CN1160533A - Blood collection tube assembly - Google Patents
Blood collection tube assembly Download PDFInfo
- Publication number
- CN1160533A CN1160533A CN 97101057 CN97101057A CN1160533A CN 1160533 A CN1160533 A CN 1160533A CN 97101057 CN97101057 CN 97101057 CN 97101057 A CN97101057 A CN 97101057A CN 1160533 A CN1160533 A CN 1160533A
- Authority
- CN
- China
- Prior art keywords
- layer
- oxide
- coating
- assembly
- plasma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Laminated Bodies (AREA)
Abstract
The present invention is a plastic container coated with a multi-layer barrier coating. The multi-layer barrier coating is useful for providing an effective barrier against gas permeability in containers and for extending shelf-life of containers, especially plastic evacuated blood collection devices.
Description
The present invention relates to container, especially the plastics blood collection tube provides a kind of multilayer barrier coating of effective barrier layer of anti-G﹠W infiltration.
Along with people more and more emphasize to use the plastics curable product, need seek to improve the goods barrier properties of forming by polymer especially.
This class curable product that can be obtained suitable benefit by its barrier properties of improvement includes, but are not limited to collection tube, especially for the collection tube of blood collection.
Blood collection tube has some performance standard requirements to being applicable in the medical application.These performance standards are included in to have in 1 year time limit and keep about original extraction volume more than 90%, and radiation-curable sterilization and the ability of interference experiment and analysis not.
Therefore need seek to improve plastics that barrier properties, especially some performance standard of the goods of being made up of polymer be met find time blood collection tube and in medical application effective and available goods.
The present invention relates to a kind of plastic composite material container that on the surfaces externally and internally of preformed composite material vessel, has deposited two-layer at least barrier material with multilayer barrier coating.Desirable is the ground floor that this barrier material comprises the polymeric material on the outer surface that is applied to preformed composite material vessel, is applied to the second layer of the metal-oxide on the ground floor and is applied to the 3rd layer of inorganic oxide on the second layer.
The preferably high crosslinked acrylate polymer of ground floor (priming coat).Coating can be formed on the inner surface portion of container, outer surface part, or on the surfaces externally and internally part.
The second layer of barrier coat preferably can be the metal-oxide that is selected from the IVA main group metal, or the mixture of oxide and metal.
The 3rd layer of barrier coat preferably can be Si oxide based composition and use thereof in packaging, for example SiO
x(wherein X is 1.0-2.5); Or alumina base compositions.More preferably, the 3rd layer is the Si oxide based composition and use thereof in packaging that is applied on the second layer.
Preferably, priming coat is the mixture of mono acrylic ester (being isobornyl acrylate) and diacrylate monomer (being epoxy diacrylate or diacrylate polyurethane), as US4490774,4696719,4647818, disclosed in 4842893,4954371 and 5032461, these disclosures are incorporated herein by reference.This priming coat solidifies by electron beam or ultraviolet radiation source.
What meet the requirements is that ground floor mainly is to be formed by linked, and they are selected from the mixture of polyacrylate and polyacrylate and mono acrylic ester, and its mean molecule quantity is 150-1000, and the vapour pressure under the standard temperature and pressure (STP) is 1 * 10
-6-1 * 10
-1Torr.More preferably, this material is a diacrylate.
Preferably, the thickness of acrylate priming coat is about 1-10 micron, more preferably is about 1-5 micron.
Best, the second layer that is deposited on the ground floor comprises for example SnO of metal-oxide
x, GeO
xOr PbO
xThe deposition of this class film is preferably undertaken by the mixture that comprises tetramethyl tin and oxygen in the polymerization of the enhanced audio frequency capacitively coupled of magnetic arc chamber ionic medium body.
Preferably, the thickness of metal-oxide is about 50-250 dust, more preferably is about 75-200 dust.
The 3rd layer that is deposited on the second layer comprises oxide-based composition for example Si oxide or aluminium oxide.This class film is preferably produced by volatility organosilicon or organo-aluminum compound.
Si oxide or alumina base compositions provide densification on the second layer, the coating of anti-water vapour penetration.Preferably, the thickness of Si oxide or alumina layer is about 500-2500 dust, and more preferably trilaminar thickness is three to five times of second layer thickness.Can chap when coating layer thickness is about 5000 dusts, thereby can not be effective as the barrier layer.
Randomly, the 4th layer can be deposited on the 3rd layer, and they preferably comprise vinylidene chloride-methyl methacrylate-methacrylate acrylate copolymer (PVDC), heat curing epoxy thing coating, polyparaphenylene parylene polymer or polyester.
Preferably, the thickness of PVDC layer is about 2-15 micron, more preferably is about 3-5 micron.
Preferably carry out in vacuum chamber to the method for container coating base coat, curable monomer component is measured and is added in the vaporizer system of heating in vacuum chamber, and this material is atomized in this system, evaporates and is condensate on the surface of container.After monomer deposition is to the surface of container, by suitable device for example the electronic beam curing device be cured.Can repeat to deposit with curing schedule up to the sedimentary deposit that has reached institute's requested number.
The method of deposition second layer barrier film is as follows: (a) at first use the ground floor on the oxygen plasma pretreating containers first time; (b) in plasma, controllably flow into the air-flow that comprises organotin and oxygen or oxidant gas chemical compound; (c) to the ground floor deposition oxide, pressure is maintained at about below the 500 milli torrs.
The method that deposits the 3rd layer of barrier film is as follows: (a) with the second layer on the plasma pretreating containers that is coated with for the first time aerobic; (b) in plasma, controllably flow into the air-flow that includes organic silicon compound and oxygen or oxidant gas; (c) deposition oxide on the second layer meanwhile makes pressure be maintained at about below the 500 milli torrs in deposition process.
Although pre-treatment step is randomly, can be sure of that pre-treatment step has improved the bonding quality of interlayer.
