WO2000023509A1 - Polyolefin microporous breathable film having improved tear, impact strength, and softness and method of making same - Google Patents
Polyolefin microporous breathable film having improved tear, impact strength, and softness and method of making same Download PDFInfo
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- WO2000023509A1 WO2000023509A1 PCT/US1999/023856 US9923856W WO0023509A1 WO 2000023509 A1 WO2000023509 A1 WO 2000023509A1 US 9923856 W US9923856 W US 9923856W WO 0023509 A1 WO0023509 A1 WO 0023509A1
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- polypropylene
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
- A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
- A61F13/51401—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
- A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
- A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties
- A61F13/51458—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable
- A61F13/51462—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable being defined by a value or parameter
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
- A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
- A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties
- A61F13/51464—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being stretchable or elastomeric
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
- A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
- A61F13/51474—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its structure
- A61F13/51478—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its structure being a laminate, e.g. multi-layered or with several layers
- A61F13/5148—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its structure being a laminate, e.g. multi-layered or with several layers having an impervious inner layer and a cloth-like outer layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
Definitions
- This invention relates generally to a polyolefm microporous breathable film and method of making same. More specifically this invention is directed toward filled
- WVTR High tear strength
- dart impact strength high dart impact strength
- extrusion is intended to include extrusion, coextrusion, extrusion coating, or combinations thereof, whether by tubular methods, planar methods, or
- An "oriented” material is defined herein as a material which, when heated to an appropriate temperature above room temperature (e.g., 96 °C), will have a free shrink of about
- polymer shall include all possible molecular configurations of the material.
- structures include, but are not limited to isotactic, syndiotactic and random molecular
- polyethylene refers to families of resins obtained by substantially polymerizing the gas ethylene C 2 H 4 . Polyethylenes having densities ranging
- LDPE low density polyethylenes
- LLDPE linear low density polyethylene
- polyethylene to be employed in the film of the invention refers to the copolymers comprised of a major amount of ethylene with a minor amount of one or more comonomers selected
- alpha olefins such as butene-1, 4-methyl petene-1, hexene-1, octene-1 , etc. in which the molecules thereof comprise long chains with few side chains or
- linear polymer may be intertwined, but the forces tending to hold the molecules together are
- Linear low density polyethylene has a density preferably in the range from about 0.911
- the Melt Flow Index of LLDPE generally ranges from between about 0.1 to about 10.0 grams per ten minutes and preferably between from about 0.5 to about 3.0
- LLDPE resins of this type are commercially available and are manufactured in low pressure vapor phase and liquid phase processes using transition metal
- LLDPE is well known for its structural strength and anti-stress cracking properties. Also, LLDPE is known for its favored properties in the heat shrink process, and thus is well suited to make a heat shrinkable film as discussed above. Also, very low density linear low density polyethylenes (VLDPE) may be employed, and such have a density from about 0.010
- g/cc to about 0.860 g/cc, or less.
- polypropylene as used herein which polypropylene is a type of polyolefm that may be employed in the film of the present invention, refers to families of resins obtained by substantially polymerizing the gas propylene, C 3 H 6 .
- weight distribution can be regulated over wide ranges. Further modifications are obtained by other processes, such as halogenation, and compounding additives. Background
- polymers usually polyefins
- polyolefm usually a polyolefm
- polyethylene with a filler, usually CaCO 3 , while very useful and widely used as a film with good WVTR, often, but not necessarily, in combination with non-woven polymers (for use in diapers, adult incontinence devices, surgical garments, feminine hygiene articles, housewrap
- glue, hot melt, or melt blown adhesive techniques can be used, but these traditional attachment techniques all require the additional cost and process complexity of operating the
- polyethylene films have been deficient in a number of other performance categories.
- polypropylene films were quite stiff, thus not suitable for providing a comfortable feel against
- a hot melt type adhesive gluing system such as a breathable film diaper
- a polypropylene breathable film provides greater resistance to glue burn through.
- a polypropylene breathable film assures product integrity. Also, the use of a
- polypropylene breathable film enables the use of higher temperature glues, as well as a smaller quantity of glue to achieve adequate product bond strength. Accordingly, there is a commercial need for a polypropylene microporous breathable film with improved tear strength, improved dart impact strength, as well as a soft feel.
- Dart impact strength is approximately double that found in previously available polypropylene breathable films.
