U.S. patent application number 10/522147 was filed with the patent office on 2005-11-17 for container formed from multimodal ethylene polymer.
Invention is credited to Gorgerin, Michel Oswald.
Application Number | 20050255265 10/522147 |
Document ID | / |
Family ID | 29797273 |
Filed Date | 2005-11-17 |
United States Patent
Application |
20050255265 |
Kind Code |
A1 |
Gorgerin, Michel Oswald |
November 17, 2005 |
Container formed from multimodal ethylene polymer
Abstract
A container is disclosed comprising a multimodal ethylene
polymer having a standard density of at least 950 kg/m.sup.3 and a
fluidity index MI.sub.2 of from 1 to 10 g/10 min, said multimodal
ethylene polymer comprising: from 20 to 65 wt %, based on the total
weight of the multimodal ethylene polymer, of a fraction comprising
ethylene polymer (A) having a density of more than 965 kg/m.sup.3
and a fluidity index MI.sub.2(A) of at least 10 g/10 min; and from
80 to 35 wt %, based on the total weight of the multimodal ethylene
polymer, of a fraction comprising a copolymer (B) of ethylene and
at least one alpha-olefin containing from 3 to 12 carbon atoms, and
having a fluidity index MI.sub.2(B) of less than 10 g/min and a
content of said alpha-olefin(s) of 0.1 to 5 mol %.
Inventors: |
Gorgerin, Michel Oswald;
(Soignies, BE) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER
LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Family ID: |
29797273 |
Appl. No.: |
10/522147 |
Filed: |
January 24, 2005 |
PCT Filed: |
July 18, 2003 |
PCT NO: |
PCT/EP03/07941 |
Current U.S.
Class: |
428/35.7 |
Current CPC
Class: |
C08L 23/0815 20130101;
C08L 2205/02 20130101; C08L 23/06 20130101; Y10T 428/1352 20150115;
C08L 23/0815 20130101; C08L 23/06 20130101; C08L 2666/06 20130101;
C08L 2666/06 20130101 |
Class at
Publication: |
428/035.7 |
International
Class: |
B65D 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 25, 2002 |
EP |
02078183.7 |
Claims
1. Container comprising a multimodal ethylene polymer having a
standard density of at least 935 kg/m.sup.3 and a fluidity index
MI.sub.2 of from 1 to 10 g/10 min, said multimodal ethylene polymer
comprising: from 20 to 65 wt %, based on the total weight of the
multimodal ethylene polymer, of a fraction comprising ethylene
polymer (A) having a density of more than 950 kg/m.sup.3 and a
fluidity index MI.sub.2 (A) of at least 10 g/10 min; and from 80 to
35 wt %, based on the total weight of the multimodal ethylene
polymer, of a fraction comprising a copolymer (B) of ethylene and
at least one alpha-olefin containing from 3 to 12 carbon atoms, and
having a fluidity index MI.sub.2 (B) of less than 10 g/min and a
content of said alpha-olefin(s) of 0.1 to 5 mol %.
2. Container comprising ethylene polymer having a standard density
of at least 935 kg/m.sup.3, a fluidity index MI.sub.2 of from I to
10 g/10 min, a Vicat point of at least 126.5.degree. C. and a
resistance to slow cracking, measured according to ASTM D 1693
(1980), condition A of at least 60 hours.
3. Container according to claim 1, wherein the standard density of
the ethylene polymer (A) is more than 965 kg/m.sup.3.
4. Container according to claim 1, wherein the proportion of
ethylene polymer (A) is from 30 to 40 wt %.
5. Container according to claim 1, wherein the standard density of
the multimodal ethylene polymer is at least 950 kg/m.sup.3.
6. Container according to claim 1, which has a volume of less than
2 L.
7. Container according to claim 1, which is formed only of said
multimodal ethylene polymer.
8. Container according to claim 1, wherein polymer (A) is a
homopolymer of ethylene.
