JP2781777B2 - Blood collection test tube assembly - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a multilayer barrier coating that provides an effective barrier to gas and water permeability in containers, especially plastic blood collection tubes.

[0002]

BACKGROUND OF THE INVENTION With the increasing tide of the use of plastic medical devices, there is a special need for improved barrier properties of products made from polymers.

[0003] Medical devices that can greatly benefit from improved barrier properties include, but are not limited to, collection tubes and especially those used for blood collection.

[0004] Test tubes for blood collection require certain acceptable performance criteria for use in medical applications. Such performance criteria include the ability to maintain about 90% or more of the original collection volume over one year, the ability to sterilize with radiation,
Also includes the ability to not interfere with testing or analysis.

[0005]

Accordingly, the barrier properties of products made from polymers, in particular plastic vacuum blood collection tubes, which meet certain performance criteria and can be used effectively for medical applications. There is a need for improvements.

[0006]

SUMMARY OF THE INVENTION The present invention is a plastic composite container having a multi-layer barrier coating of at least two barrier materials that has been applied to the entire exterior surface of a preformed composite container. Preferably,
The barrier material includes a first layer of a polymeric material and a second layer of an inorganic material applied over the first layer.

[0007] The first layer, which is a primer coating,
Preferred are highly crosslinked acrylic polymers.
The coating can be formed on the interior surface, on the exterior surface, or on both sides of the container.

The second layer of the barrier coating is preferably SiO _x, wherein x is from 1.0 to about 2.0.
Silicon oxide based compounds such as 0); or aluminum oxide based compounds. The most preferred second layer is a silicon oxide based compound applied over the first layer.

[0009] The primer coating is preferably
U.S. Patent Nos. 4,490,774, 4,696,719, 4,647,818
Nos. 4,842,893, 4,954,371 and 5,032,461 (the disclosures of which are incorporated herein by reference) monoacrylates (e.g., isobornyl acrylate) and diacrylate monomers (e.g., epoxy Diacrylate or urethane diacrylate). The primer coating is cured by an electron beam or ultraviolet radiation source (c
ured).

Preferably, the first layer has an average molecular weight of between 150 and 1,000 and 1 × 10 ^-6 under standard temperature and pressure.
And a substantially cross-linked compound selected from the group consisting of polyacrylates having a vapor pressure of from 1 to 10 ^-1 Torr, and mixtures of polyacrylates and monoacrylates. Most preferably, the substance is a diacrylate.

[0011] The step of applying the primer coating to the container is preferably performed in a vacuum chamber. The monomer compounds curable in the vacuum chamber are metered into a heated evaporation system where they are atomized, evaporated and condensed on the surface of the container. After deposition of the monomer on the container surface, the deposit is cured by a suitable method such as electron beam curing. The deposition and curing procedure can be repeated until the desired number of layers is reached.

[0012] Preferably, the thickness of the acrylic primer coating is from about 0.1 to about 10 microns, and most preferably, from about 0.5 to about 5 microns.

A preferred second layer applied over the first layer is
Preferably, it is a compound containing silicon oxide such as SiOx. Such desirable coatings are derived from volatile organosilicon compounds.

The method of depositing the coating comprising silicon oxide is as follows: (a) pretreating the first layer of the vessel with a first plasma coating of oxygen; (b) a gas stream comprising an organosilicon compound. Flowing into the plasma while limiting it; and
(c) depositing silicon oxide on the first layer while maintaining the pressure during deposition at about 500 μm Hg or less;

It is believed that the pretreatment step improves the adhesion between the second layer and the primer coating.

The organosilicon compound is preferably combined with oxygen, or optionally with helium, or another inert gas such as argon or nitrogen, and at least a portion of the plasma is preferably magnetically , Most preferably by an unbalanced magnetron, converges near the surface of the first layer during deposition.
d).

The silicon oxide based compound creates a dense, vapor impervious coating on the primer coating. The preferred thickness of the silicon oxide base layer is from about 100 to about 10,000 angstroms (Å), and most preferably from about 1,000 to about 3,000Å. Coatings of 10,000 m2 or more will crack and therefore have no barrier effect.

Plastic test tubes coated with a multi-layer barrier coating consisting of a primer coating and an oxide layer can be used for testing tubes made of polymeric compounds and mixtures thereof without conventional coatings of barrier materials, or for oxide coatings. Substantially much better retention of vacuum and retention of collection volume can be maintained compared to a single test tube. Furthermore, the resistance of the test tube to impact is much better than that of glass. Most notable is the clarity of the multilayer coating and the substantial durability of its resistance to impact.

