U.S. patent application number 16/216259 was filed with the patent office on 2019-06-20 for bottle closure assembly including a polyethylene composition.
This patent application is currently assigned to NOVA Chemicals (International) S.A.. The applicant listed for this patent is NOVA Chemicals (International) S.A.. Invention is credited to Cliff Baar, Ian Gibbons, Amin Mirzadeh, Eric Vignola, XiaoChuan Wang.
Application Number | 20190185232 16/216259 |
Document ID | / |
Family ID | 65237073 |
Filed Date | 2019-06-20 |
View All Diagrams
United States Patent
Application |
20190185232 |
Kind Code |
A1 |
Wang; XiaoChuan ; et
al. |
June 20, 2019 |
BOTTLE CLOSURE ASSEMBLY INCLUDING A POLYETHYLENE COMPOSITION
Abstract
The present disclosure describes bottle closure assemblies which
are made at least in part with a high density unimodal
polyethylene. The bottle closure assembly includes a cap portion,
an elongated tether portion and a retaining means portion. The
retaining means portions engages a bottle neck or an upper portion
of a bottle. The elongated tether portion connects at least one
point on the cap portion to at least one point on the retaining
means portion so as to prevent loss of the cap portion from a
bottle.
Inventors: |
Wang; XiaoChuan; (Calgary,
CA) ; Gibbons; Ian; (Calgary, CA) ; Vignola;
Eric; (Airdrie, CA) ; Baar; Cliff; (Calgary,
CA) ; Mirzadeh; Amin; (Calgary, CA) |
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Applicant: |
Name |
City |
State |
Country |
Type |
NOVA Chemicals (International) S.A. |
Fribourg |
|
CH |
|
|
Assignee: |
NOVA Chemicals (International)
S.A.
Fribourg
CH
|
Family ID: |
65237073 |
Appl. No.: |
16/216259 |
Filed: |
December 11, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62607589 |
Dec 19, 2017 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29L 2031/56 20130101;
B65D 53/02 20130101; B29K 2023/065 20130101; B65D 41/34 20130101;
B65D 55/16 20130101; B29K 2105/0094 20130101 |
International
Class: |
B65D 55/16 20060101
B65D055/16; B65D 53/02 20060101 B65D053/02; B65D 41/34 20060101
B65D041/34 |
Claims
1. A bottle closure assembly comprising: a cap portion, a tether
portion, and a retaining means portion, the cap portion being
molded to reversibly engage and cover a bottle opening, the
retaining means portion being molded to irreversibly engage a
bottle neck or an upper portion of a bottle, and where the tether
portion connects at least one point on the cap portion to at least
one point on the retaining means portion, wherein the cap portion,
optionally the tether portion, and optionally the retaining means
portion comprise a high density polyethylene which is not a polymer
blend and has a density of from 0.940 to 0.965 g/cm.sup.3, a melt
index, I.sub.2 of less than 35 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
2. A bottle closure assembly comprising: a cap portion, an
elongated tether portion, and a retaining means portion, the cap
portion being molded to reversibly engage and cover a bottle
opening, the retaining means portion being molded to irreversibly
engage a bottle neck or an upper portion of a bottle, and the
elongated tether portion being molded to connect at least one point
on the cap portion to at least one point on the retaining means
portion, wherein the cap portion, optionally the elongated tether
portion, and optionally the retaining means portion are made from a
high density polyethylene which is not a polymer blend and has a
density of from 0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of
less than 35 g/10 min, a molecular weight distribution,
M.sub.W/M.sub.n of less than 5.0, and a unimodal profile in a GPC
chromatograph.
3. A bottle closure assembly comprising: an integrally molded: cap
portion, tether portion, and retaining means portion; the cap
portion being molded to reversibly engage and cover a bottle
opening, the retaining means portion being molded to irreversibly
engage a bottle neck or an upper portion of a bottle, and the
tether portion being molded to connect at least one point on the
cap portion to at least one point on the retaining means portion;
wherein the integrally molded: cap portion, tether portion and
retaining means portion are made from a high density polyethylene
which is not a polymer blend and has a density of from 0.940 to
0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 35 g/10 min, a
molecular weight distribution, M.sub.W/M.sub.n of less than 5.0,
and a unimodal profile in a GPC chromatograph.
4. A bottle closure assembly comprising: an integrally molded: cap
portion, elongated tether portion, and retaining means portion; the
cap portion being molded to reversibly engage and cover a bottle
opening, the retaining means portion being molded to irreversibly
engage a bottle neck or an upper portion of a bottle, and the
elongated tether portion being molded to connect at least one point
on the cap portion to at least one point on the retaining means
portion; wherein the integrally molded: cap portion, elongated
tether portion and retaining means portion are made from a high
density polyethylene which is not a polymer blend and has a density
of from 0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less
than 35 g/10 min, a molecular weight distribution, M.sub.W/M.sub.n
of less than 5.0, and a unimodal profile in a GPC
chromatograph.
5. A bottle closure assembly comprising: an integrally molded: cap
portion, elongated tether portion, and retaining collar portion;
the cap portion being molded to reversibly engage and cover a
bottle opening, the retaining collar portion being molded to
irreversibly engage a bottle neck or an upper portion of a bottle,
and the elongated tether portion being molded to connect at least
one point on the cap portion to at least one point on the retaining
collar portion; wherein the integrally molded: cap portion,
elongated tether portion and retaining collar portion are made from
a high density polyethylene which is not a polymer blend and has a
density of from 0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of
less than 35 g/10 min, a molecular weight distribution,
M.sub.W/M.sub.n of less than 5.0, and a unimodal profile in a GPC
chromatograph.
6. A bottle closure assembly comprising: a closure portion, an
elongated tether portion, and a retaining collar portion, the
closure portion being molded to reversibly engage and cover a
bottle opening, the elongated tether portion comprising a tether
strip which is frangibly connected along a portion of its upper
edge to a descending annular edge of the closure portion and which
is frangibly connected along a portion of its lower edge to an
upper annular edge of the retaining collar portion, the tether
strip being integrally formed with and connected at one end to at
least one point on the closure portion and integrally formed with
and connected at another end to at least one point on the retaining
collar portion, the frangible sections being breakable when the
closure portion is removed from a bottle opening, but where the
closure portion remains connected to the retaining collar via the
tether strip; wherein the cap portion, the elongated tether portion
and the retaining collar portion are integrally molded from a high
density polyethylene which is not a polymer blend and has a density
of from 0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less
than 35 g/10 min, a molecular weight distribution, M.sub.W/M.sub.n
of less than 5.0, and a unimodal profile in a GPC
chromatograph.
7. The bottle closure assembly of claim 1 wherein the high density
polyethylene which is not a polymer blend has a melt index, I.sub.2
of less than 15 g/10 min.
8. The bottle closure assembly of claim 2 wherein the high density
polyethylene which is not a polymer blend has a melt index, I.sub.2
of less than 15 g/10 min.
9. The bottle closure assembly of claim 3 wherein the high density
polyethylene which is not a polymer blend has a melt index, I.sub.2
of less than 15 g/10 min.
10. The bottle closure assembly of claim 4 wherein the high density
polyethylene which is not a polymer blend has a melt index, I.sub.2
of less than 15 g/10 min.
11. The bottle closure assembly of claim 5 wherein the high density
polyethylene which is not a polymer blend has a melt index, I.sub.2
of less than 15 g/10 min.
12. The bottle closure assembly of claim 6 wherein the high density
polyethylene which is not a polymer blend has a melt index, I.sub.2
of less than 15 g/10 min.
13. The bottle closure assembly of claim 1 wherein the high density
polyethylene which is not a polymer blend has a molecular weight
distribution, M.sub.W/M.sub.n from about 2.0 to about 4.5.
14. The bottle closure assembly of claim 2 wherein the high density
polyethylene which is not a polymer blend has a molecular weight
distribution, M.sub.W/M.sub.n from about 2.0 to about 4.5.
15. The bottle closure assembly of claim 3 wherein the high density
polyethylene which is not a polymer blend has a molecular weight
distribution, M.sub.W/M.sub.n from about 2.0 to about 4.5.
16. The bottle closure assembly of claim 4 wherein the high density
polyethylene which is not a polymer blend has a molecular weight
distribution, M.sub.W/M.sub.n from about 2.0 to about 4.5.
17. The bottle closure assembly of claim 5 wherein the high density
polyethylene which is not a polymer blend has a molecular weight
distribution, M.sub.W/M.sub.n from about 2.0 to about 4.5.
18. The bottle closure assembly of claim 6 wherein the high density
polyethylene which is not a polymer blend has a molecular weight
distribution, M.sub.W/M.sub.n from about 2.0 to about 4.5.
Description
[0001] This application claims the benefit of the filing date of
U.S. Provisional Application No. 62/607,589, which was filed on
Dec. 19, 2017. The contents of U.S. Provisional Application No.
62/607,589 are incorporated herein by reference in their
entirety.
[0002] The present disclosure is directed to bottle closure
assemblies which are made at least in part with a high density
unimodal polyethylene. The bottle closure assembly includes a cap
portion, a tether portion and a retaining means portion.
[0003] The manufacture of simple one-piece closures using
polyethylene compositions is well known to persons skilled in the
art.
[0004] Bottle closure systems and designs incorporating an
integrated tethering means, which secures a cap portion to a bottle
after the cap portion has been removed from a bottle opening are
also well known. Such designs typically involve molding processes
which present a more complicated and longer flow path for a chosen
plastic material relative to simple one-piece closure designs. As
such, it would be beneficial to make tethered closure systems using
a thermoplastic material which shows good performance in molding
applications, especially those which involve longer and more
tortuous flow paths in a mold. It would also be advantageous, in
some instances, to make a tethered closure system using a material
that has sufficient stress crack resistance and flexibility. In
these embodiments the tethering portion would be both strong enough
to prevent loss of the cap portion once it has been removed from a
bottle opening, and flexible enough to allow the tethering portion
to be formed or bent into suitable closure system designs.
[0005] The present disclosure concerns bottle closure assemblies
that include a cap portion, a tether portion and a retaining means
portion, where the bottle closure assembly is made at least in part
from a high density unimodal polyethylene.
[0006] An embodiment of the present disclosure provides a bottle
closure assembly which includes a cap portion, a tether portion and
a retaining means portion, the bottle closure assembly being made
at least in part from a high density polyethylene which is not a
polymer blend and has a density of from 0.940 to 0.965 g/cm.sup.3,
a melt index, I.sub.2 of less than 35 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1A shows an embodiment of a bottle closure assembly
fitted to a bottle opening and in a "closed" or "sealed" position.
FIG. 1B shows an embodiment of a bottle closure assembly as a cap
portion is rotated in order to bring about its removal from a
bottle opening. FIG. 1C shows an embodiment of a bottle closure
assembly after a cap portion has been removed from a bottle
opening. FIG. 1C shows how an elongated tether portion connects at
least one point on a cap portion to at least one point on a
retaining collar portion once a cap portion has been removed from a
bottle opening.
[0008] FIG. 2A shows an embodiment of a bottle closure assembly
fitted over a bottle opening and before a cap portion has been
removed from a bottle. FIG. 2B shows an embodiment of a bottle
closure assembly after a cap portion has been removed from a bottle
opening. FIG. 2B also shows how an elongated tether portion
connects at least one point on a cap portion to at least one point
on a retaining collar portion once a cap portion has been removed
from a bottle opening, thereby preventing its loss.
[0009] FIG. 3A shows an embodiment of a bottle closure assembly.
FIG. 3B shows an embodiment of a bottle closure assembly after a
cap portion has been removed from a bottle opening. FIG. 3B also
shows how an elongated tether portion connects at least one point
on a cap portion to at least one point on a retaining collar
portion once a cap portion has been removed from a bottle opening,
thereby preventing its loss. FIG. 3C shows how an elongated tether
portion connects at least one point on a cap portion to at least
one point on a retaining collar portion once a cap portion has been
removed from a bottle opening. FIG. 3C further shows that a bottle
can be a carton, a container, or any other suitable containment
vessel which has or is fitted with an aperture or opening which can
be covered or sealed using a bottle closure assembly.
[0010] FIG. 4A shows an embodiment of a bottle closure assembly in
the absence of a bottle. The bottle closure assembly has a cap
portion, an elongated tether portion and a retaining collar
portion. FIG. 4B shows an embodiment of a bottle closure assembly
fitted over a bottle opening and before a cap portion has been
removed from a bottle opening. FIG. 4C shows an embodiment of a
bottle closure assembly after a cap portion has been removed from a
bottle opening.
[0011] FIG. 5A shows an embodiment of a bottle closure assembly in
the absence of a bottle. FIG. 5B shows an embodiment of a bottle
closure assembly as a cap portion is rotated in order to bring
about its removal from a bottle opening.
[0012] FIG. 6A shows an embodiment of a bottle closure assembly
which fits over a bottle opening. FIG. 6B show an embodiment of a
bottle closure assembly after a cap portion has been removed from a
bottle opening. FIG. 6B shows how an elongated tether portion
connects at least one point on a cap portion to at least one point
on a retaining collar portion once a cap portion has been removed
from a bottle opening.
[0013] FIG. 7A shows an embodiment of a bottle closure assembly
fitted to a bottle opening and in a "closed" or "sealed" position.
