Note: Descriptions are shown in the official language in which they were submitted.
CA 02326808 2000-09-28
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TITLE OF THE INVENTION
Oriented, Propylene Polymer Film With Improved Oxygen Barrier Property
CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR
DEVELOPMENT
Not Applicable
FIELD OF INVENTION
This invention resides in the chemical arts. It relates to film formed from
polymers of
1o propylene.
BACKGROUND OF INVENTION
Predominately crystalline homopolymer of propylene, the polypropylene of
commerce, has achieved tonnage use in many applications. One of them is the
manufacture
of film, especially biaxially oriented film used in the packaging of, for
example, snack foods
1s such as potato chips and the like. Indeed, such film has become known as
"BOPP" film.
Polypropylene film, while having advantageous properties, for example,
chemical
resistance and excellent barrier to moisture, is not a good burner to oxygen;
oxygen
transmission through the film is too high for many packaging film uses. This
problem of
oxygen barrier property also exists in the case of films formed from
predominately
2o crystalline, random copolymers of propylene and other 1-olefins such as
ethylene and 1-
butene. Efforts to solve this problem have included laminating the film with
film of another
synthetic resin having a good oxygen burner property, and incorporating
additives such as,
for example, so-called hard resin, in the propylene polymer composition from
which the film
is formed. For one reason or another, such efforts have not been entirely
satisfactory.
CONftRMAT'ION COPY
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BRIEF SUMMARY OF THE INVENTION
This invention is based on the discovery that melt blending with predominantly
crystalline polypropylene a graft copolymer of predominantly crystalline
polypropylene and
certain polymerized monomer material gives a composition that in the form of
biaxially
oriented film is a good barrier to oxygen transmission. However, the invention
is broader
than this discovery.
The invention, in summary, broadly comprises oriented film formed from a melt
blend consisting essentially of
(1) propylene polymer material selected from the group consisting of
predominantly
1o crystalline polypropylene and predominantly crystalline copolymers and
terpolymers of
propylene and 1-olefin material selected from the group consisting of ethylene
and the
butenes, which copolymers and terpolymers have more than 50 mole % propylene
units; and
(2) graft copolymer material selected from the group consisting of graft
copolymers
of
15 (a) propylene polymer material selected from the group consisting of
predominantly crystalline polypropylene and predominantly crystalline
copolymers
and terpolymers of propylene and 1-olefin material selected from the group
consisting of ethylene and the butenes, which copolymers and terpolymers have
more
than 50 mole % propylene units, and
20 (b) polymerized monomer material selected from the group of monomers
consisting of styrene, p-alkylstyrenes, acrylic acid, alkacrylic acids, alkyl
acrylates,
alkyl alkacrylates, acrylonitrile, and vinyl acetate with or without ethylene,
the alkyls
in these monomers with alkyl substituents having one-four carbons,
the concentration of the graft copolymer material being such that the rate of
oxygen
25 transmission through the film is substantially less than if no graft
copolymer material were
present.
DETAILED DESCRIPTION OF THE INVENTION
The propylene polymer material in one general embodiment of the blend from
which
the oriented film of this invention is formed is composed of only one
propylene polymer of
3o the recited group. In another general embodiment it is composed of more
than one such
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WO 00/44815 PGT/IB00/00060
polymer. All of the members of the goup from which the propylene polymer
material is
selected, and processes for making them, are generally known.
The gaff copolymer material in one general embodiment of the blend from which
the
oriented film of this invention is formed is composed of only one gaff
copolymer of the
recited group. In another general embodiment it is composed of more than one
such grafted
polymer. In more specific embodiments of these general embodiments, the
grafted,
polymerized monomer material comprises only one grafted, polymerized monomer.
In other,
more specific embodiments of these general embodiments, the gaffed,
polymerized
monomer material comprises more than one gaffed, polymerized monomer. The
members of
1o the group of gaff copolymers, and processes for making them, are generally
known.
Examples of such processes are a radiation process such as that disclosed in
EP 519, 341,
issued August 14,1996, and a. peroxide process such as that disclosed in the
same patent. The
relevant disclosures of this patent are incorporated herein by reference.
In both processes, and especially in the peroxide process, a significant
amount (as
15 much as 80 weight % of the graft copolymer product remaining after removal
of unreacted
monomer material) of the propylene polymer material is not gaffed. Hence, in
some
embodiments the gaff copolymer product furnishes not only the gaff copolymer
material
component, but all of the propylene polymer material component of the blend.
