be tested with gas consumed by the container rather than a barrier coating. The inside of the container being tested is exposed to the filling gas and is tested for degassing. If there is an effective barrier coating, a very small amount of gas will be charged as the barrier coating will prevent entry into the vessel wall. If there is no barrier coating, the fill gas will be consumed a significant portion by the vessel wall in a very short period of time. The amount of gas entering the walls and the presence of a barrier coating will determine the amount of gas removal into the vessel.

Finally, the method of degassing measurement will determine how fast it can be measured. The preferred measurement technique is known as the microflow technique. The microflow technique used in this method allows the presence and effectiveness of the barrier coating to be confirmed within seconds, potentially in seconds or less.

The degassing method can distinguish between coated and uncoated plastic tubes within seconds and even less than a second.

Surface diffusion and outgassing are synonymous. Each term refers to a vacuum that is initially adsorbed or absorbed by the wall 346, such as the wall of the container and draws a vacuum (which creates the air movement indicated by arrow 352 in FIG. 29) within the container having the wall. It refers to a fluid that passes into an adjacent space by a force that becomes a part of a motif and forcibly moves the fluid from the outside of the wall to the inside of the container. Degassing or diffusion is considered a kinetic, relatively rapid process. For walls 346 that are substantially resistant to penetration along path 350, degassing molecules such as 354, which are closest to the interface 356 between the wall 346 and the barrier layer 348, It is thought to be expelled quickly. This differential degassing is achieved by a large amount of molecules such as 354 near the interface 356 shown as degassing and further away from the interface 356, such as 358 not shown as degassing. Is presented by other molecules of

VI.B. Thus, another method is contemplated for inspecting the barrier film on the vapor outgassing material, including several steps. A sample of material is provided that degasses the gas and has at least one partially barrier film. A pressure differential is provided across the barrier layer such that at least a portion of the material to be degassed is initially present on the high pressure side of the barrier layer. During the test, the outgassed gas transported to the low pressure side of the barrier layer is measured to determine whether the barrier layer is present or how effective it is to the barrier layer.

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

VI.B. Optionally, the 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 is provided optionally on the vessel wall, optionally on the inner surface of the vessel wall. In addition, the blocking film may be provided on the outer surface of the container wall. Optionally, the material for outgassing the gas may be provided in the form of a film.

VI.B. The blocking film may be a full or partial coating of any of the currently described blocking films. The blocking 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. Typically, the blocking layer may be a SiOx blocking layer, and the thickness may be about 20 to 30 nm.

VI.B. In the case of coated walls, the inventors have found that diffusion/degassing can be used to measure coating integrity. Optionally, a pressure differential may be provided across the barrier membrane by at least partially evacuating the lumen or inner 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, the uncoated PET wall 346 of a container exposed to the ambient air may gase a certain number of oxygen and other gas molecules, such as 354, from its inner surface for some time after the vacuum is drawn. Will remove it. If the same PET wall is coated on the inside with a barrier coating 348, the barrier coating will stop, delay or reduce this outgassing. This is true, for example, for SiOx barrier coating 348 that outgasses less than plastic surfaces. By measuring the difference in outgassing between coated and uncoated PET walls, the barrier effect of the coating 348 on the outgassed material can be quickly measured.

VI.B. If the barrier coating 348 is said to be incomplete due to known or theoretical holes, cracks, gaps, or insufficient thickness or density or area of the composition, the PET wall is preferentially degassed through such imperfections, thereby degassing. Will increase the total amount of. The first source of gas collected is not from the exterior of the item, but from dissolved gases or vaporizable constituents on the (lower) surface of the plastic item next to the coating. The amount of outgassing beyond the baseline level (e.g., the amount passed or discharged by a standard coating with no or minimal achievable imperfection or an average and acceptable degree of imperfection) is the completeness of the coating. It can be measured in a variety of ways to measure.

VI.B. The measurement can be carried out, for example, by providing a degassing measurement cell communicating between the lumen and the vacuum source.

VI.B. The measurement cell can 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 outgassed material can be measured. The measurement can be carried out in the molecular flow mode of operation. An exemplary measurement is the measurement of the volume of gas outgassed through the barrier per time interval.

VI.B. The gas removed from the low pressure side of the barrier layer may be measured under conditions effective to distinguish the presence or absence of the barrier layer. Optionally, conditions effective to distinguish the presence or absence 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. Test durations of less than, 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 presence or absence of the blocking film can be ascertained with at least a 6-sigma level of certainty within any of the identified time intervals.

VI.B. Optionally, the gas outgassed on the low-pressure side of the barrier layer is measured under conditions effective to measure the barrier enhancement factor (BIF) of the barrier layer compared to the same material without the barrier layer. BIF, for example, provides two groups of identical vessels, adds a barrier to one group of vessels, and provides barrier properties (such as rate of outgassing per minute or other suitable measure) on vessels with barriers. It can be tested and measured by performing the same test on containers lacking a barrier and taking the ratio of the properties of the material with and without the barrier. For example, if the rate of gas removal through the barrier layer is one third of the rate of gas removal without the barrier layer, the barrier layer has a BIF of 3.

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

VI.B. Measurement of the number or partial pressure of individual gas species (such as oxygen, helium, CO ₂ or water vapor) degassed from the sample can be performed more quickly than the atmospheric pressure test, but the test rate is only a fraction of the degassing above. It is reduced to the extent of all measured days. For example, if oxygen and nitrogen are outgassed from the PET wall in a ratio of about 4:1 of the atmosphere, but only oxygen outgassing is measured, a test measuring all species outgassed from the vessel wall is the same sensitive test. As a result, it is necessary to carry out about 5 times (converted to the number of detected molecules to obtain a sufficient statistical query result).

VI.B. For a given 　 sensitivity 　 level 　 the 　 gas removal from the surface 　 all 　 species 　 occupying the volume 　 the method 　 with oxygen 　 atoms 　 the same 　 specific 　 species 　 providing a much more reliable 　 testing 　 better than 　Eventually, 　in-line 　 measurement 　 practical 　 utility 　 　 gas removal 　 data 　 can be created 　. Optionally, 　 these 　 in-line 　 measurements are 　 manufactured 　 for all 　 containers 　 can be performed 　 for 　 peculiar or 　 separated 　 reduce the 　 number of defects 　 potentially measured (potentially removed)

VI.B. In the actual 　 measurement, the 　outward 　 visible 　 gas removal 　 amount 　 changing 　 factor is 　 above 　 gas removal 　 in the test 　 vacuum 　 according to the 　 vacuum 　 leaking unstable Leakage is, for fluids, for example to bypass the solid wall of the item, a blood tube and a closure between the syringe plunger and the syringe barrel between the container and the cap, or between the container inlet and the inlet the vessel is seated (the incomplete or improperly seated Actually, it means 　 which means 　 fluid that flows between 　 and threads. The word “leakage” is a 　 meaning 　 mainly through the 　 openings 　 in plastics 　 items 　 gas/gas movement 　.

VI.B. Leakage 　 and 　 (if necessary 　 in a given 　 situation) 　 penetration 　 be magnetized 　 to the basic 　 level of gas removal 　 water 　, so 　 acceptable 　 test 　 results 　 the container 　 vacuumed 　 not properly formed 　 and its location 　 not suitable 　　Because the container 　 wall 　 penetration 　 unacceptable 　 　 level 　 does not support 　 (container 　 wall 　 is not damaged 　 properly 　 formed) 　 and has enough coating 　 block

VI.B. Degassing is done by 　atmospheric pressure　measurement (after the initial 　vacuum is drawn 　　in a given 　time 　in a container 　　 pressure 　 change 　) or 　from a sample 　by measuring the flow rate of gas to be measured 　 varying 　 or the quantity of gas to be measured 　 or 　In the molecular flow mode of operation, the instrument can be used to measure mass and flow rates.　 employing 　 micro-flow 　 technology 　 　 this type of 　 commercially available 　 material 　 examples of equipment available 　 imported from Indiana 　 　 imported from Indiana See US Pat. Nos. 5861546, 6308556, 6584828 and EP1356260, incorporated herein by reference, for further description of this known equipment. Uncoated 　 Tubes 　 Barrier 　 Coated 　 Polyethylene 　 Terephthalate (PET) 　 Tubes 　 Very 　 Quickly 　 Reliable 　 Differentiating 　 Gas Removal 　 See also an example in A1 of measurement 　 8167

VI.B. Regarding 　 containers made of polyethylene 　 terephthalate (PET), 　 micro flow 　 speed is different for 　 SIO 　 coated 　 surface 　 vs. uncoated 　 surface. 　For example, in 　EP EP2251671 A2 　Work example 　8, 　As shown in Fig. 31　　　, 　 test was executed 　 30 seconds 　 　 run 　 after 　 〘〘〘〘〘or more As this speed for uncoated PET is described again in Fig. 31, the test is significantly higher than the measured rate for SiOx- coated PET was less than 6 micrograms after the running for 30 seconds.

VI.B. One possible explanation for this difference in flow rate is PET uncoated is that containing about 0.7 percent moisture equilibrium; such a high water content is considered to cause the observed high micro flow rate. SIOｘ-coated 　Ｔ　 plastic is used, and 　SIOｘ　 coating is 　 more 　 higher 　 level of moisture than the uncoated 　 　 　 　 surface. However, under 　test 　 conditions, 　blocking 　 coating prevents 　 moisture 　 bulk 〰 　 from plastic 　 further 　 prevents 　, and 　 micro flow 　 speed becomes 　 more 　. It is expected that the microflow rates of oxygen or nitrogen from the uncoated PET plastic versus SiOx coated PET will also be distinguishable.

VI.B.　 changes in the above 　 test for PTU tubes are 　 appropriate 　 if 　 other 　 materials are used. For example, 　polyolefins and plastics tend to have 　moisture content 　 almost no 　. An example of a polyolefin having a low moisture content is a cyclic polymer that has a lower permeation speed than the olefin permeation rate, which is a co-olefin that has a lower moisture content and a lower water permeation rate than that of the olefin. In the case of COC, uncoated COC plastics can have similar or even lower microflow rates to SiOx coated COC plastics. This is likely due to the higher surface moisture content of the SiOx-coating and the lower equilibrium bulk moisture content and lower penetration rate of the uncoated COC plastic surface. This makes it more difficult to differentiate between 　not coated 　coated 　COC　 items.

The present invention shows that exposing the surface of the COC article to be tested (uncoated and coated) to moisture results in improved and consistent microflow separation between the uncoated plastic and the SiOx coated COC plastic. This is shown in the example of EP2251671 A2 and the example of EP2251671 A2, and also in 57. The moisture exposure may be a simple exposure to a relative humidity ranging from 35% to 100%, as in the relative humidity room controlled or mild (humidifier) or poor circulation (vaporizer) directly exposed to the water source, the latter is 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 uncoated COC plastics is capable of removing moisture or other gases onto an already saturated SiOx-coated COC surface. It seems to increase the content. In addition, 　 contains 　 carbon dioxide, oxygen, 　 nitrogen, 　 water vapor or 　 for example 　 other 　 mixtures such as air and 　 other 　 gases 　 coated and 　 uncoated 　 exported tubes 　 exported Carbon dioxide exposure (or "spiking") is particularly effective in this regard if the tube is made of COC.

ＶＩ．Ｂ　 Therefore, 　before the 　 degassed 　 gas is measured 　, the barrier film can be in contact with water and vapor, for example. Water vapor, for example, can be brought into contact with the 　 blocking membrane 　35% 　 to 　 10 0%, 　 or 　 40% 　 to 　 100%, 　 or 　 40% 　 to 　 50% of 　 relative water 　 provided. In lieu of water 　 or 　 in water, 　 blocking membrane is in contact with 　 oxygen, 　 nitrogen 　 or 　 oxygen 　 and 　 a mixture of nitrogen and 　 for example, 　 surroundings 　 air. Other materials can also be used in the degassing test, including carbon dioxide, nitrogen and inert gases (eg argon). Exemplary contact time is 0.1 seconds to one hour, optionally, from 1 second to 50 minutes, alternatively 10 seconds to 40 minutes, alternatively from 1 minute to 30 minutes, optionally from 5 minutes to 25 minutes, alternatively 10 minutes to There are 20 　 minutes 　 number 　.

In addition, the 　wall (346) that removes gas is 　as an example, like the 　bar and 　 shown in the 　11 　 　 to the left of the 　 wall (346) 　 to the upper 　 wall (346) 　 gas flows into the wall (346) and then the gas flows into the left 　 or 2 　 　It can be 　 spiked 　 or supplemented 　 from the opposite 　 side with one 　gassing　substance 　exposed to 　blocking layer (348). After gas inflow 　 　 from the left 　 wall 　 or 　 other 　 material 　 spiking 　 after 　 spiked 　 substance 　 from the right (or 　 the opposite of) 　 gas is measured 　 when measured 　 gas removed 　Through 　 the whole 　 path (350) 　 contrary to the 　 substance moving 　, 　 when the spiked 　 substance 　 gas removal 　 is measured 　 the reminder 　 wall (346-) 　 　 exists 　 because it is measured 　 and permeation Gas inflow is 　above 　 coating (348) is applied 　 as an example 　 one day 　, and 　 and 　 the above 　 coating (34 8) was applied 　 after 　 and 　 gas removal was tested in different days 　 the next day 　 　 　

VI.B. Another possible way to increase the separation of the microflow reaction between the uncoated plastic and the SiOx coated plastic is to change the measured pressure and/or temperature. In the case of measuring the gas removal, increasing the pressure or reducing the temperature is better than in the uncoated, non-coated COC, there is more than the non-coated COC. There are more than one molecule that can be combined with more than one molecule. Therefore, the outgassed gas is 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 with a pressure of Torr to 50 Torr. The outgassed gas may be measured at a temperature of -10°C to 150°C, optionally 0°C to 100°C, optionally 0°C to 50°C, optionally 0°C to 21°C, and optionally 5°C to 20°C. . For COC the temperature can be about 80°C or higher.

Another particular embodiment is an improved method and improved system for the separation of plasma coated COC plastic articles or surfaces versus uncoated articles or surfaces.

In contrast to PET resins that have substantially dissolved moisture (ca. 0.1 to 0.2 weight percent), cyclic olefin copolymer (COC) compositions comprising TOPAZ-brand resins have a lower equilibrium moisture (ca. 0.01%). Has. Microflow analysis to differentiate the degassing rate between uncoated and plasma coated COCs using moisture degassing is more difficult.

It has been found that the filling and injection of carbon dioxide (CO ₂ ) into the COC article or surface improves the microflow signal separation between the uncoated and plasma coated injection molded COC articles. The increased discrimination will provide a better determination of coating uniformity for performance optimization and a faster discrimination of in-line real-time evaluation of an acceptable or unacceptable coated article. Thus, CO ₂ is a preferred filling material for carrying out a degassing method comprising filling the article to be inspected according to the invention.

Preferred conditions for the use of the filling material, for example the use of CO ₂ as the filling material are as follows:

Filling time: 0.1 seconds to one hour, optionally, from 1 second to 50 minutes, alternatively 10 seconds to 40 minutes, alternatively from 1 minute to 30 minutes, optionally from 5 minutes to 25 minutes, alternatively 10 minutes to 20 minutes ． A 12 to 14 minute fill time is particularly considered.

Filling pressure: 16 psi (1 atm) to 48 psi (3 atm), preferably 20 psi to 30 psi, and particularly preferably 25 psi. Pressures higher than 3 atm when performing filling are undesirable, as the coated vessel and coating can stretch, causing defects such as cracks and swelling in the coating and/or substrate.

The typical parameters and conditions for filling a CO ₂ were displayed in the main protocol for filling with CO _2. The parameters given in the basic protocol can be varied by +/-50% or less when performing filling. Similar conditions are suitable for carrying out filling with one of the other filling materials, if appropriately modified in consideration of other physicochemical properties of the other filling materials described herein.

CO ₂ or other filling material can be filled into the coated article immediately after coating.

Helium, include argon, neon, hydrogen, and acetylene but not limited to, a micro flow method improved coating over the plasma considered for coated degassing nine minutes another untested added with or filled with gases, low standby natural abundance and COC resins It has a high 　 solubility in 　. However, like the 　bawa 　 　 examples show 　, 　N2 can also be used 　 successfully 　. Under standard 　 temperature and 　 pressure (７60Ｔｏｒｒ) 　 liquid 　 fluid, 　 but 　 analysis 　 conditions 　 vapors (for example, 　 silicon 　 substances, 　 and 　 methylene 　 chlorides 　 such as 　 halogens).

The injection or filling of CO ₂ into the plastic product can be performed as part of the final step in the plasma coating operation, or as a separate operation as the off-gas during the micro-flow measurement step.

VI.B. In the 　 arbitrary 　 embodiment of this 　 disclosure, the 　to measure the gas removal 　 is to adopt the 　 microcantilever 　 measurement technique 　. Such 　 technique is 　 potentially 　 10-12 　ｇ. (picogram) 　 to 　 10-15 　 　 to 　 size 　 in gas removal 　 more 　 less 　 mass 　 possible 　 measurement of 　 possible 　These 　More 　 　 mass 　 detections 　 1 　 seconds, 　 selectively 　 　 less than 1 　 s 　, 　 selectively 　 micro 　 　 not only other 　 coatings 　 as well as 　 non-coated 　 surface is possible 　

VI.B. In some 　 cases, 　microcantilever (MCL) 　sensors 　because of 　gassing or 　absorption of molecules 　 bend the shape 　 or 　 move or change 　 respond to the 　 provided 　 　In some 　 cases, 　microcantilever (MCL) 　 sensors can respond 　 due to 　 shifting at the resonance 　 frequency. In other 　 cases 　, the 　 above 　 MCL 　 sensors can be changed 　 in these 　 both 　 ways 　 or 　 different 　 ways 　. They can be operated in different environments such as 　gas　environment, 　liquids　or 　vacuum 　. In the gas, there are a micro cantilever sensor can operate as an artificial nose, whereby eight kinds of polymer-bending pattern of the array of micro-production-coated silicon cantilever has a solvent, spices and drinking water and the other, the characteristics of the steam. In addition, 　 arbitrary 　 operated 　 by technology, 　 arbitrary 　 other 　 types of 　 electronic nose are also considered.