FIG. 7B shows an embodiment of a bottle closure assembly after a
cap portion has been removed from a bottle opening. FIG. 7B shows
how an elongated tether portion connects at least one point on a
cap portion to at least one point on a retaining collar portion
once a cap portion has been removed from a bottle opening.
[0014] FIG. 8-12. FIGS. 8 through 12 show a gel permeation
chromatograph for the high density polyethylene of Examples 1
through 5 respectively.
[0015] FIG. 13A shows a perspective view of a closure having a
tether proxy. FIG. 13B shows a front elevation view of a closure
having a tether proxy. In FIGS. 13A and 13B a tether proxy connects
a cap portion to a tamper evident band.
[0016] FIG. 14A shows a perspective view of a closure having a
tether proxy after much of the tamper evident band has been
removed. In FIG. 14A a tether proxy connects a cap portion to the
remaining section of the tamper evident band.
[0017] FIG. 14B shows a front elevation partial cross-sectional
schematic view of a closure having a tether proxy and being mounted
on a pre-form for shear deformation testing. Prior to mounting the
closure on the pre-form, much of the tamper evident band was
removed. The tether proxy connects a cap portion to the remaining
section of the tamper evident band. To measure shear deformation of
the tether proxy, the remaining section of the tamper evident band
is clamped in a stationary position to the pre-form, while the cap
portion is rotated within a torque tester, as shown.
[0018] FIG. 14C shows a side elevation partial cross-sectional
schematic view of a closure having a tether proxy and being mounted
on a pre-form for tear deformation testing. The tamper evident band
was deflected down and away from the cap portion, while leaving the
tether proxy intact. The tether proxy connects the cap portion to
the downwardly deflected tamper evident band. To measure tear
deformation of the tether proxy, the downwardly deflected tamper
evident band is clamped in a stationary position to the pre-form,
while the cap portion is rotated within a torque tester, as
shown.
[0019] FIGS. 15A and 15B show a perspective view and a front
elevation view respectively, of a tether proxy after much of the
cap portion and much of the tamper evident band have been removed.
To measure tensile deformation of the tether proxy, the remaining
section of the cap portion and the remaining section of the tamper
evident band are each clamped and then drawn apart in a vertical
direction, within a tensile tester, as shown.
[0020] Any suitable bottle closure assembly design including a cap
portion or a closure portion, a tether portion and a retaining
means portion is contemplated for use in the present disclosure, so
long as it is made at least in part using a high density
polyethylene as described herein. Some specific non-limiting
examples of suitable bottle closure assemblies for use in the
present disclosure are disclosed in U.S. Pat. Nos. 3,904,062;
4,474,302; 4,557,393; 4,564,114; 4,573,602; 4,583,652; 4,805,792;
5,725,115; 8,443,994; 8,720,716; 9,493,283; and 9,776,779; U.S.
Pat. Pub. Nos 2004/0016715 and 2008/0197135; U.S. Design Pat. No.
D593,856; and WO 2015/061834; all of which are incorporated herein
by reference. For further reference, some bottle closure assembly
designs which may be used in embodiments of the present disclosure
are shown in FIGS. 1-7.
[0021] An embodiment of the disclosure is a bottle closure assembly
including: a cap portion, a tether portion, and a retaining means
portion, the cap portion being molded to reversibly engage and
cover a bottle opening, the retaining means portion being molded to
irreversibly engage a bottle neck or an upper portion of a bottle,
and where the tether portion connects at least one point on the cap
portion to at least one point on the retaining means portion,
wherein the cap portion, optionally the tether portion, and
optionally the retaining means portion are made from a high density
polyethylene which is not a polymer blend and has a density of from
0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 35
g/10 min, a molecular weight distribution, M.sub.W/M.sub.n of less
than 5.0, and a unimodal profile in a GPC chromatograph.
[0022] An embodiment of the disclosure is a bottle closure assembly
including: a cap portion, an elongated tether portion, and a
retaining means portion, the cap portion being molded to reversibly
engage and cover a bottle opening, the retaining means portion
being molded to irreversibly engage a bottle neck or an upper
portion of a bottle, and the elongated tether portion being molded
to connect at least one point on the cap portion to at least one
point on the retaining means portion, wherein the cap portion,
optionally the elongated tether portion, and optionally the
retaining means portion are made from a high density polyethylene
which is not a polymer blend and has a density of from 0.940 to
0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 35 g/10 min, a
molecular weight distribution, M.sub.W/M.sub.n of less than 5.0,
and a unimodal profile in a GPC chromatograph.
[0023] An embodiment of the disclosure is a bottle closure assembly
including an integrally molded: cap portion, tether portion, and
retaining means portion; the cap portion being molded to reversibly
engage and cover a bottle opening, the retaining means portion
being molded to irreversibly engage a bottle neck or an upper
portion of a bottle, and the tether portion being molded to connect
at least one point on the cap portion to at least one point on the
retaining means portion; wherein the integrally molded: cap
portion, tether portion and retaining means portion are made from a
high density polyethylene which is not a polymer blend and has a
density of from 0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of
less than 35 g/10 min, a molecular weight distribution,
M.sub.W/M.sub.n of less than 5.0, and a unimodal profile in a GPC
chromatograph.
[0024] An embodiment of the disclosure is a bottle closure assembly
including an integrally molded: cap portion, elongated tether
portion, and retaining means portion; the cap portion being molded
to reversibly engage and cover a bottle opening, the retaining
means portion being molded to irreversibly engage a bottle neck or
an upper portion of a bottle, and the elongated tether portion
being molded to connect at least one point on the cap portion to at
least one point on the retaining means portion; wherein the
integrally molded: cap portion, elongated tether portion and
retaining means portion are made from a high density polyethylene
which is not a polymer blend and has a density of from 0.940 to
0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 35 g/10 min, a
molecular weight distribution, M.sub.W/M.sub.n of less than 5.0,
and a unimodal profile in a GPC chromatograph.
[0025] An embodiment of the disclosure is a bottle closure assembly
including an integrally molded: cap portion, elongated tether
portion, and retaining collar portion; the cap portion being molded
to reversibly engage and cover a bottle opening, the retaining
collar portion being molded to irreversibly engage a bottle neck or
an upper portion of a bottle, and the elongated tether portion
being molded to connect at least one point on the cap portion to at
least one point on the retaining collar portion; wherein the
integrally molded: cap portion, elongated tether portion and
retaining collar portion are made from a high density polyethylene
which is not a polymer blend and has a density of from 0.940 to
0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 35 g/10 min, a
molecular weight distribution, M.sub.W/M.sub.n of less than 5.0,
and a unimodal profile in a GPC chromatograph.
[0026] An embodiment of the disclosure is a bottle closure assembly
including: a cap portion, an elongated tether portion, and a
retaining collar portion, the cap portion being molded to
reversibly engage and cover a bottle opening, the retaining collar
portion being molded to irreversibly engage a bottle neck or an
upper portion of a bottle, the elongated tether portion including a
tether strip which is frangibly connected along a portion of its
upper edge to a descending annular edge of the cap portion and
which is frangibly connected along a portion of its lower edge to
an upper annular edge of the retaining collar portion, the tether
strip being integrally formed with and connected at one end to at
least one point on the cap portion and integrally formed with and
connected at another end to at least one point on the retaining
collar portion, the frangible sections being breakable when the cap
portion is removed from a bottle opening, but where the cap portion
remains connected to the retaining collar portion via the tether
strip; wherein the cap portion, the elongated tether portion and
the retaining collar portion are integrally molded from a high
density polyethylene which is not a polymer blend and has a density
of from 0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less
than 35 g/10 min, a molecular weight distribution, M.sub.W/M.sub.n
of less than 5.0, and a unimodal profile in a GPC
chromatograph.
[0027] An embodiment of the disclosure is a bottle closure assembly
including: a cap portion, an elongated tether portion, and a
retaining collar portion, the cap portion being molded to
reversibly engage and cover a bottle opening, the elongated tether
portion including a tether strip which is frangibly connected along
a portion of its upper edge to a descending annular edge of the cap
portion and which is frangibly connected along a portion of its
lower edge to an upper annular edge of the retaining collar
portion, the tether strip being integrally formed with and
connected at one end to at least one point on the cap portion and
integrally formed with and connected at another end to at least one
point on the retaining collar portion, the frangible sections being
breakable when the cap portion is removed from a bottle opening,
but where the cap portion remains connected to the retaining collar
via the tether strip; wherein the cap portion, the elongated tether
portion and the retaining collar portion are integrally molded from
a high density polyethylene which is not a polymer blend and has a
density of from 0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of
less than 35 g/10 min, a molecular weight distribution,
M.sub.W/M.sub.n of less than 5.0, and a unimodal profile in a GPC
chromatograph.
[0028] An embodiment of the disclosure is a bottle closure assembly
including: a cap portion, a tether portion, and a retaining means
portion, the cap portion being molded to reversibly engage and
cover a bottle opening, the retaining means portion being molded to
irreversibly engage a bottle neck or an upper portion of a bottle,
and where the tether portion connects at least one point on the cap
portion to at least one point on the retaining means portion,
wherein the cap portion, optionally the tether portion, and
optionally the retaining means portion are made from a high density
polyethylene which is not a polymer blend and has a density of from
0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 15
g/10 min, a molecular weight distribution, M.sub.W/M.sub.n of less
than 5.0, and a unimodal profile in a GPC chromatograph.
[0029] When integrally molded the bottle closure assembly presents
long flow paths for a plastic material to fill during
manufacturing. In the present disclosure, the term "integrally
molded" means that that components referred to are molded in a
single continuous mold.
[0030] In some embodiments, the cap portion is molded to reversibly
engage and cover a bottle opening or aperture from which a liquid
or other type of foodstuffs can be dispensed and so is removable
therefrom.
[0031] In some embodiments, the retaining means portion, which, in
some embodiments, may be a retaining collar portion, is generally
not to be removed, or is not easily removable from a bottle and in
some embodiments of the disclosure, the retaining collar engages a
bottle neck, or an upper portion of a bottle.
[0032] In some embodiments, the tether portion, which, in some
embodiments, may be an elongated tether portion, connects at least
one point of the cap portion to at least one point on the retaining
means portion, so that when the cap portion is removed from a
bottle opening, the cap portion remains flexibly fixed to the
bottle via the tether portion and the retaining means portion.
[0033] In the present disclosure, the terms "bottle", "container",
"jar", "carton", "pouch", "package" and the like may be used
interchangeably in the present disclosure. That is, a "bottle
closure assembly" may also be considered a "container closure
assembly", a "jar close assembly", a "carton closure assembly", a
"pouch closure assembly", a "package closure assembly" and the
like. A person skilled in the art will understand that a "bottle
closure assembly" as described in the present disclosure can be
used to close or seal a number of different types of structural
containers having different designs and contours.
[0034] The terms "cap", "closure", "closure portion", "cap portion"
and the like, are used in the present disclosure to connote any
suitably shaped molded article for enclosing, sealing, closing or
covering etc., a suitably shaped opening, a suitably molded
aperture, an open necked structure or the like used in combination
with a container, a bottle, a jar and the like.
[0035] In an embodiment of the disclosure the retaining means
portion can reversibly or irreversible engage a bottle neck, a
shoulder section of a bottle, or an upper portion of a bottle, or a
fitment (e.g. a fitment on a pouch or a carton).
[0036] In an embodiment of the disclosure, the retaining means
portion can also serve as a tamper evident band (TEB).
[0037] In the present disclosure, the term "bottle neck" should be
construed to mean a bottle neck per se but also any sort of similar
or functionally equivalent structure such as a spout, a spigot, a
fitment, or the like.
[0038] In an embodiment of the disclosure the retaining means
portion is molded or shaped to reversibly or irreversible engage a
bottle neck, a shoulder section of a bottle, or an upper portion of
a bottle.
[0039] In an embodiment of the disclosure the retaining means
portion is a retaining collar portion which reversibly or
irreversibly engages a bottle neck, a shoulder section of a bottle,
or an upper portion of a bottle.
[0040] In an embodiment of the disclosure the retaining collar
portion is circularly or annularly shaped so as to reversibly or
irreversibly engage a bottle neck, a shoulder section of a bottle,
or an upper portion of a bottle.
[0041] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, a tether portion and a retaining
means portion where the cap portion, the tether portion and the
retaining means portion are all integrally molded in one piece.
[0042] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, a tether portion and a retaining
collar portion where the cap portion, the tether portion and the
retaining collar portion are all integrally molded in one
piece.
[0043] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, an elongated tether portion and a
retaining means portion where the cap portion, the elongated tether
portion and the retaining means portion are all integrally molded
in one piece.
[0044] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, an elongated tether portion and a
retaining collar portion where the cap portion, the elongated
tether portion and the retaining collar portion are all integrally
molded in one piece.
[0045] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, a tether portion and a retaining
means portion where the cap portion, the tether portion and the
retaining means portion are separately molded.
[0046] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, a tether portion and a retaining
collar portion where the cap portion, the tether portion and the
retaining collar portion are separately molded.
[0047] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, an elongated tether portion and a
retaining means portion where the cap portion, the elongated tether
portion and the retaining means portion are separately molded.
[0048] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, an elongated tether portion and a
retaining collar portion where the cap portion, the elongated
tether portion and the retaining collar portion are separately
molded.
