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USH2000H1 - Method for making polyolefin/filler films having increased WVTR - Google Patents

Method for making polyolefin/filler films having increased WVTR Download PDF

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Publication number
USH2000H1
USH2000H1 US08/691,106 US69110696A USH2000H US H2000 H1 USH2000 H1 US H2000H1 US 69110696 A US69110696 A US 69110696A US H2000 H USH2000 H US H2000H
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Prior art keywords
film
filler
wvtr
films
polyethylene
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US08/691,106
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English (en)
Inventor
Jeffrey Alan Middlesworth
Kevin Arthur Brady
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Priority to US08/691,106 priority Critical patent/USH2000H1/en
Assigned to EXXON CHEMICAL PATENTS INC. reassignment EXXON CHEMICAL PATENTS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BRADY, KEVIN A., MIDDLESWORTH, JEFFREY A.
Priority to EP97935263A priority patent/EP0921943B1/fr
Priority to CA002261610A priority patent/CA2261610A1/fr
Priority to PCT/US1997/013580 priority patent/WO1998005502A1/fr
Priority to AT97935263T priority patent/ATE226887T1/de
Priority to DE69716744T priority patent/DE69716744T2/de
Priority to AU38247/97A priority patent/AU740098B2/en
Application granted granted Critical
Publication of USH2000H1 publication Critical patent/USH2000H1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0032—Ancillary operations in connection with laminating processes increasing porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/06—Embossing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0641—MDPE, i.e. medium density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/20—Fibres of continuous length in the form of a non-woven mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene

Definitions

  • This invention relates generally to polyolefin films having greatly increased water vapor transmission rate, herein after denoted as WVTR and methods of making same. More specifically this invention is directed toward filled polyethylene films having increased WVTR at a given filler loading, and a given set of process conditions.
  • Yet another limitation of the conventional Z-N filled and oriented films is related to both WVTR and production rates. Specifically, with a given conventional filled polyethylene, to attain a certain WVTR, a certain filler loading had to be used. In general, within limits, the higher the filler loading, the more difficult to process (the above referenced production problems such as large void creation and tear offs are exacerbated by a higher filler loading, as the film maker seeks to maximize production rates).
  • U.S. Pat. No. 4,777,073 suggests a permeability and strength of polyethylene/filler combinations may be attained by combining a LLDPE described as being made using a Zeigler-Natta or chromium catalysts, with fillers such as CaCO 3 present in the LLDPE from 15 to 35 percent by volume which is equivalent to 34-62% by weight.
  • the metallocene catalyzed polyethylenes (m-polyethylene) will have a molecular weight distribution (defined as the ratio of weight average molecular weight to number average molecular weight M w /M n ) generally less than 3, preferably less than 2.5.
  • the drawdown of a filled m-polyethylene will be more than 10, preferably more than 20, more preferably more than 30 percent less than the ultimate drawdown of a filled Z-N polyethylene, where the relationship in the filled Z-N polyethylene between the filler amount and basis weight (minimum) for films follow the general equation:
  • W is the minimum basis weight in g/m2 in the film.
  • water vapor transmission rate (WVTR) of a filled m-polyethylene is at least 10 percent greater, preferably at least 20 percent, more preferably at least 30 percent greater than a filled Z-N polyethylene, at the same filler loading and thickness (basis weight), where the Z-N polyethylene/filler WVTR is described by the equation:
  • WVTR ⁇ 10,900+320 (weight % CaCO 3 )
  • WVTR ⁇ 9967+358 (weight % CaCo 3 )
  • FIG. 1 illustrates the drawdown advantage of filled m-polyethylene over Z-N polyethylene with a plot of minimum basis weight in g/m2 versus filler loading.
  • FIG. 2 illustrates the WVTR advantage of m-polyethylene versus Z-N polyethylene in a plot of WVTR versus percentage of filler CaCO 3 both at 2.7:1 draw ratio and 22 g/m 2 basis weight
  • This invention concerns certain polyethylene/filler films that will have high WVTR and the ability to be drawn down to low basis weights and methods for making same. Particularly useful in these films and methods will be m-polyethylenes.