Most preferably, the container of the present invention is a device for collecting blood. The blood collection device may be a decompressed blood collection tube or a non-depressurized blood collection tube. The blood collection tubes are desirably made from polyethylene terephthalate, polypropylene, polyethylene naphthalate, or copolymers thereof.

Printing can be performed on the multilayer barrier coating applied to the container of interest. For example, product identification, barcode, brand name, company logo, lot number,
The expiration date, and other data and information, are all included on the barrier coating. Further, a matte finish or a corona emitting surface can be applied over the barrier coating so that the surface is suitable for writing additional information on the label. Furthermore, pushable labels can be applied over the barrier coating, for example, to correspond to unique labels in various hospitals.

[0021] Preferably, the multilayer barrier coating according to the invention provides a transparent or colorless appearance and can be printed thereon.

As a further advantage, the method of the present invention provides a reduction in gas permeability in three-dimensional objects that cannot be achieved with conventional deposition methods, typically using thin films.

Surprisingly, an acrylic primer coating on the plastic surface followed by SiO
coating of _x gives less oxide coating of carbon atom content, the better barrier coating as compared to those coated with SiO _x directly obtained has been found on the plastic. Uniform continuous with good adhesion and minimal defects on plastic surface,
Producing a gas-impermeable SiO _x coating is considered difficult. Poor adhesion is believed to be due to the presence of low molecular weight hydrocarbon molecules on the plastic surface (dust particles and defects formed during injection molding). Amorphous regions on the surface of polyolefins with highly mobile side chains also cause poor adhesion of SiOx to the polymer. Such plastic surfaces include polyolefins such as polypropylene and polyethylene.

The highly crosslinked layer of the acrylic compound
It has been found to improve the adhesion of the SiOx to the plastic surface and to improve the thermomechanical stability of the overall coated system. In addition, the acrylic primer coating serves as a smoothing (leveling) layer that covers the particles and defects on the surface of the polymer and reduces the defect density of the deposited inorganic coating. The excellent binding properties of the acrylic compound are also based on the fact that the acrylic compound is polar, and that the polarity provides a means of good bond formation between the SiO _x and the acrylic compound. In addition, good bond formation has been found to be made between a plastic test tube made of polypropylene and an acrylic compound.
Thus, the present invention provides a means for substantially improving the barrier properties of polypropylene test tubes. The adhesion of both acrylic and oxide coatings can be further substantially improved by surface pretreatment methods such as flame or oxygen plasma. Thus, the significant reduction in product permeability is based on the substantially improved SiO _x surface coating obtained by applying an acrylic primer coating to the plastic product surface.

The plastic blood collection tubes coated with the multilayer barrier coating of the present invention do not interfere with tests and analyzes typically performed on blood in the tubes. Such tests include, but are not limited to, routine chemical analysis, biological inertness, hematology, blood chemistry,
Includes clinical tests on blood type, toxicological analysis or therapeutic drug monitors and other body fluids. In addition, plastic blood collection tubes coated with a barrier coating can be run on automated machines such as centrifuges, and without substantial changes in optical or mechanical and functional properties. Exposure to some level of radiation during the sterilization process.

[0026]

The present invention may be embodied in other specific forms and is not limited to any of the specific embodiments described in detail by way of example only. Various other modifications will be apparent and readily made by those skilled in the art without departing from the scope and spirit of the invention. The scope of the invention is determined by the claims and their equivalents.

In the drawings in which like parts are designated by like numerals throughout the several views, FIGS. 1 and 2 show a typical example having a side wall 11 and a plug 14 extending from an open end 16 to a closed end 18. Shown is a test tube 10 for blood collection. The plug 14 includes a lower annulus or skirt 15 that extends to and presses against the interior surface 12 of the side wall to hold the plug 14 in place.

FIG. 2 diagrammatically shows that there are three mechanisms for changing the degree of vacuum in a blood collection tube: (A) gas permeation through the material of the stopper; (B) test. Permeation of gas through the tube; (C) Leak at the stopper / tube interface.
Therefore, if there is substantially no gas permeation and leakage, good vacuum holding and good collection volume holding can be obtained.

FIG. 3 shows a preferred embodiment of the present invention, a plastic test tube coated with at least two layers of barrier material. The preferred embodiment includes many components that are substantially identical to the components of FIGS. Thus, except for using the suffix "a" to define the components of FIG.
1 and 2 are numbered identically.

