CA2266079C - A method of sterilizing a package material - Google Patents

A method of sterilizing a package material Download PDF

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Publication number
CA2266079C
CA2266079C CA002266079A CA2266079A CA2266079C CA 2266079 C CA2266079 C CA 2266079C CA 002266079 A CA002266079 A CA 002266079A CA 2266079 A CA2266079 A CA 2266079A CA 2266079 C CA2266079 C CA 2266079C
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CA
Canada
Prior art keywords
hydrogen peroxide
container
sterilizing
plastic surface
package material
Prior art date
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Expired - Fee Related
Application number
CA002266079A
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French (fr)
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CA2266079A1 (en
Inventor
Thomas Bjerborn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tetra Laval Holdings and Finance SA
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Tetra Laval Holdings and Finance SA
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Application filed by Tetra Laval Holdings and Finance SA filed Critical Tetra Laval Holdings and Finance SA
Publication of CA2266079A1 publication Critical patent/CA2266079A1/en
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Publication of CA2266079C publication Critical patent/CA2266079C/en
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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20Gaseous substances, e.g. vapours
    • A61L2/208Hydrogen peroxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B55/00Preserving, protecting or purifying packages or package contents in association with packaging
    • B65B55/02Sterilising, e.g. of complete packages
    • B65B55/04Sterilising wrappers or receptacles prior to, or during, packaging
    • B65B55/10Sterilising wrappers or receptacles prior to, or during, packaging by liquids or gases
    • B65B55/103Sterilising flat or tubular webs
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/20Targets to be treated
    • A61L2202/23Containers, e.g. vials, bottles, syringes, mail

Abstract

Containers which are ready to be filled or a package material having a plastic surface can be sterilized by hydrogen peroxide in gaseous phase being supplied to the previously heated plastic surface, the entire sterilization procedure being performed with the hydrogen peroxide in gaseous phase.

Description

A METHOD OF STERILIZING A PACKAGE
MATERIAL
The present invention refers to a method of steril-S izing a package material. More precisely the invention refers to a method of sterilizing a package material having a plastic surface by means of hydrogen peroxide in gaseous phase being supplied to the previously heated plastic surface.
lo Sterile containers which are ready to be filled can be obtained in various ways. One method of sterilization implies that the plastic containers are sealed directly in connection with the manufacturing procedure, e.g. when blow moulded. Due to the collapse of the container at a sub-sequent lowering of the temperature the sealing in this case results in considerable problems. The container must therefore be stored at an elevated temperature since the volume of air enclosed in the container will decrease if the temperature is decreased. Such a storage is both cumbersome and costly. In order to avoid this, among other materials hydrogen peroxide is nowadays utilized in a liquid or gaseous phase, the inside of the containers then being sterilized.
Hydrogen peroxide is a very potent but not especially stable oxidant, and an advantage is that only plain water is formed as by-product. However, the half-life of hydrogen peroxide is very long, and the sterilizing agent has thus to be removed after it has been allowed to exert its effect.
Hydrogen peroxide is supposed to exert its anti-microbial activity through its powerful oxidizing effect by acting on components in the cytoplasmic membrane of the microorganisms. In the sterilizing procedure hydrogen peroxide is used as a water solution which is sprayed into a container. When the container is subsequently heated the CA 02266079 l999-03-l7 hydrogen peroxide is gasified and can be ventilated away after having exerted its effect.
According to an alternative sterilizing procedure a container is in a first step subjected to hydrogen peroxide in gaseous phase, which is allowed to condensate on the inside of the container. By this procedure a homogeneous coating of hydrogen peroxide is obtained, which completely covers the package material. In a subsequent step the condensated gas is again gasified and is finally ventilated away. By this procedure an acceptable death rate of micro-organisms for commercial sterilization can be achieved.
When for example plastic containers are sterilized these are in practice coated with a commercial standard solution, called "Oxonia Aktiv", which among other things contains hydrogen peroxide and peracetic acid. The solution is allowed to act for some minutes, and the containers are then rinsed with clean sterile water. Such a procedure is both complicated and time consuming.
A further problem is that with certain plastics in the package material, above all polyester, residues of hydrogen peroxide are obtained which are adsorbed on the inside of the container as a result of spraying, coating or condensation. They can afterwards have a negative influence on the filling material, for example by changing the colour. The authorities have established limit values which must not be exceeded for residues of hydrogen peroxide.
It is rather unusual to treat such a package material as a polyester aseptically since this type of material mostly is used for soft drinks and the like. However, there exists a great interest from the market for an aseptic bottle of polyethylene terephtalate (PET).
In order to minimize the risk of residual product formation the hydrogen peroxide can be ventilated away, e.g. at the elevated temperature or by sterile air being blown into the container. Such a procedure is costly and it .

