CN1161386A - Apparatus and method for plasma processing - Google Patents
Apparatus and method for plasma processing Download PDFInfo
- Publication number
- CN1161386A CN1161386A CN 97101060 CN97101060A CN1161386A CN 1161386 A CN1161386 A CN 1161386A CN 97101060 CN97101060 CN 97101060 CN 97101060 A CN97101060 A CN 97101060A CN 1161386 A CN1161386 A CN 1161386A
- Authority
- CN
- China
- Prior art keywords
- gas
- wall surface
- supply
- goods
- monomer
- 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
- Chemical Vapour Deposition (AREA)
Abstract
An apparatus and method for facilitating plasma processing and in particular chemical plasma enhanced vapor deposition, plasma polymerization or plasma treatment of barrier materials onto the interior surface of containers barrier materials are useful for providing an effective barrier against gas and/or water permeability in containers and for extending shelf-life of containers, especially plastic evacuated blood collection devices.
Description
The present invention relates to be convenient to especially barrier material on the gas deposition, plasma polymerization or the container for plasma treatment internal surface that improve of chemical plasma of equipment that Cement Composite Treated by Plasma uses and method, so that effective blocking layer that can stop gas and/or water infiltration is provided.
Plastic containers often do not possess chemistry and the physical property that is used for suitably storing and/or handling its predetermined inclusion, so this frosting can or be coated the film that can eliminate these defectives with the chemical process modification and the value that increases original plastic containers thus.The example of container comprises having gas and/or water vapor permeation effect and surface and the reactive blocking layer of inclusion.
What Special Significance was arranged most is blood collection tube, syringe or the collection containers of plastics curable product as vacuumizing.
The vacuum plastics tubing is permeable for airborne gas and water vapor, and along with the time in the past substantial loss vacuum tightness.The consequence of loss of vacuum degree is to have reduced the ratio of extraction volume and blood addition (blood to additive).Like this, just be necessary to improve the blocking layer character of plastics tubing, wherein should satisfy some standard of performance.
The method of improving plastic containers blocking layer character comprises from the metal of vacuum deposition source such as plasma chemical vapor deposition, plasma polymerization, plasma sputtering etc. and the deposition of metal oxide film.The general method that plastic containers is applied plasma-deposited coating or modification is that one or more containers are put into a kind of vacuum chamber that contains low pressure process gas and the electrode of energy is provided to plasma body.In most of the cases, these methods all are that coating is coated on the container outer surface.
Therefore, be necessary to make to be coated with and be placed on improving one's methods and equipment of vessel surface inside.
The present invention puts on apparatus and method on the plastic containers inner wall surface to barrier film coating or processing by Cement Composite Treated by Plasma.This coating can significantly improve the performance on container blocking layer and the surface reaction of container with processing.
It is desirable to, barrier film coating silicon oxide-containing component is as SiO
x, the quantity ratio of Sauerstoffatom and Siliciumatom wherein, x, about 15-about 2.0.
Preferred equipment of the present invention is included under the vacuum condition transport of reactant gases body and applies to the device of plastic containers internal volume with energy and give internal tank so that to the reactant gases energising or induce the device that becomes plasma body, provides barrier film with activation in the inner wall surface of plastic containers.
Preferred version is that the equipment that is used for the container for plasma treatment inner wall surface comprises the multitube system that is connected with inner surface of container and/or expose.Described multitube system preference comprises that the transport of reactant gases body produces and keep the device of vacuum tightness in the container to the device of container with in treating processes.Present device also is included in device that internal tank energizes so that can produce plasma body.
Preferably, the transport of reactant gases body comprises monomer source to the device of container, oxidizer source and optional source of diluent gas.
Preferably, produce and keep that the vacuum in the container is a vacuum pump in the treating processes.
Preferably, the device of generation plasma body comprises the electrode and the energy.
Therefore, the method for barrier film coating in the container inner wall surface comprised the following steps:
(a) opening end of container is arranged on the vacuum multitube system;
(b) outer surface of container is put in position with the device that internal tank is energized gone up;
(c) container is vacuumized;
(d) add reactant gases toward container;
(e) energize at internal tank; With
(f) produce plasma body and therefore the barrier film coating is applied on the container inner wall surface at internal tank.
Randomly, method steps can repeat can be coated with inside or the coating second layer block film coating all over container equably so that guarantee the block film coating.
Randomly, the inner wall surface of container can or be coated non-barrier coating in advance with the chemical process modification.Non-barrier coating can make the inner wall surface of container significantly strengthen, stablize and be level and smooth, so that can improve the bonding of barrier coating and inner wall surface.
The other selection scheme of the present invention is formerly to have applied on the barrier film coating to apply top layer.Top layer can be protected the barrier film coating basically and give the surface chemistry that improves the final product performance, as the surface reaction of the predetermined inclusion of container in inhibition or raising and the use.
Preferably, monomer source is silicone ingredients such as hexamethyldisiloxane (HMDSO), tetraethoxy-silicane (TEOS) or tetramethyl-silicomethane (TMS).
