CN1160535A - Blood collection tube assembly - Google Patents
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- CN1160535A CN1160535A CN 97101059 CN97101059A CN1160535A CN 1160535 A CN1160535 A CN 1160535A CN 97101059 CN97101059 CN 97101059 CN 97101059 A CN97101059 A CN 97101059A CN 1160535 A CN1160535 A CN 1160535A
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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 the multilayer barrier coating of a kind of effective barrier gas and water infiltration.
Along with people more and more emphasize to use the plastics curable product, need seek to improve the barrier properties of the goods of making by polymer especially.
This class includes, but not limited to collection tube by the curable product that its barrier properties of improvement can obtain suitable benefit, 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 comprise having about original extraction volume more than 90% of maintenance in 1 year time limit, and radiation-curable sterilization and not interference experiment and analysis.
Need to seek to improve the barrier properties of the goods of making by polymer thus, especially some performance standard plasticity blood drawing liquid collection tube that will obtain satisfying 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 the organic and inorganic materials of multilamellar.Desirable is the ground floor that the barrier coat material has the polymeric material on the outer surface that is applied to preformed composite material vessel, has the second layer that is applied to the organic and inorganic material sequence coating on the ground floor and is applied to the 3rd layer of organic material on the second layer.
The preferably high crosslinked acrylate polymer of ground floor (priming coat).Coating can be in the inner surface area of container, outer surface region, or form on the surfaces externally and internally zone.
The second layer is a plurality of organic and inorganic coating of sequence preferably.Preferably the sequence coating can be represented with following equaling:
The second layer=∑ (inorganic coating+organic coating+inorganic coating) n
N=0-10 wherein.
More preferably inorganic coating is Si oxide compositions, for example SiO
x(wherein x is 1.0-2.5); Or alumina base compositions.More preferably organic coating is high crosslinked acrylate polymer.
Randomly, the 3rd layer of preferably a kind of organic barrier compositions of barrier coat, for example polyvinylidene chloride (PVDC) preferably is applied on the second layer.
Preferably, priming coat is the mixture of a kind of mono acrylic ester (being isobornyl acrylate) and diacrylate monomer (being epoxy diacrylate or diacrylate polyurethane), as US 4490774,4696719,4647818, disclosed in 4842893,4954371 and 5032461, these disclosures are incorporated herein by reference.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 10 microns of about 1-, more preferably is about 5 microns of about 1-.
Be deposited on the second layer on the ground floor and preferably have a plurality of coatings of sequence, this coating comprises by Si oxide based composition and use thereof in packaging SiO for example
xThe coating of forming, they be obtain by volatilizable organic compound and acrylate.
The Si oxide based composition and use thereof in packaging provides a kind of densification, the coating of steam impenetrability, and preferably, the thickness of silicon oxide based coating is about 100-2000 dust (A), more preferably is about 500-1000 dust.Cracking can appear in the above coating of 5000 dusts, can not be effective as the barrier layer thus.
Acrylate provides the platform that is used to deposit inorganic coating.Preferably, the thickness of acrylate coatings is about 0.1-10 micron, more preferably is about 0.5-3 micron.
Randomly, the 3rd layer can be deposited on the second layer, and they preferably comprise vinylidene chloride-methyl methacrylate-methacrylate acrylate copolymer (PVDC), thermoset 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.
Apply to container that the method for ground floor preferably carries out in vacuum chamber, 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.But repeated deposition and curing schedule are up to the sedimentary deposit that has reached institute's requested number.
The method of depositing silicon oxide-base coating is as follows: (a) with the ground floor on the first plasma pretreating containers that is coated with aerobic; (b) in plasma, controllably flow into the air-flow that includes organic silicon compound; (c) depositing silicon oxide on ground floor meanwhile makes pressure be maintained at about 500 microns below the Hg in deposition process.
Although pre-treatment step is randomly, can be sure of that pre-treatment step improved the bonding quality between the second layer and the ground floor.
Preferably with organo-silicon compound and oxygen with randomly helium or other noble gases such as argon or nitrogen mix, and preferably magnetic is constrained to the small part plasma in the surface near ground floor in deposition process, is more preferably undertaken by counter-balanced magnetron not.