9. Container according to claim 1, wherein the multimodal ethylene
polymer has a fluidity index MI.sub.2 of from 1 to 3 g/10 min.
10. Container according to claim 1, wherein the multimodal ethylene
polymer has a density of no more than 962 kg/m.sup.3.
11. Container according to claim 1, wherein the multimodal ethylene
polymer has a Mw/Mn of 9 or less.
12. Container according to claim 1, wherein the multimodal ethylene
polymer has a Mw/Mn of at least 5.
13. Container according to claim 1, wherein the multimodal ethylene
polymer has a ratio MI.sub.2(A)/MI.sub.2 of from 5 to 200.
14. Container according to claim 1, wherein the MI.sub.2 (B) is
from 0.08 to 0.8 g/10 min.
15. Container according to claim 1, wherein the copolymer (B)
comprises units derived from ethylene and butene-1.
16. Container according to claim 1, wherein the multimodal ethylene
polymer is obtained by polymerisation in at least two reactors
connected in series.
17. Container according to claim 1 or 2, which is a bottle.
18. Bottle Container according to claim 1 or 2, which is a bottle
that has been sterilised.
19. (canceled)
Description
[0001] The present invention relates to containers comprising a
composition based on multimodal ethylene polymer. It also relates
to a process for manufacturing said containers and their use as
bottles containing foodstuffs, and more particularly milk.
[0002] It is known to use polyethylene, and more particularly
bimodal polyethylene, for the manufacture of containers. For
example, WO 01/14122 discloses large (>2 L, preferably at least
30 L) containers made from blow-moulded HDPE having a density of
945-960 kg/m.sup.3 and MI.sub.21 of 3-8 g/10 min. and comprising
bimodal HDPE made by first forming a high-density homopolymer and
then forming a low-density copolymer, the high-density homopolymer
comprising about 45-50 wt % of the composition. U.S. Pat. No.
6,194,520 discloses bimodal polymer blends suitable for
blow-moulding typically having an MI.sub.21 of at least 2 g/10 min
and a flow ratio (MI.sub.21/MI.sub.2) of at least 60. These are
made by first forming a low-density block preferably comprising
45-50 wt % of the composition and then the high-density block.
Although blow-moulding into small bottles is mentioned, there is no
discussion of the stiffness of the bottles.
[0003] EP 533 160A discloses a bimodal polyethylene resin typically
having a density of 945-980 kg/m.sup.3 and MI.sub.21 of 10-25 g/10
min, comprising 10-35 wt % of a homopolymer having a density of at
least 960 kg/m.sup.3 and an MI.sub.2 of at least 30 g/10 min, and
65-90 wt % of a copolymer having a density of less than 955
kg/m.sup.3 and an MI.sub.21 of 2-6 g/10 min. The resin is said to
have low haze, and is particularly suitable for films. There is no
disclosure of its use in containers, particularly not in small
bottles.
[0004] Despite the above-mentioned disclosure relating to small
bottles, commercially produced small bottles such as those for milk
are currently typically made from monomodal polymers derived from a
chromium or titanium catalyst. There is a continuing desire to
reduce the weight of such bottles whilst maintaining the physical
properties such as stress crack resistance and stiffness.
[0005] We have discovered a multimodal composition for bottles
which provides improved stiffness compared with conventional
bottles, and hence enables such a weight reduction. The
compositions can also have an increased density without reducing
the stress crack resistance, which permits improved processing.