Preferably, oxidizer source is air, oxygen or Nitrous Oxide.
Preferably, source of diluent gas is a rare gas element, as helium, argon or inactive gas such as nitrogen.
Preferably, electrode is inductive character or the capacitive couplings metal electrode that is winding, pinnacle rod or flat board or curve template form.Best is that electrode is with the energy such as low frequency ac (AC), radio frequency (RF) or microwave frequency current potential, or continuous or pulsed energy supply.
Best is that the method that barrier coating is applied to the container inner wall surface comprises the following steps:
(a) opening end of container is arranged on the appropriate location of vacuum multitube system;
(b) outside surface of container is placed on the appropriate location with the electrode that is connected with the energy;
(c) with vacuum pump container is vacuumized and make container internal pressure be maintained at about 300 the milli torrs;
(d) control silicone ingredients and oxidizer composition and optional inert gases composition flow through the multitube system and enter container;
(e) give the electrode energy supply so that energy is given the composition of internal tank;
(f) form glow discharge plasma at internal tank; With
(g) deposited barrier layer film coating on the container inner wall surface.
Preferably, the step of method can repeat, and wherein the electrode of step (b) can be put back to the position on container outer surface.
Another kind method, the step of method can repeat, its break with the electrode of connecting step (b) and/or close with connect step (d) become shunting so that pulsed energy of plasma or become fractional flow or both to produce simultaneously to improve the performance on blocking layer.
In addition, replaceable method steps is as follows:
(h) make the electrode outage; With
(i) make electrifying electrodes so that energize.
Replacement method in addition is as follows:
(h) stopping the middle composition of step (d) flows; With
(i) control flowing once more as the composition in the step (d).
Another kind of replacement method is as follows:
(h) stop to flow of the middle composition of step (d);
(i) electrode in the step (e) is cut off the power supply; With
(j) repeating step (d)-(g).
Coating is arranged on the container inner wall surface and container as the method that vacuum processing chamber of the present invention uses, all having many obvious characteristics and advantage surpasses in the past in vacuum chamber coating is coated in method on the container outer surface.
The noticeable feature of the present invention is the effect that container can play its independent vacuum chamber, and reaction plasma-induced or that improve wherein takes place, and the result is in the container inner wall surface modification or in the lip-deep deposition of container inner wall.Apparatus and method for of the present invention does not require vacuum chamber.Vacuum chamber needs suitable disposal field and control when being used for most of deposition method.
The present invention can enhance productivity.The present invention allows to carry out on-line operation on each independent container, and this method with common many container periodical operation is opposite.Big periodical operation chamber and needs the long step-down time because chamber volume and chamber exhaust increase.Therefore, under situation of the present invention, can eliminate the loading and unloading of container in the periodical operation chamber.
The present invention is important to be characterised in that the lip-deep barrier film coating of container inner wall can be protected basically and avoids physical damnification.When the barrier film coating is in container when outside, as normal conditions because operation in process of production, shipment or since final use worn and torn.Therefore, the barrier film coating is on the container inner wall surface time, because the damage of block film coating is reduced significantly, so can improve the container usefulness of working life.
Additional features of the present invention is that the quality of the barrier film coating on the barrier film coating container outer wall on the inner wall surface is high significantly.This is because the inner wall surface of container is easy to touch pollutent in process of production unlike external container, as oil, grease and dust.These pollutents on the wall of container might cause that coating is inhomogeneous, defective and binding property are bad.The inside of container does not need to remove accumulative coating or particle, because each container that will apply all is new " chamber " of handling.In addition, be externally owing to provide the device of energy, so can not stand to change its electrology characteristic and the coating congregation that makes the method degraded to internal tank.
The other characteristics of the present invention are to provide the device of energy to change, to move and/or rotation in the outside of container, can guarantee the homogeneity of block film coating basically under various different positionss and place to internal tank.Therefore, can not cause " shielding " in the plasma process process as on container outer wall, carrying out Cement Composite Treated by Plasma.
Other shortcoming of batch system is wherein handled on container outer wall, comprises that container " is fixed " on electrode and the variation of container dimensional, as " arc ".These situations are not problem in the present invention.In addition, the unitary deficiency of large-scale batch operation can cause loss very big on the turnout, and online unitary loss will be accessory as the many pipelines of use (because the price of every pipeline is lower).Because in the simplification of Wiring technology, so but can be better than the alternate batch process to improve its roughness and toolability.Can believe that according to the present invention container can be by operating on the line, and not out of service along pipeline.
Additional advantages of the present invention are that the power supply device of internal tank is the outside at container, so it was both also cheap easily to change this device.Like this by being easy to change the device as electrode, together with changing reactant gases to making production line be suitable for the condition of meeting specific requirement.Therefore only doing very little change in production line just can make single production line handle the container of different configurations.
Most preferably, container of the present invention is a blood collection device.This blood collection device or vacuum blood collecting tube or antivacuum blood collection tube.The blood collection tube requirement is made by polyethylene terephthalate, polypropylene, poly-naphthalic acid ethylidene ester or multipolymer.
