CN101203624B - Sealing of plastic containers - Google Patents

Sealing of plastic containers Download PDF

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Publication number
CN101203624B
CN101203624B CN2006800041058A CN200680004105A CN101203624B CN 101203624 B CN101203624 B CN 101203624B CN 2006800041058 A CN2006800041058 A CN 2006800041058A CN 200680004105 A CN200680004105 A CN 200680004105A CN 101203624 B CN101203624 B CN 101203624B
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ampoule
coating
metal
sealing
titanium
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CN101203624A (en
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I·G·C·麦克阿弗
P·E·塔什科
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Breath Ltd
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Breath Ltd
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Abstract

An ampoule (4) of plastics material contains a solution of an inhalation or injectable pharmaceutical, and an outer surface of the ampoule is coated with a metal or metal compound or with a polymer deposited by vapour deposition so as to reduce moisture egress from the ampoule and reduce contamination of ampoule contents from external sources. Labels are easily applied to the coating.

Description

The sealing of containers of plastic material
Invention field
The present invention relates to the sealing of container, relate to coating, be specifically related to ampoule is applied, to reach sealing effectiveness the container made of plastics material that can be used for makeup and/or pharmaceutical preparation.The invention still further relates to container sealing or coating, relate in particular to ampoule sealing or coating.
Background of invention
Medicine and cosmetic formulations are in the various encapsulation, comprise the encapsulation that glass, metal, plastic material and natural materials are made.For liquid preparation, for example solution or suspension encapsulate and must maintenance seal, with anti-leak.But all these containers all exist a large amount of technical difficulties and the actual difficulty of using.
Some preparations can comprise high volatile volatile material or other less molecule, and they can see through the diffuse of container and come out.For for example perfume, this is a very special problem.Because product may lose usefulness, fragrance or fragrance, be restricted its storage period.Therefore, the container that is used for these products is made by impermeable material, for example uses glass, and these materials are quite expensive usually.Because can not use the cheap material of plastic material and so on, cause high packaging cost.
In a single day pharmaceutical preparation in the container may carry out sterilization under high temperature or condition of high voltage, perhaps load under aseptic condition, must be enough firm, and to keep sterility.This causes higher production cost again easily.
Using atomizer is known to patient's pulmonary administration, makes that patient can administration in eupnea.Medicine provides with unitary dose ampoule (UDA) form, wherein comprises the solution of smaller size smaller (being generally the 1-5 milliliter), and this ampoule is made by plastic material usually.A kind of method of making ampoule is (BFS) to make by Blow-Fill-Seal (blowing-can-sealing) under aseptic condition, forms ampoule by extrusion molding in this method, with the method can solution of many parts of still basic single steps.If desired, and if described content be not thermolability, can carry out heat sterilization, for example can sterilize to ampoule by the terminal sterilization method, promptly after can and sealed ampoule, sterilize.These methods are that administrative authority generally confirms and accepts in the worldwide.
A known problem of existing ampoule is that they make oxygen, other gas and other volatile compound enter in the ampoule, makes water (moisture) leave ampoule.Test to content finds that in storage process, pollutent can see through the plastic material of ampoule wall, absorbs in the system agent.In a concrete example, in ampoule, found the Vanillin of the amount that can't receive, cause product failure, make administrative authority's refusal permit using the ampoule of the security measures of not taking precautions against this outside contamination.
As the example of a specific question, US FDA requires to cover ampoule outward with air-tight pouch recently, in order to avoid the content of ampoule is contaminated.The material of described air-tight pouch is three layer laminates of paper and/or polymkeric substance, aluminium, new LDPE (film grade) (LDP) normally.This sealed pouch is counted as a kind of acceptable solution.
Ampoule normally makes with the form of the lath of a plurality of independent unitary doses, for example five one plates, ten plates or 30 one plates.Therefore, a problem of air-tight pouch is that if comprise several ampoules in a capsule, then when opening sealed pouch, using first ampoule, remaining ampoule is exposed to environment, may be contaminated.