  • films of m-polyethylene and filler can be made with lower amounts of filler and still attain substaintially the same WVTR as previously known and used Z-N polyethylene/filer combinations (at higher filler loadings) are also contemplated.
  • This invention further includes certain m-polyethylenes, 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 are desirable.
  • the resulting films, and film composites, (including coextruded and laminated films) have combinations of properties rendering them superior and unique to films or film composites previously available.
  • the filled m-polyethylene films disclosed herein are particularly well suited for use in producing certain classes of high WVTR films, consumer and industrial articles using the films in combination with for instance, polymeric woven or non-woven materials.
  • consumer articles include, but are not limited to diapers, adult incontinence devices, feminine hygiene articles, medical and surgical gowns, medical drapes, industrial apparel, building products such as “house-wrap”, roofing components, and the like made using one or more of the films disclosed herein.
  • films having increased WVTR of the present invention may also be used in metallized films with a high WVTR, according to the disclosure of U.S. Pat. No. 5,055,338, fully incorporated herein for purposes of U.S. Patent practice.
  • Fabrics suitably laminated to the breathable film in the housewrap of the present invention include any high strength fabric which can be bonded to the breathable film without adversely affecting the water vapor permeability or the resistance to air permeability of the breathable film, i.e. the fabric must generally have a suitably open mesh to avoid substantialy blocking the micropores of the breathable film.
  • the fabric may be woven of any suitable material, but is preferably non woven polyolefin such as, for example, low density polyethylene, polypropylene, and preferably linear, low density polyethylene or high density polyethylene.
  • the fabric should have an elongation (ASTM D1682) less than about 30%: an Emendorf tear strength (ASTM D689) of at least about 300 g, preferably at least about 600 g and especially at least about 900 g: and a break load (ASTM D1682) of at least about 15 lb/in., preferably at least about 25 lb/in., and especially at least about 30 lb/in/
  • ASTM D1682 Emendorf tear strength
  • the fabrics are believed to be prepared from HDPE films having outer layers of ethylene vinyl acetate coextruded on either side of the HDPE or heat seal layers. The films are fibrillated, and the resulting fibers are spred in at least two transverse directions at a strand count of about 6010 per inch.
  • the spread fibers are then cross laminated by heat to produce a nonwoven fabric of 3-5 mils with about equal MD and TD strength.
  • These fabrics have excellent strength properties in both MD and TD for reinforcing the breathable film, an open structure to avoid substantially blocking the micopores of the breathable film when laminated thereto, and an outer layer of ethylene vinyl acetate copolymer for heat sealability.
  • the fabric and the breathable film are laminated together to form the breathable composite of the invention.
  • the lamination may be effected by facing the film and the fabric together and applying heat and pressure.
  • the laminating temperatures to which the film and fabric are exposed should be sufficient to achieve lamination, but should not be too high in order to avoid the flow of the film polymer into the microporous spaces and consequent reduction in water vapor transmissibility.
  • the fabric is heated on a hot roller, preferably at 200°-240° F., and then pressed, prefeably at a pressure of about 50-100 psi, into contact with the unheated film to bond the fabric and film into laminate.
  • Preferred fabrics are commercially available under the trade designation DD1001, CC-2001 and CC-3001 CLAF nonwoven HDPE Fabrics.
  • the filled m-polyethylene films when oriented after film formation, would surprisingly and unexpectedly have high WVTR when compared to a filled polyethylene film made using previously available Z-N catalyzed polyethylenes.
  • films based on low density m-polyethylenes filled with CaCO3 are exemplified herein, the films may be made using combinations of m-polyethylenes with other polyolefins and with other fillers or filler combinations.
  • the films may be made using combinations of m-polyethylenes with other polyolefins and with other fillers or filler combinations.