Can be with organotin and organo-silicon compound and oxygen and randomly mix with helium or other noble gases such as argon or nitrogen.
Preferably, going up the method that deposits barrier coat at matrix (as the plastics collection tube) comprises the steps:
(a) select a kind of i that comprises) polyfunctional acrylate, or the ii) curable component of the mixture of mono acrylic ester and polyfunctional acrylic ester;
(b) the described component of flash distillation is in described chamber;
(c) on the outer surface of described container condensation through first tunic of evaporated components;
(d) solidify described film;
(e) on this film, carry out the plasma surface treatment of oxygen;
(f) evaporation organotin component and with volatility organotin component mix with a kind of oxidant constituents and randomly a kind of inert composition formation one outdoor airflow;
(g) indoor at this by a branch of or multi beam air-flow component generation glow discharge plasma;
(h) in this plasma, controllably flow into this air-flow, be constrained to the small part plasma simultaneously therein;
(i) at the second layer that on described ground floor, deposits stannum oxide;
(j) second layer is carried out the oxygen surface treatment;
(k) evaporation organosilicon component and with volatility organosilicon component mix with a kind of oxidant constituents and randomly a kind of inert composition formation one outdoor airflow;
(l) indoor at this by a branch of or multi beam air-flow component generation glow discharge plasma;
(m) in this plasma, controllably flow into this air-flow, be constrained to the small part plasma simultaneously therein;
(n) the 3rd layer of cvd silicon oxide on the described second layer;
Randomly, between the plastic substrate and first oxide skin(coating), can add bottom or smooth (Planarization) layer, before the deposition second layer, apply other and stop enhancement layer with oxygen plasma treatment first oxide skin(coating) and on discontinuous metal oxide layer.
Compare with pipe of making by polymer composition and its mixture that does not contain the barrier material coating or the pipe that only has oxide coating, apply and plastic tube with last coating can keep better vacuum, extraction volume and thermodynamics integrity basically with the multilayer barrier coating.In addition, the impact resistance of this pipe is better than glass.Be the transparency of laminated coating and shock resistance, anti abrasive persistency more significantly.Another characteristic of discontinuous oxide coating and the medical sterilization method of routine for example γ irradiation or oxirane (ETO) sterilization to compare be stable.
More preferably, container of the present invention is a blood collection device.This blood collection device both can be a kind of blood collector of evacuation, also can be a kind of blood collection tube of not evacuation.This blood collection tube is preferably by polyethylene terephthalate, and polypropylene gathers naphthalenedicarboxylic acid ethyl ester or its copolymer and makes.
Printing can be carried out on the multilayer barrier coating that is coated on the relevant container.For example can the print product evaluation on barrier coat, bar code, brand name, corporate logo, lot number, effect duration and other data and information.In addition, on barrier coat, can apply matt finish or corona discharge surface, so that this surface is suitable for writing down additional information on label.In addition, for example can on barrier coat, stick pressure-sensitive bonding label so that adapt to the too much label of various hospitals.
Preferably, multilayer barrier coating of the present invention has transparent or colorless appearance and can stick print content thereon.
Other advantages of the inventive method are the gas permeabilities that has reduced three-dimensional body, and this is irrealizable with the method institute of conventional employing thin film deposition.
Have been found that organic material (acrylate) provides the good platform that is used to produce fine and close IVA main group oxide barrier material in the present invention.
Find that also high crosslinked acrylate layer improved the bonding between the mixture layer of frosting and metal-oxide, and they have improved the thermodynamic stability of coating system.In addition, the acrylate priming coat has smooth (Planarization) (all being coated with) layer, lip-deep granule of overlie polymer and defective and the effect that reduces the defect concentration on the sedimentary inorganic coating.Because acrylate is a polar substances, this polarity forms the good binding between discontinuous metal-oxide and the acrylate approach is provided, so acrylate also has the good binding characteristic.In addition, have been found that between plastic tube of making by polypropylene and acrylate and formed good binding.Therefore, the invention provides mainly is the method for improving the polypropylene tube barrier properties.For example flame or oxide Cement Composite Treated by Plasma can further be improved the bonding characteristic of acrylate coatings and oxide coating by process for surface preparation.Owing to improved the surface coverage of metal-oxide basically, so the permeability of goods reduces significantly, and coverage is to obtain by the priming coat that has applied acrylate in surface of plastic products.
To can not disturb experiment and the analysis of usually blood in the pipe being carried out with the plastics blood collection tube that multilayer barrier coating of the present invention applies.This class experiment includes but not limited to that conventional chemical analysis, biologically inert, hematology, hematochemistry, blood group, oxicity analysis or medicine monitoring and other comprise the clinical experiment of body fluid.In addition, the plastics blood collection tube that applies with barrier coat can stand the processing of automation such as centrifuge, and can be exposed in sterilization process in the radiation of certain intensity, and does not change optics or machinery and functional characteristic basically.
Fig. 1 is the perspective view with typical blood collection tube of stopper;
Fig. 2 is the longitudinal sectional drawing of cutting open along Fig. 1 line 2-2;
Fig. 3 is the pipe that is similar to Fig. 1, does not have stopper but has the longitudinal sectional drawing of the tubular container of multilayer barrier coating;
Fig. 4 is the pipe that is similar to Fig. 1, has the longitudinal sectional drawing of the tubular container of stopper and multilayer barrier coating;
Fig. 5 is the longitudinal sectional drawing that explanation has another embodiment of the invention of the pipe that is similar to Fig. 1 stopper and multilayer barrier coating (comprising its pipe and stopper);
Fig. 6 is the local amplification sectional view of explanation flash distillation plant;
Fig. 7 illustrates plasma deposition system;
Fig. 8 is the sketch map that explanation is deposited on the layer on the matrix;
Fig. 9 is the ESCA spectrogram of IV main group chemical compound and inorganic oxide discontinuity layer.