Piezoresistive, 　 Piezoelectric 　 and 　 Capacitiveness 　 Approaches 　 　 Some 　 MK 　 Electronic 　 designs 　 are applied 　 at the time of exposure to chemicals 　 The movement of 　MCLs 　 or change in shape 　 　 　 change

VI.B. One 　 specific 　 example of 　 measuring the outgassing can be done as follows. In the presence of degassed material, at least one microcantilever having the property of moving or changing in a different shape is provided. The microcantilever is exposed to the degassed material under conditions effective to cause the microcantilever to move or change to a different shape. After that, a 　moving 　 or a different 　 shape is detected.

VI.B. As an example, before and after exposing the microcantilever to the degassing, the shape of the microcantilever is shifted or changed by reflecting the energy incident beam from a portion of the microcantilever, and deflection of the reflected beam at a point spaced apart from the cantilever. It can measure and detect moving or different shapes. Optionally, the 　above 　 shape 　 under a given 　 condition 　 the amount the beam deflects 　 is proportional to the 　 distance of the beam 　 from the reflection point 　 because it is 　 away from the cantilever 　 measured at a point

VI.B. Examples of energy 　 incident 　 beams 　 some 　 suitable 　 examples are 　 photons 　 beams, 　 electrons 　 beams 　 or a combination of two or more of them. In addition, 　2　 or more 　 different 　 beams 　 different 　 incidence 　 and/or 　 following the reflected 　 paths 　 from the above 　 　 　 reflected 　 one 　 or more 　 from the viewpoint 　 shape 　 or 　 or One type of 　 that is 　 specific 　 of energy 　 incident 　 beam is 　 laser 　 beam and the same 　 coherent 　 　 beam of photons. The 　＂photon'' described in this specification is defined as 　 by itself 　 as it contains 　 not only 　 particle 　 or 　 photon 　 energy, but also 　 wave 　 energy.

VI.B. Another example of measurement is 　 performing 　 change at 　 resonance 　 frequency 　 in an effective 　 amount 　 environment 　 meets a substance 　 resonance 　 at frequency 　 of change 　 use of specific 　 MCLs. This 　 type of 　 measurement can be performed as follows. When degassed material is present, at least one microcantilever resonating at a different frequency is provided. It is possible to expose the microcantilever to the outgassed material under conditions effective to make the microcantilever resonate at different frequencies. Thereafter, the 　 different 　 resonance 　 frequencies 　 is detected by 　 arbitrary 　 appropriate 　 means.

VI.B. For example, the 　 different 　 resonance 　 frequency can be 　 resonant by entering 　 energy 　 into the 　 above 　 micro cantilever 　 resonating 　 by exposing the 　 to the removal of gas 　 before 　 and 　 after detection 　Differences between the 　 resonance 　 frequencies 　 of the above 　MCL are measured 　 before exposure 　 and after 　 to outgassing. In addition, instead of 　 measuring the difference 　 in the 　 resonance 　 frequency 　 it will be provided with a 　 specific 　 resonance 　 frequency 　 if there is 　 sufficient 　 concentration 　 or quantity 　 gas removed 　 substance exists 　. Different 　 resonance 　 frequency 　 or 　 sufficient 　 amount of 　 degassed 　 which signals the existence 　 of the 　 fair 　 frequency is detected using 　 harmonic 　 vibration 　 sensor.

As an example of the 　MCL　 technology that measures the removal of gas, the 　MCL　 device can be integrated 　 into a 　 container 　 and 　 vacuum 　 pump connected 　 quartz 　 vacuum 　 tube. Commercially available 　Pressure resistance 　Cantilever, 　 Wheatstone 　 Bridge 　 Circuit, 　 Positive 　 Feedback 　 Controller, 　 Excitation 　 Piezoelectric element 　 and 　 Phase 　 Fixed 　 Loop ( Demodulator 　 　 　 　 　 　 　 　 　 　

• 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;

ㆍ Hayato Sone, Ayumi Ikeuchi, Takashi Izumi, Haruki Okano and Sumio Hosaka Femtogram Mass Biosensor Using Self-Sensing Cantilever for Allergy Check, Jpn. See J. Appl. Phys. 43 (2006) 2301).

For detection, 　for 　for manufacturing 　 for 　 for 　 for 　, 　 one side 　 of the micro cantilever can 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. The vacuum 　 coated 　 container 　 surface 　 desorption 　 water vapor 　 combines with gelatin 　, from the 　 surface 　 of the cantilever 　 laser 　 deflection 　 measured 　 bar and 　, and the frequency of the cantilever changes 　 　 resonant It is considered that the 　 change in 　 mass of 　 uncoated 　 container 　 　 coated 　 can change 　 in a few 　 seconds, and 　 reproducibility 　 high 　.　 linked with cantilever 　 technology 　 　 quoted above 　 detects 　 species removed 　 and 　 quantifies 　 used 　 number 　 specific 　 MCLs 　 and 　 equipments 　 　 　 　 　 　 　

Moisture 　 detection (phosphoric acid) 　 or 　 oxygen 　 detection 　 other coatings 　 instead of 　 gelatin 　 coating described above 　 or 　 in addition to 　 to be applied on 　MCLs　.

VI.B. In addition, one of the 　current 　considerations 　gas removal 　 test 　 setups 　 can be combined with 　 a coating station, which can provide a 　 coating, for example a SiO' coating, for example, a 　 PECVD coating 　 station. 　In such 　arrangement, 　measurement 　cell (362) can be used as 　bypass (386) and 　for 　ＰＶＤ　 using 　 main 　 vacuum 　 channel, and the same 　 shown above. In one 　 embodiment, 　 degree 　 30 　 　 (362) 　 Normally displayed 　 measurement 　 cell is 　 above 　 bypass 　 channel (38 6) 　 main 　 vacuum 　 duct (measured  4) and the duct (measurement  4) is composed of 6 two sides. Can be integrated in the same 　 container 　 support 　 　.

VI.B. This combination of the above 　measurement cell (362) and the 　above 　 container 　 support (50) is 　selectively used in the 　EPDCＤ　to ensure that the 　vacuum is not 　 broken 　. Alternatively, the vacuum pump for PECVD are short and, preferably, the residual reaction to pump some or all of the material gas will be run for a standardized time (and pump down to less than 1 Torr in the subsequent coating step, pump-down Have a small amount of 　 air, 　 nitrogen 　 oxygen 　 or another 　 gas spilling 　 　 or 　 process 　 gass 　 diluting 　 different options). This will promote the combined process of coating the container and testing the coating for the presence and blocking levels.

VI.B. In addition, 　After reviewing the 　 specification 　, 　 gas removal 　 measurement is 　 to measure 　 effectiveness of the barrier 　 other 　 or 　 in addition to this 　 many 　 purposes. 　 　 　 　 　 　For example, 　to measure the degree of 　gas removal 　 of the walls 　 　 uncoated 　 or 　 for coated containers 　 test can be done. This 　 test is 　for example, 　 less than a certain amount 　 removes gas 　 uncoated 　 polymers 　 needed 　 can be done 　.

VI.B. It may be used with respect to the film that are not blocked as a line test coated or uncoated - another example, such degassing measurements stop test or film of measuring a change in the degassing of the film, as transverse to the measuring cell have. The above 　 test is the same as 　aluminum 　 coatings 　 or 　 EＶＯＨ 　 blocking 　 coatings 　 or 　 packaging 　 films 　 layers 　 different 　 types of 　 coatings 　 useful in measuring the continuity 　 or 　 useful

VI.B. These 　gas removal 　 measurements 　 are also applied 　 on the outside of the container 　 wall 　 and into the above 　 container 　 walls 　 inside 　 to remove gas 　 tested 　 barrier membrane and 　 the same 　 measuring 　 cell and 　, which is the same as 　 measuring 　 cell and 　It can be used. In this case, 　blocking 　 coating 　 penetration 　 after 　 substrate 　 film 　 or 　 through wall 　 for penetration 　 flow 　 differential. These 　 measurements would be especially useful in the case of 　very 　 or 　porous 　film 　 or 　 substrates 　 like walls 　 or 　 walls are 　 permeable 　.

VI.B. These 　gas removal 　 measurements can also be used to determine the effectiveness of the barrier film, which is the inner layer of the container wall, film, etc. In this case, the measurement cell is used to remove gases through a barrier film of layers or layers farther from the measurement cell than the barrier film. In addition, any outgassing through the layer adjacent to the measurement cell will be detected.

VI.B. These 　gas removal 　 measurement 　 also 　 if the barrier film 　 does not exist on any 　 part of the substance 　 partially 　 the barrier 　 coated 　 of the substance 　 gas removal 　 the degree of 　 and the rate of gas removal 　 that is expected 　 and the rate of gas removal 　It can be used to measure the percentage of coverage of the pattern.

VI.B. One kinds of examination techniques which may be used with any gas removal test example, be used to increase the speed of testing for the degassing of the container in this specification of a portion of the container to be tested by inserting the plunger or the closure to the container It is to 　 to reduce the void 　 volume 　 　 void 　 volume of the container 　. Reduce the void 　 volume 　 container 　 given 　 vacuum 　 level 　 further 　 pump 　 down 　, 　 test 　 reduce the interval.

VI.B. Currently 　Described 　Degassing 　Measurements 　 and 　 Others 　All 　Described 　 Blocking 　 Measurements 　 About the 　Many 　 Other 　 Applications 　 This 　 Specifications 　 Review 　 After 　 Review 　

VII. PECVD-treated 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 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 　 thickness of 　 also marked 　SiOx coating A container with a coating 90 is contemplated. Coatings up to 1000 nm, or 900 nm or so, or 800 nm or so, or 700 nm or so, or 600 nm or so, or 500 nm or so, or 400 nm or so, or 300 nm or so, or 200 nm or so, or approximately 100 nm , or 90 nm or so, or at least 80 nm or so, or 70 nm or so, or 60 nm or so, or 50 nm or so, or 40 nm or so, or 30 nm, or 20 nm or so, or 10 nm or so, or 5 nm approximately There are 　 thickness 　 　. In addition to the 　 indicated 　 minimum 　 thickness 　 one 　 one 　 　 specific 　 thickness 　 　 in addition to the 　 indicated 　 above the 　 maximum 　 thickness 　 of which 　 is obviously more than one 　The thickness of the SiOx or other coating can be measured, for example, by a transmission electron microscope (TEM), and its composition can be measured by X-ray photoelectron spectroscopy (XPS).

VII. It is believed that the choice of a material that does not penetrate the coating and the properties of the applied SiOx coating can affect the barrier efficacy. For example, 　 not to be penetrated 　 common 　 intended 　 substances 　 middle 　 two 　 examples are 　 oxygen 　 and water/water vapor. In common, 　materials are 　one 　 better 　 shielding film than the other 　. This is considered to be because 　partly 　 due to the 　 different 　 mechanism 　 than that 　 water 　 permeates 　 　 through coating 　 permeates 　 　 such 　.

VII. Oxygen 　 permeation is influenced by 　 thickness, 　existence of cracks 　 and 　 other 　 physical details of the coating and the same 　 　 physical characteristics of the coating. On the other hand, 　moisture 　 transmission is considered to be influenced 　 usually 　 by 　 chemicals 　 factors above 　 physical 　 factors 　, for example, 　 by coating 　 to materials 　. In addition, 　this 　inventors 　 these 　 chemical 　 factors 　 at least one 　 in the coating 　 　 as the 　 practical 　 concentration, 　 is the 　 more permeable 　 and the speed of the 　 high barrier Since SIoｘ　coating 　 often contains 　ＯＨ　 moieties 　, it contains 　ＯＨ　 moieties at a high 　 ratio 　physically 　 normal 　 coating is 　 better than oxygen 　Physically normal carbon-based barrier, such as amorphous carbon or diamond-like carbon (DLC) are together typically SiOx have a better barrier against water than that one, which typically is lower, the carbon-based barrier concentration of the OH moiety Because.

VII. However, other factors lead to a preference for SiOx coatings such as oxygen barrier efficacy and close chemical similarity to glass and quartz. Glass and quartz (if used as the base material of the container) are the two substances known for long, as well as substantial inactivity property for many substances commonly contained in a container that presents a very high barrier against oxygen and water permeation. Therefore, it is generally desirable to optimize the water-based barrier properties, such as the water vapor transmission rate (WVTR) of the SiOx coating, rather than selecting a different or different type of coating to act as a water-permeable barrier.

VII. Several methods considered to improve the WVTR of SiOx coatings are as follows.

VII. In the deposited 　coating, the 　concentration 　 ratio of 　organic 　 moieties (carbon 　 and 　 oxygen 　 compounds) can be increased 　 for the 　ＯＨ　 moieties. This can be accomplished by increasing the rate of oxygen being supplied, for example, by increasing the rate of oxygen supplying or reducing the rate of supply of one or more other constituents. Is a lower incidence of OH moieties to increase the reaction degree of the oxygen supply and hydrogen in the silicon source is believed to be due to to produce further volatile water in PECVD outlet and locked or reduce the concentration of an integrated OH moiety in the coating.

VII. Plasma 　 generation 　 power 　 level 　, 　 apply power 　 for a longer period 　 or do both 　 and in the 　 ECV D 　 process 　 more 　 higher 　 　 received. Because the 　 increase in applied 　 energy 　 tends to 　 warp 　 processed 　 containers 　 　, because 　 plastic 　 tubes 　 or 　 other 　 devices 　 coatings 　 used 　 if it is used 　 to generate 　 pipes should absorb more power 　 　 　This is because all 　RF　 are considered 　 in the 　 context of this 　 application. During the cooling 　 time 　 separate 　 series 　 two 　 or more 　 pulses 　 adopt energy 　, during 　 adding energy 　 　 the above 　 containers 　 cooling, 　 　 for a short period of time 　 applied thinner and 　 　 selected more coating By selecting the 　 frequency of 　 applied 　 coating 　 and/or 　 each 　 energy 　 applied 　 steps 　 with 　 time and 　 together, 　 one 　 or more 　 coatings to be removed 　 or twisting or distorting 　 by applying For example, during 　process 　continue supplying 　, 　 1 　 milliseconds 　 　 　 　 　 　 　 milliseconds 　 　 operation 　 interrupting 　 duty and water cycle 　 　 power is used After that, 　 between pulses 　 continues 　 according to the flow, 　 process 　 gas is 　 refrigerant. Readjusted for another alternative is replicator (power applicator) to a power source by limiting the plasma was added to the magnet, and the effective power epeulrikeyisyeon (heating or hydraulic, as opposed to subsequent to coated undesirable, in practice, the power gradual coating) Increase 　. This 　 means 　 of the applied 　 energy 　 total 　 watts-per hour 　 more 　 more 　 coating 　 formation 　 leads to the application of energy. For example, see 　US 　 Patents 　 Nos. 5, 904, and 952　.

VII. You can use 　Oxygen 　 post-treatment of the coating 　to remove 　OＨ　moieties from the 　coating previously 　deposited 　. It is also thought that this treatment removes residual volatile organosilicon compounds or silicon or oxidizes the coating to form another SiOx.

VII. Plastic 　 basic 　 material 　 tube can be 　 preheated 　.

VII. The same 　 other 　 　 volatility 　 source of silicon 　 like hexamethyldisilazane (HMDD) could be used 　 part of 　 or 　 all of silicon. Because these 　compounds 　supply 　have 　 oxygen 　 moieties 　 　 do not have 　 　 　 go to 　 〤 　 　 supply 　 change the gas 　 solve the problem 　. One source of 　 among 　 　 moieties 　 in the ＨＭＤＳＯ-source 　 coating is 　 unreacted 　ＨＭＤSO 　 existing 　 oxygen 　 of atoms 　 at least 　 added.

VII. Composite coatings such as carbon-based coatings mixed with SiOx can be used. For example, 　reaction 　 conditions 　 change 　 supply 　 gas 　 organic silicon 　 compound 　 as well as alkanes 　 alkenes 　 or 　 alkynes and the same 　 substitution 　 or the same 　 substituting 　 or For example, see 　US 　 Patent 　 Nos. 5, 904, and 952 　 mentioned in the 　-related 　 part. ＂For example, 　If it contains 　 same as propylene 　 　 low grade 　 provides 　 carbon 　 moiety 　, and 　 deposited 　 films 　 most of the above 　 properties (light 　 transmittances 　 improves the time 　 improves 　 　 　 　 　 properties are excluded) ． However, due to the use of 　methane, 　methanol 　 or acetylene 　 due to its nature 　 silicon-in 　 films are produced. If a trace amount of 　 gaseous 　 is included 　 in the gas 　 flow 　 provides 　 nitrogen 　 moieties in the deposited 　 films 　 increases the deposition 　 speed 　 and 　 on the glass 　 responds to the change in the transmission 　 and 　 and changes the properties 　 　 and 〮 2 But the addition of nitrogen oxide in the gas stream increases the deposition rate and improves the optical properties, and tends to decrease the film hardness. "Suitable hydrocarbon gas is methane, ethane, ethylene, propane, acetylene, or can be two or more in combination of these have.

VII. Diamond-like 　 Carbon (DLC) 　 coating can be formed 　 as a deposited 　 agent 　 1 　 or 　 the only 　 coating. This can be done by changing the reaction conditions or by supplying methane, hydrogen, and helium to the 　PECVＤ　 process, for example, 　. Because these 　 reactions 　 feeds 　 have oxygen 　 do not 　, the 　ＯＨ　 moieties could not be formed. As an example, a SiOx coating can be applied on the inside of a tube or syringe barrel and an external DLC coating can be applied on the outer surface of the tube or syringe barrel. Alternatively, both SiOx and DLC coatings may be applied as a single layer or multiple layers of an inner tube or syringe barrel coating.

VII. Referring to Fig. 2, the barrier or other type of coating 90 reduces the penetration of the atmosphere and gases through the inner surface (88). Alternatively, a barrier or other type of coating 90 reduces the contact between the inner surface (88) and the contents of the container (80). The barrier or other type of coating may include, for example, SiOx, amorphous (eg, diamond-like) carbon, or a combination thereof.

VII. The arbitrary coatings described in this specification can be used to coat plastic surfaces, for example. It can also be used, for example, as a 　 barrier for gases or liquids, and optionally as a barrier for water vapor, oxygen and/or air. In addition, the 　coated 　 surface can be used 　 to prevent 　 and/or 　 chemical 　 effects 　 for 　 compounds 　 or 　 compositions 　 if the surface is 　 not coated 　For example, 　insulin 　precipitation 　 or 　 blood 　 coagulation 　 or 　 platelets 　 activation 　 or a compound 　 or a composition of 　prevention 　 preventing or reducing 　.