[0006] Accordingly in a first aspect the present invention provides
a container comprising a multimodal ethylene polymer having a
standard density of at least 935 kg/m.sup.3 and a fluidity index
MI.sub.2 of from 1 to 10 g/10 min, wherein said multimodal ethylene
polymer comprises:
[0007] from 20 to 65 wt %, based on the total weight of the
multimodal ethylene polymer, of a fraction comprising ethylene
polymer (A) having a density of more than 950 kg/m.sup.3 and a
fluidity index MI.sub.2 (A) of at least 10 g/10 min; and
[0008] from 80 to 35 wt %, based on the total weight of the
multimodal ethylene polymer, of a fraction comprising a copolymer
(B) of ethylene and at least one alpha-olefin containing from 3 to
12 carbon atoms, and having a fluidity index MI.sub.2 (B) of less
than 10 g/min and a content of said alpha-olefin(s) of 0.1 to 5 mol
%.
[0009] Preferably the container is less than 2 L in size, and
preferably comprises a single layer of the above-defined polymer.
However containers made of several layers of different resins, one
or more or all of which is as defined above, are also within the
scope of the invention.
[0010] It is also preferred that the amount of ethylene polymer (A)
is from 30 to 40 wt %.
[0011] A further aspect of the invention provides a container
comprising ethylene polymer having a standard density of at least
935 kg/m.sup.3, a fluidity index MI.sub.2 of from 1 to 10 g/10 min,
a Vicat point of at least 126.5.degree. C. and a resistance to slow
cracking, measured according to ASTM D 1693 (1980), condition A of
at least 60 hours. The ethylene polymer of this aspect of the
invention is preferably multimodal.
[0012] By <<multimodal ethylene polymer>> is meant an
ethylene polymer comprising at least two fractions having different
fluidity indices (MI.sub.2) so that it possesses a broad or
multimodal molecular weight distribution. For the purposes of this
invention, the term <<multi-modal>> need not
necessarily be taken to mean that the GPC of the final multi-modal
polymer exhibits two distinct molecular weight peaks.
[0013] The (multimodal) ethylene polymer used in the present
invention has generally a standard density which does not exceed
965 kg/m.sup.3. For the purposes of the present invention, the
standard density is measured according to the standard ISO 1183-3
(1999). The standard density preferably does not exceed 962
kg/m.sup.3, more particularly not 958 kg/m.sup.3. The standard
density is preferably at least 951 kg/m.sup.3, more preferably at
least 955 kg/m.sup.3.
[0014] We have found that small (<2 L) containers of the
invention have a stiffness as measured by load at maximum load
crushing which can be more than 10% better than that of
conventional bottles. Furthermore, they can be made at a higher
density without reducing the stress crack resistance. Higher
densities are particularly valuable for the long-life milk market,
where it is necessary to sterilise the bottles with steam; a higher
density means that the sterilisation temperature can be raised,
thereby shortening the sterilisation period and increasing
throughput. With monomodal polymers, such an increase in density
would result in poorer stress crack resistance. However the
compositions of the invention maintain excellent ESCR values even
as the density is increased.
[0015] The ethylene polymer used in the present invention
preferably possesses a fluidity index (MI.sub.2) measured at
190.degree. C. under a load of 2.16 kg according to the standard
ASTM D 1238 (1998) of less than 4 g/10 min. MI.sub.2 values of less
than 2 g/10 min are particularly preferred. The fluidity index
MI.sub.2 is at least 1 g/10 min, preferably at least 1.2 g/10 min.
Fluidity indices of 1.4 to 1.8 g/10 min are particularly
preferred.
[0016] Preferably the standard density of the ethylene polymer is
at least 950 kg/m.sup.3. It is also preferred that the ethylene
polymer used in the present invention has a molecular weight
distribution Mw/Mn of no more than 9. However it is preferably at
least 5. The ratio MI.sub.2(A)/MI.sub.2 is preferably from 5 to
200.
[0017] Preferably the standard density of the ethylene polymer (A)
in the ethylene polymer of the invention is more than 965
kg/m.sup.3. The fraction of ethylene polymer (A) is preferably at
least 30% by weight compared with the total weight of the
multimodal ethylene polymer. The fraction of ethylene polymer (A)
preferably does not exceed 45 wt %, more particularly it does not
exceed 40 wt % compared with the total weight of the multimodal
ethylene polymer.