- Machine Direction tear strength is more than triple that found in previously available
- Figure 1 shows the geometry of interdigitating rollers
- Figure 2 shows a machine direction orientation roller
- Figure 3 shows a transverse direction orientation roller
- FIG. 4 is a cross-sectional of view of an exemplary Water Vapor Transmission Rate (WVTR) test cell.
- WVTR Water Vapor Transmission Rate
- This invention concerns certain breathable films made from a polypropylene and filler blend that exhibit high WVTR, and the ability to be drawn down to low basis weights, as well as methods for making same. Particularly useful in the disclosed films and methods is impact
- copolymer polypropylene This invention further includes certain polypropylenes, their conversion into
- the filled polypropylene films disclosed herein are particularly well suited for use in
- Such consumer articles include, but are not limited to diapers, adult incontinence
- building products such as "house-wrap", roofing components, filtration media, controlled atmosphere packaging and the like made using one or more of the films disclosed herein.
- films of the present invention may be used in metallized films with a high WNTR, according to the disclosure of U.S. Patent 5,055,338, which is to be fully
- polypropylene and film processes including, blow molding, casting, or cast melt embossing.
- the preferred process is a cast melt embossed film process.
- the films of the present invention can be formed into a single layer film, or one
- polypropylene films described herein can be formed or utilized in the form of a resin blend where the blend
- components function to modify the WVTR, the physical properties, the draw-down, the sealing, the cost, or other parameters.
- blend of the present invention may also be included in laminated structures. As long as a
- film, multi layer film, or laminated structure includes one or more polypropylene and filler blend film layers having the WVTR, or draw-down, and the like of the film disclosed herein,
- the polyolefin precursor film component can be. any film forming polyolefin blend, as long as the majority of the polyolefin component is a polypropylene. Examples of suitable
- polypropylene materials are:
- Fillers useful in this invention may be any inorganic or organic material having a low
- the filler should be a rigid material having a non-smooth hydrophobic surface, or
- particle size of the filler is between about 0.5-5.0 microns for films generally having a
- inorganic fillers examples include calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium, sulfate, barium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, .glass powder, zeolite, silica clay, etc.
- Calcium carbonate (CaCO 3 ) is particularly preferred for its low cost, its whiteness, its inertness, and its availability.
- the selected inorganic filler, such as calcium carbonate is
- the surface treatment of the filler should improve binding of the filler to
- a preferred coating for the filler is calcium stearate which is both FDA compliant and readily available.
- Organic fillers such as wood powder, and other cellulose type powders may be used.
- Polymer powders such as Teflon® powder and Kevlar ® powder can also be used.
- the amount of filler added to the polyolefin precursor depends on the desired properties of the film including dart impact strength, tear strength, WVTR, and stretchability. However, it is believed that a film with good WVTR generally cannot be produced as is
- the minimum amount of filler (about twenty percent by weight) is needed to assure
- the preferred filler range is about thirty percent (30%) to about seventy percent (70%) by weight, based on the total weight of
- More preferred filler loading will be about forty percent
- polyolefin/filler combinations will be understood to be contemplated as embodiments of our invention as long as the final film, after orientation, exhibits WVTR, or draw-down similar to that described herein.
- the polyolefin/filler blend allows film extrusion at higher throughput levels.
- Low density polyethylene with a Melt Flow Index of about 0.9 to 25.0 grams per ten minutes (being preferred), and a density of about 0.900 to 0.930 may be used.
- Final preparation of a breathable film is achieved by stretching the filled polyolefin precursor film to form interconnected voids. Stretching or "orientation" of the film is achieved
- TD transverse direction
- film 100 is contracted by the apex 18 of a plurality of teeth spaced a distance or pitch (W) apart.
- each tooth extends into the open space 20 between the teeth on the opposing
- Machine direction orientation is accomplished by stretching the film through a gear-like
- the tooth depth (d), is preferably 0.100",
- the depth may be up to about 1.000" as mechanical
- the depth of interengagement of the roller teeth determines the amount of orientation imparted on the film. A balance must be drawn between the depth of engagement of the roller
- certain films and articles made therefrom have higher WVTR than previously thought possible.
- the WVTR of such films should be above
- the dry side is near 0%.
- the amount of water vapor in the air stream is precisely measured by
- PMIR pulse modulated infra red
- WVTR of 8700 g/ ⁇ r/day @ 37.8°C is used as a reference.
- the testing protocols are based on
- the Mocon Wl has a single test cell
- Air is pumped through a desiccant dryer, then through the test cell, and
- the Mocon W600 has six measurement cells with PMIR data fed into a computer.