[0049] In embodiments of the disclosure, when separately molded the
cap portion, the tether portion and the retaining means portion may
be fixed together using any means known in the art. For example,
the cap portion, the tether portion and the retaining means portion
may be glued together, or welded together using applied heat,
sonication or other methods known in the art for fusing plastic
materials together.
[0050] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, a tether portion and a retaining
means portion where the cap portion, the tether portion and the
retaining means portion are made from the same or different
materials.
[0051] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, a tether portion and a retaining
collar portion where the cap portion, the tether portion and the
retaining collar portion are made from the same or different
materials.
[0052] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, an elongated tether portion and a
retaining means portion where the cap portion, the elongated tether
portion and the retaining means portion are made from the same or
different materials.
[0053] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion, an elongated tether portion and a
retaining collar portion where the cap portion, the elongated
tether portion and the retaining collar portion are made from the
same or different materials.
[0054] In an embodiment of the present disclosure, the "tether
portion" is of sufficient length and/or has a design which allows
removal of a "cap portion" from a bottle opening while at the same
time preventing the loss of the cap portion by maintaining a
connection between the cap portion and a bottle, container or the
like by forming a connection between at least one point on the cap
portion and at least one point on a "retaining means portion".
[0055] In an embodiment of the present disclosure the tether
portion may be an "elongated tether portion", where "elongated"
means that the tether portion will have at least one dimension
(length) which is larger than at least one other dimension (width
or height/thickness) or vice versa. Or considered another way,
"elongated" means that the tether has a length which is greater
than its width and/or height/thickness.
[0056] In an embodiment of the present disclosure the tether
portion will have dimensions (e.g. width and/or height/thickness)
which offer sufficient strength to prevent facile cleavage or
breakage of the tether when placed under stress or duress, such as
for example when the tether is subjected to bending or flexional
forces. For example, in an embodiment of the disclosure, the tether
will have sufficient width and/or height/thickness so as to prevent
facile breakage of the tether when masticated.
[0057] In an embodiment of the present disclosure, the "elongated
tether portion" is of sufficient length and/or has a design which
allows removal of a "cap portion" from a bottle opening while at
the same time preventing the loss of the cap portion by maintaining
a connection between the cap portion and a bottle, container or the
like by forming a connection between at least one point on the cap
portion and at least one point on a "retaining means portion".
[0058] In embodiments of the disclosure, the retaining means
portion may be a "retaining collar portion" which engages some
portion of a bottle neck or an upper portion of a bottle, container
or the like.
[0059] In embodiments of the disclosure, the retaining means
portion may be a "retaining collar portion" which irreversibly
engages some portion of a bottle neck, a spout, a spigot, a fitment
on a pouch, or the like.
[0060] Alternatively, the retaining means portion may be a
"retaining collar portion" which engages a bottle neck, or an upper
portion of a bottle, container or the like.
[0061] In an embodiment of the disclosure, the retaining collar
portion may rotatably engage a bottle neck, or upper portion of a
bottle, container or the like.
[0062] In an embodiment of the disclosure, the retaining means
portion is a retaining collar portion which is molded to
irreversibly engage a bottle neck or an upper portion of a bottle,
container or the like.
[0063] In an embodiment of the disclosure, the retaining collar
portion is annularly shaped or circularly shaped and can fit over
and engage a bottle neck or an upper portion of a bottle, container
or the like.
[0064] The cap portion may be a single contiguous piece, or it may
itself comprise one or more cap portion structures.
[0065] The tether portion in the present disclosure need not serve
as a hinged connection between a cap portion and a retaining means
portion (such as for example a retaining collar portion), and the
tether portion need not comprise a hinged portion or area, but the
tether portion may in some embodiments of the disclosure comprise a
hinge and when present the hinge may be a so called "living
hinge".
[0066] In an embodiment of the disclosure the elongated tether
portion has a length which is sufficient to allow the cap portion
of the bottle closure assembly to swing or hang out of the way of a
bottle opening, aperture or the like so as not to interfere with
the dispensation of the bottle contents, while at the same time
tethering the cap portion to a bottle via the retaining means
portion.
[0067] The cap portion may itself be a screw cap which threadingly
engages a threaded system on a bottle neck, spigot, spout, valve,
fitment on a pouch, or the like. The cap portion may alternatively
be a snap cap which reversibly engages a bottle neck, spigot, spout
or the like. The cap portion may also reversibly engage a retaining
collar portion in a snap fitting or in a complementary arrangement
of threaded structures. The cap portion may comprise a first cap
portion and a second cap portion, where the first cap portion
engages the second cap portion in a snap fitting, and the second
cap portion engages a bottle neck, or upper portion of a bottle in
a reversible or irreversible manner. For example a second cap
portion may have a threaded structure which threadingly engages a
threaded system on a bottle neck. Alternatively, the second cap
portion may itself engage a bottle neck by any suitable type of
snap fitting. The cap portion may also comprise more than two cap
portions.
[0068] In an embodiment of the disclosure, the bottle closure
assembly includes a cap portion adapted to close an opening in a
bottle or the like by making a frictional engagement with the
opening.
[0069] In an embodiment of the disclosure, the cap portion has
internal threads which mate with external threads surrounding an
opening in a bottle, such as on a bottle neck, spigot, or spout for
example.
[0070] In an embodiment of the disclosure, the retaining collar
portion is adapted to cooperate with a shoulder or a flange on the
neck of a bottle or an upper portion of a bottle which is to be
sealed by the cap portion.
[0071] In an embodiment of the disclosure, the retaining collar
portion is annularly or cylindrically shaped and fits onto the neck
of a bottle and is coupled to the same, using any suitable coupling
means, such as a snap fitting, or a threaded engagement. In an
embodiment, the retaining collar portion is molded to snap fit onto
a bottle neck, bottle aperture, spigot, spout or the like. In an
embodiment, the retaining collar portion may be threaded onto a
bottle neck, bottle aperture, spigot, spout or the like. In an
embodiment the retaining collar portion may itself have an internal
threading system which mates with external threads on a bottle
neck, bottle aperture, spigot, spout or the like. In an embodiment,
the retaining collar portion is dimensioned to be engaged beneath a
flange or shoulder molded into a bottle neck or an upper portion of
a bottle. For example, the retaining collar portion may have an
annular radial dimension which prevents it from moving past an
annular shoulder integrally molded into a bottle neck or into an
upper portion of a bottle. In this case the annular outwardly
extending shoulder on a bottle neck or on an upper portion of a
bottle acts as a camming surface which prevents movement of the
retaining collar toward a bottle opening. Such a shoulder on a
bottle could for example have a tapered outer annular edge which
allows the retaining collar portion to be slipped onto the bottle
in an irreversible manner. In an embodiment of the disclosure,
there may be outwardly extending annularly spaced bosses or the
like on a bottle neck or an upper portion of a bottle, against
which the retaining collar abuts to hold it on to a bottle neck,
bottle aperture, spigot, spout or the like. Persons skilled in the
art will appreciate that other means could be used to secure the
retaining collar portion to a bottle neck, the upper portion of a
bottle, a spout, spigot and the like.
[0072] In an embodiment of the disclosure, the elongated tether
portion includes a connecting strip having a first end connected to
a least one point of the cap portion and a second end connected to
at least one point of the retaining collar portion, a lower edge
and an upper edge, wherein when the cap portion is fitted on to a
bottle opening, the connecting strip at least partially encircles a
bottle neck, spout, or the like between the cap portion and the
retaining collar portion, and where at least a portion of the upper
edge of the connecting strip is frangibly connected to a lower edge
of the cap portion, and where at least a portion of the lower edge
of the connecting strip is frangibly connected to an upper edge of
the retaining collar portion, and where when the cap portion is
removed from a bottle opening by breaking the frangible connections
between the cap portion, the connecting strip and the retaining
collar portion, the cap portion remains secured to retaining collar
portion and the bottle via the connecting strip.
[0073] In an embodiment the elongated tether portion is a
cylindrically adapted connecting strip which at least partially
encircles a bottle neck, spout, or the like and is located between
the cap portion and the retaining collar portion prior to removal
of the cap portion form a bottle opening.
[0074] In an embodiment the elongated tether portion has a first
end which is connected to at least one point on the cap portion and
a second end which is connected to at least one point on the
retaining collar portion.
[0075] In an embodiment, the cap portion, the elongated tether
portion and the retaining collar portion are integrally molded so
that the elongated tether portion has a first end which is
connected to at least one point on the cap portion and a second end
which is connected to at least one point on the retaining
collar.
[0076] In an embodiment, the cap portion, the elongated tether
portion and the retaining collar portion are integrally molded so
that the elongated tether portion has a first end which is
connected to at least one point on the cap portion and a second end
which is connected to at least one point on the retaining collar
portion, and wherein the elongated tether portion has an upper edge
and a lower edge, where at least a portion of the upper edge is
frangibly connected to a lower edge of the cap portion, and at
least a portion of the lower edge is frangibly connected to an
upper edge of the retaining collar portion, the frangibly connected
portions being breakable when the closure is removed from a bottle
opening.
[0077] In an embodiment of the disclosure, the frangible
connections or frangibly connected portions are regularly or
irregularly spaced molded sections (e.g. pins) having a dimension
suitably small to allow facile breakage.
[0078] Frangible connections or frangibly connected portions can
also be thought of as defining a weakening line along which the
elongated tethering portion can be separated from the cap portion
and the retaining collar portion. Such weakening lines can be
generally defined as open sections alternating with bridging
sections, where the bridging sections have a dimension suitably
small to allow facile breakage. Alternatively, the weakening lines
are defined by lines of plastic which have been made thin enough to
break under stress.
[0079] In an embodiment of the disclosure, a single piece of a
molded plastic having a suitable shape, is purposely weakened (by
for example, regular or irregularly spaced cuts) along
predetermined lines to define a cap portion, an elongated tether
portion and a retaining collar portion, wherein the cap portion is
shaped to reversibly engage and cover a bottle opening, the
retaining means portion is shaped to irreversibly engage a bottle
neck or an upper portion of a bottle, and where the elongated
tether portion connects at least one point on the cap portion to at
least one point on the retaining means portion.
[0080] In an embodiment of the disclosure, the bottle closure
assembly includes an upper cap portion, an intermediate elongate
tethering portion, and a lower retaining collar portion, where the
intermediate elongate tethering portion has a first end permanently
connected to at least one point of the upper cap portion and a
second end permanently connected to at least one point on the lower
retaining collar portion, wherein the intermediate elongate
tethering portion is'partially joined to a lower annular edge of
the upper cap portion along a first peripheral weakening line and
the intermediate elongate tethering portion is partially joined to
an upper annular edge of the lower retaining collar portion along a
second peripheral weakening line, wherein removal of the upper cap
portion from a bottle separates the upper cap portion from the
intermediate elongate tethering portion along the first peripheral
weakening line and separates the lower retaining collar portion
from the intermediate elongate tethering portion along the second
weakening line, while maintaining a linkage between the upper cap
portion and the lower retaining collar portion through the
intermediate elongate tethering portion.
[0081] In an embodiment of the disclosure, and with reference to
FIGS. 1A-1C, the bottle closure assembly includes: an upper cap
portion, 1 dimensioned to reversibly cover and close a bottle
opening, a lower retaining collar portion, 10 dimensioned to
irreversibly engage a bottle neck, or an upper portion of a bottle,
and an elongated tether portion, 5 being dimensioned as a strip
which at least partially encircles a bottle neck between the upper
cap portion and the lower retaining collar portion, the strip
including a first end, a second end, an upper edge and a lower
edge, the upper edge of which is in part contiguous with the upper
cap portion, the lower edge of which is in part contiguous with the
lower retaining collar portion, whereby removal of the upper cap
portion from a bottle (by for example rotation about a threaded
system on the bottle neck) separates the elongated tether portion
from the upper cap portion and the lower retaining collar portion,
while at the same time leaving the upper cap portion attached to
the lower retaining collar via the elongated tether portion.
[0082] In an embodiment of the disclosure, and with reference to
FIGS. 2A and 2B, the bottle closure assembly includes: an upper cap
portion, 1 dimensioned to reversibly cover and close a bottle
opening, 2 a lower retaining collar portion, 10 dimensioned to
irreversibly engage a bottle neck, 3 or an upper portion of a
bottle, and an elongated tether portion, 5 being dimensioned as a
strip which at least partially encircles a bottle neck between the
upper cap portion and the lower retaining collar portion, the strip
including a first end, 6 a second end, 7 an upper edge, 11 and a
lower edge, 12, the upper edge of which is in part frangibly
attached, 8 to the upper cap portion, and in part contiguous with
the upper cap portion, the lower edge of which is in part frangibly
attached, 9 to the lower retaining collar portion and in part
contiguous with the lower retaining collar portion, whereby removal
of the upper cap portion from a bottle will rupture the frangible
attachments while leaving the upper cap portion attached to the
lower retaining collar portion via the elongated tether portion. In
an embodiment and with reference to FIG. 2B, the bottle opening may
have peripheral threads, 15 which engage threads on the inside of
the cap portion.