On inner wall surface, scribble the plastics tubing of block film coating, with form by polymer composition and composition thereof, the plastics tubing that has the block film coating on the outer wall surface of pipe is compared, and can keep much better vacuum tightness, extract volume and hot mechanical integrity.In addition, the shock resistance of pipe is more far better than Glass tubing.
It should be noted that most the transparency of block film coating and to the weather resistance of anti-shock resistance and wearlessness basically.
In addition, the plastics blood collection tube that scribbles the block film layer can bear automaticmachines such as whizzer and can contact the irradiation of certain level in sterilizing process.
Description of drawings
Fig. 1 is the skeleton view of representational band stopper blood collection tube.
Fig. 2 is the longitdinal cross-section diagram that 2-2 along the line gets Fig. 1 pipe.
Fig. 3 is similar Fig. 1 pipe but does not have stopper, contains the longitdinal cross-section diagram of the cast container of barrier coat.
Fig. 4 is that the simple synoptic diagram with equipment takes place explanation plasma body of the present invention.
Fig. 5 is the synoptic diagram that the pipe that is connected with the winding electrode with Fig. 4 equipment is described.
The present invention may be embodied in other particular form and is not limited to illustrate as an example and at length In any particular of describing. Clearly, concerning the person of ordinary skill in the field not Depart from and be easy to do various modifications under the scope and spirit of the present invention. Scope of the present invention will be wanted by appended right Ask book and equivalent thereof to be judged.
With reference to accompanying drawing, wherein same reference number refers to same part, Fig. 1 in whole accompanying drawings With the representational blood collection tube 10 of 2 explanations, it has from openend 16 along extending blind end 18 Sidewall 11 and comprise the stopper 14 of following annulus or annular lateral margin 15, lateral margin puts in and presses On side wall inner surfaces 12 to keep stopper 14 in position.
Fig. 2 illustrates three kinds of mechanism that change blood collection tube vacuum are described: (A) gas oozes through stopper material Thoroughly; (B) gas is through pipe infiltration (C) seepage on stopper pipe contact-making surface. So, when basically there not being gas Body infiltration and when not having seepage will keep good vacuum and keep good blood drawing volume.
Fig. 3 illustrates the preferred embodiments of the invention, and plastic tube scribbles one deck barrier material at least. Excellent The many parts that select embodiment to comprise are basically identical with part among Fig. 1 and 2. Cause This, the numeral number of same part of finishing said function is identical with Fig. 1 and 2 same composition part, Except using subscript " a " with those parts among identification Fig. 3.
Referring now to Fig. 3, the preferred embodiment of the invention, collecting pipe sub-assembly 20 comprises plastic tube 10a, Has the sidewall 11a that extends to blind end 18a from openend 16a. Barrier coat 25 spreads all over the interior table of pipe The face major part is except openend 16a.
Barrier coat of the present invention is by plasma-deposited, and this plasma is by one or more spies The composition of deciding reaction gas flow produces in the inside of pipe. It is desirable to, reactant gas comprises unit gas Composition and oxidant gas composition. Pipe is placed on the correct position with vacuum multitube system, makes reaction The property gas componant can reach the inside of controlled inflow pipe. The extra power of pipe is given flowed energy so that at pipe Deposit barrier coat on the inwall.
Deposition process of the present invention be in deposition process in the multitube system about 70 the milli torr (mTorr)-Yue Carry out under the 2000 milli torr pressure, and in the deposition process of barrier coat, preferably manage inner pressure At the about 2000 milli torrs of about 70 milli torrs.
Matrix is greatly under about 25 ℃ room temperature in the deposition process. That is to say, at depositing operation Matrix need not specially heat in the process.
With reference to Fig. 4, equipment of the present invention comprises vacuum multitube system 22. Vacuum multitube system comprise to Few five tube connectors 24,26,28,30 and 32 and connector 34, desirable connector is rubber Packing ring.
Tube connector 24,26,28,30 and 32 leads to respectively isolation valve 42,44,46,48 With 50. Valve 42,44,46,48 and 50 lead to respectively monomer source of the gas 52, oxidant gas source 54, Vavuum pump 56, discharge filter 58 and source of diluent gas 60. Present device also comprises energy-producing Device comprises outer electrode system 62 and the energy 64. The energy preferably includes adjuster 66, amplifier 68 and oscillator 70.
By any suitable forming plastic pipe method, such as injection molding, with end-blocking extruding, blowing, injection-blow molding Deng after producing pipe, the openend of pipe is connected at the connector place with vacuum multitube system and makes institute The valve that has is in closed condition. Open valve 46 starts vavuum pump straight with the pressure that reduces in the pipe more then To the about 0.001 milli torr of vacuum ranges-Yue 100 milli torrs.