The present invention may be embodied in other the concrete form, but is not limited to be only used for retouch in detail for example In any concrete scheme of stating, under scope and spirit of the present invention for the skilled skill of this area Various other the changes of art personnel are apparent and are easy to preparation. Scope of the present invention will by Appended claim and its equivalent scope are determined.
Referring to accompanying drawing, wherein identical reference number represents the same parts of its a few width of cloth figure, Fig. 1 and Fig. 2 table Shown typical blood collection tube 10, it has the sidewall 11 that extends to blind end 18 from openend 16 With the stopper 14 of being furnished with base circle part or plug lateral margin 15, the plug lateral margin extends into interior and presses to sidewall Inner surface 12 is to keep on the spot stopper 14.
Fig. 2 illustrates in blood collection tube, and vacuum has three kinds to change mechanism: (A) by the stopper material The gas permeation of material; (B) by the gas permeation of pipe with (C) in the leakage of stopper with the pipe contact position. Therefore When not having gas permeation and leakage exists, will have good vacuum maintenance and extract the volume guarantor Hold.
Fig. 3 shows the preferred embodiment of the invention, and what at least two-layer barrier material of usefulness applied moulds The material pipe. Preferred embodiment comprises many basically parts identical with the parts of Fig. 1 and 2. Therefore, Play the like figure notation identical with those parts of Fig. 1 and 2 of similar effect, just at figure Use those parts of subscript " a " mark in 3.
Referring now to Fig. 3,, preferred embodiment of the invention collection tube assembly 20 comprises plastic tube 10a, It has the sidewall 11a that extends to sealed end 18a from openend 16a. Barrier coat 25 is except openend 16a The major part that runs through tube outer surface outward. Barrier coat 25 has for example acrylate material of polymeric material Ground floor 26, the IV main group metal oxide materials and the second layer 27, inorganic material is silica for example The 3rd layer 28 of the thing based composition and use thereof in packaging and organic upper coating be the 4th layer 29 of PVDC for example.
Fig. 4 illustrates another embodiment of the invention, and wherein collection tube assembly 40 has on the spot sealing The stopper 48 of the openend 41 of pipe 42. Just as can be seen, sidewall 43 extends to close from openend 41 End-blocking 44, stopper 48 have and run through the annular upper portion 50 of managing 42 top. Stopper 48 has the bottom Annular section or plug lateral margin 49, the plug lateral margin stretches into and presses to for the sidewall 43 that keeps on the spot stopper 48 Inner surface 46. Stopper also has partition part 52 and is used for inserting sleeve pipe.
Just can pass through partition when therefore, in a single day the user gets as shown in Figure 4 the container that includes sample 52 insert sleeve pipes, and part and the inclusion in the extraction tube 42 fully are to carry out various realities to this sample Test. What cover the pipe range major part is multilayer barrier coating 45. Multilayer barrier coating 45 covers basically The overwhelming majority except open end 41. Multilayer barrier coating 45 has polymeric material for example third The ground floor 54 of olefin(e) acid ester, metal oxide is SnO for examplex，GeO
xOr PbOxThe second layer 56, Inorganic material for example the 3rd layer 57 of silicon oxide material and organic barrier material for example PVDC the 4th Layer 58. The difference of the embodiment of Fig. 4 and Fig. 3 is to have applied layer 54 and 56 at pipe After this pipe when inserting stopper 48, can be evacuated. In addition, can be on pipe after vacuumizing The coated with multiple layer barrier coat.
Fig. 5 represents another embodiment of barrier coat and pipe. The effect of another embodiment and figure Embodiment shown in 4 is similar. Therefore, play like embodiment with Fig. 4 of similar effect In the identical figure notation of those parts, just in Fig. 5, use those parts of subscript " a " mark.
Referring now to Fig. 5,, in another embodiment of the present invention 60, multilayer barrier coating 45a coats Stopper 48a top 50a and the pipe 42a whole outer surface. 45a is at pipe for the multilayer barrier coating The place has serrated face 62 with the stopper interface. The alignment serrated face is so that it can determine whether the container that to seal Damaged. This class embodiment for example can be used to stopper airtight container on the spot. In case sample by Pack in this pipe, sample just can not be owing to removing of stopper is damaged so. In addition, alignment serrated face So that can be determined the container that whether seals suffers damage. This structure is for example at misapply medicine experiment, sample Be suitable in product evaluation and the quality control.
In another embodiment of the invention, multilayer barrier coating 45 repeatedly or in turn is coated with Be layed onto on the interior and/or outer surface of pipe. Preferably, apply at least twice.
Should be clear as one of skill in the art, this class pipe can comprise with additive at inside pipe wall Or the reagent of coating form.
The multilayer barrier coating has formed clear or transparent barrier layer basically. Therefore has at least two-layer resistance The inclusion of the plastic tube of the multilayer barrier coating of obstructing material is visible basically for the observer, The content of identifying simultaneously can represent in the multilayer barrier coating after in being added to plastic tube.
The ground floor of multilayer barrier coating can pass through immersion coating. Roll and apply or spraying acrylate list The mixture of body or monomer then forms at pipe by the UV solidification process.
The acrylate polymer material also can be by the evaporation described among the US 5032461 and curing and Be coated on the pipe, the disclosure part is incorporated herein by reference.
Acrylate evaporation and curing comprise and at first acrylate monomer are atomized into 50 microns liquid Drip, flash off then through the surface of heating, thereby produce propylene a kind of and the identical chemistry of original monomer The acid esters molecular vapors.
Almost having any acrylate of chemistry that requires can buy. They normally each Molecule has one, two or three acrylate groups. Can use among the present invention single-, two-and three The various mixtures of-acrylate. Most preferably be mono acrylic ester and diacrylate.
Acrylate is reactive the strongest a kind of in the chemicals. When they being exposed to UV or electronics Solidify rapidly in the time of in the bundle irradiation, form a kind of crosslinked structure. It is high temperature resistant and anti-that this structure is given coating The mill characteristic.