VII.A. Coated 　 containers

The coatings described herein are 　 made of plastic 　 or glass 　 can be applied in various 　 containers, most notably 　 plastic 　 tubes and 　 syringes. 1 to 5000 nm, or from 10 to 1000 nm, or from 10 to 500 nm, or 10 to 200 nm, or from 20 to 100 nm, or from 30 to 1000 nm, or from 30 to 500 nm, or from 30 to 1000 nm, or 20 to 100 nm, or 80 to apply any one of the above-described precursor at substrate or a substrate of 150 nm thickness, and optionally cross-linking or polymerizing the coating in the PECVD process (run or the both) The process of 　 including 　 providing lubrication 　 surface 　, 　substrate, 　for example, 　injecting 　lubricating 　 coating 　 on the inside 　 of the barrel of the syringe is considered. In addition, the 　 applied 　 by the 　 process 　 is considered to be 　 new 　.

The 　 coating of 　SiwOxCyHz like 　 specified in the definition clause 　 has practicality 　 as a 　 hydrophobic 　 film. These 　 types of 　 coatings are considered to be 　 hydrophobic 　 regardless of whether they function as 　 lubrication 　 films. Compared to the corresponding 　coated or 　 uncoated 　 surface, and if the 　wetness 　 tension of the 　 surface is reduced 　, the coating 　 or 　 treatment is defined as 　＂hydrophobic 　. Thus, hydrophobicity is a function of both the uncoated substrate and the treatment.

The degree of hydrophobicity of a coating can be changed by changing its composition, properties or deposition method. For example, a coating of SiOx with little or no hydrocarbon content is more hydrophilic than a coating of SiwOxCyHz as defined in the definition clause. Generally speaking, the higher the content of the C-Hx (eg, CH, CH ₂ or CH ₃ ) moiety of the coating by weight ratio, volume ratio or molar ratio relative to the silicone content, the higher the hydrophobicity of the coating.

Hydrophobic 　 film 　 or 　 coating is 　 very 　 thin, 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 50 nm, or nm, or 　 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 　 thickness 　. Coatings up to 1000 nm, or 900 nm or so, or 800 nm or so, or 700 nm or so, or 600 nm or so, or 500 nm or so, or 400 nm or so, or 300 nm or so, or 200 nm or so, or approximately 100 nm , or 90 nm or so, or at least 80 nm or so, or 70 nm or so, or 60 nm or so, or 50 nm or so, or 40 nm or so, or 30 nm, or 20 nm or so, or 10 nm or so, or 5 nm approximately There are 　 thickness 　 　. In addition to the 　 indicated 　 minimum 　 thickness 　 one 　 one 　 　 specific 　 thickness 　 　 in addition to the 　 indicated 　 above the 　 maximum 　 thickness 　 of which 　 is obviously more than one 　

One of such 　 hydrophobic 　 layers 　 or 　 coatings 　 　 usefulness 　 　 　 in the 　 collected 　 from the blood 　, for example, 　 polyethylene 　 terephthalate 　 separated by heat 　 produced 　The hydrophobic layer 　 or 　 coating may be applied on top of the hydrophilic SiOx coating on the inner surface of the tube. The SiOx coating improves the barrier properties of the thermoplastic tube, and the hydrophobic layer 　 or 　 coating changes the surface energy of the tube tube and the blood contact surface. Hydrophobic 　 layer 　 or 　 coating can be made 　 by providing 　 selected 　 precursors 　 from the identified 　 precursors in this 　 specification. For example, the 　above 　 hydrophobic 　 layer 　 or 　 coating 　 precursor may contain 　hexamethyldisiloxane (HMDSO) or 　octamethylcyclotetrasiloxane (OMCTP) 　.

Hydrophobic 　 layer 　 or 　 coating 　 other 　 use is 　 glass 　 cell 　 manufacture 　 tube manufacture 　. The 　tube has 　a hydrophobic 　 layer 　 or 　 coating 　 on the 　 wall, 　 glass 　 the surface 　 defining 　 lumen 　, and contains citrate 　 reagent. Hydrophobic 　 layer 　 or 　 coating can be made 　 by providing 　 selected 　 precursors 　 from the identified 　 precursors in this 　 specification. For other examples, 　above 　 hydrophobic 　 layer 　 or 　 coating 　 precursor may contain 　hexamethyldisiloxane (HMDSO) or 　octamethylcyclotetrasiloxane (OMCTP). Another 　 source 　 material for the hydrophobic 　 layer is 　 following 　 formula 　 alkyl 　 trimethoxysilane.

R-Si(OCH ₃ ) ₃

Here, 　R is a hydrogen atom or an organic substituent such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkane, epoxide, and the like. In addition, combinations of two or more of these are also contemplated.

Using the aforementioned 　alkyl　trimethoxysilane　precursor, 　acid　or 　base　catalytic action　and　heating　　condensation 　precursor 　condensation (ROＨ　others 　 and other by-products can be selectively removed by crosslinking 　　　　　　　　　Polymers can be formed. For a specific 　 example 　Shimojima et. al. J. Mater. Chem., 2007, 17, 658-663 　.

In particular, a lubricating layer or the coating if the siloxane liquid organic compound at the end of the coating process, can be applied as a subsequent coating after applying the SiOx barrier coating on the inside surface 88 of the container 80 to provide a lubricous surface have.

Optionally, after the lubricity 　 film 　 or coating is applied, it may be post-cured after the PECVD process. UV- disclosed (free radical or a cation), an e-beam developed in (E- beam) and UV- and heat novel siloxane cycloaliphatic acids for curing purposes contains a column as described in (Ruby paper Chakraborty, 2008) There are 　radiation 　 hardening 　 approaches that can be used.

Another approach that provides lubricity 　 or 　 coating 　 is to use 　 lubricated 　 thermoplastic 　 containers 　 injection 　 molding 　 silicon 　 release agents (ｄｅｍｏｄｉｎｇｅｎ) For example, 　 during the molding 　 process 　 in-situ 　 heat 　 lubricity 　 layer 　 or 　 coating 　 formation 　 cause 　 reminder 　 different types 　 and 　 potential 　 　 one of which is used 　 　Or, the 　above mentioned 　monomers could be 　doped with traditional 　 brothers 　to achieve the same 　 result.

In particular, the 　 　 　 　 on the 　 inside 　 surface of the syringe 　 barrel 　 like the 　 further 　 described below 　 is considered. The surface of the syringe 　 　 lubrication 　 inside 　 surface 　 in the barrel 　 during operation 　 in the barrel 　 required to advance the plunger 　 plunger 　 active force 　 or 　 the prefilled syringe plunger pushes the plunger inside and disassembles the lubricant from the syringe plunger After being attached to the barrel, it is possible to 　to move the plunger 　 to move 　 to reduce the necessary 　 breakout 　 force 　. As described elsewhere herein, a lubricity layer or a coating may also be applied to the inner surface 88 of the container 80 to improve the adhesion of the subsequent coating of SiOx.

Therefore, the 　coating (90) may include 　coating 　 or 　 layer of SiOx and 　 layer 　 or 　 coating 　 and/or 　 hydrophobic 　 which is characterized as 　 as specified in the 　 definition clause 　. Lubricity 　 layer 　 or 　 coating 　 and/or 　 SiwOxCyHz coating 　 or 　 hydrophobic 　 layer may be deposited between the SiOx layer 　 or 　 coating and the inner surface of the vessel. Alternatively, a 　SiOx layer 　 or 　 coating may be deposited between the 　lubricated 　 layer 　 or 　 coating 　 and/or 　 hydrophobic 　 layer 　 or 　 coating and 　 inside 　 surface 　 of the container. Or, 　 can be used 　 alternately 　 between two 　 coating 　 compositions 　 or 　 progressive 　 3 or more layers 　. (1) 　 layer 　 or 　 coating and 　 (2) lubricity 　 layer 　 or 　 coating 　 and/or 　 hydrophobic 　 layer 　 can also be used 　 of SiOx.　 layer 　 or 　 coating of SiOx is 　 lubricity 　 layer 　 or 　 coating 　 and/or 　 hydrophobic 　 layer 　 or 　 the coating 　 adjacent, 　 or 　 other 　 or material 　 or at least one 　 separated 　 　 separate 　 　A layer 　 or 　 coating of SiOx may be deposited adjacent to the inner surface of the container. Alternatively, the 　lubricated 　 layer 　 or 　 coating 　 and/or 　 hydrophobic 　 layer 　 or 　 coating may be deposited 　 adjacent to the 　 inside 　 surface of the container.

SiOx and lubricity 　 layer 　 or 　 coating 　 and/or 　 on the adjoining 　 layer 　 of the 　 layer 　, 　 here 　 the other 　 measures considered 　 in the 　 definition clause 　 is a combination of SiwOx 　 specified in the 　 definition clause Gradient composites are 　lubricated 　 layers 　 or 　 coatings 　 and/or 　 hydrophobic 　 layers 　 or 　 coatings 　 and have a transition or interface of an intermediate composition between separate layers of SiOx 　 separated layers, or an intermediate material distinct layer or coating of intermediate composition between them It may be a lubricating 　 layer 　 or 　 coating 　 and/or 　 hydrophobic 　 layer 　 or 　 coating 　 and SiOx separated layers, or a single layer 　 or 　 coating that changes continuously or stepwise with a composition more similar to SiOx, while experiencing coating in a vertical direction.

In the above 　gradient 　complex, the 　gradient is 　in the direction of 　and 　can be changed. For example, the lubricity 　 layer 　 degree can be 　 coating 　 and/or 　 hydrophobic 　 layer 　 or 　 coating can be applied 　 directly 　 on the substrate 　 from the surface of SiOx and gradually changed in composition. Alternatively, the 　 composition of SiOx can be 　 applied directly 　 on the substrate 　 lubricity 　 layer 　 degree 　 coating 　 and/or 　 hydrophobic 　 layer 　 or 　 from the 　 surface of the coating 　 gradually change in composition 　. Because the 　coating of one 　composition is 　adhered to the above 　coating 　 better than the other 　, so if the 　composition adheres well, 　if the example is 　, 　 is applied to the substrate, especially if 　 is applied directly to the substrate. There is a distance of the gradient coating may further be less compatible with the substrate than the adjacent portion of the distant portions gradient coating, which to the coating characteristics are gradually changed at any point, an adjacent point in substantially the same depth in the coating are substantially the same composition It is considered that 　substantially 　 different 　 depths 　 physically 　 more 　 wider 　 parts have 　 more 　 various characteristics 　 have 　 can 　. In addition, the coating portion to form a better barrier film from the substrate or against the material transfer is to prevent the coated portion of the more distal of forming the further falling quality protection film is not contaminated with the material to be subjected paper or disturbance by the blocking It is considered that there is 　 directly 　 against the substrate 　.

The above-mentioned 　coating is 　instead of 　gradient 　, 　optional 　 of the composition 　 without substantial 　 gradient 　 between one 　 or 　 coating and 　 next 　 has a 　 rapid 　 transition 　. Such coatings are, for example, a layer or coating non-may provide gas to generate a steady-state flow in the plasma state and, given the subsequent power for the system with a short plasma discharge is produced by forming a coating on a substrate. When you try to applying the subsequent coating, even if there is a gradual transition at the interface between the gas for the transfer coating of little or no are removed gas for the next coating introduce another layer on the surface of activated plasma, and before coating of the back substrate or its outermost Or 　before forming 　 the coating 　 normal-state 　 applied.

VII.A.1.a. Exemplary 　 containers

VII.A.1.a. Referring to Fig. 2, more and more details of the containers such as (80) are shown. The 　 shown above is 　 opposite to the 　 closing end (84), and has a 　 opening (82) at the 　 one side of the 　 and generally 　 tubular. Further, the 　 above 　 container (80) has a wall 86 defining the 　 inner surface 88. An example of the above 　 container (80) is 　for medical use 　 in the laboratory 　 for 　 of the patient 　 receiving a 　 vein 　 puncture 　 sample 　 receiving 　 dead blood 　 by a specialist 　 like a tube 　 used as a regular 　 　

VII.A.1.a. The above 　 container (80) is 　for example, 　can be made of 　thermoplastic materials 　. Examples of suitable 　thermoplastic 　 materials are 　polyolefins such as 　polyethylene 　 terephthalate 　 or 　 polypropylene 　 or cyclic 　 polyolefins 　 polymers 　.

VII.A.1.a. The container 80 may be manufactured by injection molding, blow molding, machining (machining), any suitable method or other suitable means, such as produced from the stock tubing (tubing stock). The PPD can be used to form a coating on the inner surface of SiOx.

VII.A.1.a. If intended to be used as a vacuum blood collection tube, the container 80 is preferably enough to substantially withstand a substantially total internal vacuum without deformation when exposed to external pressure or atmospheric pressure, and other coating process conditions of 760 Torr There is strong 　 　. In the thermoplastic container 80, for the appropriate size and coated container 80 made of suitable material having a higher glass transition temperature than the processing temperature of the process, for example, a cylinder having sufficient wall thickness relative to its diameter and material By providing 　 a mold 　 wall (8 6) 　 these 　 characteristics 　 can be provided 　.

VII.A.1.a. Samples 　 collection 　 tubes 　 and 　 syringes and 　 medical 　 containers 　 or 　 containers are 　relatively 　 small and 　 relatively 　 thick 　 walls 　 　 not being compressed to the atmosphere 　 not compressed 　 　 　Therefore, 　 they are 　 stronger 　 than carbonated 　 drinks 　 bottles 　 or other 　 large 　 or 　 thin 　 wall 　 plastics 　 containers.　Designed for 　 use as a vacuumed 　 container 　 designed 　 sample 　 collection 　 while the tubes are 　 stored 　 are completely 　 designed to withstand 　 　 because 　 they are 　 used as a vacuum 　

VII.A.1.a. Once the vessels are fitted with their own vacuum chambers, the vessels need to be placed in a chamber without the need to place the vessels, which are usually carried out at very low pressures. There is no need to place a chamber for processing. If you make a container use it as your own vacuum chamber, you can quickly configure the processing equipment and make it faster because of the unloading and loading of the parts from the individual vacuum chambers, and the configuration is quicker. Also, for 　specific 　 examples, 　 support the device (to align the gas 　 tubes 　 and 　 other 　 devices), 　 seal the device 　 (container 　 support to be created 　 vacuum 　 to create and vacuum 　 pump) A container and a support that will move the device between processing steps and stages is considered.

VII.A.1.a. Is used as a vacuum blood collection tube container 80 without penetrating through the air or significant the volume tube does not leak to a (by bypassing the closure) while the life of the wall 86 of the other atmospheric gases, intended　Useful 　For the purpose 　Useful 　During internal 　Vacuum 　, 　External 　Atmospheric pressure 　It should be able to 　. If the above 　molded 　 container (80) 　can't meet these 　 requirements 　 can be treated 　 by coating the 　inside 　 surface (88) with 　blocking or other type of coating (90). Samples 　 collection 　 tubes 　 and 　 syringes 　 barrels 　 　 these 　 devices 　 interior 　 surfaces 　 treated / or 　 coated 　 existing 　 polymers 　 devices 　 better 　 offer advantages 　 offer a variety of products 　． In addition, it is desirable to measure the various characteristics of the devices before and/or after the treatment and/or coating or before and/or after the treatment.

More 　 　 example 　 containers are 　 syringes described here 　.

VII.A.1.b. Containers with walls coated with a hydrophobic coating

VII.A.1.b. Another example is a container containing a water-soluble sodium citrate reagent with a wall provided with a hydrophobic layer or a coating on the inside and the surface. The hydrophobic layer 　 or 　 coating may also be applied on top of the hydrophilic SiOx coating on the inner surface of the 　 container. The SiOx coating improves the barrier properties of plastic 　 and the hydrophobic layer 　 or 　 coating changes the surface energy of the contact surface of the container 　 wall 　 container 　 inside 　 composition 　 and 　 composition.

VII.A.1.b. The wall is made of a thermoplastic material with an inner surface defining a lumen.

VII.A.1.b. The vessel according to Example VII.A.1.b was applied as described herein, acting as an oxygen barrier and extending the life of the vacuumed blood collection tube made of thermoplastic material, on the inner surface of the tube. The first layer of SiOx may have a 　 or 　 coating. Like the 　 specified in the definition clause 　characterized, 　hydrophobic 　 layer 　 or 　 coating 　 on the inside 　 surface of the container 　 blocking 　 film 　 or 　 coating 　 on the surface 　 can be applied 　 hydrophobic 　In the blood collection tube or syringe, the coating is selectively effective in reducing platelet activation in plasma exposed to the inner surface and treated with a sodium citrate additive, compared to an uncoated wall of the same type.

VII.A.1.b. PECVD is used to form a hydrophobic 　 layer 　 or 　 coating on the inner surface. Unlike conventional citrate blood collection tubes, a blood collection tube with a hydrophobic layer, such as defined here, requires a baking coating on silicone on the vessel wall, such as conventionally applied to make the surface of the tube hydrophobic. Do not.

VII.A.1.b. For example, 　ＨＭＤSO　 or 　OMCTS and the same 　 same 　 precursor 　 and 　 different 　 　 　 　 　 can also be applied to the conditions of the reaction 　 　 　 both sides.

VII.A.1.b. When a blood 　 collection 　 tube 　 or 　 a syringe 　 is prepared 　, a citrate 　 sodium 　 anticoagulation 　 a reagent 　 is placed in a tube 　 　 can be collected 　 and the tube is sealed and vacuum collected and vacuumed and the tube is collected and vacuum 　 　 　 　 　 　The 　 constituents 　 and 　 formulation of the above 　reagents 　 are notified to the relevant companies. 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. SiOx barrier coated double-walled plastic container-COC, PET, SiOx layers

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

VII.A.1.c. The walls comprise an oxygen barrier 　 or 　 coating of SiOx having a thickness of about 10 to about 500 Angstroms.

VII.A.1.c. In one embodiment shown in Fig. 36, the 　 container (80) has 　respectively 　 made of the same 　 or different 　 materials 　 internal 　 wall (408) 　 and 　 outer 　 wall (40 days). Embodiments of this type one specific example Poly such as the inner surface 412 of one wall and a polyethylene terephthalate (PET) molded into SiOx copolymer (COC), cyclic olefin with a coating as described earlier with respect to It can be made from esters 　 molded 　 other 　 walls 　. If necessary, 　 tie 　 coating 　 or 　 layer 　 or 　 coating can be inserted 　 between inside 　 and 　 outer 　 walls 　 to promote 　 adhesion between them. The advantage of this 　wall 　 structure 　 is that 　 walls with different 　 characteristics 　 can be combined 　 with 　 individual 　 characteristics of each 　 wall 　 can form a complex.