Form the necessary reacting gas composition of plasma again by the multitube system for the inside at pipe In the inlet tube. At first open valve 42 in order to make the monomer gas composition at the about 125 milli torrs of pressure, flow velocity approximately 1.0sccm and inflow multitube system under about 74 °F room temperature. Open valve 44 is in order to make oxidation again The inflow under about 175 milli torr pressure, about 22sccm flow velocity and about 74 °F room temperature of agent gas componant is many Body system.
Monomer gas composition and oxidant gas composition preferred and inert gas composition before inflow pipe exists Mix in the multitube system. The amount of these gases that so mix is controlled so that can by flow speed controller Regulate the velocity ratio of ground control reacting gas stream composition. Before to the electric system energising, finish inner reaction tube gas The mixing of body composition.
Most preferably, the monomer gas composition is preferably HMDSO and the oxidant gas composition is preferably oxygen in order to form and cvd silicon oxide (SiO in the inner wall surface of pipex) barrier coat.
Make the barrier coat that is deposited on the pipe internal surface reach predetermined thickness. The about 500A-of coating layer thickness About 5000A. Best, the about 3000A of the about 1000A-of oxide coating thickness.
Randomly, make the general control system that comprises the computer control part, with each the composition section in the system The connection that divides will make its acceptance export control instruction from the status information of each composition and to them.
The convenient pressure of reaction gas mixtures is between about 70 milli torrs and about 2000 milli torrs, preferably about 150 the milli torrs and 600 the milli torrs between and preferably about 300 the milli torrs.
It is desirable to, organosilicon such as HMDSO are used as the monomer gas composition, at 25 ℃ and about 80 millis Under torr-Yue 190 milli torrs, the about 0.1-50sccm of its flow velocity is preferably at the about 15sccm of about 0.5sccm-And best about 1.0sccm.
It is desirable to, air is used as the oxidant gas component, at 25 ℃ of lower and about 110 milli torr-Yue Under the 200 milli torrs, the about 50sccm of the about 0.1-of its flow velocity, preferably at the about 35sccm of about 15-and best At about 22sccm.
Reacting gas such as oxygen, F2、Cl
2、SO
2Or N2O can be used for preliminary treatment or post processing in case with resistance The barrier coating precursors reaction.
Preferably, oxidizer source is air, oxygen or nitrous oxide.
Preferably, source of diluent gas is inert gas, such as helium, argon or non-reactive gas such as nitrogen.
The example of suitable organo-silicon compound is to be liquid or gas and to have boiling point about 0 under about room temperature ℃-Yue 200 ℃, comprise tetramethyl tin, tetraethyl tin, tetra isopropyl tin, tetra allylic tin, diformazan Base monosilane, trimethyl silyl, diethylsilane, propyl silane, phenyl silane, hexamethyl second Silane, 1,1,2,2-tetramethyl disilane, two (trimethyl silane) methane, two (dimetylsilyl) Methane, six-methyl disiloxane, vinyltrimethoxy silane, VTES, second Methoxylsilane, ethyl trimethoxy silane, divinyl tetramethyl disiloxane, hexamethyl two silicon Azane (hexamethyldsilazane), divinyl hexam ethylcyclotrisiloxane, trivinyl-pentamethyl three O-N-Si alkane (trivinyl-pentamethyltrisiloxazane) tetraethoxysilane and tetramethoxy-silicane.
In preferred organosilicon, 1,1,3,3-tetramethyl disiloxane, trimethyl silyl, pregnancy are arranged Base disiloxane, vinyl trimethyl silyl, MTMS, vinyl trimethoxy silicon Alkane and HMDS. The boiling point of these preferred organo-silicon compound is respectively 71 ℃, 55.5 ℃, 102 ℃, 123 ℃ and 127 ℃.
Diluent gas optional in the air-flow is helium, argon or nitrogen. Non-reactive gas can be used for reactant gas Dilution.
Specific gas or mixture can be the barrier coat precursors, as being suitable for SiOxThe siloxanes on barrier layer or Silane is suitable for methane, hexane of polymerized hydrocarbon or diamond-like coating etc.
In order to make reacting gas carry out favourable reaction, to produce plasma, it is in the energy supply of the inside of pipe Through manage outside electrode by inductive or capacitively coupled be winding, pinnacle rod, flat board or curve ruler, The metal electrode of ring-type or cylindric form. Dull and stereotyped 62 are shown in Fig. 4 and winding 74 is shown in Fig. 5.
Preferably, with the energy give electrifying electrodes, the energy can be low frequency ac (AC), radio frequency (RF), Or the microwave frequency current potential, provide with continous way or pulsed.
Best is with desirable about 5 Wa-Yue 150 watts RF power stage electrifying electrodes, preferably to make an appointment with 40 watts of 15 Wa-Yue and be preferably about 20 watts.
The result is electrical breakdown and process gas ionization in pipe, namely in each independent pipe, produce grade from Daughter. To plasma energising from 1 second to 20 minute, preferred 5 seconds to 2 minutes. Processing gas Condensation and chemical reaction can produce desired coating or contained tube wall is carried out modification. Matrix can be to appoint What is fit to the material of vacuum. Such as plastics.
