CN1711310A - Process and apparatus for depositing plasma coating onto a container - Google Patents

Process and apparatus for depositing plasma coating onto a container Download PDF

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Publication number
CN1711310A
CN1711310A CN 200380103073 CN200380103073A CN1711310A CN 1711310 A CN1711310 A CN 1711310A CN 200380103073 CN200380103073 CN 200380103073 CN 200380103073 A CN200380103073 A CN 200380103073A CN 1711310 A CN1711310 A CN 1711310A
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container
syringe
plasma polymerization
layer
sec
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CN 200380103073
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CN100347229C (en
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C·M·魏卡特
P·J·奥康纳
I－F·胡
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Abstract

The present invention describes a method and an apparatus for plasma coating the inside surface of a container to provide an effective barrier against gas transmission. The method provides a way to deposit rapidly and uniformly very thin and nearly defect-free layers of polyorganosiloxane and silicon oxide on the inner surface of a container to achieve more than an order of magnitude increase in barrier properties.

Description

The method and apparatus of deposition plasma coating in container
The present invention relates to be used in container, more particularly at the internal surface of container, the preferred method and apparatus of the coating that deposition plasma forms in plastic containers.
For many years, plastic containers are used for packing soda pop and noncarbonated beverage products always.The human consumer preferably uses the plastics such as polyethylene terephthalate (PET) or polypropylene (PP), because their anti-crackings, in light weight and transparent.Unfortunately, because oxygen and carbon dioxide is had than higher perviousness, limited the preservation period of plastics packed beverage.
The effort of being devoted to plastic containers are handled to give its lower oxygen and carbon dioxide perviousness is known.Such as, people such as Laurent (WO 9917333) have narrated use plasma enhanced chemical vapor deposition process (PECVD) and have been coated with SiO for the internal surface of plastic containers xThe method of layer.In general, SiO xCoating provides effective obstruct to gas penetration, yet, for plastic containers, SiO xTo the obstruct that forms effective gas penetration is not enough.
At United States Patent (USP) 5,641, in 559, Namiki has narrated on the outside surface of PET and PP bottle the deposition plasma polymerized silicic compound, has deposited SiO then xThe method of layer.The thickness of polymerized silicic compound is 0.01～0.1 μ m, and SiO xThe thickness of layer is 0.03～0.2 μ m.Though Namiki discloses the silicon compound and the SiO of plasma polymerization xThe combination of layer (wherein x is 1.5～2.0) provides than all better barrier property of any independent one deck among both, but total depositing time of coating is about 15 minutes, and this application for commerce is unpractiaca.Moreover the method that Namiki narrated is imperfect, because the place of monomer deposition beyond required matrix of too many plasma polymerization arranged.This unwanted deposition causes the transformation efficiency of precursor-coating too low, pollutes and the equipment of making dirty, also causes basal body coating layer inhomogeneous.
Therefore, wish to invent a kind of be used for evenly and promptly being coated with container, the particularly method of coat plastics container, this method can provide effective obstruct to gas penetration, and reduces and pollute.
By a kind of method of protecting barrier layer for preparing being provided for container with internal surface, the present invention is intended to solve prior art problems, this method comprises the steps: a) under partial vacuum and in the atmosphere of oxygen enrichment, makes first silicoorganic compound carry out plasma polymerization with the uniform organopolysiloxane layer of deposition one layer thickness on inner surface of container under polymerizing condition; And b) under partial vacuum, makes second silicoorganic compound under polymerizing condition, carry out plasma polymerization and be stacked and placed on silicon oxide layer on the identical or different organopolysiloxane layer with deposition.
On the other hand, the present invention is a kind of improved equipment that is used for the coating that deposition plasma forms on the surface of container, and this equipment has: a) have chamber, inboard and the outer outer conduction resonant cylindrical shell of surveying; B) electric organ that electromagnetic field can be provided in the microwave region and link to each other with the outer survey of resonator cavity; C) outside waveguide between conduction resonant cylindrical shell and the electric organ, the inboard of outer conduction resonant cylindrical shell can be directly guided microwave in this waveguide; D) be arranged in outer conduction resonant cylindrical shell, the permeable cylindrical tube of microwave, this pipe is at one end closed, opens at the other end, makes it possible to feed in the container; E) be arranged at least one conducting plates of resonator cavity; And e) is used to open the lid of an end; Wherein improvements comprise the syringe that is fixed in lid, this syringe be porous, co-axial, vertically reciprocal or rotate round the longitudinal axis, perhaps their combination, this syringe can insert in the container, makes it have at least part to extend in the container.
