Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2~!~2~2~
EVACUATED CONTAINER FOR COLLECTING BLOOD
BACKGROUND OF THE INVENTION
The present invention relates to an evacuated
container for collecting blood. More particularly, it
relates to an evacuated tubular container for collecting
5 blood wherein a change of the inside vacuum with the
passage of time till use is little. Namely, the inside
pressure at a vacuum of the container hardly changes for
the duration of storage.
An evacuated container for collecting blood is
10 used for tests and measurements such as a biochemical
test, a serological test, a hematological test, a
measurement of blood sugar, a blood-clotting test, an
erythrocyte sedimentation rate test and a bacteriological
test. Usually, a container for collecting blood comprises
15 a tube with one closed end and one open end, and a rubber
stopper which is fitted on the open end. Before use, the
above-mentioned container comprising a tube with one
closed end and a rubber stopper is evacuated. Then, the
inside pressure of the evacuated container is kept in a
' 20 suitable vacuum condition in order to enable to collect a
necessary amount (2 to 20 mQ ) of blood.
Hitherto a material of the tube with one closed
end in the above-mentioned evacuated container has been
glass. However, glass is fragile in h~n(1lin~, procedure
25 of high-speed centrifugation and the like. Therefore,
recently glass has been replaced by synthetic resins.
As synthetic resins used in an eYacuated
container for collecting blood, there are selected a
polyester, a polyethylene, a polypropylene and the like.
30 Among them, a polyester is employed in general by reason
that a polyester is better than a polyethylene, a
polypropylene or the like as to gas impermeability.
However, a polyester is inferior to glass in gas
impermeability because oxygen gas and nitrogen gas pass
35 through the tube made of a polyester. Therefore, a vacuum
condition can not be kept inside the container comprising
- 2 - 2~2~2~
the tube made of a polyester in case of a long-term
storage. The evacuated container for collecting blood
comprising the tube made of a currently used synthetic
resin has an inferior gas impermeability in comparison
5 with that of an evacuated container for collecting blood
comprising the tube made of glass. By reason o-f the
mentioned above, studies of packaging material for an
evacuated container for collecting blood comprising the
tube made of the synthetic resin have been carried out,
10 for instance, the evacuated container for collecting blood
is vacuously packaged for storage, the specific gas is
filled inside a package of the evacuated container for
collecting blood, and the like.
An object of the invention is to provide an
15 evacuated container for collecting blood comprising the
tube made of a synthetic resin which has an excellent gas
impermeability. According to the present invention, the
inside of the evacuated container for collecting blood can
be kept at a vaccum over a long period of time till use.
This and the other objects of the present
invention will become apparent from the description
hereinafeter.
SUI~M~RY OF THE INVENTION
In accordance with the present invention, there
is provided an evacuated container for collecting blood,
which comprises:
a tube with one closed end and one open end;
said tube prepared from a composition comprising
99.5 to 92 % by weight of polyethylene terephth~l~te, 0.5
to 8 % by weight of a polyamide having m-xylylene group
and 1 to lOO ppm, based on said polyethylene terephthalate
and said polyamide having m-xylylene group, of a
transition metal; and
a stoppering means for stoppering the open end of
said tube to keep the inside of said tube at a vaccum.
According to the evacuated container as mentioned
above the object of the present invention can be attained.
- 3 _ 2Ct~2S.323
DETAILED I)ESCRIPTION
Now, there is explained an evacuated container
for collecting blood of the present invention in detail.
In the present invention, the term " a stoppering
5 means" implies a means for fitting on the open end of the
tube in the evacuated container for collecting blood.
That is, the open end of the tube is stoppered with the
stoppering means to keep the inside of the tube at a
vaccum. The stoppering means can be pierced with a blood
10 drawing needle. On the occasion of using the evacuated
container for collecting blood of the present invention,
one end of a blood drawing needle is inserted into a vein
and the other end of the blood drawing needle is inserted
into the evacuated container through the stoppering means.
15 Blood is drawn into the evacuated container through the
blood drawing needle due to the vaccum in the container.