The variation of the inventive method is that it can pass through certain methods in the inside of container liquid level coating In any, such as dip-coating, be coated with and carry out from spin coating, spraying or solvent, and then use by this The suitable plasma that bright method produces makes liquid crosslinked or solidify, cause liquid become solid, semisolid, Or gel coat.
Multiple optical means well known in the prior art all can be used for determining the thick of in settling chamber deposited film Degree perhaps shifts out its film thickness of rear mensuration to goods in the settling chamber.
Can coat thin barrier layer component to various matrixes with the inventive method. This matrix comprises, but does not limit In, packaging material, container, bottle, tank, pipe and medical apparatus.
Many methods also all can be used for the deposited barrier layer component except plasma-deposited, these method bags Draw together, but be not limited to, radio frequency discharge, direct or dual ion beam deposition, sputter or evaporation.
Do not departing from many other improvement under the scope and spirit condition of the present invention to the art The technical staff significantly and also is easy to carry out.
The following example is not the restriction to any particular of the present invention, and only is exemplary.
Embodiment 1
Polypropylene (PP) pipe is connected with vacuum multitube system, and manage outer peripheral be wound with outside parallel-plate electrode.At first the inside with pipe is evacuated to the about 60 milli torrs of vacuum tightness.Then through the multitube system the air inlet tube of about 400 milli torrs in and give about 30 seconds of 30 watts of power of electrifying electrodes by the vibrator of 38MHz, so that surface activation process to be provided.When plasma body is switched on, the total pressure that the monomer gas of hexamethyldisilane steam is added in the pipe up to gaseous mixture is about 725 milli torrs through multitube.Kept plasma-deposited about 1 minute, then 30 seconds of air.
At SiO
xAfter being deposited on the inner wall surface of pipe, pipe is separated with multitube.The infiltration efficiencies of pipe is shown in Table 1.
PP pipe and the vacuum multitube system external parallel plate electrode outside with being centered around pipe is connected.The about 60 milli torrs of vacuum tightness will be evacuated to earlier in the pipe.Then in the following air leading-in conduit of about 600 milli torr pressure.Again in the steam feeding tube of hexamethyldisiloxane in pipe the total pressure of gaseous mixture be about 1.0 torrs.Under 38MHz and 22 watts to electrifying electrodes about 2 minutes, the result is generation SiO in pipe
xPlasma body.
At SiO
xAfter being deposited on the inwall of pipe, pipe and multitube are disconnected.The infiltration efficiencies of pipe is shown in Table 1.
Embodiment 3
Polyethylene terephthalate (PET) is managed be connected with vacuum multitube system and be connected with the external parallel plate electrode that is centered around the pipe outside.At first the about 65 milli torrs of vacuum tightness will be evacuated in the pipe.Then in following air inlet tube of about 600 milli torr pressure.Again in the hexamethyldisiloxane steam feeding tube in pipe the total pressure of gaseous mixture be about 1.0 torrs.Under 38MHz and 22 watts, caused SiO in about 2 minutes to electrifying electrodes
xPlasma body produces in pipe.
At SiO
xAfter being deposited on the inner wall surface of pipe, will managing with multitube and separate, the penetrating quality of pipe the results are shown in the table 1.
Embodiment 4
PET is managed be connected with vacuum multitube system and be connected with the outside plate electrode that has end bent around the duct occlusion end.Earlier being evacuated to the about 65 milli torrs of vacuum tightness in the pipe.And then in the pressure inlet tube of oxygen with about 300 milli torrs.Hexaethyldisiloxane steam introducing total pressure in pipe is about 400 milli torrs.Under 38.5MHz and 22 watts, made plasma body generation in pipe in about 5 minutes to electrifying electrodes.
SiO
xAfter deposition on the inside pipe wall surface, will manage with multitube and separate.The penetrating quality of pipe the results are shown in the table 1.
Embodiment 5
Pipe by the PP system is connected with vacuum multitube system and be centered around the duct occlusion end on have an end bent outside plate electrode be connected.The about 65 milli torrs of vacuum tightness will be evacuated to earlier in the pipe.Then about 400 the milli torrs pressure directly the oxygen ingress pipe in.Again in the hexamethyldisiloxane ingress pipe in pipe the total pressure of gaseous mixture be about 750 torrs in the least.In 38.5MHz and 22 watts plasma body is produced continue in pipe about 5 minutes post plasmas manage in formation.
SiO
xAfter deposition on the inside pipe wall surface, will manage with multitube and separate.The penetrating quality of pipe the results are shown in the table 1.
Embodiment 6
Pipe by the PP system is connected with vacuum multitube system and be centered around the duct occlusion end on have an end bent outside plate electrode be connected.Earlier being evacuated to the about 65 milli torrs of vacuum tightness in the pipe.Oxygen is entered in the pipe under the pressure of about 400 milli torrs.Be 700 milli torrs toward the interior hexamethyldisiloxane total pressure in pipe of introducing of pipe again.Again under 38.5MHz and 22 watts about 2.5 minutes and make plasma body formation in pipe to electrifying electrodes.