By dipping or spraying PVDC is coated on the second layer, under about 50 ℃, uses air drying then.
More 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) this component of flash distillation is in this chamber;
(c) first tunic of condensation evaporation component on the outer surface of this container;
(d) solidify this film;
(e) a kind of organosilicon component of evaporation also will be mixed with a kind of oxidant constituents and randomly a kind of inert composition through the organosilicon component of evaporation, form a kind of outdoor airflow;
(f) indoor at this by a branch of or multi beam air-flow component generation glow discharge plasma;
(g) this air-flow of controlled inflow in plasma is constrained to the small part plasma simultaneously therein;
(h) coating of depositing silicon oxide on the close ground floor;
(i) repeat above-mentioned steps (a)-(d), thereby on silicon oxide coatings, deposit acrylate coatings; With
(j) repeat above-mentioned steps (e)-(h), thus on described acrylate coatings the depositing silicon oxide coating.
Randomly, this method also comprises:
(k) immersion coating PVDC on silicon oxide coatings.
Randomly, but before immersion coating PVDC on the silicon oxide coatings about 1-10 time of repeating step (i)-(j).
Randomly, container and/or ground floor can carry out flame treatment or plasma oxygen processing or Corona discharge Treatment before coated second layer coating.
Use the multilayer barrier coating, comprise priming coat, the plastic tube that applies with oxide coating and last coating can extract volume and its mechanical integrity than not having the pipe of being made up of polymer composition and its mixture of barrier material coating or the pipe that only contains oxide coating to keep the vacuum space better in the prior art basically.In addition, the impact resistance of pipe is better than glass.Be the transparency of laminated coating and shock resistance, anti abrasive persistency more significantly.
More preferably, container of the present invention is a blood collection device.This blood collection device both can be a kind of evacuation blood collection tube, also can be a kind of blood collection tube of not evacuation.Preferably this blood collection tube is 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 on barrier coat, can print and comprise product evaluation, 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 apply the content of printing thereon.
The advantage of the inventive method is to reduce the gas permeability of three-dimensional body, and this is irrealizable with the method institute of conventional employing thin film deposition.
Having been found that the acrylate organic material provides in the present invention is used to produce fine and close SiO
xThe platform of barrier material.
Also the high crosslinked acrylate layer of discovery has been improved frosting and SiO
xBetween bonding, and improved the thermodynamic stability of coating system all sidedly.In addition, the acrylate priming coat has leveling (planarization) (homogenize) coating, in the effect that covers granule and imperfection on the polymer surfaces and reduce the defect concentration on the deposition inorganic layer.Because acrylate is a polar substances, this polarity is to SiO
xAnd the good binding between the acrylate forms 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 oxygen plasma treatment can further be improved the bonding characteristic of acrylate coatings and oxide coating by process for surface preparation., owing to improved SiO
xSurface coating, so the permeability of goods reduces significantly, and cover layer is to obtain by the priming coat that has applied acrylate on surface of plastic products.
Because the PVDC layer has stopped up SiO
xDefective on the coating and/or scrambling and improved SiO
xLayer.In addition, the PVDC coating has been improved SiO
xAbrasion property.
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 are 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 contact a certain amount of irradiation in disinfecting process, 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 is the explanation plasma deposition system.
Fig. 8 is the sketch map that explanation is deposited on the layer on the matrix.
The present invention can be summarized in other concrete form, but be not limited to only be used for describing in detail for example Any concrete scheme. Under scope and spirit of the present invention for the knack people of this area Various other the changes of member are apparent and easy to implement. Scope of the present invention will be by appended Claim and its equivalent scope determine.
Referring to accompanying drawing, wherein identical reference number represents the same parts of whole a few width of cloth figure, Fig. 1 and Fig. 2 Represented typical blood collection tube 10, it has the sidewall that extends to blind end 18 from openend 16 11 and be furnished with the stopper 14 of base circle part or plug lateral margin 15, lateral margin extends into interior and presses to sidewall Inner surface 12 is used for keeping on the spot stopper 14.
