(19)

&    
(11) EP 1 762 252 A1
(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.:

14.03.2007 Bulletin 2007/11 A61L 2/18 (2006.01) A61L 12/12 (2006.01)
B65B 55/10 (2006.01)
(21) Application number: 05108331.9

(22) Date of filing: 12.09.2005

(84) Designated Contracting States: (72) Inventors:

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • Dötsch, Werner
HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI 53545 Linz am Rhein (DE)
SK TR • Woost, Otmar
Designated Extension States: 06406 Bernburg (DE)
AL BA HR MK YU
(74) Representative: Vande Gucht, Anne et al
(71) Applicant: SOLVAY (Société Anonyme) Solvay S.A.
1050 Bruxelles (BE) Département de la Propriété Industrielle,
Rue de Ransbeek, 310
1120 Bruxelles (BE)

(54) Aqueous solution suitable for the chemical sterilization of packaging materials, process for
its preparation and its use

(57) Aqueous solution suitable for the chemical ster- at 105 °C of at most 10 mg/kg. The same solution can
ilization of packaging materials, comprising hydrogen be used as dip bath liquid in dip bath aseptic packaging
peroxide and at least one foodstuff-compatible stabilizer. processes and as well as spraying liquid in spray aseptic
This solution has a maximum phosphorous content ex- packaging processes.
pressed as PO43- of 10 mg/kg, and presents a dry residue
EP 1 762 252 A1

Printed by Jouve, 75001 PARIS (FR)

 EP 1 762 252 A1

Description

[0001] The present invention is related to aqueous solutions suitable for the chemical sterilization of packaging ma-
terials, especially those containing hydrogen peroxide. It is also related to a process for the preparation of these aqueous
5 solutions and to their use for the chemical sterilization of packaging materials.
[0002] It is known to use hydrogen peroxide solutions for the chemical sterilization of packaging materials. Two such
aseptic packaging processes exist. The first is a dip bath packaging process, in which the packaging materials are dipped
in the hydrogen peroxide solution, such as described for instance in the European patent application EP 0342485. The
sterilization in such processes is usually operated at a high temperature of typically 80 °C. In order to prevent that the
10 hydrogen peroxide decomposes at this high temperature, a high amount of stabilizer must be present in the sterilizing
solution.
[0003] The second aseptic packaging process is a spray packaging process, in which the packaging materials are
purged with a hydrogen peroxide solution, such as described for instance in the German patent application DE 19945500.
The hydrogen peroxide solutions used in these processes must have a very low dry residue in order to prevent incrus-
15 tations in the evaporator or spraying section and to avoid thereby frequent cleaning. The dry residues can, amongst
others, originate from the stabilizers present in the H2O2 solution. Thus, the spray technology requires a low amount of
stabilizer.
[0004] Up to now it has therefore been unavoidable to use two different hydrogen peroxide solutions for the two
processes. This forces the users of packaging machines, who have most often both processes on site, to dispose of
20 two different storage facilities with the possibility of mistake when taking one of the two products.
[0005] In an attempt to develop one single hydrogen peroxide solution which could be used in both spray and dip bath
processes, the United States patent application US 2004/0247755 of SOLVAY INTEROX GmbH proposes a new food-
stuff-compatible stabilizer, i.e. aminotrismethylene phosphonic acid. This stabilizer can effectively be used in low amounts,
especially in the dip bath processes. However, the dry residue of these H2O2 solutions is still too high in order to be also
25 suitable in the spray technology.
[0006] The purpose of the present invention consists in developing a new hydrogen peroxide solution which can be
used for the chemical sterilization of packaging materials in both dip bath and spray processes and which has the
following features :

30 • it is safe
• it fits with pharmacopoeia standards
• it does not contain harmful contaminants such as anthraquinones coming for the auto-oxidation process for the
manufacture of hydrogen peroxide
• it avoids incrustations or deposits in heater blocks of the spray process equipment or on the rubber rollers of the
35 bath process equipment
• it is stable for transport and storage
• it meets legal requirements for food grade quality or any other regulation that applies
• it is stable for at least 120 h during operation
• it contains a stabilizer which is soluble in water or in dilute acids for easy cleaning and maintaining of the packaging
40 machines.