Employed monomeric substance has lower molecular weight, is 150-1000, is preferably 200-300, and the vapour pressure under standard temperature and pressure (STP) is about 1 * 10-6-1×10
-1Torr (namely has ratio More lower boiling material). Vapour pressure is about 1 * 10-2Torr is preferred. Polyfunctional acrylic ester is special Preferably. Employed monomer has at least two two keys (being most thiazolinyl). Use among the present invention The high-vapor-pressure monomer can evaporate at low temperatures, therefore (cracking) can not be degraded in heating process. Do not exist unreacted degradation products to mean the film tool that is formed by these low-molecular-weights, high-vapor-pressure monomer By the volatile quantity that forms that reduces. The result basically monomer of all depositions is reactive, and when being exposed to Be solidified into the film of intact in the time of in the irradiation bomb. Although this film is very thin, these characteristics can make it provide Basically continuous coating. Film through solidifying has fabulous caking property and anti-organic solvent and inorganic salts Chemical erosion.
Because the reactivity of acrylate, the characteristic of physical characteristic and the cured film that formed by these components, So polyfunctional acrylate is the monomer material of particularly suitable. The general formula of this class polyfunctional acrylic ester Be:
Wherein: R1Aliphatic, alicyclic or aliphatic-alicyclic group of mixing;
R
2Hydrogen, methyl, ethyl, propyl group, butyl or amyl group; With
N is 2-4.
This class polyfunctional acrylic ester also can be used in combination with various mono acrylic esters, for example has those mono acrylic esters of following formula:
Wherein: R2Definition as above;
X
1H. Epoxy, 1,6-hexylene glycol, tripropylene glycol or urethane; With
R, s are 1-18.
X
3CN or COOR3, R wherein3It is the alkyl with 1-4 carbon atom. Most of feelings X under the condition3CN or COOCH3。
Diacrylate with following formula is particularly preferred:
Wherein: X1, r and s definition are as above.
Curing is to realize by two keys of opening reaction molecular. Curing can for example be launched red by the energy Outward, the device of electronics or ultra-violet radiation is realized.
Fig. 6 has illustrated the method that applies acrylate coatings. A kind of acrylate monomer 100 directly passes through A high frequency evaporimeter 102 is then by a ultrasonic atomizer 104 and be imported into vacuum chamber 106 In. Monomer droplet is by ultrasonic atomizatio, on the pipe of rotation or condensation on film contained on the rotating cylinder 108 Place evaporation drop.
Monomer liquid through condensation passes through electron beam gun 110 hardening with radiation subsequently.
The second layer of multilayer barrier coating and the 3rd barrier coat can be by radio frequency discharges, direct or double ion The bundle deposition, the chemical vapour desposition that sputter or plasma strengthen forms, such as US4698256, 4809876,4992298 and 5055318 is described, and these disclosures are incorporated herein by reference.
For example, the deposition process of the second layer and the 3rd barrier coat is by producing in the chamber that vacuumizes in advance Giving birth to a kind of glow discharge plasma realizes. And plasma is directly from one or more flow groups Produce in the branch, preferably from air-flow itself, produce. Goods are placed in the plasma, and are preferred The plasma of ground proximity constraint, air-flow controllably flow in the plasma. The thickness of the second layer is for about The 50-250 dust is preferably the 75-200 dust. Barrier film is deposited on basically to desired thickness. The thickness of the 3rd layer of coating is about 100-10000 dust. Foot when being lower than about 500 dust, thickness can not be provided Enough stops, and can chap during greater than about 5000 dust when thickness, stops so reduced effectively. More excellent Selection of land, the thickness of the 3rd layer of oxide coating is about 1000-3000 dust.
Another method of deposition barrier coat is to use the magnet confining plasma. Preferably, on matrix The magnetization Enhancement Method of depositing silicon oxide-base film is in the chamber of the air-flow glow discharge that vacuumizes in advance Carry out. Air-flow preferably contains at least two kinds of components: volatilizable organosilicon or organotin component, and a kind of Oxidant constituents is oxygen for example, nitrous oxide, carbon dioxide or air and a kind of optional inert gas.
The organo-silicon compound and the organotin chemical combination that are suitable for that in plasma deposition method, are used for air-flow The example of thing is to be in a liquid state at ambient temperature or the material of gaseous state, and the boiling point that has is about 0-200 ℃, These materials comprise tetramethyl tin, tetraethyl tin, tetra isopropyl tin, tetra allylic tin, dimethyl methyl silicon Alkane, trimethyl silyl, diethylsilane, propyl silane, phenyl silane, hexamethyldisilane, 1,1,2,2-tetramethyl disilane, two (trimethyl silyl) methane, two (dimethyl silanes Base) methane, HMDO, vinyltrimethoxy silane, VTES, second Methoxylsilane, ethyl trimethoxy silane, divinyl tetramethyl disiloxane, hexamethyl two silicon Azane, divinyl hexam ethylcyclotrisiloxane, trivinyl pentamethyl three silica azane (trivinyl penta Methyltrisiloxazane), tetraethoxysilane and tetramethoxy-silicane.
Preferred organosilicon is 1,1,3,3-tetramethyl disiloxane, trimethyl silyl, six Methyl disiloxane (HMDSO), vinyl trimethylsilane, MTMS, vinyl three Methoxy silane and HMDS. The boiling point of these preferred organo-silicon compound is respectively 71 ℃, 55.5 ℃, 102 ℃, 123 ℃ and 127 ℃.
The air-flow of optional inert gas is helium, argon or nitrogen preferably.
Volatility organotin and organosilicon form best before inflow is indoor and oxygen component and inert gas Component is mixed. Amount by flow governor control these gases that mix like this is controlled air-flow in order to regulate The velocity ratio of component.
Various optional method well known in the prior art can be used to measure the thick of deposited film in the settling chamber Spend, or after goods shift out, can measure the thickness of film from the settling chamber.