VII.A.1.c. As an example, the inner wall 408 may be made of PET coated on the inner surface 412 with a SiOx blocking film, and the outer wall 410 may be made of COC. As shown elsewhere in this specification, PET coated with SiOx is an excellent oxygen barrier, while COC is an excellent barrier against water vapor, providing a low water vapor transmission rate (WVTR). These 　composites 　 containers 　 have excellent 　 barriers 　 properties 　 can be 　 oxygen 　 and 　 water vapor 　 both. This structure is, for example, as manufactured, and containing a water-soluble reagent and investigated with respect to the medical sample collection tubes vacuum having a practical life, therefore, the tube is outside the water vapor through the composite wall while maintaining its service life A barrier must be provided to prevent 　 from transmitting 　 or 　 oxygen 　 or other 　 gass 　 internally 　.

VII.A.1.c. As another example, the inner wall 408 may be made of COC coated on the inner surface 412 with a SiOx blocking film, and the outer wall 410 may be made of PET. This 　 structure is considered 　 for example 　 manufactured 　 bar and 　 containing 　 water-soluble 　 sterilization 　 fluid 　 pre-filled 　 syringe. The SiOx barrier will prevent oxygen from entering the syringe through the wall. The interior 　 wall prevents 　 inflow 　 or 　 outflow of 　 water and 　 same 　 or 　 outflow, 　 reminder 　 water soluble 　 sterilization 　 　 in the fluid 　 prevents the 　 water from 　 trapped substances 　 　 　 　 　In addition, the COC inner wall of the water the syringe to prevent the passage out (the concentrating as much as you do not want to aqueous sterile fluid) into consideration, and the syringe outer non-sterile water or other fluid derived from said aqueous sterile fluid It will prevent 　 from entering 　 into the syringe 　 and 　 the above 　 contents are 　 not sterilized 　. In addition, the 　COC　inner 　wall is considered to be useful for 　reducing 　braking 　 force 　 or 　 friction of the plunger 　 against the 　 inner 　 wall of the syringe.

VII.A.1.d. How to make a double-walled plastic container-COC, PET, SiOx layers

VII.A.1.d. Another 　 embodiment is a method of making a container having an outer polymer layer, one layer made of COC, or a walled container with a coating 　 and another layer made of polyester 　 or an inner polymer layer surrounded by a coating 　 or 　 coating. The container is made by a process comprising introducing layers of COC and polyester resin 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 a PPD 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 that SiOx is defined as before and a SiOx barrier layer or a coating is applied to the interior of the vessel wall. Another optional additional step is the post-treatment of the SiOx film 　 or 　 coating with a process gas 　 or 　 gas 　 reactant which is essentially composed of oxygen and does not contain volatile silicon compounds.

VII.A.1.d. Optionally, the SiOx coating may be formed at least partially from a silazane feed gas.

VII.A.1.d. The container 80 shown in FIG. 36, for example, the later the first injection the interior wall of the forming cavity-forming and moving the center and the inner wall forming since from the first molding cavity with larger molding cavity of the second E, 　 above 　 　 2 　 molding 　 cavities 　 inside 　 inside 　 wall 　 external 　 by molding 　 inside 　 outside 　 can be made. Optionally, the 　 tie layer 　 or 　 coating may be provided on the 　 above 　 tie layer 　 outer 　 wall 　 transition 　 pre-molded 　 molded 　 inner 　 wall 　 outer 　 surface 　

VII.A.1.d. Further, the container 80 shown in FIG. 36, for example, the first center from the first core is inserted, and injection molding an outer wall in the molding cavity and, after the forming the first wall of the molding cavity After removal 　 size 　 smaller 　 production 　 2 　 center 　 inserted 　, 　 above 　 molding 　 cavities 　 still 　 remaining 　 outside 　 wall 　 by molding from the outside 　 outside 　 to be produced from inside 　 　Optionally, the 　 tie 　 layer 　 or 　 coating may be provided on the surface 　 on the 　 tie 　 layer 　 inner 　 wall 　 over-molding 　 prior to 　 molded 　 outer 　 wall 　 inside 　 surface

VII.A.1.d. In addition, the 　 container (80) shown in 　 also 　36 can be made with 　2　 shots 　 molds 　. This is 　for example, 　inside 　 from nozzle 　 top 　 inner 　 wall 　 material 　 and 　 top 　 outer 　 wall 　 material 　 concentric circles 　 outer 　 molding from the nozzle 　 injection 　Optionally, the 　 tie 　 layer 　 or 　 coating may be provided 　 from the 　 concentric 　 nozzle 　 placed between the top 　 inner 　 and 　 the lowest 　 nozzles 　The above 　 nozzles can supply 　 each 　 wall 　 materials 　 at the same time 　. One useful 　 means is 　inner 　 wall 　 supplying material 　 inside 　 wall 　 supplying material 　 just before 　 external 　 through nozzle 　 external 　 wall 　 supplying material 　 starting 　. If there is an intermediate substance 　 concentric circle 　, the order 　 flow 　 starts with 　 external 　 nozzle 　 and continues with intermediate material 　 nozzle 　 after 　 internal 　 nozzle 　 start 　. In addition, 　supply 　 start 　 order 　 compared to the previous 　 description 　 in reverse 　 order, 　 inside 　 starting from the nozzle 　 outward 　 can work.

VII.A.1.e. Coated 　 or 　 container made of glass

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

VII.A.1.e. Also, the 　container (80) can be used 　 as a 　 used as a 　 for a 　 or a type of 　 used in 　 for soda 　 lime 　 glass, 　 borosilicate 　 glass 　 or 　 other 　 glass 　 formulations 　 optional. In addition, it is considered that 　any 　 material 　 manufactured 　 arbitrary 　 shape 　 or 　 size 　 other 　 containers 　 will be used in 　 system (20). Reducing the ion influx in one feature of glass as an impurity, such as in a blood collection tube vacuum from the glass into the contents of the container, such as a reagent or blood, purpose or, for example, sodium, calcium to coat the glass containers It means that there are 　cans 　. Like on surfaces that are in sliding contact with other parts, due to the different function of coating the whole or part of a glass 　 container 　 provides lubricity 　 to the coating 　, for example, 　 insertion or removal of a stopper, or 　 of sliding components such as pistons in a syringe 　To facilitate passage. The reason for 　 coating a glass 　 container 　 and another 　 is like 　 reagent 　 or 　 blood 　, 　 intended for 　 containers 　 intended 　 samples 　 above 　 　 to the wall of the vessel 　 and the speed of adhesion to the walls 　 and the 　 and the 　 to prevent blood from contacting 　 　

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

VII.B. Syringes

VII.B. The previous 　 explanation is 　usually 　blood 　 collection 　 tube 　 or 　 more 　 generally like 　 sample 　 reception 　 tube (80) 　 one side 　 end 　 permanently 　 closed 　 closed 　 closed 　 closed 　The device is not 　limited to such 　device.

VII.B.　Other examples of 　appropriate 　containers 　shown in Tokyo 　20 are 　medical 　syringes (252) 　 syringes 　 barrels (250). Such 　syringes (252) are supplied pre-filled 　for medical 　technology 　used 　sometimes 　saline, 　pharmaceutical 　 formulations 　 etc. In addition, the prefilled syringes 252 have the inner surface of the prefilled syringe 252 so that the contents of the syringe 252 do not come 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 SiOx barrier or other type of coating. Barrier or other types of coatings can be used to avoid the discoloration of the constituents of the plastic through the inner surface (254) and the contents of the barrel.

VII.B. In general, the molded 　injector 　barrel (250) receives 　 plunger (258) 　 rear end (26) 　 and 　 subcutaneous 　 injection, nozzle 　 or 　 　 receives the contents of the syringe 　 2 　 and dispenses the contents of the syringe 　26) 　Can be opened 　 on both sides 　. However, the 　shear (260) can be 　optionally 　can be capped 　, and the plunger (258) is 　optionally 　 above 　 pre-filling 　 syringe (252) is used 　 fits both sides and closes both sides 　 　 closes 　 5 　have. The cap is 　above 　 cap (262) is removed 　 (optionally) 　 avoid 　 injection 　 or 　 other 　 delivery 　 channel 　 on the front end (260) 　 the above 　 syringe 　 until it is used for the purpose of using the 　 2 　 2 weeks Or it can be installed to keep the assembled syringe in place while the prefilled syringe (252) is stored for the purpose of processing the assembled syringe.

Other 　appropriate 　 containers are 　201 years 　 May 　11 days 　 filed 　PCT/US11/36097 and 2010 　Jun 　28 　 filed US61/359,434, 　 described in。 and attached examples It is a syringe 　＂ studded 　 needle 　 syringe.

VII.B. Syringes

VII.B. The previous 　 explanation is 　usually 　blood 　 collection 　 tube 　 or 　 more 　 generally like 　 sample 　 reception 　 tube (80) 　 one side 　 end 　 permanently 　 closed 　 closed 　 closed 　 closed 　The device is not 　limited to such 　device.

VII.B.　Other examples of 　appropriate 　containers 　shown in Tokyo 　20 are 　medical 　syringes (252) 　 syringes 　 barrels (250). Such 　syringes (252) are supplied pre-filled 　for medical 　technology 　used 　sometimes 　saline, 　pharmaceutical 　 formulations 　 etc. In addition, the prefilled syringes 252 have the inner surface of the prefilled syringe 252 so that the contents of the syringe 252 do not come 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 SiOx barrier or other type of coating. Barrier or other types of coatings can be used to avoid the discoloration of the constituents of the plastic through the inner surface (254) and the contents of the barrel.

VII.B. In general, the molded 　injector 　barrel (250) receives 　 plunger (258) 　 rear end (26) 　 and 　 subcutaneous 　 injection, nozzle 　 or 　 　 receives the contents of the syringe 　 2 　 and dispenses the contents of the syringe 　26) 　Can be opened 　 on both sides 　. However, the 　shear (260) can be 　optionally 　can be capped 　, and the plunger (258) is 　optionally 　 above 　 pre-filling 　 syringe (252) is used 　 fits both sides and closes both sides 　 　 closes 　 5 　have. The cap is 　above 　 cap (262) is removed 　 (optionally) 　 avoid 　 injection 　 or 　 other 　 delivery 　 channel 　 on the front end (260) 　 the above 　 syringe 　 until it is used for the purpose of using the 　 2 　 2 weeks Or it can be installed to keep the assembled syringe in place while the prefilled syringe (252) is stored for the purpose of processing the assembled syringe.

Another 　appropriate 　syringe is 　2011 years 　 May 　11 days 　 filed 　PCT/US11/36097 and 2010 　 June 　28 days 　 filed in US 　61/359,434, which was added from 　 explained. This is a 　with a 　syringe 　＂ a studded 　needle 　syringe.

Generally, when the syringe barrel is coated, a PECVD coating method described herein is a coated substrate surface, some or all of the inner surface of the barrel, the gas for the PECVD reaction fills the interior lumen of the barrel plasma inside the lumen of the barrel It is performed to be created in some or all of the 　.

VII.B.1.a. Lubricity 　 Coating 　 Coated 　 Barrel 　 Syringe

VII.B.1.a. These 　 types of 　 lubricity 　 coatings 　 with 　 can be manufactured by the 　 following 　 process.

VII.B.1.a. Like the 　 defined 　 　 above, a 　 precursor is provided.

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 lubricating surface with a lower plunger force or breakout force than an untreated substrate.

VII.B.1.a. Examples 　 one of 　 　 　 or 　 sub-parts 　 for each, 　 selectively 　 application 　 step is performed by evaporating the 　 above 　 precursor and providing it near the substrate.

VII.B.1.a. Plasma is formed near the substrate. Optionally, the 　the 　 precursor is provided in the substantially absence of 　 nitrogen. Optionally, the 　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 1 to 5000 nm, or 10 to 1000 nm, or 10 to 　 500 nm or 10 to 200 nm or 　20 to 　 100 nm or 　 30 to 　 10 nm　 or 　 30 to 　 100 nm or 　 30 to 　 100 nm or 　 30 or 50 nm to 1000 nm, or 30 to 50 nm Alternatively, it may be applied at an average thickness of 20 to 100 nm, or 80 to 150 nm. Optionally, the 　above 　substrate contains 　glass. Optionally, 　substrate is 　polymer, optionally polycarbonate polymer, optionally 　olefin polymer, optionally 　cyclic olefin copolymer, optionally 　 polypropylene polymer, optionally 　 polyester polymer, optionally 　 polyethylene terephthalate It contains a polymer. The COC is considered especially for the 　syringe 　 and 　syringe 　 barrel.

VII.B.1.a. Optionally, the plasma is, for example, at an RF frequency as defined above, for example, at a frequency of 10 kHz to less than 300 MHz, optionally 1 to 50 MHz, alternatively 10 to 15 MHz, and optionally 13.56 MHz. It is generated by applying electric power to a gaseous reactant including the precursor using electrodes that receive electric power.

VII.B.1.a. Plasma is optionally supplied with power of 0.1 to 25 W, alternatively 1 to 22 W, selectively 　 3 to 　 1７W, and more than 　 selectively 　 5 to 14 W, optionally 7 to 11 W, and optionally 8 W　 is generated by applying 　 energy 　 to the 　 gas 　 reaction 　 material containing 　 precursor 　 using the electrodes. The ratio of power to plasma volume is 10 W/ml, optionally 6 W/ml to 0.1 W/ml, optionally 5 W /ml to 0.1 W/ml, optionally 4 W/ml to 0.1 W/ml, optionally less than 　2 W/ml to 0.2 W/ml 　. Low 　 power 　 level is 　 lubricity 　 coating 　 preparation 　 the most 　 advantage 　 (for example, 　2 to 3. 5Ｗ 　 power 　 level and 　 given power in the example) These power levels are suitable for applying lubricating layers to syringes and sample tubes and vessels of similar shape with a void volume of 1 to 3 mL in which the PPD plasma is generated. It is believed that for larger or smaller objects the applied power will increase or decrease as the process scales with respect to the size of the substrate.

VII.B.1.a. Another example is a lubricating coating of the present invention on the inner wall of a syringe barrel. The coating is produced from the PECVD process using the following materials and conditions. Optionally, the 　cyclic 　 precursor is selected from 　 monocyclic siloxane, polycyclic siloxane, or a combination of two or more of these 　 for lubricity 　 layers 　 as defined 　 somewhere 　 in the specification 　. Examples of suitable 　cyclic precursors include 　optionally 　with other 　precursors　substances 　mixed at any ratio 　　 octamethylcyclotetrasiloxane (OMCTS). Optionally, the cyclic 　 precursor is 　 indispensably composed of octamethycyclotetrasiloxane (OMCTS) 　, which is 　 produced 　 　 lubricity 　 layer 　 basic and 　 new 　 cladding properties 　 or the surface activity 　 or Like decrease and 　, it means 　 that 　 can exist 　 in a quantity that does not change 　.

VII.B.1.a. Sufficient 　plasma 　 generation 　 power 　 input, 　 for example, 　 in the original 　 specification 　 one 　 or more 　 in working examples 　 successfully used 　 or 　 in this specification 　 provided 　 to induce the formation of a coating 　 provided

VII.B.1.a. Here, the materials and conditions employed in at least about 25% against the syringe plunger active force or break-out force to move through the syringe barrel to an uncoated syringe barrel, or at least 45%, or at least 60%, or decreases by more than 60% It is effective in ordering. 20　to 　９5　%, 　or 　30　to 　80　%, 　 or 　40　 to 　7 5　%, 　 or 　60　 to low 　　 　 　 　 　 　 　

VII.B.1.a. Another 　 embodiment is 　inside 　 on the wall, 　 in the definition clause 　 as defined 　 as 　 　 characterized 　 with a hydrophobic layer 　: the coating is similar 　 composition 　 lubricants 　 made in contact with the substrate, but not as described It is manufactured under the conditions that are effective in forming a hydrophobic surface with 　.

VII.B.1.a. Optionally, the 　above 　substrate contains 　glass 　 or 　polymer. Optionally, 　 above 　 glass is 　 borosilicate 　 glass. The 　polymer is 　optionally a polycarbonate polymer, optionally 　olefin polymer, optionally 　cyclic olefin copolymer, optionally 　polypropylene polymer, optionally 　polyester polymer, optionally 　polyethylene terephthalate polymer.

VII.B.1.a. Another embodiment is a syringe comprising a plunger, a syringe barrel and a lubricity layer. The syringe barrel has an inner surface that slides and receives the plunger. The lubricity layer 　 or 　 coating is provided on a part 　 or 　 of the inner surface of the syringe barrel. The lubricating layer 　 or 　 coating 　 can optionally be less than 1000 nm thick and can be effective in reducing the breakout force or plunger activating force required to move the plunger within the barrel. Also, the 　 plunger 　 　 reduction in the 　 barrel 　 　 of the plunger 　 glide 　 friction 　 coefficient 　 decrease 　 or 　 plunger 　 force 　 reduction 　 is expressed as 　 　 terms are referred to as 　.

VII.B.1.a. The syringe (544) includes a 　 plunger (54 6) 　 and a syringe 　 barrel (548). The syringe 　 barrel (548) has a 　 plunger (54 6) 　 slides 　 receives 　 inside 　 surface (52). In addition, the inner surface (552) of the syringe barrel (548) includes a lubricity layer or a coating (5554). The lubricating layer or coating 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, is less than 50 nm thickness, adhesion of the plunger after storage It is effective in reducing the plunger force required to move the plunger within the barrel after the breakout force or the plunger or after the active force is released. Lubricity 　 layer 　 or 　 coating is characterized as 　 uncoated 　 surface 　 plunger 　 active force 　 or 　 breakout 　 force 　.

VII.B.1.a. One of the 　 types of 　 one can be used alone 　 or in a combination of two or more of these 　 to provide 　 lubricity 　 layer.

VII.B.1.a. In addition to utilizing a vacuum process, a low temperature air (non-vacuum) plasma process also optionally non such as helium or argon may be utilized to derive the molecule ionization and deposition through the precursor monomer vapor transmission in an oxidizing atmosphere. In addition, 　heat 　CVD can be considered 　 by flash (ｆｌａｓｈ) 　 pyrolysis 　 deposition 　.

VII.B.1.a. The above 　 approaches are similar to 　 surface 　 coating 　 and 　 cross-linking 　 mechanisms can occur 　 at the same time 　 　 vacuum 　 PECVD.