[0083] In an embodiment of the disclosure, and with reference to
FIGS. 3A-3C, the bottle closure assembly includes: an upper cap
portion, 1 dimensioned to reversibly cover and close a bottle
opening, a lower retaining collar portion, 10 dimensioned to
irreversibly engage a bottle neck, 3 or an upper portion of a
bottle, and an elongated tether portion, 5 being dimensioned as a
strip which at least partially encircles a bottle neck between the
upper cap portion and the lower retaining collar portion, the strip
having a first end, 6 a second end, 7 an upper edge, and a lower
edge, the upper edge of which is in part frangibly attached to the
upper cap portion by frangible elements, 20 (such as for example
breakable pins), and in part contiguous with the upper cap portion,
the lower edge of which is in part frangibly attached to the lower
retaining collar portion by frangible elements, 20 (such as for
example breakable pins) and in part contiguous with the lower
retaining collar portion, whereby removal of the upper cap portion
from a bottle opening will rupture the frangible attachments while
leaving the upper cap portion attached to the lower retaining
collar portion via the elongated tether portion, 5. In an
embodiment and with reference to FIG. 3B, the bottle neck and
opening may have peripheral threads, 15 which engage threads on the
inside of the cap portion.
[0084] In an embodiment of the disclosure, and with reference to
FIGS. 4A-4C, the bottle closure assembly includes a cap portion, 1,
an elongated tether portion, 5, and a retaining collar portion,
10.
[0085] In an embodiment of the disclosure, and with reference to
FIGS. 5A and 5B, the bottle closure assembly includes: a cap
portion, 1 a tether portion, 5 and a retaining means portion, 10
the cap portion being molded to reversibly engage and cover a
bottle opening, the retaining means portion being molded to
irreversibly engage a bottle neck or an upper portion of a bottle,
18 and the tether portion being molded to connect at least one
point on the cap portion to at least one point on the retaining
means portion, the cap portion and the retaining collar portion
extending coaxially with each other, the tether portion including a
tabbed tether strip which is integrally formed with and secured at
its respective ends (6 and 7) to the cap portion and the retaining
collar portion, the tether strip being joined to the cap portion
and the retaining collar along a preselected length of the tether
strip to be manually separated from the cap portion and the
retaining collar portion by frangible elements, 20 of a preselected
thickness to permit the elongated tether strip to be manually
separated from the cap portion and the retaining collar portion
along the pre-selected length, the tether strip being of such
length so as to permit the cap portion to be removed from a bottle
opening while at the same remaining attached to the bottle via the
tether strip and the retaining collar. In an embodiment and as
shown in FIG. 5B, a cap portion may have a circular top wall, 16
and a descending annular side wall 17.
[0086] In an embodiment of the disclosure the bottle closure
assembly includes: a cap portion having a top wall and a side wall,
an elongated tether portion, and a retaining collar portion, the
cap portion being molded to reversibly engage and cover a bottle
opening, the retaining collar portion being annular and being
molded to irreversibly engage a ridge or flange on a bottle neck or
on an upper portion of a bottle, and the elongated tether portion
being integrally molded with the cap portion and the retaining
collar portion to connect at least one point on the cap side wall
to at least one point on the retaining collar portion, wherein the
elongated tether portion runs between the cap side wall and the
retaining collar portion along the circumference of the cap portion
when the cap portion is on a bottle and the elongated tether
portion connects at least one point on the cap side wall to at
least one point on the retaining collar portion when the cap
portion is removed from a bottle.
[0087] In an embodiment of the disclosure, and with reference to
FIGS. 6A and 6B, the bottle closure assembly includes an upper cap
portion, 1 an intermediate elongate tethering portion, 5 and a
lower retaining collar portion, 10 where the intermediate elongate
tethering portion has a first end permanently connected to at least
one point of the upper cap portion and a second end permanently
connected to at least one point on the lower retaining collar
portion, wherein the intermediate elongate tethering portion is
partially joined to a lower annular edge of the upper cap portion
along a first peripheral weakening line defined by perforations, 25
and the intermediate elongate tethering portion is partially joined
to an upper annular edge of said lower retaining collar portion
along a second peripheral weakening line defined by perforations,
25 wherein removal of the upper cap portion from a bottle separates
the upper cap portion from the tethering portion along the first
peripheral weakening line and separates the lower retaining collar
portion from the tethering portion along the second weakening line,
while maintaining a linkage between the upper cap portion and the
lower retaining collar portion through the intermediate elongated
tethering portion.
[0088] In an embodiment of the disclosure and with reference to
FIGS. 6A and 6B, a bottle neck 3, may have an annular groove 28,
which presents a flange onto which the cap portion, 1 may
reversibly engage in a snap fit arrangement. In an embodiment and
with reference to FIGS. 6A and 6B a bottle neck may have an
outwardly extended annular flange, 29 which prevents a retaining
collar portion, 10 from being removed from a bottle neck.
[0089] In an embodiment of the disclosure, and with reference to
FIGS. 7A and 7B, the bottle closure assembly includes a cap
portion, 1, an elongated tether portion, 5, and a retaining collar
portion, 10. The elongated tether portion connects at least one
point of the cap portion at a first end, 6 to at least one point of
the retaining collar portion at a second end, 7. The elongated
tether portion may be further joined to the cap portion along a
frangible connection 8. The elongated tether portion may be further
joined to the retaining collar portion along a frangible connection
9. Separation of the cap portion from the elongated tether portion
along a frangible connection 8 along with separation of the
retaining collar portion from the elongated tether portion along a
frangible connection 9, allows removal of the cap portion from a
bottle opening while at the same time securing it to the bottle via
the elongated tether portion and the retaining collar portion.
[0090] In an embodiment of the disclosure, the bottle closure
assembly includes: a cap portion, the cap portion being dimensioned
to cover and close a bottle opening, a retaining collar portion,
and an elongated tether portion which forms an elastic connection
between at least one point on the cap portion and at least one
point on the retaining collar portion.
[0091] In an embodiment of the disclosure, the retaining means
portion is integrally molded into a bottle, container or the
like.
[0092] In an embodiment of the disclosure, the retaining collar
portion is integrally molded into a bottle, container or the
like.
[0093] In an embodiment of the disclosure, the tether portion fixes
the cap portion to the retaining collar portion which remains
secured to the bottle, making it difficult to separate the cap
portion from the bottle, thereby preventing its loss, while at the
same time allowing rotation of the cap portion for facile removal
and replacement of the same from and onto a bottle opening.
[0094] In an embodiment of the present disclosure, the bottle
closure assembly is made in part or in full using a high density
polyethylene which is not a polymer blend and has a density of from
0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 35
g/10 min, a molecular weight distribution, M.sub.W/M.sub.n of less
than 5.0, and a unimodal profile in a GPC chromatograph.
[0095] In an embodiment of the disclosure the cap portion,
optionally the tether portion, and optionally the retaining collar
portion are made from a high density polyethylene which is not a
polymer blend and has a density of from 0.940 to 0.965 g/cm.sup.3,
a melt index, I.sub.2 of less than 35 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
[0096] In an embodiment of the disclosure, the cap portion, the
tether portion, and the retaining collar portion are all integrally
molded from a high density polyethylene which is not a polymer
blend and has a density of from 0.940 to 0.965 g/cm.sup.3, a melt
index, I.sub.2 of less than 35 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
[0097] In an embodiment of the present disclosure, the bottle
closure assembly is made in part or in full using a high density
polyethylene which is not a polymer blend and has a density of from
0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 30
g/10 min, a molecular weight distribution, M.sub.W/M.sub.n of less
than 5.0, and a unimodal profile in a GPC chromatograph.
[0098] In an embodiment of the disclosure the cap portion,
optionally the tether portion, and optionally the retaining collar
portion are made from a high density polyethylene which is not a
polymer blend and has a density of from 0.940 to 0.965 g/cm.sup.3,
a melt index, I.sub.2 of less than 30 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
[0099] In an embodiment of the disclosure, the cap portion, the
tether portion, and the retaining collar portion are all integrally
molded from a high density polyethylene which is not a polymer
blend and has a density of from 0.940 to 0.965 g/cm.sup.3, a melt
index, I.sub.2 of less than 30 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
[0100] In an embodiment of the present disclosure, the bottle
closure assembly is made in part or in full using a high density
polyethylene which is not a polymer blend and has a density of from
0.940 to 0.965 g/cm.sup.3, a melt index, I.sub.2 of less than 15
g/10 min, a molecular weight distribution, M.sub.W/M.sub.n of less
than 5.0, and a unimodal profile in a GPC chromatograph.
[0101] In an embodiment of the disclosure the cap portion,
optionally the tether portion, and optionally the retaining collar
portion are made from a high density polyethylene which is not a
polymer blend and has a density of from 0.940 to 0.965 g/cm.sup.3,
a melt index, I.sub.2 of less than 15 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
[0102] In an embodiment of the disclosure, the cap portion, the
tether portion, and the retaining collar portion are all integrally
molded from a high density polyethylene which is not a polymer
blend and has a density of from 0.940 to 0.965 g/cm.sup.3, a melt
index, I.sub.2 of less than 15 g/10 min, a molecular weight
distribution, M.sub.W/M.sub.n of less than 5.0, and a unimodal
profile in a GPC chromatograph.
[0103] Suitable high density unimodal polyethylene for use in the
manufacture of part or all of the bottle closure assembly are
described in more detail below.
[0104] In an embodiment of the present disclosure, the high density
polyethylene is not a polymer blend. The phrase "polymer blend" as
used in the present disclosure means a polyethylene composition
which is comprised of at least two major different polymer
composition components (by "major" it is meant that each of the
different polymers comprise at least 5 or more weight percent of
the total weight of the polymer blend). That is, in an embodiment
of the disclosure, the high density polyethylene is neither the
result of in situ reactor blending of different polymers (including
those made with multiple catalysts and/or different reactors
operating under different conditions) or dry blending or melt
blending methods.
[0105] In an embodiment of the present disclosure, the high density
polyethylene has a density from 0.940 to 0.967 g/cm.sup.3. In
further embodiments of the present disclosure, the high density
polyethylene has a density of from 0.940 to 0.965 g/cm.sup.3, or
from 0.949 to 0.963 g/cm.sup.3.
[0106] In an embodiment of the disclosure, the high density
polyethylene has a melt index, I.sub.2 as determined according to
ASTM D1238 (2.16 kg/190.degree. C.) of less than about 35 g/10
min.
[0107] In an embodiment of the disclosure, the high density
polyethylene has a melt index, I.sub.2 as determined according to
ASTM D1238 (2.16 kg/190.degree. C.) of less than about 30 g/10 min.
In further embodiments of the disclosure, the high density
polyethylene has a melt index, I.sub.2 as determined according to
ASTM D1238 (2.16 kg/190.degree. C.) of less than about 28 g/10 min,
or less than about 26 g/10 min, or less than about 24 g/10 min, or
less than about 22 g/10 min, or less than about 20 g/10 min, or
less than about 18 g/10 min, or less than about 15 g/10 min, or
less than about 10 g/10 min.
[0108] In an embodiment of the disclosure, the high density
polyethylene has a melt index, I.sub.2 as determined according to
ASTM D1238 (2.16 kg/190.degree. C.) of from 0.5 to less than 10.0
g/10 min. In further embodiments of the disclosure, the high
density polyethylene has a melt index, I.sub.2 as determined
according to ASTM D1238 (2.16 kg/190.degree. C.) of from 0.5 to 9.5
g/10 min, or from 1.0 to 9.0 g/10 min, or from 2.5 to 7.5 g/10 min,
or from 2.0 to 9.5 g/10 min, or from 2.5 to 9.5 g/10 min.
[0109] In an embodiment of the disclosure, the high density
polyethylene has a melt index, I.sub.2 as determined according to
ASTM D1238 (2.16 kg/190.degree. C.) of at least 10.0 g/10 min.
[0110] In an embodiment of the disclosure, the high density
polyethylene has a melt index, I.sub.2 as determined according to
ASTM D1238 (2.16 kg/190.degree. C.) of from 10.0 to 30.0 g/10 min.
In further embodiments of the disclosure, the high density
polyethylene has a melt index, I.sub.2 as determined according to
ASTM D1238 (2.16 kg/190.degree. C.) of from greater than 10.0 to
28.0 g/10 min, or from greater than 10.0 to 26.0 g/10 min, or from
greater than 10.0 to 24.0 g/10 min, or from greater than 10.0 to
22.0 g/10 min, or from greater than 10.0 to 20.0 g/10 min, or from
greater than 10.0 to 19.5 g/10 min, or from 10.0 to 28.0 g/10 min,
or from 10.0 to 26.0 g/10 min, or from 10.0 to 24.0 g/10 min, or
from 10.0 to 22.0 g/10 min, or from 10.0 to 20.0 g/10 min, or from
10.0 to 19.5 g/10 min.
[0111] In an embodiment of the disclosure, the high density
polyethylene has a melt flow ratio (MFR) defined by
I.sub.21/I.sub.2 of less than about 40. In further embodiments of
the disclosure, the high density polyethylene has a melt flow
ratio, I.sub.21/I.sub.2 of less than about 30, or from about 15 to
about 30, or from about 20 to about 30.
[0112] In an embodiment of the present disclosure, the high density
polyethylene has a unimodal profile in a gel permeation
chromatograph obtained according to the method of ASTM D6474-99.
