U.S. patent application number 10/958314 was filed with the patent office on 2005-04-14 for blister package.
This patent application is currently assigned to Honeywell International Inc.. Invention is credited to Blum, John B., Luciano, Sandra E..
Application Number | 20050077202 10/958314 |
Document ID | / |
Family ID | 29254189 |
Filed Date | 2005-04-14 |
United States Patent
Application |
20050077202 |
Kind Code |
A1 |
Blum, John B. ; et
al. |
April 14, 2005 |
Blister package
Abstract
Blister packages are provided which are formed from multilayered
films having a lid-stock film which is heat sealed directly to a
fluoropolymer film. A polymeric base layer is adhered to a
fluoropolymer layer via a first intermediate adhesive tie layer; a
support layer is adhered to the fluoropolymer layer via a second
intermediate adhesive tie layer; and a metallic foil layer is
adhered to the support layer via a third intermediate adhesive tie
layer. The blister has a greatly improved moisture barrier over
blister packages of the prior art.
Inventors: |
Blum, John B.; (Middletown,
DE) ; Luciano, Sandra E.; (North East, MD) |
Correspondence
Address: |
HONEYWELL INTERNATIONAL INC.
101 COLUMBIA ROAD
P O BOX 2245
MORRISTOWN
NJ
07962-2245
US
|
Assignee: |
Honeywell International
Inc.
|
Family ID: |
29254189 |
Appl. No.: |
10/958314 |
Filed: |
October 5, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10958314 |
Oct 5, 2004 |
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10241095 |
Sep 11, 2002 |
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60375389 |
Apr 25, 2002 |
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Current U.S.
Class: |
206/528 ;
206/484 |
Current CPC
Class: |
Y10T 428/1355 20150115;
Y10T 428/1338 20150115; Y10T 428/1352 20150115; B65D 75/36
20130101; B32B 27/08 20130101 |
Class at
Publication: |
206/528 ;
206/484 |
International
Class: |
B65D 083/04 |
Claims
What is claimed is:
1. A multilayered film which comprises: a) a polymeric base layer;
b) a fluoropolymer layer adhered to said polymeric base layer via a
first intermediate adhesive tie layer; c) a support layer adhered
to said fluoropolymer layer via a second intermediate adhesive tie
layer; and d) a metallic foil layer adhered to said support layer
via a third intermediate adhesive tie layer.
2. The multilayered film of claim 1 wherein said polymeric base
layer comprises a material selected from the group consisting of
polyamides, polyolefins, cyclic olefin copolymers, polyesters,
poly(vinyl chloride), poly vinylidene chloride, polystyrene,
acrylics and combinations thereof.
3. The multilayered film of claim 1 wherein said polymeric base
layer comprises poly(vinyl chloride).
4. The multilayered film of claim 1 wherein said fluoropolymer
layer comprises a polychlorotrifluoroethylene homopolymer or
copolymer.
5. The multilayered film of claim 1 wherein said support layer
comprises a material selected from the group consisting of
polyolefins, polyamides, polyesters, polystyrene, poly(vinyl
chloride), polyvinylidene chloride, polyurethanes and combinations
thereof.
6. The multilayered-film of claim 1 wherein said support layer
comprises polyethylene terephthalate.
7. The multilayered film of claim I wherein said metallic foil
comprises an aluminum foil.
8. The multilayered film of claim 1 wherein said first intermediate
adhesive tie layer comprises a material selected from the group
consisting of a polyurethane, an epoxy, a polyester, an acrylic, an
anhydride modified polyolefin and blends thereof.
9. The multilayered film of claim 1 wherein said second
intermediate adhesive tie layer comprises a blend of (1) an
olefm-containing polymer selected from the group consisting of at
least one functionalized polyolefin; at least one copolymer of
ethylene and at least one comonomer selected from the group
consisting of acrylic acid, alkyl acrylic acid, acrylates, and
alkyl acrylates; and blends thereof and (2) a
styrene-ethylene-butylene-styrene block copolymer.
10. The multilayered film of claim 1 further comprising a paper
adhered to said foil layer via an intermediate adhesive tie
layer.
11. The multilayered film of claim 1 wherein said film has a
moisture transmission rate of less than about 0.05 .mu.m/100
in.sup.2/day per mil thickness of said fluoropolymer layer.
12. A multilayered film which comprises: a) a polymeric base layer;
b) a fluoropolymer layer having a first surface adhered to said
polymeric base layer; and c) a metallic foil layer adjacent to a
second surface of said fluoropolymer layer.
13. The multilayered film of claim 12 wherein said fluoropolymer
film comprises a polychlorotrifluoroethylene homopolymer or
copolymer.
14. The multilayered film of claim 13 wherein said metallic foil is
laminated, directly or indirectly, to said second surface of said
fluoropolymer layer.
15. The multilayered film of claim 14 including a support layer
adhered to said second surface of said fluoropolymer film, with
said metallic foil being adhered to said support layer.
16. The multilayered film of claim 15 wherein said support layer is
adhered to said metallic foil by an intermediate adhesive tie
layer.
17. The multilayered film of claim 16 wherein said polymeric base
layer comprises a material selected from the group consisting of
polyamides, polyolefins, cyclic olefin copolymers, polyesters,
poly(vinyl chloride), polyvinylidene chloride, polystyrene,
acrylics and combinations thereof.