[0018] Correspondingly, the fraction of ethylene copolymer (B) in
the multimodal ethylene polymer is preferably at least 55%, more
particularly at least 60 wt % by weight compared with the total
weight of the multimodal ethylene polymer. The fraction of ethylene
copolymer (B) preferably does not exceed 70 wt %.
[0019] The composition used in the present invention generally
contains at least 95%, preferably at least 98% by weight of the
whole of the polymer (A) and the copolymer (B). Most particularly
preferred is a composition consisting substantially only of polymer
(A) and copolymer (B).
[0020] Preferably, the polymer (A) is an ethylene homopolymer. For
the purposes of the present invention, <<ethylene
homopolymer>> means an ethylene polymer consisting mainly of
monomer units of ethylene and substantially devoid of monomer units
derived from other olefins. However polymer (A) may also be an
ethylene copolymer with one or more alpha-olefins containing from 3
to 12 carbon atoms.
[0021] By ethylene copolymer with one or more alpha-olefins
containing from 3 to 12 carbon atoms (copolymer (B)) is meant a
copolymer comprising monomer units derived from ethylene and
monomer units derived from at least one alpha-olefin containing
from 3 to 12 atoms of carbon. The alpha-olefin may be selected from
among olefinically unsaturated monomers such as butene-1,
pentene-1, hexene-1, octene-1. Butene-1 is particularly preferred.
The content of alpha-olefin in the copolymer (B) is preferably at
least equal to 0.2 mol %, in particular at least equal to 0.3 mol
%. The content of alpha-olefin in the copolymer (B) is most
preferably no more than 4 mol %, and particularly no more than 3
mol %. Particularly good results are obtained with alpha-olefin
contents in the copolymer (B) of 0.5 to 2 mol %.
[0022] The standard density SD of the polymer (A) [SD(A)] is
preferably at least 968 kg/m.sup.3, more particularly at least 970
kg/m.sup.3. Preferably, polymer (A) is characterised by an
MI.sub.2(A) of at least 30 g/10 min, more particularly at least 50
g/10 min. Preferably, the value of MI.sub.2(A) does not exceed 500
g/10 min, values of less than 400 g/10 min being particularly
preferred. Fluidity indices MI.sub.2(A) of 80 to 200 g/10 min have
given good results.
[0023] Copolymer (B) preferably has an MI.sub.2(B) of at least 0.03
g/10 min, more particularly of at least 0.06 g/10 min. An
MI.sub.2(B) of at least 0.08 g/10 min is most preferred. The
MI.sub.2(B) preferably does not exceed 2 g/10 min, values of no
more than 1 g/10 min being particularly preferred. Most preferred
are MI.sub.2(B) values of 0.08 to 0.8 g/10 min.
[0024] The multimodal ethylene polymer used in the present
invention may be obtained by any suitable technique. It is
possible, for example, to perform the mixing of polymer (A) and
copolymer (B) by any known process such as, for example, the molten
mixing of the two preformed polymers. The polymer may also be
produced in a single reactor using multi-catalysts to generate the
different, desired polymer components. For example polymer (A)
would be formed using a catalyst with a sufficiently different
comonomer incorporation and molecular weight potential at given
hydrogen and comonomer composition in the polymerisation reactor to
that of the catalyst used to produce copolymer (B) such that the
desired bi-modal or multi-modal polymer is produced. The different
catalysts selected may be co-supported, separately supported or
unsupported. Preferred, however, are processes in which polymer (A)
and copolymer (B) are prepared in at least two successive
polymerisation stages. Whilst the polymers may be produced in any
order, it is particularly preferred that the preparation of polymer
(A) is performed first and then the preparation of the copolymer
(B) in the presence of the polymer (A) obtained from the first
polymerisation stage. Preferably polymer (A) is produced in the
absence of any alpha-olefins containing more than 3 carbon atoms.