would thus be desirable if shorter ventilation times could be used, which would result in a lower cost per container.
The purpose of the invention is to eliminate or reduce the drawbacks mentioned above which arise during a sterilization by means of hydrogen peroxide according to the state of the art.
In order to achieve this purpose the method according to the invention has obtained the characterizing features of claim 1.
A sterilizing process with a condensation of hydrogen peroxide comprises four phases of different time intervals:
a heating phase, a gassing phase, a holding phase, and a ventilation phase.
During the heating phase the container is heated to a 1S suitable temperature. The heating phase is not necessary.
However, it reduces the amount of condensate which later on has to be ventilated away.
During the gassing phase gaseous hydrogen peroxide is injected into the previously heated container and over the surface which is to be exposed to the treatment, onto which the gas condensates, and a condensate in the form of droplets is formed. The gas used is a mixture of air and a gasified solution of hydrogen peroxide. The solution of hydrogen peroxide is supplied as a commercial grade which consists of about 65 ~ water and about 35 ~6 hydrogen peroxide. However, other concentrations can of course be used in dependence of other parameters.
During the holding phase the condensate is allowed to exhibit its effect, and during the ventilation phase the container is ventilated, the condensate again being trans-formed into gaseous phase and removed from the container.
In this connection hot air is used which has been prefil-tered and sterilized by means of filtration.
Experiments were performed with the purpose of achieving an equally effective sterilization as that which allows the hydrogen peroxide used to exert its effect in the form of a condensated gas. In these experiments the hydrogen peroxide was according to the invention allowed to remain in the gaseous phase during the entire sterilization 5 procedure.
In comparison with the sterilization by means of condensation described above the method according to the invention implies briefly that the containers are steril-ized with gasified hydrogen peroxide, the containers first being heated to a temperature which is higher than the dew point of the gas used. The containers are then blown to dryness with hot sterile air.
During the sterilization procedure the containers are thus for a certain period of time exposed to gaseous hydrogen peroxide of a specific temperature, dew point and flow rate. Apart from the hydrogen peroxide concentration these parameters are important in order to achieve an effective killing. In this connection the dew point is the temperature the gaseous hydrogen peroxide must be cooled to in order to obtain a condensation, a water solution of hydrogen peroxide being separated. This temperature is dependent on the hydrogen peroxide content in the gas. The dew point is adjusted to be used in an existing sterilizing equipment.
Preliminary experiments have shown that the amount of residual hydrogen peroxide per unit area varied after contact with different types of package material. Certain problems were obtained with polyester as a package mater-ial, and thus the experiments were concentrated on such a material by using bott,les of polyethylene terephftalate.
However, other types of containers which are ready to be filled were also studied.

CA 02266079 l999-03-l7 Example 1. Comparison between sterilizing effects.
A comparison was performed between the sterilizing effect achieved by means of gassing/condensation and that with gassing alone according to the invention. The effici-S ency with regard to killing microorganisms in the form ofa logarithmic reduction was defined as the number of organ-isms in a reference sample minus the number of surviving organisms.
PET bottles were inoculated with spores of Bacillus 10 subtilis NCA 7252, and after the respective sterilization treatment the results were statistically evaluated with a conventional procedure (based on the method with "Most Probable Number") which is well known to the man skilled in the art.
IS The containers to be subjected to gassing/condensa-tion or gassing alone according to the invention, respect-ively, received the same treatment during the gassing phase and the holding phase, which treatment by way of earlier experiments had been found to be optimal.
Thus, in the sterilization procedure a gassing phase of 3 sec was used with gaseous hydrogen peroxide, the gas having a temperature of 90 ~C, a dew point of 65 ~C, and a flow rate of 40 kg/h. The length of the holding phase was 1 sec.
Those containers which should be subjected to gassing/condensation were during the heating phase heated to 50-55 ~C, and the containers were ventilated for 10 sec with sterile air of 70 ~C having a flow rate of 40 kg/h.
During the gassing/condensation the ventilation time was adjusted in such a way that all ~isible condensate had evaporated. Those containers which had been subjected to gassing alone according to the invention were during the heating phase sub~ected to a temperature of 70-80 ~C, and during the ventilation phase the containers were fluxed for 2 sec with sterile air of 80 ~C at a flow rate of 60 kg/h.