  • Films contemplated by certain embodiments of the present invention may be made utilizing m-polyethylenes, by processes including, blown and cast, prefered is a cast film process.
  • the films of the present invention can be formed into a single layer film, or may be one layer or more of a multi-layer film or film composite.
  • the m-polyethylene films described in this disclosure can be formed or utilized in the from a resin blend where the blend components can function to modify WVTR, physical properties, draw-down sealing, cost, or other functions. Both blend components and functions provided thereby will be known to those of ordinary skill in the art. Films of the present invention may also be included in laminated structures.
  • a film, multi layer film, or laminated structure includes one or more m-polyethylene/filler film layers having the WVTR, or draw-down, and the like of the film, and the M w /M n , CDBI and the like of the m- polyethylene , in the ranges described herein, it will be understood to be contemplated as an embodiment of the present invention.
  • the polyolefin component can be any film forming polyloefin or polyolefin blend, as long as the majority of the polyolefin component is a polyolefin with the following features:
  • a metallocene catalyzed polyolefin preferred is a m-polyethylene, preferably a linear low density m-polyethylene with a density in the range of from about 0.90-0.940, preferred 0.910-0.935, more preferred 0.912-0.925 g/cc.
  • Densities referred to herein will generally be polymer or resin densities, unless otherwise specified.
  • m-polyethylenes will be useful in the techniques and applications described herein. Included components: ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene dodecene copolymers, ethylene-1-pentene copolymers, as well as ethylene copolymers of one or more C4 to C20 containing alpha-olefins, diolefins, and combinations thereof.
  • a nonexclusive list of such polymers ethylene, 1-butene, 1-pentene; ethylene, 1-butene, 1-hexene; ethylene, 1-butene, 1-octene; ethylene, 1-butene, decene; ethylene, 1-pentene, 1-hexene; ethylene, 1-pentene, 1-octene; ethylene, 1-pentene, decene; ethylene, 1-octene; 1-pentene; ethylene 1-octene; decene; ethylene, 4-methyl-1-pentene, 1-butene; ethylene 4-methyl-1-pentene, 1-pentene; ethylene, 4methyl-1-pentene, 1-hexene; ethylene 4-methyl-1-pentene, 1-octene; ethylene, 4-methyl-1-pentene, decene. Included in the ethylene copolymers will be one or more of the above monomers included at a total level of 0.2 to 6 mole percent, preferably 0.5 to 4 mole percent
  • Fillers useful in this invention may be any inorganic or organic material having a low affinity for and a significantly lower elasticity than the polyolefin component.
  • 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 microns for films generally having a thickness of between 1-6 mils prior to stretching.
  • 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 is particularly preferred for low cost, whiteness, inertness, and availability.
  • the inorganic filler such as calcium carbonate are preferably surface treated to be hydrophobic so that the filler can repel water to reduce agglomeration of the filler.
  • the surface coating should improve binding of the filler to the polymer while allowing the fuller to be pulled away from the polyolefin under stress.
  • a preferred coating is calcium stearate which is 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 polyethylene depends on the desired properties of the film including tear strength, water vapor transmission rate, 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 20 percent by weight of the polyolefin/filler composition.
  • the minimum amount of filler is needed to insure the interconnection within the film of voids created at the situs of the filler particularly by the stretching operation to be subsequently performed on the precursor film. Further, it is believed that useful films could not be made with an amount of the filler excess of about 70 percent by weight of the polyolefin/filler composition. Higher amounts of filler may cause difficulty in compounding and significant losses in strength of the final breathable film.
  • fillers with much higher or much lower specific gravities may be included in the polyolefin at amounts outside the weight ranges disclosed, they will be understood to be contemplated as embodiments of our invention as long as the final film, after orientation has WVTR or drawn down similar to that described herein.
  • Final preparation of a breathable film is achieved by stretching the filled m-polyethylene precursor film to form interconnected voids. Stretching or “Orientation” of the film may be carried out monoaxially in the machine direction (MD) or the transverse direction(TD) or in both directions(biaxially) either simultaneously or sequentially using conventional equipment and processes following cooling of the precursor film.