Fig. 2 illustrates in blood collection tube vacuum has three kinds to change mechanism: (A) pass through stopper material Gas permeation; (B) by the gas permeation of pipe with (C) in the leakage of stopper with the pipe contact position. Therefore work as Do not have gas permeation and leak when not existing, will have good vacuum space and good extraction volume Keep.
Fig. 3 shows the preferred embodiment of the invention, and what at least two-layer barrier material of usefulness applied moulds Material pipe, preferred embodiment comprise many basically parts identical with Fig. 1 and 2 parts. 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 have polymeric material for example acrylate One deck 26, the second layer 27 of the inorganic and organic coating of a plurality of sequences and organic upper coating be PVDC for example The 3rd layer. The second layer preferably has a plurality of sequence coatings that represent with following formula:
The second layer=∑ (inorganic coating+organic coating+inorganic coating) n
N=0-10 wherein.
Fig. 4 illustrates another embodiment of the invention, and wherein collection tube assembly 40 has the original position 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, plug lateral margin stretch into and press to be used in the side inner surface 46 of sidewall 43 former The position keeps stopper 48. 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, with part and the inclusion in the extraction tube 42 fully, to carry out various to this sample Experiment. What cover the pipe range major part is multilayer barrier coating 45. Multilayer barrier coating 45 is covered basically Covered the overwhelming majority except open end 41. Multilayer barrier coating 45 has of polymeric material One deck 54, the inorganic and organic material of a plurality of sequences be the second layer of Si oxide and acrylate and organic for example Barrier material is the 3rd layer of PVDC for example. The difference of the embodiment of Fig. 4 and Fig. 3 is this pipe Can be evacuated when after pipe has applied layer 54 and 56, inserting stopper 48. In addition, Can be to coated with multiple layer barrier coat on the pipe after vacuumizing.
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 Has serrated face 62 with the stopper interface. Whether the alignment serrated face is decreased in order to can measure the container of sealing Bad. This class embodiment can be used to for example use stopper original position airtight container. In case sample is loaded into In this pipe, sample just can not be owing to removing of stopper is damaged so. In addition, can align serrated face with Whether the container that just can measure sealing is damaged. This structure is for example in misapply medicine experiment, sample identification Be suitable in 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 inside pipe wall comprise additive 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 be on the multilayer barrier coating after in being loaded into plastic tube mark.
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, then they are flashed off the surface of heating, thereby produce a kind of and the identical chemistry of original monomer The acrylate molecular vapors.
The acrylate that almost has any chemistry requirement can have been bought. They are each molecule normally Has one, two or three acrylate groups. Can use among the present invention single-, two-and three-the third The various mixtures of olefin(e) acid ester. 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 radiation, 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 is about 1 * 10 in the vapour pressure of standard temperature and pressure (STP)-6-1×10
-1Torr (namely has More lower boiling material). Vapour pressure is about 1 * 10-2Torr is preferred. Polyfunctional acrylic ester is Particularly preferred. Employed monomer has at least two two keys (being most thiazolinyl). Among the present invention The high-vapor-pressure monomer that uses can evaporate at low temperatures, therefore can not be degraded in heating process. No Exist unreacted degradation products to mean by these low-molecular-weights, the film that the high-vapor-pressure monomer forms has Reduce the volatile quantity that forms. The result basically monomer of all depositions is reactive, and when being exposed to spoke Be solidified into the film of intact when penetrating in the source. Although this film is very thin, these characteristics can make it that base is provided Continuous coating on the basis. 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 material, 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 and s definition 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 and realizing.
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, through the Drop Condensation of evaporation on the pipe of rotation or be contained in rotating cylinder 108 On film on.
Monomer liquid through condensation passes through electron beam gun 110 radiation curings subsequently.
The second layer of multilayer barrier coating, a kind of inorganic material can be by radio frequency discharge, direct or two from Son bundle deposition, sputter or plasma chemistry vapor deposition and form at acrylate coatings are such as USP 4698256,4809876,4992298 and 5055318 is described, and these disclosures are incorporated herein conduct Reference.