The polymerisation stages may each be carried out, independently of
one another, in suspension in an inert hydrocarbon diluent or in
gaseous phase. A process comprising at least two polymerisation
stages in suspension in a hydrocarbon diluent is preferred. The
hydrocarbon diluent is generally chosen from among aliphatic
hydrocarbons containing from 3 to 10 carbon atoms. Preferably, the
diluent is chosen from among propane, isobutane, hexane or their
mixtures.
[0025] In addition to the multimodal ethylene polymer, the
composition used in the present invention may contain conventional
additives such as antioxidants, antacids, UV stabilisers, dyes,
fillers, antistatic agents and lubricating agents. The total
content of additives is typically 5 wt % compared with the total
weight of the composition used in the present invention. For white
grade milk bottles for example, 1 or 4.5 wt % pigment (TiO2) is
used.
[0026] The final composition used for the manufacture of containers
according to the invention may be obtained by any suitable known
means. It is possible, for example, to employ two successive
stages, comprising first mixing the multimodal ethylene polymer and
where applicable the additives at ambient temperature, and then
continuing the mixing in the molten state in an extruder. The
temperature of the second stage is generally from 100 to
300.degree. C., in particular from 120 to 250.degree. C., more
particularly from about 130 to 210.degree. C. An alternative method
consists of introducing the additives and where applicable the
other compounds into the already molten multimodal ethylene
polymer.
[0027] It is also possible to prepare initially a masterbatch
comprising a first fraction of the multimodal ethylene polymer and
any additives, the masterbatch being rich in additives and
optionally in other compounds. The masterbatch is then mixed with
the remaining fraction of the multimodal ethylene polymer, for
example during the manufacture of granules of the composition.
[0028] The containers according to the invention may be obtained by
any known technique for the manufacture of objects. Extrusion
blow-moulding, injection blow-moulding and injection-stretch blow
moulding are all suitable.
[0029] The examples which are described below serve to illustrate
the invention. The meanings of the symbols used in these examples,
the methods of measurement and the units of these quantities are
explained below:
[0030] [A]: fraction of ethylene polymer (A) expressed in wt %
compared with the total weight of the multimodal ethylene
polymer.
[0031] [B]: fraction of ethylene copolymer (B) expressed in wt %
compared with the total weight of the multimodal ethylene
polymer.
[0032] MI.sub.2: fluidity index of the multimodal ethylene polymer,
expressed in g/10 min, measured at 190.degree. C. under a load of
2.16 kg according to the standard ASTM D 1238 (1998).
[0033] MI.sub.2(A): fluidity index of the ethylene polymer (A),
expressed in g/10 min, measured at 190.degree. C. under a load of
2.16 kg according to the standard ASTM D 1238 (1998); in cases
where the multimodal ethylene polymer is manufactured by a process
of two successive polymerisation stages, said value is measured on
a sample of the polymer (A) taken from the first reactor.
[0034] MI.sub.2(B): fluidity index of the ethylene copolymer (B),
expressed in g/10 min, measured at 190.degree. C. under a load of
2.16 kg according to the standard ASTM D 1238 (1998); in cases
where the multimodal ethylene polymer is manufactured by a process
of two successive polymerisation stages, said value is calculated
on the basis of the MI.sub.2 and MI.sub.2(A) values.
[0035] SD: standard density of the multimodal ethylene polymer,
expressed in kg/m.sup.3, measured according to the standard ISO
1183-3 (1999).
[0036] SD (A): standard density of the ethylene polymer (A),
expressed in kg/m.sup.3, measured according to the standard ISO
1183-3 (1999); in cases where the multimodal ethylene polymer is
manufactured by a process of two successive polymerisation stages,
said value is measured on a sample of the polymer (A) taken from
the first reactor.
[0037] SCB (B): comonomer content of copolymer (B) as measured by
the number of short-chain branches per 1000 C.