Fig. 1 is the explanatory view that is used to be coated with the equipment of container inside.
Use is at the equipment described in the WO 0066804, and it is favourable implementing method of the present invention, though this is not unique, this equipment has been made some modifications to Fig. 1 and produced.This equipment 10 has outer conduction resonant chamber 12, and it is (the also referring to have the outer conduction resonant cylindrical shell in chamber) of tubular preferably.Equipment 10 comprises an electric organ 14 that links to each other with the outer survey of resonator cavity 12.This electric organ 14 can provide electromagnetic field in the microwave region, more particularly is equivalent to the field of frequency 2.45GHz.Electric organ 14 is installed on the box 13 that resonator cavity 12 is outer to be surveyed, and the electromagnetic radiation that it provided is taken to resonator cavity 12 by waveguide 15 fully vertical with axis A1, that manifest along the window of the radius extension of resonator cavity 12 and the inboard by being arranged in resonator cavity 12.
Pipe 16 is to be positioned at resonator cavity inboard, the permeable hollow cylinder of microwave, and pipe 16 is sealed by wall 26 at the one end, opens at the other end to make it possible to stretch in the container for the treatment of to be handled by PECVD.Container 24 can be comprised by glass, pottery, matrix material and plastics manufacturing by any non electrically conductive material.Container 24 is plastics preferably, such as polyalkylene terephthalates, comprise polyethylene terephthalate and polybutylene terephthalate; Polyolefine comprises polypropylene and polyethylene; Polycarbonate; Polyvinyl chloride; PEN; Polyvinylidene chloride; Polymeric amide comprises nylon; Polystyrene; Urethane; Resins, epoxy; Acrylic resin comprises polymethylmethacrylate; And poly(lactic acid).
Then, the open end of pipe 16 is sealed by lid 20, makes can partly to vacuumize in pipe 16 defined spaces, sets up low dividing potential drop in the inboard of container 24.Container 24 is remained on the support 22 of container 24 at neck.Applying portion vacuum advantageously all in the inboard of container 24 and the outside makes container 24 distortion to avoid container 24 to be subjected to too big pressure reduction.Partial vacuum in the container inside and the outside is different, in outside of containers retaining part vacuum, makes and is not wishing that the outside of carrying out sedimentary container 24 does not form plasma body.Preferably, the partial vacuum of container 24 inboards remains on 20～200 μ ar, and is pumped into 20～100mbar in the outside of container 24 or is lower than the partial vacuum of 10 μ bar.
Lid 20 matches with syringe 27 on being fixed on container 24, makes to small part to extend in the container 27, contains the active fluid of reactive monomer and carrier with introducing.Syringe 27 can be designed to such as be porous, opening, vertically reciprocal, that rotate, co-axial and their combination.Just as used in this, word " porous " is to use its traditional meaning, means that it has the hole, also generally refers to all gas-pervious passages, and it can comprise one or more slits.The porous syringe that a preferred embodiment of syringe 27 is a kind of openings is more preferably a kind of opening, has the fractionated porosity, promptly has the syringe of the porosity of different grades, and this syringe preferably extends on the length of entire container almost.The pore dimension of syringe 27 makes the flow uniformity coefficient of the active precursor gas on container 24 internal surfaces realize optimizing along with enlarging towards the bottom of container 24.Fig. 1 illustrates this difference of porosity with shade in various degree, this figure explanation porosity of 1/3rd 27a on syringe be lower than this syringe in the porosity of 1/3rd 27b, and in the porosity of 1/3rd 27b be lower than the porosity of 1/3rd 27c under this syringe.The porosity of syringe 27 is generally 0.5 μ m～1mm.Yet classification can be taked various forms, from illustrated staged to real continous way.The diameter in syringe 27 transverse section can from just less than container 24 the internal diameter (generally from 40mm) of narrow part change between the 1mm.
