Abstract: To provide a method capable of simply producing a medical glass container with little elution of alkali components. A distilled water 20 in which microbubbles have been generated is sprayed onto an inner surface 52 of a vial 50 to thereby remove a degraded portion by forming process on the inner surface 52 of the vial 50. Thus, the inner surface 52 of the vial 50 is exposed to the distilled water 20 containing microbubbles to thereby remove alkali components adhering in a condensed manner to the degraded portion by forming process, thereby simply producing the vial 50 with little elution of the alkali component or the like.
MEDICAL GLASS CONTAINER AND
METHOD FOR PRODUCING MEDICAL GLASS CONTAINER
Technical Field
[0001] The present invention relates to a medical glass
container with little elution of alkali components or the like from
the inner wall surface of the glass and a method for producing the
same.
Background Art
[0002] As a glass container for use in storage of medicine and
the like, a vial or an ampule is known, for example. A vial or the
like is formed from, for example, a glass tube. The main ingredient
of glass almost contains alkali components. The alkali components,
such as alkali boric acid, are known to adhere to the inner wall
of the vial or the like or coagulate thereon. When such alkali
components are eluted into medicine contained in the vial or the
like in the case where the vial or the like is used as a storage
container of medicine, i.e., for medical use, there is a possibility
that the medicine deteriorate. To solve the problem, the inner
surface of the vial is subjected to sulfa treatment by ammonium
sulfate or a silica film is covered thereon (Patent Document 1).
[0003] A method is known in which, when a vial is hot formed
from a glass tube, by injecting pressurized air or pressurized inert
gas from an opening of the vial while hot forming the bottom of
the vial, an alkali boric acid component volatilized from the glass
during the hot forming of the bottom of the vial is discharged from
the inside of the vial (Patent Document 2).
[0004] It is also known that, in a process of forming a vial
from a borosilicate glass tube, a degraded portion by forming
process on the inner side of the vial is removed by gas flame after
the bottom is formed (Patent Document 3).
[Prior Art]
[0005]
[Patent Document 1] Japanese Examined Patent Application
Publication No. 6-76233
[Patent Document 2] Japanese Unexamined Patent Application
Publication No. 63-170233
[Patent Document 3] International Publication No. WO
2006/123621
Summary of Invention
Problems to be Solved by the Invention
[0006] The elution of alkali components from a vial or the like
is suppressed by subjecting the inner surface of the vial or the
like to sulfa treatment by ammonium sulfate or covering a silica
film thereon. However, in a process of producing the vial or the
like, other raw materials are required and moreover production
processes increase, which causes a problem in that the cost
inevitably increases.
[0007] In contrast, the technique of injecting pressurized air
or pressurized inert gas from the opening of the vial while hot
forming the bottom of the vial also has advantages in that other
raw materials are not required and an increase in the number of
production processes is relatively small. However, there is a
possibility that, simply by removing alkali components volatilized
during hot forming, the alkali components that do not volatilize
and adhere to the glass surface remain, and are eluted into medicine
after hot forming. Moreover, by the technique of applying flame
from the outside of the bottom of the vial for heating as described
in Patent Document 2, the surface temperature of the inner surface
of the vial does not become high, resulting in a possibility that
the alkali comiponents do not volatilize, and remain on the inner
surface.
[0008] The technique of removing the degraded portion by
forming process on the inner side of the vial with gas flame as
disclosed in Patent Document 3 has advantages in that other raw
materials are not required and an increase in the number of
production processes is relatively small. However, in the method
including removing the degraded portion by forming process after
forming the bottom, of the vial, and then forming an opening of the
vial in a process of forming the vial, an existing vial production
facility cannot be utilized, and thus another production facility
is needed. Moreover, the degraded portion by forming process
generated when the opening is formed is not removed. Moreover,
since vials are processed one by one, the processing time inevitably
increases.
[0009] The invention has been made in view of the circumstances.
It is an object of the invention to provide a method capable of
easily producing a medical glass container with little elution of
alkali components or the like.
[0010] It is another object of the invention to provide a method
capable of batch processing a plurality of glass containers.
Means for Solving the Problems
[0011] (1) In a medical glass container according to the
invention, a degraded portion by forming process on the inner
surface of a glass container or an intermediate article thereof
is removed by water in which microbubbles have been generated.