Deposition process of the present invention preferably carries out under higher power and relative low pressure. In the deposition process, pressure is remained on be lower than about 500 milli torrs (mTorr), preferably, in the deposition of film The pressure of this chamber should be maintained at about 43-490 milli torr in the process. The pressure of system is more low, the speed of deposition More slow, and the pressure of system is more high, the speed of deposition is more fast. When the plastic products for the treatment of coating are thermo-responsive The time, can use higher system pressure so that the heat that stands at depositional stage chien shih matrix reaches minimum, This be because for the polymer of low Tg (vitrification point) for example polypropylene and PET (Tg is respectively-10 ℃ and 60 ℃) should avoid substrate temperature too high.
Make matrix and sedimentary system electrical isolation (except with plasma electrically contacts), and in deposition Matrix is in is lower than about 80 ℃ temperature. Namely need not consider to add hot basal body.
Referring to Fig. 7, the system that is used to deposit barrier coat (comprising the second and the 3rd barrier layer) comprises the reative cell 170 of a sealing, in this reative cell, forms plasma, and wherein matrix and pipe 171 are placed in and are used for deposit film on the sample supporting mass 172.Matrix can be any vacuum compatible material, for example plastics.One or more strands of gases are transported in this reative cell by gas delivery system 173.Produce electric field by power supply 174.
Reative cell can be the adequate types of carrying out any plasma enhanced chemical vapor deposition (PECVD) or plasma polymerization method.In addition, can change reative cell, so that in a reative cell, apply one or more goods with oxide skin(coating) simultaneously.
The pressure of chamber is by mechanical pump 188 controls that are connected with chamber 170 by valve 190.
At first pipe to be coated is contained on the sample supporting mass 172 of chamber 170.The pressure of chamber is reduced to about 5 milli torrs by mechanical pump 188.The operating pressure that is used for the chamber of PECVD or plasma polymerization process is about 90-140 milli torr, and be by monomer input port 176 with process gas, oxygen and barrier layer precursor flow in this chamber and realization.
Thin film is deposited on the pipe and the outer surface of sequence layer, and has desired uniform thickness or depositing operation can periodically be interrupted, so that the heat of matrix and/or electrode reaches minimum and/or mechanically remove particulate matter from these goods.
This system is suitable for the low frequency operation.The example of frequency is 40kHz.But, for example have some advantages in the radio-frequency region at several megahertzes during operation in higher frequency.
According to disclosure text, employed barrier film or its mixture can contain conventional additives and the characteristic of the goods made by it does not had the composition of negative interaction.
The 4th layer of the multilayer barrier coating can be passed through immersion coating, and the aqueous emulsion that rolls and apply or spray polyvinylidene chloride or homopolymer or copolymer then is formed on the 3rd layer by air drying.
The 4th layer of vinylidene chloride-acrylonitrile-methyl methacrylate-acrylic acid methyl ester .-acrylic copolymer preferably, thermoset epoxy thing coating, parylene polymer, or polyester.
Preferably, the 4th layer is the parylene polymer.Parylene is the generic name by the series of polymers member of U.S. Union Carbide Corp (Union Carbide Corporation) development.The basic element that is called as the series of parylene N is parylene (poly-P-exlylene), the straight chain crystalline material:
Parylene C, second member of parylene series are produced by the identical monomer as parylene N, and by obtaining modification with a hydrogen in the chlorine atom substituted aroma hydrocarbon.
Parylene D, the 3rd member of parylene series are produced by the same monomer as parylene N, and by obtaining modification with two hydrogen in the chlorine atom substituted aroma hydrocarbon.
More preferably, polymeric layer is vinylidene chloride-methyl methacrylate-methacrylate acrylate copolymer (PVDC).This polymer can have been bought, and commodity are called DARAN
R8600-C (trade mark of W.R.Grace and Co.), by GRACE, Organic Chemicals Division, Lexington, Mass sells.
The 4th layer of barrier coat, a kind of polymeric material, can be to apply the parylene polymer by the method that is similar to vacuum metallizing on the second layer, described in US3342754 and 3300332, these disclosures be incorporated herein by reference.In addition, the 3rd layer can be 1,1-dichloroethylene-acrylonitrile-methyl methacrylate-acrylic acid methyl ester .-acrylic copolymer, it is to pass through immersion coating, the aqueous emulsion that rolls and apply and spray a kind of polymer, then be coated on the second layer by this coating of air drying, as US5093194 and 4497859 described, these disclosures are incorporated herein by reference.
As shown in Figure 8, acrylate coatings A and second and trioxide base coating B have defective or scrambling C.Can be sure of only can not realize the covering fully of matrix D with acrylate and oxide-base coating.So the 4th layer of coating of PVDC.E can be coated on the trioxide base coating, to produce complete basically barrier layer on matrix surface.
Can apply various matrixes by method of the present invention with barrier coat.This class matrix includes but not limited to, packaging material, container, bottle, cylinder, pipe and medical devices.
To not disturb experiment and the analysis that blood in the pipe is carried out with the plastics blood collection tube that the multilayer barrier coating applies.This class experiment includes, but not limited to the conventional chemical analysis, biologically inert, and the hematology, hematochemistry, blood group, oxicity analysis or medicine monitoring and other comprise the clinical experiment of body fluid.In addition, the plastics blood collection tube that applies with barrier coat can stand the processing of automation such as centrifuge, and can be exposed in sterilization in the irradiation of certain intensity, and does not change optics or machinery and functional characteristic basically.
The plastics blood collection tube that applies with the multilayer barrier coating can keep reaching 90% original extraction volume in the time limit in 1 year.The indivisible vacuum of existence in the pipe or the pressure of reduction are depended in the maintenance of extracting volume.The change of extracting volume directly and vacuum (pressure of reduction) change over direct ratio.Therefore, the maintenance of extraction volume depends on that good vacuum keeps.The plastic tube that applies with barrier coat has stoped the gas infiltration by this tube material basically, so that the vacuum of maintenance and increase pipe keeps and extract the maintenance of volume.The plastic tube that does not have laminated coating of the present invention can keep about 90% extraction volume at about 3-4 a middle of the month.