The results indicated that a sufficient killing effect was achieved in the form of a logarithmic reduction of at least log 5 (105) with both sterilizing methods.

S Example 2. Comparison between evolved residual amounts.
Experiments were performed in order to study if any residues were obtained in PET containers sterilized accord-ing to the invention. At the same time a comparison was performed with polyethylene (PE) bottles.
Bottles of PET and PE were subjected to the same sterilization treatment as in Example 1 apart from that the time after the filling of the bottles, the storage time, was varied and that the ventilation time after the two sterilization procedures was 2 sec. Residual hydrogen lS peroxide in each container was measured by means by a vial HP-10 (Chemetrics, 90298-31) according to the instructions of the manufacturer. The results obtained are shown i Table 1.
~0 Table 1. Residual hydrogen peroxide (ppm) after sterilization (2 sec ventilation time).
Material PE PET
2s Storage time (min) 5 10 30 90 Gassing 0.5 3 3 3 Condensation - 10 >10 The results show that no significant residual hydro-gen peroxide was obtained with polyethylene. It is also possible to reduce residual hydrogen peroxide to an accept-able level in a PET container which has been subjected to gassing according to the invention and then ventilated for such a short ventilation time as 2 sec. About 3 times more residuals are obtained in a PET bottle sterilized by means o~ condensation. This tendency is maintained even with such a short ventilation time as 15 sec (Table 2).

.. , . ~ .. , ,, . . . .. . , ... ., ~

Table 2. Residual hydrogen peroxide (ppm) after sterilization (15 sec ventilation time).
S Material PE PET
Storage time (min) 5 30 250 Gassing 0 0.3 0.1 Condensation 0 0.8 0.2 Thus, when gassing according to the invention low residual amounts were obtained of the sterilization medium hydrogen peroxide used together with an effective killing.
This reduction in the number of microorganisms can also be lS increased by increasing the dew point (the gas concentra-tion) or by prolonging the gassing phase. However, if the dew point is increased too much the residual amounts will increase with the gassing procedure according to the inven-tion.
The sterilization method according to the invention is preferably intended to be used for sterilizing con-tainers which are ready to be filled and/or for a package material having a plastic surface which can comprise a polyester, e.g. polyethylene terephtalate. However, the method is not limited to containers which are ready to be filled. On the contrary, it is an advantage if a container is sterilized as a "preform", i.e. before it - for example by means of blow moulding - has obtained its final form which has a difficult geometry from a sterilizing point of view. In this case smaller residual amounts per unit area will be obtained in the completed container. The package material in the form of a sheet or a web can thus in the same way as a container which is ready to be filled be subjected to the above mentioned four phases, heating phase, gassing phase, holding phase, and ventilation phase, the sterilization being effected by means of the method W O 98/16259 8 PCT/S~97/01575 according to the invention. In this connection the package material may well be treated continuously.

,

Claims (5)

1. Method of sterilizing a plastic surface by hydrogen peroxide in gaseous phase being supplied to the previously heated plastic surface, characterized in that the entire sterilization procedure is performed with the hydrogen peroxide in gaseous phase and that the plastic surface is heated to a temperature which is higher than the dew point for the hydrogen peroxide in gaseous phase.
2. Method as claimed in claim 1, characterized in that the plastic surface comprises a polyester.
3. Method as claimed in claim 1, characterized in that the plastic surface comprises polyethylene terephtalate.
4. Method as claimed in claim 1 of sterilizing a package material for a container, characterized in that the package material having a plastic surface is sterilized before the container has obtained its final form.
5. Method as claimed in claim 4, characterized in that the package material having a plastic surface is sterilized continuously.
CA002266079A 1996-10-14 1997-09-19 A method of sterilizing a package material Expired - Fee Related CA2266079C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE9603735A SE507994C2 (en) 1996-10-14 1996-10-14 Ways of sterilizing packaging material
SE9603735-3 1996-10-14
PCT/SE1997/001575 WO1998016259A1 (en) 1996-10-14 1997-09-19 A method of sterilizing a package material

Publications (2)

Publication Number Publication Date
CA2266079A1 CA2266079A1 (en) 1998-04-23
CA2266079C true CA2266079C (en) 2003-08-12