The perviousness of LDP has also limited the mark of ampoule, and this is owing to must carry out scrutiny to being used for directly being printed on the printing ink on the ampoule and being used for the tackiness agent of pasted paper label, can not see through ampoule and pollute the content of ampoule to guarantee them.
Some ampoules have been full of the rare gas element of nitrogen and so on.Even in air-tight pouch, nitrogen is still outer with ampoule, there is certain balance in the gas in the sealed pouch.When air-tight pouch was opened, more nitrogen can lose from ampoule.
The LDP ampoule is translucent, and some photochromicss of storing in these ampoules can be destroyed after long time stored and exposure.Air-tight pouch provides the solution of part, in case still air-tight pouch is opened, the ampoule of the inside can expose again one uncertain period before using.
In addition, the LDP pipe is quite general for cosmetic applications.But need avoid oxygen to enter in the content of some pipe, for example when these contents when being liposome or other to the material of oxygen sensitive.Therefore LDP and other such material can not be used for making the pipe that is used for these makeup usually.
An object of the present invention is to solve or improve at least the problems referred to above.A target of the preferred embodiment for the present invention provides a kind of alternate, is more preferably the method for improved sealing and/or coating container, and container, particularly ampoule by described method sealing and/or coating also are provided.
Summary of the invention
The present invention is based on to use and comprises sealing ply metal or that comprise polymkeric substance coating is provided on container made of plastics material.
In first aspect, the invention provides a kind of ampoule, it comprises the coating of the sedimentary following material by vapour deposition process: (a) metal or metallic compound, perhaps (b) polymkeric substance.
Usually, the invention provides a kind of container that is used for comprising liquid, this container is made by plastic material, comprises the coating of metal or metallic compound or the coating of polymkeric substance.
In second aspect, the invention provides a kind of method that container made of plastics material moisture leaks that reduces, this method comprises that the outside surface to described container applies coating or the polymeric coating that comprises metal or metallic compound.
In the third aspect, the invention provides a kind of method that container made of plastics material is sealed, this method comprises that the outside surface to described container applies coating or the polymeric coating that comprises metal or metallic compound.
Fourth aspect present invention provides a kind of ampoule has been applied the method for label, and this method comprises coating or the polymeric coating that described ampoule is applied metal or metallic compound, then this coating is applied label.
Described coating can apply in the following manner: plastic layer at first is provided, and applying coating on plastic layer perhaps by for example extrusion molding or other method, prepares the cated plastic layer of coating tool then.
In the preferred embodiment of the present invention, described coating is the coating of metal or metallic compound, is more preferably metallic coating.
Detailed Description Of The Invention
The container of the present invention's coating is the ampoule with coating of metal or metallic compound.Described ampoule can be in an independent ampoule or the plate ampoule.In use, find the described coating content of sealed ampoule effectively, reduce of the loss of ampoule content, reduce the pollution that comes from the outside content to the external world.
Ampoule is made of plastics usually, is other polymkeric substance that uses in polypropylene or polyethylene (low density or highdensity) or manufacturing ampoule or the drink industry, for example polyethylene terephthalate specifically.In addition, described ampoule comprises medicament and pharmaceutically acceptable carrier usually, and described medicament is for example inhalation or injection drug.
Not necessarily requiring described sealing is completely; but preferably completely; make after the required time of test; for example for the situation of ampoule; satisfy the requirement of administrative authority; make that the ampoule content is adequately protected, making does not need to carry out other step, for example carries out the outside with air-tight pouch and coats.Therefore coating can cover at least 50% of ampoule exterior surface area, and perhaps at least 70%, 80%, 90% or 95%.Very preferably the whole substantially outside of ampoule is all coated.