Referring now to FIG. 3, the collection test tube assembly 20, which is a preferred embodiment of the present invention, comprises a plastic test tube 10a having a side wall 11a extending from an open end 16a to a closed end 18a. The barrier coating 25 covers most of the outer surface of the test tube except for the open end 16a. Barrier coating 25 comprises a first layer 26 of an acrylic polymer material and a second layer 27 of a compound containing silicon oxide.

FIG. 4 shows a test tube assembly 40 for collection.
Illustrates yet another embodiment of the present invention that includes a stopper 48 for closing the open end 41 of a test tube 42. As shown, the side wall 43 extends from the open end 41 to the closed end 44,
The stopper 48 has an annular upper portion 50 protruding from the tip of the test tube 42. The plug 48 has a lower annulus or skirt 49 that extends to and presses against the inner surface 46 of the side wall 43 to hold the plug 48 in place. In addition, the stopper has a septum 52 for receiving a cannula tube therethrough.

Therefore, when a user receives a container as shown in FIG. 4 containing a sample therein, the user may remove some or all of the contents of test tube 42 in order to perform various tests on the sample. A cannula tube can be inserted through septum 52 for acceptance. Covering a substantial portion of the length of the test tube is a multilayer barrier coating 45. The multilayer barrier coating 45 covers substantially most of the test tube except for the open end 41. The multilayer barrier coating 45 comprises a first layer 54 of a polymeric material and a second layer 56 of an inorganic material. FIG. 4 shows that the test tubes have layers 54 and 5
3 is different from the embodiment of FIG. 3 in that the test tube can be depressurized at the same time that the stopper 48 is installed after the test tube 6 is applied. Alternatively, the multilayer barrier coating can be applied after the test tube is depressurized.

FIG. 5 shows an additional embodiment of the barrier coating and test tube. This alternative embodiment functions in a similar manner to the embodiment illustrated in FIG. Accordingly, except for using the suffix "a" to identify the components of FIG. 5, similar components that perform similar functions are numbered identically to the components of the embodiment of FIG.

Referring now to FIG. 5, a further embodiment 6 of the present invention is shown.
0 indicates that the multilayer barrier coating 45a is
50a and the entire outer surface of test tube 42a. The multi-layer barrier coating 45a has a serration (serr)
ation) 62 at the interface between test tube and stopper. Serrations are registered so that it is possible to determine if the sealed container has been touched (reg
istered). Such an embodiment can be used, for example, to seal a stoppered container. Once the sample is placed in the test tube, the stopper is removed and cannot be touched. Additionally, serrations can be registered to determine whether the sealed container has been touched. Such considerations are suitable, for example, for drug abuse testing, specimen identification and quality control.

In yet another embodiment of the present invention, the multilayer barrier coating 45 is repeatedly applied to the inside and / or outside of the test tube. Preferably, the coating is
Applied at least twice.

It will be appreciated by those skilled in the relevant art that such test tubes may contain some reagents in the form of additives or coatings on the inner wall of the test tube.

The multilayer barrier coating forms a substantially transparent or translucent barrier. Thus, the contents of a plastic test tube having a multilayer barrier coating comprising at least two layers of barrier material are substantially visible to an observer, while at the same time identifying information is provided by the multilayer barrier coating applied to the plastic test tube. Later it can be displayed on it.

The first layer of the multilayer barrier coating can be formed on a test tube by immersion coating of an acrylic polymer, roll coating or spraying of an aqueous emulsion, and subsequent air drying.

Acrylic polymer materials can also be obtained by performing an evaporation and curing process as described in US Pat. No. 5,032,461, the disclosure of which is incorporated herein by reference. , Can be applied to test tubes.

In the acrylic evaporation and curing method, an acrylic monomer is first atomized into droplets of about 50 microns,
It then involves flushing them to the heated surface. This method produces a vapor of acrylic molecules having the same chemistry as the original monomer.

Acrylic compounds are available with almost any desired chemistry. These compounds usually have one, two or three acrylic groups per molecule. Various mixtures of mono, di and triacrylates are useful in the present invention. The most preferred are
Monoacrylate and diacrylate.

Acrylic compounds form one of the most reactive classes of chemicals. They cure rapidly when exposed to UV or electron beam radiation to form crosslinked structures. This gives the coating resistance to high temperatures and abrasion.