Still make circumference of cannon bone around about 90 degree of its rotation and under 38.5MHz and 22 watts, switched on again 2.5 minutes once more to electrode in vacuum condition following time.
SiO
xAfter deposition on the inside pipe wall surface, will manage with multitube and separate.The penetrating quality of pipe the results are shown in the table 1.
Embodiment 7
Make pipe be connected with vacuum multitube system and be connected with the belt electrode that is centered around the tube opening end with the winding electrode that is centered around the duct occlusion end by the PP system.Vacuum will be evacuated to earlier in the pipe.Now make air under about 200 milli torr pressure in the inlet tube.So under 11.7MHz and 62 watts about 30 seconds, improved the surface energy that increases the liquid diffusion oxidized the causing of inner air tube plasma body to electrifying electrodes.
Then pipe and vacuum multitube are disconnected and coat the Refrigerant R 113 solution of 1% diacrylate three propylidene diester in the inside of pipe.Solvent evaporation is made stay the diacrylate coating in the pipe.Then pipe is connected with electrode once more with the vacuum multitube.Under the energy same as described above, frequency and electrode situation, about 150 milli torrs in pipe, by the processing of 2 minutes air plasmas, it is crosslinked that diacrylate is in position gone up.
Air is had under the pressure in the ingress pipe at about 150 milli torrs.
Introduce Hexaethyl two silica steam total pressure in pipe again and be about 250 milli torrs.Again under 11.7MHz and 62 watts about 3 minutes and make plasma body formation in pipe to electrifying electrodes.
The plasma body of hexamethyldisiloxane/air mixture forms once more in pipe and exceeds three times and cause SiO
xThe blocking layer deposits with four successive layer forms.
Then the protectiveness apical tier is deposited on the SiO near the HMDSO that uses plasma polymerization
xThe blocking layer.Then under about 300 milli torrs the hexamethyldisiloxane inlet tube under 11.7MHz and 62 watts about 60 seconds again to electrifying electrodes.
Embodiment 8
Polystyrene (PS) pipe is connected with vacuum multitube system and is connected with the outside coiled pipe type electrode of surrounding tube blind end.At first being evacuated to the about 30 milli torrs of vacuum tightness in the pipe.Then under about 250 milli torr pressure through the multitube system the air inlet tube of 22sccm in.Again in 50 milli torrs depress power through the multitube system the steam inlet tube of the HMDS of 1.0sccm in, cause that the total pressure of gaseous mixture reaches 300 milli torrs in the pipe.About 5 minutes so that plasma body generation in pipe under 11MHz and 20 watts to electrifying electrodes.
SiO
xAfter deposition on the inner wall surface of pipe, pipe and multitube are disconnected.The penetrating quality of pipe the results are shown in the table 1.
Table 1
The embodiment oxygen permeability
Cc/m
2/ atm/ days
The PP pipe, uncoated contrast
(embodiment 1) 55.9
The PP pipe, (embodiment 1) 26.1
The PP pipe, contrast (embodiment 2) 50.0
PP manages (embodiment 2) 33.7
The PET pipe, (embodiment 3) 1.75
The PET pipe, contrast (embodiment 3) 2.33
PET manages (embodiment 4) 1.47
The PET pipe, contrast (embodiment 4) 2.33
The PP pipe, W/ does not rotate (embodiment 5) 32.4
The PP pipe, contrast W/ does not rotate (embodiment 5) 57.1
The PP pipe, W/ rotates (embodiment 6) 25.8
The PP pipe, contrast W/ rotates (embodiment 6) 57.1
The PP pipe, contrast (embodiment 7) 77.1＜PP pipe, (embodiment 7) 4.42PS pipe, uncoated contrast 145 (embodiment 8) PS pipe, (embodiment 8) 77.3
Claims (31)
1, a kind of the block film coating is added to method on the plastic substrate inner wall surface, this method comprises:
(a) be placed on the plastics of inner wall surface and cause described opening end to be connected on the correct position having opening end, blind end, outside, inside and outer wall with vacuum multitube system with monomer source of supply, oxygenant source of supply and vacuum source of supply;
(b) outer wall surface of described plastics is placed on the correct position with electrode assemblie;
(c) the described inside of described goods is vacuumized;
(d) carry monomer gas and oxidant gas in the described inside of described goods;
(e) carry alternating current to described electrode; With
(f) thus making described gas ionization is coated onto the block film coating on the inner wall surface of described container so that can form plasma body.
2, the process of claim 1 wherein that described matrix is a three-dimensional body.
3, the method for claim 2, wherein said matrix is a blood collection tube.
4, the process of claim 1 wherein that described monomer gas is air, oxygen or Nitrous Oxide.
5, the process of claim 1 wherein that described oxidant gas is air, oxygen or Nitrous Oxide (nitrous oxygen).
6, the process of claim 1 wherein that the monomer gas of the about 15sccm of about 0.5sccm-is transported to described goods.