The term "unimodal" is herein defined to mean there will be only
one significant peak or maximum evident in the GPC-curve. A
unimodal profile includes a broad unimodal profile. Alternatively,
the term "unimodal" connotes the presence of a single maxima in a
molecular weight distribution curve generated according to the
method of ASTM D6474-99. In contrast, by the term "bimodal" it is
meant that there will be a secondary peak or shoulder evident in a
GPC-curve which represents a higher or lower molecular weight
component (i.e. the molecular weight distribution, can be said to
have two maxima in a molecular weight distribution curve).
Alternatively, the term "bimodal" connotes the presence of two
maxima including peaks and/or shoulders in a molecular weight
distribution curve generated according to the method of ASTM
D6474-99. The term "multi-modal" denotes the presence of two or
more maxima including peaks and/or shoulders in a molecular weight
distribution curve generated according to the method of ASTM
D6474-99.
[0113] In an embodiment of the present disclosure, the high density
polyethylene has an environmental stress cracking resistance (ESCR)
Condition B (10% IGEPAL) of at least 1 hour.
[0114] In an embodiment of the present disclosure, the high density
polyethylene has an ESCR Condition B (10% IGEPAL) of from 1 to 10
hours.
[0115] IGEPAL.RTM. CO-630 is a polyoxyethylene (9) nonylphenylether
available from SIGMA-ALDRICH.RTM. which has a M.sub.n of 617 the
structure below.
##STR00001##
[0116] In an embodiment of the disclosure, the high density
polyethylene has a weight average molecular weight (Mw) from about
20,000 to about 100,000. In other embodiments of the disclosure the
high density polyethylene has a weight average molecular weight
(Mw) from about 25,000, to about 85,000, or from about 30,000 to
about 85,000, or from about 35,000 to about 80,000, or from about
40,000 to about 80,000, or from about 40,000 to about 75,000, or
from about 45,000 to about 80,000, or from 50,000 to 75,000, or
from 55,000 to 75,000.
[0117] In an embodiment of the disclosure, the high density
polyethylene has a molecular weight distribution (M.sub.w/M.sub.n)
of less than about 5.0. In further embodiments of the disclosure,
the high density polyethylene has a molecular weight distribution
(M.sub.w/M.sub.n) of less than about 4.5, or less than about 4.0,
or less than about 4.0, or less than about 3.5, or less than about
3.0, or from about 2.0 to about 5.0, or from about 2.0 to about
4.5, or from about 2.0 to about 4.0, or from about 2.0 to about
3.5, or from about 2.5 to about 4.0, or from about 2.5 to about
3.5.
[0118] In an embodiment of the disclosure, the high density
polyethylene has a z-average molecular weight (Mz) from about
75,000 to about 450,000. In other embodiments of the disclosure the
high density polyethylene has a weight average molecular weight
(M.sub.Z) from about 100,000, to about 400,000, or from about
100,000 to about 350,000, or from about 75,000 to about 300,000, or
from about 75,000 to about 250,000, or from about 100,000 to about
250,000, or from about 75,000 to 225,000, or from about 75,000 to
about 200,000, or from about 100,000 to about 225,000, or less than
about 450,000, or less than about 400,000, or less than about
350,000, or less than about 300,000, or less than about 250,000, or
less than about 200,000.
[0119] In an embodiment of the disclosure, the high density
polyethylene has a Z-average molecular weight distribution
(M.sub.Z/M.sub.W) of less than about 4.5. In further embodiments of
the disclosure, the high density polyethylene has a z-average
molecular weight distribution (M.sub.Z/M.sub.W) of less than about
4.0, or less than about 3.5, or less than about 3.0, or from about
2.0 to about 4.5, or from about 2.5 to about 4.0, or from about 2.0
to about 3.5.
[0120] In an embodiment of the disclosure, the high density
polyethylene has an amount of terminal unsaturation of at least
0.35 per 1000 carbons (or per 1000 carbon atoms), or at least 0.40
per 1000 carbons, or at least 0.45 per 1000 carbons, or greater
than 0.45 per 1000 carbons, or at least 0.50 per 1000 carbons, or
greater than 0.50 per 1000 carbons, or at least 0.55 per 1000
carbons, or greater than 0.55 per thousand carbons, or at least
0.60 per 1000 carbons, or greater than 0.60 per 1000 carbons, or at
least 0.65 per 1000 carbons, or greater than 0.65 per 1000 carbons,
or at least 0.70 per 1000 carbons, or greater than 0.70 per 1000
carbons.
[0121] In an embodiment of the disclosure, the high density
polyethylene has a total amount of unsaturation (which includes
internal, side chain, and terminal unsaturation) of at least 0.40
per 1000 carbons (or per 1000 carbon atoms), or at least 0.45 per
1000 carbons, or at least 0.50 per 1000 carbons, or greater than
0.50 per 1000 carbons, or at least 0.55 per 1000 carbons, or
greater than 0.55 per 1000 carbons, or at least 0.60 per 1000
carbons, or greater than 0.60 per thousand carbons, or at least
0.65 per 1000 carbons, or greater than 0.65 per 1000 carbons, or at
least 0.70 per 1000 carbons, or greater than 0.70 per 1000 carbons,
or at least 0.75 per 1000 carbons, or greater than 0.75 per 1000
carbons.
[0122] In an embodiment of the present disclosure, the high density
polyethylene is an ethylene homopolymer.
[0123] As used herein, the term "homopolymer" is meant to convey
its conventional meaning, that the polymer is prepared using only
ethylene as a deliberately added polymerizable monomer.
[0124] In an embodiment of the present disclosure, the high density
polyethylene is a polyethylene copolymer.
[0125] By the term "ethylene copolymer" or "polyethylene
copolymer", it is meant that the product polymer is the product of
a polymerization process, where ethylene and one or more than one
comonomer were deliberately added or was deliberately present as
polymerizable olefins.
[0126] In an embodiment of the disclosure the high density
polyethylene is a polyethylene copolymer of ethylene and one or
more than one alpha olefin.
[0127] Suitable alpha olefin comonomers for polymerization with
ethylene to make the high density polyethylene include 1-butene,
1-hexene and 1-octene.
[0128] Examples of polyethylene homopolymers which are useful as
the high density polyethylene in the present disclosure are
SCLAIR.RTM. 2908 and SCLAIR.RTM. 2907 which are commercially
available from NOVA Chemicals Corporation. Examples of polyethylene
copolymers which are useful as the high density polyethylene in the
present disclosure are SCLAIR.RTM. 2710 and SCLAIR.RTM. 2807 which
are commercially available from NOVA Chemicals Corporation.
[0129] In an embodiment of the disclosure the polyethylene
copolymer includes from about 0.1 to about 5 weight %, in some
cases less than about 3 weight %, in other instances less than
about 1.5 weight % of an alpha olefin chosen from 1-butene,
1-hexene, 1-octene and mixtures thereof.
[0130] In an embodiment of the disclosure, the polyethylene
copolymer includes polymerized ethylene and 1-butene.
[0131] In an embodiment of the disclosure, the polyethylene
copolymer has a density of from about 0.945 to about 0.960
g/cm.sup.3 as determined according to ASTM D 792. In other
embodiments of the disclosure the polyethylene copolymer has a
density of from about 0.948 to about 0.958 g/cm.sup.3, or from
about 0.949 g/cm.sup.3 to about 0.955 g/cm.sup.3.
[0132] Examples of polyethylene copolymers which are useful as the
high density polyethylene in the present disclosure include by way
of non-limiting example, SCLAIR.RTM. 2710, and SCLAIR.RTM. 2807,
each of which is commercially available from NOVA Chemicals
Corporation.
[0133] In an embodiment of the disclosure, the polyethylene
homopolymer has a density from about 0.955 to about 0.967
g/cm.sup.3 as determined according to ASTM D 792. In other
embodiments of the disclosure the polyethylene homopolymer has a
density of from about 0.958 to about 0.965 g/cm.sup.3, or from
about 0.958 to about 0.963 g/cm.sup.3, or from about 0.959 to 0.963
g/cm.sup.3.
[0134] Examples of polyethylene homopolymers which are useful as
the high density polyethylene in the present disclosure include by
way of non-limiting example, SCLAIR.RTM. 2907, and SCLAIR.RTM.2908,
each of which is commercially available from NOVA Chemicals
Corporation.
[0135] In an embodiment of the disclosure, the high density
polyethylene suitable for use in the present disclosure may be
prepared using conventional polymerization processes, non-limiting
examples of which include gas phase, slurry and solution phase
polymerization processes. Such processes are well known to those
skilled in the art.
[0136] In an embodiment of the disclosure, the high density
polyethylene may be prepared using conventional catalysts. Some
non-limiting examples of conventional catalysts include chrome
based catalysts and Ziegler-Natta catalysts. Such catalysts are
well known to those skilled in the art.
[0137] Solution and slurry phase polymerization processes are
generally conducted in the presence of an inert hydrocarbon
solvent/diluent, such for example, a C.sub.4-12 hydrocarbon which
may be unsubstituted or substituted by a C.sub.1-4 alkyl group,
such as, butane, pentane, hexane, heptane, octane, cyclohexane,
methylcyclohexane or hydrogenated naphtha. A non-limiting example
of a commercial solvent is Isopar E (C.sub.8-12 aliphatic solvent,
Exxon Chemical Co.). The monomers are dissolved in the
solvent/diluent.
[0138] A slurry polymerization process may be conducted at
temperatures of from about 20.degree. C. to about 180.degree. C.,
or from 80.degree. C. to about 150.degree. C., and the polyethylene
composition being made is insoluble in the liquid hydrocarbon
diluent.
[0139] A solution polymerization process may be conducted at
temperatures of from about 180.degree. C. to about 250.degree. C.,
or from about 180.degree. C. to about 230.degree. C., and the
polyethylene composition being made is soluble in the liquid
hydrocarbon phase (e.g. the solvent).
[0140] A gas phase polymerization process can be carried out in
either a fluidized bed or a stirred bed reactor. A gas phase
polymerization typically involves a gaseous mixture including from
about 0 to about 15 mole % of hydrogen, from about 0 to about 30
mole % of one or more C.sub.3-8 alpha-olefins, from about 15 to
about 100 mole % of ethylene, and from about 0 to about 75 mole %
of an inert gas at a temperature from about 50.degree. C. to about
120.degree. C., or from about 75.degree. C. to about 110.degree.
C.
[0141] Suitable alpha olefins which may be polymerized with
ethylene in the case of a polyethylene copolymer are C.sub.3-8
alpha olefins such as one or more of 1-butene, 1-hexene, and
1-octene.
[0142] In an embodiment of the disclosure the high density
polyethylene is made in a solution phase polymerization
reactor.
[0143] In an embodiment of the disclosure the high density
polyethylene is prepared by contacting ethylene and optionally an
alpha-olefin with a polymerization catalyst under solution
polymerization conditions.
[0144] In an embodiment of the disclosure the high density
polyethylene is made with a Ziegler-Natta polymerization
catalyst.
[0145] In an embodiment of the disclosure the high density
polyethylene is made in a single solution phase polymerization
reactor.
[0146] In an embodiment of the disclosure, the high density
polyethylene is made in a solution polymerization process using a
Ziegler-Natta catalyst.
[0147] In an embodiment of the disclosure the high density
polyethylene is made in a single solution phase polymerization
reactor using a Ziegler-Natta catalyst.
[0148] The term "Ziegler-Natta" catalyst is well known to those
skilled in the art and is used herein to convey its conventional
meaning. Ziegler-Natta catalysts comprise at least one transition
metal compound of a transition metal selected from groups 3, 4, or
5 of the Periodic Table (using IUPAC nomenclature) and an
organoaluminum component that is defined by the formula:
AI(X').sub.a(OR).sub.b(R).sub.c
wherein: X' is a halide (for example chlorine); OR is an alkoxy or
aryloxy group; R is a hydrocarbyl (for example an alkyl having from
1 to 10 carbon atoms); and a, b, or c are each 0, 1, 2, or 3 with
the provisos, a+b+c=3 and b+c+c.gtoreq.1. As will be appreciated by
those skilled in the art of ethylene polymerization, conventional
Ziegler-Natta catalysts may also incorporate additional components
such as an electron donor. For example, an amine or a magnesium
compound or a magnesium alkyl such as butyl ethyl magnesium and a
halide source (which is typically a chloride such as tertiary butyl
chloride). Such components, if employed, may be added to the other
catalyst components prior to introduction to the reactor or may be
added directly to the reactor. The Ziegler-Natta catalyst may also
be "tempered" (i.e. heat treated) prior to being introduced to the
reactor (again, using techniques which are well known to those
skilled in the art and published in the literature).
[0149] In an embodiment of the disclosure, the high density
polyethylene has less than 1.5 ppm, or less than 1.3 ppm, or
.ltoreq.1.0 ppm, or .ltoreq.0.9 ppm, or .ltoreq.0.8, or less than
0.8 ppm, or .ltoreq.0.75 ppm, or less than 0.50 ppm of titanium
(Ti) present.
[0150] In an embodiment of the disclosure, the high density
polyethylene has less than 1.5 ppm, or less than 1.3 ppm, or
.ltoreq.1.0 ppm, or .ltoreq.0.9 ppm, or .ltoreq.0.8 ppm, or
.ltoreq.0.75, or .ltoreq.0.60 ppm of aluminum (Al) present.
[0151] In an embodiment of the disclosure, the high density
polyethylene has less than 0.5 ppm, or less than 0.4 ppm, or
.ltoreq.0.3 ppm, or .ltoreq.0.2 ppm, or 5. 0.15 ppm, or .ltoreq.0.1
ppm, of chlorine (Cl) present.