The monomeric substances used were from 150 to 1,0
00, preferably a relatively low molecular weight in the range of 200 to 300, and a vapor pressure between about 1 × 10 ⁻⁶ Torr and 1 × 10 ⁻¹ Torr (ie, a relatively low boiling point) at standard temperature and pressure. Substance)
It is. A vapor pressure of about 1 × 10 ^-2 Torr is preferred. Polyfunctional acrylic compounds are particularly preferred. The monomers used have at least two double bonds (ie have multiple olefin groups). The high vapor pressure monomers used in the present invention can evaporate at low temperatures and therefore do not degrade (decompose) in the heating step. The absence of non-reactive degradation products means that films formed from these low molecular weight, high vapor pressure monomers have low volatile components. As a result, substantially all of the attached monomers are reactive and form a complete coating when exposed to a radiation source. These properties make it possible to provide a substantially continuous coating, despite the fact that the coating is very thin. The cured coating exhibits excellent adhesion and resists chemical attack by organic solvents and inorganic salts.

Polyfunctional acrylic compounds are particularly useful monomeric materials because of their reactivity, physical properties, and the nature of cured coatings formed from such compounds. The general formula of such a polyfunctional acrylic compound is:

Embedded image Wherein R1 is a mixture of aliphatic, alicyclic or aliphatic-alicyclic groups; R2 is hydrogen, methyl, ethyl, propyl, butyl or pentyl; and n
Is 2 to 4].

Such multi-reactive acrylic compounds having the formula: can also be used in combination with various monoacrylates:

Embedded image Wherein R ² is as defined above; X ¹ is
H, epoxy, 1,6-hexanediol, tripropylene glycol or urethane; and r, s is 1-18
X ³ is CN or COOR ³ , wherein R ³ is 1
An alkyl group having 4 carbon atoms. Most often, X ³ is CN or COOCH ₃ .

Diacrylates having the following formula are particularly preferred:

Embedded image Wherein X ¹ , r and s are as defined above. Curing is achieved by opening the double bonds of the reactive molecules. This is achieved using an energy source such as an instrument that emits infrared, electron or ultraviolet radiation.

FIG. 6 illustrates a process of applying an acrylic coating. Acrylic compound monomer 100 is a dielectric evaporator
It passes through 102 and further through an ultrasonic atomizer 104 to a vacuum chamber 106. The monomer droplets are ultrasonically atomized and the droplets are evaporated, where they condense on a test tube or film placed on drum 108.

The condensed monomer liquid is then cured by radiation using an electron beam gun 110.

The second layer of the multilayer barrier coating, which is an inorganic material, can be used as disclosed in US Pat. Nos. 4,698,256, 4,809,876, 4,992,298 and 5,055,318, which are incorporated herein by reference. Radio frequency wave radiation, direct or dual ion beam deposition,
It can be formed on the acrylic coating by sputtering or plasma enhanced chemical vapor deposition.

For example, one method of depositing an oxide coating is provided by generating a glow discharge plasma in a previously depressurized chamber. The plasma is obtained from one or more components of the gas stream, and is preferably
A stream of gas is obtained from the thing. The product is placed in the plasma, preferably near the focused plasma, and the gas flow is regulated into the plasma. A silicon oxide-based coating is deposited on the substrate at the desired thickness. The thickness of the oxide coating is from about 100 angstroms (Å) to about 10,00010. A thickness of less than about 100 mm cannot provide a sufficient barrier, and
Above thicknesses may crack and reduce the barrier effect. Most preferably, the thickness of the oxide coating is from about 1,000 to about 3,000.

Another method of applying an oxide coating is by focusing a plasma using a magnet. Preferably, the magnetically enhanced deposition of the silicon oxide-based coating on the substrate is preferably performed by glow discharge from a gas flow in a pre-depressurized chamber. The gas stream preferably consists of at least two components: a volatile organosilicon component and an oxidizer component such as oxygen, nitrous oxide, carbon dioxide or air, and optionally an inert gas component.

Examples of suitable organosilicon compounds that can be used in the gas flow of the plasma deposition process include the following, which are liquids or gases at about room temperature and have a boiling point of about 0 ° C. to about 150 ° C. when evaporated: Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, hexamethyldisilane, 1,1,2,2-tetramethyldisilane, bis (trimethylsilane) methane, bis (dimethylsilyl) methane, hexamethyldisiloxane, Vinyltrimethoxysilane, vinyltriethyloxysilane, ethylmethoxysilane, ethyltrimethoxysilane, divinyltetramethyldisiloxane, hexamethyldisilazane, divinylhexamethyltrisiloxane, trivinylpentamethyltrisiloxazane, tetraethoxysilane and tetra Methoxysilane.