However, in
most embodiments the gaff copolymer product supplies only part of the
propylene product
2o material.
Also, in both processes, and especially in the peroxide process, non-grafted
polymerized monomer material is formed. The quantity of such can be as much as
50% by
weight of the gaff copolymer material product of the process in each case.
However, the
presence of such in the melt blend generally can be tolerated.
25 In general, satisfactory results are obtained with the concentration of the
graft
copolymer material in the blend being about 10-90 weight % of the propylene
polymer
material.
In addition to the essential components, that is, the propylene polymer
material and
the gaff copolymer material, most embodiments of the melt blend comprise at
conventional
30 concentrations stabilizer material selected from the group consisting of
antioxidants, heat
stabilizers, ultraviolet tight inhibitors, and the like. Moreover, embodiments
of the melt
blend can comprise at conventional concentrations other additives, for
example, nucleating
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agent material, filler material, extender material, colorant material, antacid
material,
mechanical property improver material (for example, a polyolefin type rubber
such as
ethylene-octene copolymer rubber), and the like.
The melt blend and the oriented film thereof are made by conventional ways and
means.
While most embodiments of the oriented film of this invention are in biaxial
orientation, film of monoaxial orientation is within the broader concepts of
this invention.
The best mode now contemplated of carrying out the invention is depicted by
Examples 1-23 set forth in the following tables. These Examples illustrate
specific
to embodiments of the oriented film of this invention, their compositions, and
typical data
including oxygen transmission data obtained in physical testing of them.
These data were obtained in work in which oriented film samples of the
formulations
set forth in the following tables were made, and the physical properties
indicated in the tables
were measured.
15 In that work grafted copolymer products were made by the peroxide process.
The
starting propylene polymer material for such products consisted of a propylene
homopolymer resin (polymer + conventional stabilizer material, added at the
time of
production of the polymer, at a concentration intended to stabilize the
polymer until it is
compounded for use) commercially available from Montell USA Inc. as KPO10.
Typical
2o properties of this resin include: spherical particles; melt flow rate = 10
dg/min at 230oC and
2. l6Kg; porosity = 0.44 cc/g; and room temperature xylene insoluble fraction:
96.5 wt%.
The monomer material used to make the various grafted polymers were these
mixtures: methyl methacrylate and methyl acrylate, methyl methacrylate and
methacrylic
acid, and methyl methacrylate and acrylonitrile. The concentration of the
methyl acrylate in
2s these mixtures was 5 mole %.
The peroxide was t-butyl peroxy-2-ethyl hexanoate. It was used while in
solution (50
wt%) in mineral spirits. The solution is commercially available from Elf
Atochem North
America, Inc., as Lupersol PMS.
In each Example 100 parts (all parts are by weight) of the resin were
introduced into
3o a mechanically agitated reactor, the interior of the reactor was inerted by
nitrogen flushing,
and the reactor contents were heated to and maintained at reaction
temperature. Then, 95
4
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WO 00/44815 PCT/IBOOI00060
parts of monomer material per 100 parts of resin were introduced into the
reactor at the rate
per minute of 1 part of monomer material per 100 parts of resin, while at the
same time the
peroxide solution was introduced into the reactor~at a rate equivalent to 1
mole of peroxide
per 100 moles of monomer material being introduced. After introduction of the
monomer
material and the peroxide solution were completed, and while continuing
agitation of the
reactor contents, they were maintained at 125oC for 30 minutes, and then the
temperature
was raised to 140oC for 1.5-2.0 hours while purging with nitrogen residual
monomer
material from the graft copolymer product particles.
A sample of the composition of each Example, the formulation of which is set
forth
to in the tables, was prepared by admixing graft copolymer particles with
particles of a broad
molecular weight distribution polypropylene resin ("BMWD PP"), and additional
stabilizer
material. The resin is commercially available from Montell USA Inc. as KM210.
Typical
properties of this resin include: Mw/Mn >6; melt flow rate = 1.1 g/min at
230oC and
2. l6Kg; and room temperature xylene insoluble fraction = 97.8 wt%. The
quantity of
BMWD PP in the sample was such as to give the Effective Add Level of the total
polymerized monomer material (both that which was grafted to the KPO10
polymer, and that
which was not gaffed to the KPO10 polymer) reported for the Example in the
following
tables. The stabilizer material in all examples comprised a conventional-for-
film antacid and
a conventional-for-ftlrn phenolic antioxidant at a 1:4 wt ratio. In Example 5,
however, the
2o stabilizer material comprised a different, but conventional-for-film,
antacid, a different, but
conventional-for-film, phenolic antioxidant, and a conventional-for-film,
phosphite type
stabilizer at approximately a 1:1:1 wt ratio. While the different composition
of the stabilizer
material in Example 5 is believed not to have skewed the results, it is
reported here for
accuracy. In this regard, because the stabilizer material is not at the
heart,of the invention, it
is not considered necessary to enable the best mode to be practiced to
identify specifically
the stabilizer material components, as long as the chemical types of the
components are
disclosed.