- Nitrogen is fed through a desiccant dryer, then through the active test cell, then past the PMIR
- measurement cells are purged simultaneously for an eight-minute period. This is followed by an eight-minute test cycle for each of the six measurement cells. Total testing time is fifty-six
- the films produced by the disclosed method have physical
Abstract
A polyolefin microporous breathable film having improved tear and impact strength as well as a soft feel is provided by a film including a polypropylene precursor film and a filler. Other embodiments include a second polymer component.
Description
POLYOLEFIN MICROPOROUS BREATHABLE FILM HAVING
IMPROVED TEAR, IMPACT STRENGTH, AND SOFTNESS
AND METHOD OF MAKING SAME
RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application 60/104,455 filed October 16, 1998 and U.S. Provisional Patent Application 60/104,948 filed October 20, 1998.
BACKGROUND OF THE INVENTION
Field
This invention relates generally to a polyolefm microporous breathable film and method of making same. More specifically this invention is directed toward filled
polypropylene microporous breathable films having an improved Water Vapor Transmission
Rate (WVTR), high tear strength, high dart impact strength, and a soft feel.
Definitions
As used therein the term "extrusion" is intended to include extrusion, coextrusion, extrusion coating, or combinations thereof, whether by tubular methods, planar methods, or
combinations thereof.
An "oriented" material is defined herein as a material which, when heated to an appropriate temperature above room temperature (e.g., 96 °C), will have a free shrink of about
5% or greater in at least one linear direction.
Unless specifically set forth and defined or otherwise limited, the term "polymer" as
used herein generally includes, but is not limited to, homopolymers, copolymers, such as, for
example, block, graft, random and alternating copolymers, terpolymers, etc. and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term
"polymer" shall include all possible molecular configurations of the material. These
structures include, but are not limited to isotactic, syndiotactic and random molecular
configurations.
The term "polyethylene" as used herein refers to families of resins obtained by substantially polymerizing the gas ethylene C2H4. Polyethylenes having densities ranging
from about 0.900 g/cc to about 0.935 g/cc are typically called low density polyethylenes (LDPE).
The term "linear low density polyethylene" (LLDPE) as used herein for a type of
polyethylene to be employed in the film of the invention, refers to the copolymers comprised of a major amount of ethylene with a minor amount of one or more comonomers selected
from C3 to about C10 or higher alpha olefins such as butene-1, 4-methyl petene-1, hexene-1, octene-1 , etc. in which the molecules thereof comprise long chains with few side chains or
branched structures achieved by low pressure polymerization. The side branching which is
present will be short as compared to non-linear polyethylenes. The molecular chains of a
linear polymer may be intertwined, but the forces tending to hold the molecules together are
physical rather than chemical and thus may be weakened by energy applied in the form of heat. Linear low density polyethylene has a density preferably in the range from about 0.911
g/cc, more preferably in the range of from about 0.912 g/cc to about 0.928 g/cc for film making purposes. The Melt Flow Index of LLDPE generally ranges from between about 0.1 to about 10.0 grams per ten minutes and preferably between from about 0.5 to about 3.0
grams per ten minutes. LLDPE resins of this type are commercially available and are manufactured in low pressure vapor phase and liquid phase processes using transition metal
catalysts. LLDPE is well known for its structural strength and anti-stress cracking properties.
Also, LLDPE is known for its favored properties in the heat shrink process, and thus is well suited to make a heat shrinkable film as discussed above. Also, very low density linear low density polyethylenes (VLDPE) may be employed, and such have a density from about 0.010
g/cc to about 0.860 g/cc, or less.
The term "polypropylene" as used herein which polypropylene is a type of polyolefm that may be employed in the film of the present invention, refers to families of resins obtained by substantially polymerizing the gas propylene, C3H6.
By varying the comonomers, catalysts and methods of polymerization, properties such
as density, melt index, crystallinity, degree of branching, molecular weight and molecular
weight distribution can be regulated over wide ranges. Further modifications are obtained by other processes, such as halogenation, and compounding additives. Background
Techniques for the preparation of films having good WVTR from highly filled
polymers, usually polyefins, is known. In the past, a combination of a polyolefm, usually a
polyethylene, with a filler, usually CaCO3, while very useful and widely used as a film with good WVTR, often, but not necessarily, in combination with non-woven polymers (for use in diapers, adult incontinence devices, surgical garments, feminine hygiene articles, housewrap
composites, protective apparel, roofing materials and the like), has exhibited some limitations
that have become well known in the industry. Among the most serious of the limitations of filled film polyethylene is the extreme
difficulty in producing a cost effective lamination between polypropylene nonwoven materials and filled polyethylene breathable films. Traditional attachment techniques such as
glue, hot melt, or melt blown adhesive techniques can be used, but these traditional
attachment techniques all require the additional cost and process complexity of operating the
laminating system as well as the cost of the adhesive itself. The preferred method of heat
lamination to attach the filled polyethylene film to the polypropylene nonwoven materials was found to be generally not reliable because of the difference in the melting points of the
polypropylene nonwoven material (about 161°C) and the polyethylene film (about 125°C). It has been found that to achieve an adequate lamination bond strength between these two materials, pin holes or damage to the filled polyethylene breathable film occurred at the bond
site to the polypropylene nonwoven material.