Among the preferred organosilicon compounds, 1,1,3,
3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, vinyltrimethoxysilane and hexamethyldisilazane. These preferred organosilicon compounds have boiling points of 71 ° C, 101 ° C, 55.5 ° C, 102 ° C, 123 ° C and 127 ° C, respectively.

The inert gas as a gas flow option is preferably helium, argon or nitrogen.

The evaporated organosilicon component is preferably
Before flowing into the chamber, it is mixed with the oxygen component and the inert gas component. The amounts of these mixed gases are controlled by flow controllers so that the flow ratios of the components of the gas stream can be adjusted appropriately.

Various optical methods known in the art can be used to measure the thickness of the deposited coating in the deposition chamber, or the thickness of the coating can be determined by removing the product from the deposition chamber. Can be measured after

The deposition method of the present invention is preferably performed at relatively high power and very low pressure. A pressure of less than about 500 millitorr (mTorr) must be maintained throughout the deposition, and preferably the chamber is maintained between 43 and 49
0 mTorr pressure. Lower system pressures result in lower deposition rates, and higher system pressures provide faster deposition rates. High substrate temperature is polypropylene and PE
Polymers with low Tg such as T (Tg is −10 ° C. and 60 ° C., respectively) must be avoided so that when the plastic product being coated is heat sensitive, the amount of heat the substrate is exposed to during deposition is reduced. To minimize, high system pressures can be used.

The substrate is electrically insulated from the deposition system (except for electrical contact with the plasma) and is at a temperature below about 80 ° C. during deposition. That is, the substrate is not even heated.

In FIG. 7, the system for depositing a silicon oxide based thin film includes a closed reaction chamber 170 in which a plasma is formed and a substrate or test tube 171 is applied to deposit a thin film of material. It is placed on the support 172. The substrate can be any material that can withstand vacuum, such as plastic. One or more gases are supplied to the reaction chamber from a gas supply system. The electric field is created by power supply 174.

The reaction chamber is a plasma enhanced chemical vapor deposition (PEC).
Any suitable type of performing either the VD) or the plasma polymerization process may be used. Further, the reaction chamber can be modified to simultaneously coat one or more products in the chamber with an oxide layer.

The chamber pressure is regulated by a mechanical pump 188 connected to the chamber 170 by a valve 190.

The test tubes to be coated are first placed on a sample support 172 in a chamber 170. The pressure in the chamber is reduced to about 5 mTorr by a mechanical pump 188. The operating pressure of the chamber is from about 90 to about 140 mTorr in a PECVD or plasma polymerization process, which is achieved by flowing the process gases oxygen and trimethylsilane through the monomer inlet 176.

A thin coating is deposited on the exterior surface of the test tube to have the desired uniform thickness, or alternatively, the deposition process comprises:
Minimizing heating of the substrate and / or electrode; and /
Alternatively, it can be interrupted periodically to physically remove particulate matter from the product.

The magnets 196 and 198 are placed behind the electrode 200 to create an appropriate combination of magnetic and electric fields in the plasma area around the test tube.

The system is suitable for operation at low frequencies.
An example frequency is 40 kilohertz. But,
Some benefit can be obtained from operation at higher frequencies, such as the radio frequency range of several megahertz.

The silicon oxide-based coatings or mixtures thereof used in accordance with the present disclosure may contain conventional additives and ingredients which do not adversely affect the properties of the product being made.

Various substrates can be coated with a barrier coating by the process of the present invention. Such substrates include, but are not limited to, packaging, containers, bottles, jars, test tubes, and medical devices.

Plastic blood collection tubes coated with a multilayer barrier coating do not interfere with tests and analyzes typically performed on blood in the tubes. Such tests include, but are not limited to, routine chemical analysis, biological inertness, hematology, blood chemistry, blood typing, toxicology analysis or therapeutic monitoring and other clinical tests on body fluids. In addition, plastic blood collection test tubes coated with a barrier coating,
It can be used in automated machines such as centrifuges, and can be exposed to some level of radiation during the sterilization process without substantial changes in optical or mechanical and functional properties.

A plastic blood collection tube coated with a multilayer barrier coating can hold 90% of its original collection volume for one year. Retention of the collection volume is due to the presence of a substantial vacuum or reduced pressure in the test tube. The collection volume changes in direct proportion to the change in vacuum (vacuum). Thus, retention of the collection volume is due to good vacuum retention. Plastic test tubes coated with a barrier coating substantially prevent the permeation of gas through the test tube material and maintain and enhance test tube vacuum retention and collection volume retention. Plastic test tubes without the multi-layer coating according to the present invention can retain a collection volume of about 90% for about 3-4 months.