[0012] The medical glass container refers to a glass container
in which liquid medicine are stored and held and can be taken out
from the opening for use. Examples include glass containers
generally referred to as a vial or an ampule. Such medical glass
containers are formed from a glass tube by heat processing. In the
heat processing, alkali components or the like may adhere in a
condensed manner to the inner surface of the glass container. Also
in an intermediate article of the glass container, the alkali
components or the like may similarly adhere in a condensed manner.
The region where such alkali components or the like adhere in a
condensed manner is referred to "a degraded portion by forming
process" in this description. The degraded portion by forming
process may occupy a part or the whole of the inner surface of the
glass container or the intermediate article thereof.
[0013] When the inner surface of the glass container or the
intermediate article thereof is exposed to water in which
microbubbles have been generated, the alkali components adhering
in a condensed manner to the inner surface are removed. The
microbubbles refer to fine bubbles having a micrometer-order
diameter. However, it is not necessarily required to maintain the
micrometer-order diameter from the generation to collapse of the
bubbles. The microbubbles include those having a micrometer-order
diameter obtained by shrinkage of bubbles having a millimeter-order
diameter or those having a nanometer-order diameter obtained by
shrinkage of bubbles having a micrometer-order diameter. Examples
of component gas of the microbubbles include, but not limited
thereto, air, hydrogen, oxygen, nitrogen, carbon dioxide, ozone,
fluorine, chlorine, bromine, iodine, argon, and helium. Among the
above, air, oxygen, nitrogen, carbon dioxide, etc., that are assumed
to have little effect on medicine are preferable.
[0014] (2) A method for producing a medical glass container
according to the invention includes spraying water in which
microbubbles have been generated to the inner surface of a glass
container or an intermediate article thereof to remove a degraded
portion by forming process on the inner surface of the glass
container or the intermediate article thereof.
[0015] When the inner surface of the glass container or the
intermediate article thereof is exposed to water in which
microbubbles have been generated, the alkali components adhering
in a condensed manner to the inner surface are removed.
[0016] (3) The water may be purified water.
[0017] Thus, a washing process of the glass container or the
intermediate article thereof after the degraded portion by forming
process is removed can be omitted. The purified water refers to
water from which impurities have been removed by techniques, such
as distillation, filtration, or ion exchange. Examples include
distilled water, RO water, and ion exchange water.
[0018] (4) A method for producing a medical glass container
according to the invention includes immersing a glass container
or an intermediate article thereof in a water tank, and generating
microbubbles in the water tank to remove a degraded portion by
forming process on the inner surface of the glass container or the
intermediate article thereof,
[0019] (5) A plurality of glass containers or intermediate
articles thereof may be immersed in the water tank.
[0020] Thus, the removal of the degraded portion by forming
process in the plurality of glass containers or intermediate
articles thereof can be batch processed.
[0021] {6) The water tank may be filled with purified water.
[0022] Thus, a washing process of the plurality of glass
containers or the intermediate articles thereof after the degraded
portion by forming process is removed can be omitted.
[0023] (7) As the glass container, a glass container obtained
by heat processing a glass tube into a container shape having a
bottom and an opening is mentioned.
[0024] (8) As the intermediate article of the glass container,
an intermediate article obtained by heat processing a glass tube
into a container shape having a bottom. Then, the intermediate
article from which the degraded portion by forming process has been
removed is formed into a glass container when an opening is heat
processed.
[0025] (9) The invention may be construed as a medical glass
container produced by the method for producing a medical glass
container.
Advantages of the Invention
[0026] According to the invention, the inner surface of a glass
container or an intermediate article thereof is exposed to water
in which microbubbles have been generated to remove alkali
5
components adhering in a condensed manner to the inner surface
thereof, thereby simply producing a medical glass container with
little elution of alkali components.
[0027] Moreover, according to the invention, a plurality of
glass containers or intermediate articles thereof are immersed in
a water tank, and microbubbles have been generated in water of the
tank, thereby batch processing the removal of a degraded portion
by forming process in the plurality of glass containers or
intermediate articles thereof.
Brief Description of Drawing
[0028]
[Fig. 1] Fig. 1 is a schematic cross sectional view
illustrating a method for producing a medical glass container
according to a first embodiment of the invention.
[Fig. 2] Fig. 2 is a schematic cross sectional view
illustrating a method for producing a medical glass container
according to a second embodiment of the invention.