[0152] In an embodiment of the disclosure, the high density
polyethylene has less than 4.0 ppm, or less than 3.0 ppm, or
.ltoreq.2.5 ppm, or .ltoreq.2.0 ppm, of magnesium (Mg) present.
[0153] In an embodiment of the disclosure, the high density
polyethylene has less than 0.4 ppm, or less than 0.3 ppm, or
.ltoreq.0.25 ppm, or .ltoreq.0.20 ppm, of chromium (Cr)
present.
[0154] In an embodiment of the disclosure the high density
polyethylene includes one or more nucleating agents.
[0155] In an embodiment of the disclosure the high density
polyethylene includes a nucleating agent or a mixture of nucleating
agents.
[0156] The high density polyethylene may be compounded or
dry-blended either by a manufacturer or a converter (e.g., the
company converting the resin pellets into the final product). The
compounded or dry-blended high density polyethylene may contain
fillers, pigments and other additives. Typically, fillers are inert
additives, such as, clay, talc, TiO.sub.2 and calcium carbonate,
which may be added to the high density polyethylene in amounts from
about 0 weight % up to about 50 weight %, in some cases, less than
30 weight % of fillers are added. The compounded or dry-blended
high density polyethylene may contain antioxidants, heat and light
stabilizers, such as, combinations of one or more of hindered
phenols, phosphates, phosphites and phosphonites, typically, in
amounts of less than about 0.5 weight % based on the weight of the
polyethylene compositions. Pigments may also be added to the high
density polyethylene in small amounts. Non-limiting examples of
pigments include carbon black, phthalocyanine blue, Congo red,
titanium yellow, etc.
[0157] The high density polyethylene may contain a nucleating agent
or a mixture of nucleating agents in amounts of from about 5 parts
per million (ppm) to about 10,000 ppm based on the weight of the
polyethylene polymer. The nucleating agent may be chosen from
dibenzylidene sorbitol, di(p-methyl benzylidene) sorbitol,
di(o-methyl benzylidene) sorbitol, di(p-ethylbenzylidene) sorbitol,
bis(3,4-dimethyl benzylidene) sorbitol, bis(3,4-diethylbenzylidene)
sorbitol and bis(trimethyl-benzylidene) sorbitol. One commercially
available nucleating agent is bis(3,4-dimethyl benzylidene)
sorbitol.
[0158] Optionally, additives can be added to the high density
polyethylene. Additives can be added to the high density
polyethylene during an extrusion or compounding step, but other
suitable known methods will be apparent to a person skilled in the
art. The additives can be added as is or added during an extrusion
or compounding step. Suitable additives are known in the art and
include but are not-limited to antioxidants, phosphites and
phosphonites, nitrones, antacids, UV light stabilizers, UV
absorbers, metal deactivators, dyes, fillers and reinforcing
agents, nano-scale organic or inorganic materials, antistatic
agents, lubricating agents such as calcium stearates, slip
additives such as erucimide or behenamide, and nucleating agents
(including nucleators, pigments or any other chemicals which may
provide a nucleating effect to the high density polyethylene). The
additives that can be optionally added are typically added in
amount of up to 20 weight percent (wt %).
[0159] One or more nucleating agent(s) may be introduced into the
high density polyethylene by kneading a mixture of the polymer,
usually in powder or pellet form, with the nucleating agent, which
may be utilized alone or in the form of a concentrate containing
further additives such as stabilizers, pigments, antistatics, UV
stabilizers and fillers. It should be a material which is wetted or
absorbed by the polymer, which is insoluble in the polymer and of
melting point higher than that of the polymer, and it should be
homogeneously dispersible in the polymer melt in as fine a form as
possible (1 to 10 .mu.m). Compounds known to have a nucleating
capacity for polyolefins include salts of aliphatic monobasic or
dibasic acids or arylalkyl acids, such as sodium succinate, or
aluminum phenylacetate; and alkali metal or aluminum salts of
aromatic or alicyclic carboxylic acids such as sodium
.beta.-naphthoate, or sodium benzoate.
[0160] Examples of nucleating agents which are commercially
available and which may be added to the high density polyethylene
are dibenzylidene sorbital esters (such as the products sold under
the trademark Millad 3988.TM. by Milliken Chemical and
Irgaclear.TM. by Ciba Specialty Chemicals). Further examples of
nucleating agents which may added to the high density polyethylene
include the cyclic organic structures disclosed in U.S. Pat. No.
5,981,636 (and salts thereof, such as disodium bicyclo [2.2.1]
heptene dicarboxylate); the saturated versions of the structures
disclosed in U.S. Pat. No. 5,981,636 (as disclosed in U.S. Pat. No.
6,465,551; Zhao et al., to Milliken); the salts of certain cyclic
dicarboxylic acids having a hexahydrophtalic acid structure (or
"HHPA" structure) as disclosed in U.S. Pat. No. 6,599,971 (Dotson
et al., to Milliken); and phosphate esters, such as those disclosed
in U.S. Pat. No. 5,342,868 and those sold under the trade names
NA-11 and NA-21 by Asahi Denka Kogyo, cyclic dicarboxylates and the
salts thereof, such as the divalent metal or metalloid salts,
(particularly, calcium salts) of the HHPA structures disclosed in
U.S. Pat. No. 6,599,971. For clarity, the HHPA structure generally
includes a ring structure with six carbon atoms in the ring and two
carboxylic acid groups which are substituents on adjacent atoms of
the ring structure. The other four carbon atoms in the ring may be
substituted, as disclosed in U.S. Pat. No. 6,599,971. An example is
1,2-cyclohexanedicarboxylicacid, calcium salt (CAS registry number
491589-22-1). Still further examples of nucleating agents which may
added to the high density polyethylene include those disclosed in
WO2015042561, WO2015042563, WO2015042562 and WO 2011050042.
[0161] Many of the above described nucleating agents may be
difficult to mix with the high density polyethylene that is being
nucleated and it is known to use dispersion aids, such as, for
example, zinc stearate, to mitigate this problem.
[0162] In an embodiment of the disclosure, the nucleating agents
are well dispersed in the high density polyethylene.
[0163] In an embodiment of the disclosure, the amount of nucleating
agent used is comparatively small--from 5 to 3000 parts by million
per weight (based on the weight of the high density polyethylene)
so it will be appreciated by those skilled in the art that some
care is taken to ensure that the nucleating agent is well
dispersed. In an embodiment of the disclosure, the nucleating agent
is added in finely divided form (less than 50 microns, or for
example less than 10 microns) to the high density polyethylene to
facilitate mixing. In some embodiments, this type of "physical
blend" (i.e., a mixture of the nucleating agent and the resin in
solid form) is generally preferable to the use of a "masterbatch"
of the nucleator (where the term "masterbatch" refers to the
practice of first melt mixing the additive--the nucleator, in this
case--with a small amount of the high density polyethylene--then
melt mixing the "masterbatch" with the remaining bulk of the high
density polyethylene).
[0164] In an embodiment of the disclosure, an additive such as
nucleating agent may be added to the high density polyethylene by
way of a "masterbatch", where the term "masterbatch" refers to the
practice of first melt mixing the additive (e.g., a nucleator) with
a small amount of the high density polyethylene, followed by melt
mixing the "masterbatch" with the remaining bulk of the high
density polyethylene.
[0165] In an embodiment of the disclosure, the high density
polyethylene further includes a nucleating agent or a mixture of
nucleating agents.
[0166] Since the high density polyethylene is used in bottle
closure assemblies typically used for food contact applications,
the additive package, if present, should meet the appropriate food
regulations, such as, the FDA regulations in the United States.
[0167] In an embodiment of the disclosure, the high density
polyethylene described above is used in the formation of molded
articles. For example, articles formed by continuous compression
molding and injection molding are contemplated. Such articles
include, for example, bottle closure assemblies, caps, hinged caps,
screw caps, closures and hinged closures for bottles.
[0168] The high density polyethylene described above is used in the
formation of bottle closure assemblies. For example, bottle closure
assemblies formed in part on in whole by compression molding and/or
injection molding are contemplated.
[0169] In one embodiment, the bottle closure assembly including the
high density polyethylene described above has good organoleptic
properties. The bottle closure assemblies are well suited for
sealing bottles, containers and the like, for examples bottles that
may contain drinkable water, and other foodstuffs, including but
not limited to liquids that are pressurized (e.g. carbonated
beverages or appropriately pressurized drinkable liquids). The
bottle closure assemblies may also be used for sealing bottles
containing drinkable water or non-carbonated beverages (e.g.
juice). Other applications, include bottle closure assemblies for
bottles and containers containing foodstuffs, such as for example
ketchup bottles and the like.
[0170] The bottle closure assemblies of the current disclosure can
be made according to any known method, including for example
injection molding and/or compression molding techniques that are
well known to persons skilled in the art. Hence, in an embodiment
of the disclosure a bottle closure assembly including the high
density polyethylene (defined above) is prepared with a process
including at least one compression molding step and/or at least one
injection molding step.
[0171] Further non-limiting details of the disclosure are provided
in the following examples. The examples are presented for the
purpose of illustrating selected embodiments of this disclosure, it
being understood that the examples presented do not limit the
claims presented.
EXAMPLES
[0172] Melt indexes, I.sub.2, I.sub.5, I.sub.6 and I.sub.21 for the
polyethylene composition were measured according to ASTM D1238
(when conducted at 190.degree. C., using a 2.16 kg, a 5 kg, a 6.48
kg and a 21 kg weight respectively).
[0173] M.sub.n, M.sub.w, and M.sub.z (g/mol) were determined by
high temperature Gel Permeation Chromatography with differential
refractive index detection using universal calibration (e.g.
ASTM-D6474-99). GPC data was obtained using an instrument sold
under the trade name "Waters 150c", with 1,2,4-trichlorobenzene as
the mobile phase at 140.degree. C. The samples were prepared by
dissolving the polymer in this solvent and were run without
filtration. Molecular weights are expressed as polyethylene
equivalents with a relative standard deviation of 2.9% for the
number average molecular weight ("Mn") and 5.0% for the weight
average molecular weight ("Mw"). The molecular weight distribution
(MWD) is the weight average molecular weight divided by the number
average molecular weight, M.sub.W/M.sub.n. The z-average molecular
weight distribution is M.sub.z/M.sub.n. Polymer sample solutions (1
to 2 mg/mL) were prepared by heating the polymer in
1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at
150.degree. C. in an oven. The antioxidant
2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in
order to stabilize the polymer against oxidative degradation. The
BHT concentration was 250 ppm. Sample solutions were
chromatographed at 140.degree. C. on a PL 220 high-temperature
chromatography unit equipped with four Shodex columns (HT803,
HT804, HT805 and HT806) using TCB as the mobile phase with a flow
rate of 1.0 mL/minute, with a differential refractive index (DRI)
as the concentration detector. BHT was added to the mobile phase at
a concentration of 250 ppm to protect the columns from oxidative
degradation. The sample injection volume was 200 mL. The raw data
were processed with Cirrus GPC software. The columns were
calibrated with narrow distribution polystyrene standards. The
polystyrene molecular weights were converted to polyethylene
molecular weights using the Mark-Houwink equation, as described in
the ASTM standard test method D6474.
[0174] Primary melting peak (.degree. C.), heat of fusion (J/g) and
crystallinity (%) was determined using differential scanning
calorimetry (DSC) as follows: the instrument was first calibrated
with indium; after the calibration, a polymer specimen is
equilibrated at 0.degree. C. and then the temperature was increased
to 200.degree. C. at a heating rate of 10.degree. C./min; the melt
was then kept isothermally at 200.degree. C. for five minutes; the
melt was then cooled to 0.degree. C. at a cooling rate of
10.degree. C./min and kept at 0.degree. C. for five minutes; the
specimen was then heated to 200.degree. C. at a heating rate of
10.degree. C./min. The DSC Tm, heat of fusion and crystallinity are
reported from the 2.sup.nd heating cycle.
[0175] The short chain branch frequency (SCB per 1000 carbon atoms)
of the polyethylene composition was determined by Fourier Transform
Infrared Spectroscopy (FTIR) as per the ASTM D6645-01 method. A
Thermo-Nicolet 750 Magna-IR Spectrophotometer equipped with OMNIC
version 7.2a software was used for the measurements. Unsaturations
in the polyethylene composition were also determined by Fourier
Transform Infrared Spectroscopy (FTIR) as per ASTM D3124-98.
Comonomer content can also be measured using .sup.13C NMR
techniques as discussed in Randall, Rev. Macromol. Chem. Phys., C29
(2&3), p 285; U.S. Pat. No. 5,292,845 and WO 2005/121239.
[0176] Polyethylene density (g/cm.sup.3) was measured according to
ASTM D792.
[0177] Hexane extractables were determined according to ASTM
D5227.
[0178] Shear viscosity was measured by using a Kayeness WinKARS
Capillary Rheometer (model #D5052M-115). For the shear viscosity at
lower shear rates, a die having a die diameter of 0.06 inch and L/D
ratio of 20 and an entrance angle of 180 degrees was used. For the
shear viscosity at higher shear rates, a die having a die diameter
of 0.012 inch and L/D ratio of 20 was used.