18. The multilayered film of claim 17 wherein said support layer
comprises a material selected from the group consisting of
polyolefins, nylons, polyesters, polystyrene, poly(vinyl chloride),
polyvinylidene chloride, polyurethanes and combinations
thereof.
19. The multilayered film of claim 18 wherein said polymeric base
layer comprises poly(vinyl chloride).
20. The multilayered film of claim 19 wherein said support layer is
adhered to said second surface of said fluoropolymer layer by an
intermediate adhesive tie layer.
21. The multilayered film of claim 22 wherein said fluoropolymer
layer is adhered polymeric base layer is adhered to said polymeric
base layer via an intermediate adhesive tie layer.
22. The multilayered film of claim 21 wherein said support layer
comprises polyethylene terephthalate.
23. The multilayered film of claim 21 wherein said support layer
comprises a polyamide.
24. The multilayered film of claim 21 wherein said metallic foil
comprises an aluminum foil.
25. The multilayered film of claim 13 wherein said polymeric base
layer comprises poly(vinyl chloride).
26. The multilayered film of claim 25 wherein said metallic foil
layer comprises an aluminum foil.
27. A package formed from the multilayered film of claim 12.
28. The package of claim 27 wherein said polymeric base layer and
said fluoropolymer layer are in the form of a blister and said
metallic foil layer forms a lid for said blister.
29. A package formed from the multilayered film of claim 1.
30. A pharmaceutical package comprising: a) a shaped blister
container which is formed from a multilayered film comprising: i. a
polymeric base layer; and ii. a fluoropolymer layer adhered to the
polymeric base layer via a first intermediate adhesive tie layer;
b) a pharmaceutical product contained within the shaped blister
container; and c) a lid sealed onto a surface of the container,
which lid comprises: i. a support layer adhered to the
fluoropolymer layer via a second intermediate adhesive tie layer;
and ii. a metallic foil layer on the support layer via a third
intermediate adhesive tie layer.
31. The pharmaceutical package of claim 30 wherein said
pharmaceutical product comprises a tablet or a capsule.
32. The pharmaceutical package of claim 30 wherein said
fluoropolymer comprises a polychlorotrifluoroethylene homopolymer
or copolymer.
33. The pharmaceutical package of claim 32 wherein said base layer
comprises poly(vinyl chloride).
34. A package comprising: a) a shaped container which is formed
from a multilayered film comprising: i. a polymeric base layer; and
ii. a fluoropolymer layer adhered to the polymeric base layer via a
first intermediate adhesive tie layer; b) a product contained
within the shaped container; and c) a lid sealed onto a surface of
the container, which lid comprises: i. a support layer adhered to
the fluoropolymer layer via a second intermediate adhesive tie
layer; and ii. a metallic foil layer on the support layer via a
third intermediate adhesive tie layer.
35. A pharmaceutical package comprising: a) a shaped blister
container which is formed from a multilayered film comprising: i. a
polymeric base layer; and ii. a fluoropolymer layer having a first
surface adhered to said polymeric base layer; b) a pharmaceutical
product contained within said shaped blister container; and c) a
lid sealed onto a surface of the container, said lid being adjacent
to a second surface of said fluoropolymer layer.
36. The package of claim 35 wherein said lid comprises a metallic
foil layer.
37. The package of claim 36 wherein said fluoropolymer film
comprises a polychlorotrifluoroethylene homopolymer or
copolymer.
38. The package of claim 37 wherein said lid comprises a support
layer adhered to said second surface of said fluoropolymer film,
with said metallic foil layer being adhered to said support
surface.
39. The package of claim 38 wherein said base layer comprises
poly(vinyl chloride).
40. The package of claim 38 wherein said support layer comprises
polyethylene terephthalate.
41. The package of claim 39 wherein said metallic foil layer
comprises an aluminum foil.
42. The package of claim 41 wherein said support layer is adhered
to said second surface of said fluoropolymer film by an
intermediate adhesive tie layer.
43. The package of claim 42 wherein said fluoropolymer layer is
adhered to said polymeric base layer by an intermediate adhesive
tie layer.
44. The package of claim 43 wherein said support layer is adhered
to said metallic foil layer by an intermediate adhesive tie
layer.
45. A process for forming a pharmaceutical package comprising: a)
forming a multilayered film for holding a pharmaceutical product
by: i) forming a polymeric base layer; ii) applying a fluoropolymer
layer onto said polymeric base layer, which layers are attached via
a first intermediate adhesive tie layer; and iii) molding said film
into a shaped blister container, which container has an outer
surface, an inner surface, and a cavity; b) placing a
pharmaceutical product into said cavity; and c) heat sealing a lid
onto the outer surface of said container, which lid comprises: i. a
support layer adhered to said fluoropolymer layer via a second
intermediate adhesive tie layer; and ii. a metallic foil layer
adhered to said support layer.
46. The process of claim 45 wherein said pharmaceutical product
comprises a tablet or a capsule.
47. The process of claim 45 wherein said base layer and said
fluoropolymer layer are coextruded.
48. The process of claim 45 wherein said base layer and said
fluoropolymer layer are laminated together.
49. The process of claim 45 wherein said molding comprises
thermoforming.
50. The process of claim 45 fuirther comprising adhering a paper to
said foil layer via an intermediate adhesive layer.
51. The process of claim 45 wherein said fluoropolymer layer
comprises a polychlorotrifluoroethylene homopolymer or
copolymer.