VII.B.1.a. In this 　 specification 　 arbitrary 　 coating 　 or 　 for coatings considered 　 and other 　 means 　 inside of the container (8 8) 　 not evenly applied over the entire 　. For example, in 　closed end (84), 　in the container 　 in comparison with the 　 semicircle 　 part, and 　 different or different 　 coating 　 inside the 　 cylinder type 　 can be included in the container 　, or may be selectively enclosed in the 　 part. This means that is not provided with a lubricous surface for some or all of the cylindrical part of the barrel to a plunger or piston sliding closure is provided somewhere, and in particular consideration with respect to the syringe barrel or the sample collection tubes as described below.

VII.B.1.a. Optionally, the 　above 　precursor could be provided in the presence of 　nitrogen and 　substantially absent 　 or 　absent 　. In the contemplated 　 one 　 embodiment, 　precursor 　 holo 　 transferred to the substrate, passed through 　 PECVD 　 coated 　 and hardened.

VII.B.1.a. Optionally, the 　precursor could be provided at an absolute pressure less than 　1 Torr.

VII.B.1.a. Optionally, the precursor can be provided near the plasma emission.

VII.B.1.a. In any one of the embodiments, the substrate is a glass or a polymer, for example, a polycarbonate polymer, an olefin polymer (for example, a cyclic 　 olefin 　 copolymer 　 or a polypropylene 　 polymer), 　 or 　 polyester polymer (for example, It may contain more than one 　 of polyethylene terephthalate polymer).

VII.B.1.a. In one of the above 　 examples 　, 　plasma is 　as defined in this specification 　as and 　 at the 　 frequency 　 powered 　 electrodes 　 using the 　 power-supplied 　 electrodes 　 generating electric power to the reacting material 　

VII.B.1.a. In one of the above 　 examples 　, 　plasma produces 　 lubricity 　 layer 　 with enough 　 electric power 　 supplied 　 electrodes 　 using 　 above 　 precursors 　 containing 　 gas 　 generated 　 to the reaction material Plasma is optionally 0.1 to 25 W, alternatively 1 to 22 W, selectively 　3 to 　17W, 　and more selectively 　5 to 14 W, for example 　6　 or 　７．5W, optionally 7 to 11 W, Optionally, it is generated by applying 　energy 　 to the 　 gas 　 reaction 　 material containing the precursor 　 using electrodes supplied with electric power of 8 W. The ratio of power to plasma volume is 10 W/ml, alternatively 6 W/ml to 0.1 W/ml, 　 Optionally 4 W/ml to 0.1 W/ml, Optional 4 W/ml to 0.1 W/ml, Optionally 3 W/ml to 0.2 W/ml, Optionally 　 2 W/ml to 0.2 There are 　 smaller than W/ml 　. Low 　 power 　 level is 　 lubricity 　 coating 　 preparation 　 the most 　 advantage 　 (for example, 　2 to 3. 5Ｗ 　 power 　 level and 　 given power in the example) These power levels are suitable for applying lubricating layers to syringes and sample tubes and vessels of similar shape with a void volume of 1 to 3 mL in which the PPD plasma is generated. It is believed that for larger or smaller objects the applied power 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 performing the above coatings by polymerizing or cross-bonding both coatings to form a lubricating surface with lower plunger action or breakout forces than the untreated substrate. Hardening can occur during 　 application 　 process 　 like 　 PECVD 　, or it can be performed by other 　 treatments, or at least it can be completed.

VII.B.1.a. Although were used to show them herein plasma deposition a coating characterized in, the chemical composition of the starting while still desorb a solid film attached to the base substrate material can be employed a different deposition process is preserved as much as possible.

VII.B.1.a. For example, 　 coating 　 material 　 coating 　 spraying 　 substrate 　 coating 　 pure 　 precursor 　 or 　 solvent-diluted 　 electric bulb 　 coating 　 　 　 from the vaporized state 　 　 by applying a thin film 　 　It can be done. Preferably, the 　the 　 coating is 　heat 　 energy, 　ＵV 　 energy, 　 electron 　 beam 　 energy, 　 plasma 　 energy 　 or 　 using 　 arbitrary combination of 　 and can be cross-coupled 　

VII.B.1.a. In addition, it is also considered to apply 　 silicon 　 precursor 　 on the surface 　 and then perform a separate 　 hardening 　 process 　 like the 　bar and 　 described above. The conditions of application 　 and 　 curing 　 are similar to the conditions used 　 for pre-coated 　 polyfluoroalkyl 　 ethers 　 used under the trademark 　TriboGlide® 　You can find more information about this process at http://www.triboglide.com/process.htm.

VII.B.1.a. In such a 　 process, the 　 part of the 　 coated part could be 　 optionally 　 atmospheric pressure 　 plasma 　 pre-processed 　. This 　 pre-treatment 　 in the next 　 step 　 sprays 　 　 so as to be immersed in the 　 lubricant 　 cleans and activates the surface.

VII.B.1.a. If any of the above 　 precursors 　 or 　 polymerized 　 precursor chain 　, the lubricating 　 fluid is 　 and then 　 treated 　 sprayed onto the surface. For example, 　IVEK　precision 　 distributing 　 technology can be used to precisely spray the fluid and create a uniform coating.

VII.B.1.a. After 　above 　coating 　again 　atmospheric pressure　plasma 　 use 　, 　to the parts 　 or cross-coupled. All of these 　coatings 　fixed and 　 improved the performance of the lubricant.

VII.B.1.a. Optionally, 　atmospheric pressure 　 plasma 　 in the container 　 　 surroundings 　 from the air 　 water 　, in this case 　 gas 　 supply and 　 vacuum 　 extraction 　 equipment is not required. However, 　optionally 　 during 　 being generated 　 the container 　 at least 　 practically 　 closed to 　 power demand 　 minimizing 　 container 　 external 　 surface 　 or 　 preventing contact with substances 　.

VII.B.1.a.i. Lubricity coating: SiOｘ blocking, 　 lubricity 　 layer, 　 surface treatment.

Surface treatment

VII.B.1.a.i. Another 　 embodiment is 　 comprising a barrel 　 defining a lumen 　 and accommodating the plunger 　 slidable 　, that is, 　 inner 　 surface and 　 sliding 　 contacting 　 plunger 　 internally 　

VII.B.1.a.i. The above 　 syringe 　 barrel can be made of 　 thermoplastic 　 series 　 materials 　 can be made.

VII.B.1.a.i. Optionally, the inner surface of the barrel is coated with a SiOx barrier film or a coating as described elsewhere herein.

VII.B.1.a.i. A lubricating layer 　 or 　 coating is applied to 　 all 　 or part of the inner surface of the barrel, on the plunger or both, or on the SiOx barrier layer previously applied. Lubricity 　 layer 　 or 　 coating can be 　 provided, 　 applied and 　 hardened 　 as described 　 somewhere in the examples 　 VII.B.1.a 　 or 　 this 　 specification.

VII.B.1.a.i. For example, the lubricity layer 　 or 　 coating may be applied by 　 PECVD in any 　 embodiment. The 　 lubricity 　 layer 　 or 　 coating is deposited from 　organic silicon 　 precursor, and has a thickness of less than 　1000　 nm　.

VII.B.1.a.i. Surface 　 treatment is 　 above 　 lubrication 　 layer, 　 top 　 thermoplastic 　 series 　 material 　 or 　 both 　 　 filtering or 　 extractable 　 reducing 　 effective 　 amount 　 or the amount of coating 　 above 　Therefore, the 　 treated 　 surface can 　 act as a 　 solute 　 retainer. These 　surface 　 treatments are 　skin 　 coatings, such as at least 　1　nm　thickness 　and 　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 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, you can get a 　skin 　 coating.

VII.B.1.a.i. In this 　 specification, the 　 ＂filtration 　 is from the 　 container 　 wall and the same 　 substrate 　, the same as the syringe and the 　 contents of the container 　 transfers 　 material. Normally, 　filterables are 　intentional 　 contents 　 store 　, and after 　 　 above 　 contents 　 analysis 　 above 　 container 　 from the wall 　 intended 　 contents 　 in 　 what 　 material is measured. ＂Extraction 　 is 　 in terms of conditions 　 　 from the substrate 　 from the substrate 　 to the medium 　 to determine what 　 substances will be removed 　 can be removed 　 by removing 　 from the container 　 or the contents of the dispersing 　

VII.B.1.a.i. The surface treatment performed by the solute retainer may optionally be a 　specified as defined in the definition clause 　, a hydrophobic 　 layer 　 or 　 in this specification 　 previous 　 specified 　 bar and 　 same 　 SiOx layer 　 or 　. In one embodiment, the surface treatment may be applied by the deposition of the 　SIOｘ　 or the 　hydrophobic 　 layer 　. Selectively provides said surface treatment lubricating layer is further applied by using both the high-power or strong oxidizing conditions, or both, than is used for generating, hardness is stronger, thinner continuous solute retainer 539 can do. The surface treatment is less than 100 nm depth from the lubricating layer, and optionally less than 50 nm deep, optionally less than 40 nm deep, optionally less than 30 nm deep, optionally less than 20 nm deep, optionally less than 10 nm deep ，　Selectively 　5　nm　 depth 　, 　optionally 　3　nm　 depth 　, 　optionally 　1　nm　 depth 　nm　 depth 　nm　 depth 　nm　 depth 　nm　 selectively less than 10　　　　n.

VII.B.1.ai The solute retainer is contemplated to provide basal lubricity and low solute filtration performance for other layers, including the substrate, as needed. This retainer may contain large sized solute molecules and oligomers (e.g., HMDSO, OMCTS, fragments thereof and siloxane monomers such as mobile phase oligomers derived from lubricants, e.g., "filterable retainer") It needs to be a solute retainer for and does not have to be a gas (O ₂ /N ₂ /CO ₂ /water vapor) barrier. However, the solute retainer may also be a gas barrier film (eg, the SiOx coating according to the present invention). A good filterable retainer can be produced without gas barrier performance by vacuum or atmospheric pressure-series PECVD processes. The “filterable barrier” is sufficiently thin, so when the syringe plunger moves, the plunger easily penetrates the “solute retainer” and exposes the sliding plunger nipple just below the lubricating layer or coating, resulting in lower plunger activity or brake than the untreated substrate. It forms a lubricating surface with out force.

VII.B.1.a.i. In another 　 embodiment, 　surface treatment could be performed by 　exposing the 　 surface 　 in a plasma 　 environment 　 to oxygen 　 previously applied 　 lubricating 　 　 oxidizing the surface of the layer. The plasma environment to form the SiOx coating described herein can be used. In addition, 　atmospheric pressure 　plasma 　 conditions 　can be employed in 　 oxygen-rich 　 environments.

VII.B.1.a.i. Even if it is formed, the 　 lubricity 　 layer 　 or 　 coating 　 and 　 solute 　 retainer can be 　 selectively 　 simultaneously 　 hardened. In another 　 embodiment, the 　lubricated 　 layer 　 or 　 coating is 　 at least 　 partially 　 cured, 　 selectively 　 completely 　 hardened, 　 hardened 　 after 　 surface 　 treatment 　 provided, 　 applied water, can be applied

VII.B.1.a.i. The lubricating layer 　 or 　 coating and solute retainer is constructed and present in a relative amount effective to provide a breakout force, plunger actuation force, or both lower than the corresponding force required in the absence of the lubricating layer 　 or 　 coating and surface treatment. . That is, the 　 solute 　 retainer's 　 thickness 　 and 　 composition is 　 below 　 　 lubrication 　 layer 　 or 　 coating during 　 lubricating the plunger 　 　 lubricating 　 layer 　 or the content of the filter 　 from the coating The solute 　 retainer is 　 easy 　 　 　 if the plunger moves 　 　 lubrication 　 layer 　 or 　 coating still 　 function 　 plunger 　 lubricates 　 thin enough 　.

VII.B.1.a.i. In the 　 days 　 examples considered, 　 lubricity 　 and 　 surface 　 treatment can be applied 　 on the barrel 　 inner 　 surface. In other examples considered, the lubricity and surface treatments can be applied on the plunger. In the 　 and other 　 examples considered, 　 lubrication 　 and 　 surface 　 treatment can be applied 　 on the barrel 　 inner 　 surface and 　 on the plunger. Among these 　 examples 　 　 in one 　, 　 on the inside of the syringe 　 barrel 　 optional 　SIo 　 blocking 　 layer 　 or 　 coating 　 present or absent 　

VII.B.1.a.i. One example of 　 to be considered is 　multilayer, 　for example, 　inner 　 of the barrel 　 applied on the 　 composition 　3 middle 　. Layer 　 or 　 coating (1) is 　oxidation 　 at atmospheric pressure 　ＨＭＤSO, 　ＯＭCＴS　 or 　 both sides 　 　 ECVD 　 manufactured 　SI water 　 　 　 　Such a 　 atmosphere can be provided by supplying 　 and 　 oxygen 　 gas to the 　 PECVD coating 　 described in the 　 specification 　, for example. Layer 　 or 　 coating (2) is 　 non-oxidation 　 in the atmosphere 　 applied 　OMCTS 　 　 lubricity 　 layer 　 or 　 coating work 　 can be. Such 　non-oxidation 　 atmosphere 　, for example, 　as described in the 　 specification 　 　 coating 　 equipment can be 　 selectively supplied with 　 　 substantially completely by supplying 　 　 or the absence of 　 　 practically 　The subsequent solute retainer can be formed as a solute retainer with oxygen and higher power using OMCTS and/or HMDSO, by treatment to form a thin 　 surface 　 layer 　 or 　 coating of SiOx or a hydrophobic 　 layer 　 or 　 coating.

VII.B.1.a.i. Specific 　 these 　 multi-layered 　 or 　 coatings are considered to have 　 at least 　 some degree 　 following 　 optional 　 advantages 　 one or more 　. The solute retainer may define an internal silicon and cross between and prevented from moving to the contents, or somewhere in the syringe, the contents of the transmitted and to have less presence of silicon particles the possible contents lubricating layer or coating and a syringe of the injector action Since the chances for 　 will be reduced 　, 　 they are 　 dealing with silicon 　 so 　 reported 　 difficult 　 　 can be solved 　. Also, 　can solve the problem 　to move the coating 　 further 　 or 　 from the lubrication point 　 lubrication 　 layer 　 or 　 improve the interface between the syringe 　 barrel 　 and the plunger 　. For example, 　brake 　 free 　 force can be reduced 　 can 　 and 　 can reduce 　 pull on a moving 　 plunger 　 　 can 　 or 　 selectively 　 both 　 can be reduced 　

VII.B.1.a.i. If the solute 　retainer 　 breaks 　, the solute 　 retainer 　continuously 　 lubricity 　 layer 　 or 　 coating 　 and 　 syringe 　 barrel 　 attached to the 　 content, and 　 particles are 　 capable of conveying 　 to contain

VII.B.1.a.i. In addition, 　 these 　 specific 　 coatings 　 in particular 　 blocking 　 coating, 　 lubrication 　 layer 　 or 　 coating 　 and 　 surface 　 treatment 　 the same 　 device, 　 examples, if 　 it provides the features of the 　 〶 provided on the device. Optionally, all of the SiOx barrier coating, lubricity layer and surface treatment can be applied within one PPD device, significantly reducing the amount of handling required.

Other 　advantages 　can be obtained 　 by using the same 　 precursors 　 and changing the process 　 blocking 　 coating, lubricating 　 layer and 　 solute 　 forming a retainer. The for instance, SiOx gas barrier film or coating can be applied by using OMCTS precursor under high power / high O2 conditions, followed by a lower power and / or oxygen to substantially or use of OMCTS precursor does not completely exist coating Lubricity 　 film 　 or 　 coating 　 can be applied and 　 surface 　 treatment can be completed by using 　OMCTS　 precursor under 　 medium power and 　 oxygen 　.

VII. B. 1.ｂ ＳｉＯＸ　coated 　internal 　 and 　 barrier film 　 coated 　 with outer 　 　 with a barrel 　 syringe

VII.B.1.b. Another 　 embodiment shown in Fig. 50 is 　 injecting a 　 plunger (54 6), 　 barrel (54 8) 　 and 　 internal 　 and 　 external 　 blocking 　 coatings 　 (54 inclusive) The above 　barrel (548) is 　which defines 　lumen (64) 　can be made of 　thermoplastic 　series 　materials 　can be made. The barrel (548) can have an inner surface (52) and an outer surface (606) that accommodates the plunger (546) for sliding down, and the barrier coating 554 of SiOx, where x is about 1.5 to about 2.9, is the barrel. It can be provided on the inner surface 552 of 548. A barrier coating (602) of resin can be applied on the outer surface (606) of the barrel (548).

VII.B.1.b. In certain examples, the ``thermoplastic''-based material is optionally a polyolefin, for example a polypropylene or a cyclic olefin copolymer (e.g., a material marketed under the TOPAS® trade name), a polyester such as polyethylene tere. Phthalates, polycarbonates, such as bisphenol A polycarbonate thermoplastics or other materials. Composite syringe barrels having either of these materials as the outer layer and the same or different of these materials as the inner layer are contemplated. Also, any of the composite syringe barrels or material combinations of sample tubes described elsewhere herein may be used.

VII.B.1.b. In certain embodiments, the resin may optionally comprise polyvinylidene chloride in homopolymer or copolymer form. For example, PvDC homopolymers (generic 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 latex or other dispersion.

VII.B.1.b. In certain embodiments, the syringe barrel 548 may optionally include a lubricity layer disposed between the plunger and the barrier coating of SiOx. Suitable lubricity layers are described herein.

VII.B.1.b. In certain embodiments, the lubricating layer may be selectively applied by PECVD and may optionally include a material characterized as 　 as defined in the definition clause.

VII.B.1.b. In certain embodiments, the syringe barrel 548 is a surface 　 treatment 　 the 　 lubricity 　 layer, the constituents of the material 　 thermoplastic 　 series 　 or both 　 filtering with the lumen 604 　 to reduce the surface activity 　 effective 　May include treatment.

VII. B. 1.c SIOＸ　Coated 　Inner 　 and 　 Barrel with coating 　 Outside 　 　 Having a 　 Syringe 　 Manufacturing 　 Method

VII.B.1.c. Another embodiment is the method of manufacturing a syringe described in any of the embodiments of Part VII.B.1.b comprising a plunger, barrel and inner and outer barrier coatings. A barrel is provided with an inner surface and an outer surface for receiving the plunger for sliding. A barrier coating of SiOx is provided on the inner surface of the barrel by means of a PPD. A barrier coating of resin is provided on the outer surface of the barrel. The above 　 plunger 　 and 　 barrel are assembled to provide 　 syringe 　.