7, the process of claim 1 wherein that the oxidant gas of the about 35sccm of about 15sccm-is transported to described goods.
8, the process of claim 1 wherein that described goods are to be evacuated to about 0.001 milli torr-Yue 100 milli torrs.
9, the process of claim 1 wherein that described monomer gas is transported to described goods under about 80 milli torrs-Yue 190 milli torrs.
10, the process of claim 1 wherein that described oxidant gas is transported to described goods under about 110 milli torrs-Yue 200 milli torrs.
11, the process of claim 1 wherein that step (d) also comprises diluent gas.
12, the method for claim 11, wherein said diluent gas is a rare gas element.
13, the method for claim 12, wherein said rare gas element are helium, argon or non-reactive gas.
14, the method for claim 12, wherein said non-reactive gas is a nitrogen.
15, the process of claim 1 wherein that described alternating current is low-frequency ac electric current, radio frequency or microwave frequency.
16, a kind of being used for applies the multitube system that plasma body is used to the inwall of plastics, comprising:
(a) be used to connect and/or the described inwall that exposes described plastics in the device of described multitube system;
(b) be used for carrying the device of monomer to described container;
(c) be used for the device of delivery of oxidizing agent to described container;
(d) be used for producing and keeping the device of vacuum tightness at described goods; With
(e) be used for device at described internal tank intake.
17, the equipment of claim 16, wherein being used to carry monomer to the described device of described container is valve.
18, the equipment of claim 16, wherein being used for delivery of oxidizing agent is valve to the device of described container.
19, the equipment of claim 16, the device that wherein is used for to described internal tank energy supply is an electrode.
20, the equipment of claim 16 wherein, is used to connect and/or the described inwall that exposes described plastics is a rubber cradle in the described device of described multitube system.
21, the equipment of claim 16 also comprises the device that is used for measuring described goods pressure.
22, the equipment of claim 16 also comprises the device that is used to keep pressure reduction between described goods and the described multitube.
23, the equipment of claim 22, the described device that wherein is used to keep pressure reduction is a valve.
24, the equipment of claim 16, wherein said electrode are the inductive character windings.
25, the method on a kind of inner wall surface that the block film coating is applied to plastic substrate, this method comprises:
(a) be placed on the plastics of inner wall surface and cause described opening end to be connected on the correct position having opening end, blind end and outer wall with vacuum multitube system with monomer source of supply, oxygenant source of supply and vacuum source of supply;
(b) the described outer wall surface of described plastics is placed on the correct position with electrode assembly;
(c) make the described inside of described goods be evacuated to about 0.001 milli torr-Yue 100 milli torrs;
(d) be delivered to the described inside of described goods at the about 50sccm of about 0.1sccm-and about 80 milli torrs-following HMDSO monomer gas of Yue 190 milli torrs;
(e) under the about 35sccm of about 15sccm-and about 110 milli torrs-Yue, 200 milli torrs the described inside of atmospheric oxidation agent gas delivery to described goods; With
(f) radio-frequency power supply is flowed to the about 50MHz of about 5MHz-and about 15 Wa-Yue 40 watts described electrode.
26, the method on a kind of inner wall surface that the block film coating is applied to plastic substrate, this method comprises:
(a) be placed on the plastics of inner wall surface and cause described opening end to be connected on the correct position having opening end, blind end, outside, inside and outer wall with vacuum multitube system with monomer source of supply, oxygenant source of supply and vacuum source of supply;
(b) outer wall surface of described plastics is placed on the correct position with electrode assemblie;
(c) the described inside of described goods is vacuumized;
(d) monomer gas and oxidant gas are delivered to the described inside of described goods;
(e) radio-frequency power supply is delivered to described electrode;
(f) thus making described gas ionization is coated onto the block film coating on the inner wall surface of described container so that form plasma body;
(g) stop radio-frequency power supply in the step (e); With
(h) repeating step (e)-(f).
27, the method for claim 26, wherein step (d) also comprises diluent gas.
28, a kind of the method for block film coating on the inner wall surface of plastic substrate, this method comprises:
(a) be placed on the plastics of inner wall surface and cause described opening end to be connected on the correct position having opening end, blind end, outside, inside and outer wall with vacuum multitube system with monomer source of supply, oxygenant source of supply and vacuum source of supply;
(b) outer wall surface of described plastics is placed on the correct position with electrode assemblie;
(c) the described inside of described goods is vacuumized;
(d) monomer gas and oxidant gas are delivered to the described inside of described goods;
(e) radio-frequency power supply is delivered to described electrode;
(f) thus making described gas ionization is coated onto the block film coating on the inner wall surface of described container so that form plasma body;
(g) stop gas delivery in the step (d); With
(h) repeating step (d).
29, the method for claim 28, wherein step (d) also comprises diluent gas.