52. The process of claim 45 wherein said the polymeric base layer
comprises a material selected from the group consisting of
polyamides, polyolefins, cyclic olefin copolymers, polyesters,
poly(vinyl chloride), polyvinylidene chloride, polystyrene,
acrylics and combinations thereof.
53. The process of claim 45 wherein said support layer comprises a
material selected from the group consisting of polyolefins,
polyamides, polyesters, polystyrene, poly(vinyl chloride),
polyvinylidene chloride, polyurethanes and combinations
thereof.
54. The process of claim 45 wherein said support layer comprises
polyethylene terephthalate.
55. The process of claim 45 wherein said metallic foil comprises an
aluminum foil.
56. The process of claim 45 wherein said first intermediate
adhesive tie layer comprises a material selected from the group
consisting of a polyurethane, an epoxy, a polyester, an acrylic, an
anhydride modified polyolefin and blends thereof.
57. The process of claim 45 wherein said second intermediate
adhesive tie layer comprises a blend of (1) an olefin-containing
polymer selected from the group consisting of at least one
functionalized polyolefm; at least one copolymer of ethylene and at
least one comonomer selected from the group consisting of acrylic
acid, alkyl acrylic acid, acrylates, and alkyl acrylates; and
blends thereof and (2) a styrene-ethylene-butylene-s- tyrene block
copolymer.
58. A process for forming a package comprising: a) forming a
multilayered film for holding a product by: i) forming a polymeric
base layer; ii) applying a fluoropolymer layer onto said polymeric
base layer, which layers are attached via a first intermediate
adhesive tie layer; and iii) molding said film into a shaped
container, which container has an outer surface, an inner surface,
and a cavity; b) placing a product into the cavity; and c) heat
sealing a lid onto the outer surface of the container, which lid
comprises: i. a support layer adhered to said fluoropolymer layer
via a second intermediate adhesive tie layer; and ii. a metallic
foil layer adhered to said support layer.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates to improved blister packages. More
particularly, the invention pertains to multilayered films for
forming improved blister packages having a lid-stock film which is
capable of being heat sealed directly to fluoropolymer films,
including polychlorotrifluoroethylene (PCTFE) homopolymers or
copolymers.
[0003] 2. Description of the Related Art
[0004] It is known to produce multilayered structures to take
advantage of different properties exhibited by the various layers
in the structures. Typical of multilayered structures are
multilayered films in which different layers have specific
characteristics. These films may then be used in packaging
applications having customized properties that may be required for
a particular packaged product. For example, films which are used to
protect food, medicines, paints, adhesives, biomaterials,
chemicals, etc., require properties such as good thermal and
environmental stability, UV blocking characteristics, transparency
in visible light wavelengths and an excellent moisture barrier.
[0005] In many packaging applications it is desirable to utilize
fluoropolymer films which are particularly desirable because they
have an excellent moisture barrier property. This property is
extremely important when the films are used to form packages for
products intended for human consumption. Most fluoropolymers,
especially PCTFE and ethylene-chlorotrifluoroethylene (ECTFE),
exhibit such excellent moisture barrier properties, making them
exceptionally good polymers as barrier packaging material.
[0006] In forming packaging films, such fluoropolymers are
typically laminated with other polymeric films to form multilayered
structures, with only a thin layer of the fluoropolymer needed to
take advantage of the desirable properties. However, one
significant problem is that fluoropolymers do not adhere strongly
to most other polymers. In fact, many fluoropolymers are known for
their non-stick characteristics. Various attempts have been made to
produce multilayer fluoropolymer films. For example, multilayered
structures wherein at least one layer is a fluoropolymer and the
other layer is a thermoplastic homopolymer or copolymer, have been
used for the production of highly oriented, dimensionally stable
fluoropolymer films. In such structures, a tie layer or
intermediate adhesive layer is necessary to bond the film layers.
Multilayer films containing PCTFE and thermoplastic polymer layers
are also known. See, for example, U.S. Pat. Nos. 5,874,035 and
5,945,221. However, the structures of the multilayered films are
limited because of the inability of fluoropolymer films to
sufficiently stick to certain lid-stock film materials, even with
an intermediate adhesive layer.
[0007] In a typical prior art multilayered blister packaging film,
a fluoropolymer layer is attached to a polymeric base layer, e.g.
polyvinyl chloride, via an intermediate adhesive layer. A lid-stock
film comprised of a polyethylene terephthalate layer attached to an
aluminum foil is then adhesively sealed to the base layer to
encapsulate a product within the package. This structure has been
found to provide sufficient adhesion between the polymeric base
layer and the lid-stock film. This structure is also quite
effective in preventing the transmission of water vapor and other
moisture from the blister side of the film and from the lid-stock
side of the package. However, one significant problem associated
with prior art blister package multilayered film is that a
considerable amount of moisture also enters into the package from
between the layers by seeping in through the sides of the package.
This is because while fluoropolymer films are known to exhibit
excellent moisture barrier properties, other thermoplastic polymers
such as polyesters or polyolefins typically have poor moisture
barrier properties. Therefore, one potential solution would be to
use multiple fluoropolymer films in a package. However, this is a
very costly solution to the problem as fluoropolymers are quite
expensive. Another potential solution would be to eliminate the
non-fluoropolymer films from the structure altogether. However,
while the other thermoplastic layers may not provide a good
moisture barrier, they do provide other desirable characteristics,
such as good mechanical strength, which are necessary for a final
product. Furthermore, one additional problem remains the fact that
the adhesives of the prior art have not been able to sufficiently
adhere fluoropolymer films to other thermoplastic polymer layers in
multilayered films. Accordingly, thus far, no prior art structure
has functioned to prevent moisture from entering the package
through the sides.