If the multilayer barrier coating is also applied or is applied on the inner surface of plastics blood collection tube, this barrier coat can be that blood repels (hemorepellent) and/or has the characteristic of clot activator so.
Should be clear, whether the plastic composite material container is evacuated not difference according to the present invention.The barrier coat that exists on the container outer surface has the effect of the general integrity of the container that keeps being equipped with sample so that can suitably handle to them, and to user without any pollution.The transparency that applies or be applied to the barrier coat on the container is significant and has wear-resistant and marresistance.
Be used for the composition that barrier coat of the present invention can contain conventional additive and the characteristic of the goods made thus do not had negative interaction.
The following examples only are for example, rather than to the restriction of any specific embodiments of the present invention.
Embodiment 1
Method with multilayer barrier coating coating plastic matrix
Go up coating one deck acrylate coatings indoor to polypropylene tube and film (matrix), in this indoor isobornyl acrylate with 60: 40: (IBA: mixture EDA) is input in the vaporizer epoxy diacrylate, is being flashed on this indoor matrix under about 343 ℃ and is carrying out condensation.To be cured through the monomer film of condensation photochemical light source then by 365nm.
Mixture with micro-detergent that contains equivalent and deionized water (DI) solution cleans with acrylate coatings (IBA: the EDA) matrix of Tu Fuing then.With the rinsing fully in DI water of this matrix, carry out air drying subsequently.Then will be coated up to them in the matrix accumulation vacuum at room temperature of cleaning.
Then the matrix through cleaning is fixed on the supporting mass, supporting mass is positioned at the centre of the electrode of vacuum chamber.Make this chamber airtight, make pressure of foundation reach 5 milli torrs with mechanical pump.
Electrode configuration is the alnico magnets coupling on the internal capacitance ground and the titanium electrode back side.This specific configuration is owing to collision probability between electronics and the reactant gas molecules increases the ability that the interelectrode aura of constraint is provided.The end product that applies magnetic field is similar with the electric power that is applied to the increase on the electrode, but does not have the shortcoming of higher Impact energy and increase matrix heat.Use magnetron discharge to allow under lower pressure, to operate and increase basically polymer deposition speed.
Import by stainless steel tube by the oxide precursor compositions that the mixture of tetramethyl tin (TMT) and oxygen is formed near electrode.Gas is just mixed in inlet tube before input is indoor.Flow velocity is by rustless steel metering valve Artificial Control.Powered operation under the audio frequency of use 40kHz provides electric power to electrode.Be used for the polymeric TMT/O of plasma on polymeric matrix
2The system parameter of thin film deposition as follows:
Surface preparation: TMT flow velocity=0sccm
Pressure of foundation=5 milli torrs
Oxygen flow=6～7sccm
System pressure=120 milli torrs
Power=30 watt
Time=0.5-1.0 minute
Oxide deposition: TMT flow velocity=2.75-3.25sccm
Oxygen flow=3.5-4.0sccm
System pressure=160-180 milli torr
Power=30 watt
Sedimentation time=0.75 minute
At the SnO that has deposited about 150 dusts
xAfter, oxygen flow is advanced in this chamber and by following system parameter carries out the oxygen plasma treatment second time:
Surface preparation pressure of foundation=5 milli torrs
Oxygen flow=10sccm
System pressure=140 milli torrs
Power=50 watt
Time=2 minute
Then will import by stainless steel tube by the precursors of inorganic oxides that the mixture of trimethyl silane (TMS) and oxygen is formed near electrode.Gas was mixed in the monomer input pipe before being input into this chamber.Flow velocity is by rustless steel metering valve Artificial Control.Powered operation under the audio frequency of use 40kHz provides electric power to electrode.Be used for the polymeric TMS/O of plasma on polymeric matrix
2The system parameter of thin film deposition as follows:
Oxide deposition: TMS flow velocity=1.5-2sccm
Oxygen flow=2.5-3.0sccm
System pressure=90-160 milli torr
Power=30 watt
Sedimentation time=4 minute
At the SiO that has deposited about 1000 dusts
xAfter, make reactor cooled.Open reactor then, take out matrix.The results are shown in the table 1.
Embodiment 2
Method with multilayer barrier coating coating plastic matrix
Clean polyethylene terephthalate (PET) film with micro-detergent that contains equivalent and deionized water (DI) solution.After with this film of solution rinsing, make this film carry out air drying and storage 12 hours under vacuum.
Then this film is placed the settling chamber and make pressure reach about 5 milli torrs with mechanical pump.
Electrode configuration is the alnico magnets coupling on the internal capacitance ground and the titanium electrode back side.This specific configuration increases the ability that retrains interelectrode aura that provides because of collision probability between electronics and the reactant gas molecules.The end product that applies magnetic field is similar with the electric power that is applied to the increase on the electrode, but does not have the shortcoming of higher Impact energy and increase matrix heat.Use magnetron discharge to allow under lower pressure, to operate and increase basically polymer deposition speed.
At first use oxygen plasma pretreatment film 30 seconds then, the flow velocity of oxygen is about 6SCCM, and system pressure is about 120 milli torrs, and power is about 30W.