[0038] ESCR-A: resistance to slow cracking, expressed in hours,
measured according to the standard ASTM D 1693 (1980), condition A,
by immersion in an aqueous solution containing 10 vol % of
nonylphenoxy-poly(ethyleneo- xy)ethanol at 50.degree. C., of a
plate obtained by compression of the composition used in the
present invention according to the standard ASTM D 1928 (1980).
[0039] Stiffness: Empty bottles are crushed at 23.degree. C. at a
constant speed (5 mm/minute). The crushing machine measures the
force needed to maintain the crushing speed, which depends on the
degree of crushing. This crushing force curve has a maximum called
the Top Load, measured in N.
[0040] Vicat point (1 kg load): According to ASTM 1525, the
softening temperature of the resin is determined by measuring the
temperature at which a specified type of needle loaded with 1 kg
can pass through the sample.
EXAMPLES 1-4
[0041] A composition comprising the following was blow-moulded
using a Stork wheel machine into 1 L bottles:
[0042] 95.3 parts by weight of multimodal ethylene polymer
manufactured by the same general process as disclosed in
EP-A-603935;
[0043] 4.5 parts by weight TiO.sub.2 (for Examples 2 and 3
only);
[0044] 0.05 parts by weight of calcium stearate;
[0045] 0.05 parts by weight hydrotalcite;
[0046] 0.08 parts by weight Irganox B900.
[0047] The characteristics of the multimodal ethylene polymers used
in the Examples are given in Table 1 below.
[0048] The characteristics of the bottles obtained are also given
in Table 1 below. Example 1 was a natural colour resin--ie with no
pigment--whilst Examples 2 to 4 were white.
EXAMPLES 5-6
Comparative
[0049] Compositions were blow-moulded into bottles as in Examples 1
to 3, except that instead of the above multimodal polymer, a
monomodal ethylene polymer also produced using a Ziegler catalyst
was used, whose characteristics are given in Table 1 below. The
other additives in the composition were identical. SEC analysis
showed the overall molecular weight distribution of these polymers
to be very similar to those of Examples 1 to 4.
[0050] A comparison of Example 2 with Example 6 shows that the
bottles according to the invention have a superior stiffness
compared with those formed from monomodal polyethylene having a
similar MI.sub.2. This means that the bottles of the invention can
be made lighter without any loss of performance. Furthermore, the
higher density of the bottle of Example 2 compared with that of
Example 6 results in a higher Vicat point, which permits a higher
sterilisation temperature to be used, resulting in shorter
sterilisation times. With monomodal polymers, such an increase in
density would result in poorer stress crack resistance. However it
can be seen here that the ESCR values of Examples 1-4 are
substantially better than those of Examples 5 and 6.
1TABLE 1 Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Mono Mono Property
Bimodal Bimodal Bimodal Bimodal modal modal Type Units natural
white white white natural white MI.sub.2 g/10 min 1.9 1.9 1.7 1.8
1.8 1.8 Flake SD* kg/m.sup.3 954.7 955 955 954.3 956.0 952.0 Mw
120005 103000 128280 120810 Mn 17103 13900 19092 21005 Mw/Mn 7.02
7.4 6.72 5.75 MI.sub.2(A) g/10 min 76.6 76.2 72.5 112.6 -- -- SD(A)
kg/m.sup.3 970.1 969.6 970.1 970.2 -- -- MI.sub.2(B) g/10 min -- --
[A] wt % 35 35 35 30 -- -- [B] wt % 65 65 65 70 -- -- SCB (B) /1000
C 1.6 1.6 1.6 1.6 0.3-0.5{circumflex over ( )} 1.3-1.5{circumflex
over ( )} ESCR-A hour 71.4 61.9 71.7 25.sup.# Stiffness: N 723
626.9 Top load Vicat point .degree. C. 126.7 127.3 125.5 *density
of resin before addition of additives {circumflex over ( )}value
for whole resin # average value
* * * * *