For example, provide a kind of by in the chamber that vacuumizes in advance, producing a kind of glow discharge plasma The method of deposition oxide coating. Plasma produces from one or more air-flow components, and is preferred Ground produces from air-flow itself. Goods place plasma, preferably near the plasma that retrains Body, air-flow controllably flow in the plasma. The silicon oxide based thin film deposition on matrix until reach Desired thickness. The thickness of oxide coating is about 100-10000 dust. Be lower than about 500 when the thick end Can not provide enough barrier layers during dust, and can chap during greater than about 5000 dust when thickness, thereby reduce Effective barrier layer. More preferably, the thickness of oxide coating is about 1000-3000 dust.
Another method of deposition oxide coating is to use the magnet confining plasma. Preferably, at matrix The magnetization Enhancement Method of upper depositing silicon oxide-base film be vacuumize in advance by air-flow glow discharge Carry out in the chamber. Air-flow preferably contains at least two kinds of components: volatilizable organosilicon component, oxidant group Divide for example oxygen, nitrous oxide, carbon dioxide or air and a kind of optional inert gas.
The example that is used for the organo-silicon compound that are suitable for of air-flow in plasma deposition method is at ring Be in a liquid state under the temperature of border or the material of gaseous state, the boiling point that has when volatilization is about 0-150 ℃, these Material comprises dimethyl silane, trimethyl silyl, diethylsilane, propyl silane, phenyl silicon Alkane, hexamethyldisilane, 1,1,2,2-tetramethyl disilane, two (trimethyl silyl) methane, two (two The methyl silicane base) methane, HMDO, vinyltrimethoxy silane, vinyl three ethoxies Base silane, the ethyl methoxy silane, ethyl trimethoxy silane, divinyl tetramethyl disiloxane, HMDS, divinyl hexam ethylcyclotrisiloxane, trivinyl pentamethyl three silica azane (trivinyl pentamethyl trisiloxazane), tetraethoxysilane and tetramethoxy-silicane.
Preferred organosilicon is 1,1,3,3-tetramethyl disiloxane, trimethyl silyl, hexamethyl two Siloxanes, vinyl trimethylsilane, MTMS, vinyltrimethoxy silane and six The methyl disilazane. The boiling point that these preferred organo-silicon compound have be respectively 71 ℃, 55.5 ℃, 102 ℃, 123 ℃ and 127 ℃.
The air-flow of optional inert gas is helium, argon or nitrogen preferably.
Volatility organosilicon component is preferably mixed with oxygen component and inert composition before indoor flowing into Close. Control the amount of these gases of such mixing by flow governor and control the air-flow component in order to regulate Velocity ratio.
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 electric 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 the about 490 milli torrs of 43-in the process. The pressure of system is more low, the speed of deposition Spend more slowly, and the pressure of system is more high, and the speed of deposition is more fast. When the plastic products for the treatment of coating are temperature-sensitives The sense the time, can use higher system pressure, so that the heat that stands at depositional stage chien shih matrix reaches Little, 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 for depositing silicon oxide-base film comprises the reative cell of a sealing 170, in this reative cell, form plasma, and wherein matrix and pipe 171 are placed in sample and prop up Hold and be used for the film of deposition materials on the body 172. Matrix can be any vacuum compatible material, for example moulds Material. One or more strands of gases are transported in this reative cell by gas delivery system 173. Pass through electric power Feedway 174 produces electric field.
Reative cell can be to carry out any enhancing plasma chemistry vapor deposition (PECVD) or plasma The adequate types of body polymerization. In addition, can change reative cell, so as in a reative cell simultaneously Apply one or more goods with oxide skin(coating).
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 PEVCD or plasma polymerization process is about 90-140 milli torr, and be by monomer input port 174 with process gas, oxygen and trimethyl silyl flow in this chamber and realization.
Thin film is deposited on the outer surface of pipe, 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 specific material 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 Si oxide base film or its mixture can contain some conventional additives and the characteristic of the goods made thus do not had the composition of negative interaction.
The 3rd layer of aqueous emulsion that can pass through immersion coating, roll and apply or spray polyvinylidene chloride or homopolymer or copolymer of multilayer barrier coating then is formed on the second layer by air drying.
The 3rd layer of vinylidene chloride-acrylonitrile-methyl methacrylate-acrylic acid methyl ester .-acrylic copolymer preferably, thermoset epoxy thing coating, parylene polymer, or polyester.
