USOO677381.

8B2

(12) United States Patent (10) Patent No.: US 6,773,818 B2

Cretekos et al. (45) Date of Patent: Aug. 10, 2004

(54) METALLIZED, METALLOCENE- 5,019.447 A 5/1991 Keller ........................ 428/327

CATALYZED, POLYPROPYLENE FILMS s: A
2Y- -
16S ES . . . . .i.
allon et al. .
"S.S.R.
(75) Inventors: George F. Cretekos, Farmington, NY E. A
2-a-s-s-s
1810: E. et al. ...
aZaV1 ......
- - - SEE:
- --

(US); Moris Amon, Pittsford, NY (US) 5,162.278 A 11/1992 Razavi ...... ... 502/152
rr. A O 1 O 5,254,394. A 10/1993 Bothe et al. ... ... 428/212
(73) Assignee: ExxonMobil Oil Corporation, Irving, 5,462.807. A 10/1995 Halle et al. ....... ... 428/500
TX (US) 5,468.440 A 11/1995 McAlpin et al. ............ 264/291
- 5,529,843 A 6/1996 Dries et al. ....... ... 428/336
(*) Notice: Subject to any disclaimer, the term of this 6,268,062 B1 * 7/2001 DeMeuse ... ... 428/461
patent is extended or adjusted under 35 6,410,124 B1 * 6/2002 Peet .......... ... 428/215
U.S.C. 154(b) by 0 days. 6,503,635 B1 * 1/2003 Kong et al. ................. 428/461
(21) Appl. No.: 10/236,701 FOREIGN PATENT DOCUMENTS
EP 668 157 A1 8/1995
(22) Filed: Sep. 6, 2002 WO WO 99/67094 12/1999
O O WO WO OO/58088 10/2000
(65) Prior Publication Data WO WO 01/03920 1/2001
US 2004/0053066 A1 Mar. 18, 2004 WO WO 03/072357 9/2003
(51) Int. Cl. .......................... B32B 27/32; B32B 15/08 * cited by examiner
(52) U.S. Cl. ........................ 428/461; 428/515; 428/516 Pririmary Examiner
E iner D. L WCCC
T ZO
(58) Field of Search ................................. 428/515, 516, (74) Attorney, Agent, or Firm-Rick F. James
428/461
(57) ABSTRACT
(56) References Cited
U.S. PATENT DOCUMENTS
An oriented multilayer film containing a core layer and a
first skin layer, wherein the first skin layer includes a
3,753,769 A 8/1973 Steiner ................... 117/122 H metallocene-catalyzed propylene homopolymer or
4,214,039 A 7/1980 Steiner et al. .............. 428/414 copolymer, and the first skin layer is metallized. The film
4,377,616 A 3/1983 Ashcraft et al. ............ 428/213 may also contain additional layers, Such as a Second skin
4,447,494 A 5/1984 Wagner, Jr. et al. ........ 428/349 layer for heat-Sealing, and one or more tie layers. The film
4,632,869 A 12/1986 Park et al. ............... 428/315.5 may be laminated to other films or non-films. The film
4,794,096 A 12/1988 Ewen ......................... 502/117 exhibits excellent water vapor transmission rates (WVTR)
4,865,908 A 9/1989 Liu et al. .................... 428/248
4,892.851 A 1/1990 Ewen et al. ................ 502/104 and oxygen transmission rates (OTR).
4,961,992 A 10/1990 Balloni et al. .............. 428/332
4,975,403 A 12/1990 Ewen ......................... 502/113 20 Claims, No Drawings
 US 6,773,818 B2
1 2
METALLIZED, METALLOCENE wherein the core layer has a first Surface and a Second
CATALYZED, POLYPROPYLENE FILMS Surface, the first skin layer has a first and a Second Surface,
the Second Surface of the first skin layer is contiguous to and
in contact with the first Surface of the core layer, and the first
TECHNICAL FIELD Surface of the first skin layer is metallized.
The present invention relates to a film that contains a skin The oriented multilayer film may optionally comprise a
layer of metallocene-catalyzed, Substantially isotactic pro Second Skin layer on the Side of the core layer opposite the
pylene homopolymer or metallocene-catalyzed propylene first skin layer, and one or more tie layers between the core
copolymer. The film may be oriented. The skin layer may be layer and the first skin layer and between the core layer and
metallized on its outer Surface. the Second skin layer (if any). A coating may optionally be
applied to one or both outer Surfaces of the film, including
BACKGROUND the outer Surface of the core layer if a Second Skin layer is
not present, the Outer Surface of the Second skin layer, and
Metallocene-catalyzed propylene polymers, which have the metallized surface of the first skin layer. The film may
low melting temperatures relative to conventional propylene 15 optionally be laminated to a Substrate at one or both of its
polymers, are known. Due to their relatively low melting outer Surfaces, again including the Outer Surface of the core
temperatures, metallocene-catalyzed propylene polymers layer if a Second skin layer is not present, the outer Surface
have been described as a useful heat Seal material, e.g., as of the Second skin layer, and the metallized Surface of the
the heat-sealable outer layer of a multilayer film in U.S. Pat. first skin layer.
No. 5,468,440. The 440 patent suggests temperatures at The oriented multilayer film may have an oxygen trans
which metallocene-catalyzed, isotactic polypropylene mission rate (OTR) of s 20 cc/m°/24 hr, as determined in
plaqueS or cast Samples can be stretched in laboratory accordance with ASTM D 3985 at 73° F (23° C) and 0%
equipment. The Suggested temperatures, however, are not relative humidity (RH), and a water vapor transmission rate
Suitable for continuous orientation processing. The 440 (WVTR) of s().50 g/m/24 hr, as determined in accordance
patent further fails to disclose metallizing the metallocene 25 with ASTM F 1249 at 100° F (37.8° C) and 90% RH.
catalyzed polypropylene layer or layers. There is also provided a process for producing an oriented
U.S. Pat. Nos. 5,529,843 and 5,462.807 also describe the multilayer film, comprising:
advantages of a multilayer film that has an outer layer that a) coextruding melts corresponding to the core layer and
contains a metallocene-catalyzed polymer. The 843 and the first skin layer to form a coextruded sheet;
807 patents, however, fail to disclose or Suggest the use of b) cooling the coextruded sheet;
a metallocene-catalyzed propylene polymer in a metallized c) orienting the coextruded sheet to form an oriented
skin layer of a multilayer film. multilayer film; and
Metallocene-catalyzed, isotactic polypropylenes have a d) metallizing the oriented multilayer film on the first
very narrow molecular weight distribution, i.e., a very 35 Surface of the first skin layer.
narrow range of chain lengths. Ziegler-Natta-catalyzed, iso A multilayer film according to the present invention
tactic polypropylenes, by contrast, have a broad range of provides Several advantages, mainly as a result of the
chain lengths, which average out at the desired level. For advantageous interface between the first skin layer and the
good operability in the oriented polypropylene (OPP) metal layer deposited thereon. It possesses unexpectedly
process, those of skill in the art typically desire a broad Superior oxygen transmission rates (OTR) and water vapor
40
molecular weight distribution. The high molecular weight transmission rates (WVTR), both initially after manufacture
tails of Ziegler-Natta-catalyzed polypropylenes tend to dis and throughout the various Stages of the converting process.