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CA002266079A Expired - Fee Related CA2266079C (en) 1996-10-14 1997-09-19 A method of sterilizing a package material

Country Status (15)

Country Link
US (1) US6682696B1 (en)
EP (1) EP1021210B1 (en)
JP (1) JP2001502277A (en)
CN (2) CN1145498C (en)
AT (1) ATE314098T1 (en)
AU (1) AU719367B2 (en)
BR (1) BR9712234A (en)
CA (1) CA2266079C (en)
DE (1) DE69735012T2 (en)
DK (1) DK1021210T3 (en)
ES (1) ES2255102T3 (en)
ID (1) ID21220A (en)
NZ (1) NZ334621A (en)
SE (1) SE507994C2 (en)
WO (1) WO1998016259A1 (en)

Families Citing this family (15)

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US6808681B2 (en) * 1996-10-14 2004-10-26 Tetra Laval Holdings & Finance Sa Method of sterilizing a package material
SE511861C2 (en) * 1998-04-07 1999-12-06 Tetra Laval Holdings & Finance Method and apparatus for producing a sterile packaging container
DE19949692A1 (en) * 1999-10-15 2001-04-19 Gea Finnah Gmbh Sterilization of temperature-sensitive especially polyethylene terephthalate bottles moving on a conveyor, using a peroxide aerosol and sterile air
DE10114758B4 (en) * 2001-03-20 2013-01-31 Ptm Packaging Tools Machinery Pte. Ltd. Method for sterilizing containers
ITTO20020367A1 (en) * 2002-05-03 2003-11-03 Tetra Laval Holdings E Finance METHOD AND PACKAGING MACHINE FOR THE REALIZATION OF SEALED PACKAGES OF VARSABLE FOOD PRODUCTS STARTING FROM PRE-TR BLASTED
SE524496C2 (en) * 2002-12-13 2004-08-17 Tetra Laval Holdings & Finance Control of sterilizing device
ES2295727T3 (en) * 2004-05-21 2008-04-16 DEUTSCHE SISI-WERKE GMBH & CO. BETRIEBS KG PROCEDURE AND DEVICE FOR FILLING FLEXIBLE SHEET BAGS.
CN101306726B (en) * 2007-05-18 2011-05-18 上海斯开龙包装有限公司 Sterile filling and packaging machine
JP6049616B2 (en) * 2011-07-08 2016-12-21 四国化工機株式会社 Disinfection method for packaging containers using dilute hydrogen peroxide-containing gas
WO2014183155A1 (en) * 2013-05-13 2014-11-20 Saban Ventures Pty Limited Residual sterilant test method
JP6858196B2 (en) * 2016-09-27 2021-04-14 オリヒロエンジニアリング株式会社 Aseptic filling and packaging machine and aseptic filling method for film packaging bags of contents
US11305029B2 (en) 2017-02-20 2022-04-19 Dai Nippon Printing Co., Ltd. Gasifier for sterilizer and cleaning method of gasifier for sterilizer
DK3600456T3 (en) 2017-03-27 2023-10-02 Regeneron Pharma PROCEDURE FOR STERILIZATION
US20230136844A1 (en) * 2020-04-03 2023-05-04 Tetra Laval Holdings & Finance S.A. A packaging machine comprising a disinfection/sterilization station, disinfection/sterilization station and method for disinfection/sterilizing in a packaging machine
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Also Published As

Publication number Publication date
CN1145498C (en) 2004-04-14
DK1021210T3 (en) 2006-05-15
CA2266079A1 (en) 1998-04-23
CN1519033A (en) 2004-08-11
BR9712234A (en) 1999-08-31
EP1021210A1 (en) 2000-07-26
ES2255102T3 (en) 2006-06-16
ID21220A (en) 1999-05-06
SE9603735L (en) 1998-04-15
SE9603735D0 (en) 1996-10-14
WO1998016259A1 (en) 1998-04-23
AU719367B2 (en) 2000-05-04
JP2001502277A (en) 2001-02-20
EP1021210B1 (en) 2005-12-28
CN1233190A (en) 1999-10-27
DE69735012D1 (en) 2006-02-02
NZ334621A (en) 2000-09-29
ATE314098T1 (en) 2006-01-15
SE507994C2 (en) 1998-08-10
DE69735012T2 (en) 2006-07-13
CN100415303C (en) 2008-09-03
US6682696B1 (en) 2004-01-27
AU4730097A (en) 1998-05-11

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