F.~c~mI~les of the stoppering means are, for instance, a
rubber stopper having an elasticity ~n~hling to remove and
fit; a stoppering means comprising a means for
20 impermeating gas and a means for sealing; and the like.
In the present invention, the term u a tube with
one closed end" means a tube which can be used in an
evacuated container for collecting blood. Examples of the
tube with one closed end are, for instance, a tube having
25 an outer diameter of 10 to 16 mm ( ~ i, a length of 60 to
170 mm and a thickness of 1 to 2 mm, and the like.
The polyethylene terephthalate used in the
present invention is a widely used polyester which may be
obtained by ~ reacting ethylene glycol, and terephthalic
30 acid or an ester thereof (especially, dimethyl
terephthalate). Also, the above polyethylene
terephthalate includes a polyethylene terephthalate
containing recurrent units of ethylene terephthalate in a
ratio not less than 80 %. ~ mples of copolymerizable
35 components are, for instance, isophthalic acid,
naphth~l~nedicarboxylic acid, a p-oxybenzoic acid
derivative; butanediol, and the like.
It is preferred in molding that the molecular
' '; ,' : ,
- 4 - 2 ~ 3
weight of the above-mentioned polymer of the polyester is
0.6 to û.9 as intrinsic viscosity [ ~7 ] to give a
satisfactory tube with the closed end. Such intrinsic
viscosity is a value measured at 25~C in a solution
5 obtained by dissolving 0.25 g of the polymer in lûO mQ
of a mixture of 3 parts by weight of phenol and 2 parts by
weight of 1,1, 2, 2-tetrachloroethane.
The polyamide having m-xylylene group used in the
present invention comprises as an amine component at least
10 one ~ min~ selected from the group consisting of (1)
m-xylylenedi~min~, (2) a mixture of m-xylylenerli~min~ and
p-xylylenerli~min~, and (3) a mixture of m-
xylylf?ne~ mine and h~ methylene~ min~; and as an acid
component at least one carboxylic acid selected from the
15 group consisting of adipic acid, pimelic acid, suberic
acid, azelaic acid and sebacic acid. As the polyamide
having m-xylylene group of the present invention, poly-m-
xylylene adipamide is preferable. It can be considered
that the polyamide having m ;sylylene group of the present
20 invention plays a role in the improving of gas
impermeability of the tube with the closed end.
As a transition metal used in the present
invention, there are exemplified cobalt, nickel, rhodium
and the like. In the present invention, a transition
metal is used in a form of a salt. ~x~mr)les of salts of
the transition metals used in the present invention are,
for instance, cobalt acetate, cobalt naphthenate, cobalt
stearate, nickel acetylacetonate, nickel chloride, rhodium
chloride, and the like.
The tube of the present invention which is
prepared by mixing a polyamide having m-xylylene group and
a salt of a transition metal, absorbs oxygen gas.
The material of the tube with the closed end of
the present invention is a mixture of polyethylene
terephthalate, a polyamide having ~ ylylene group and a
salt of a transition metal. A mold may be charged with
the three components at once in a molding step.
Alternatively, the three components ma~ be previously
~ 5 2~2~3
mixed be~ore charging a mold with the mixture of the three
components.
Since the tube with the closed end of the present
invention is molded by mixing a polyamide having m-
5 xylylene group, it is possible to yellow a product.
However, such yellow in the product can turn colorless by
well k~l~nci n~ constitution of the above-mentioned three
components. Also, such yellow can be made inconspicuous
by adding up to 4 % by weight, based on the
10 polyethylene terephthalate, of a master pellet containing
a blue pigment or purple pigment to the mixture of the
three components. As the master pellet, polyethylene
terephthalate is used. The master pellet contains, for
instance, 1 % of the pigment. It is preferable that the
15 master pellet containing a blue pigrnent or purple pigment
is added to the mixture in the equal amount to that of a
polyamide having m-xylylene group. F;~mpl~.q of such
pigment used in the present invention are, for instance,
Blue No. 1 (C I 42090), Blue No. 2 (C I 73015), Blue No.
20 201 (C I 73000), Blue No. 202 (C l 42052), Blue NoO 203 (C
; I 42052), Blue No. 204 (C I 69825), Blue No. 403, Purple
No. 201 (C I 60725), and the like.