Modes for Carrying Out the Invention
[0029] He reinafter, preferable embodiments of the invention
will be described. It is a matter of fact that this embodiment is
simply one embodiment of the invention, and can be modified insofar
as the gist of the invention is not altered.
[0030]
[First Embodiment]
Hereinafter, a first Embodiment of the invention will be
described. According to a method for producing a medical glass
container according to the first embodiment, distilled water 20
in which microbubbles have been generated is sprayed onto an inner
surface 52 of a vial 50 to thereby remove a degraded portion by
forming process on the inner surface 52.
[0031] As illustrated in Fig. 1, the distilled water 20 is
sprayed from a nozzle 21. The nozzle 21 forms a flow path allowing
the distilled water 20 to flow. The nozzle 21 has an outer diameter
and a length allowing the nozzle 21 to enter the inside of the vial
50 from an opening 50 thereof. Although not illustrated in Fig,
1, to the nozzle 21, a device similar to a microbubble generating
device 17 is connected. From the device, the distilled water 20
containing microbubbles is flown into the nozzle 21,
[0032]
[Vial 50]
The vial 50 has an opening 51 and a bottom 53 formed by heat
processing of a glass tube. As the heat processing of a glass tube,
a technique employing a so-called horizontal automatic-forming
machine of fixing the glass tube so that the axial direction becomes
horizontal, and forming the opening 51 and the bottom 53 at one
end thereof or a technique employing a so-called vertical
automatic-forming machine of fixing the glass tube so that the axial
direction becomes vertical, and forming the opening 51 and the
bottom 53 at one end thereof. In the case of such heat processing
of the glass tube, a degraded portion by forming process generates
on the inner surface of the glass tube. To the degraded portion
by forming process, alkali components or the like contained in the
glass tube adhere in a condensed manner.
[0033]
[Removal of degraded portion by forming process]
As illustrated in Fig, 1, the position of the nozzle 21 is
fixed relative to the vial 50 so that the nozzle 21 is inserted
into the inner space of the vial 50 from the opening 51 of the vial
50, and the distilled water 20 sprayed from the nozzle 21 is applied
to the inner surface 52 near the bottom 53, The nozzle 21 is
detachable relative to the vial 50 as indicated by the arrow in
Fig, 1, In Fig, 1, the distilled water 20 sprayed from the nozzle
21 is illustrated by the dashed dotted line,
[0034] The vial 50 is rotated around the axis with a rotating
machine (not illustrated) while the distilled water 20 being sprayed
to the inner surface 52 of the vial 50, so that the distilled water
20 is uniformly applied to the inner surface 52 near the bottom
53. By the application of the distilled water 20 containing
microbubbles at high pressure, the alkali components or the like
adhering in a condensed manner to the degraded portion by forming
process are removed. The action of the microbubbles is not
necessarily clear. However, it is assumed that when the
microbubbles shrink and collapse, the temperature and the pressure
increase to generate free radicals, such as OH •, and, by the action
of the free radical, the alkali components or the like adhering
in a condensed manner to the degraded portion by forming process
are removed.
[0035] When the nozzle 21 is moved toward the opening 51 from
the state illustrated in Fig. 1 along the axis of the vial 50, the
position to which the distilled water 20 containing microbubbles
is applied is scanned in the axial direction of the vial 50 from
the inner surface 52 near the bottom 53 of the vial 50 to the inner
surface 52 near the opening 51. During the scanning, the vial 50
is rotated with the rotating machine (not illustrated) . Thus, the
alkali components or the like thoroughly adhering to the inner
surface 52 of the vial 50 are uniformly removed. Thus, the elution
of the alkali components or the like from the inner surface 52 of
the vial 50 is suppressed.
[0036] The direction in which the nozzle 21 is moved relative
to the vial 50 is not limited. For example, the nozzle 21 may move
from the inner surface 52 near the bottom 53 to the inner surface
52 near the opening 51, the nozzle 21 may move in the reverse
direction, or the nozzle 51 may move from a portion near the center
of the bottom 53 and the opening 51 toward the opening 51 or the
bottom 53.
[0037]
[Effects of this embodiment]
According to this embodiment, the distilled water 20
containing microbubbles is sprayed to the inner surface 52 of the
vial 50 to remove the alkali components or the like adhering in
a condensed manner to the degraded portion by forming process,
thereby simply producing the vial 50 with little elation of the
alkali components or the like.