[0007] To this end, the present invention concerns an aqueous solution suitable for the chemical sterilization of pack-
aging materials, comprising hydrogen peroxide and at least one foodstuff-compatible stabilizer, characterized in that it
has a maximum phosphorous content expressed as PO43- of 10 mg/kg, and in that it presents a dry residue at 105 °C
45 of at most 10 mg/kg.
[0008] One of the characteristic features of the present invention resides in the use of a foodstuff-compatible stabilizer
in a sufficiently low amount, combined with a low amount of impurities in order to yield a low dry residue. This combination
has made it possible to provide one single hydrogen peroxide solution which can be used in both aseptic packaging
processes which are the dip bath and the spray processes.
50 [0009] The aqueous solution of the present invention has a maximum phosphorous content expressed as PO43- of
10 mg/kg. This content is often lower than or equal to 8 mg/kg. In most cases it is lower than or equal to 5 mg/kg. It is
preferably lower than or equal to 2,5 mg/kg. Generally, it is higher than or equal to 0,1 mg/kg. The phosphorous content
is measured by the well known ICP-method.
[0010] The aqueous solution of the invention has a maximum chloride content of 1 mg/kg. This content is often lower
55 than or equal to 0,75 mg/kg. In most cases it is lower than or equal to 0,5 mg/kg. It is preferably lower than or equal to
0,1 mg/kg, and most preferably lower than or equal to 0,05 mg/kg. Generally, it is higher than or equal to 0,005 mg/kg.
[0011] The aqueous solution of the invention presents a dry residue at 105 °C of at most 10 mg/kg. This dry residue
is often higher than or equal to 5 mg/kg. The dry residue is measured by the gravimetric method according to the following

2
 EP 1 762 252 A1

procedure:

1. Place a platinum dish in a muffle furnace at 900 °C for 1 h.

2. Cool the dish in a dessicator and then weigh to the nearest 0.0001 g; let this weight be B, g.
5 3. Weigh to the nearest 0.0001 g a 100 ml beaker and record the weight; add to this beaker :

• 100 g of sample (if the H2O2 concentration is 50 % or lower)

• 50 g of sample (if the H2O2 concentration is higher than 50 %).

10 4. Reweigh the beaker to the nearest 0.0001 g. The weight difference of the beaker before and after the sample
addition will be W, g.
5. Dilute the sample to approximately 100 ml with demineralised water if using 50 g of sample.
6. Transfer progressively and carefully the sample into a platinum evaporating dish, surrounded by cold water. If
the dish is extremely clean (it will be shiny), it would be iced down. Caution must be taken: the decomposition of
15 hydrogen peroxide is accompanied by the production of substantial amount of heat and gas formation; sample must
be added carefully, in small portions, with adequate cooling.
7. Evaporate the solution carefully until dry, on the steam bath. Caution must be taken: failure to completely decom-
pose the hydrogen peroxide prior to evaporation could concentrate the sample sufficiently to produce an explosion
hazard.
20 8. Place the dish in an oven at 105 °C for at least 1 hour.
9. Cool in a dessicator for 30 minutes and weigh the dish to the nearest 0.0001 g. Let this weight be A, g.
10. Calculate the residue at 105 °C using the equation :

25

[0012] Where :
30
• A (in g) is the weight of the dish containing the evaporation residue
• B (in g) is the weight of the empty dish
• W (in g) is the weight of the sample added to the dish.