When having applied a plate ampoule, when from this plate, getting next ampoule, the possibility of result causes a side or partly not coated of remaining end ampoule, therefore expose, this only may reduce slightly or can not reduce coating overall sealing effectiveness---it is very little that exposed portions is compared with total surface area, and the common maximum zone of the thickness that is in plastics, the i.e. junction of adjacent ampoule.Therefore the present invention can be used to apply independent container or ampoule, also is used for being applied as plate manufacturing, and the ampoule that takes off one by one.
Coating material can be selected from many kinds can be coated in metal and metallic compound on the ampoule for example.Described coating can comprise aluminium, copper, carbon, chromium, silver, zirconium, tantalum, tungsten, titanium, cobalt, gold, palladium, platinum, and their alloy, comprise steel, and their compound, the compound that comprises metal and gas, for example carbonitride, stannic oxide, Indium sesquioxide, silicon-dioxide.In these coating materials some are more expensive than other coating material, and to the container and the only disposable basically container of ampoule of a large amount of manufacturings and so on, coating preferably comprises the mixture or the alloy of aluminium, titanium, chromium, silver, copper or above-mentioned element.Particularly preferred coating comprises aluminium, titanium, chromium or tetrahedral amorphous carbon, perhaps is made up of these materials.
Can use many different technology applying coatings.Suitable coating method comprises physical vapor deposition, for example sputter, and arc deposited.Splash coating can randomly have the UV lacquer, with supercoat and raising tackiness.
As an example of physical vapor deposition, sputtering sedimentation carries out in vacuum chamber, and wherein atom (normally ar atmo) is ionized and quickens, bump target material, for example aluminium.Coating material is by physical method but not chemical process or thermology method enter gas phase.Ar atmo is driven away the aluminium atom in the bump palladium, the aluminium atomic collision container to be applied of these disengagings then, and this method has applied fine and close coating.Argon (Ar) ion can produce in ion gun, gives ion kinetic energy then, makes ion towards the target for the treatment of sputter, perhaps is orientated in the plasma body that comprises Ar+ and electronics.
Chemical vapour deposition or CVD are the general designations that comprises by a group of methods of vapour deposition solid material, and be similar with physical vapor deposition (PVD) in some respects.The difference of PVD is that precursor is solid-state, makes to treat that sedimentary material is evaporated by solid target, is deposited on the base material.And be suitable under the certain situation of the present invention, CVD needs high temperature usually, and this has limited the material that can apply.In addition, cost may be too high for the disposable products of extensive manufacturing ampoule and so on for the CVD method.
In the arc deposited method, in a vacuum, generation comprises the ionic plasma body between anode and target (normally negative electrode).In filterable cathode arc, make strainer from the ion of the plasma body neutrophil granule by being used for removing macrobead and so on towards base material.These ion depositions form coating from the teeth outwards.Filterable vacuum cathode electric arc can be under lower temperature applying coating, its temperature even be lower than the sputter coating machine is lower than 70 ℃, can hang down and reach room temperature, therefore is particularly suitable for the thermally sensitive base material of plastics and so on.But the plastics that can tolerate the highest about 120 ℃ temperature can use the sputtering technology coating.Can use filterable cathode arc to prepare metal or carbon or alloy coat, also can prepare compound coat by introducing reactant gas near the base material in coating chamber.
These various deposition techniques are well-known in the art.Detailed description to the thin film technique that comprises physical vapor deposition and vacuum arc deposition can be referring to the ThinSolid Films of John A.Thornton and D.W.Hoffman, 171,5 (1989); The Thin Film Processes that J.Vossen and W.Kern write, Academic Press, N.Y., 1978, and Boxman, R.L; Sanders, D.; The Handbook of Vacuum Arc Science and Technology that Martin, P.J. write
Figure S06804105820070808D000051
1995 William AndrewPublishing/Noyes.Sputtering equipment can be buied from many supply and marketing merchants, comprises the CPFilms Inc. of U.S. Martinsville.FCVA equipment also can be buied from many supply and marketing merchants, comprises the NanofilmTechnologies International Pte.Ltd of Singapore.Filterable cathodic vacuum arc technology is also at United States Patent (USP) the 6th, 761, and 805,6,736,949,6,413,387 and 6,031, further describe in No. 239, the reference in content of these patent documentations is incorporated into herein.For the present invention, preferably described coating applies by physical vapor deposition or arc deposited.