tribute the Stretching forces more uniformly in oriented The film, moreover, is Surprisingly operable in orientation
films, preventing StreSS concentrations, and ultimately pro processes, and, when Subsequently metallized, demonstrates
Viding more uniform orientation and improved operability. good metal adhesion between the metal layer and the
Therefore, although the narrow composition distribution of 45
metallizable skin layer, e.g., the first skin layer.
metallocene-catalyzed, isotactic propylene polymers causes
them to be looked upon favorably for film properties, e.g., DETAILED DESCRIPTION
heat-Sealability, their narrow molecular weight distribution Skin Layers
causes them to be looked upon negatively for operability in First Skin Layer
the OPP process. 50 A multilayer film according to the present invention
For this reason, multilayer films, and especially oriented comprises a first skin layer. The first skin layer may com
multilayer films, disclosed in the prior art have generally prise a metallocene-catalyzed propylene homopolymer or a
used traditional Ziegler-Natta-catalyzed polymers, which metallocene-catalyzed propylene copolymer. The
have a broad molecular weight distribution, in the Skin or metallocene-catalyzed propylene homopolymer may be a
metallization layer and/or the core layer to distribute orien 55 metallocene-catalyzed, Substantially isotactic propylene
tation StreSSes more uniformly and avoid film breakage homopolymer. The phrases “Substantially isotactic propy
during orientation. lene homopolymer” or “substantially isotactic
polypropylene', as used herein, generally refer to propylene
SUMMARY polymers which have an isotacticity of 85% or greater (as
60 measured by Solubility in Xylene). Exemplary isotactic pro
There is provided an oriented multilayer film, comprising: pylene polymers and/or methods for making Such polymers
a) a core layer comprising a polyolefin; and are described in the following patent documents: U.S. Pat.
b) a first skin layer comprising a polyolefin Selected from Nos. 5,529,843; 5,162,278; 5,158,920; 5,155,080; 5,036,
the group consisting of (i) a metallocene-catalyzed, 034; 4,975,403; 4,892.851; and 4,794,096, all of which are
Substantially isotactic propylene homopolymer, (ii) a 65 incorporated herein by reference.
metallocene-catalyzed propylene copolymer, and (iii) AS described above, the metallocene-catalyzed propylene
blends thereof, polymers of the first skin layer may include homopolymers
 US 6,773,818 B2
3 4
and/or copolymers that contain other monomeric units, as in ethylene-butene-1 copolymers (EB), propylene-butylene
the case of a copolymer of propylene and ethylene or an random copolymers (PB), and ethylene-propylene block/
C-olefin having from 4 to 20 carbon atoms, e.g., butene-1, impact copolymers (EP). More specific examples of terpoly
pentene-1, hexene-1, heptene-1, 4-methyl-1-pentene, merS for the Second Skin layer include random ethylene
octene-1 or combinations thereof. Also contemplated are propylene-butene-1 terpolymers (EPB), and block
metallocene-catalyzed propylene terpolymers, including, terpolymers of ethylene, propylene and butene-1. Ethylene
but not limited to, propylene-ethylene-butene-1, propylene propylene-butene-1 random terpolymers appropriate for use
ethylene-pentene-1, propylene-ethylene-hexene-1, in the Second skin layer include those containing from 0.25
propylene-ethylene-octene-1, and the like. to 7 wt.% random ethylene and from 0.25 to 35 wt % random
The metallocene-catalyzed propylene polymer, whether a butene-1, with the balance being made up of propylene. The
homopolymer or copolymer, may have a melting point of amounts of the random ethylene and butene-1 components
s 160° C., or s 154 C., or s 145° C., preferably from 120° in these terpolymers are typically in the range of from 5 to
C. to 155° C., e.g., from 130° C. to 150° C. The foregoing 25 wt % (ethylene plus butene-1), based on the total weight
melting point ranges were determined by an EXXonMobil of the copolymer. The copolymers and terpolymers typically
method outlined herein below. In general, the melt flow rate 15 have a melt flow rate in the range of from 0.5 to 20 g/10 min,
of the metallocene-catalyzed propylene polymers will be in e.g., from 5 to 10 g/10 min., and a melting point in the range
the range of from 0.5 g/10 min to 20 g/10 min at 230 C., of s 160° C.
for example, from 2.5 g/10 minto 15 g/10 min, e.g., from 4 In certain embodiments of the invention, the Second skin
g/10 min to 9 g/10 min, as measured by ASTM D-1238 at layer may comprise a polyethylene. Suitable polyethylenes
230° C. for the Second skin layer include very low density polyeth
The first skin layer may also comprise blends of two or ylene (VLDPE), low density polyethylene (LDPE), linear
more propylene homopolymers, or blends of two or more low-density polyethylene (LLDPE), medium density poly
propylene copolymers, or at least one propylene homopoly ethylene (MDPE) or high density polyethylene (HDPE).
mer and at least one propylene copolymer, each differing in These ethylene polymers generally have a melt indeX rang
their molecular or macro properties or both. The only 25 ing from 0.3 to 15 g/10 min, as measured by ASTM D-1238
requirement of Such blends, aside from the physical prop (a190°C.
erties described above, is that they have a majority compo VLDPE, which is sometimes referred to as ultra low
nent or components, i.e., more than 50 weight percent, that density polyethylene (ULDPE), is a very low density poly
are metallocene-catalyzed propylene homopolymers or ethylene typically having a density at or below 0.915 g/cm,
copolymers. In other embodiments, the first skin layer will e.g., from about 0.86 to about 0.915 g/cm. VLDPE is
consist essentially of a metallocene-catalyzed propylene typically produced in a high pressure, peroxide-catalyzed
homopolymer, a metallocene-catalyzed propylene reaction or in a solution process. When produced using a
copolymer, or blends thereof. By “consist essentially,” it is metallocene or single-site catalyst, VLDPE is commonly
meant that the first skin layer excludes all other film-forming referred to as a type of plastomer.
polyolefins, including Ziegler-Natta-catalyzed polypropy 35 LDPE typically has a density in the range of from 0.90
lenes. g/cm to 0.94 g/cm, e.g., from 0.910 g/cm to 0.926 g/cm.