Equipment 10 also comprises at least one conducting plates in resonator cavity, be used for carrying out to the geometrical shape of resonator cavity tuning, so that the plasma distribution in the container 24 is controlled.Though and inessential, more preferably as illustrated in fig. 1, equipment 10 comprises two annular conducting platess 28 and 30, they are arranged in resonator cavity 12, and round pipe 16.Conducting plates 28 and 30 moves mutually, makes them in axial both sides attached to pipe 16, and waveguide 15 is led in the resonator cavity 12 by this pipe.Conducting plates 28 and 30 design make it possible to electromagnetic field is regulated, in sedimentary process mid-point combustion with keep plasma body.Use slide bar 32 and 34 can regulate the position of conducting plates 28 and 30.
Can realize the deposition of organopolysiloxane and SiOx layer as follows.Make the gaseous mixture that comprises balanced gas and working gas (the being called all gas mixture together) syringe 27 of flowing through, its concentration and electric work density and time all are enough to form the coating with desired gas barrier property.
Just as used in this, term " working gas " refers to a kind of active substance, and under standard temperature and pressure (STP), they can be can not be gas also, can be aggregated in and form coating on the matrix.The example of suitable working gas comprises the silicoorganic compound such as silane, siloxanes and silazane.The example of silane comprises tetramethylsilane, trimethyl silane, dimethylsilane, methyl-monosilane, the dimethoxy dimethylsilane, methyltrimethoxy silane, tetramethoxy-silicane, Union carbide A-162, di ethoxy di methyl-monosilane, Union carbide A-162, the triethoxy vinyl silanes, tetraethoxysilane (also being called tetraethyl orthosilicate, i.e. TEOS), the dimethoxy-methyl phenyl silane, phenyltrimethoxysila,e, 3-Racemic glycidol oxygen propyl trimethoxy silicane, 3-methacryloyl propyl trimethoxy silicane, the diethoxymethyl phenyl silane, three (2-methoxy ethoxy) vinyl silanes, phenyl triethoxysilane and dimethoxy diphenyl silane.The example of siloxanes comprises tetramethyl disiloxane, hexamethyldisiloxane and octamethyltrisiloxane.The example of silazane comprises hexa methyl silazane and tetramethylsilazanes.Siloxanes is preferred working gas, and tetramethyl disiloxane (TMDSO) is particularly preferred.
As used herein, term " balanced gas " is to carry working gas by electrode and final activity or the non-active gas that arrives on the matrix.The example of suitable balanced gas comprises air, O 2, CO 2, NO, N 2O and their combination.Oxygen (O 2) be preferred balanced gas.
In the first plasma polymerization step, in oxygen-enriched atmosphere, make first silicoorganic compound on the internal surface of container, carry out plasma polymerization, the internal surface of container can carry out surface modification in advance, such as carrying out roughening, crosslinked or surface oxidation, also can not carry out surface modification in advance.As used herein, term " oxygen-enriched atmosphere " means that balanced gas contains at least 20% oxygen, more preferably contains at least 50% oxygen.Therefore, for purpose of the present invention, air is suitable balanced gas, but N 2Be not.
The molar percentage that accounts for all gas mixture at balanced gas is before 80 moles of %, and per-cent is irrelevant therewith on the quality entity of organopolysiloxane layer, beginning from then on, the quality entity upper variation of this layer.The power density that is used to prepare the plasma body of organopolysiloxane layer is preferably greater than 10MJ/kg, more preferably greater than 20MJ/kg, most preferably greater than 30MJ/kg; Preferably less than 1,000MJ/kg is more preferably less than 500MJ/kg, most preferably less than 300MJ/kg.
In this first step, plasma body preferably continues to be more preferably less than 2 seconds, most preferably less than 1 second less than 5 seconds; And preferably be longer than 0.1 wonderfully, and more preferably be longer than 0.2 second, to form thickness, be more preferably less than 200 , most preferably less than 100 preferably less than 500 ; Be preferably greater than 25 , more preferably greater than the organopolysiloxane layer of 50 .
Preferably, be more preferably less than 200 /sec, be preferably greater than 50 /sec, implement the first plasma polymerization step more preferably greater than the sedimentation velocity of 100 /sec with less than 500 /sec.
The preferred chemical constitution of organopolysiloxane layer is SiO xC yH z, x is 1.0～2.4 here, y is 0.2～2.4, and z is more than or equal to 0, more preferably no more than 4.