VII.B.1.c. For effective coating of plastic articles with water-soluble latex (uniform wetting), it is considered useful to match the surface tension of the latex to the plastic substrate. This can be done, for example, by reducing the surface tension of the latex (surfactants or solvents) and/or performing corona pretreatment of plastic articles and/or chemical priming of plastic articles independently or in combination. It can be done by

VII.B.1.c. Optionally, the resin is dip-coated latex on the outer surface of the barrel, spray-coated on the outer surface of the barrel, or applied through both, providing plastic-based articles that provide improved gas and vapor barrier performance. can do. Polyvinylidene chloride plastic laminate articles can be made that provide improved gas barrier performance versus non-laminated plastic articles.

VII.B.1.c. In certain embodiments, the resin may optionally be heat cured. The resin can optionally be cured by removing water. Water can be removed by thermally curing the resin, exposing the resin to a partial vacuum or low humidity environment, catalytically curing the resin or other means.

VII.B.1.c. It is considered that an effective thermal cure schedule is finally dried to allow PvDC crystallization, providing barrier performance. The primary curing may be performed at a high temperature of 180 to 310° F. (82 to 154° C.), for example, depending on the heat resistance of the thermoplastic material. The barrier performance after the first curing may optionally be about 85% of the final barrier performance reached after the final curing.

VII.B.1.c. Final curing is carried out at a temperature ranging from ambient temperature such as about 65 to 75°F (18 to 24°C) for a long period of time (such as 2 weeks) to a high temperature such as 122°F (50°C) for a short period of time such as 4 hours. Can be.

VII.B.1.c. In addition to good barrier performance, PvDC-plastic laminate articles are optionally contemplated to provide one or more desirable properties such as colorless transparency, good gloss, abrasion resistance, printability and resistance to mechanical deformation.

VII. B. 2 Plungers

VII. B. 2. a Blocking 　 coated 　 piston 　 front

VII.B.2.a. Another embodiment is a plunger for a syringe comprising a piston and a push rod. The piston has a front, side and rear portion configured to be movably seated within a syringe barrel that is generally cylindrical. The above 　 front has 　 blocking 　 coating. The push rod engages the rear portion and is configured to advance the piston in the syringe barrel.

VII. B．2．ｂ． 　Uses a 　lubricating 　 layer in contact with each other

VII.B.2.b. Another embodiment is a plunger for a syringe comprising a piston, a lubricating layer and a push rod. The piston has a front side, a generally cylinder-shaped side 　 and a 　 rear part 　. The side is 　 configured to be 　 movable 　 within the 　 syringe 　 barrel 　. The lubricity layer is in contact with the 　 top 　 side. The push rod engages the rear portion of the piston and is configured to advance the piston in the syringe barrel.

VII. B. 3．ａ Two 　 parts 　 syringe 　 and 　 lure 　 fitting

VII.B.3.a Another example is a syringe comprising a plunger, a syringe barrel and a Luer fitting. The syringe includes a barrel having an inner surface for receiving a plunger for sliding. The Luer fitting includes a Luer taper having an inner passage defined by an inner surface. The Luer fitting is formed as a separate component from the syringe barrel and is bonded to the syringe barrel by a coupling. The inner passageway of the Luer taper optionally has a barrier coating of SiOx.

VII.B.3.b Studded 　needle syringe

VII.B.3.b 　Other examples are: 　2011 　 May 　11 days 　 filed 　PCT/US11/36097 and 2010 　 June 　2９ the US　61/359,434, filed on the 　It is a 　syringe that includes a needle　syringe＂), a 　syringe 　barrel, 　 and 　 plunger. The needle is a 　 hollow with a 　 normal 　 size in the range of 　18　 to 　29　 gauge 　. The syringe barrel has an inner surface slidably receiving the plunger. The embedded 　 needle can be 　injection 　 of the syringe 　 can be attached to the syringe 　, and can be assembled by using 　 or 　adhesive 　. The cover is 　can be placed on the 　syringe 　assembly 　sealed 　 needle 　. The syringe 　 assembly should be sealed so that the 　 vacuum 　 is maintained in the syringe 　 so that the coating process can be made possible.

VII.B.4. General 　 Lubrication 　 Layer 　 or 　 Coating

VII.B.4.a. Product and lubricity by process

VII.B.4.a. Another embodiment is a lubricity layer. This coating may be of the type manufactured by the process, as described herein, as described herein, for lubricating and preparing the coating.

VII.B.4.a. Any one of the lubricating 　 coatings 　 precursors mentioned in this specification 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 lubricating surface with a lower plunger force or breakout force than an untreated substrate.

VII.B.4.a. Another 　 example is a 　 application method of a 　 lubricating layer. The organosilicon precursor is applied to the substrate under conditions effective to form the coating. The coating is polymerized, crosslinked, or both, to form a lubricating surface with a lower plunger force or breakout force than an 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, optionally an organosilicon precursor, optionally linear siloxane, linear silazane, monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or these It is a lubricating layer 　 or 　 coating deposited by the PPD from a feed gas containing any combination of two or more of them. The coating is between 1.25 and 1.65 g/cm3, alternatively 1.35 to 1.55 g/cm3, alternatively 1.4 to 1.5 g/cm3, alternatively 1.44 to 1.48 g, as measured by X-ray reflectance (XRR). It can have a density between /cm3　　.

VII.B.4.b. Another aspect of the invention is an organometallic precursor, optionally an organosilicon precursor, optionally linear siloxane, linear silazane, monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or these It is a lubricating layer 　 or 　 coating deposited by the PPD from a feed gas containing any combination of two or more of them. The coating has as a degassing component one or more oligomers comprising repeating -(Me)2SiO-moieties, as determined by gas chromatography/mass spectrometry. Optionally, the coating meets the limitations of any one of Examples VII.B.4.a. Optionally, the coating outgassing component as measured by gas chromatography/mass spectrometry is substantially free of trimethylsilanol.

VII.B.4.b. Optionally, the coating degassing component may be at least 10 ng/test of oligomers comprising repeating -(Me) ₂ SiO-moieties, as determined by gas chromatography/mass spectrometer using the following test conditions. have:

-GC column: 30m X 0.25mm DB-5MS (J&W Scientific),

0.25 μm film thickness

ㆍ Flow: 1.0 ml/min, uniform flow mode

ㆍ Detector: Mass Selection Detector (MSD)

ㆍ Scan mode: Split scan (10:1 split ratio)

• Degassing conditions: 1½” (37mm) chamber, purged 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 for 5 minutes at 300°C.

300°C.

VII.B.4.b. Optionally, the outgassing component may comprise at least 20 ng/test of oligomers comprising repeating -(Me)2SiO- moieties.

VII.B.4.b. Optionally, the feed gas is monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane or any combination of two or more thereof, e.g., monocyclic siloxane, monocyclic silazane. Glasses or any combination of two or more of them.

VII.B.4.b. The 　lubricated 　 layer 　 or 　 coating of any 　 embodiment is measured by a transmission electron microscope 　1 to 5000 nm, or 10 to 1000 nm or 10 to 200 nm or 　20 to 10 nm or an average thickness of 10 nm or 30 nm to 10 nm or 30 nm or 50 nm in thickness. There is a number. Preferred 　 ranges are 　30 to 1000 nm and 20 to 100 nm, and the very 　 preferred range is 80 to 150 nm　. At a single measurement point, the 　absolute 　 thickness of the coating can be 　 higher 　 than the 　 average 　 thickness 　 range 　 limit, or 　 or 　 more 　 lower 　. However, 　 usually varies 　 relative to the average 　 thickness 　 within the given 　 thickness 　 range 　.

VII.B.4.b. Another aspect of the present invention is a lubricating layer 　 or 　 coating deposited by PPD from a feed gas comprising monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or any combination of two or more thereof. to be. The coating is normalized to 100% of carbon, oxygen and silicon, as determined by X-ray photoelectron spectroscopy (XPS), and the atomic concentration of carbon exceeds 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.A.

VII.B.4.b. Optionally, the atomic concentration of carbon is (calculated based on XPS conditions in Example 15 of Ep　2251455) Lubricity 　 when the coating 　 was made 　 organic silicon 　 present in the precursor 　 in the 　 atomic relation 　 of the carbon 　 to 80% of the concentration Or 10 to 70 atomic percent, or 20 to 60 atomic percent, or 30 to 50 atomic percent, or 35 to 45 atomic percent, or 37 to 41 atomic percent.

VII.B.4.b. Another aspect of the present invention is a lubricating layer deposited by PPD from a feed gas comprising monocyclic siloxane, monocyclic silazane, polycyclic siloxane, polycyclic silazane, or any combination of two or more thereof. It is a coating. The coating is normalized to 100% of carbon, oxygen and silicon, as measured by X-ray photoelectron spectroscopy (XPS), and has an atomic concentration of silicon that is less than the atomic concentration of silicon in the atomic formula for the feed gas. Have. Refer to 　 Example 　 15 　 of EP2２５１４５５

VII.B.4.b. Optionally, the atomic concentration of silicon is 1 to 80 atomic percent, or 10 to 70 atomic percent, or 20 to 60 atomic percent, or 30 to 55 atomic percent (calculated based on the XPS conditions in Example 15 of EP22151455) , Or 40 to 50 atomic percent, or 42 to 46 atomic percent.

VII.B.4.b. In addition, lubricity layers having a combination of any two or more properties recited in Section VII.B.4 are explicitly contemplated.

VII.C. Container general

VII.C. Coated containers or containers described herein and made according to the methods described herein may be used for receiving and/or storage and/or delivery of compounds or compositions. The compound or composition is, for example, air-sensitive, oxygen-sensitive, sensitive to humidity and/or to mechanical influences. It may be a biologically active compound or composition, for example a medicament such as insulin or a composition comprising insulin. In another aspect, it can be a biological fluid, optionally a bodily 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 blood (transfusion from donor to recipient or reintroduction of blood from patient to patient) or insulin. It is a product that is administered to a subject.

VII.C. In addition, the coated container or container, described herein and manufactured according to the method described herein, is used to protect the compound or composition contained in its interior space from the mechanical and/or chemical effects of the surface of the uncoated container material. Can be used. For example, 　insulin 　precipitation 　 or 　 blood 　 coagulation 　 or 　 platelets 　 activation 　, it can be used to prevent or reduce the precipitation and/or coagulation or platelet activation of the components of the compound or composition.

VII.C. In addition, for example, it may be used to protect the compound or composition contained therein from the environment outside of the container by preventing or reducing the inflow of one or more compounds into the inner space of the container from the environment surrounding the container. Such environmental compounds may be gases or liquids, for example atmospheric gases or liquids including oxygen, air and/or water vapor.

VII.C. In addition, containers coated as described herein can be vacuumed and stored in a vacuum. For example, the coating makes it possible to maintain a better vacuum compared to a corresponding container that is not coated. In one aspect of this embodiment, the coated container is a blood collection tube. In addition, the tube may contain an agent that prevents blood clotting or platelet activation, such as EDTA or heparin.

VII.C. Any one of the above-described embodiments may be, for example, from about 1 cm to about 200 cm, optionally from about 1 cm to about 150 cm, optionally from about 1 cm to about 120 cm, optionally from 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 produced by providing a container having and treating it with a probe electrode as described below. In particular, for longer lengths in this range, it is contemplated that the relative motion between the probe and the vessel may be useful during coating formation. This can be done, for example, by moving the container with respect to the probe or by moving the probe with respect to the container.

VII.C. It is contemplated that in these embodiments, the coating may be thinner or less complete than would be preferred for a barrier coating, since in some embodiments the vessel does not require a high barrier integrity of the evacuated blood collection tube. do.

VII.C. An optional feature of any of the preceding embodiments has a central axis.

VII.C. As an optional feature of any one of the preceding embodiments, the vessel wall is at least substantially straight, over a range of a radius of bend at a central axis of about 100 times the outer diameter of the vessel, without breaking the wall. It is flexible enough to bend at least once at °C.

VII.C. As an optional feature of any one of the preceding embodiments, the radius bent at the central axis is about 90 times, or 80 times, or 70 times, or about 60 times, or about 50 times the outer diameter of the container, 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 It is about 3 times, or about 2 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 may be the 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 keep 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 a silicone elastomer or a thermoplastic polyurethane, or any material suitable for contact with blood or insulin, as two examples.

VII.C., VII.D. In an alternative embodiment, the container has an inner diameter of at least 2 mm, or at least 4 mm.

VII.C. As an optional feature of any of the preceding embodiments, the container is a tube.

VII.C. As an optional feature of any of the preceding embodiments, the lumen has at least two open ends.

　 common 　 conditions for all 　 embodiments

In this 　considered 　random 　 embodiment, 　many 　 common 　 conditions, 　 example 　 　 random 　 　 arbitrary 　 combination 　 can be used. Alternatively, there may be 　arbitrary 　different 　 terms described 　in the original 　 specification 　 or 　 claims.

I. Arbitrary 　Example 　Substrate

I.A. Arbitrary 　Example 　Container

Containers are 　samples 　 collection 　 tubes, 　 examples 　 　 blood 　 collection 　 tubes, 　 or 　 syringes, 　 or 　 syringes 　 parts, 　 examples 　 　 barrels 　 or 　 pistons 　 or 　 pistons 　 or 　The board can be 　 closed 　 tube, 　 example 　 medical 　 sample 　 collection 　 tube. The substrate may be the inner wall of a vessel having a lumen having a void volume of 0.5 to 50 mL, alternatively 1 to 10 mL, alternatively 0.5 to 5 mL, and alternatively 1 to 3 mL. The substrate surface may be part or all of the inner surface of the container having at least one opening and the inner surface, and the gaseous reactant fills the inner lumen of the container, and the plasma is in some or all of the inner lumen of the container. There are 　can 　 to be created.

I.B. Syringe 　 and 　 parts

The board can be 　 syringe 　 barrel 　 　 　. Syringe 　 barrel 　 plunger 　 glide 　 has a surface 　 can be 　 coated 　 plunger 　 glide 　 surface 　 at least 　 can be placed on a part 　. The coating can have a lubricity layer. Lubricity layer 　 or 　 coating can be 　 inside the barrel 　 surface. The lubricious layer 　 or 　 coating may be 　 on the plunger. Special 　 in the sun 　, the 　 board can be 　 　 needle 　 syringe 　 or 　 studded 　 needle 　 part of the syringe.

I.C.　 container that holds the stopper

The substrate has a stopper that accepts the surface at the entrance of the container. The substrate is 　to receive the stopper 　 applied 　 the opening of the container 　 generally 　 conical 　 or 　 cylindrical 　 inner 　 surface 　 can be.

I.D. stopper

The substrate is 　slide 　 surface of the stopper. The substrate can be 　coated 　by providing 　a single 　substantially 　in a vacuumed 　container 　providing a number of 　stoppers 　. Chemical vapor deposition has 　plasma 　 reinforcement 　 chemical 　 weather 　 deposition date 　 number 　, and the stopper has 　 plasma 　 contact 　. Chemical vapor deposition has 　plasma 　 reinforcement 　 chemistry 　 weather 　 deposition date 　 number of times. Plasma is formed in the upstream of the stopper and produces a plasma product, and the above-mentioned plasma product can be in contact with the stopper.

The closure can be defined as a 　coated 　substrate 　optionally 　lubricated 　layer 　coated 　stopper. The substrate is 　can be mounted on a container that defines 　lumen 　, and the surface of the closure facing the lumen can be coated with 　 coating.

The coating can be effective in reducing the permeation of the stopper's metal ionic constituents into the container lumen.

I.E. Any 　Example 　Substrate

The board can be 　 container 　 wall can be 　 　. A portion of the vessel wall in contact with the closure's wall-contacting surface may be coated with a coating. The coating can be a 　composite of a 　material with a 　1　 layer and a 　2　 layer. The first 　 1 　 layer 　 or 　 coating has 　 elastic 　 and 　 contact with the 　 stopper. The 　 control 　 1 　 layer of the coating can be 　 effective in reducing the transmission of more than one 　 metal ion constituents of the stopper into the container lumen. The 　2　layer 　 or 　coating is 　can be in contact with the 　inside 　wall of the container. The 　2　 layer is effective in reducing 　friction 　 between the 　 inside 　 wall of the container 　 and the 　 stopper 　 when the 　 stopper is 　 seated in the container.

Also, the 　random 　 embodiment 　 first 　 1 　 and 　 first 　 2 　 layers contain 　 carbon 　 and 　 hydrogen 　 　 enriched 　 characteristics of 　 in the coating 　 　 defined 　 in the 1st layer 　 is greater than 　 in the 1 　 and 2 　.

The 　 coating of any 　 embodiment can be applied 　 by 　 plasma 　 reinforcement 　 chemical vapor deposition 　.

The 　substrate of any 　 embodiment is a glass or a polymer, or a polycarbonate polymer, or a olefin polymer, or a cyclic olefin copolymer, or a polypropylene polymer, or a polyester polymer, or a polyethylene terephthalate polymer, or a polyethylene terephthalate polymer, or a combination thereof. Any combination of two or more of them, 　 complex 　 or 　 may include a mixture.

II.　Gas 　 Reactant 　 or 　 Process 　 Gas 　 Limits of any 　 Example

II.A 　 Random 　 Example 　 Deposition 　 Conditions

If used, the plasma for PECVD can be generated under reduced pressure, and the reduced pressure can be less than 300 mTorr, alternatively less than 200 mTorr, and more alternatively less than 100 mTorr. The physical and chemical properties of the coating can be set by setting the ratio of O ₂ and organosilicon precursor in the gaseous reactant and/or setting the power used to generate the plasma.

II.C. Any 　Example 　Precursor

The organosilicon 　 precursor is described 　 in this 　 specification.

Organosilicon 　 compounds can contain octamethylcyclotetrasiloxane (OMCTS) 　 in a certain 　 sun, especially 　 lubricity 　 coating is formed 　. The above 　solar 　arbitrary 　for the examples 　organosilicone 　compound can be composed of 　octamethylcyclotetrasiloxane (OMCTS) basically 　. Organosilicon 　 compounds can be 　 constant 　 in the sun, 　 especially 　 barrier properties 　 when the coating is formed 　 hexamethyldisiloxane or 　 or 　 contain 　.

Reaction 　gas can also contain 　 hydrocarbons 　 can. Hydrocarbons can contain 　methane, 　ethane, 　ethylene, 　propane, 　acetylene, or a combination of two or more of these.