Before coated articles, preferably carry out cleaning surfaces or other surface preparation usually, to remove the tackiness of pollutent and improvement coating.For container of the present invention, the water cleaning is just enough usually.Made or comprised the embodiment of polymkeric substance by polymkeric substance for goods to be applied of the present invention, these goods can clean with known step, in addition may need more careful processing.In addition, in the water process of cleaning, polymkeric substance may absorb water, and these water must be removed afterwards, to obtain the vacuum coat tackiness.Also can just apply without any processing, in the case in addition the operation of cleaning of logotype water also can save.
Described goods may can only keep clean the short period of time, unless be in the special environment, for example are filled with the container of drying nitrogen, perhaps are in the UV/ ozone chamber.Selection provides cleaning and/or the surface preparation site part as the coating site, and is perhaps arranged side by side with the coating site.Another Consideration is that new polymkeric substance (being commonly used to form the polymkeric substance of ampoule in blowing-filling-Sealing Method) that be shaped or molding may just can produce enough tackinesss to the coating that is about to obtain without any need for surface preparation.
In an application of the invention, can prepare ampoule by the following method: at first form ampoule, then ampoule is applied coating.A kind of method of known formation ampoule is blowing-filling-sealing (BFS), and applying step can be increased in the ampoule production line easily, before being right after after the BFS step, encapsulating and/or labelling.Ampoule comprises the solution of about 1-5 milliliter (derivable volume) usually.
Described coated designs is used for finishing as mentioned above the sealing of container.The suitable degree of depth is at least 20 nanometers, preferably is at least 50 nanometers, and proper depth is up to 50 microns in addition, preferably the highest 20 microns.Described profile depth also can be from least 100 nanometers to the highest 10 microns.
In a specific embodiment of the present invention, ampoule is made by plastic material, comprises the aluminum coating that applies by the sputter coating.More particularly, ampoule comprises the inhalation drug solution that is present in the pharmaceutically acceptable carrier.Therefore, in the example that the present invention uses, use blowing-filling-packing technique to obtain comprising 2.5 milliliters of ampoules that contain the preparation of salbutamol salt brine solution.This ampoule is made by LDP, is the form of ten one plates when leaving pad device.Described plate uses the sputter coating machine to apply the external aluminium coating that the degree of depth is about 300 nanometers, obtains glittering metal appearance.These ampoules are with the method encapsulation of routine, but coating outside carrying out.Give patient with these ampoules with becoming plate, tear next ampoule at every turn.Remaining ampoule remains on (at this moment the size of plate has reduced) in the plate, until taking off and use next ampoule, continues successively, all is used until all ampoules.
In the other embodiment of the present invention, ampoule is made by plastic material, comprises the coating of the aluminium, chromium or the titanium that apply with sputter coating or filterable cathode arc, comprises the injectable drug solution that is present in the pharmaceutically acceptable carrier.Described solution can be for example water for injection or injection salt solution.Common volume is equal to or less than 30 milliliters, is equal to or less than 25 milliliters, is equal to or less than 20 milliliters, is equal to or less than 15 milliliters, perhaps is equal to or less than 10 milliliters.For other embodiment of the present invention, ampoule can be made into the form of five one plates, ten plates, 15 plates or more a plurality of plates, tears in needs and uses.
In another embodiment of the present invention, applied the titanium layer that the degree of depth is about 150 nanometers for plastic ampoule by sputter coating.
In another embodiment of the present invention, on plastic ampoule, applied the tetrahedral amorphous carbon of dark about 100 nanometers.