[0038] Since the distilled water 20 is sprayed from the nozzle
21, it is not necessary to wash the vial 50 after the degraded portion
by forming process is removed.
[0039]
[Modified example of this embodiment]
In this embodiment, after a glass tube is heat processed to
form the vial 50, the degraded portion by forming process is removed.
However, the forming of vial 50 may be completed after the degraded
portion by forming process is removed in an intermediate article
before formed into the vial 50. The development of the degraded
portion by forming process due to the heat processing of the glass
tube is likely to occur in the formation of the bottom 53 of the
vial 50. Therefore, after the degraded portion by forming process
described above is removed from the intermediate article of the
vial 50 in which the bottom 53 of the vial 50 is formed and the
opening 51 is not yet formed, the opening 51 thereof may be heat
processed.
[0040] In order to more efficiently remove the degraded
portion by forming process, the inner surface 52 of the vial 50
may be polished with a brush while spraying the distilled water
20 containing microbubbles from the nozzle 21.
[0041]
[Second Embodiment]
A method for producing a medical glass container according
to a second embodiment includes immersing the vial 50 in a tank
11, and generating microbubbles in water of the tank 11 to remove
a degraded portion by forming process on the inner surface of the
vial 50.
[0042] As illustrated in Fig. 2, the tank 11 has a capacity
such that a plurality of vials 50 can be immersed therein. The tank
11 has an inner basket 12. The inner basket 12 can support the vial
50, and allows purified water or microbubbles to flow through
openings of the basket. The inner basket 12 is illustrated by the
dash line in Fig. 2. The tank 11 is filled with distilled water
13.
[0043] Near the bottom of the tank 11, two ports 14 and 15 are
provided. The ports 14 and 15 allow distilled water to flow. To
the ports 14 and 15, the microbubble generating device 17 is
connected via a tube 16. In Fig. 2, the tube 16 is illustrated by
the chain double-dashed line.
[0044] The microbubble generating device 17 generates
microbubbles in distilled water by known techniques. Examples of
techniques of generating microbubbles include an ultra high-speed
rotation/shearing method, a method of mixing gas and liquid under
pressure, and an ultrasonic method. The microbubble generating
device 17 has a pump function of circulating the distilled water
13 in the tank 11. By the pump function, the distilled water 13
in the tank 11 is circulated so that the distilled water discharged
from the port 15 is returned from the port 14. During the
circulation, microbubbles have been generated in the distilled
water 13.
[0045] The vial 50 is the same as that in the first embodiment
described above, and thus the detailed description is omitted here.
[0046]
[Removal of degraded portion by forming process]
As illustrated in Fig. 2, a plurality of the vials 50 that
are supported by the inner basket 12 with the opening 51 facing
down are immersed in the distilled water 13 of the tank 11, Then,
when the microbubble generating device 17 is operated, the distilled
water 13 containing microbubbles flows into the tank 11 from the
port 14. When the inner surface of the vial 50 is exposed to the
distilled water 13 containing microbubbles, the alkali components
or the like adhering in a condensed manner to the degraded portion
by forming process are removed by the action of the microbubbles.
The action of the microbubbles is not necessarily clear. However,
it is assumed that when the microbubbles shrink and collapse, the
temperature and the pressure increase to generate free radicals,
such as OR-, and, by the action of the free radical, the alkali
components or the like adhering in a condensed manner to the degraded
portion by forming process are removed. The vial 50 from which the
degraded portion by forming process has been removed is pulled up
from the tank 11, and then dried.
[0047]
[Effects of this embodiment]
According to this embodiment, the inner surface of the vial
50 is exposed to the distilled water 13 containing microbubbles
to thereby remove the alkali components or the like adhering in
a condensed manner to the degraded portion by forming process,
thereby simply producing the vial 50 with little elution of alkali
components.
[0048] Since a plurality of the vials 50 are immersed in the
tank 11 and microbubbles have been generated in the tank 11, the
removal of the degraded portion by forming process in the plurality
of the vials 50 can be batch processed.
[0049] The tank 11 is filled with the distilled water 13, and
thus it is not necessary to wash the vial 50 after the degraded
portion by forming process is removed.
[0050]
[Modified example of this embodiment]
In this embodiment, after a glass tube is heat processed to
form the vial 50, the degraded portion by forming process is removed.