If a multi-layer barrier coating is also coated or applied to the interior of a plastic blood collection tube, the barrier coating is blood repellent and / or has anticoagulant properties. Can have.

It will be appreciated that it does not matter whether the plastic container is depressurized or not according to the present invention. The presence of a barrier coating on the outer surface of the container helps the user maintain the universal integrity of the container holding the sample so that it can be properly disposed of without any contamination. Of note is the transparency of the barrier coating when coated or applied to the container and the resistance to abrasion or scratching.

The barrier coatings used in accordance with the present disclosure may include conventional additives and ingredients that do not adversely affect the properties of the product being made.

The following examples do not limit any particular aspect of the present invention, but are merely illustrative.

[0074]

EXAMPLE 1 Plastic barrier coating with multilayer coating
Acrylic compound coating was applied to polypropylene test tubes and thin films (substrates) having various thicknesses in a room. Into the room, tripropylene glycol diacrylate (TPGDA) was fed to an evaporator and flash evaporated at about 343 ° C. onto a substrate in the room to condense. The condensed monomer film was then E-beam cured by an electron beam gun.

Acrylic compound coating (TPGD)
The substrate coated with A) was then washed with a mixture consisting of a solution of equal volumes of microdetergent and deionized (DI) water. The substrate was thoroughly rinsed with DI water and air dried. The washed substrate was then stored at room temperature in a vacuum oven until coated.

The washed substrate was then mounted on a support placed midway between the electrodes in a glass vacuum chamber. The chamber was sealed and a mechanical pump was used to obtain a base pressure of 5 mTorr.

The configuration of the electrode is such that a permanent magnet placed behind the titanium electrode is internally capacitively coupled. This particular configuration provides the ability to converge the glow between the electrodes because the probability of collision between electrons and reactant gas molecules is increased.
The net result of using a magnetic field is similar to increasing the power used at the electrodes without the disadvantages of higher impact energy and increased substrate heating. Magnetron irradiation allows operation in the low pressure region and a substantial increase in polymer deposition rate.

A monomer consisting of a mixture of trimethylsilane (TMS) and oxygen was introduced from a stainless steel tube near the electrodes. The gases were mixed in the monomer inlet tubing before being introduced into the chamber. The flow rate was manually adjusted with a stainless steel metering valve. A power supply operated at a frequency of 40 kHz was used to power the electrodes. TM polymerized on a polymer substrate
The system variables used to deposit the S / O ₂ thin coating were as follows: Surface pretreatment: TMS flow rate = 0 sccm Base pressure = 5 mTorr Oxygen flow rate = 10 sccm System pressure = 140 mTorr Power = 50 Watts Time = 2 minutes Oxide deposition: TMS flow rate = 0.75-1.0 sccm Oxygen flow rate = 2.5-3.0 sccm System pressure = 90-100 mTorr Power = 30 Watts Coating time = 5 minutes Reaction after thin film is deposited The vessel was cooled. Then
The reactor was opened and the multilayer barrier coated substrate was removed.

Example 2: Applying a multi-layer barrier coating
Acrylic compound coating was applied to polypropylene test tubes and films (substrates) of various thicknesses in a room. A 60:40 mixture of isobornyl acrylate: epoxy diacrylate (IBA: EDA) was fed into the chamber and flashed at about 343 ° C. onto a substrate in the chamber and condensed. The condensed thin film of monomer is then
UV cured with 365 nm actinic radiation.

Acrylic compound coating (IBA: E)
The substrate coated with DA) was then washed with a mixture consisting of a solution of equal volumes of microdetergent and deionized (DI) water. Substrates were rinsed thoroughly with DI water and air dried. The washed substrate was then stored at room temperature in a vacuum oven until coated.

The washed substrate was then mounted on a support placed midway between the electrodes in a glass vacuum chamber. The chamber was sealed and a mechanical pump was used to obtain a base pressure of 5 mTorr.

The configuration of the electrode is such that a permanent magnet placed behind the titanium electrode is internally capacitively coupled. This particular configuration provides the ability to converge the glow between the electrodes because the probability of collision between electrons and reactant gas molecules is increased.
The net result of using a magnetic field is similar to increasing the power used at the electrodes without the disadvantages of higher impact energy and increased substrate heating. Magnetron irradiation allows operation in the low pressure region and a substantial increase in polymer deposition rate.