In a film Structure according to the present invention, the LDPE may be derived solely from ethylene, e.g., in a high
first skin layer may be contiguous to and in contact with the preSSure, peroxide-catalyzed reaction, or from ethylene
core layer. Alternatively, one or more intermediate, or tie, together with a comonomer, including but not limited to
layerS may be disposed between the first skin layer and the 40 higher olefin comonomers containing 4 to 10 carbon atoms,
core layer. In Such a case, the first skin layer will be e.g., butene-1, hexene-1, or octene-1, e.g., in a gas phase
contiguous to and in contact with a tie layer, and the core linear low density polyethylene (LLDPE) process or in a
layer will be contiguous to and in contact with a tie layer. AS Solution LLDPE process using Ziegler-Natta, metallocene,
will be readily understood, if there is only one tie layer or Single-site catalysts.
disposed between the first skin layer and core layer, then the 45 LLDPE typically has a density in the range of from 0.88
tie layer that is contiguous to and in contact with the core to 0.94 g/cm, preferably from 0.89 to 0.92 g/cm. It may be
layer is the same tie layer that is contiguous to and in contact derived from ethylene together with other higher
with the first skin layer. comonomers, Such as butene-1, hexene-1 or octene-1.
Second Skin Layer MDPE typically has a density in the range of from 0.926
A multilayer film according to the present invention may 50 to 0.94 g/cm.
optionally comprise a Second skin layer. The Second skin HDPE is a substantially linear polyolefin having a density
layer may be any of the coextrudable, orientable film of, for example, from about 0.95 g/cm or higher, e.g., from
forming resins known in the art, including Substantially about 0.952 g/cm to about 0.970 g/cm, and a melting point
isotactic polypropylene, Substantially Syndiotactic of, for example, from about 266 F. to about 299 F. (from
polypropylene, copolymers of propylene with ethylene and/ 55 about 130° C. to about 148° C).
or an O-olefin having from 4 to 20 carbon atoms, and Alternative thermnoplastic materials for the Second skin
terpolymers of propylene with ethylene and/or butene-1 layer include polyamides and polyesters, as well as co- and
and/or another C-olefin(s). The phrase “Substantially Syn terpolymers of ethylene and ethylenically unsaturated car
diotactic polypropylene', as used herein, generally refers to boxylic acids, Such as methyl acrylate, butyl acrylate, ethyl
a propylene polymer that has a syndiotacticity of 70% or 60 acrylate, ethylene acrylic acid, ethylene methacrylic acid,
greater based on racemic pentads (measured according to combinations of these monomers, ionomers of the acid
'C NMR spectroscopy). The coextrudable, orientable film copolymers, ethylene-vinyl alcohol (EVOH), ethylene-vinyl
forming resins of the Second skin layer include, but are not acetate, maleic anhydride-grafted or modified polymer Such
limited to, Ziegler-Natta-catalyzed (Z-N) and metallocene as Styrene maleic anhydride, polyethylene and polypropy
catalyzed (m) polymers 65 lene polymerS modified with maleic anhydride, and the like.
More Specific examples of copolymers for the Second skin Blends of any of the foregoing homopolymers, copolymers
layer include ethylene-propylene random copolymers, and terpolymers are also contemplated.
 US 6,773,818 B2
S 6
For certain embodiments, it may be desirable for the opposed and edge-contacting concave disks. The cavitating
Second skin layer to be a heat-Seal layer. Several of the agent(s) may be present in the core layer at <30, or <20, or
materials identified above are illustrative heat-sealable <10 or in the range of from 2-10 wt %, based on the total
materials, including the polyolefinic copolymers, weight of the core layer.
terpolymers, and blends thereof. The cavitating agent(s) may be added to the core layer by
In a film Structure according to the present invention, the blending the cavitating agent(s) and the film-forming poly
Second skin layer may be contiguous to and in contact with olefin at a temperature above the melting point of the
the core layer, on a side of the core layer opposite the first film-forming polyolefin. This blending may take place in an
skin layer. Alternatively, one or more intermediate, or tie, extruder, Such as a co-rotating, intermeshing twin Screw
layerS may be disposed between the Second Skin layer and extruder.
the core layer. In Such a case, the Second skin layer will be To preserve the Structural integrity of the core layer, a thin
contiguous to and in contact with a tie layer, and the core layer of the film-forming polyolefin of the core layer,
layer will be contiguous to and in contact with a tie layer. AS without the cavitating agent(s), may be coextruded on one or
will be readily understood, if there is only one tie layer both sides of the film-forming polyolefin of the core layer.
disposed between the Second skin layer and core layer, then 15 In this case, the total of the cavitating agent(s)-containing
the tie layer that is contiguous to and in contact with the core layer and the non-cavitating agent(s)-containing layer(s)
layer is the same tie layer that is contiguous to and in contact may be considered the overall core layer of the film.
with the Second skin layer. In addition to, or as an alternative to, the cavitating agent,
Core Layer the core layer may comprise an opacifying agent(s).
A multilayer film according to the present invention Examples of the opacifying agent(s) include iron oxide,
comprises a core layer. The core layer preferably comprises carbon black, titanium dioxide, talc, and combinations
a film-forming polyolefin, Such as, for example, an isotactic thereof. The opacifying agent(s) may be present in the core
propylene homopolymer (iPP), a propylene co- or terpoly layer in an amount of from 1 to 15 wt %, or 1 to 8 wt %, or
mer preferably made up of 90 wt % or more of propylene, 2 to 4 wt %, based on the total weight of the core layer.
high density polyethylene (HDPE), linear low density poly 25 Aluminum is another example of an opacifying agent that
ethylene (LLDPE), syndiotactic polypropylene (sPP), or may be used in the core layer of the present film Structure.
combinations thereof. The film-forming polyolefins of the Aluminum may be included in the core layer as an opaci
core layer may be Ziegler-Natta-catalyzed or metallocene fying agent in an amount of from 0.01 to 1.0 wt %, or 0.25
catalyzed. to 0.85 wt %, based on the total weight of the core layer.
The contemplated propylene polymers will generally Tie Layer(s)
have a melting point of 2130 C. and a melt-flow rate AS previously described, one or more intermediate, or tie,
(MFR) of from 0.5 to 8 g/10 min, e.g., from 1.5 to 5 g/10 layers may be disposed between the first skin layer and the
min. Specific examples thereof include, but are not limited core layer, and one or more intermediate, or tie, layerS may
to, Fina 3371 (commercially available from Fina Oil and be disposed between the Second skin layer and the core
Chemical Company) and PD 4712E1 (commercially avail 35 layer. A tie layer of the present film Structure may comprise
able from ExxonMobil Chemical). The contemplated ethyl any of the materials disclosed above in reference to the first
ene polymers will generally have a melt indeX ranging from skin layer, Second skin layer, or core layer.