However, the forming of vial 50 may be completed after the degraded
portion by forming process is removed in an intermediate article
before formed into the vial 50. The development of the degraded
portion by forming process due to the heat processing of the glass
tube is likely to occur in the formation of the bottom 53 of the
vial 50. Therefore, after the degraded portion by forming process
described above is removed from the intermediate article of the
vial 50 in which the bottom 53 of the vial 50 is formed and the
opening 51 is not yet formed, the opening 51 may be heat processed.
[0051] In order to more efficiently remove the degraded
portion by forming process, irradiation with ultrasonic waves may
be used in combination in water of the tank 11. In order to
efficiently guide microbubbles into the vial 50 in the tank 11,
an electrode may be disposed in the tank 11 to supply a voltage
at required timing.
[Description of reference numerals]
[0052]
11 • ••-tank
13, 20•••distilled water (purified water)
50 • • -vial (medical glass container)
51 • • -opening
52 • - -inner surface (degraded portion by forming process)
53 • • -bottom
CLAIMS
1. A medical glass container, in which a degraded portion by
forming process on the inner surface of a glass container or an
intermediate article thereof is removed by water in which
microbubbles have been generated.
2. A method for producing a medical glass container, comprising:
spraying water in which microbubbles have been generated to
the inner surface of a glass container or an intermediate article
thereof to remove a degraded portion by forming process on the inner
surface of the glass container or the intermediate article thereof.
3. The method for producing a medical glass container according
to claim 2, wherein the water is purified water.
4. A method for producing a medical glass container, comprising:
immersing a glass container or an intermediate article
thereof in a water tank, and
generating microbubbles in water of the tank to remove a
degraded portion by forming process on the inner surface of the
glass container or the intermediate article thereof.
5. The method for producing a medical glass container according
to claim 4, comprising immersing a plurality of glass containers
or intermediate articles thereof in the water tank.
6. The method for producing a medical glass container according
to claim 4 or 5, wherein the tank is filled with purified water.
7. The method for producing a medical glass container according
to any one of claims 2 to 6, wherein the glass container is obtained
by heat processing a glass tube into a container shape having a
bottom and an opening.
8. The method for producing a medical glass container according
to any one of claims 2 to 6, wherein
the intermediate article of the glass container is obtained
by heat processing a glass tube into a container shape having a
bottom; and
an opening is heat processed in the intermediate article from
which the degraded portion by forming process is removed.
9. A medical glass container, which is produced by the method for
producing a medical glass container according to any one of claims
2 to 8.
To provide a method capable of simply producing a medical
glass container with little elution of alkali components.
A distilled water 20 in which microbubbles have been generated
is sprayed onto an inner surface 52 of a vial 50 to thereby remove
a degraded portion by forming process on the inner surface 52 of
the vial 50. Thus, the inner surface 52 of the vial 50 is exposed
to the distilled water 20 containing microbubbles to thereby remove