  • MD machine direction
  • TD transverse direction
  • TD transverse direction
  • Film orientation may also be carried out in a tentering device with or without MD orientation to impart TD orientation to the film.
  • the film is gripped by the edges for processing through the tentering device.
  • Stretching of melt embossed precursor films with a tentering device at a film speed of about 200-500 per minute produces breathable films having the desired water vapor permeability.
  • the resulting films had a greater permeability in the areas of reduced thickness in comparison to the areas of greater thickness.
  • a range of stretching ratios from 2:1 to 5:1 prove satisfactory for MD stretching with a ratio of 4:1 being preferred.
  • a range of stretching ratios of 2:1 to 5:1 prove satisfactory for TD stretching with a ratio of 3:1 being preferred.
  • tension be maintained on the film during the heat setting and cooling to minimize shrinkback.
  • ambient temperature i.e., room temperature
  • the holding force may be released.
  • the film may contract somewhat (snapback) in the TD but will retain a substantial portion of its stretched dimension.
  • Heat setting can be accomplished by maintaining the film under tension in the stretched condition at the heat setting temperature for about 1-2 minutes. Preferably, however, the heat setting and cooling is carried out while permitting the film to contract slightly, but still under stress.
  • the controlled shrinkback of from 5 to 30%, preferably between 15 and 25%, of the maximum stretched width has given particularly good results in eliminating storage shrinkage.
  • certain films and articles made therefrom have higher WVTR than previously thought possible.
  • the WVTR of such films should be above 100 g/m 2 /day @ 37.8° C., 90% RH, preferably above 1000, more preferably above 3000 g/m 2 /day @ 25° C.
  • FIG. 2 illustrates the WVTR advantage of m-polyethylene versus Z-N polyethylene in a plot of WVTR versus percentage percentage of filler CaCO 3 .
  • the films of embodiments of the present invention will have a much higher WVTR at the same filler loading than previously known Z-N polyethylene based filled films.
  • the inventive films will have a WVTR at least 10% higher than the WVTR of the comparative films described by the equation:
  • WVTR ⁇ 10,900+320 (weight % CaCO 3 )
  • a m-polyethylene/filler combination film can be stretched (oriented or tentered in the TD) less than a Z-N polyethylene combination film, and still achieve substantially the same WVTR (at generally the same filler loadings).
  • m-polyolefins to form the films of the invention with other materials such as other linear polyethylenes (HDPE, MDPE, LLDPE), low density polyethylene (LDPE), polypropylene (PP) (homopolymers and copolymers), polybutene-1 (PB), ethylene vinyl acetate (EVA), or other ethylene polar comonomer copolymers and the like to fabricate useful articles.
  • Such potential blend polyolefins may be conventional Zeigler-Natta catalyzed, chromium catalyzed, free radical initiated, and the like.
  • WVTR of the layer or layers intended to impart WVTR should generally be within limits disclosed above.
  • any blend component or components additive or additives should be chosen such that the desired WVTR of the film remains at or above the targeted or desired value.
  • Any blend should preferably contain a majority of m-polyethylene as the polyolefin component, specifically greater than 50 weight percent, preferably greater than 60 weight percent, more preferably greater than 70 (75?) percent, based on the total weight of the polyolefin
  • the WVTR test measures the quantity of water vapor that is able to pass through a film.
  • a Mocon Permatran W-1 unit is used to measure WVTR by passing a stream of dry air across the surfaces of the film. The dry air picks up moisture that has passed, from wet pads underneath the film, through to the top surface.
  • the moisture level is measured by an infrared (IR) detector and converted to a voltage which can be measured on a chart recorder.
  • IR infrared
  • films of m-polyethylene resins of certain embodiments of the present invention can be combined with other materials, depending on the intended function of the resulting film.
  • Embodiments of the present invention offer a significant and unexpected improvement in the ability for the formulations to be drawn down.