Prior art polypropylene breathable films, while having lamination advantages over
polyethylene films, have been deficient in a number of other performance categories.
Specifically, prior art polypropylene films oriented by traditional Machine Direction
Orientation, Transverse Direction Orientation, or Biaxial Orientation (all well known in the art) have exhibited very low tear and impact strength. In addition, the resultant
polypropylene films were quite stiff, thus not suitable for providing a comfortable feel against
human skin when used for disposables or garments.
For those applications wherein the polypropylene breathable film is not laminated directly to a nonwoven polypropylene, or which by the nature of the product, requires
utilization of a hot melt type adhesive gluing system (such as a breathable film diaper
backsheet), a polypropylene breathable film provides greater resistance to glue burn through. Thus, the use of a polypropylene breathable film assures product integrity. Also, the use of a
polypropylene breathable film enables the use of higher temperature glues, as well as a smaller quantity of glue to achieve adequate product bond strength.
Accordingly, there is a commercial need for a polypropylene microporous breathable film with improved tear strength, improved dart impact strength, as well as a soft feel. SUMMARY
We have discovered that producing a precursor film from a polypropylene and filler
(preferably Calcium Carbonate) blend, then incrementally orienting the precursor film in the
machine direction, or the transverse direction, or both, will yield a reasonably soft film (to the touch) with good dart impact and good tear strength. It was further discovered that adding a
minority amount of a low density polyethylene to the polypropylene and filled blend greatly
improves extrusion processability. It was further discovered that the addition of a minority amount of an elastomer or a plastomer further improved dart impact strength and tear
strength, and contributed to an even softer film feel against human skin. Dart impact strength is approximately double that found in previously available polypropylene breathable films.
Machine Direction tear strength is more than triple that found in previously available
Machine Direction Oriented and Biaxially Oriented polypropylene breathable films.
Transverse Direction tear strength is more than triple that found in previously available
Transverse Direction Oriented and Biaxial Oriented polypropylene breathable films. Such dramatic improvements in the physical properties of films are unexpected and surprising.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the Polyolefm Microporous Breathable Film of the present
invention may be had from the drawing figures, wherein:
Figure 1 shows the geometry of interdigitating rollers; Figure 2 shows a machine direction orientation roller;
Figure 3 shows a transverse direction orientation roller; and
Figure 4 is a cross-sectional of view of an exemplary Water Vapor Transmission Rate (WVTR) test cell.
DETAILED DESCRIPTION Introduction
This invention concerns certain breathable films made from a polypropylene and filler blend that exhibit high WVTR, and the ability to be drawn down to low basis weights, as well as methods for making same. Particularly useful in the disclosed films and methods is impact
copolymer polypropylene. This invention further includes certain polypropylenes, their conversion into
fabricated articles such as films, articles made from such films, and applications in which such articles having high WVTR combined with good physical properties such as improved dart impact strength, improved tear strength and soft feel are desirable. The resulting films,
and film composites, (including coextruded and laminated films) have combinations of properties which render them superior and unique to films or film composites previously
available.
The filled polypropylene films disclosed herein are particularly well suited for use in
producing certain classes of high WVTR films, consumer and industrial articles which use the
filled polypropylene films in combination with, for instance, polymeric woven or non-woven materials. Such consumer articles include, but are not limited to diapers, adult incontinence
devices, feminine hygiene articles, medical and surgical gowns and garments, other medical garments, drapes and absorption pads, surgical drapes, industrial apparel, sportswear,
building products such as "house-wrap", roofing components, filtration media, controlled
atmosphere packaging and the like made using one or more of the films disclosed herein.