After carrying out the oxygen pretreatment, make the metal oxide precursor compositions of forming by tetramethyl tin (TMT) and oxygen by stainless steel tube input near electrode.Gas was mixed in the monomer input pipe before being input into this chamber.Flow velocity by metering valve control tetramethyl tin and oxygen.Audio frequency by about 40kHz provides electric power to electrode.Deposition SnO
xSystem parameter as follows:
Surface preparation: oxygen gas flow rate=6sccm
System pressure=120 milli torrs
Power=30 watt
Sedimentation time=30 minute
Oxide deposition: TMT flow velocity=12sccm
Oxygen gas flow rate=3.2sccm
System pressure=140 milli torrs
Power=30 watt
Sedimentation time=45 second
Depositing SnO
xAfter, oxygen flow is advanced in this chamber, the plasma of generation has been removed remaining carbon from the surface of film.Carry out the oxygen plasma treatment second time by following system parameter then:
Surface preparation: oxygen flow=5sccm
System pressure=120 torrs
Power=30 watt
Time=60 second
Then by the mixture deposition last oxide skin(coating) of following system parameter with trimethyl silane (TMS) and oxygen:
TMS flow velocity=5.8sccm
Oxygen flow=3.3sccm
System pressure=120 milli torrs
Power=30 watt
Sedimentation time=4 minute
Make this chamber cooling and taking-up through the PET of coating film subsequently.Through the results are shown in the table 1 of the PET of coating film.Polymer as shown in Figure 9, the laminar composite of stannum oxide and Si oxide have been shown by ESCA and the sem analysis that film is carried out.
Estimate the oxygen infiltration (OTR) of all substrates in oxide coating below with the foregoing description preparation.
(i) oxygen infiltration (OTR):
Adopt MO CON O
xThe oxygen infiltration (OTR) of-TRAN 2/20 (by Modern Controls, limited company sells, 7500 Boone Avenue N., Minneapolis, MN 55428) test membrane or plate sample.The one-sided of film sample is exposed in 1 atmospheric 100% oxygen atmosphere.The oxygen that sees through the infiltration of this sample film is entrained in the nitrogen carrier gas stream on the opposite side of this film and with a coulomb sensor.The signal of telecommunication that produces is directly proportional with the oxygen amount that sees through sample.At 30 ℃ and 0% relative humidity (R.H) test sample down.Before measuring the oxygen infiltration, make sample adapt to 1-20 hour.The results are shown in the table 1, unit is cc/m
2-atm-days.
Adopt MO CON O
xThe oxygen infiltration (OTR) of-TRAN 1000 (by Modern Controls, limited company sells, 7500 Boone Avenue N., Minneapolis, MN 55428) testing tube sample.Adopt the adapter stationary pipes, so that 100%O is immersed in the outside of pipe
2In the atmosphere, the inboard of pipe is washed with the nitrogen carrier gas simultaneously.Then this pipe is tested under 20 ℃ and 50%R.H..Before the steady seepage of testing tube, make they balance 2-14 days.The results are shown in the table 1, unit is cc/m
2-atm-days.
The atoms of elements percent that (ii) exists in the oxide coating:
Adopt the Surface Science Model spectrometer of SSx-100X ray photoelectric (ESCA) to measure the atoms of elements percentage rate that exists in the oxide coating.The film sample is placed in the spectrometer, measure and deposit to surperficial the elementary composition of about 100 dusts that.Use argon ion etch surface then as follows: with 5000V and 9-10mA ar-ion beam irradiation specimen surface.After 5 seconds, repeating this step totally 5 times with the ESCA spectral manipulation.Then the etch time is increased to 20 seconds, then handles and repeat this step totally 10 times with ESCA.At last, the etch time is increased to 40 seconds and obtains ESCA spectrum up to forming whole acrylate or polymeric matrix.The silicon that exists in by ESCA spectrum in about 0-1.3 minute etch time can clearly illustrate that oxide skin(coating).
Sample acrylate SnO
xSiO
xOTR oxygen transmission rate
Coating coating coating (cc/m
2-atm-days)
30℃，0％?RH
The PP pipe, contrast 60
PP manages IBA: DA does not have 20
PP pipe do not have and has＜and 9
PP pipe do not have and has＜and 9
The PET film does not have 30
The PET film does not have 16
The different norborneol of IBA: DA=: epoxy diacrylate (60: 40), UV is solidified
SiO
xCoating=1000-3000 dust (measuring) by scanning electron microscope
Doped tin oxide coatings=70-200 dust (measuring) by scanning electron microscope
The PP=polypropylene
The standard wall thickness of pipe=40 mils
PET thickness=1 mil
Claims (18)
1, a kind of sample assembly comprises:
Has an opening, a sealed end, the plastic containers of an inner surface and an outer surface; Be coated on the described container outer surface and cover the multilayer barrier coating of the described outer surface major part of described container, described coating has the ground floor that comprises acrylate priming coat material, at the second layer that comprises metal-oxide on the described ground floor with comprise the 3rd layer of inorganic oxide material on the described second layer.
2, the assembly of claim 1 also is included in the closing cock on the described opening of described container, thereby constitutes container and closing cock interface.
3, the assembly of claim 2, wherein said plastic containers are pipes, and described closing cock is an elastic plug.
4, the assembly of claim 1, wherein said multilayer barrier coating comprise the align closely knit serrated face adjacent with described sealing interface with described container.
5, the assembly of claim 1, wherein said ground floor are single-and the polyblends of two-acrylate.
6, the assembly of claim 1, the wherein said second layer is SnO
x, GeO
xAnd PbO
x
7, the assembly of claim 1, wherein said the 3rd layer is aluminium oxide or Si oxide based composition and use thereof in packaging.
8, the assembly of claim 7, wherein said the 3rd layer comprises Si oxide.
9, the assembly of claim 7, the wherein said second layer is by radio-frequency discharge, direct ion bundle deposition, dual ion beam deposition, sputter, the enhanced plasma system of enhanced chemical vapour desposition of plasma or magnetic and sedimentary.
10, the assembly of claim 1, also comprise one on described the 3rd layer by the thermoset epoxy thing, described the 4th layer of forming of parylene polymer, homopolymer, copolymer or polyester.
11, the assembly of claim 10, wherein said ground floor comprise polymeric acrylate and described the 3rd layer and comprise Si oxide and described the 4th layer and comprise polyvinylidene chloride.