35 [0013] The aqueous solution of the invention generally presents a conductivity of from 20 to 150 PS/cm, particularly
from 50 to 90 PS/cm. The conductivity is measured according to the method of the standard DIN IEC 60746-1. The
conductivity of the aqueous solution can de adjusted by the addition therein of a salt, such as for instance ammonium
nitrate.
[0014] The aqueous solution of the invention usually presents a hydrogen peroxide concentration of from 10 to 50 %
40 wt, in particular from 20 to 45 % wt, most preferably from 30 to 40 % wt, typically of about 35 % wt. The hydrogen peroxide
concentration is measured according to the ISO standard 7157 (draft version).
[0015] The aqueous solution of the invention usually presents a maximum acidity of 5 mmol/kg.
[0016] The aqueous solution of the invention contains a foodstuff-compatible stabilizer. This stabilizer can be chosen
from foodstuff-compatible phosphonic acids. An example is the aminotrismethylene phosphonic acid described in the
45 patent application US 2004/0247755 the content of which is incorporated herein by reference. The amount of stabilizer
is generally at least 0,5 mg (100 % stabilizer) per kg of H2O2 solution, in particular at least 1 mg per kg H2O2 solution.
The amount is usually lower than or equal to 50 mg (100 % stabilizer) per kg of H2O2 solution, especially lower than or
equal to 10 mg per kg of H2O2 solution, and preferably lower than or equal to 8 mg per kg of H2O2 solution. The amount
is for instance about 5 mg (100 % stabilizer) per kg of H2O2 solution. The stabilizer can be used in the form of an aqueous
50 solution, for instance containing 45 % wt of stabilizer.
[0017] Due to the presence of the stabilizer, the hydrogen peroxide concentration in the aqueous solution of the
invention presents a high stability. It is usually so that the relative percentage of titration loss after 16 h at 96 °C is lower
than or equal to 5 % of the initial hydrogen peroxide concentration. The stability is measured according to the method
of the ISO standard 7161 (draft version).
55 [0018] The aqueous solution of the present invention can be prepared by any adequate method which allows to prepare
an aqueous solution of hydrogen peroxide and to purify it to such an extent that the dry residue is such as described
above, and by adding thereto a foodstuff-compatible stabilizer in a low enough quantity so that the dry residue is as
described above.

3
 EP 1 762 252 A1

[0019] A possible process for the preparation of a hydrogen peroxide solution consists in the well known auto-oxidation
process using anthraquinones, hydrogen and oxygen such as described in the Kirk-Othmer Encyclopedia of Chemical
Technology, 1981, 3rd Edition, vol 13, pages 16-21.
[0020] A possible process for the purification of the so obtained hydrogen peroxide solution consists in treating the
5 hydrogen peroxide solution by reverse osmosis using a membrane. Examples can be found in the patent applications
EP 0930269 and W02005/033005 owned by SOLVAY (Société Anonyme).
[0021] The invention therefore also concerns a process for the preparation of the aqueous solution described above,
wherein the hydrogen peroxide solution, before adding thereto the stabilizer, is purified by reverse osmosis using a
membrane.
10 [0022] The aqueous solution of the invention can advantageously be used for the chemical sterilization of packaging
materials. The invention is therefore also related to the use of the aqueous solution described above for the chemical
sterilization of packaging materials.
[0023] One of the advantages of the aqueous solution of the invention resides in the fact that the same solution can
be used as dip bath liquid in dip bath aseptic packaging processes as well as spraying liquid in spray aseptic packaging
15 processes.
[0024] Another advantage resides in the high stability of the aqueous solution of the invention especially when it is
used in dip bath aseptic packaging processes. This stability is expressed as follows : the hydrogen peroxide concentration
does not differ from the initial value by more than 10 % during at least 120 h of operation.
[0025] Due to the low stabilizer content, the risk of incrustations and blockages in the heaters of a spray packaging
20 machine is minimized.
[0026] The invention is further described by way of illustration in the following

examples.