0.5 to 15 g/10 min. Specific examples thereof include, but In particular embodiments, the tie layer will be chosen to
are not limited to, HDPE M-6211 and HDPE M-6030 from maximize compatibility with the skin layer thereon and to
Equistar Chemical Company, and HD-6704.67 from Exx 40 maximize adhesion between Said skin layer and core layer.
onMobil Chemical. For example, if the Second skin layer comprises, e.g.,
Cavitated Core Layer EVOH, a tie layer comprising a maleic anhydride-grafted or
If it is desired to produce an opaque film Structure, a modified polymer may preferably be disposed between the
cavitating agent(s) can be added to the core layer. A Suitable Second skin layer and the core layer.
cavitating agent(s) includes any organic or inorganic mate 45 Other Ingredients
rial that is incompatible with (the term “incompatible” is In order to modify or enhance certain properties of the
used in the Sense that the materials are two distinct phases), present multilayer film for Specific end uses, it is possible for
and has a higher melting point than, the film-forming one or more of the layers to contain appropriate additives in
polyolefin of the core layer, at least at the orientation effective amounts. As will be readily understood by one of
temperature. For example, the cavitating agent(s) may be 50 ordinary skill in the art, an “effective amount' is an amount
any of those described in U.S. Pat. Nos. 4,377,616 and Sufficient to achieve the desired effect, e.g., an antiblocking
4,632,869, the entire disclosures of which are incorporated effect for antiblock additives or an antistatic effect for
herein by reference. Specific examples of the cavitating antistatic additives. Examples of Suitable additives may
agent(s) include polybutylene terephthalate (PBT), nylon, an include, but are not limited to, waxes, pigments, colorants,
acrylic resin, an ethylene-norborene copolymer, Solid or 55 antioxidants, antioZonants, antifogs, antistats, slip additives,
hollow preformed glass Spheres, metal beads or Spheres, antiblock additives, fillerS Such as calcium carbonate, diato
ceramic Spheres, calcium carbonate, and combinations maceous earth, carbon black, and combinations thereof. In
thereof. When the core layer comprising a cavitating agent certain embodiments of the present invention, the metallized
(S) is Subjected to uniaxial or biaxial orientation, a cavity layer is free of additives, except for those additives that are
forms, providing a film having an opaque appearance. 60 added by the resin manufacturer, e.g., anti-oxidants or
The average diameter of the cavitating agent may be from stabilizers.
0.1 to 10 um. The agent may be of any desired shape or it More Specific examples of antistatic additives, which can
may be Substantially Spherical in shape. This does not mean be used in amounts ranging from 0.05 to 3 weight 9%, based
that every cavity will be the same size. It means that, in upon the total weight of the layer into which they are being
general, each cavity will tend to be of like shape when like 65 incorporated, include alkali metal Sulfonates, polyether
particles are used, even if they vary in dimensions. For modified polydiorganosiloxanes, polyalkylphenylsiloxanes
example, a cavity may assume a shape defined by two and tertiary amines.
 US 6,773,818 B2
7 8
More specific examples of antiblock additives include are not critical, in certain embodiments, the multilayer film
finely divided, inorganic antiblock materials, Such as may have a total thickness ranging from 10 um to 75 um,
SYLOID, a synthetic amorphous silica gel that may e.g., from 12 um to 25 lum. The thickneSS relationship of the
comprise, e.g., 99.7% SiO, diatomaceous earth comprising, layerS may be Such that the core layer constitutes from 40 to
e.g., 92% SiO, 3.3% Al-O, and 1.2% Fe.O., and obtain 95 percent of the total film thickness, the first skin layer and
able in various grades with average particle Sizes ranging Second skin layer (if present) may constitute from 1 to 15
from 5 um to 10 um (the particles may be porous and percent of the total film thickness, and the intermediate, or
irregularly shaped); dehydrated kaolin clays, Such as tie, layer(s) (if present) may constitute from 0 to 20 percent
of the total film thickness.
KAOPOLITE SF comprising, e.g., 55% SiO, 44% Al-O, For example, the first and Second Skin layerS may each
0.4% Fe2O, which has an average particle size of 0.7 um range from 0.5um to 5 Lim, e.g., from 1 um to 3 um, while
(the particles may be thin flat platelets); and Synthetic the core layer may range from 9.5 um to 74.5 tim, or from
precipitated silicates, such as SIPERNAT 44, comprising, 10 um to 23. In general, the core layer should be of sufficient
e.g., 42% SiO, 36% Al-O, 22% Na-O 22%, which has an thickness to provide the necessary bulk properties, including
average particle size of 3–4 microns (the particles may be barrier, Stiffness, and the like, that are desired for product
porous and irregularly shaped). Spherical Silica particles 15 protection and good performance on packaging equipment.
may be used as well. The amount of antiblock ranges, Orientation
typically, from 0.002 to 0.5 wt %, based upon the total Generally, a film may be oriented in the direction of
weight of the layer into which it is being incorporated. extrusion, i.e., “machine direction” (MD) orientation, and/or
Typical slip additives include higher aliphatic acid a film may be oriented in the direction perpendicular to the
amides, higher aliphatic acid esters, waxes and metal Soaps. direction of extrusion, i.e., “transverse direction” (TD) ori
A Silicone oil or Silicone gum having a Viscosity that ranges entation. In a blown film, orientation is generally effected by
from 10,000 to 2,000,000 cSt is another example of a controlling, e.g., the take-up and blow-up ratio parameters.
Suitable slip additive. An exemplary fatty amide slip additive In a cast film, MD orientation may be effected by varying the
is erucamide. The Slip additive may be present in amounts take-up speed, and TD orientation may be effected with the
ranging from 0.1 to 2 wt %, based upon the total weight of 25 use of tenter equipment, generally Subsequent to extrusion.
the layer into which it is being incorporated. A multilayer film according to the present invention may
One example of a Suitable antioxidant is a phenolic be uniaxially or biaxially oriented. In a preferred
antioxidant, Such as IRGANOX 1010, which is commer embodiment, a multilayer film according to the present
cially available from Ciba-Geigy. Antioxidants may be invention is biaxially oriented by stretching it from 3 to 7
present in an amount ranging from 0.1 to 2 wt %, based upon times, e.g., from 4.5 to 5.5 times, in the MD and from 5 to
the total weight of the layer into which they are being 10 times, e.g., from 8 to 10 times, in the TD.
incorporated. Surface-treating
One or more barrier additives may be employed in one or A multilayer film according to the present invention may
more of the layers of the present invention. Suitable barrier be Surface-treated on one or both of its outer Surfaces to
additives include, but are not limited to, low molecular 35 render the Surface more receptive to metallization, coating,
weight resins, Such as hydrocarbon resins, and more printing ink, or lamination. The film may be Surface-treated
particularly, petroleum resins, Styrene resins, cyclopentadi during orientation, after orientation, or, e.g., in a metalliza
ene resins, terpene resins, and alicyclic resins. These types tion chamber. The Surface treatment can be carried out by
of barrier additives are further described in U.S. Pat. No. any method, including, but not limited to, corona discharge
5,254,394, which is incorporated herein by reference. 40 treatment, flame treatment, or plasma treatment. Although
Examples of Suitable, commercially available resins include any of these techniques may be effectively employed, a
PICCOLYTE, REGALREZ, and REGALITE, each of particularly desirable method of Surface-treatment is the
which are available from Hercules Corp., ESCOREZ, avail So-called corona discharge treatment method, which com
able from ExxonMobil Chemical, and ARKON, available prises exposing the film Surface to a high Voltage corona
from Arakawa Chemical Co. A barrier additive(s) may be 45 discharge while passing the film between a pair of Spaced
present in a range of from 0.1 to 15 wt %, or from 0.5 to 10 electrodes. The outer surface(s) of the film may be treated to
wt %, or from 1 to 5 wt %, or from 1 to 3 wt %, based upon a Surface tension level of at least about 35 dyneS/cm, e.g.
the total weight of the layer into which it is being incorpo from about 38 to 55 dynes/cm, in accordance with ASTM
rated. Standard D2578-84.