A monomer consisting of a mixture of trimethylsilane (TMS) and oxygen was introduced from a stainless steel tube near the electrodes. The gases were mixed in the monomer inlet tubing before being introduced into the chamber. The flow rate was manually adjusted with a stainless steel metering valve. A power supply operated at a frequency of 40 kHz was used to power the electrodes. The system variables used for the deposition of the thin film of plasma polymerized TMS / O ₂ on the polymer substrate were as follows: Surface pretreatment: TMS flow rate = 0 sccm Base pressure = 5 mTorr Oxygen flow rate = 10 Sccm system pressure = 140 mTorr power = 50 watts time = 2 minutes Oxide deposition: TMS flow rate = 0.75-1.0 sccm oxygen flow rate = 2.5-3.0 sccm system pressure = 90-100 mTorr power = 30 watts Coating time = 5 minutes Thin coating After was deposited, the reactor was cooled. Then
The reactor was opened and the multilayer barrier coated substrate was removed.

Example 3: Having a multilayer barrier coating
Comparison of One Substrate and One Substrate All substrates prepared according to Examples 1 and 2 above were
The oxygen permeability (OTR) of the oxide coating was evaluated.

(I) Oxygen Permeability A sample of a thin film or plate was prepared using MO CON Ox-TRAN
(Modern Controls, Inc., 7500 Boone Avenue N., Minne
apolis, MN 55428) for oxygen permeability (OTR). One side of the thin film sample
Exposed to one atmosphere of 100% oxygen outside. Oxygen permeating through the sample film was entrained by a nitrogen carrier gas flowing on the other side of the film and detected by a coulometric sensor. An electrical signal was generated in proportion to the amount of oxygen transmitted through the sample. Samples at 30 ° C and relative humidity
(RH) Tested at 0%. Samples were conditioned for 1 to 20 hours prior to measuring oxygen permeability. The results are reported in Table 1 in units of cc / m ² -atm-day.

The sample in the test tube was MO CON Ox-TRAN 1,0
00 (Modern Controls, Inc., 7500 Boone Avenue N., Min
neapolis, sold by MN 55428) for oxygen permeability (OTR). A package adapter was used to position the test tube such that the test tube exterior was placed in 100% oxygen ambient and the test tube interior was flushed with a carrier gas of nitrogen. The test tube is then kept at 20 ° C and 5 ° C.
Tested at 0% RH. The tubes were allowed to equilibrate for 2-14 days before measuring the steady state permeability. The results are reported in Table 1 in units of cc / m ² -atm-day.

(Ii) Atomic% of Elements Existing in Oxide Film Model of Surface Science
An SSx-100 X-ray photoelectron spectrometer (ESCA) was used to determine the atomic percent of elements present in the oxide film. A thin film sample is placed in the spectrometer and the composition of the element
Measured for 00 angstroms. The surface was then argon ion etched as follows: 5
An argon ion beam of 000 V and 9-10 mA was irradiated on the sample surface. After 5 seconds, an ESCA spectrum was taken and this procedure was repeated a total of 5 times. Then, the etching time was increased to 20 seconds and ESCA was performed. This step was performed 10 times in total. Finally, the etch time was increased to 40 seconds and ESCA spectra were acquired until reaching the acrylic or polymer substrate body. The oxide layer can be etched from about 0 minutes to about
This was clearly indicated by the presence of silicon in the ESCA spectrum for 1.3 minutes.

(Iii) Analysis of the data in Table 1 and FIGS. 8 and 9 FIGS. 8 and 9 show the atomic% versus etching time for oxide samples attached to acrylic primer coated polypropylene and unacrylic polypropylene. Show. The data in Table 1 demonstrate that for these plasma deposition processes, the improved barrier properties correlate well with the improved gas barrier performance as a result of using a multilayer barrier coating. SiO _x deposition on acrylic treated surfaces results in less surface degradation and therefore a denser barrier structure. The data demonstrate that the acrylic-oxide coating method significantly improves the barrier properties of the plastic substrate, as the acrylic coating itself does not provide a detectable improvement to the barrier.