The organosilicon 　 precursor can be delivered at a 　 speed of 　6 sccm or less, optionally 2.5 sccm 　 or less, selectively 1.5 sccm 　 or less, and optionally 1.25 sccm 　 or less. Larger 　 containers 　 or 　 conditions or 　 sizes 　 different 　 changes 　 require most of the precursor. The precursor can be provided at an absolute pressure of less than 1 Torr.

II.D. Arbitrary 　Example 　Carrier　Gas

Carrier gas include, for example, argon, helium, xenon, neon, inert gases other for the other components of the process gas in the deposition conditions, or two or more any combination of inert gas of them, or be comprised of these There is a number.

II.E.　Oxidation 　gas of any 　 embodiment

The oxidizing gas may include or consist of oxygen (O ₂ and/or O ₃ (commonly known as ozone)), nitrous oxide, or any other gas that oxidizes the precursor in the PECVD under the conditions employed. The oxidizing gas contains about one standard volume of oxygen. The gaseous reactant or process gas may be at least substantially free of nitrogen.

III Arbitrary 　 Example 　 Plasma

The plasma of an arbitrary PECVD embodiment can be formed in the vicinity of the substrate. Plasma is 　 in a certain 　 case, especially 　 when preparing a SiOx coating, 　 non-hollow-cathode 　 plasma mile 　 number. In other 　 some 　, 　especially 　 when preparing 　 coatings 　 non-hollow-cathodes 　 plasmas 　 not desirable. Plasma is 　 depressurized 　 gas can be formed 　 from reactants. Sufficient plasma generating power input can be provided to induce the formation of the coating on the substrate.

IV.　RF　power of any 　 embodiment

The precursor is a 　 electrode that is 　 charged at a 　 frequency of 　10 kHz to 2.45 GHz, or about 13 to about 14 MHz 　 contacted with a 　 plasma created by 　 applying energy to the 　 periphery of the precursor.

The precursor is 　wireless 　 frequency, 　 selectively 　 10 kHz 　 to 300 MHz 　 or less, selectively 1 to 50 MHz, more 　 selectively 10 to 15 MHz, and optionally 13.56 MHz 　 charged at a 　 frequency 　 as an electrode 　 to the 　 　 surroundings of the precursor 　 energy There is 　can be in contact with the ground 　plasma.

The precursor is 　0.1 to 25 W, optionally 1 to 22 W, optionally 　 1 to 　 10 W, more selectively 　 1 to 5 W, optionally 　 2 　 to 　 4 Ｗ, 　 for example 　 　 3Ｗ, 　 selectively More 　selectively 　5 to 14 W, for example 　6 　 or 　７．5W, 　optionally by using electrodes supplied with power of 7 to 11 W, for example 8 W 　 by applying energy 　 around the 　 of the precursor　Can be in contact with the 　plasma created.

The precursor is 　10 W/ml or less 　plasma 　 volume, or 6 W/ml to 0.1 W/ml 　 plasma 　 volume, or 5 W/ml to 0.1 W/ml 　 plasma 　 volume, or 　4 W/ml to 0.1 W/ml Plasma 　 volume, or 　 power in the 　 plasma 　 volume of 　2 W/ml to 0.2 W/ml 　 power 　 using the supplied electrodes 　 by adding energy 　 to the surrounding 　 of the precursor 　 being in contact with the 　.

Plasma can be formed by excitation of 　reaction 　 mixture 　 electromagnetic 　 energy, or 　 microwave 　 energy.

V. Optional 　 embodiment 　 different 　 process 　 options

The application step of applying the coating to the substrate can be performed by evaporating the precursor and providing it near the substrate.

The employed 　 chemical vapor deposition is 　ＰＶＤ days 　 　, the deposition time is 　 1 　 　 30 　 seconds, 　 degrees 　 2 　 to 　 10 　 　〙 alternatively 　 3 　 　The purpose of 　 to selectively limit the deposition time 　 to prevent 　 from overheating 　 of the substrate 　 to increase the production speed 　 and 　 process 　 gas and 　 to reduce the use of constituents 　 　The purpose of 　 to extend the deposition 　 time 　 selectively 　 can be 　 specific 　 evaporation 　 conditions 　 to provide 　 thicker 　 coating 　.

VI.　 Coating 　 Properties of any 　 Example

VI.A.　 lubricity 　 characteristics of any 　 embodiment

The 　container (for example, 　syringe 　 barrel 　 and/or 　 plunger) with 　 lubricity 　 coating 　 according to the present invention 　 has a 　 and is more 〦 or higher than the 　 uncoated 　 container ． They have a higher lubricity than a container coated with a SiOx coating described above. They can also have a higher lubrication activity than the above-described 　SiOx coating 　coated 　container 　. The embodiments can be performed under effective conditions to form a lubricity surface of a substrate with a lower sliding force or breakout force (or optionally both) than an untreated substrate. Optionally, the 　material 　 and 　 conditions 　 slip 　 or breakout force 　 uncoated 　 syringe 　 on barrels 　 at least 　 about 　 25%, or 　 at least 　 50%, or 6% or less 　 6% or less 　 6% or 6% Expressed differently, the coating may have a lower frictional resistance than the uncoated surface, and optionally the frictional resistance is at least 25%, more preferably at least 45%, even more preferably at least as compared to the uncoated surface. It is characterized by being reduced by 60%.

Lubricity 　 coating provides 　 constant 　 plunger 　 power 　 selectively 　 reducing the difference 　 between 　 brake 　 loss 　 force (Fi) and 　 downhill force (Fm) 　For Fi and Fm　, 　 low 　 but 　 too 　 not too low 　 having a value 　 is desirable. Too low, and resistance level roneun too low Fi, which means that the (extreme is zero), the time is fast / can lead to unintended flow, for example, are not fast when you do not advance the intention of the filled syringe component or control It can cause a discharge.

In order to obtain sufficient lubricity (for example, the syringe can be moved in the syringe, the plunger can be moved in the syringe, but the plunger is not controlled and the F is not controlled, and the following and the F-m glass movements should be avoided). 　

Fi: 2.5 to 5 lbs., preferably 2.7 to 4.9 lbs., in particular 2.9 to 4.7 lbs.;

Fm: 2.5 to 8.0 lbs., preferably 3.3 to 7.6 lbs., in particular 3.3 to 4 lbs.

More 　 Advantageously, the 　Fi and 　Fm values can be found in the 　 table in the 　 example.

Lubricity 　 coating provides 　 constant 　 plunger 　 power 　 selectively 　 reducing the difference 　 between 　 brake 　 loss 　 force (Fi) and 　 downhill force (Fm) 　

VI.B.　 hydrophobicity 　 properties of any 　 embodiment

The embodiment can be carried out under conditions effective to form a hydrophobic layer or coating on the substrate. Alternatively, the hydrophobic characteristics of the coating is a hydrophobic coating on a substrate, characterized in that which is set by setting the power used for setting the ratio of oxygen (O ₂₎ and the organosilicon precursor in the gas reactants and / or to create a plasma How to manufacture. Optionally, the coating has a lower wetting tension than the uncoated surface, optionally 20 to 72 dyne/cm, alternatively 30 to 60 dyne/cm wetting tension, alternatively 30 to 40 dyne/cm, alternatively 34 It can have a wetting tension of dyne/cm. Optionally, the coating can be more hydrophobic than an uncoated surface.

VI.C.　 thickness of any 　 embodiment

Optionally, the 　coating can have 　the thickness 　determined 　by the 　quantity mentioned 　 at the beginning 　 initiation 　 by a transmission electron microscope (TEM).

Here, for the 　 desirable 　 lubricity 　 coating, the indicated 　 thickness 　 range is 　 average 　 thickness 　 indicates 　 a little 　 roughness 　 lubricity 　 has the 　 lubrication characteristics of the coating 　 strengthen 　Therefore, the 　 thickness of these 　 lubrication 　 coatings 　 coating 　 overall 　 advantageous 　 not uniform 　 (see above) However, 　 uniform 　 thickness 　 lubricity 　 coating is also considered. At a single 　 measurement point, 　Absolute 　 thickness of the coating, 　Average 　From the thickness 　preferably 　+/- 50%, 　more 　preferably 　+/- 25% and 　more 　more 　+/with the maximum deviation of 15% 　There are 　 higher 　 or 　 lower than the range. However, 　 usually varies 　 in this 　 detailed 　 explanation 　 average 　 about thickness 　 given 　 thickness 　 range 　.

VI.D.　 composition of any 　 embodiment

Optionally, the 　 lubricity 　 coating can be composed of SiwOxCyHz or SiwNxCyHz. In general, it has an atomic ratio of SiwOxCy, where w is 1, x is about 0.5 to about 2.4, y is about 0.6 to about 3, preferably w is 1, and x is about 0.5 to 1.5, y is 0.9 to 2.0, more preferably w is 1, x is 0.7 to 1.2, and y is 0.9 to 2.0. The atomic ratio can be determined by X-ray photoelectron spectroscopy (XPS). Considering the hydrogen atom, the coating is thus in one aspect, for example, w is 1, x is 1 as w, x is about 0.5 to about 2.4, y is about 0.6 to about 3, and z is about 2 To about 9 SiwOxCyHz. Typically, the atomic ratio is Si 100:O 80-110: C 100-150 in certain coatings of the present invention. Specifically, the atomic ratio may be Si 100: O 92-107: C 116-133, and this coating thus contains carbon and oxygen and 36% to 41% carbon normalized to 100% silicon.

In addition, 　ｗ has 　1 and 　number 　, 　ｘ has 　 about 　0. 5　 to 　1. 5, 　ｙ 　about 　2　 to 　 about 　3, 　 and 6〙 days In addition, the coating may have 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). In addition, the concentration of 　atomic 　 is 　25　~　45%　carbon, 　25　~　65%　 silicon, 　and 　10　~　35% 　 oxygen. In addition, the concentration of 　atomic 　 is 　30　~　40%　 carbon, 　32　~　52% 　 silicon, 　 and 　20　~　2７% 　 oxygen. In addition, the concentration of 　atomic 　 is 　33　~　378% 　carbon, 　378　~　47% 　 silicon, 　and 　22　~　26% 　 oxygen.

Optionally, the coating is normalized to 100% of carbon, oxygen and silicon, as measured by X-ray photoelectron spectroscopy (XPS), and is 　 better 　 　 number 　 than the atomic concentration of carbon in the atomic formula for organosilicon 　 precursor, It has an atomic concentration of carbon. For example, the atomic concentration of carbon is 1 to 80 atomic percent, or 10 to 70 atomic percent, or 20 to 60 atomic percent, or 30 to 50 atomic percent, or 35 to 45 atomic percent, or 37 to 41 atomic percent. Increasing examples are considered.

Optionally, in the coating, the atomic ratio of carbon to oxygen may be increased compared to the organosilicon precursor and/or the atomic ratio of oxygen to silicon may be decreased compared to the organosilicon precursor.

Optionally, the coating is normalized to 100% of carbon, oxygen and silicon, as measured by X-ray photoelectron spectroscopy (XPS), and is less than the atomic concentration of silicon in the atomic formula for the feed gas, There are 　can 　 to have concentration. For example, the atomic concentration of silicon 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. Decreasing examples are contemplated.

As another 　 option, 　Organic silicon 　 　 total 　 formula and 　 compared to 　 　 　 　 of 　 can be increased 　 　 or 　SI: O 　 atomic cost is considered to be reduced 　 special 　 special 　

VI.E. Random 　Example 　Gas removal 　Type

The above-described organosilicon precursor, for example a coating made of a lubricity or SiOx barrier coating, contains one or more oligomers containing repeating -(Me) ₂ SiO-moieties, as measured by gas chromatography/mass spectrometry. It has as a degassing component. The coating degassing component can be measured by gas chromatography/mass spectrometry. For example, the coating degassing component is at least 10 ng/test, and at least 20 ng/test of oligomers containing repeating -(Me) ₂ SiO-moieties, as measured using the following test conditions. I can have it.

ㆍ GC column: 30m X 0.25mm DB-5MS (J&W Scientific), 0.25μm film 　 thickness

ㆍ Flow: 1.0 ml/min, uniform flow mode

ㆍ Detector: Mass Selection Detector (MSD)

ㆍ Scan mode: Split scan (10:1 split ratio)

ㆍ Degassing 　Condition: 1½” (37mm) chamber, purge at 85℃ for 3 hours, flow 　60 ml/min

Oven temperature: 40° C. (5 minutes) to 300° C. at a rate of 10° C./min; Hold for 5 minutes at 300°C.

Optionally, the 　lubricating 　 coating has 　trimethylsilanol 　 at least 　 practically 　 free 　 gas removal 　 ingredients 　 can be 　.

VI.E. 　Other 　Coatings 　 Properties of any 　 Example

The coating is between 1.25 and 1.65 g/cm3, or between 1.35 and 1.55 g/cm3, or between 1.4 and 1.5 g/cm3, or between 1.44k and 1.5 g/cm3 as measured by X-ray reflectance (XRR). It can have a density of between, or between 1.44 and 1.48 g/cm3. Optionally, the organic silicon 　 compound is octamethylcyclotetrasiloxane 　 　, and the coating has a higher density than the density of the coating made from HMDSO as an organic silicon compound under the same PEVD reaction conditions.

The coating optionally prevents or reduces the precipitation of the compounds or components of the composition in contact with the coating, in comparison to the 　 barrier property coated surface using 　 uncoated surface and/or HMDSO as a precursor, and in particular prevents insulin precipitation or blood coagulation. It can be prevented or reduced.

The substrate is 　 protected 　 contained in 　 or contained 　 compound 　 or 　 composition 　 uncoated 　 container 　 material 　 surface 　 mechanical 　 and/or 　 　 protects from the influence of 　 chemical 　 　

The substrate can be a container to prevent or reduce coagulation of a composition or a compound that is in contact with the interior and surface of the container. A compound 　 or 　 composition is a biologically active compound or composition, for example 　 　 　 can be 　, for example, a compound 　 or 　 composition 　 contains insulin 　 　 contains 　 can 　, sedimentation can be reduced 　 or can be prevented 　 　Alternatively, the compound 　 or 　 composition could be a 　biological fluid, for example a bodily fluid, for example blood or a blood fraction, so that 　blood 　 coagulation could be 　 reduced or 　 prevented.

Forming, 　 Coating 　 and 　 Test 　 Basics 　 Protocol for 　 Tubes

The containers tested in the following working examples were formed and coated according to the following exemplary protocols, except as otherwise indicated in the individual examples. Certain parameter values given in the following basic protocols, such as power and process gas flow, are typical values. If the parameter values have changed compared to these conventional values, this will be indicated in subsequent working examples. The same applies to the type and composition of the process gas.

Protocol for forming COC tubes

Cyclic olefin copolymer (COC) tubes of the type and size commonly used as vacuum blood collection tubes (“COC tubes”) are available from Topas AG, Frankfurt am Main, Germany, with dimensions as follows: Injection molded from ® 8007-04 Cyclic Olefin Copolymer (COC) resin: 75 mm long, 13 mm outer diameter and 0.85 mm wall thickness, each having a volume of about 7.25 cm 3 and closed, round ends.

SiOx 　Tubes 　Inside 　Coating 　Protocol

The vessel holder (50) is E.I., Wilmington, Delaware, USA. It is made of Delrin® acetal resin, available from du Pont de Neumours, has an outer diameter of 1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The vessel holder 50 is housed in a Delrin® structure that allows the device to move in and out of the electrode 160.

The 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 measured approximately 3 inches (76 mm) high (inside) and was 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, Delaware, USA) around the outside of the tube. ) Was inserted with the basic sealing (Figure 45). The tube (80) was 　extended (stopped) 　1/8 inch (3　mm) 　diameter 　 brass 　 or 　 on the counter electrode (108) 　 sealed 　 　 pressed against the plasma and moved to the 　 screen.

The copper plasma screen 610 is a perforated copper foil material (K&amp;S Engineering, Chicago, IL, USA, part #LXMUW5 copper mesh) cut to fit the outer diameter of the tube, and is radially acting as a stop for tube insertion. It was supported in place by a joint surface 494 extending to the side (see Fig. 45). The two pieces of copper mesh fit snugly around the brass probe or counter electrode 108 to maintain 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 inches or 0.343 mm). The brass probe or counter electrode 108 extends through a Swagelok® fitting (available from Swagelok, Solon Ohio, USA) at the bottom of the vessel holder 50 and extends through the vessel holder 50 base structure. The brass probe or counter electrode 108 was grounded to the casing of the RF matching network.

The gas delivery port 110 has 12 holes in the probe or counter electrode 108 along the length of the tube (three on each of the four sides are 90 degrees to each other), and aluminum blocking the end of the gas delivery port 110 These are the two holes in the cap. The gas delivery port 110 was connected to a stainless steel assembly consisting of Swagelok® fittings incorporating a manual ball valve for exhaust, a thermocouple pressure gauge and a bypass valve connected to the vacuum pumping line. In addition, process gases, oxygen and hexamethyldisiloxane (HMDSO) were connected to a gas delivery port 110 to flow through the gas delivery port 110 (under process pressure) into the interior of the tube.

The gas system is an Aalborg® GFC17 mass flow meter (Part # EW-32661-34, Cole, Barrington, Illinois, USA) to controllably flow oxygen into the process at 70 sccm (or at a specific flow reported for a specific example). -Parmer Instrument) and a polyether ether ketone ("PEEK") capillary tube (outer diameter, "OD" 1/16-inch (1.5-mm.), inner diameter, "ID" 0.004 with a length of 52. 5 inches (1.33 m) Inches (0.1 mm)). The PEEK capillary ends were inserted with liquid hexamethyldisiloxane ("HMDSO", Alfa Aesar® part number L16970, NMR grade, available from Johnson Matthey PLC, London). Liquid HMDSO was drawn through the capillary tube due to the lower pressure in the tube during the process. Thereafter, the HMDSO was vaporized as vapor at the outlet of the capillary tube as it entered the low pressure region. Gas 　 injection 　 pressure was 　７．2Ｔｏｒｒ　.

To prevent condensation of liquid HMDSO past this point, the gas flow (including oxygen) was diverted to the pumping line if it did not flow into the interior of the treatment tube through a Swagelok® 3-way valve. Once the tube was installed, the vacuum pump valve was opened to the vessel holder 50 and the inside of the tube.

The Alcatel rotary vacuum pump and blower 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 the 3-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 controlling the vacuum. In addition to the tube pressure, the gas delivery port 110 and the pressure inside the gas system were also measured using a thermocouple vacuum gauge connected to the gas system. This pressure was typically less than 8 Torr.