Preferably, the 3rd 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 same 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-methacrylic acid ester methyl ester-methacrylate acrylate copolymer (PVDC).This polymer can have been bought, and commodity are called DARAN
(R)8600-C (trade mark of W.R.Grace and Co.), by GRACE, Organic Chemicals Division, Lexington, Mass sells.
The 3rd 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 U.S. Pat 3342754 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, described as US 5093194 and 4497859, these disclosures are incorporated herein by reference.
As shown in Figure 8, acrylate coatings A and silicon oxide based coating B have defective or scrambling C.Can be sure of only can not realize the covering fully of matrix D with silicon oxide based coating and acrylate coatings, although Si oxide and acrylate coatings with sequence have reduced defective and scrambling basically, but the final coating of PVDC, E, can be coated on the last silicon oxide coatings, and on matrix surface, produce barrier layer completely.
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 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 in to a certain degree the irradiation, 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 (hemorepellent) of blood repulsion and/or have 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 existence of the barrier coat 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.
Method with multilayer barrier coating coating plastic matrix
Apply one deck acrylate coatings indoor going up to polypropylene tube and film (matrix) with all thickness, indoor three polypropyleneglycol diacrylates (TPGDA) are input in the vaporizer at this, are being flashed on this indoor matrix under about 343 ℃ and are carrying out condensation.To carry out electronic beam curing by electron beam gun through the monomer film of condensation then.
Mixture with micro-detergent that contains equivalent and deionized water (DI) solution cleans the matrix that scribbles acrylate coatings (TPGDA) 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 glass evacuated 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 special 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 the matrix heat of higher Impact energy and increase.Use magnetron discharge to allow under lower pressure, to operate and increase basically polymer deposition speed.
Import by stainless steel tube by the monomer that the mixture of trimethyl silyl (TMS) and oxygen is formed near electrode.Gas be imported into before indoor mixed in the monomer inlet tube.Flow velocity is by rustless steel metering valve Artificial Control.The power supply that use is operated under the audio frequency of 40kHz provides electric power to electrode.Be used for plasma polymerization TMS/O on polymeric matrix
2The system parameter of thin film deposition as follows:
Surface preparation: TMS stream=0sccm
Pressure of foundation=5 milli torrs
Oxygen flow=10sccm
System pressure=140 milli torrs
Electric power=50 watt
Time=2 minute
Oxide deposition: TMS stream=0.75-1.0sccm
Oxygen flow=2.5-3.0sccm
System pressure=90-100 milli torr
Electric power=30 watt
Sedimentation time=5 minute
After thin film deposition, make reactor cooled.Open reactor then, take out matrix.
The repetitive coatings acrylate coatings carries out the sedimentary technology of oxide subsequently.
The protection top coat of the aqueous emulsion by immersion coating PVDC copolymer and solidified 10 minutes down at 65 ℃ obtains the final coating that average thickness is about 6 microns then.
Embodiment 2
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 carry out UV through the monomer film of the condensation actinic light source by 365nm then solidifies.
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 glass evacuated chamber.Make this chamber airtight, make pressure of foundation reach 5 milli torrs with mechanical pump.
Alnico magnets coupling on the electrode configuration internal capacitance ground and the titanium electrode back side.This special configuration provides the ability of the aura between the constraint electrode because of magnetic impact rate between electronics and the reactant gas molecules increases.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 the matrix heat of higher Impact energy and increase.Use magnetron discharge to allow under lower pressure, to operate and increase basically polymer deposition speed.
Import by stainless steel tube by the monomer that the mixture of trimethyl silyl (TMS) and oxygen is formed near electrode.Gas be imported into before indoor mixed in the monomer inlet tube.Flow velocity is by rustless steel metering valve Artificial Control.Use the power supply of operating under the audio frequency of 40kHz to provide electric power to electrode.Be used for plasma polymerization TMS/O on polymeric matrix
2The hierarchy number of thin film deposition as follows:
Surface preparation: TMS stream=0sccm
Pressure of foundation=5 milli torrs
Oxygen flow=10sccm
System pressure=140 milli torrs
Electric power=50 watt
Time=2 minute
Oxide deposition: TMS stream=0.75-1.0sccm
Oxygen flow=2.5-3.0sccm
System pressure=90-100 milli torr
Electric power=30 watt
Sedimentation time=5 minute
After thin film deposition, make reactor cooled.Open reactor then, taking-up has the multilayer barrier coating of material.