[0008] Preventing moisture from entering the package from the sides
is a problem which is equally important as preventing moisture from
entering from a top or bottom surface of the package.
Unfortunately, this problem is not appreciated by users of prior
art packaging structures. To be sure, the failure to sufficiently
prevent all moisture from seeping into a package will cause the
product stored within the package to be compromised. It is
therefore desirable to provide a multilayered structure having an
improved moisture barrier between a PCTFE or other fluoropolymer
layer and another polymeric layer, which is capable of blocking
substantially all moisture from entering a blister package. The
present invention provides an effective solution to this compelling
need.
SUMMARY OF THE INVENTION
[0009] The invention provides a multilayered film which
comprises:
[0010] a) a polymeric base layer;
[0011] b) a fluoropolymer layer adhered to the polymeric base layer
via a first intermediate adhesive tie layer;
[0012] c) a support layer adhered to the fluoropolymer layer via a
second intermediate adhesive tie layer; and
[0013] d) a metallic foil layer adhered to the support layer via a
third intermediate adhesive tie layer.
[0014] This invention also provides a multilayered film which
comprises:
[0015] a) a polymeric base layer;
[0016] b) a fluoropolymer layer having a first surface adhered to
the polymeric base layer; and
[0017] c) a metallic foil layer adjacent to a second surface of the
fluoropolymer layer.
[0018] The invention further provides a package, preferably a
pharmaceutical package comprising:
[0019] a) a shaped container, preferably in blister form, which is
formed from a multilayered film comprising:
[0020] i. a polymeric base layer; and
[0021] ii. a fluoropolymer layer adhered to the polymeric base
layer via a first intermediate adhesive tie layer;
[0022] b) a pharmaceutical product contained within the shaped
blister container; and
[0023] c) a lid sealed onto a surface of the container, which lid
comprises:
[0024] i. a support layer adhered to the fluoropolymer layer via a
second intermediate adhesive tie layer; and
[0025] ii. a metallic foil layer adhered to the support layer via a
third intermediate adhesive tie layer.
[0026] This invention additionally provides a pharmaceutical
package comprising:
[0027] a) a shaped blister container which is formed from a
multilayered film comprising:
[0028] i. a polymeric base layer; and
[0029] ii. a fluoropolymer layer having a first surface adhered to
the polymeric base layer;
[0030] b) a pharmaceutical product contained within the shaped
blister container; and
[0031] c) a lid sealed onto a surface of the container, the lid
being adjacent to a second surface of the fluoropolymer layer.
[0032] The invention further provides a process for forming a
package, preferably a pharmaceutical package, comprising:
[0033] a) forming a multilayered film for holding a product,
preferably a pharmaceutical product by:
[0034] i) forming a polymeric base layer;
[0035] ii) applying a fluoropolymer layer onto the polymeric base
layer, which layers are attached via a first intermediate adhesive
tie layer; and
[0036] iii) molding the film into a shaped blister container, which
container has an outer surface, an inner surface, and a cavity;
[0037] b) placing a product, such as a pharmaceutical product, into
the cavity; and
[0038] c) heat sealing a lid onto the outer surface of the
container, which lid comprises:
[0039] i. a support layer adhered to the fluoropolymer layer via a
second intermediate adhesive tie layer; and
[0040] ii. a metallic foil layer on the support layer.
[0041] The invention therefore provides a desirable multilayered
packaging film having excellent moisture barrier properties and
which exhibits excellent adhesion of a fluoropolymer layer to
polymer films, and blister packages formed therefrom.
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] FIG. 1 is a schematic representation of a pharmaceutical
package encapsulating a pharmaceutical product in which moisture is
prevented from entering the package through the sides.
[0043] FIG. 2 is a schematic representation of a prior art package
in which moisture is not prevented from entering the package
through the sides.
[0044] FIG. 3 is a schematic representation of a lid-stock and a
thermoformed blister prior to sealing the lid-stock onto the
fluoropolymer layer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] The multilayered film structure of the present invention
allows for a fluoropolymer layer to be directly bonded to a
lid-stock film in blister packaging with superior adhesive
properties. In this construction, the packaged product is in
contact with the fluoropolymer layer. This results in a significant
reduction in the moisture vapor transmission rate into the package
as compared to the usual application of fluoropolymer packaging
films. Other properties also provided are chemical resistance,
transparency to ultraviolet radiation, and clarity for ease of
product detection.
[0046] The multilayered film of the invention is depicted in FIGS.