One or more layers of the present multilayer film may also 50 In certain embodiments of the present invention, at least
include a nucleator(s), such as MILLAD 3938 available the Outer Surface of the first skin layer, i.e., the Skin layer to
from Milliken, in order to enhance crystal Structure. be metallized, is Surface-treated.
In a particular embodiment of the present invention, the Surface-treating the outer Surface(s) of the film may help
Second skin layer is compounded with a wax for lubricity. insure that the metal layer and/or coating layer, if any, will
Any Wax useful in thermoplastic films may be employed. 55 be strongly adherent thereto, thereby reducing the possibility
The wax may be present in the Second Skin layer in an that the metal layer and/or coating layer is peeled or Stripped
amount ranging from 2 to 15 wt %, based upon the total from the film.
weight of the Second Skin layer. Metallization
Typically, a commercially available intensive mixer, Such One or both of the outer Surfaces, Such as, for example,
as those of the Bolling- or Banbury-type, can be employed 60 the outer surface of the first skin layer, of a multilayer film
in mixing a concentrate of the additive material and the according to the present invention may be metallized via the
polymer(s) of the Selected layer until there is a uniform application thereto of a thin layer of metal (the outer Surface
dispersion of the additive material in the polymer or polymer of the first skin layer is the surface of the first skin layer that
blend. is opposite the core layer (or opposite the tie layer, if one is
Film and Film Layer Thickness 65 present between the first skin layer and the core layer)).
Although the thickness of the multilayer film, and the The outer surface(s) may be metallized by vacuum
thicknesses of the individual layers of the multilayer film, deposition, or any other metallization technique, Such as
 US 6,773,818 B2
9 10
electroplating or Sputtering. The metal may be aluminum, or Strate. Laminating the Outer Surface(s) may, for many appli
any other metal capable of being vacuum deposited, cations including packaging, labeling or imaging
electroplated, or Sputtered, Such as, for example, gold, Zinc, applications, Serve to complete the Structure necessary for
copper, or Silver. the given application.
Typically, a metal layer is applied to an optical density of 5
from 1.5 to 5.0, or from 1.8 to 2.6. Optical density is a Examples of Substrates that may be employed include, but
measure of the absorption of Visual light, and is determined are not limited to: a separate polymer film; a metal foil, Such
by Standard techniques. To calculate optical density, a com as aluminum foil; cellulosic webs, e.g., numerous varieties
mercial densitometer may be used, Such as a Macbeth model of paper Such as corrugated paperboard, craft paper,
TD 932, Tobias Densitometer model TDX or Macbeth glassine, and cartonboard; nonwoven tissue, e.g., spun
model TD903. The densitometer is set to zero with no film bonded polyolefin fiber and melt-blown microfibers; a met
Specimen. A film Specimen is placed over the aperture plate allizing layer, etc.
of the densitometer with the test Surface facing upwards. The According to one embodiment of the present invention,
probe arm is pressed down and the resulting optical density the outer Surface of the first skin layer is metallized and then
value is recorded. 15
laminated to a polymer film, e.g., a monolayer or multilayer
The resulting metallized film exhibits excellent oxygen polymer film. The film laminated to the outer surface of the
transmission rate (OTR) and water vapor transmission rate present film may include a slip Surface, a Seal Surface, a
(WVTR) characteristics. For example, a metallized film printed Surface, or a combination thereof.
according to the present invention may exhibit an OTR of
s20.cc/m/24 hr, as determined in accordance with ASTM For especially rigorous processes of converting the
D 3985 at 73° F (23° C) and 0% relative humidity (RH), present film into a commercial article, the metallized first
and a WVTR of s ().50 g/m/24 hr, as determined in accor skin layer and/or the, e.g., printed Second skin layer, are
dance with ASTM F1249 at 100° F (37.8° C) and 90% RH. protected via lamination, Such that the metallized layer
These improved physical properties make the film ideally and/or printed layer end up on the inside of a multilayer film
Suited for packaging food products, including those com 25 Structure.
prising liquids. The outer surface(s) of the present multilayer film may be
Coating laminated to a Substrate by employing a Suitable adhesive,
A multilayer film according to the present invention may e.g., a hot melt adhesive Such as low density polyethylene,
have a coating layer applied to one or both of its outer ethylene-methacrylate copolymer, water-based adhesives
Surfaces. For example, the outer Surface of the first skin layer Such as polyvinylidene chloride latex, and the like.
may have a coating applied thereon, and/or the Outer Surface Alternatively, the lamination may be accomplished via
of the second skin layer may have a coating applied thereon. extrusion lamination using, e.g., a polyethylene or ethylene
Preferably, any coating applied onto the Outer Surface of the
first skin layer is applied after the Outer Surface of the first co- or terpolymer. In certain embodiments, the outer Surface
skin layer has been metallized, i.e., the coating is actually 35 may be laminated to a Substrate via heat lamination, which
applied onto the metal layer that has been deposited on the uses heat and pressure to apply a lamination film onto a
first skin layer. substrate and improves the durability of the Substrate with
Examples of coatings that may be employed include out the need for more expensive water-based lamination or
acrylic coatings, Such as those described in U.S. Pat. NoS. environmentally unfriendly Solvent-based lamination.
3,753,769 and 4,865,908, both of which are incorporated 40 Process of Making the Film
herein by reference, acrylonitrile coatings, polyvinylidene A multilayer film according to the present invention may
chloride (PVDC) coatings such as those described in U.S. be formed by (i) coextruding melts for the core layer and
Pat. Nos. 4,214,039, 4,447,494, 4,961,992, 5,019,447 and first skin layer, together with the melts for any additional
5,057,177, all of which are incorporated herein by reference, layers, through, e.g., a flat sheet extruder die at a temperature
and a vinyl alcohol polymer coating, such as VINOL 325 45
available from Air Products, Inc. that may range from 200 C. to 250 C. to form a coextruded
The coating may be applied in an amount Such that there sheet, (ii) casting the coextruded sheet onto a cooling drum,
will be deposited upon drying a Smooth, evenly distributed and (iii) quenching the coextruded sheet. The sheet may then
layer that is Sufficient to further enhance the, e.g., Sealability be reheated and oriented to form a film, and (optionally)
and/or barrier characteristics of the final product. For 50 Surface-treated, metallized, coated, and/or laminated, each
example, the coating may be applied in an amount on the as described earlier.
order of from about 0.01 to about 0.2 mill thickness, which The film may be printed by any means, including, but not
may be roughly equivalent to 0.2 to 3.5g per 1000 sq. in. of limited to, letterpreSS, offset, Silk Screen, electroStatic and
film. Alternatively, the coating may be present in an amount photographic methods. More Specific examples of printing
of from 1 to 25 wt %, preferably 7 to 15 wt %, based on the 55
methods include thermal dye transfer (including dye
weight of the entire film. The coating on the film is Subse Sublimation), lithographic printing, flexographic printing,
quently dried by hot air, radiant heat or by any other gravure printing, hot Stamping, Valley printing, roll-leaf
convenient means. printing and Spanishing. Alternatively, printed matter may be
Prior to the application of the coating, the film Surface to provided to a film according to the present invention by
be coated may be Surface-treated or primed with a primer 60
laminating a Second film containing a printed layer to the
layer. An appropriate primer includes, but is not limited to, present film, as has been described.
a poly(ethyleneimine) primer and an epoxy primer.