In the second plasma polymerization step, second silicoorganic compound that can be identical or different with first silicoorganic compound, on aforesaid organopolysiloxane layer, carry out plasma polymerization, form silicon oxide layer, perhaps different organopolysiloxane layers.In other words, the above organopolysiloxane layer of one deck with different chemical composition is possible, is favourable sometimes.Silicon oxide layer is SiO preferably xLayer, x is 1.5～2.0 herein.
For the second plasma polymerization step, balanced gas is stoichiometric to balanced gas and working gas preferably to the mol ratio of gaseous mixture.Such as, be oxygen at balanced gas, and working gas is under the situation of TMDSO, preferred balanced gas is 85～95% to the mol ratio of all gas.The power density that is used to prepare the plasma body of silicon oxide layer is preferably greater than 10MJ/kg, more preferably greater than 20MJ/kg, most preferably greater than 30MJ/kg; Preferably, be more preferably less than 300MJ/kg less than 500MJ/kg.
In this second step, plasma body continues preferably to be more preferably less than 5 seconds less than 10 seconds, preferably is longer than 1 second, less than 500 , is more preferably less than 300 with formation thickness, most preferably less than 200 , is preferably greater than 50 , more preferably greater than the silica coating of 100 .
Preferably, be more preferably less than 200 /sec, be preferably greater than 50 /sec, implement the step of second plasma polymerization more preferably greater than the sedimentation velocity of 100 /sec with less than 500 /sec.
The total thickness of first plasma polymerization layer and second plasma polymerization layer is more preferably less than 500 preferably less than 1,000 , is more preferably less than 400 , most preferably less than 300 , is preferably greater than 100 .Total depositing time of plasma polymerization (promptly being used for first and second layers depositing time) is more preferably less than 10 seconds preferably less than 20 seconds, most preferably less than 5 seconds.
Be surprised to find that, can be promptly on the internal surface of container deposit thickness very thin coating uniformly, with to such as O 2And CO 2Form barrier layer etc. micromolecular infiltration.Just as used in this, term " thickness is even " refers to variation at whole applying area floating coat thickness less than 25%.Preferred coatings does not ftracture in fact or aperture.Preferred intercept improvement factor (BIF, be untreated bottle with handle the ratio of bottle to the transmitance of specific gas) be 10 at least, more preferably be 20 at least.
The following examples are used for illustrative purposes, scope of the present invention are not construed as limiting.
Embodiment-on the PET bottle, prepare plasma coating
Use equipment as shown in FIG. 1 in this embodiment.In this embodiment, container 24 is PET bottles that are suitable for the 500mL of soda pop.Bottle 24 inserts the pipe 16 that is arranged in resonator cavity 12.Lid 12 adapts with the classifying porous syringe 27 that is fixed on the opening on the bottle, makes syringe 27 reach 1cm place at the bottom of bottle.By with three section 2.5 " (6.3cm) long porous hollow stainless steel tube (external diameter 0.25 " (0.64cm), internal diameter 0.16 " (0.41cm)) weld together and make this syringe; every section pipe has different porositys, form as illustrated in fig. 1 single 7.5 " (19cm) multi-level injection device.The pore dimension of/3rd 27a is 20 μ m on this syringe, and the pore dimension of 1/3rd 27b is 30 μ m in the syringe, and the pore dimension of 1/3rd 27c is 50 μ m (perforated tube is available from Mott companies) under the syringe.
Partial vacuum is all set up in the inboard and the outside at bottle 24.The outside of bottle 24 remains on 80mbar, and remains on 10 μ bars during its inboard beginning.As follows, on the internal surface of bottle 24, deposit an organo-siloxane layer equably.Speed with 10sccm makes TMDSO and O 2Flow through syringe 27 together, the dividing potential drop of container inside is raise.In case dividing potential drop reaches 40 μ bars (being generally less than 1 second), apply the power (being equivalent to power density is 120MJ/kg) 0.5 second of 150W, forming thickness is the organo-siloxane layer of 50 .
According to the methods below, on this organo-siloxane layer, deposit a SiO equably xLayer.TMDSO and O 2Flow with 10sccm and 80sccm flows through syringe 27 together respectively, and the dividing potential drop of bottle 24 inboards is raise.In case dividing potential drop reaches 60 μ bars (being generally less than 1 second), apply the power (being equivalent to power density is 120MJ/kg) 3.0 seconds of 350W, forming thickness is the SiO of 150 xLayer.