Each sample was melt extruded from either a 34 mm co-rotating, intermeshing
Leistritz LSM twin screw extruder at a barrel temperature of 240oC, a screw
speed of 250
rpm, and a throughput rate of 13.6 kg/hr, or a 40mm co-rotating, intermeshing
Werner &
Pfleiderer ZSK twin screw extruder at a barrel temperature of 210oC, a screw
speed of 500
rpm, and a throughput rate of 73 kg/hr.
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WO 00/44815 PCT/IB00/00060
The thus extruded sample was cast at 250oC into a 25 mil (635aem) thick sheet
which
was quenched on a water-cooled chill roll.
Subsequently, all four sides of a 2 in (5.1 cm) by 2 in (5.1 cm) specimen of
the sheet
were clamped on a TM Long stretcher, and after being heated to a temperature
of 140-160oC
the specimen was stretched biaxially by the machine at the stretch rate of
9000% per min to a
stretch ratio of 6:1 in both directions. The thickness of the thus obtained
biaxially oriented
film specimen was approximately 1 mil (25aem).
All film specimens thus obtained were aged at 23oC and 50% relative humidity
for at
least two weeks. Thereafter the following physical properties were measured by
the indicated
1o methods.
Tensile Strength, Young's Modulus and ASTM D882
Elongation-(7a,-break
Oxygen transmission rate ("OTR") ASTM D3985-81
(at 23.3oC and dry condition)
[The OTR is expressed as "cc x miUm2/24hrs",
(equivalent to "cc x ZSxm /m2/24hrs").]
Haze and clarity Measured with a Byk Gardner
YK Haze-Guard meter
The following tables set forth the composition of the oriented film of each
Example,
2o and the data obtained in measuring the physical properties thereof. These
data were obtained
on samples made at different times. In the case of multiple samples of a
composition made at
different times there were normal variations in the physical measurement data.
These were
averaged and the averages are reported in the tables along with the number of
values
averaged as indicated in the "No. of Data Points" lines.
Further, the first table includes for comparison the data obtained on a
commercial,
film grade, polypropylene resin (polypropylene + conventional stabilizer
material).
Abbreviations in the tables, and their meanings, are:
"AN" means acrylonitrile.
"MAA" means methacrylic acid.
"MeAc" means methyl acrylate.
"PP" means polypropylene.
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WO 00/44815 PCT/IB00/00060
"PP-g-PMMA" means the graft copolymer product that consists essentially of
polypropylene
grafted with polymerized methyl methacrylate and polymerized methyl acrylate.
"PP-g-PMMA/AN" means the graft copolymer product that consists essentially of
polypropylene grafted with polymerized methyl methacrylate and polymerized
acrylonitrile.
"PP-g-PMMA/MAA" means the graft copolymer product that consists essentially of
polypropylene grafted with polymerized methyl methacrylate and polymerized
methacrylic
acid.
"na" means not available.
7
CA 02326808 2000-09-28
WO 00/44815 PGT/IB00/00060
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11
CA 02326808 2000-09-28
WO 00/44815 PCT/IB00/00060
The data of the above tables demonstrate the outstanding oxygen barrier
properties of
the oriented film of this invention.
Other embodiments and features of advantage of this invention will become
readily
apparent to those exercising ordinary skill in the art after reading the
foregoing disclosures.
Such embodiments are within the spirit and scope of the claimed subject matter
unless
expressly excluded therefrom by claim language or by not being within the
doctrine of
equivalents.
DEFINITIONS
The term "film" as used in this specification means a sheet, the thickness of
which is
l0 10 mils (254 aem) or less.
The expression "consisting essentially of in this specification excludes an
unrecited
substance at a concentration suffcient to substantially adversely affect the
essential
properties and characteristics of the composition of matter being defined,
while permitting
the presence of one or more unrecited substances at a concentration or
concentrations
15 insufficient to substantially adversely affect said essential properties
and characteristics.
12