1 and 3. FIG. 1 depicts a blister package of the invention after
insertion of a pharmaceutical product and heat sealing of a
lid-stock to the thermoformed film. FIG. 3 depicts the films of the
invention prior to heat sealing the lid-stock to the thermoformed
film. The multilayered film comprises a fluoropolymer layer 14
adhered to a polymeric base layer 10, a support layer 18 adhered to
the fluoropolymer layer 14 and a metallic foil layer 22 on the
support layer. In the preferred embodiment of the invention, the
polymeric base layer 10 comprises a material such as polyamides,
polyesters, polyolefins, including polyethylenes (PE) and
polypropylene (PP), poly(vinyl chloride) (PVC), polyvinylidene
chloride (PVdC), cyclic olefin copolymers (COC), polystyrene (PS),
acrylics such as Barex.RTM., available from BP and combinations
thereof Non-limiting examples of suitable polyethylenes are low
density polyethylene (LDPE), linear low density polyethylene
(LLDPE), linear medium density polyethylene (LMDPE), linear
very-low density polyethylene (VLDPE), linear ultra-low density
polyethylene (ULDPE), high density polyethylene (HDPE). Of these,
the most preferred is low density polyethylene. Preferred
polyesters include polyethylene terephthalate (PET) and glycol
modified polyethylene terephthalate (PETG). Cyclic olefin polymers
are described, for example, in U.S. Pat. Nos. 5,218,049; 5,783,273
and 5,912,070 which are incorporated herein by reference. Most
preferred are copolymers of ethylene and norbornene. Cyclic olefins
may be obtained commercially from Mitsui Petrochemical Industries,
Ltd. of Tokyo, Japan, or Ticona of Summit, N.J.
[0047] Suitable polyamides within the scope of the invention are a
wide range of polyamide homopolymers or copolymers. Useful
polyamide homopolymers include poly(4-aminobutyric acid)(nylon 4),
poly(6-aminohexanoic acid) (nylon 6, also known as
poly(caprolactam)), poly(7-aminoheptanoic acid) (nylon 7),
poly(8-aminooctanoic acid)(nylon 8), poly(9-aminononanoic acid)
(nylon 9), poly(10-aminodecanoic acid)(nylon 10),
poly(11-aminoundecanoic acid)(nylon 11), poly(12-aminododecanoic
acid)(nylon 12). Useful polyamide copolymers include nylon 4,6,
poly(hexamethylene adipamide) (nylon 6,6), poly(hexamethylene
sebacamide)(nylon 6,10), poly(heptamethylene pimelamide)(nylon
7,7), poly(octamethylene suberamide)(nylon 8,8), poly(hexamethylene
azelamide)(nylon 6,9), poly(nonamethylene azelamide)(nylon 9,9),
poly(decamethylene azelamide) (nylon 10,9),
poly(tetramethylenediamine-co-oxalic acid)(nylon 4,2), the
polyamide of n-dodecanedioic acid and hexamethylenediamine (nylon
6,12), the polyamide of dodecamethylenediamine and n-dodecanedioic
acid (nylon 12,12) and the like. Other useful polyarmide copolymers
include caprolactam/hexamethylen- e adipamide copolymer (nylon
6,6/6), hexamethylene adipamide/caprolactam copolymer (nylon
6/6,6), trimethylene adipamide/hexamethylene azelaiamide copolymer
(nylon trimethyl 6,2/6,2), hexamethylene
adipamide-hexamethylene-azelaiamide caprolactam copolymer (nylon
6,6/6,9/6), poly(tetramethylenediamine-co-isophthalic acid) (nylon
4,I), polyhexamethylene isophthalamide (nylon 6,I), hexamethylene
adipamide/hexamethylene-isophthalamide (nylon 6,6/6I),
hexamethylene adipamide/hexamethyleneterephthalamide (nylon
6,6/6T), poly (2,2,2-trimethyl hexamethylene terephthalamide),
poly(m-xylylene adipamide) (MXD6), poly(p-xylylene adipamide),
poly(hexamethylene terephthalamide), poly(dodecamethylene
terephthalamide), polyamide 6T/6I, polyamide 6/MXDT/I, polyamide
MXDI, and the like. Also included are other nylons which are not
particularly delineated here, as well as combinations of those
described herein. Of these polyamides, preferred polyamides include
nylon 6, nylon 6,6, nylon 6/6,6 as well as mixtures of the same. Of
these, nylon 6 is most preferred.
[0048] The polyamides used in the practice of this invention may be
obtained from commercial sources or prepared in accordance with
known preparatory techniques. For example, poly(caprolactam) can be
obtained from Honeywell International Inc., Morristown, N.J. under
the trademark CAPRON.RTM..
[0049] This polymeric base layer 10 is either laminated to or
coextruded with a fluoropolymer layer 14. Fluoropolymers suitable
to form the fluoropolymer layer 14 include, but are not limited to,
ethylene-chlorotrifluoroethylene (ECTFE),
ethylene-tetrafluoroethylene copolymer, fluorinated
ethylene-propylene copolymer, perfluoroalkoxyethylene,
polychlorotrifluoroethylene (PCTFE) homopolymer or copolymer,
polytetrafluoroethylene, polyvinylfluoride, polyvinylidene
fluoride, and copolymers and blends thereof. Particularly preferred
fluoropolymers include homopolymers and copolymers of PCTFE and
copolymers of ECTFE. As used herein, copolymers include polymers
having two or more monomer components. Such copolymers may contain
up to 10%, and preferably up to 8% by weight of other comonomers,
such as vinylidene fluoride and tetrafluoroethylene. Fluoropolymer
films are described, for example, in U.S. Pat. Nos. 4,510,301,
4,544,721 and 5,139,878. Most preferred fluoropolymers are PCTFE
fluoropolymers available as ACLAR(.RTM. films from Honeywell
International Inc. of Morristown, N.J.