  • a lower limit of 2.5, more practically 3.5 mils has routinely been observed (as extruded) upstream, i.e. before orientation.
  • films of embodiments of the present invention may be drawn down to a practical limit of 2 mils, providing a significant advantage in terms of either economics or a combination of economics and softness. The softness comes abvout due to the decreased modulus of the lower thickness.
  • Ultimate drawdown is defined as minimum gage (or basis weight) before the onset of draw resonance at a given extruder rate (e.g., lb/hr).
  • the films of embodiments of the present invention will have ultimate drawdown more than 20%, preferably 25%, more preferably 30% less than that of filled Z-N polyethylene which, from FIG. 2 has an ultimate drawdown described by the general formula:
  • Examples 1-3 were fabricated from EscoreneTM LL 3003.09 on a 6 inch Marshall & Williams cast extrusion line at normal processing conditions processing conditions listed in Table 1a.
  • Example 1 used a 50/50 weight ratio of the polyethylene to CaCO 3
  • examples 2-3 used a 65/35 ratio of polyethylene to filler all films were subsequently oriented (TD) to three different basis weights as seen in Table 1.
  • Examples 4-9 were fabricated from ExceedTM ECD-112, under the same processing conditions as examples 1-3.
  • Examples 4-6 used a 50/50 weight ratio of the polyethylene to CaCO 3
  • examples 7-9 used a 65/35 ratio of polyethylene to filler. All films were subsequently oriented (TD) to three different basis weights as seen in Table 2.
  • Examples 10-15 are run as in Example 4-9, but the polyolefin component was a blend of LD-202 (12-MI, 0.917 g/cc low density polyethylene available from Exxon Chemical Co.) and ECD112. As can be seen from the data in Table 3, at the same basis weight Examples 4-6, and 7-9, the corresponding films of Examples 10-15 had somewhat lower, but still acceptable WVTR. Also of note is Example 15 which was the lowest basis weight attainable in this series (1-15) of examples (again orientation was TD).
  • Examples 16-23 were extruded similar conditions to the previous examples, into two (2) thickness of precursor (before orientation) film (4.5 and 6 mils) and oriented in the MD at 175° F. While WVTR results for this set of examples appear to be substantially the same for both metallocene and Z-N polyethylenes, it is anticipated that when the orientation speed is increased, the m-LLDPE will show improved WVTR, over the Z-N-LLDPE, just as found in the TD orientation in examples 1-15. The results are shown in Tables 4 and 5.
  • Examples 24 and 25 were extruded under substantially the same conditions as the previous examples. Examples 24 is substantially the same in polyethylene/filler content as example 4 and example 25 is substantially the same make-up as example 1.
  • Example 24 was drawn (oriented) at a 2.7:1 draw ratio, while example 25 was drawn at a 3.8:1 ratio. These examples show that the m-LLDPE at a lower (28%) draw ratio than the Z-N LLDPE, example 24 has generally the same WVTR. The results are shown in Table 6.
  • Example 2 Example 3 Basis Wt., g/m 2 22.1 22.5 18.7 Yield, yd 2 /lb. 24.6 24.1 29.0 Emb. Cal., mils 1.17 1.13 .98 Gurley, seconds 1137 Off-Scale Off-Scale WVTR, g/m 2 /24 5100 300 500 MD Tear, g 473 486 386 TD 170° F.
  • Example 2 Example 3 Basis Wt., g/m 2 22.1 22.5 18.7 Yield, yd 2 /lb. 24.6 24.1 29.0 Emb. Cal., mils 1.17 1.13 .98 Gurley, seconds 1137 Off-Scale Off-Scale WVTR, g/m 2 /24 5100 300 500 MD Tear, g 473 486 386 TD 170° F.