30, the method on a kind of inner wall surface that the block film coating is coated onto plastic substrate, this method comprises:
(a) be placed on the plastics of inner wall surface and cause described opening end to be connected on the correct position having opening end, blind end and outer wall with vacuum multitube system with monomer source of supply, oxygenant source of supply and vacuum source of supply;
(b) the described outer wall surface of described plastics is placed on the correct position with electrode assemblie;
(c) the described inside of described goods is evacuated to about 0.001 milli torr-Yue 100 milli torrs;
(d) be delivered to the described inside of described goods at the about 50sccm of about 0.1sccm-and about 80 milli torrs-following HMDSO monomer gas of Yue 190 milli torrs;
(e) under the about 35sccm of about 15sccm-and about 110 milli torrs-Yue, 200 milli torrs the described inside of atmospheric oxidation agent gas delivery to described goods;
(f) radio-frequency power supply is flowed to the about 50MHz of about 5MHz-and about 5 Wa-Yue 40 watts described electrode;
(g) stop gas delivery in the step (d);
(h) stop radio-frequency power supply in the step (e); With
(i) repeating step (d)-(h).
31, the method for claim 30, wherein step (d) also comprises diluent gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97101060 CN1161386A (en) | 1996-01-30 | 1997-01-27 | Apparatus and method for plasma processing |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US593,975 | 1996-01-30 | ||
| CN 97101060 CN1161386A (en) | 1996-01-30 | 1997-01-27 | Apparatus and method for plasma processing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1161386A true CN1161386A (en) | 1997-10-08 |
Family
ID=5165489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97101060 Pending CN1161386A (en) | 1996-01-30 | 1997-01-27 | Apparatus and method for plasma processing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1161386A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101223299B (en) * | 2005-07-12 | 2010-12-01 | 三菱重工食品包装机械株式会社 | Tectorial membrane forming device for forming tectorial membrane on internal surface of container, production method for internal surface tectorial membrane container |
| CN104386918A (en) * | 2014-10-22 | 2015-03-04 | 宁波正力药品包装有限公司 | Preparation method of barrier film for inner wall of glass bottle |
| CN104752633A (en) * | 2013-12-31 | 2015-07-01 | 中国科学院微电子研究所 | Thin film packaging method |
-
1997
- 1997-01-27 CN CN 97101060 patent/CN1161386A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101223299B (en) * | 2005-07-12 | 2010-12-01 | 三菱重工食品包装机械株式会社 | Tectorial membrane forming device for forming tectorial membrane on internal surface of container, production method for internal surface tectorial membrane container |
| CN104752633A (en) * | 2013-12-31 | 2015-07-01 | 中国科学院微电子研究所 | Thin film packaging method |
| CN104386918A (en) * | 2014-10-22 | 2015-03-04 | 宁波正力药品包装有限公司 | Preparation method of barrier film for inner wall of glass bottle |
| CN104386918B (en) * | 2014-10-22 | 2017-07-07 | 宁波正力药品包装有限公司 | A kind of preparation method of vial inwall barrier film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1082569C (en) | Microwave plasma processing apparatus and method therefor | |
| EP0787828B1 (en) | Process for plasma processing | |
| CN1030616A (en) | Method with plasma enhanced silicon oxide deposition | |
| EP0958400B1 (en) | Method and apparatus for plasma deposition of a thin film onto the interior surface of a container | |
| EP1111087B2 (en) | Apparatus and method for forming thin film | |
| US6001429A (en) | Apparatus and method for plasma processing | |
| CN1831192A (en) | Film formation method and apparatus for semiconductor process, and storage medium | |
| JP5157169B2 (en) | GAS BARRIER LAMINATE, ORGANIC ELECTROLUMINESCENCE ELEMENT AND METHOD FOR PRODUCING GAS BARRIER LAMINATE | |
| CN1656245A (en) | Multistation coating device and method for plasma coating | |
| JP2006507197A (en) | Method and apparatus for depositing a plasma coating on a container | |
| CN1881543A (en) | Method and apparatus for forming silicon oxide film and program | |
| CN1460130A (en) | System and method for depositing inorganic/organic dielectric films | |
| CN1881544A (en) | Method and apparatus for forming silicon nitride film | |
| WO2006075490A1 (en) | Transparent gas barrier film | |
| CN1161386A (en) | Apparatus and method for plasma processing | |
| CN1716538A (en) | Film formation apparatus and film forming device | |
| JP4899863B2 (en) | Thin film forming apparatus and thin film forming method | |
| JP2723472B2 (en) | Apparatus and method for depositing borophosphosilicate glass on a substrate | |
| WO2008001723A1 (en) | Thin film forming apparatus and thin film forming method | |
| JP2006219721A (en) | Method for producing functional film, functional film, display element and display device | |
| JP2006307346A (en) | Thin-film-forming method and thin-film-forming apparatus | |
| JP4133353B2 (en) | Method for producing silicon oxide thin film or titanium oxide thin film | |
| CN1795289A (en) | Chemical vapor deposition film formed by plasma cvd process and method for forming same | |
| WO2015025782A1 (en) | Device for producing gas barrier film and method for producing gas barrier film | |
| CN1692177A (en) | Worktable device, film formation apparatus, and film formation method for semiconductor process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1002964 Country of ref document: HK |