The repetitive coatings acrylate coatings carries out the sedimentary technology of oxide subsequently.
The protection top coat of the aqueous emulsion by immersion coating PVDC copolymer and solidified 10 minutes down at 65 ℃ obtains the final coating that average thickness is about 6 microns then.
Embodiment 3
Has and do not have the comparison of multilayer barrier coating of material
Estimate the oxygen infiltration (OTR) of all substrates in oxide coating of pressing the foregoing description 1 and 2 preparations below.
(i) oxygen infiltration (OTR):
Employing MOCON Ox-TRAN 2/20 (by Modern Controls, limited company sells, 7500 Boone Avenue N., and Minneapolis, MN 55428) to film or its oxygen infiltration (OTR) of plate specimen test.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 of 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.Sample is test under 30 ℃ and 0% relative humidity (R.H.).Before the oxygen infiltration of measuring sample, make sample adapt to 1-20 hour.The results are shown in the table 1, unit is cc/m
2-atm-days.
Adopt the oxygen infiltration (OTR) of MOCON Ox-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 measuring the steady seepage of pipe, make they balance 2-14 days.The results are shown in the table 1, unit is cc/m
2-atm-days.
Table 1 sample acrylate SiO
xAcrylate SiO
xThe PVDC oxygen permeability
Coating coating coating coating coating (cc/m
2-atm-days)
30 °; The 0%RHPP film; Contrast do not have not have do not have does not have no 1500PP plate and does not have to have or not and do not have no 37PP plate TPGDA and have or not and do not have the no 65PP plate of no 3.5PP plate nothing and have or not nothing to have 0.04PP to manage; Contrast do not have not have do not have does not have no 70PP pipe IBA: DA and does not have no 70PP pipe and do not have to have or not and do not have 40～60PP pipe IBA: DA and have or not and do not have 4.3～6.4PP pipe IBA: DA and have or not have and have 2.5PP pipe TPGDA to have or not have the 5PC film is arranged, and contrast does not have no 1700PC film 110 and do not have not have no 559PC film 110 and have or not and do not have 6.4～8.3PC film 110 and have 110 to have or not 0.1～0.2PC film not have to have or not and do not have 8
The different norborneol of IBA: DA=: epoxy diacrylate (60: 40), UV is solidified
TPGDA=three polypropyleneglycol diacrylates, electronic beam curing
SiO
xCoating=1000-3000 dust (measuring) by scanning electron microscope
The PC=Merlon
The PP=polypropylene
Plate=7.5 mil thick
Film=3 mil thick
The standard wall thickness of pipe=40 mils
The crosslinkable acrylate of 110=, UV is solidified
Claims (19)
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 organic priming coat material and have the second layer of the inorganic and organic coating of sequence on described ground floor.
2, the assembly of claim 1 also has comprise organic material on the described second layer the 3rd layer.
3, 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.
4, the assembly of claim 1, wherein said multilayer barrier coating comprise in abutting connection with the closely knit serrated face of the alignment of described container and described sealing interface.
5, the assembly of claim 1, wherein said ground floor are mono acrylic ester-and the polyblends of two-acrylate.
6, the assembly of claim 1, the wherein said second layer are the inorganic and organic coatings of sequence, and they comprise aluminium oxide or Si oxide based composition and use thereof in packaging and acrylate.
7, the assembly of claim 6, wherein said sequence coating is coated on the described ground floor according to following formula:
∑ (inorganic coating+organic coating+inorganic coating) n
N=0-10 wherein;
Inorganic coating=aluminium oxide or Si oxide; With
Organic coating=acrylate.
8, the assembly of claim 6, wherein by radio-frequency discharge, direct ion bundle deposition, dual ion beam deposition, sputter, the enhanced plasma system of plasma chemistry vapor deposition or magnetic and deposit the described inorganic coating of the described second layer.