  • Example 16 Example 17 50% CaCO 3 50% CaCO 3 50% CaCO 3 50% CaCO 3 in in in ECD-115 in ECD-115 LL3003.09 LL3003.09 4:1 Draw 6:1 Draw 4:1 Draw 6:1 Draw PROPERTY Ratio Ratio Ratio Ratio Basis Weight, 54.7 34.5 54.84 34.87 g/m 2 Embossed 2.43 1.93 3.29 2.79 Caliper, mils WVTR, 6100 7950 6500 7250 g/m 2 /24 hours Gurley Poro- 855 307 581 379 sity, sec/100 cc MD Tensile 1094 1289 1084 1344 at 5%, g/in MD Tensile 2290 3034 2192 3041 at 10%, g/in MD Tensile 4540 — 3774 — at 25%, g/in MD Tensile 7273 7725 5085 6135 at Break, g/in MD Elong.
  • Example 21 50% CaCO 3 50% CaCO 3 50% CaCO 3 50% CaCO 3 in in in ECD-115 in ECD-115 LL3003.09 LL3003.09 4:1 Draw 6:1 Draw 4:1 Draw 6:1 Draw PROPERTY Ratio Ratio Ratio Ratio Basis Weight, 63.19 47.95 65.72 44.47 g/m 2 Embossed 3.30 2.68 3.20 2.55 Caliper, mils WVTR, 5450 7500 6250 7800 g/m 2 /24 hours Gurley Poro- 1151 363 541 282 sity, sec/100 cc MD Tensile 1336 1597 1370 1659 at 5%, g/in MD Tensile 2837 3691 2758 3686 at 10%, g/in MD Tensile 5598 — 4736 5025 at 25%, g/in MD Tensile 9294 9934 6131 7479 at Break, g/in MD Elong.
  • Example 24 Example 25 mLLDPE Z-N LLDPE 50% CaCO 3 50% CaCO 3 2.7:1 draw 3.8:1 draw PROPERTY ratio ratio Yield yd 2 /lb 23.62 26.23 Basis Weight g/m 2 23.13 20.85 Embossed Caliper mils 1.26 1.61 Gurley Porosity Seconds/100 cc 251 230 WVTR g/m 2 /24 hours 7613 7688 MD Tensile at 5% Elg. grams/in 195.5 174.7 MD Tensile at 10% Elg. grams/in 269.1 272.9 MD Tensile at 25% Elg. grams/in 301.7 321.8 MD Tensile at Break grams/in 477.6 431.7 MD Elong.

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  • Organic Chemistry (AREA)
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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
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US08/691,106 1996-08-01 1996-08-01 Method for making polyolefin/filler films having increased WVTR Abandoned USH2000H1 (en)

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US08/691,106 USH2000H1 (en) 1996-08-01 1996-08-01 Method for making polyolefin/filler films having increased WVTR
EP97935263A EP0921943B1 (fr) 1996-08-01 1997-07-31 Films stratifies de nwf respirants tres permeables a la vapeur d'eau et prepares a partir de films precurseurs de polyolefine/charge moules a chaud
CA002261610A CA2261610A1 (fr) 1996-08-01 1997-07-31 Films stratifies de nwf respirants tres permeables a la vapeur d'eau et prepares a partir de films precurseurs de polyolefine/charge moules a chaud
PCT/US1997/013580 WO1998005502A1 (fr) 1996-08-01 1997-07-31 Films stratifies de nwf respirants tres permeables a la vapeur d'eau et prepares a partir de films precurseurs de polyolefine/charge moules a chaud
AT97935263T ATE226887T1 (de) 1996-08-01 1997-07-31 Aus schmelzgeprägten polyolefin/füllstoff ausgangsfolien hergestellte atmungsaktive folien/nwf-laminate mit hoher wasserdampfpermeabilität.
DE69716744T DE69716744T2 (de) 1996-08-01 1997-07-31 Aus schmelzgeprägten Polyolefin/Füllstoff Ausgangsfolien hergestellte atmungsaktive Folien/NWF-Laminate mit hoher Wasserdampfpermeabilität.