Laminating A multilayer film according to the present invention is
One or both outer Surfaces of a multilayer film according Suitable for a wide range of applications, including, in
to the present invention may be laminated to a Substrate. For 65 addition to those already described herein above and many
example, the outer Surface of the first skin layer may be others not expressly recited herein, controlled atmosphere
metallized and Subsequently laminated to a protective Sub packaging and long-term display of Snack foods.
 US 6,773,818 B2
11 12
Definitions and Testing Protocols
TABLE I-continued
Thermal Properties
Melt Flow Rate (MFR): ASTM D-1238, condition L (Q) 230° C. 5
Melt Index (MI): ASTM D-1238, condition E (Q) 190° C. Polymer Melting Point AHf*
Oxygen ASTM D 3985 at 73° F (23° C) and 0%
Transmission Rate: relative humidity (RH) Fina 6573xHC Z-N EP copolymer 146 C. 71 J/g
Water Vapor ASTM F 1249 at 100° F (37.8° C) and 90% Fina 3371 Z-NPP homopolymer 161° C. 114 J/g
Transmission Rate: RH 10 C/min
*T or melting point determined by above procedure
Melting Point, T. ** AHf determined by above procedure
A weighed polymer Sample, equilibrated to 25 C., is
heated beyond its melting point at a rate of 10° C. per EXAMPLES
minute. The sample is cooled at 10 C. per minute to 25 C.,
and allowed to equilibrate for 3 minutes. The sample is then 15 Examples 1-4
reheated at 10 C. per minute. The melting point is defined Examples 1-4 compare the oxygen transmission rate
as the point where, during melting of the Sample, the peak (OTR) (cc/m/24 hr) as a function of the energy density
endothermic heat flow required to maintain the 10 C. per (J/m) Supplied to an in-chamber plasma Surface treater for
minute temperature rate is observed. The crystal heat of a pair of films and film laminates. The results from the
fusion (AH?) is calculated from the area under the curve, comparison are presented at Table II, wherein the entries in
from the point the Sample begins to melt to the point where the tables represent OTR (cc/m/24 hr).
melting is completed. This method has been described The first film, a comparative film identified as PP in Table
herein above as the ExxonMobil melting point method, and II, has a total thickness of 18 um and the following 3-layer
has been used to calculate each and every disclosed melting Structure:
point recited herein. 25
Melting Behavior
The thermal properties (melting point and crystal heat of
fusion AH?) of seven polymer samples were measured. The 2". SKIN Fina 6573XHC-an EP copolymer plus antiblock
first four polymer Samples, including a pair of metallocene (0.75 um thick)
catalyzed propylene homopolymers and a pair of CORE Fina 3371-a Ziegler-Natta-catalyzed propylene homopolymer
metallocene-catalyzed EP copolymers, are preferred poly (16.75 um thick)
1 SKIN Fina 3371-a Ziegler-Natta-catalyzed propylene homopolymer
olefins for the first skin layer of the present invention. The (0.5 um thick)
fifth polymer Sample was also a metallocene-catalyzed EP
copolymer, but, as will be seen, it had a melting point The Second film, a film according to the present invention
outside the preferred range. The Sixth and Seventh Samples 35
were a Ziegler-Natta-catalyzed EP copolymer and a Z-N- identified as mPP in Table II, has a total thickness of 18 um
catalyzed propylene homopolymer, respectively. Propylene and the following Structure:
based polymers that are metallocene-catalyzed tend to have
a melting point that is 8-12 C. lower than Ziegler-Natta
catalyzed propylene-based polymers having comparable 40 2". SKIN Fina 6573XHC-an EP copolymer plus antiblock
ethylene comonomer content. For example, Fina 6573xHC (0.75 um thick)
Z-N EP copolymer has an approximately equal ethylene CORE Fina 3371-a Ziegler-Natta-catalyzed propylene homopolymer
comonomer content as Fina EOD0103, but a melting point (16.75 um thick)
1 SKIN Fina EOD 98-09-a metallocene-catalyzed propylene
that is 12 C. lower. homopolymer having a MFR of 3 g/10 min (0.5 um thick)
The weighed samples were equilibrated to 25 C., and 45
heated beyond melting at a rate of 10° C. per minute. The
samples were cooled, at a rate of 10° C. per minute, to 25 For each of Examples 1-4, PP films and mPP films
C., and allowed to equilibrate for 3 minutes. The samples received (1) flame-treatment on the outer Surface (the Sur
were then reheated at 10 C. per minute. The melting points face opposite the core) of the first skin layer to a Surface
of the Samples were defined as the points where, during 50 tension level of approximately 50 dyne/cm prior to being
melting of the Samples, the peak endothermic heat flow wound after the biaxial orientation process, (2) varying
required to maintain the 10 C. per minute temperature rate degrees of plasma-treatment on the outer Surface of the first
was observed. The crystal heat of fusion (AH?) was calcu skin layer in the vacuum chamber of a metallizer just prior
lated from the area under the curve from the point each to being metallized, and (3) a metal layer on the outer
Sample began to melt to the point where melting was 55 Surface of the first skin layer. Regarding the varying degrees
completed. of plasma treatment, the energy Supplied to the in-chamber
plasma Surface treater was varied in each of Examples 1-4,
TABLE I from 0J/m° (indicating no plasma treatment) to 600 J/m to
a high of 1,130J/m. The gas supplied to the in-chamber
Thermal Properties 60 plasma Surface treater was a blend of argon and carbon
dioxide.
Polymer Melting Point AHf*
For Example 1, the OTR of PP and mPP films was
Fina EOD9809 mPP homopolymer 154 C. 76 J/g measured just prior to lamination.