Although described embodiments of the present invention with regard to the coating that is applied on the ampoule, the present invention more preferably relates to the container that is used for receiving fluids in some embodiments, and it is made by plastic material, comprises the coating of metal or metallic compound.These containers can be by comprising polyethylene or polyacrylic polymkeric substance is made, and also can have the highest 100 milliliters, preferred the highest 50 milliliters, more preferably the highest 20 milliliters maximum packing volume.Described container can be used to comprise the liquid of volatile matter effectively, if do not use this container, just these volatile matter may penetrate plastic containers with unacceptable degree.
The present invention also provides and to have reduced the method that the moisture in the container that plastic material makes leaks, this method comprises that the outside surface to described container applies the coating that comprises metal or metallic compound, the method that the present invention also provides container that plastic material is made to seal, this method comprises that the outside surface to described container applies the coating that comprises metal or metallic compound.In these methods, described coating and applying method thereof are preferably as further describing in conjunction with above embodiment of the present invention.
Another concrete grammar of the present invention is the method for sealed ampoule, described ampoule comprises inhalation medicine or the injectable drug in the pharmaceutically acceptable carrier of being present in of 0.5-10 milliliter (for example water for injection or salt solution), and this method is included in the coating that applies metal or metallic compound at least on the outside surface of ampoule 70%.
Coating of the present invention has character extra or as an alternative, promptly can apply label on coating.Therefore, another kind of method of the present invention is the method that ampoule is applied label, and this method comprises the coating that ampoule is applied metal or metallic compound, and coating is applied label.
Can use tackiness agent that label is bonded on the ampoule that applied.Also can or be printed on the ampoule that applied, for example printing ink is sprayed on the ampoule that applied the label spraying.
Various embodiment of the present invention provides a large amount of advantages, can see in the embodiment of any specific, a part or whole these advantages.Sealed ampoule by the present invention; Reduce for example loss of moisture, reduced the pollution that comes from the outside.Because the shape of ampoule, this method has sealed each ampoule effectively separately, but ampoule still can be made with the form of five one plates, 10 plates, 30 plates etc.With respect to a plate ampoule is encapsulated in the air-tight pouch, this is a kind of improvement, at this moment, when getting next ampoule in the slave plate, remaining ampoule is sealing substantially still, in contrast be, when the air-tight pouch that comprises many ampoules was opened, all ampoules all were exposed to environment.
After applying coating, than being easier to label is put on ampoule, perhaps use conventional ink printing label, and the restriction that can not be subjected to selecting printing ink or have the solvent that applies before.
The ampoule that has applied metallic coating according to the present invention also has attractive outward appearance.Have been found that coating is a successive, incrust and for example friction had a wear resistance.
In another embodiment, the coating that applies comprises polymkeric substance, uses vapour deposition process to apply or deposit.The method that is used for vapor deposition polymerization thing film is seen and is set forth in for example United States Patent (USP) the 6th, 022,595; 4,013,532; 4,673,588; With 4,921, No. 723, the reference in content of these documents is incorporated into herein.For example, the 1-2 month in 2006, described applying poly-concrete grammar in the 10-11 page or leaf to inferior dimethylbenzene coating at MedicalDevice Technology.
Therefore, the ampoule of an embodiment of the invention comprises by the sedimentary polymeric coating of vapour deposition process.Described coating can be to gather inferior dimethylbenzene or comprise to gather inferior dimethylbenzene, and polymeric coating of the present invention is suitable to be applied by chemical Vapor deposition process.
In these embodiments, the barrier properties of sedimentary polymeric film can be improved the sealing of container.
Described ampoule can prepare in the following manner: form ampoule, ampoule is applied coating.For other embodiment of the present invention, ampoule can comprise the inhalation medicine that is present in the pharmaceutically acceptable carrier or the solution of injectable drug specifically.
The present invention also provides and reduced the method that moisture leaks out from the container that plastic material is made, and this method comprises that employing vapour deposition process (for example chemical Vapor deposition process) applies the coating that comprises polymkeric substance to the outside surface of container.