In the present invention, the tube is prepared by
mixing a polyamide having m-xylylene group, a widely used
25 polyester and a salt of a transition metal in order to
give the tube with the closed end which has an excellent
gas impermeability and to absorb oxygen gas. It is
considered that: a salt of a transition metal is a
catalyst to accelerate such behavior.
In the evacuated cont~iner for collecting blood
;~ comprising the tube made of the synthetic resin of the
present invention which has an excellent gas
impermeability, as described above, oxygen gas is absorbed
and then the inside of the evacuated container for
' 35 collecting blood can be kept at a vacuum during a long
- period of time before use.
In the present invention, it is necessary that
each mixed ratio in the above-mentioned mixture is 99.5 to
. ,
- 6 ~ 2~2.~2~
92 % by weight, preferably 99 to 96 % by weight as
polyethylene terephthalate and 0. 5 to 8 % by weight,
preferably 1 to 4 % by weight as a polyamide having
m-xylylene group. In case that a ratio of a polyamide
5 having m-xylylene group is more than 8 % by weight,
transparency is deteriorated and a cost for material of
the tube is made expensive. On the other hand, in case
that a ratio of a polyamide having m-xylylene group is
less than û. 5 % by weight, the capacity for absorbing
10 oxygen gas is deteriorated.
In the present invention, it is necessary to
contain 1 to 100 ppm, preferably 2 to 50 ppm of a salt of
a transition metal. In case that a content of a salt of a
transition metal is more than 100 ppm, the obtained tube
15 is colored to deteriorate transparency and a cos t for
material of the tube is made expensive. On the other
hand, in case that a content of a salt of a transition
metal is less than 1 ppm, the function of the catalysis
which accelerates to absorb o-~Lygen gas is deteriorated.
The polymer used for preparing the tube with the
closed end of the present invention may contains
additive(s) which does not exert a bad influence.
Examples of the additives are, for instance, an
antioxidant, an agent for blocking ultraviolet rays, an
25 a~ ry agent for extruding, an additive for improving
the polymers and the like.
The present invention is more specifically
described and e~pl~;necl by means of the following
Examples, Comparative Example and Test Examples in which
30 all parts are by weight unless otherwise noted. It is to
be understood that the present invention is not limited to
the Examples, the Comparative Examples and the Test
Examples, and various changes and modifications may be
made in the invention without departing from the spirit
35 and scope thereof.
Fl~mples 1 to 10 and Comparative Examples 1 to 3
Using material(s) shown in Table 1, each tube
7 2 ~ 2 3
with one closed end and one open end for collecting 5 m Q
of blood having a thickness of 1.3 mm, a length of 75 mm
and an inner diameter of 10. 8 mm, was prepared. Thus
obtained tube was tightly stoppered with a rubber stopper
5 made of butyl gum.
In each group, ten containers were prepared.
In Table 1, polyethylene terephthalate, poly-m-
xylylene adipamide and a dye classified in anthraquinones
were used as a polyester, a polyamide having m-xylylene
10 group and a blue pigment, respectively.
Table 1
Ratio by weight ofConcentration
Number PolyestertPolyamide havingof cobalt
m-xylylene group/Master pellet (ppm)
containing blue pigment
. Ex. 1 100/1/0 23
20 Ex. 2 100/1/0 5
Ex. 3 100/1/2 5
Ex. 4 100/2/0 10
Ex. 5 100/2/0 5
Ex. 6 100/2/0
25 Ex. 7 100/4/0 100
Ex. 8 100/4/0 20
Ex. 9 100/4/0 10
Ex. 10 100/4tO 2
Com. Ex. 1 100/0/0 0
' 30 Com. Ex. 2 100/4/0 0
Com. Ex. 3 100/0/2 0
~;~
Test Example 1
35In each group ten containers were employed to
measure inside pressure thereof.
A pressure inside each of the containers obtained
according to Examples 1 to 10 and Comparative Examples 1
- 8 - 2 ~
to 3 was reduced to 460 mmHg (300 mmHg vac.) to give a
evacuated container for collecting blood.