9, the assembly of claim 2, wherein said the 3rd layer is the thermoset epoxy thing, parylene polymer, vinylidene chloride-acrylonitrile-methyl methacrylate-acrylic acid methyl ester .-acrylate copolymer or polyester.
10, the assembly of claim 1, wherein said ground floor comprise polymeric acrylate and the described second layer comprises Si oxide and polymeric acrylate.
11, the assembly of claim 1, also be included in the multilayer barrier coating on the inner surface of described container, this barrier coat has the ground floor that comprises acrylate priming coat material, comprises the second layer of the inorganic and organic coating of sequence and the 3rd layer of the organic material of the described second layer on described ground floor.
12, the multilayer barrier coating has:
The ground floor that comprises the acrylate material;
The second layer that comprises the inorganic and organic coating of sequence on described ground floor;
With on the described second layer, comprise the 3rd layer of organic material.
13, the coating of claim 12, the wherein said second layer comprise the inorganic and organic coating of sequence, and they comprise aluminium oxide or Si oxide based composition and use thereof in packaging and acrylate.
14, the coating of claim 12, wherein said the 3rd layer is polyvinylidene chloride.
15, the method for deposit multilayer barrier coat on plastic substrate comprises:
(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) the ground floor acrylate films of the described evaporated components of condensation on the outer surface of described matrix;
(d) solidify described acrylate films;
(e) a kind of organosilicon component of evaporation also will be mixed with a kind of oxidant constituents and randomly a kind of inert composition through the organosilicon component of evaporation, form one outdoor airflow;
(f) indoor at this by a branch of or multi beam air-flow component generation glow discharge plasma;
(g) this air-flow of controlled inflow in plasma is constrained to the small part plasma simultaneously therein;
(h) deposition one deck silicon oxide coatings on described ground floor;
(i) repeat above-mentioned steps (a)-(d), thereby on described silicon oxide coatings, deposit acrylate coatings; With
(j) repeat above-mentioned steps (e)-(h), thus on described acrylate coatings the depositing silicon oxide coating.
16, the method for claim 15 also comprises:
(k) immersion coating PVDC on described silicon oxide coatings.
17, the method for claim 15 also comprises:
(k) repeating step (i)-(j) is about 1-10 time.
18, the method for claim 17 also comprises:
(1) immersion coating PVDC on described silicon oxide coatings.
19, the method for claim 15, the described ground floor of wherein said acrylate coatings is handled by oxygen plasma.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97101059 CN1160535A (en) | 1996-01-30 | 1997-01-27 | Blood collection tube assembly |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US593,976 | 1996-01-30 | ||
| CN 97101059 CN1160535A (en) | 1996-01-30 | 1997-01-27 | Blood collection tube assembly |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1160535A true CN1160535A (en) | 1997-10-01 |
Family
ID=5165488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97101059 Pending CN1160535A (en) | 1996-01-30 | 1997-01-27 | Blood collection tube assembly |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1160535A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1516642B (en) * | 2001-06-18 | 2010-05-26 | 贝克顿迪肯森公司 | Multilayer containers and process for forming multilayer containers |
| CN105307696A (en) * | 2013-05-15 | 2016-02-03 | 贝克顿·迪金森公司 | Manual flow regulation for blood collection |
| CN108968979A (en) * | 2014-10-14 | 2018-12-11 | 贝克顿·迪金森公司 | It is manipulated using the blood sample of open celled foam |
-
1997
- 1997-01-27 CN CN 97101059 patent/CN1160535A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1516642B (en) * | 2001-06-18 | 2010-05-26 | 贝克顿迪肯森公司 | Multilayer containers and process for forming multilayer containers |
| CN105307696A (en) * | 2013-05-15 | 2016-02-03 | 贝克顿·迪金森公司 | Manual flow regulation for blood collection |
| CN108968979A (en) * | 2014-10-14 | 2018-12-11 | 贝克顿·迪金森公司 | It is manipulated using the blood sample of open celled foam |
| CN108968979B (en) * | 2014-10-14 | 2022-06-03 | 贝克顿·迪金森公司 | Blood sample manipulation with open cell foam |
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