The present invention also provides a kind of method of sealed ampoule, described ampoule comprises inhalation medicine or the injectable drug in the pharmaceutically acceptable carrier of being present in of 0.5-10 milliliter, this method comprises uses vapour deposition process applying polymer coating at least 70% ampoule outside surface, the method that ampoule is applied label also is provided, this method comprises uses vapour deposition process to the ampoule applying polymer coating, then coating is applied label.
Other optional and preferable feature of the present invention relevant with the metallic compound coating with metal can be carried out necessary change to the coating that comprises polymkeric substance.
About applying the aspect of the present invention of other plastic containers, described method be generally used for to content can incur loss or by gas and other volatile substance pollution and under the situation about being damaged (for example VITAMIN, spices, perfume etc.) encapsulate.The invention provides the encapsulation of being made by plastic material (for example LDP), its cost is lower than glass, three layer laminates, pottery etc.
The present invention is described in following examples with reference to the accompanying drawings, among the figure:
Fig. 1 has shown the frontview according to the plate that comprises ten ampoules with aluminium coating of the present invention;
Fig. 2 and Fig. 3 have shown the situation of getting next ampoule in the plate of Fig. 1;
Fig. 4 has shown the frontview that has applied the plate that comprises ten ampoules of titanium according to of the present invention.
Embodiment
Embodiment 1
Blowing-filling-the sealing equipment of use standard, prepared the plate that comprises 10 ampoules by new LDPE (film grade), each ampoule comprises 3 milliliters of salbutamol solution.Observe ampoule, correctly fill to determine content, these ampoules of manual confirmation are all untouched not moving.The plate of ampoule is placed the filterable cathode arc coating machine that the aluminium target is housed.Airtight this machine, pump is drawn into capable vacuum operating.The beginning coat operations and continues to carry out, till the coat-thickness monitor records thickness and is 300 nanometers.Stop coating, discharge vacuum, open the chamber.
Ampoule after the coating (1) is shown in Fig. 1-3.Fig. 1 shows ten untouched not moving ampoules that leave coating chamber, twists its head (3) in use, twists off neck (2), discharges content.
The ampoule of the coating of gained has the outward appearance of glittering metal quality, fully with the coating of aluminium thin layer.
Described aluminum coating is a successive on the whole surface of ampoule, and is smooth and do not have obvious defects.Coating is firmly stuck to ampoule, can not peel off, and have wear resistance.
See Fig. 2, single ampoule (4) is taken off from the plate that comprises 10 ampoules, and do not tear the ampoule that takes off and the coating of the junction (5) between remaining nine ampoule plates.
Tested the globality of ampoule, proved that they remain intact, comprise with coating before the solution of equal volume.Whether use has been tested the content of four ampoules independently based on the method for atomic absorption, to measure by aluminum pollution.In each is independently tested, note aluminium content less than 1ppm, surpass the lower limit of detection method, prove that in all cases the aluminium content after the coating in the interior solution of ampoule is zero substantially.These result's proofs are in coating process, and ampoule wall does not produce breach.
Embodiment 2
Use standard blow-filling-sealing equipment, prepared the plate that comprises five ampoules by new LDPE (film grade), each ampoule comprises 3 mL of saline solution.Observe ampoule, to determine correctly to have filled content, these ampoules of manual confirmation remain intact.
The plate of described ampoule is inserted in the filterable cathodic vacuum arc equipment that the titanium target is housed.Airtight this machine, pump are taken out to carry out vacuum operating.The beginning coat operations and continues to carry out, till the coat-thickness monitor records thickness and is 300 nanometers.Stop coating, discharge vacuum, open the chamber.
The ampoule (6) that has shown the coating that makes among Fig. 4 finds that it has glittering outward appearance, is coated with titanium lamina basically fully, and this coating is omited the aluminum coating dimness than embodiment 1.