Additionally the films of the present invention may be used in metallized films with a high WNTR, according to the disclosure of U.S. Patent 5,055,338, which is to be fully
incorporated herein by reference in its entirety. Production of the Films
Films contemplated by certain embodiments of the present invention may be made
using polypropylene and film processes including, blow molding, casting, or cast melt embossing. The preferred process is a cast melt embossed film process. In extrusion
processes, the films of the present invention can be formed into a single layer film, or one
layer or more of a multi-layer film or film composite. Alternatively, the polypropylene films described herein can be formed or utilized in the form of a resin blend where the blend
components function to modify the WVTR, the physical properties, the draw-down, the sealing, the cost, or other parameters.
Both blend components and the parameters provided thereby will be well known to those of ordinary skill in the art. The breathable films made from the polypropylene and filler
blend of the present invention may also be included in laminated structures. As long as a
film, multi layer film, or laminated structure includes one or more polypropylene and filler blend film layers having the WVTR, or draw-down, and the like of the film disclosed herein,
such film, multi layer film or laminated structure will be understood to be contemplated as an
embodiment of the present invention.
Polyolefin Precursor Film
The polyolefin precursor film component can be. any film forming polyolefin blend, as long as the majority of the polyolefin component is a polypropylene. Examples of suitable
polypropylene materials are:
It will be understood that, in general, we contemplate that a large number of
polypropylenes will be useful in the techniques and applications described herein. Filler
Fillers useful in this invention may be any inorganic or organic material having a low
affinity for and a significantly lower elasticity than the film used as the polyolefin precursor. Preferably, the filler should be a rigid material having a non-smooth hydrophobic surface, or
a material which is treated to render its surface hydrophobic. The preferred mean average
particle size of the filler is between about 0.5-5.0 microns for films generally having a
thickness of about 1 to about 6 mils prior to stretching.
Examples of the inorganic fillers include calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium, sulfate, barium
sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, .glass powder, zeolite, silica clay, etc.
Calcium carbonate (CaCO3) is particularly preferred for its low cost, its whiteness, its inertness, and its availability. The selected inorganic filler, such as calcium carbonate is
preferably surface treated to be hydrophobic so that the filler can repel water to reduce
agglomeration. Also, the surface treatment of the filler should improve binding of the filler to
the polyolefin precursor while allowing the filler to be pulled away from the precursor film
under stress. A preferred coating for the filler is calcium stearate which is both FDA compliant and readily available.
Organic fillers such as wood powder, and other cellulose type powders may be used.
Polymer powders such as Teflon® powder and Kevlar ® powder can also be used.
The amount of filler added to the polyolefin precursor depends on the desired properties of the film including dart impact strength, tear strength, WVTR, and stretchability. However, it is believed that a film with good WVTR generally cannot be produced as is
taught herein with an amount of filler less than about twenty percent (20%) by weight of the
combined polyolefin/filler blend.
The minimum amount of filler (about twenty percent by weight) is needed to assure
the interconnection within the polyolefin precursor film of voids created at the situs of the filler - particularly by the stretching operation to be subsequently performed. Further, it is
believed that useful films could not be made with an amount of the filler in excess of about seventy percent (70%) by weight of the combined polyolefin/filler composition. It has been
found, however, that higher amounts of filler may cause difficulty in compounding and
significant losses in strength of the final breathable film. The preferred filler range is about
thirty percent (30%) to about seventy percent (70%) by weight, based on the total weight of
the combined polyolefin/filler blend. More preferred filler loading will be about forty percent
(40%) to about sixty percent (60%) by weight.
While a broad range of fillers has been described at a broad range of inclusion
parameters based on weight percentages, still other embodiments of the present invention are contemplated. For instance, fillers with much higher or much lower specific gravity may be
included with the polyolefin precursor at amounts outside the weight ranges disclosed. Such
polyolefin/filler combinations will be understood to be contemplated as embodiments of our invention as long as the final film, after orientation, exhibits WVTR, or draw-down similar to that described herein.
Film Physical Property Modification
It was also found that the addition of small amounts of low density polyethylene to
the polyolefin/filler blend allows film extrusion at higher throughput levels. Low density polyethylene with a Melt Flow Index of about 0.9 to 25.0 grams per ten minutes (being preferred), and a density of about 0.900 to 0.930 may be used.
Still further improvements in the dart impact strength and tear strength of the film are
possible by the addition of plastomers, elastomers, styrenic block co-polymers (styrene-
isoprene-styrene, styrene-butadiene-styrene), metallocene catalyzed polyethylene, ethylene propylene elastomer polymers, ethylene propylene diene elastomeric polymers or
combinations thereof, Ethylene-vinly-acetate, Ethylene-methacrylate, Ethylene-ethyl-
acrylate, and the like, or rubbers. Other commonly available material grades include, but are
not limited to, those appearing in the following table.