[0179] To determine CDBI(50), a solubility distribution curve is
first generated for the polyethylene. This is accomplished using
data acquired from the TREF technique. This solubility distribution
curve is a plot of the weight fraction of the copolymer that is
solubilized as a function of temperature. This is converted to a
cumulative distribution curve of weight fraction versus comonomer
content, from which the CDBI(50) is determined by establishing the
weight percentage of a copolymer sample that has a comonomer
content within 50% of the median comonomer content on each side of
the median (See WO 93/03093 and U.S. Pat. No. 5,376,439). The
CDBI(25) is determined by establishing the weight percentage of a
copolymer sample that has a comonomer content within 25% of the
median comonomer content on each side of the median
[0180] The temperature rising elution fractionation (TREF) method
used herein was as follows. Polymer samples (50 to 150 mg) were
introduced into the reactor vessel of a crystallization-TREF unit
(Polymer ChAR.TM.). The reactor vessel was filled with 20 to 40 ml
1,2,4-trichlorobenzene (TCB), and heated to the desired dissolution
temperature (e.g., 150.degree. C.) for 1 to 3 hours. The solution
(0.5 to 1.5 ml) was then loaded into the TREF column filled with
stainless steel beads. After equilibration at a given stabilization
temperature (e.g., 110.degree. C.) for 30 to 45 minutes, the
polymer solution was allowed to crystallize with a temperature drop
from the stabilization temperature to 30.degree. C. (0.1 or
0.2.degree. C./minute). After equilibrating at 30.degree. C. for 30
minutes, the crystallized sample was eluted with TCB (0.5 or 0.75
mL/minute) with a temperature ramp from 30.degree. C. to the
stabilization temperature (0.25 or 1.0.degree. C./minute). The TREF
column was cleaned at the end of the run for 30 minutes at the
dissolution temperature. The data were processed using Polymer ChAR
software, Excel spreadsheet and TREF software developed
in-house.
[0181] High temperature GPC equipped with an online FTIR detector
(GPC-FTIR) was used to measure the comonomer content as the
function of molecular weight.
[0182] Plaques molded from the polyethylenes were tested according
to the following ASTM methods: Bent Strip Environmental Stress
Crack Resistance (ESCR) at Condition B at 10% and 100% IGEPAL at
50.degree. C., ASTM D1693; notched Izod impact properties, ASTM
D256; Flexural Properties, ASTM D 790; Tensile properties, ASTM D
638; Vicat softening point, ASTM D 1525; Heat deflection
temperature, ASTM D 648.
[0183] Dynamic mechanical analyses were carried out with a
rheometer, namely Rheometrics Dynamic Spectrometer (RDS-II) or
Rheometrics SR5 or ATS Stresstech, on compression molded samples
under nitrogen atmosphere at 190.degree. C., using 25 mm diameter
cone and plate geometry. The oscillatory shear experiments were
done within the linear viscoelastic range of strain (10% strain) at
frequencies from 0.05 to 100 rad/s. The values of storage modulus
(G'), loss modulus (G''), complex modulus (G*) and complex
viscosity (.eta.*) were obtained as a function of frequency. The
same rheological data can also be obtained by using a 25 mm
diameter parallel plate geometry at 190.degree. C. under nitrogen
atmosphere.
[0184] Example 1 is a high density polyethylene homopolymer having
a melt index I.sub.2 of 5 g/10 min, a density of 0.960 g/cm.sup.3,
and a molecular weight distribution Mw/Mn of 2.67. The unimodal
polyethylene homopolymer of Example 1, was made using a
Ziegler-Natta catalyst in a solution olefin polymerization process.
This resin is commercially available from NOVA Chemicals
Corporation as SCLAIR 2907. A GPC profile for the resin is given in
FIG. 8.
[0185] Example 2 is a high density polyethylene copolymer having a
melt index I.sub.2 of 6.7 g/10 min, a density of 0.954 g/cm.sup.3,
and a molecular weight distribution Mw/Mn of 2.72. The unimodal
polyethylene copolymer of Example 2, was made using a Ziegler-Natta
catalyst in a solution olefin polymerization process. This resin is
commercially available from NOVA Chemicals Corporation as SCLAIR
2807. A GPC profile for the resin is given in FIG. 9.
[0186] Example 3 is a high density polyethylene homopolymer having
a melt index I.sub.2 of 7 g/10 min, a density of 0.961 g/cm.sup.3,
and a molecular weight distribution Mw/Mn of 2.99. The unimodal
polyethylene homopolymer of Example 3, was made using a
Ziegler-Natta catalyst in a solution olefin polymerization process.
This resin is commercially available from NOVA Chemicals
Corporation as SCLAIR 2908. A GPC profile for the resin is given in
FIG. 10.
[0187] Example 4 is a high density polyethylene copolymer having a
melt index I.sub.2 of 17 g/10 min, a density of 0.951 g/cm.sup.3,
and a molecular weight distribution Mw/Mn of 2.72. The unimodal
polyethylene copolymer of Example 4, was made using a Ziegler-Natta
catalyst in a solution olefin polymerization process. This resin is
commercially available from NOVA Chemicals Corporation as SCLAIR
2710. A GPC profile for the resin is given in FIG. 11.
[0188] Example 5 is a high density polyethylene copolymer having a
melt index I.sub.2 of 32 g/10 min, a density of 0.951 g/cm.sup.3,
and a molecular weight distribution, Mw/Mn of 2.88, and which is
made using a Ziegler-Natta catalyst in a solution olefin
polymerization process. This resin is commercially available from
NOVA Chemicals Corporation as SCLAIR.RTM. 2712. A GPC profile for
the resin is given in FIG. 12.
[0189] Further details of the high density polyethylenes of
Examples 1-5 are shown in Table 1, along with their plaque
data.
TABLE-US-00001 TABLE 1 Resin and Plaque Properties Example No. 1 2
3 4 5 Density (g/cm.sup.3) 0.960 0.954 0.961 0.951 0.951
Rheology/Flow Properties Melt Index I.sub.2 (g/10 min) 5 6.7 7 17
32 Melt Flow Ratio (I.sub.21/I.sub.2) 27 28.2 25.7 24 22.7 Stress
Exponent 1.32 1.33 1.29 1.27 1.24 Shear Viscosity at 10.sup.5
s.sup.-1 7.00 7.4 6.7 6.00 5.90 (240.degree. C., Pa-s) Shear
Viscosity Ratio 4.21 3.82 1.85 1.66 1.49 .eta. (10 s.sup.-1)/.eta.
(1000 s.sup.-1) at 240.degree. C. Shear Viscosity Ratio 75 59.4 60
19.62 .eta. (100 s.sup.-1)/.eta. (100000 s.sup.-1) at 240.degree.
C. GPC - conventional M.sub.n 27405 26005 21623 19622 14928 M.sub.w
73262 70836 65028 53372 43003 M.sub.z 183608 185530 174598 123854
95318 Polydispersity Index 2.67 2.72 3.03 2.72 2.88
(M.sub.w/M.sub.n) M.sub.z/M.sub.w 2.51 2.62 2.32 2.22 Branch
Frequency - FTIR (uncorrected for chain end --CH.sub.3) Uncorrected
<0.5 0.7 1.3 SCB/1000 C Uncorrected comonomer content (mol %)
Internal unsaturation 0.030 0.040 0.03 0.060 0.080 (/1000 C) Side
chain 0.030 0.030 0.03 0.050 0.050 unsaturation (/1000 C) Terminal
unsaturation 0.720 0.720 0.71 0.790 0.850 (/1000 C) Comonomer ID --
1-butene -- 1-butene 1-butene TREF -- 78.8 -- 72.8 68.7 CDBI.sub.50
(%) TREF -- 66.9 -- 59.6 50.5 CDBI.sub.25 (%) DSC Primary Melting
Peak 132.13 130.04 132.1 127.75 126.99 (.degree. C.) Heat of Fusion
(J/g) 226.30 215.7 229.8 205.40 210.40 Crystallinity (%) 78.05
74.37 79.2 70.82 72.55 Environmental Stress Crack Resistance ESCR
Cond. B at 3 3 3 2 0 100% (hours) ESCR Cond. B at 10% 4 3 3 1 0
(hours) Flexural Properties (Plaques) Flex Secant Mod. 2% 1018 886
1075 787 786 (MPa) Impact Properties (Plaques) Izod Impact
(ft-lb/in) 0.80 1.13 1.2 0.76 0.66 Other properties Hexane
Extractables 0.21 0.24 0.23 0.33 0.43 (%) VICAT Soft. Pt. (.degree.
C.) - 129 127 129.5 123.9 122 Plaque Heat Deflection Temp. 75 74
83.6 65.4 66 [.degree. C.] @ 66 PSI
Neutron Activation Analysis (NAA)
[0190] Neutron Activation Analysis, hereafter NAA, was used to
determine catalyst residues in ethylene polymers and was performed
as follows. A radiation vial (composed of ultrapure polyethylene, 7
mL internal volume) was filled with a polyethylene polymer product
sample and the sample weight was recorded. Using a pneumatic
transfer system the sample was placed inside a SLOWPOKE.TM. nuclear
reactor (Atomic Energy of Canada Limited, Ottawa, Ontario, Canada)
and irradiated for 30 to 600 seconds for short half-life elements
(e.g., Ti, V, Al, Mg, and Cl) or 3 to 5 hours for long half-life
elements (e.g. Zr, Hf, Cr, Fe and Ni). The average thermal neutron
flux within the reactor was 5.times.10.sup.11/cm.sup.2/s. After
irradiation, samples were withdrawn from the reactor and aged,
allowing the radioactivity to decay; short half-life elements were
aged for 300 seconds or long half-life elements were aged for
several days. After aging, the gamma-ray spectrum of the sample was
recorded using a germanium semiconductor gamma-ray detector (Ortec
model GEM55185, Advanced Measurement Technology Inc., Oak Ridge,
Tenn., USA) and a multichannel analyzer (Ortec model DSPEC Pro).
The amount of each element in the sample was calculated from the
gamma-ray spectrum and recorded in parts per million relative to
the total weight of the polyethylene polymer sample. The N.A.A.
system was calibrated with Specpure standards (1000 ppm solutions
of the desired element (greater than 99% pure)). One mL of
solutions (elements of interest) were pipetted onto a 15
mm.times.800 mm rectangular paper filter and air dried. The filter
paper was then placed in a 1.4 mL polyethylene irradiation vial and
analyzed by the N.A.A. system. Standards are used to determine the
sensitivity of the N.A.A. procedure (in counts/pg).
[0191] The high density polyethylenes of Examples 1-4 are as
described above. Examples 6-9 are commercially available polymers
having a melt index, I.sub.2 ranging from about 1.5 to about 11.0
g/10 min and densities ranging from about 0.951 g/cm.sup.3 to about
0.955 g/cm.sup.3.
TABLE-US-00002 TABLE 2 NAA of Polyethylene Polymers Example Al
(ppm) Cl (ppm) Mg (ppm) Ti (ppm) 1 0.96 0.14 <2 0.19 2 0.58 0.1
<2 0.69 3 0.511 0.074 <1 0.288 4 0.19 0.11 <1 0.16 6 66.3
20.2 3.61 7.27 7 65.2 32.6 4.05 12.19 8 25.1 9.54 2.89 0.923 9 26.2
11.3 3.97 1.01
[0192] The data provided in Table 2 shows that the polymers of
Examples 1-4 have much reduced residual catalyst component levels
(e.g. aluminum, chlorine, magnesium and titanium) when compared to
several other commercially available products (Examples 6 through
9). Compare for example, Examples 1-4 which have less than 1 ppm of
aluminum (Al), and less than 0.7 ppm of titanium (Ti) present
(where "ppm" is parts per million of element per mass of polymer,
e.g. milligrams of element/kilograms of polymer) with Examples 6-9
which have Al levels of from about 25 ppm to about 66 ppm, and Ti
levels of from about 1 to about 12 ppm. Examples 1-4 also have much
lower levels of chlorine (Cl) and magnesium (Mg), which don't
exceed about 0.15 ppm and 2 ppm respectively.
[0193] For end use applications, especially those which may come in
contact with foodstuff it may be desirable to employ products
having lower levels of catalyst component residues. Lower catalyst
residues may lead to better organoleptic properties and help
preserve the original taste and odor of the packaged contents.
[0194] The high density polyethylene described above can be used in
the formation of bottle closure assemblies. For example, bottle
closure assemblies formed in part on in whole by compression
molding and/or injection molding are contemplated.
[0195] In one embodiment, the bottle closure assembly includes the
high density polyethylene described above and has good organoleptic
properties. Hence, the bottle closure assemblies are well suited
for sealing bottles, containers and the like, for examples bottles
that may contain drinkable water, and other foodstuffs, including
but not limited to liquids that are pressurized or
non-pressurized.
[0196] In an embodiment of the disclosure a bottle closure assembly
including a high density polyethylene defined as above is prepared
with a process including at least one compression molding step
and/or at least one injection molding step.