Therefore the invention provides the plastic containers of coating and make method.

Claims (14)

1. method that the molding ampoule of the solution of the inhalation medicine that comprises the 1-5 milliliter or injectable drug is sealed, described ampoule comprises main body, neck and head elements, described ampoule is made by polyethylene or polypropylene, twist its head in use, twist off neck, discharge solution, this method comprises: form ampoule by blowing-can-sealing, directly the outside surface of ampoule is applied the coating that comprises metal or metallic compound by physical vapor deposition or arc deposited, the degree of depth of described coating is up to 20 microns, makes described coating cover the outside surface of ampoule at least 70%.
2. the method for claim 1 is characterized in that, the degree of depth of described coating is at least 20 nanometers.
3. method as claimed in claim 1 or 2 is characterized in that described metal is selected from aluminium, titanium and chromium.
4. method as claimed in claim 3 is characterized in that described metal is an aluminium.
5. method as claimed in claim 3 is characterized in that described metal is a chromium.
6. method as claimed in claim 3 is characterized in that described metal is a titanium.
7. molding ampoule, described ampoule comprises main body, neck and head elements, described ampoule is made up of polyethylene or polyacrylic polymer and the coating that directly is attached to described polymkeric substance, described coating is metal or the metallic compound that applies by physical vapor deposition or arc deposited, the degree of depth of described coating is up to 20 microns, described coating covers the outside surface of described ampoule at least 70%, described ampoule comprises the inhalation medicine of 1-5 milliliter or the solution of injectable drug, twist its head in use, twist off neck, discharge solution.
8. ampoule as claimed in claim 7 is characterized in that described coating is a metallic film.
9. ampoule as claimed in claim 8 is characterized in that, described coating is selected from the mixture and the alloy of aluminium, titanium, chromium, silver, copper and above-mentioned substance.
10. ampoule as claimed in claim 7 is characterized in that, described ampoule prepares by the following method: form ampoule by blowing-can-sealing, then to described ampoule applying coating.
11. ampoule as claimed in claim 8 is characterized in that, the degree of depth of described coating is at least 20 nanometers.
12. ampoule as claimed in claim 11 is characterized in that, described ampoule comprises aluminum coating.
13. ampoule as claimed in claim 11 is characterized in that, described ampoule comprises the titanium coating.
14. ampoule as claimed in claim 11 is characterized in that, described ampoule comprises chromiumcoating.
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GB0502666A GB0502666D0 (en) 2005-02-09 2005-02-09 Sealing of plastic containers
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GB0509210A GB0509210D0 (en) 2005-02-09 2005-05-05 Sealing of plastic containers
PCT/GB2006/000433 WO2006085063A1 (en) 2005-02-09 2006-02-09 Sealing of plastic containers

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EP2585295B1 (en) * 2010-06-22 2016-03-23 Novo Nordisk A/S Medical container protected against cracking
JP5654385B2 (en) * 2011-02-28 2015-01-14 大和製罐株式会社 Ampoule made of synthetic resin and manufacturing method thereof
ES2586280T3 (en) * 2013-07-16 2016-10-13 Fresenius Kabi Deutschland Gmbh Ampule for a medicinal liquid and procedure for the manufacture of a vial

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EP0808873A2 (en) * 1996-05-20 1997-11-26 Daikyo Seiko, Ltd. Sanitary container and production process thereof
US6162205A (en) * 1997-11-04 2000-12-19 Mateial Engineering Technology Laboratory, Incorporated Container for therapeutic use

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JP2004267663A (en) * 2003-03-12 2004-09-30 Toppan Printing Co Ltd Ampoule

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0808873A2 (en) * 1996-05-20 1997-11-26 Daikyo Seiko, Ltd. Sanitary container and production process thereof
US6162205A (en) * 1997-11-04 2000-12-19 Mateial Engineering Technology Laboratory, Incorporated Container for therapeutic use

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