Stretching or Orienting
Final preparation of a breathable film is achieved by stretching the filled polyolefin precursor film to form interconnected voids. Stretching or "orientation" of the film is achieved
by incrementally orienting the polyolefin precursor film in the machine direction (MD),
transverse direction (TD), or both. Films can be incrementally oriented by a number of mechanical techniques, however, the preferred technique is to stretch the film in the space between pairs of interdigitating rollers, as shown in Figure 1. Therein it may be seen that the
film 100 is contracted by the apex 18 of a plurality of teeth spaced a distance or pitch (W) apart.
The apex 18 of each tooth extends into the open space 20 between the teeth on the opposing
roller. The amount of interengagement depends both on the tooth depth (d) and the relative
position of the rollers.
Machine direction orientation is accomplished by stretching the film through a gear-like
pair of rollers 16 as shown in Figure 2. Transverse direction orientation is accomplished by
stretching the film through a pair of disk-like rollers 26 as shown in Figure 3.
The preferred embodiment employs rollers with a tooth pitch, W = 0.080", however a pitch of about 0.040" to 0.500" is also acceptable. The tooth depth (d), is preferably 0.100",
however, a tooth depth of about 0.030" to 0.500" is also acceptable. For the transverse direction
orientation rollers, as shown in Figure 3, the depth may be up to about 1.000" as mechanical
interference is less of an issue when using transverse direction rollers 26.
The depth of interengagement of the roller teeth determines the amount of orientation imparted on the film. A balance must be drawn between the depth of engagement of the roller
teeth and the level of filler in the film, as many physical properties of the film are affected as depicted in the following table.
Relationships between process and formulation factors
Properties of Films Produced WNTR
In an embodiment of the present invention, certain films and articles made therefrom have higher WVTR than previously thought possible. The WVTR of such films should be above
about 100 g/m /24 hr @ 37.8°C, 100% RH, preferably above about 1000 g/m2/24 hr @ 37.8°C,
100% RH, more preferably above about 2000 g/m2/24 hr @ 37.8°C, 100% RH. Some
applications benefit from film with up to about 10,000 g/m2/24 hr @ 37.8°C, 100% RH WVTR
and above (e.g. garments, etc.). TEST METHODS
Water Vapor Transmission Rate (WVTR) Both a Mocon Wl, and a Mocon W600 instrument can be used to measure water evaporated from a sealed wet cell at 37.8°C through the test film and into a stream of dry air or
nitrogen. It is assumed that the relative humidity on the wet side of the film is near 100%), and
the dry side is near 0%. The amount of water vapor in the air stream is precisely measured by
a pulse modulated infra red (PMIR) cell. Following appropriate purging of residual air, and after
reaching a steady state water vapor transmission rate, a reading is taken. WVTR of the test films are reported at Grams of Water/Meter/Day @ 37.8°C. The output of the unit has been calibrated
to the results obtained with a film of known WVTR. Typically, a Celgard 2400 film having a
WVTR of 8700 g/πr/day @ 37.8°C is used as a reference. The testing protocols are based on
ASTM 1249-90. The diagram depicted in Figure 4 illustrates the basic operation of the Mocon units.
Mocon Wl
As illustrated generally by reference to Figure 4, the Mocon Wl has a single test cell and
an analog chart recorder. Air is pumped through a desiccant dryer, then through the test cell, and
then past the PMIR sensor. A five-minute purge of residual air is followed by a six-minute test cycle with controlled air flow. The result is a steady state value for WVTR. The purge and test
cycles are controlled manually. The unit is calibrated to a film with a known WVTR every twelve hours. Calibration results are control charted and adjustments are made to the instrument
calibration accordingly.
Mocon W600
The Mocon W600 has six measurement cells with PMIR data fed into a computer.
Nitrogen is fed through a desiccant dryer, then through the active test cell, then past the PMIR
sensor. In addition to data compilation, a computer controls test cycle sequencing. All
measurement cells are purged simultaneously for an eight-minute period. This is followed by an eight-minute test cycle for each of the six measurement cells. Total testing time is fifty-six
minutes. Two of the six measurement cells always measure reference films with a known WVTR. EXAMPLES
Example 1. Experimental grade 300-1 1-1
A blend of 52% ECC FilmLink 400 CaCO3 was combined with 48% Exxon PD 7623
Impact Copolymer Polypropylene. The film was oriented off line with interdigitating rolls of
0.100" pitch. The MD depth of engagement was 0.030", and the TD depth of engagement was 0.019".