12, the assembly of claim 1 also has the multilayer barrier coating on the inner surface of described container, and described ground floor comprises acrylate priming coat material, and the second layer on described ground floor is discontinuous metal-oxide and organic material the 3rd layer.
13, the multilayer barrier coating has:
The ground floor that comprises the acrylate material;
The second layer that comprises metal-oxide on described ground floor;
With on the described second layer, comprise the 3rd layer of inorganic oxide.
14, the coating of claim 13, wherein said the 3rd layer is aluminium oxide or Si oxide.
15, the coating of claim 13, the wherein said second layer is SnO
x, GeO
xAnd PbO
x
16, the coating of claim 13 also is included in the 4th layer of polyvinylidene chloride on described the 3rd layer.
17, in the chamber of evacuation in advance on plastic substrate the method for deposit multilayer barrier coat, comprising:
(a) select a kind of i that comprises) polyfunctional acrylate, or the ii) curable component of the mixture of mono acrylic ester and polyfunctional acrylic ester;
(b) the described component of flash distillation is in described chamber;
(c) on the outer surface of described container condensation through first tunic of evaporated components;
(d) solidify described film;
(e) evaporation organotin component and with volatility organotin component mix with a kind of oxidant constituents and randomly a kind of inert composition formation one outdoor airflow;
(f) indoor at this by a branch of or multi beam air-flow component generation glow discharge plasma;
(g) in this plasma, controllably flow into this air-flow, be constrained to the small part plasma simultaneously therein;
(h) on described ground floor, deposit stannic oxide layer;
(i) evaporation organosilicon component and with volatility organosilicon component mix with a kind of oxidant constituents and randomly a kind of inert composition formation one outdoor airflow;
(j) indoor at this by a branch of or multi beam air-flow component generation glow discharge plasma;
(k) in this plasma, controllably flow into this air-flow, be constrained to the small part plasma simultaneously therein;
(l) on the described second layer the 3rd of the depositing silicon oxide the layer; With
(m) go up the 4th layer of immersion coating PVDC to described the 3rd layer.
18, the method for claim 17, wherein said first and second layers is pretreated by oxygen plasma.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97101057 CN1160533A (en) | 1996-01-30 | 1997-01-27 | Blood collection tube assembly |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US593,958 | 1996-01-30 | ||
| CN 97101057 CN1160533A (en) | 1996-01-30 | 1997-01-27 | Blood collection tube assembly |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1160533A true CN1160533A (en) | 1997-10-01 |
Family
ID=5165486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97101057 Pending CN1160533A (en) | 1996-01-30 | 1997-01-27 | Blood collection tube assembly |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1160533A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105296965A (en) * | 2004-03-09 | 2016-02-03 | 埃克阿泰克有限责任公司 | Expanding thermal plasma deposition system |
| CN108138316A (en) * | 2015-08-18 | 2018-06-08 | Sio2医药产品公司 | Drug and other packagings with low oxygen transmission rate |
| WO2019014926A1 (en) * | 2017-07-21 | 2019-01-24 | 深圳先进技术研究院 | Medical implant device with encapsulation layer and encapsulation method of medical implant device |
-
1997
- 1997-01-27 CN CN 97101057 patent/CN1160533A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105296965A (en) * | 2004-03-09 | 2016-02-03 | 埃克阿泰克有限责任公司 | Expanding thermal plasma deposition system |
| CN108138316A (en) * | 2015-08-18 | 2018-06-08 | Sio2医药产品公司 | Drug and other packagings with low oxygen transmission rate |
| WO2019014926A1 (en) * | 2017-07-21 | 2019-01-24 | 深圳先进技术研究院 | Medical implant device with encapsulation layer and encapsulation method of medical implant device |
| US11617891B2 (en) | 2017-07-21 | 2023-04-04 | Shenzhen Cas-Envision Medical Technology Co., Ltd | Implantable medical device having package and method for packaging implantable medical device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100188289B1 (en) | Blood collection tube assembly | |
| JP3067667B2 (en) | Blood collection tube assembly | |
| JP3190585B2 (en) | Blood collection tube assembly | |
| EP0787824B1 (en) | Container with a non-ideal barrier coating sequence composition | |
| EP0787827B1 (en) | Blood collection tube assembly | |
| JP3224349B2 (en) | Blood collection tube assembly | |
| JP2000127290A (en) | Barrier covering and method for stacking barrier covering on plastic material by high output plasma chemical gas phase growth process | |
| CN108463493A (en) | The polymer substrate on the surface with the biomolecule adherency for possessing reduction and the thermoplastic article of this substrate | |
| CN1946646A (en) | Substrate, notably of glass, with a hydrophobic surface having an improved durability of the hydrophobic properties | |
| CN1432035A (en) | Barrier layer for polymers and containers | |
| JP2013063658A (en) | Method of manufacturing gas barrier laminate and gas barrier laminate | |
| CA2277679C (en) | Blood collection tube assembly | |
| JP4467868B2 (en) | High water-repellent laminate | |
| CN1771095A (en) | Method for surface modification of solid substances and surface-modified solid substances | |
| CN1160533A (en) | Blood collection tube assembly | |
| CN1160535A (en) | Blood collection tube assembly | |
| CN1160534A (en) | Blood collection tube assembly | |
| CN1795289A (en) | Chemical vapor deposition film formed by plasma cvd process and method for forming same | |
| CN1160532A (en) | Blood collection tube assembly | |
| JP5326782B2 (en) | Method for producing water-repellent article | |
| CN1160775A (en) | Non-ideal barrier coating sequence composition | |
| JP2000109581A (en) | Deposition of barrier coating film on plastic material by barrier coating and high-output plasma chemical vapor deposition | |
| JP4321706B2 (en) | Laminated body and method for producing the same | |
| JPH0671826A (en) | Glazing material for vehicle | |
| US20190225746A1 (en) | Surface-modified polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1002949 Country of ref document: HK |