25 Examples

[0027] A non-purified hydrogen peroxide solution was prepared according to the auto-oxidation process and followed
by a distillation. The fmal product presented the following features :

30 H2O2 concentration : 35 % w/w

Trace metals :
Al < 0,1 ppm
Cr 0,03 ppm
Fe 0,12ppm
35
Ni 0,02 ppm
Cl 0,1 ppm
SO42- 0,1 ppm
P as PO43- 17,3 ppm
40 Total Organic Carbon (TOC) : 50 ppm
Dry residue : 25 ppm

[0028] This solution was then purified by reverse osmosis using a membrane of the type SWC 3, supplied by the
company HYDRONAUTIX, at a pressure of about 28 bar. The final purified product presented the following features :
45

H2O2 concentration : 35 % w/w

Trace metals :
A1 < 0,005 ppm
50 Cr < 0,002 ppm
Fe < 0,005 ppm
Ni < 0,002 ppm
Cl < 0,005 ppm
SO4 2- < 0,05 ppm
55
P as PO43- < 1 ppm
TOC: < 5 ppm
Dry residue : < 2 ppm

4
 EP 1 762 252 A1

[0029] Then, aminotrismethylene phosphonic acid was added as stabilizer in an amount of 10 mg in the form of a 45
% wt aqueous solution per kg of H2O2 solution, trade name CUBLEN AP1 (manufacturer ZSCHIMMER & SCHWARZ,
MOHRSDORF GmbH & Co KG).
[0030] This stabilized aqueous H2O2 solution were successively used in dip bath aseptic packaging machines of the
5 type TBA 8, TBA 9, TBA 19 and TBA 21, as well as in spray aseptic packaging machines of the company COMBIBLOC.
Both types of machines have been operated for at least 120 h without loosing performance.

Claims
10
1. - Aqueous solution suitable for the chemical sterilization of packaging materials, comprising hydrogen peroxide and
at least one foodstuff-compatible stabilizer, characterized in that it has a maximum phosphorous content expressed
as PO43- of 10 mg/kg, and in that it presents a dry residue at 105 °C of at most 10 mg/kg.

15 2. - Aqueous solution according to claim 1, characterized in that it presents a conductivity of from 50 to 90 PS/cm.

3. - Aqueous solution according to claim 1 or 2, characterized in that it presents a hydrogen peroxide concentration
of from 35 to 40 % wt.

20 4. - Aqueous solution according to any one of claims 1 to 3, characterized in that the hydrogen peroxide concentration
presents a high stability expressed as a relative percentage of titration loss after 16 h at 96 °C of maximum 5 %.

5. - Aqueous solution according to any one of claims 1 to 4, characterized in that it presents a maximum acidity of
5 mmol/kg.
25
6. - Aqueous solution according to any one of claims 1 to 5, characterized in that the foodstuff-compatible stabilizer
is a phosphonic acid, preferably aminotrismethylene phosphonic acid.

7. - Process for the preparation of the aqueous solution of any one of claims 1 to 6, wherein the hydrogen peroxide
30 solution, before adding thereto the stabilizer, is purified by reverse osmosis using a membrane.

8. - Use of the aqueous solution of any one of claims 1 to 6 for the chemical sterilization of packaging materials.

9. - Use according to claim 8, wherein the same aqueous solution is used as dip bath liquid in dip bath aseptic packaging
35 processes as well as spraying liquid in spray aseptic packaging processes.

10. - Use according to claim 8 or 9, wherein the aqueous solution is used in a dip bath aseptic packaging process and
wherein the hydrogen peroxide concentration does not differ from the initial value by more than 10 % during at least
120 h of operation.
40

45

50

55

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EP 1 762 252 A1

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 EP 1 762 252 A1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 0342485 A [0002] • EP 0930269 A [0020]

• DE 19945500 [0003] • WO 2005033005 A [0020]
• US 20040247755 A [0005] [0016]

Non-patent literature cited in the description

• Kirk-Othmer Encyclopedia of Chemical Technology.

1981, vol. 13, 16-21 [0019]