Example 2. Experimental grade 400-4-1
A blend of 52% ECC FilmLink 400 CaCO3 was combined with 40% Exxon PD 7623
Impact Copolymer, 2% Exxon LD-200.48, 6% Exxon SLX9101. The film was oriented in interdigitating rolls of 0.080" pitch. The MD depth of engagement was 0.028", and the TD depth of engagement was 0.034".
Example 3. Experimental grade 500-9-3
A blend of 55% ECC FilmLink 400 CaCO3 was combined with 31% Exxon PD 7623
Impact Copolymer, 4% Exxon LD-200.48, 2% Ampacet 110131 TiO2, concentrate, and 8%
Exxon Exact 3131. The film was oriented in interdigitating rolls of 0.080" pitch. The MD depth
of engagement was 0.021", and the TD depth of engagement was 0.037".
The following table demonstrates the absolute values of tear strength and dart impact
strength of the film produced in three examples.
Table of Example Film Properties
Example 1 Example 2 Example 3
Based on the foregoing, the films produced by the disclosed method have physical
properties as described below:
WVTR (gm/sqm/day) 100 - 10,000
Dart Impact Strength (gm) 100 - 300 grams
MD Elongation (%) 150% - 550%
TD Elongation (%) 150% - 550% MD Elmendorf Tear Strength (gm) 20 - 300 grams
Changes and modifications in the specifically described embodiments can be carried out
without departing from the scope of the invention which is intended to be limited only by the
scope of the appended claims.
Claims
1. A breathable polypropylene/filler film comprising: an impact copolymer polypropylene precursor film; and a filler present in said precursor film in the range of from about 20% to about 70%) by weight, based on the total weight of said film, wherein said film has a dart impact strength in the range of from about 100 to about 300 grams, wherein said film has an Elmendorf tear strength in the range of from about 20 to about 300 grams, wherein said film has a WVTR in the range of from about 100 to about 10,000 gm/m2/24 hrs at 37.8°C, and wherein said film has an MD or TD elongation in the range of from about 150% to about 550%.
2. The breathable polypropylene/filler film as defined in Claim 1 wherein said impact copolymer polypropylene film is selected from a group consisting of a random copolymer polypropylene, an impact copolymer polypropylene, a metallocene catalyzed polypropylene, and combinations thereof.
3. The breathable polypropylene/filler film as defined in Claims 1 or 2, wherein the filler is selected from the group consisting of calcium carbonate, talc, clay, kaoline, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, glass powder, zeolite, silica clay, and combinations thereof.
4. The breathable polypropylene/filler film as defined in Claim 1 , wherein said filler is calcium carbonate, said calcium carbonate being present in said film in the range of from about 30% to about 60% by weight, based on the total weight of said film.
5. The breathable polypropylene/filler film as defined in Claim 1, wherein said film additionally includes at least a second polymer component selected from the group consisting of low density polyethylene, linear low density polyethylene, metallocene catalyzed polyethylene, styrene-isoprene-styrene, styrene-butadiene-styrene, ethylene propylene elastomeric polymers, ethylene propylene diene elastomeric polymers, and combinations thereof.
6. The breathable polypropylene/filler film as defined in Claim 1, wherein the film is laminated to a non-woven polymeric material by a method selected from the group consisting of adhesive lamination, heat lamination, ultrasonic lamination, and combinations thereof.
7. The breathable polypropylene/filler film as defined in Claim 1 or Claim 6 wherein said film or said combination of film and non-woven polymeric material is formed into a fabricated article selected from the group consisting of diapers, adult incontinence devices, feminine hygiene articles, surgical garments, surgical drapes, sportswear, industrial apparel, house wrap, filtration media, roofing components, and controlled atmosphere packaging.
8. A breathable polypropylene/filler film comprising: an random copolymer polypropylene precursor film; and a filler present in said precursor film in the ratio with said polypropylene in the range of about 30% top about 60%o by weight, based on the total weight of said film, wherein said film has a dart impact strength in the range of from 100 — 300 grams, wherein said film has an Elmendorf tear strength in the range of from about 20 to about 300 grams, wherein said film has a WNTR in the range of from about 100 to about 10,000 g/m2/24 hr, and wherein said film has an MD or TD elongation in the range of from about 150%> to about 550%.