AU38247/97A AU740098B2 (en) 1996-08-01 1997-07-31 Polyolefin/filler films having increased WVTR and method for making

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US20030071391A1 (en) * 1996-07-31 2003-04-17 Kevin A. Brady Process of adjusting wvtr of polyolefin film
WO2003095191A1 (fr) * 2002-05-08 2003-11-20 Vifan Usa, Inc. Films en polypropylene a remplissage eleve presentant des vides
US20040023585A1 (en) * 2001-06-19 2004-02-05 Carroll Todd R. Vapor permeable, liquid impermeable composite fabric and fabrication process
US6706228B2 (en) 1998-10-16 2004-03-16 Exxonmobil Chemical Company Process for producing polyolefin microporous breathable film
US20040157075A1 (en) * 2000-06-09 2004-08-12 Building Materials Investment Corporation Single ply thermoplastic polyolefin (TPO) roofing membranes having superior heat seam peel strengths and low temperature flexibility
US6843949B2 (en) 1996-07-31 2005-01-18 Tredegar Film Products Corporation Process for adjusting WVTR and other properties of a polyolefin film
US6953510B1 (en) 1998-10-16 2005-10-11 Tredegar Film Products Corporation Method of making microporous breathable film
US20060040091A1 (en) * 2004-08-23 2006-02-23 Bletsos Ioannis V Breathable low-emissivity metalized sheets
US20060155028A1 (en) * 2005-01-12 2006-07-13 Lee Chun D Linear low density polyethylene compositions and films
US20080096452A1 (en) * 2006-09-19 2008-04-24 Tredegar Film Products Corporation Breathable Laminate With A High Abrasion Resistance and Method of Manufacturing the Same
US20130082414A1 (en) * 2002-03-15 2013-04-04 Fiberweb, Inc. Microporous Composite Sheet Material
WO2015175593A1 (fr) 2014-05-13 2015-11-19 Clopay Plastic Products Company, Inc. Film thermoplastique mince, microporeux et perméable à l'air
US20170232652A1 (en) * 2016-02-17 2017-08-17 Berry Plastics Corporation Gas-permeable barrier film and method of making the gas-permeable barrier film
US9765459B2 (en) 2011-06-24 2017-09-19 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9827696B2 (en) 2011-06-17 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9827755B2 (en) 2011-06-23 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US10369769B2 (en) 2011-06-23 2019-08-06 Fiberweb, Inc. Vapor-permeable, substantially water-impermeable multilayer article

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US6719742B1 (en) 1998-12-30 2004-04-13 Kimberly-Clark Worldwide, Inc. Pattern embossed multilayer microporous films
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US7270723B2 (en) 2003-11-07 2007-09-18 Kimberly-Clark Worldwide, Inc. Microporous breathable elastic film laminates, methods of making same, and limited use or disposable product applications
BRPI0707178A2 (pt) 2006-01-27 2011-04-26 Clopay Plastic Prod Co materiais respiráveis e respectivos métodos de formação
DE102012219593B4 (de) 2011-10-25 2024-06-20 Vector Foiltec Gmbh Folienelement für ein eine Folie aufweisendes Gebäudeumhüllungselement sowie Verfahren und Vorrichtung zur Herstellung eines derartigen Gebäudeumhüllungselementes
US11872740B2 (en) 2015-07-10 2024-01-16 Berry Plastics Corporation Microporous breathable film and method of making the microporous breathable film
KR20200039818A (ko) 2015-11-05 2020-04-16 베리 글로벌 인코포레이티드 중합체 필름 및 중합체 필름의 제조 방법
ES2701915T3 (es) 2016-03-22 2019-02-26 Rkw Se Procedimiento para la preparación de una cinta de película cargada
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US6776947B2 (en) * 1996-07-31 2004-08-17 Exxonmobil Chemical Company Process of adjusting WVTR of polyolefin film
US20030071391A1 (en) * 1996-07-31 2003-04-17 Kevin A. Brady Process of adjusting wvtr of polyolefin film
US6843949B2 (en) 1996-07-31 2005-01-18 Tredegar Film Products Corporation Process for adjusting WVTR and other properties of a polyolefin film