alkali components adhering in a condensed manner to the degraded
portion by forming process, thereby simply producing the vial 50
with little elution of the alkali component or the like.
| # | Name | Date |
|---|---|---|
| 1 | 1327-KOL-2009-RELEVANT DOCUMENTS [26-09-2023(online)].pdf | 2023-09-26 |
| 1 | abstract-1327-kol-2009.jpg | 2011-10-07 |
| 2 | 1327-KOL-2009-RELEVANT DOCUMENTS [31-08-2022(online)].pdf | 2022-08-31 |
| 2 | 1327-kol-2009-translated copy of priority document.pdf | 2011-10-07 |
| 3 | 1327-kol-2009-specification.pdf | 2011-10-07 |
| 3 | 1327-KOL-2009-RELEVANT DOCUMENTS [31-08-2021(online)].pdf | 2021-08-31 |
| 4 | 1327-kol-2009-priority document.pdf | 2011-10-07 |
| 4 | 1327-KOL-2009-IntimationOfGrant21-06-2020.pdf | 2020-06-21 |
| 5 | 1327-KOL-2009-PatentCertificate21-06-2020.pdf | 2020-06-21 |
| 5 | 1327-KOL-2009-PA.pdf | 2011-10-07 |
| 6 | 1327-kol-2009-form 5.pdf | 2011-10-07 |
| 6 | 1327-KOL-2009-CLAIMS [27-12-2018(online)].pdf | 2018-12-27 |
| 7 | 1327-kol-2009-form 3.pdf | 2011-10-07 |
| 7 | 1327-KOL-2009-COMPLETE SPECIFICATION [27-12-2018(online)].pdf | 2018-12-27 |
| 8 | 1327-kol-2009-form 2.pdf | 2011-10-07 |
| 8 | 1327-KOL-2009-FER_SER_REPLY [27-12-2018(online)].pdf | 2018-12-27 |
| 9 | 1327-kol-2009-form 1.pdf | 2011-10-07 |
| 9 | 1327-KOL-2009-OTHERS [27-12-2018(online)].pdf | 2018-12-27 |
| 10 | 1327-kol-2009-drawings.pdf | 2011-10-07 |
| 10 | 1327-KOL-2009-FER.pdf | 2018-07-09 |
| 11 | 1327-kol-2009-description (complete).pdf | 2011-10-07 |
| 11 | 1327-KOL-2009-FORM-18.pdf | 2016-12-15 |
| 12 | 1327-KOL-2009-CORRESPONDENCE.pdf | 2011-10-07 |
| 12 | 1327-KOL-2009.pdf | 2013-02-18 |
| 13 | 1327-kol-2009-abstract.pdf | 2011-10-07 |
| 13 | 1327-KOL-2009-CORRESPONDENCE 1.1.pdf | 2011-10-07 |
| 14 | 1327-KOL-2009-ANNEXURE FORM 3.pdf | 2011-10-07 |
| 14 | 1327-kol-2009-claims.pdf | 2011-10-07 |
| 15 | 1327-KOL-2009-ASSIGNMENT.pdf | 2011-10-07 |
| 16 | 1327-KOL-2009-ANNEXURE FORM 3.pdf | 2011-10-07 |
| 16 | 1327-kol-2009-claims.pdf | 2011-10-07 |
| 17 | 1327-KOL-2009-CORRESPONDENCE 1.1.pdf | 2011-10-07 |
| 17 | 1327-kol-2009-abstract.pdf | 2011-10-07 |
| 18 | 1327-KOL-2009.pdf | 2013-02-18 |
| 18 | 1327-KOL-2009-CORRESPONDENCE.pdf | 2011-10-07 |
| 19 | 1327-kol-2009-description (complete).pdf | 2011-10-07 |
| 19 | 1327-KOL-2009-FORM-18.pdf | 2016-12-15 |
| 20 | 1327-kol-2009-drawings.pdf | 2011-10-07 |
| 20 | 1327-KOL-2009-FER.pdf | 2018-07-09 |
| 21 | 1327-kol-2009-form 1.pdf | 2011-10-07 |
| 21 | 1327-KOL-2009-OTHERS [27-12-2018(online)].pdf | 2018-12-27 |
| 22 | 1327-KOL-2009-FER_SER_REPLY [27-12-2018(online)].pdf | 2018-12-27 |
| 22 | 1327-kol-2009-form 2.pdf | 2011-10-07 |
| 23 | 1327-KOL-2009-COMPLETE SPECIFICATION [27-12-2018(online)].pdf | 2018-12-27 |
| 23 | 1327-kol-2009-form 3.pdf | 2011-10-07 |
| 24 | 1327-KOL-2009-CLAIMS [27-12-2018(online)].pdf | 2018-12-27 |
| 24 | 1327-kol-2009-form 5.pdf | 2011-10-07 |
| 25 | 1327-KOL-2009-PatentCertificate21-06-2020.pdf | 2020-06-21 |
| 25 | 1327-KOL-2009-PA.pdf | 2011-10-07 |
| 26 | 1327-kol-2009-priority document.pdf | 2011-10-07 |
| 26 | 1327-KOL-2009-IntimationOfGrant21-06-2020.pdf | 2020-06-21 |
| 27 | 1327-kol-2009-specification.pdf | 2011-10-07 |
| 27 | 1327-KOL-2009-RELEVANT DOCUMENTS [31-08-2021(online)].pdf | 2021-08-31 |
| 28 | 1327-kol-2009-translated copy of priority document.pdf | 2011-10-07 |
| 28 | 1327-KOL-2009-RELEVANT DOCUMENTS [31-08-2022(online)].pdf | 2022-08-31 |
| 29 | abstract-1327-kol-2009.jpg | 2011-10-07 |
| 29 | 1327-KOL-2009-RELEVANT DOCUMENTS [26-09-2023(online)].pdf | 2023-09-26 |
| 1 | SEARCHSTRATEGY9_11-05-2018.pdf |