[0050] The base layer 10 and the fluoropolymer layer 14 are
attached to each other via a first intermediate adhesive tie layer
12. The adhesive layer 12 may be applied either directly onto
either of the fluoropolymer layer 14 or base layer 10 by any
appropriate means in the art, such as by coating. Any suitable
adhesive, such as a polyurethane, an epoxy, a polyester, an
acrylic, an anhydride modified polyolefin and blends thereof, may
be employed. One type of adhesives includes modified polyolefin
compositions having at least one functional moiety selected from
the group consisting of unsaturated polycarboxylic acids and
anhydrides thereof. Such unsaturated carboxylic acid and anhydrides
include maleic acid and anhydride, fumaric acid and anhydride,
crotonic acid and anhydride, citraconic acid and anhydride,
itaconic acid an anhydride and the like. Of these, the most
preferred is maleic anhydride. The modified polyolefins suitable
for use in this invention include compositions described in U.S.
Pat. Nos. 3,481,910; 3,480,580; 4,612,155 and 4,751,270. Other
adhesive layers non-exclusively include alkyl ester copolymers of
olefins and alkyl esters of .alpha.,.beta.-ethylenically
unsaturated carboxylic acids such as those described in U.S. Pat.
No. 5,139,878. The modified polyolefin composition may comprise
from about 0.001 and about 20 weight percent of the functional
moiety, based on the total weight of the modified polyolefin. More
preferably the functional moiety comprises from about 0.05 and
about 10 weight percent, and most preferably from about 0.1 and
about 5 weight percent. The modified polyolefin composition may
also contain up to about 40 weight percent of thermoplastic
elastomers and alkyl esters as described in U.S. Pat. No.
5,139,878.
[0051] This fluoropolymerfbase polymer structure is thermoformed
into a blister or other shaped container using techniques that are
well known in the art. The film is molded such that the blister has
an outer surface, an inner surface and a cavity. After
thermoforming, a pharmaceutical product 24, i.e. a tablet or
capsule, is inserted into the cavity and the structure is heat
sealed with a lid-stock film by heat sealing the outer surface of
the lid-stock film directly to the fluoropolymer layer 14. In the
preferred embodiment of the invention, the lid-stock film comprises
a support layer 18 adhered to the fluoropolymer layer 14 via a
second intermediate adhesive tie layer 16, and a metallic foil
layer 22 on the support layer via a third intermediate adhesive tie
layer 20. The support layer 18 is preferably comprised of a
thermoplastic material, and is preferably a material selected from
the group consisting of polyolefins, polyamides, polyesters,
polystyrene, poly(vinyl chloride), polyvinylidene chloride,
polyurethanes and combinations thereof.
[0052] Suitable polyolefins non-exclusively include
poly(.alpha.-olefms) and copolymers and blends thereof, wherein the
.alpha.-olefin monomers have from about 2 to about 10 and
preferably from about 2 to about 6 carbon atoms. Non-limiting
examples of polyolefins include the polyethylenes described above,
polypropylene, polybutylene, polybutene-1, polypentene-1,
poly-3-methylbutene-1, poly-4-methylpentene-1, polyhexene,
copolymers of polyolefins, copolymers of olefins and other polymers
such as polyvinyl chloride, polyvinylidene chloride, polystyrene,
polyurethane, and combinations thereof. Of these, the preferred
polyolefins are polyethylene and polypropylene, with polypropylene
being most preferred. Suitable polyamides are those listed above.
Preferred polyesters non-exclusively include polyethylene
terephthalate (PET) and glycol modified polyethylene terephthalate
(PETG).
[0053] In the preferred embodiment of the invention, the second
intermediate adhesive tie layer 16 comprises an adhesive that
exhibits excellent adhesion to a fluoropolymer layer. Any suitable
adhesive may be used, and adhesive layer 16 may be the same or
different from adhesive layer 12. For example, the second
intermediate adhesive tie layer 16 may comprise a blend of
polymeric materials, namely (1) an olefin-containing polymer
selected from the group consisting of at least one functionalized
polyolefin; at least one copolymer of ethylene and at least one
comonomer selected from the group consisting of acrylic acid, alkyl
acrylic acid, acrylates, and alkyl acrylates; and blends thereof
and (2) a styrene-containing rubber. One type of olefin-containing
polymer is a ftnctionalized olefin polymer which contains at least
one functional moiety. Among the functional moieties that may be
employed are unsaturated carboxylic acids, unsaturated carboxylic
acid anhydrides, amines and epoxies. Examples of olefins employable
for the preparation of the modified polyolefins include
homopolymers or copolymers of an .alpha.-olefin such as ethylene,
propylene, butene-1, pentene-1, hexene-1,4-methyl-pentene-1 and
octene-1. Unsaturated carboxylic acids and anhydrides useful to
modify the polyolefins include maleic acid and anhydride, fumaric
acid and anhydride, crotonic acid and anhydride, citraconic acid
and anhydride, itaconic acid and anhydride and the like. Of these,
the most preferred is maleic anhydride. Suitable amines include
aliphatic or aromatic, primary, secondary and tertiary amines, such
as 2,4,6-tribromoaniline, methylamine, ethylamine, propylamine,
dimethylamine, N-methylaniline, ethylmethylamine,
2-(N-methylamine)heptan- e, sec-butyldimethylamine,
N-ethyl-N-methylaniline, trimethylamine, N,N-dimethylanaline, and
the like. Suitable epoxies include those having from about 2 to
about 20 carbon atoms. The modified polyolefms suitable for use in
this invention include compositions described in U.S. Pat. Nos.