With intercepting improvement factor (BIF) expression barrier property, it is represented the OTR oxygen transmission rate of uncoated bottle and has been coated with the ratio of the OTR oxygen transmission rate of bottle.The BIF that uses Oxtran 2/20 oxygen to see through device (available from Mocon company) measurement is 27.This is equivalent to OTR oxygen transmission rate is 0.0017cm 3/ bottle/sky.

Claims (9)

1. be used to the container with internal surface to prepare the method for protecting barrier layer, this method comprises the steps:
A) under partial vacuum and in the atmosphere of oxygen enrichment, make first silicoorganic compound under polymerizing condition, carry out plasma polymerization with the uniform organopolysiloxane layer of deposition one layer thickness on inner surface of container; And
B) under partial vacuum, make second silicoorganic compound under polymerizing condition, carry out plasma polymerization and be stacked and placed on the uniform silicon oxide layer of thickness on the identical or different organopolysiloxane layer with deposition.
2. method according to claim 1 is wherein carried out the plasma polymerization step with the so concentration and the time of the power density and first and second silicoorganic compound, makes the total thickness of organopolysiloxane and silicon oxide layer less than 400 .
3. method according to claim 1 and 2, wherein with greater than 100 /sec, implement the first plasma polymerization step less than the sedimentation velocity of 200 /sec, implement the second plasma polymerization step under the sedimentation velocity of 60 /sec being not less than 30 /sec and being not more than, and wherein total depositing time of plasma polymerization is not more than 10 seconds.
4. according to the arbitrary described method of claim 1-3, wherein use general formula SiO xC yH zThe expression organopolysiloxane, wherein x is 1.0～2.4, y is 0.2～2.4, and z is not more than 4, uses SiO xThe expression silicon oxide layer, wherein x is 1.5～2.0, and wherein this container contains the plastics of polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene or poly(lactic acid).
5. according to the arbitrary described method of claim 1-4, wherein send into the oxygen and first and second silicoorganic compound by syringe reciprocal, that rotate or co-axial or their combinations porous, opening, vertical.
6. method according to claim 5, wherein send into the oxygen and first and second silicoorganic compound by being arranged in container and being stretched over almost the classifying porous syringe of opening of entire container length, wherein porosity increases being staged or continous way on the direction of container bottom.
7. method according to claim 6, the inboard of this container and outside retaining part vacuum all wherein, wherein the partial vacuum of container inside is extremely about 200 μ bar of about 20 μ bar, and the partial vacuum of outside of containers is that 20mbar is to about 100mbar or less than 10 μ bar.
8. the equipment of the coating that deposition plasma forms on a kind of improved surface that is used at container, this equipment has:
A) have chamber, inboard and the outer outer conduction resonant cylindrical shell of surveying;
B) electric organ that can electromagnetic field is provided in the microwave region and link to each other with the outer survey of resonator cavity;
C) outside waveguide between conduction resonant cylindrical shell and the electric organ, the inboard of outer conduction resonant cylindrical shell can be directly guided microwave in this waveguide;
D) be arranged in the cylindrical tube of outer conduction resonant cylindrical shell to microwave, this pipe is at one end closed, opens at the other end, makes it possible to feed in the container;
E) be arranged at least one conducting plates of resonator cavity; With
F) be used to open the lid of an end;
Wherein improvements comprise the syringe that is fixed in lid, this syringe be porous, co-axial, vertically reciprocal or rotate round the longitudinal axis, perhaps their combination, this syringe can insert in the container, makes it have at least part to extend in the container.
9. equipment according to claim 8, wherein syringe is classifying porous and opening, and wherein porosity is being staged or continuous mode increases in the direction towards the injector orifice part.
CNB2003801030733A 2002-11-12 2003-11-10 Process and apparatus for depositing plasma coating onto a container Expired - Fee Related CN100347229C (en)

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US8512796B2 (en) 2009-05-13 2013-08-20 Si02 Medical Products, Inc. Vessel inspection apparatus and methods
US9272095B2 (en) 2011-04-01 2016-03-01 Sio2 Medical Products, Inc. Vessels, contact surfaces, and coating and inspection apparatus and methods
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