Preparation of a Tether Proxy for Deformation Testing
[0197] In order to provide a proxy of a tether portion which can be
analyzed under conditions of shear, tear and tensile deformation, a
closure (see FIGS. 13A and 13B) was compression molded as described
below and then a tamper evident band, 10* (a proxy for a retaining
means portion, 10) was formed by folding in and cutting the bottom
circular edge of the closure using a folding/slitting machine with
a modified blade, so that a tamper evident band (10*) which was
joined to the cap portion (1) by several narrow ("pin" like)
connecting sections (marked by the frangible line, 9 in FIGS. 13A
and 13B) and one larger continuous section (i.e. continuous with a
portion of the cap portion side wall), with the larger continuous
section serving as a proxy for a tether (the area marked as 40 in
FIGS. 13A and 13B). The larger continuous section or "tether proxy"
section was designed to have an arcuate length of 6 mm. The "tether
proxy" section had a cross-sectional width (or thickness) of 0.6 mm
as determined by the dimensions of the closure mold used for the
compression molding process (see below). The "tether proxy"
section, or simply "tether proxy" 40 was then subjected to shear
and tear deformations and to tensile deformation using a toque
tester unit and tensile tester unit respectively (see below).
Method of Making a Closure by Compression Molding
[0198] A SACMI Compression molding machine (model CCM24SB) and a
PCO (plastic closure only) 1881 carbonated soft drink (CSD) closure
mold was used to prepare the closures. Depending on material
density, melt index (I.sub.2) and chosen plug size, the closure
weight varied between 2.15 g and 2.45 grams, with the process
conditions adjusted to target a closure having a weight of about
2.3 grams. During the closure preparation process, the overall
closure dimensions, such as, for the example, the closure diameter
and the closure height were measured and maintained within desired
"quality-controlled" specifications. Closures with poor circularity
or with significant deformation away from the pre-defined
specifications were rejected by an automatic vision system
installed on the compression molding machine. Once the closure had
been compression molded, a tamper evident band, inclusive of one
larger continuous section (a proxy for a tether portion) was cut
into the closure bottom edge using a folding/slitting machine
fitted with a modified blade. Both experimental and simulated data
confirmed that 99% of any closure weight differences were due to
differences in the top panel thickness (of the cap portion, see
FIG. 13A) for each of the compression molded closures. For example,
in the closures prepared by compression molding, the top panel
thickness values of closures having a weight ranging from 2.15
grams to 2.45 grams were found to be slightly different, but each
of the closure side wall thicknesses were found to be identical. As
a result, any small differences in the compression molded cap
weight were expected to have no impact on the dimensions of the
tamper evident band or the tether proxy section (see above): in
each case, the tether proxy had an arcuate length of 6 mm and a
cross-sectional thickness of 0.6 mm.
[0199] Type 1 closures were compression molded from a high density,
unimodal polyethylene copolymer (Example 2) having a melt index
I.sub.2 of 6.7 g/10 min, a density of 0.954 g/cm.sup.3, and a
molecular weight distribution Mw/Mn of 2.72. This resin is
commercially available from NOVA Chemicals Corporation as SCLAIR
2807.
[0200] Type 2 closures were compression molded from a high density,
unimodal polyethylene homopolymer (Example 3) having a melt index
I.sub.2 of 7 g/10 min, a density of 0.961 g/cm.sup.3, and a
molecular weight distribution Mw/Mn of 2.99. This resin is
commercially available from NOVA Chemicals Corporation as SCLAIR
2908.
[0201] Type 3 closures were compression molded from a high density,
unimodal polyethylene copolymer (Example 4) having a melt index
I.sub.2 of 17 g/10 min, a density of 0.951 g/cm.sup.3, and a
molecular weight distribution Mw/Mn of 2.72. This resin is
commercially available from NOVA Chemicals Corporation as SCLAIR
2710.
[0202] Type 4 closures were compression molded from a high density,
unimodal polyethylene copolymer (Example 5) having a melt index
I.sub.2 of 32 g/10 min, a density of 0.951 g/cm.sup.3, and a
molecular weight distribution, Mw/Mn of 2.88. This resin is
commercially available from NOVA Chemicals Corporation as SCLAIR
2712.
[0203] The compression molding conditions used to make each closure
type are provided in Table 3.
TABLE-US-00003 TABLE 3 Compression Molding Processing Conditions
Closure Type No. 1 2 3 4 Closure Weight (g) 2.36 2.32 2.36 2.39 BT1
Temp (.degree. C.) 160 164 163 163 BT2 Temp (.degree. C.) 164 163
164 164 BT3 Temp (.degree. C.) 165 164 163 163 BT4 Temp (.degree.
C.) 165 170 161 161 BT6 Temp (.degree. C.) 170 185 170 170 BT7 Temp
(.degree. C.) 185 184 187 187 BT8 Temp (.degree. C.) 185 184 184
184 BT9 Temp (.degree. C.) 185 170 184 184 BT15 Temp (.degree. C.)
170 165 170 170 BT16 Temp (.degree. C.) 165 175 165 165 BT17 Temp
(.degree. C.) 175 175 174 174 Metering Pump Set Press 50 50 50 50
(bar) Metering Pump Actual Press 51 51 50 50 1 (bar) IN Metering
Pump Actual Press 52.9 53 28 30.6 2 (bar) OUT Pump Speed (%) 57 56
56 57 Hydraulic Operating Temp 46 47 46 46 (.degree. C.) Punch
Cooling BT18 (.degree. C.) 20 20 20 20 Cavity Cooling BT19
(.degree. C.) 20 20 20 20 Ausiliari Cooling BT20 (.degree. C.) 30
30 30 30
Shear Deformation of a Tether Proxy
[0204] A TMS 5000 Torque Tester unit manufactured by Steinfurth was
used to carry out the tether proxy shear deformation testing. The
unit was adjusted to operate in "removal torque mode". A closure
having a tether proxy section (area 40 in FIGS. 13A and 13B) with a
6 mm arcuate length and a 0.6 mm cross-sectional width connecting a
cap portion (1) to a tamper evident band 10* (a proxy for a
retaining means portion, 10) and suitable for mating with a PCO
1881 bottle finish was employed. Prior to testing, the tamper
evident band (10*) was unfolded and then almost entirely removed,
by cutting through the tamper evident band at a distance of
approximately 2 mm from each end of the tether proxy section. The
remaining portion of the tamper evident band (as shown in FIGS. 14A
and 14B) then, includes the tether proxy section having an arcuate
length of 6 mm, and a further 2 mm arcuate length section on either
side of the tether proxy section, all of which has a cross
sectional width of 0.6 mm. Adding 2 mm to either side of the tether
proxy section provides a larger surface area to grip when carrying
out the shear deformation testing. In order to support the closure
for testing in the Torque Tester unit, a modified tubular preform
was used (item 45 in FIG. 14B). The tubular pre-form 45 was made of
polyethylene terephthalate and was modified to have smooth outer
walls. Following this, a brass rod (50), having a diameter which
fit snuggly within the preform (45) was inserted as a plug to
afford rigidity to the pre-form and to prevent its deformation
during testing. Next, the closure was placed on top of the pre-form
and the remaining section of the tamper evident band (10*) was
clamped to the preform using vice grips. The closure and preform
were then mounted within the Torque Tester. The cap portion (1) was
gripped from above within a suitably designed chuck and rotated at
a removal torque speed of 0.8 rpm, relative to the clamped section
of the tamper evident band, using the Torque Tester. The shear
strength of the tether proxy (40) is defined as the maximum torque
(in inchespounds) required to separate the cap portion (1) from the
remaining section of the tamper evident band section (10*) by
breaking the tether proxy (40). The reported shear strength in
Table 4 is the average of at least 5 such shear deformation
tests.
Tear Deformation of a Tether Proxy
[0205] A TMS 5000 Torque Tester unit manufactured by Steinfurth was
used to carry out the tether proxy shear deformation testing. The
unit was adjusted to operate in "removal torque mode". A closure
having a tether proxy section (area 40 in FIGS. 13A and 13B) with a
6 mm arcuate length and a 0.6 mm cross-sectional width connecting a
cap portion (1) to a tamper evident band 10* (a proxy for a
retaining means portion, 10) and suitable for mating with a PCO
1881 bottle finish was employed. In order to support the closure
for testing in the Torque Tester unit, a modified tubular pre-form
was used (item 45 in FIG. 14C). The tubular pre-form 45 was made of
polyethylene terephthalate and was modified to have smooth outer
walls. Following this, a brass rod (50), having a diameter which
fit snuggly within the pre-form (45) was inserted as a plug to
afford rigidity to the pre-form and to prevent its deformation
during testing. Next, the closure was placed on top of the preform.
Prior to testing, the tamper evident band (10*) was deflected
downward (on the opposite side of the tether proxy section) and
away from the cap portion (1) as is shown in FIG. 14C. The downward
deflection breaks all the narrow pin sections (the frangible line 9
in FIGS. 13A and 13B) joining the top edge of the tamper evident
band to the lower edge of the cap portion while leaving the larger
continuous section, the tether proxy section (40), intact. The
tamper evident band (10*) is deflected downward and away from the
cap portion (1) until the top edge of the tamper evident band makes
an angle with the lower edge of the cap portion of about 27
degrees, while the tether portion remains intact along its 6 mm
arcuate length (see FIG. 14C). The tamper evident band (10*) was
then clamped to the pre-form in this downwardly deflected position
using vice grips. The closure and pre-form were then mounted within
the Torque Tester. The cap portion (1) was gripped from above
within a suitably designed chuck and rotated at a removal torque
speed of 0.8 rpm, relative to the clamped tamper evident band
(10*), using the Torque Tester. The tear strength of the tether
proxy (40) is defined as the maximum torque (in inchespounds)
required to separate the cap portion (1) from the downwardly
deflected tamper evident band (10*) by breaking the tether proxy
(40). The reported tear strength in Table 4 is the average of at
least 5 such tear deformation tests.
Tensile Deformation of a Tether Proxy
[0206] Tensile deformation tests were performed using a tensile
machine (an Instron 4204 universal tester, with a 1 KN (225 lbf)
capacity load cell) with the crosshead velocity set at 50 mm/min. A
closure having a tether proxy section (area 40 in FIGS. 13A and
13B) with a 6 mm arcuate length and a 0.6 mm cross-sectional width
connecting a cap portion (1) to a tamper evident band 10* (a proxy
for a retaining means portion, 10) and suitable for mating with a
PCO 1881 bottle finish was employed. Prior to testing, the tamper
evident band (10*) was unfolded and then almost entirely removed,
by cutting through the tamper evident band at a distance of
approximately 2 mm from each end of the tether proxy section (see
FIGS. 14A, 15A and 15B). The remaining portion of the tamper
evident band (as shown in FIGS. 14A, 15A and 15B) then, includes
the tether proxy section having an arcuate length of 6 mm, and a
further 2 mm arcuate length section on either side of the tether
proxy section, all of which has a cross sectional width of 0.6 mm.
Adding 2 mm to either side of the tether proxy section provides a
larger surface area to grip when carrying out the tensile
deformation testing. For the tensile deformation test, most of the
cap portion (1) was similarly cut away, leaving only a section of
the cap portion side wall connected to the what was left of the
tamper evident band (see FIGS. 15A and 15B). This "cut away"
section of the closure was then mounted in the tensile tester, with
the remaining cap portion side wall and the remaining tamper
evident band each being secured with 0.5-inch wide steel serrated
grips at a 0.25-inch grip separation. During the tensile testing,
the remaining section of the cap portion (1) and the remaining
section of the tamper evident band (10*) were drawn apart
vertically. The tensile strength of the tether proxy (40) is
defined as the maximum load (in gramsforce, gf) required to
separate the remaining cap portion (1) from the remaining tamper
evident band section (10*) by breaking the tether proxy (40). The
reported tensile strength in Table 4 is the average of at least 5
such tensile deformation tests.
TABLE-US-00004 TABLE 4 Average Shear, Tear and Tensile Deformation
of a Tether Proxy Closure Type No. 1 2 3 4 Shear Strength 11.43
10.25 9.94 9.43 (inches.pounds) Tear Strength 9.89 10.68 9.78 9.18
(inches.pounds) Tensile Strength 16183 14700 13231 12800
(grams.force)
[0207] A person skilled in the art will recognize from the data
provided in Table 4, that a tether proxy made using the
polyethylene of Example 2, has a better ability to resist shear and
tensile deformations, while the tear deformation is not
statistically different (beyond a 95% confidence level) when
compared to a tether proxy made with the polyethylene of Example 5,
which has a higher melt index, I.sub.2. A tether proxy made using
the polyethylene of Example 3, has a better ability to resist tear
and tensile deformations, while the shear deformation is not
statistically different (beyond a 95% confidence level) when
compared to a tether proxy made with the polyethylene of Example 5,
which has a higher melt index, I.sub.2. A tether proxy made using
the polyethylene of Example 4, has shear, tear and tensile
deformations which are not statistically different (beyond a 95%
confidence level) from that of a tether proxy made using the
polyethylene of Example 5. The data thus provides further evidence
that some of the high density polyethylene described herein may be
useful in the production of bottle closure assemblies, by
preventing facile separation of a cap portion from a retaining
means portion or from a bottle, and by generally helping to prevent
loss or disassociation of a cap portion (a potential plastic waste
stream) from a bottle, where the cap portion could otherwise
contribute to environmental waste concerns.
[0208] The present disclosure has been described with reference to
certain details of particular embodiments thereof. It is not
intended that such details be regarded as limitations upon the
scope of the disclosure except insofar as and to the extent that
they are included in the accompanying claims.
* * * * *