Once gas flowed into the interior of 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 70 watts. The output power was calibrated in this and all of 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 RF power supply was connected to the COMDEL CPMX1000 auto-matching, matching 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 70 watts (or the specified amount reported for a particular example) and the reflected power was 0 watts, so the applied power was delivered to the inside of the tube. The RF power supply was controlled by a laboratory timer and power over a time set to 6 seconds (or a specific time period reported for a specific example). When the RF power was started, a uniform plasma was established inside the tube. The plasma was maintained for a total of 6 seconds until the RF power was terminated by the timer. The plasma produced a silicon oxide coating of approximately 20 nm thick (or the specific thickness reported in the specific example) on the inside of the tube surface.

After coating, the gas flow returned back to the vacuum line and the vacuum valve was closed. Thereafter, the exhaust valve was opened to return the inside of the tube to atmospheric pressure (approximately 760 Torr). Thereafter, the tube was carefully removed from the vessel holder 50 assembly (after moving the vessel holder 50 assembly from the electrode 160 assembly).

CO ₂ Protocol for 　blood 　filling a tube 　

Alcatel rotary vacuum pump and a blower is attached to the vessel support 50, the tube is filled with the above-mentioned CO ₂ described above (including a vacuum pump system), and was connected to the CO ₂ source. In some cases shown in the following CO ₂ filling it was carried out in the coating apparatus immediately after applying the SiOx coating, removing the process gas. In other cases the SiOx coating is applied to the tube is removed from the coating apparatus was later mounted on the CO ₂ filling device.

The pumping system was used first used to fill any type of CO ₂ as described above, the vacuum tube from 0.3 to 1 Torr pressure. The vacuum was continued for 3 to 30 seconds to discharge the process gas. The evacuation tube was maintained at 1 to 14 minutes while the pressure of being filled with a CO ₂ pressurized to 25psi (1230 Torr) absolute pressure otherwise indicated in the working example, the amount of time. The filled tube was then transferred to the degassing measuring device described in the protocol below.

Protocol for degassing 　 measurement

VI.B. In the US 　 patent 　 No. 6, 52 8 　 　 　 　 adopted in 　 15 　 　 　 　 30 is 　 (362) 　 general the test set used in the operation for measuring a SiOx barrier coating (348), the gas removed through the coating in accordance with the protocol for the portion within the wall of the COC tube 358 manufactured in accordance with a protocol to coat the inner tube to the SiOx example for - It is a schematic diagram of business.

VI.B. Vacuum pump 364 is a second generation IMGS sensor (as indicated in the specific embodiment 2 or 14 μ / min full range), an absolute pressure sensor range: 0 to 10 Torr, in the corrected range of +/- 5% of reading get the flow measurement uncertainty (using the PC) leak-Tek program and leakage current versus time signal / plot commercially available measurement cell employing a (plot) for acquiring automatically the data 362 (leak testing tool model ME2 It is connected to the 　 downstream 　 end of the 　 intelligent 　 gas 　 leak 　 system). Configuring this equipment is to lead the gas from the interior of and supplied by the ATC use, the container 358 through the measuring cell 362 for mass flow measurements of the vapor removal gas into the container 358 from the walls in the direction of the arrow There is.

VI.B. Here the measured cell 362 is briefly shown and described, though the information is actually used was understood to be that there be some escape is the operation of a particular distinct equipment than on model number, the operation as to substantially below ． The 　cell (362) has a 　conical 　 passage (368) in which the 　 degassed flow is 　 directed. The pressure begins in the second of two side holes (370 and 372) spaced longitudinally along the passage 368 and in part is supplied to the chambers formed by the plates (378 and 380) (374 and 376) ．　 pressures accumulated in each of the 　 chambers (374　 and 　376) deflect the respective 　 diaphragms (378　 and 　380). This 　 deflection is appropriately measured between the 　conductivity 　 surfaces of the diaphragms (378　 and 　 380) and the change in electrical capacity between the 　conductivity 　 surfaces like 　 (382　 and 　384) and 　 the same 　. Bypassing the measurement cell (362) until the desired level of the vacuum is reached (362) to perform the test, and a bypass (386) is provided selectively and the first time the pump-down is speeded down.

VI.B. The 　COC　 walls (350) of the 　 used in this test were about 　0. 85　mm　 thickness 　, and the 　 coating (348) was about 　20　nm (nanometer) 　 thickness　Therefore, the ratio of 　wall (3550) 　 to 　 coating (348) 　 thickness 　 was about 　500, 00.0: 1　

VI.B. In order to measure the flow rate through the cell (362), which contains the container and chamber (360), the size and the structure of the container are substantially the same as the size and structure of the pump, and the pressure inside the pump is substantially the same as that of the 3      　 was settled in the phase, and after 　, the 　 capacitance 　 data was collected using 　 measurement 　 cell (362) 　 and converted to 　 　 gas removal 　 flow rate. The test was conducted 　2 　 times 　 for each 　 container. After the first 　 1 　 run 　, the 　 vacuum was relieved 　 by using nitrogen 　, and the container was brought to equilibrium during 　 recovery 　 time 　 with another 　 run (if any) 　 before 　. Since the glass container to the possible infiltration seen through the walls but do little to gas removal, such measurements are at least predominantly is understood to be a positive indication of leakage and the connection of the container in the measurement cell 362, the real Degassing 　 or 　 If there is a 　 　 　 rarely reflected 　.

VI.B. A table of 　 plots 　 family 　 or 　 data 　 provided 　 to show the 　 gas removal 　 results of some 　 embodiments 　 individual 　 tubes 　 per minute 　 in micrograms 　 displayed 　 　 shows the gas flow 　Flow 　 part is due to 　 leakage. In the table, 　 quantized 　 flow rate 　 data 　 points are recorded as 　 constant 　 test 　 time (on ATC　 　 minutes per test).

Work example

Examples of work are 　Refer to 　gas removal of 　EP2251671 A2 　Example, 　In particular, refer to 　Example of EP2251671 A2 　 and 　 Example 　8, 　 Example 　16, 　 Example should include 　 19, and should be understood

Example 1

CO _２ 　Filled 　 uncoated 　COC　tubes 　 on 　 gas 　 removal 　 measurement

VI.B. The initial test was performed to determine if CO ₂ is filled in the COC substantially to increase the removal ATC gas flow. Thirty uncoated COC tubes were fabricated according to the protocol for forming COC tubes. Before CO ₂ is filled, the tube was tested for gas removal in accordance with the protocol for gas removal test. The flow rate was measured using an AC with a 14 μg/min sensor. Before it is filled with a CO ₂ flow, as applicable ATC shown in Table A. Each using the CO ₂ filling time for 10 minutes after performing the measurement in the tube was filled with the same tube with CO ₂ according to the protocol for filling the blood tube with CO _2. The flow rate was re-measured in the same way and the results were recorded in Table A again.

Referring to Table A, the average flow rate of the gas removed before COC tube is filled with the CO ₂ was 1.43 micrograms per minute. After the CO ₂ is filled with the average flow rate of the gas removal tube COC was 3.48 micrograms per minute. These results show that it is possible to substantially facilitate the ATC degassing measurement is adsorbed in an amount sufficient for the tubing is CO ₂ that is not coated.

Table 　Ａ: ＣＯ _２ The effect of the filled 　COC on the 　gas removal 　

Example 2

CO ₂ Filling 　 time 　 zone 　 gas removal 　 speed

In this embodiment, it is given a change in length of the CO ₂ filling time in order to show the effect of degassing. Since the ATC test time was also increased to 5 minutes, the results of this test cannot be directly fertilized with the results of Example 1. The test was carried out otherwise similarly to the "CO ₂ after filling" of Example 1.

This 　 result is 　 presented in the 　 table 　 　, although 　 the filling time 　 increases 　 　 the filling 　 per minute 　 the increase of the flow rate 　 less 　 but the more gas removal 　 increases the time 　

Table　Ｂ： ＣＯ _２ Effect of filling time on the flow rate

Example 3

Carbon dioxide（CO _２ ）　Uncoated 　Uncoated 　Cyclic 　Olefin　Copolymer and 　SIOｘ　Coated 　Cyclic 　olefin 　Copolymer 　Improved 　Microflow 　 Separation

Cyclic olefin copolymer of 10 uncoated and coated SiOx cyclic olefin copolymer (COC) 13x75mm (0.85mm thick) injection 12 minutes to 25 psi of carbon dioxide _(CO 2) the pressure on the plasma forming tube of the coating apparatus Each pressurized during. SiOｘ coating was carried out on the plasma coating apparatus described in the protocol. The SiOx coated tube was allowed to cool to ambient temperature after the CO ₂ pressure; standard plasma coating apparatus by opening the valve using a standard tube support has been modified to CO ₂ pressurized by the CO ₂ pressure cylinder; tube was evaluated immediately after the CO ₂ pressure ．

C0 ₂ after the pressing, the tube was analyzed under the condition mentioned previously ATC equipment from 0 to 14 micrograms / liter (μg / L) Flow rate range. The results of the ten average values (Table C) showed good separation of greater than 4 μg/L units between the uncoated COC tube and the SiOｘ coated tube. When a relatively non-pressure CO ₂ (a) non-coated tubes and had a micro-flow values for all of the coated tube was smaller than (1.25-2.00 μg / L) (b ) not coated with SiOx coated tube COC COC tube There was no separation between them.

Table C. Plasma 　 Coating 　 Parameters

Table D. Uncoated in a CO ₂ purge the state COC tube and SiOx average micro flow between the COC-coated tube.

Example 4

Carbon dioxide（CO _２ ）　Uncoated 　Cyclic 　Olefin　Copolymer and 　SIOｘ　Coated 　Cyclic 　olefin 　Copolymer 　Fast Six Sigma Microflow 　Separation

Cyclic olefin copolymer of 10 uncoated and coated SiOx cyclic olefin copolymer (COC) 13x75mm (0.85mm thick) injection 12 minutes to 25 psi of carbon dioxide _(CO 2) the pressure on the plasma forming tube of the coating apparatus Each pressurized during. SiOｘ coating was carried out on the plasma coating apparatus described above. The SiOx coated tube was allowed to cool to ambient temperature after the CO ₂ pressure; standard plasma coating apparatus by opening the valve using a standard tube support has been modified to CO ₂ pressurized by the CO ₂ pressure cylinder; tube was evaluated immediately after the CO ₂ pressure ．

C0 ₂ after the pressing, the tube was analyzed under the condition mentioned previously ATC equipment from 0 to 14 micrograms / liter (μg / L) Flow rate range. Microflow data for each tube was collected approximately every 0.3 seconds.

Data Analysis:

To achieve a statistically significant six-sigma separation between the uncoated microflow and the SiOx coated microflow, the microflow mean (-3 standard deviation) of the uncoated tube is the microflow mean (+3) of the SiOx coated tube. Standard deviation). These conditions are achieved between 0.96 and 1.29 seconds after the start of the measurement, as shown in Table E.

Table E. Time of microflow (-3 standard deviation) of uncoated tube and microflow (+3 standard deviation) of SiOx coated tube

Example 5

Injecting or filling carbon dioxide through vacuum exhaust/pressurization process

Place some uncoated COC and SiOx plasma coated COC 13x75mm tubes into a pressure vessel. The vessel was evacuated at 1 Torr for 30 minutes; It is then pressurized 3-10 psig from the carbon dioxide cylinder for 30 minutes. The tubes are then evaluated using an ATC microflow instrument under the conditions described in Example 1. The microflow distinction observed between the uncoated COC tube and the plasma coated COC tube is similar to that observed for the uncoated and SiOx coated PET tubes (Figures 31 and 32), using nitrogen as a purge gas. It was much better than that.

Example 6

Injection or filling of carbon dioxide through a pressurization process

The tube was mounted in a pressurized chamber to pressurize CO ₂ gas at 75 psi 23°C for 1.5 hours. Tubes were measured using the above conditions on an ATC unit. The tube showed good separation between coated and uncoated 8007 COC 13 x 75 mm tubes.

Example 7

Under argon (Ar) 　 purge 　 　 uncoated 　 cyclic 　 olefin 　 copolymer and 　 SiOx 　 coated 　 cyclic 　 olefin 　 of copolymer 　 improved 　 microflow 　 separation

Cyclic olefin copolymer of 10 uncoated and coated SiOx cyclic olefin copolymer (COC) injection for 12 min with 25 psi of argon (Ar) pressure on the forming tube a plasma coating apparatus of 13x75 (0.85mm thick) Each 　 was pressed. SiOx coating was carried out on the plasma coating apparatus described above; The SiOx coated tube was allowed to cool to ambient temperature after the Ar pressure; standard plasma coating apparatus was modified to Ar Ar pressurized to the pressure cylinder by opening the valve using a standard tube support; tube was evaluated immediately after the Ar pressure.

After Ar 　 pressurization 　, 　 tubes were analyzed 　 with a microgram/liter (μg/L) 　 flow rate 　 range under the 　 conditions 　 previously mentioned 　.　 result (table 　F) of 10 　 average 　 values showed 　 greater than 　 1 μg/L unit 　 between 　 uncoated 　COC　 tube and 　SIoｘ　 coated 　 tube 　 was good.

Table 　 F.　 average 　 micro flow between 　 uncoated 　 uncoated 　COC　 tube and 　SiOx　 coated 　COC　 tube 　 in Argon　 purge condition.

Example 8

Nitrogen（N _２ ）　Uncoated 　Uncoated 　Cyclic 　Olefin　Copolymer and 　SIOｘ　Coated 　Cyclic 　olefin 　Copolymer 　Improved 　Microflow 　 Separation

Ten uncoated cyclic olefin copolymers and SiOｘ-coated cyclic olefin copolymers (COC) 133g75 (0.85mm thick) injection-molded tubes were placed on a plasma coating machine under a pressure of 25 PSI nitrogen (N2) for 12 minutes. SiOx coating was carried out on the plasma coating apparatus described above; SiOｘ coated tube was cooled to ambient temperature after N ₂ pressurization; Standard plasma coating apparatus opened the valve using the standard tube support and N ₂ pressure The cylinder was modified to pressurize N ₂ ; the tube was evaluated immediately after pressurization of N ₂ .

C0 ₂ after the pressing, the tube was analyzed under the condition mentioned previously ATC equipment from 0 to 14 micrograms / liter (μg / L) Flow rate range. The results of the ten average values (Table G) showed good separation between the uncoated COC tube and the SiOｘ coated tube.

Table 　G．　 average micro flow between 　 uncoated 　COC　 tube and 　SiOx　coated 　COCO tube　 under nitrogen 　 purge 　 condition.

Example 9

CO in microflow measurement ₂ Purge gas

This example shows that a short CO ₂ filling time such as 1 second can be used to improve the outgassing detection result. Each of the uncoated COC containers made of COC 8007 and COC 6015 was evacuated in an apparatus similar to the apparatus of FIG. 2, and then purged with nitrogen gas or carbon dioxide for 1 second to break the vacuum state. Then the outgassing of the tube was measured in the equipment shown in FIG. 30. The 1 second purge time with carbon dioxide instead of nitrogen resulted in increased microflow amplitude for the uncoated COC injection molded 13x75 tube (Table 1).

Table I. Comparison of microflow amplitudes (after 90 seconds) of TOPAS 8007 and 6015 tubes without coating

Example　10

Additional microflow measurement

Place some uncoated COC and SiOx plasma coated COC 13x75mm tubes into a pressure vessel. The vessel was evacuated at 1 Torr for 30 minutes; It is then pressurized 3-10 psig from the carbon dioxide cylinder for 30 minutes. The tube is then evaluated in the equipment shown in FIG. 30. As can be seen in Figure 63, the microflow distinction observed between the uncoated COC tube and the plasma coated COC tube is the same as the uncoated PET tube and the SiOx coated PET tube (EP2251671 A2 in FIGS. 31 and 32). It is similar to that observed for Figs. 31 and 32) of the application and is much better than using nitrogen as the purge gas.

While the present invention has been illustrated and described in detail in the drawings and the preceding detailed description, such drawings and description are to be regarded as illustrative or illustrative and not limiting; The invention is not limited to the disclosed embodiments. Other modifications to the disclosed embodiments may be understood and performed by one of ordinary skill in the art practicing the claimed invention from a study of the drawings, disclosure, and appended claims. In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite article “one” or “a” does not exclude the plural. The mere 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.

Claims (31)

As a blood collection container, the blood collection container
A wall having an inner surface and an outer surface defining a lumen, and a PECVD (plasma enhanced chemical vapor deposition) coating or layer or PECVD coatings on one or both of the surfaces; PECVD coatings or coatings including at least a barrier coating and a hydrophobic coating;
-A barrier coating comprising a coating of SiO _x (where x is 1.5 to 2.9);
● Si _w O _x C _y H _z or Si _w N _x C _y H _z (where w is 1, x is 0.5 to 2.4, y is 0.6 to 3, z is 2 to 9) Hydrophobic coating;
Including, a blood collection container adapted to keep blood in good condition for medical use. The blood collection container of claim 1, wherein the container is used for one or more selected from the group of receiving, storing and delivering blood or blood fractions. The blood collection container of claim 2, wherein the coated container prevents or reduces one or more selected from the group of sedimentation, coagulation and platelet activation. The blood collection container of claim 1, wherein the surface is an inner surface of a wall. The blood collection vessel of claim 1, wherein the barrier coating or layer is an average of 10 to 100 nm thick. The blood collection vessel according to claim 1, wherein the wall is made of at least one polymer compound selected from the group consisting of polyester, polyolefin, cyclic olefin copolymer and polycarbonate. The blood collection container according to claim 1, wherein the wall is made of a flexible material. The blood collection container according to claim 1, which is a blood bag, a blood tube or an evacuated blood collection tube. The blood collection container according to claim 2, wherein blood or a blood fraction is injected. The blood collection container according to claim 9, wherein the injection is administered during a blood transfusion from a donor to a recipient or reintroduction of blood from a patient back to the patient. The blood collection container of claim 1, wherein the container contains a reagent. The blood collection container of claim 11, wherein the reagent is added to the blood collection container during manufacture. The blood collection container according to claim 11 or 12, wherein the reagent is capable of preventing blood clotting or platelet activation. The method of claim 1, further comprising: a hydrophobic coating of Si _w O _x C _y H _z or Si _w N _x C _y H _z deposited between the layer or coating of SiO _x and the inner surface of the vessel wall; And a second hydrophobic coating of Si _w O _x C _y H _z or Si _w N _x C _y H _z deposited over the SiO _x coating. The blood collection vessel of claim 1, wherein the plasma for PECVD is generated by a radio frequency (RF) power supply. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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