3,481,910; 3,480,580; 4,612,155 and 4,751,270 which are
incorporated herein by reference.
[0054] The modified polyolefin composition may comprise from about
0.001 and about 10 weight percent of the functional moiety, based
on the total weight of the modified polyolefin. More preferably,
the functional moiety comprises from about 0.005 and about 5 weight
percent, and most preferably from about 0.01 and about 2 weight
percent.
[0055] Another type of olefin-containing polymer useful herein is a
copolymer of ethylene and acrylic acid, alkyl acrylic acid,
acrylates and/or alkyl acrylates. The alkyl acrylic acids or alkyl
acrylates contain alkyl groups preferably of from about 2 to about
4 carbon atoms. Preferred among these types of polymer is an
ethylene methyl acrylate copolymer.
[0056] The second tie layer 16 may also include a
styrene-containing rubber, for example, styrene block copolymers,
such as hydrogenated styrene-butadiene-styrene block copolymers,
also referred to as styrene-ethylene-butylene-styrene (SEBS) block
copolymers. Other polymeric materials may be present in the second
tie layer 16, such as high melt viscosity polyolefins.
[0057] The styrene-containing rubber may comprise, for example,
from about 1 to about 35%, and more preferably from about 5 to
about 20%, by weight based on the total weight of the second tie
layer 16.
[0058] These adhesive materials are described thoroughly in U.S.
Pat. No. 6,306,503, which is incorporated herein by reference.
Other suitable adhesive materials include those described in U.S.
Pat. Nos. 5,874,035 and 5,945,221, which are also incorporated
herein by reference.
[0059] The preferred metallic foil is an aluminum foil, although
any suitable metal foil may be substituted for aluminum if desired.
Binding the foil 22 to the support layer 18 is a third intermediate
adhesive tie layer 20. This third tie layer 20 may be any suitable
adhesive, and may comprise any of the adhesive materials described
herein. It may be the same or different from that of the other
adhesive layers. In an alternate embodiment of the invention, an
additional layer of a paper 26 may be attached to the foil layer 18
via an other adhesive tie layer. This optional paper layer 26
preferably has printed indicia thereon. Alternately, the foil layer
22 may have printed indicia thereon, e.g. indicia that describes
the identity of the product contained within the blister package.
In some applications, the foil layer may be employed without a
support layer. In addition, the support layer may be in the form of
a coating on the foil layer.
[0060] Each of the fluoropolymer layer 14, base layer 10, support
layer 18 and adhesive layers may optionally also include one or
more conventional additives whose uses are well known to those
skilled in the art. The use of such additives may be desirable in
enhancing the processing of the compositions as well as improving
the products or articles formed therefrom. Examples of such include
oxidative and thermal stabilizers, lubricants, release agents,
flame-retarding agents; oxidation inhibitors, oxidation scavengers,
dyes, pigments and other coloring agents, ultraviolet light
absorbers and stabilizers, organic or inorganic fillers including
particulate and fibrous fillers, reinforcing agents, nucleators,
plasticizers, as well as other conventional additives known to the
art. Such may be used in amounts, for example, of up to about 10%
by weight of the overall composition. Representative ultraviolet
light stabilizers include various substituted resorcinols,
salicylates, benzotriazole, benzophenones, and the like. Suitable
lubricants and release agents include stearic acid, stearyl
alcohol, and stearamides. Exemplary flame-retardants include
organic halogenated compounds, including decabromodiphenyl ether
and the like as well as inorganic compounds. Suitable coloring
agents including dyes and pigments include cadmium sulfide, cadmium
selenide, titanium dioxide, phthalocyanines, ultramarine blue,
nigrosine, carbon black and the like. Representative oxidative and
thermal stabilizers include the Period Table of Element's Group I
metal halides, such as sodium halides, potassium halides, lithium
halides; as well as cuprous halides; and further, chlorides,
bromides, iodides. Also, hindered phenols, hydroquinones, aromatic
amines as well as substituted members of those above mentioned
groups and combinations thereof. Exemplary plasticizers include
lactams such as caprolactam and lauryl lactam, sulfonamides such as
o,p-toluenesulfonamide and N-ethyl, N-butyl benylnesulfonamide, and
combinations of any of the above, as well as other plasticizers
known to the art. However, it is most preferred that each of the
fluoropolymer layer, first intermediate adhesive tie layer and
polymeric base layer are substantially transparent to provide an
overall substantially transparent film.
[0061] Each of the fluoropolymer layer 14, base layer 10 and
support layer 18 may be stretched or oriented-in any desired
direction using methods well known to those skilled in the art. For
purposes of this invention, the terms "orienting" and "stretching"
shall be used interchangeably. Examples of such methods include
those set forth in U.S. Pat. No. 4,510,301. In such a stretching
operation, the layers may be stretched uniaxially in either the
direction coincident with the direction of movement of the film
being withdrawn from the casting roll, also referred to in the art
as the "machine direction", or in as direction which is
perpendicular to the machine direction, and referred to in the art
as the "transverse direction", or biaxially in both the machine
direction and the transverse direction. The multilayered film
structure of the invention is particularly useful for forming
thermoformed three dimensionally shaped articles such as blister
packaging for pharmaceuticals. This may be done by forming the film
around a suitable mold and heating in a method well known in the
art. We have found that the fluoropolymer films of the present
invention have sufficient dimensional stability to be stretched at
least about 1.5 and preferably from about 1.5 to about 10 times in
either the machine direction or the transverse direction or both.