[0089]

[Table 1] Table 1 Sample Acrylic SiO_x Oxygen transferCoating Coating method (cc / m ² -atm-day)  PP thin film, reference experiment None None 1500 PP plate, 75 mil None Yes 37 PP plate, 75 mil TPGDA Yes 3.5 PP plate, 75 mil None Yes 65 PP test tube, Reference experiment None None 70 PP test tube IBA: DA None 70 PP Test tube No Yes 46-60 PP test tube IBA: DA Yes 4.3-6.4 IBA: DA = iso-norbornyl: Epoxy diacrylate (60:40), UV hardened TPGDA = Tripropylene glycol diacrylate, E-beam cured oxide Coating = 1000-3000 angstroms (measured by scanning electron microscope) PP = polypropylene plate = thickness 75 mil Thin film = thickness 2 mil Test tube = nominal wall thickness 40 mil

[Brief description of the drawings]

FIG. 1 is a perspective view of a typical blood collection tube having a stopper.

FIG. 2 is a longitudinal cross-sectional view of the test tube of FIG. 1 taken along line 2-2.

FIG. 3 is similar to the test tube of FIG. 1 without a stopper,
FIG. 3 is a longitudinal sectional view of a tubular container having a multilayer barrier coating.

FIG. 4 is a longitudinal sectional view of a tubular container with a multilayer barrier coating, similar to the test tube of FIG. 1 with a stopper.

FIG. 5 is a longitudinal cross-sectional view of a further embodiment of the present invention illustrating a test tube having a stopper similar to that of FIG. 1 and having a multilayer barrier coating spread over both the tube and the stopper. .

FIG. 6 illustrates an enlarged, partially sectioned diagram of a flash evaporator.

FIG. 7 illustrates a plasma deposition system.

FIG. 8 shows a polyethylene plate, acrylic and SiO.
7 illustrates the atomic percent of x versus etching time.

FIG. 9 illustrates atomic percent versus etch time for polyethylene plates and SiOx.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitchell Antoon 8048 New Brownswick Drive, Cincinnati, Ohio 45241 (56) References JP-A-5-137777 (JP, A) JP JP-A-3-162833 (JP, A) JP-A-2-167140 (JP, A) JP-A-62-207436 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61B 5 / 14 B01L 3/14 B32B 9/00

Claims (12)

(57) [Claims] 1. A plastic container comprising polyethylene terephthalate, polypropylene or polyethylene naphthalate having an open end, a closed end, an inner surface and an outer surface; and a multilayer barrier coating applied on the outer surface of the container, the coating comprising: A sample assembly comprising: a first layer comprising an acrylic primer coating material; and a second layer comprising silicon oxide or aluminum oxide adjacent to the first layer. 2. The assembly of claim 1 wherein said first layer is a mixed polymer of mono- and di-acrylates. 3. The method of claim 1, wherein said second layer is deposited by radio frequency wave radiation, direct ion beam deposition, dual ion beam deposition, sputtering, plasma enhanced chemical vapor deposition, or a magnetically enhanced plasma system. An assembly according to claim 1. 4. A method comprising: a first layer containing an acrylic primer coating material; and a second layer of a metal oxide on the first layer.
The assembly of claim 1, further comprising a multilayer barrier coating on the interior surface of the container. 5. The assembly according to claim 1, further comprising a closure at said opening of said container such that a container-closure boundary is formed. 6. The assembly according to claim 5, wherein said test tube is depressurized. 7. The assembly according to claim 5, wherein said plastic container is a test tube and said closure is an elastomeric stopper. 8. The assembly of claim 7, wherein said multi-layer barrier coating comprises a registered tamper serration adjacent the boundary of said container and closure. 9. The method according to claim 9, wherein the first layer is formed on the outer surface of the container in a pre-pressurized chamber in the following steps: (a) i) a polyfunctional acrylate, or ii) a mixture of a monoacrylate and a polyfunctional acrylate. (B) flash-evaporating said components into said chamber; (c) condensing a coating of the evaporated components on the outer surface of the container; and (d) The assembly of claim 1, wherein the assembly is applied by curing the coating. 10. A second layer is formed on the first layer in the pre-depressurized chamber in the following steps: (a) evaporating the organosilicon component to convert the volatilized organosilicon component to an oxidizing agent component and, if desired, Mixing with an inert gas component to form a gas flow outside the chamber; (b) generating a glow discharge plasma within the chamber from one or more components of the gas flow; (c) confining at least a portion of the plasma. The assembly of claim 9, wherein the gas flow is controlled while flowing into the plasma; and (d) deposited by depositing a layer of silicon oxide adjacent to the first layer. 11. The method of claim 1, wherein said oxidizing agent component is oxygen, nitrous oxide, carbon dioxide, air, or an inert compound.
Assembly according to 0. 12. The assembly of claim 10, wherein the plastic substrate is electrically isolated from the chamber except for contact with the confined plasma.