9. A method of making a microporous breathable film comprising the steps of: selecting a film forming a polyolefin precursor, said polyolefin precursor having polypropylene as a majority component; blending said film forming polyolefin precursor with a filler which is a rigid material having a low affinity for the polyolefin precursor and a lower elasticity than the polyolefin precursor, and having a non-smooth hydrophobic surface such that the filler is about 30% to about 70% of the combined weight of the filler and the polyolefin precursor; combining said polyolefin precursor/filler blend with an additive selected from a group including a plastomer, an elastomer, a styrenic block co-polymer, a rubber or a combination thereof; and stretching the combination of said blended polyolefin/filler blend and said additive to form interconnected voids.
10. The method as defined in Claim 9 wherein said step of stretching the combination uses interdigitating grooved rollers.
11. The method as defined in Claim 10 wherein said interdigitating grooved rollers are positioned in a direction selected from the group consisting of machine direction (MD), transverse direction (TD), and a combination thereof.
12. The process as defined in Claim 9 wherein said film forming polyolefin precursor is selected from the group consisting of an impact copolymer polypropylene, a random copolymer polypropylene, and a combination thereof.
13. The method as defined in Claim 9 wherein said filler is selected from the group consisting of calcium carbonate, talc, clay, kaoline, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, glass powder, zeolite, silica clay and combinations thereof.
14. The method as defined in Claim 9 further including the step of laminating the microporous breathable film to a non-woven polymer.
15. The method as defined in Claim 14 further including the step of forming said combination of microporous breathable film and non-woven polymer into an article selected from the group consisting of diapers, adult incontinence devices, feminine hygiene articles, surgical garments, surgical drapes, sportswear, industrial apparel, house wrap, filtration media, roofing components, and controlled atmosphere packaging.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU64295/99A AU6429599A (en) | 1998-10-16 | 1999-10-14 | Polyolefin microporous breathable film having improved tear, impact strength, and softness and method of making same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10445598P | 1998-10-16 | 1998-10-16 | |
US60/104,455 | 1998-10-16 | ||
US10494898P | 1998-10-20 | 1998-10-20 | |
US60/104,948 | 1998-10-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000023509A1 true WO2000023509A1 (en) | 2000-04-27 |
Family
ID=26801563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/023856 WO2000023509A1 (en) | 1998-10-16 | 1999-10-14 | Polyolefin microporous breathable film having improved tear, impact strength, and softness and method of making same |
Country Status (2)
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AU (1) | AU6429599A (en) |
WO (1) | WO2000023509A1 (en) |
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EP1673408A1 (en) * | 2003-09-29 | 2006-06-28 | Fina Technology, Inc. | Oriented films prepared using impact copolymer polypropylene |
WO2007132429A1 (en) * | 2006-05-15 | 2007-11-22 | The Procter & Gamble Company | Polymeric webs with nanoparticles |
US7749924B2 (en) | 2005-08-29 | 2010-07-06 | Bfs Diversified Products, Llc | Thermoplastic roofing membranes |
US7882671B2 (en) * | 2006-02-21 | 2011-02-08 | Bfs Diversified Products, Llc | Multi-layer co-extruded roofing membrane |
WO2015175593A1 (en) * | 2014-05-13 | 2015-11-19 | Clopay Plastic Products Company, Inc. | Breathable and microporous thin thermoplastic film |
US9656445B2 (en) * | 2001-02-20 | 2017-05-23 | Kingspan Insulation Llc | Protective drainage wraps |
WO2018038656A1 (en) * | 2016-08-24 | 2018-03-01 | Sca Hygiene Products Ab | Absorbent article with breathable backsheet |
US10717255B2 (en) | 2015-11-05 | 2020-07-21 | Berry Plastics Corporation | Polymeric films and methods for making polymeric films |
US11472085B2 (en) | 2016-02-17 | 2022-10-18 | Berry Plastics Corporation | Gas-permeable barrier film and method of making the gas-permeable barrier film |
US11584111B2 (en) | 2018-11-05 | 2023-02-21 | Windmoeller & Hoelscher Kg | Breathable thermoplastic film with reduced shrinkage |
US11612524B2 (en) | 2020-02-19 | 2023-03-28 | Colormasters, LLC | Breathable diaper backsheet |
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EP1673408A4 (en) * | 2003-09-29 | 2006-10-11 | Fina Technology | Oriented films prepared using impact copolymer polypropylene |
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US7749924B2 (en) | 2005-08-29 | 2010-07-06 | Bfs Diversified Products, Llc | Thermoplastic roofing membranes |
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