The fluoropolymer/base polymer layers may be stretched after being
adhered together by the first intermediate adhesive layer. The
multilayered film therefore exhibits improved tensile modulus,
mechanical strength, and excellent barrier properties towards both
water vapor and oxygen after being stretched.
[0062] Each layer described above may have different thicknesses.
For example, the thickness of each of the fluoropolymer layer 14,
base layer 10 and support layer 18 in the post-stretched films
structure may range from about 1.3 .mu.m to about 2540 .mu.m, and
preferably from about 1.3 .mu.m to about 1270 .mu.m. The thickness
of the post-stretched adhesive layers may vary, such as in the
range of from about lgm to about 305 .mu.m, preferably from about
1.3 .mu.m to about 25 .mu.m, and most preferably from about 2.5
.mu.m to about 20 .mu.m. While such thicknesses are preferred as
providing a readily flexible film, it is to be understood that
other film thicknesses may be produced to satisfy a particular need
and yet fall within the scope of the present invention.
[0063] In the preferred embodiment of the invention, the
fluoropolymer layer 14 and the base layer 10 are attached by
lamination under heat and pressure via the first intermediate
adhesive tie layer 12, and the support layer 18 is preferably
attached to the fluoropolymer layer 14 by lamination via the second
intermediate adhesive tie layer 16. Lamination techniques are well
known in the art. Typically, laminating is done by positioning the
individual layers on one another under conditions of sufficient
heat and pressure to cause the layers to combine into a unitary
film. Typically the films are positioned on one another, and the
combination is passed through the nip of a pair of heated
laminating rollers by techniques well known in the art. Lamination
heating may be done at temperatures ranging, for example, from
about 120.degree. C. to about 175.degree. C., preferably from about
150.degree. C. to about 175.degree. C., at pressures ranging, for
example, from about 5 psig (0.034 MPa) to about 100 psig (0.69
MPa), for a time period, for example, of from about 5 seconds to
about 5 minutes, preferably from about 30 seconds to about 1
minute. Additionally, the foil layer 22 and support layer 18 are
laminated via the third intermediate adhesive tie layer 20.
[0064] In an alternate embodiment of the invention, the
fluoropolymer layer 14 and the base layer 10 may be attached by
coextrusion. For example, the polymeric material for the individual
layers are fed into infeed hoppers of a like number of extruders,
each extruder handling the material for one or more of the layers.
The melted and plasticated streams from the individual extruders
are fed into a single manifold co-extrusion die. While in the die,
the layers are juxtaposed and combined, then emerge from the die as
a single multiple layer film of polymeric material. After exiting
the die, the film is cast onto a first controlled temperature
casting roll, passes around the first roll, and then onto a second
controlled temperature roll, which is normally cooler than the
first roll. The controlled temperature rolls largely control the
rate of cooling of the film after it exits the die. Additional
rolls may be employed. In another method, the film forming
apparatus may be one which is referred to in the art as a blown
film apparatus and includes a multi-manifold circular die head for
bubble blown film through which the plasticized film composition is
forced and formed into a film bubble which may ultimately be
collapsed and formed into a film. Processes of coextrusion to form
film and sheet laminates are generally known. Typical coextrusion
techniques are described in U.S. Pat. Nos. 5,139,878 and
4,677,017.
[0065] The result is a multilayered blister packaging film having a
moisture transmission rate of less than about 0.05 .mu.m/100
in.sup.2/day per mil thickness of the fluorocarbon layer, more
preferably from about 0.001 to about 0.05 gm/100 in.sup.2/day per
mil thickness of the fluorocarbon layer. As shown in FIG. 1, by
attaching the fluoropolymer layer directly to the lid-stock, such
that the pharmaceutical product is in direct contact with the
fluoropolymer layer, moisture is prevented from entering the sealed
package from all directions. Particularly, the blister package of
the invention is capable of preventing moisture from entering the
package from the top 30 of the package, the bottom 32 of the
package and the side 28 of the package. This is distinguished from
the prior art which does not effectively prevent moisture from
entering the package from the sides of the package. Referring to
FIG. 2, the layers of the prior art blister package are arranged
such that the fluoropolymer layer 14 is the outermost layer from
the lid-stock and the base layer 10 is directly sealed to the
lid-stock. This configuration is sufficient to prevent moisture
from entering the package from the top 30 of the package and from
the bottom 32 of the package. However, the base layer 10, which is
a poor moisture barrier, is not able to prevent moisture from
penetrating the package through the side 34. Particularly, while
moisture is able to seep in between the fluoropolymer layer and the
base layer of either configuration, the fluoropolymer placement
from the prior art structure in FIG. 2 is unable to prevent the
moisture from entering the container area of the package, while the
fluoropolymer placement in FIG. 1 effectively blocks the
transmission of the moisture. This is a particular advantage over
prior blister package constructions, because when moisture seeps in
through any location, the product sealed within is compromised.
[0066] While the present invention has been particularly shown and
described with reference to preferred embodiments, it will be
readily appreciated by those of ordinary skill in the art that
various changes and modifications may be made without departing
from the spirit and scope of the invention. It is intended that the
claims be interpreted to cover the disclosed embodiment, those
alternatives which have been discussed above and all equivalents
thereto.
* * * * *