With respect to each evacuated containerl an
inside pressure was measured at 50~C every 3 weeks, i.e.
5 at the time right after stoppering, 3 weeks after, 6 weeks
after, 9 weeks after, 12 weeks after and 15 weeks after.
As the inside pressure at the time right after stoppering
was 100 %, retension rate (%) regarding degree of a vacuum
was calculated from the measured vaiue. The results are
10 shown in Table 2.
~-.. . ... .
9 - 2~25%~
;C
~ ~ CS) ~ C~ ~ O ~ ~D ~ C~ O ~O
Oc~ ~ o o cr~ ~4 co L~' ~ ~t~ CD
- ~ ~ O o ~ ~ cn
U~
C~ ~J ,-
~ n
h C~ C~ ~ ~ 00 ~ L~ 00 C~ L~ 1~ CO
, ~ ~ ~ o o o o a~ C~3 o o a~ cn cs~ cs~
~'
~A~~ O~OOOOOOOOOOO
-, ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~ ~
~.~ r
.
o ~ ~ ~
lo 2~ 23
Test Example 2
In the same manner as described in Test Example 1
except that a pressure inside each container was reduced
to 310 mInHg (450 mmHg vac.), an inside pressure of the
5 evacuated container for collecting blood was measured.
As the inside pressure at the time right after
stoppering was 100 %, retension rate (%) regarding degree
of a vacuum was calculated from the measured value. The
results are shown in Table 3.
.. .. . , .. ,,~ .,~ ~ ,
- 1 1 - 2 ~ 2 ~
~n
~, L~ ~ ~ o c~ ~ C~ oo ~ ~ L~
o o o o o ~ o o o ~ oo ~ o~
r--~
~n
r.~ L~ L~ tD L~ CO ~ c~ o ~ ~ ~ O
.~ c~ ~ ~ ~ o o cn Lf~ CO C~ O
~, o o o o o ~ ~ ~_ o
V ~ S~ ~ C~7 00 '~ CS~ O CO ~ ~5~ L~
O ~ L~ O cn oo ~ O C~ ~
o o o o o ~ ~ O O cs~ ~ cn cn
a~
o o o o o cs~ ~ o o a~ ~ cn a~
tn
s, L~ o c~ o et~ ~ O ~ ~
O o o o o ~ o o o a~ cs, ~ cs~
:
s-~
' - o o o o o o o o o ~ o o o
~; o o o o o o o o o o o ~ o
~, n
o ~
:
- 12 - 2~32~23
Test Example 3
In the same manner as described in Test Example 1
except that a pressure inside each container was reduced
to 30 mmHg (730 mmHg vac.), an inside pressure of the
5 evacuated container for collecting blood was measured.
As the inside pressure at the time right after
stoppering was 100 %, retension rate (%) regarding degree
of a vacuum was calculated from the measured value. The
results are shown in Table 4.
.
':
- 13 2~ 23
r-l
~n
C~
n
C~
r~ ~;3 Lr)
~ ~ ~ o o o o o o oo c ~ o o o o o
:~ a,) o ~ ~ ~
- 14 ~ 3
In Test Examples 1 to 3~ the temperature 50~C was
used which is fairly high in comparison with room
temperature because the period, i.e. 15 weeks may be short
as an observing period.
As is clear from the results shown in Tables 2 to
4, the higher the concentration of cobalt is, the faster
oxygen gas is absorbed. Also, the higher the content of
the polyamide having m-xylylene group is, the faster
oxygen gas is absorbed.
Among the results in Tables 2 to 4, clifference is
recognized. The reason is that an amount of oxygen gas to
be absorbed differs due to the difference as to degree of
a vacuum. That is, the more the container for collecting
blood is evacuated, the more an amount of oxygen gas
inside the container is lowered.
Also, there was no influence on gas
impermeability even if a blue pigment was used in the
preparation of the tube of the present invention.
In addition to the ingredients used in the
20 Examples, the Comparative Examples and the Test Examples,
other ingredients can be used in the Examples, the
Comparative Examples and the Test R~r~mples as set forth in
the specification to obtain substantially the same
results.
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