Fina EOD0007 mPP homopolymer 151° C. 76 J/g
Fina EOD0103 mPP EP copolymer 134° C. 63 J/g For Example 2, the OTR of PP and mPP films was
Fina EOD0104 mPP EP copolymer 134° C. 61 J/g 65 measured after the films were laminated at the metallized
Fina EOD0106 mPP EP copolymer 114 C. N/A surface of the first skin layer to 75LBW, a conventional
3-layer film commercially available from ExxonMobil
 US 6,773,818 B2
13 14
Chemical. 75LBW has a total thickness of 19 um (75 gauge excellent OTR, thereby eliminating an extra step from the
units), a flame-treated first skin layer of HDPE (0.5 um process. Furthermore, as the energy Supplied to the
thick), a core layer of propylene homopolymer (17.75 um in-chamber plasma surface treater is increased, the PP films
thick), and a flame-treated, slip-modified Second skin layer or laminated PP films tend to slightly close the gap in OTR.
of propylene homopolymer that contains antiblock (0.75 um AS shown in Example 4, however, this does not happen at
thick). The lamination process involved extruding and cast high lamination tension, which is a Severe test for inducing
ing a molten polyethylene layer (Chevron 1017) between the crazes. This fact is especially Surprising considering that the
75 LBW (on the second skin layer side) and either the PP or melting point of metallocene-catalyzed polypropylene is
mPP film (on the metallized surface of the first skin layer), approximately 10° C. lower than that of Ziegler-Natta
and pressing together to forn. a laminate. The weight of the catalyzed polypropylene.
extruded Chevron 1017 is 7 lb/ream, and the tension on
either the PP or mPP film prior to lamination is 0.2 lb/in. Examples 5-10
For Example 3, the OTR of PP and mPP films was For Examples 5-10, Sample films A, B, and C were
measured after the laminated PP and mPP films of Example prepared. Each of films A, B, and C had a total thickness of
2 were pulled over a VFFS packaging machine forming 15
18 um (70 gauge units) and the following general structure:
collar simulator (/64" radius anvil).
For Example 4, the OTR of PP and mPP films was
measured after the films were laminated in a manner iden
tical to the procedure in Example 2, except that the tension 2". SKIN CHISSO 7794-an EPB terpolymer plus antiblock
on either the PP or mPP film prior to lamination was (1.25 um thick)
CORE Fina 3371-a Ziegler-Natta-catalyzed propylene homopolymer
increased to 0.7 lb/in. The higher tension represents a Severe 1st SKIN Different for each of A, B, and C
test for inducing crazes.
Thus, Examples 1-3 compare the films both initially after
manufacture (Example 1) and at various stages of the Film A is a film according to the present invention. Its 1
25
converting process (Examples 2 and 3). Example 4 is SKIN is 0.75 um thick, and consists of Fina EOD 01-03,
identical to Example 2, except for the higher lamination which is a metallocene-catalyzed EP copolymer having a
tension. MFR of 8 g/10 min.
Film B is a comparative film that emulates Met-HB, a film
TABLE II commercially available from ExxonMobil Chemical. Its 1
OTR (ccfm/24 hr
SKIN is 0.5um thick, and consists of HDPE.
Film C is a film according to the present invention. Its 1
Energy density PP nPP skin is 0.75 um thick, and consists of a 50/50 blend of Fina
EXAMPLE 1. EOD 01-03 and Fina EOD 00-07, which is a metallocene
35 catalyzed propylene homopolymer.
O J/m? 54 5 Each of films A, B, and C received (1) flame-treatment on
600 J/m? 21 8
1,130 J/m? 21 8 the outer Surface (the Surface opposite the core) of the first
EXAMPLE 2 skin layer to a Surface tension level of approximately 50
dyne/cm prior to being wound after the orientation process
O J/m? 29 7.5 40 (the orientation process stretched the films to a degree of 5.1
600 J/m2 25 7
1,130 J/m? 16.5 5.5 times in the MD and 8 times in the TD), and (2) a metal layer
EXAMPLE 3 on the outer Surface of the first skin layer.
OJ/m2 31 6
Films A, B, and C were laminated at the metallized
600 J/m2 23 6.5 surface of the first skin layer to 75LBW (described herein
1,130J/m 19.5 6.8
45 above). The lamination process involved extruding and
EXAMPLE 4 casting a LDPE layer between the 75 LBW (on the second
OJ/m2 16.5 5.1 skin layer side) and the films A, B, or C (on the metallized
600 J/m? 16 3.75 Surface of the first skin layer), and pressing together to form
1,130 J/m? 15.6 3.6 a laminate. The weight of the extruded LDPE varied
50 between 8 b/ream and 10 lb/ream. The OTR and WVTR of
laminated films A, B, and C was measured before and after
AS can be seen from Table II, in all instances, the mPP they were pulled over a VFFS packaging machine forming
film or laminated mPP film exhibited a better OTR than a PP
film or laminated PP film. Example 3 represents conditions collar simulator (/64" radius anvil). The results from
Examples 5-10 are presented below at Table III (OTR is
that are most like present-day commercial operation 55 given in cc/m°/24 hr, WVTR is given in g/m·/24 hr).
processes, including commercial winding tensions. The
OTR testing in Example 3 was performed after simulated TABLE III
vertical form, fill, and Sealing (VFFS) of a package. At Zero
energy density (0 J/m), the laminated mPP film outper OTR (cfm/24 hr) WVTR (gm 24 hr
formed the laminated PP film by nearly 50 percent. 60
OTR before OTR after WVTR before WVTR after
A pair of other points are notable from Table II. The mPP Ex. Film anvil anvil anvil anvil
films or laminated mPP films exhibited a remarkably low
OTR (s17.5 cc/m°/24 hr), and were especially superior to LAMINATED WITH 8 LB/REAM LDPE
the PP films or laminated PP films, at Zero energy density (0 5 B 21.2 41.2 O.10 O.18
J/m) for each of Examples 1-4. Therefore, a film according 65 6 A. 10.2 15.7 O.08 O.12
to the present invention can do without the additional plasma 7 C 4.8 12.6 O.O2 O.12
treatment of the present Examples, and still exhibit an
 US 6,773,818 B2
15 16
including certain non-thermoplastic additives within those
TABLE III-continued layers, and certain layer arrangements of the film are
exemplified, other compositions and arrangements are also
OTR (ce/m/24 hr) WVTR (gm (24 hr contemplated. Additionally, while packaging, labeling and
OTR before OTR after WVTR before WVTR after 5 imaging are included among the uses for the inventive films,
Ex. Film anvil anvil anvil anvil other uses are also contemplated. To the extent that the
foregoing description is specific, it is Solely for the purpose
LAMINATED WITH 10 LB/REAM LDPE of illustrating certain embodiments of the invention, and
8 B 27.7 86.5 O.11 0.52
should not be taken as limiting the present inventive con
9 A. 9.4 43.8 O.05 O.28 cepts to the Specific embodiments described hereinabove.
1O C 3.6 13.4 O.O2 O.12 Accordingly, the Spirit and Scope of the appended claims
should not be limited to the description of the specific
embodiments contained herein.
As can be seen from Table III, in Examples 5-10, the What is claimed is:
mPP-containing laminated films (A and C) in all cases had 15
1. An oriented multilayer film, comprising:
at least a 49% lower OTR and a 20% lower WVTR than the c) a core layer comprising a polyolefin; and
comparative film, even after simulated FFS. d) a first skin layer comprising a polyolefin Selected from
the group consisting of (i) a metallocene-catalyzed,
Examples 11-13 Substantially isotactic propylene homopolymer, (ii) a
Films D, E, and F were prepared for Examples 11, 12, and metallocene-catalyzed propylene copolymer, and (iii)
13, respectively. Each of films D, E, and F had a total blends thereof,
thickness of 18 um (70 gauge units) and the following wherein the core layer has a first Surface and a Second
general Structure: Surface, the first skin layer has a first and a Second Surface,
the Second Surface of the first skin layer is contiguous to and
in contact with the first Surface of the core layer, and the first
25 Surface of the first skin layer is metallized.
2"SKIN CHISSO 7794-an EPB terpolymer plus antiblock 2. The oriented multilayer film of claim 1, wherein the
(1.25 um thick) core layer comprises a polyolefin Selected from the group
CORE Fina 3371-a Ziegler-Nata-catalyzed propylene homopolymer consisting of a metallocene-catalyzed polypropylene (mPP),
1 SKIN Different for each of D, E, and F a metallocene-catalyzed polyethylene (mPE), a Ziegler
Natta-catalyzed polypropylene (Z-NPP), a Ziegler-Natta
catalyzed polyethylene (Z-NPE) and blends thereof.
Film D is a comparative film. Its 1' SKIN is 0.5 um thick, 3. The oriented multilayer film of claim 1, wherein the
and consists of Fina 6573, which is a Ziegler-Natta polyolefin of the first skin layer has a melting point (T) of
catalyzed propylene copolymer. from 120° C. to 155° C.
Film E is a film according to a preferred embodiment of 35
4. The oriented multilayer film of claim 1, wherein the
the invention. Its 1' SKIN is 0.5 um thick, and consists of film has an oxygen transmission rate (OTR) of s20.cc/m/
Fina EOD 0103, which is a metallocene-catalyzed propylene 24 hr, as determined in accordance with ASTM D 3985 at
copolymer. 73° F (23° C) and 0% relative humidity (RH), and a water
The 1 SKIN of Film F is 0.5um thick, and consists of vapor transmission rate (WVTR) of s ().50 g/m·/24 hr, as
determined in accordance with ASTM F 1249 at 100 F.
Fina EOD 01.06. Fina EOD 01.06 is a metallocene-catalyzed 40
(37.8° C) and 90% RH.
propylene copolymer, but it has a melting point outside the 5. The oriented multilayer film of claim 1, further com
preferred range. prising a Second skin layer, wherein the Second skin layer
Each of films D, E, and F received (1) flame-treatment on has a first Surface and a Second Surface, and the first Surface
the Outer Surface (the Surface opposite the core) of the first of the Second Skin layer is contiguous to and in contact with
skin layer to a Surface tension level of approximately 50 45 the Second Surface of the core layer.
dyne/cm prior to being wound after the orientation process 6. The oriented multilayer film of claim 5, wherein the
(the orientation process stretched the films to a degree of 5.1 Second skin layer comprises a polymer Selected from the
times in the MD and 8 times in the TD), and (2) a metal layer group consisting of a Substantially isotactic polypropylene,
on the outer surface of the first skin layer. The OTR and a Substantially Syndiotactic polypropylene, a polyethylene, a
WVTR of films D, E, and F was measured after the 50 propylene copolymer having an ethylene or C-Co C-olefin
metallization. comonomer, a propylene terpolymer having at least one of
ethylene and butene-1 as one comonomer, an ethylene-Vinyl
TABLE IV acetate (EVA), an ethylene-methyl acrylate (EMA), an
OTR
ethylene-ethyl acrylate (EEA), an ethylene-n-butyl acrylate
(ccfm/24 hr) WVTR (gfm/24 hr) 55 (EnBA), an ethylene-acrylic acid (EAA), an ethylene
methacrylic acid (EMAA), an ethylene-vinyl alcohol
Example 11-Film D 154.7 1.24 (EVOH), and blends thereof.
Example 12-Film E 14.9 O.26
Example 13-Film F 258.8 O.775 7. The oriented multilayer film of claim 6, wherein the
Second Skin layer comprises a propylene-ethylene-butene-1
60 terpolymer.
The foregoing describes in detail certain combinations of 8. The oriented multilayer film of claim 5, further com
thermoplastics and metallization of thermoplastics, their prising one or both of (i) a coating on a Second Surface of the
fabrication into useful articles Such as multilayer films, and Second skin layer and (ii) a coating on the metallized Surface
uses of these articles. Those skilled in the art will appreciate of the first skin layer.
that numerous modifications to these embodiments may be 65 9. A laminate, comprising the oriented multilayer film of
made without departing from the Scope of the invention. For claim 1 laminated at the metallized Surface of the first skin
example, while certain specific film layer compositions, layer to a Second film.
 US 6,773,818 B2
17 18
10. The laminate of claim 9, wherein the second film is a 17. The process of claim 14, further comprising a step (cc)
multilayer film comprising at least one printed layer. after the orienting step (c) and before the metallizing Step
11. The oriented multilayer film of claim 1, wherein the (d), wherein in step (cc), the oriented multilayer film is
first skin layer consists essentially of a metallocene Surface-treated on the first Surface of the first skin layer.
catalyzed, Substantially isotactic propylene homopolymer. 18. An oriented multilayer film, comprising:
12. The oriented multilayer film of claim 1, wherein the
first skin layer consists essentially of a metallocene a) a core layer comprising a polyolefin; and
catalyzed propylene copolymer. b) a first skin layer comprising a polyolefin Selected from
13. The oriented multilayer film of claim 1, wherein the the group consisting of (i) a metallocene-catalyzed,
oriented multilayer film is a biaxially oriented multilayer 1O
Substantially isotactic propylene homopolymer, (ii) a
film.
14. A process for producing the oriented multilayer film of metallocene-catalyzed propylene copolymer, and (iii)
claim 1, comprising: blends thereof,
e) coextruding melts corresponding to the core layer and wherein the core layer has a first Surface and a Second
the first skin layer to form a coextruded sheet; 15 Surface, the first skin layer has a first and a Second Surface,
f) cooling the coextruded sheet; one or more tie layers are present between the Second
g) orienting the coextruded sheet to form an oriented surface of the first skin layer and the first surface of the core
multilayer film; and layer, and the first Surface of the first Skin layer is metallized.
h) metallizing the oriented multilayer film on the first 19. The oriented multilayer film of claim 18, further
Surface of the first skin layer. comprising a Second Skin layer on the Second Surface of the
15. The process of claim 14, wherein the oriented multi core layer.
layer film further comprises a Second skin layer contiguous 20. The oriented multilayer film of claim 18, further
to and in contact with the Second Surface of the core layer, comprising a Second skin layer, wherein the Second skin
and in Step (a) of the process, melts corresponding to the 25
layer has a first Surface and a Second Surface, and one or
core layer, first skin layer, and Second skin layer are coex more tie layers are present between the first Surface of the
truded to form a coextruded sheet.
16. The process of claim 14, wherein in step (c) of the Second skin layer and the Second Surface of the core layer.
process, the coextruded sheet is biaxially oriented to form a
biaxially oriented multilayer film.