US6706228B2 (en) 1998-10-16 2004-03-16 Exxonmobil Chemical Company Process for producing polyolefin microporous breathable film
US6953510B1 (en) 1998-10-16 2005-10-11 Tredegar Film Products Corporation Method of making microporous breathable film
US20040157075A1 (en) * 2000-06-09 2004-08-12 Building Materials Investment Corporation Single ply thermoplastic polyolefin (TPO) roofing membranes having superior heat seam peel strengths and low temperature flexibility
US7501357B2 (en) 2001-06-19 2009-03-10 Kappler, Inc. Vapor permeable, liquid impermeable composite fabric and fabrication process
US20040023585A1 (en) * 2001-06-19 2004-02-05 Carroll Todd R. Vapor permeable, liquid impermeable composite fabric and fabrication process
US9790629B2 (en) * 2002-03-15 2017-10-17 Fiberweb, Llc Microporous composite sheet material
US20130082414A1 (en) * 2002-03-15 2013-04-04 Fiberweb, Inc. Microporous Composite Sheet Material
WO2003095191A1 (fr) * 2002-05-08 2003-11-20 Vifan Usa, Inc. Films en polypropylene a remplissage eleve presentant des vides
WO2005014281A1 (fr) * 2003-07-25 2005-02-17 Building Materials Investment Corporation Membranes de toiture en polyolefines thermoplastiques unicouche presentant des resistances au pelage en soudage thermique et une flexibilite a basse temperature
EP1648696A4 (fr) * 2003-07-25 2008-03-12 Building Materials Invest Corp Membranes de toiture en polyolefines thermoplastiques unicouche presentant des resistances au pelage en soudage thermique et une flexibilite a basse temperature
US7805907B2 (en) 2004-08-23 2010-10-05 E.I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US20060040091A1 (en) * 2004-08-23 2006-02-23 Bletsos Ioannis V Breathable low-emissivity metalized sheets
US20080187740A1 (en) * 2004-08-23 2008-08-07 E. I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US20080060302A1 (en) * 2004-08-23 2008-03-13 E. I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US20080057292A1 (en) * 2004-08-23 2008-03-06 E. I. Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US8431209B2 (en) 2004-08-23 2013-04-30 E I Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US8497010B2 (en) 2004-08-23 2013-07-30 E I Du Pont De Nemours And Company Breathable low-emissivity metalized sheets
US7439290B2 (en) 2005-01-12 2008-10-21 Equistar Chemicals, Lp Linear low density polyethylene compositions and films
US20060155028A1 (en) * 2005-01-12 2006-07-13 Lee Chun D Linear low density polyethylene compositions and films
US20080096452A1 (en) * 2006-09-19 2008-04-24 Tredegar Film Products Corporation Breathable Laminate With A High Abrasion Resistance and Method of Manufacturing the Same
US9827696B2 (en) 2011-06-17 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US10800073B2 (en) 2011-06-17 2020-10-13 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9827755B2 (en) 2011-06-23 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US10850491B2 (en) 2011-06-23 2020-12-01 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US11383504B2 (en) 2011-06-23 2022-07-12 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US11123965B2 (en) 2011-06-23 2021-09-21 Fiberweb Inc. Vapor-permeable, substantially water-impermeable multilayer article
US10369769B2 (en) 2011-06-23 2019-08-06 Fiberweb, Inc. Vapor-permeable, substantially water-impermeable multilayer article
US10900157B2 (en) 2011-06-24 2021-01-26 Berry Global, Inc. Vapor-permeable, substantially water-impermeable multilayer article
US10253439B2 (en) 2011-06-24 2019-04-09 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US9765459B2 (en) 2011-06-24 2017-09-19 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
US11866863B2 (en) 2011-06-24 2024-01-09 Berry Global, Inc. Vapor-permeable, substantially water-impermeable multilayer article
WO2015175593A1 (fr) 2014-05-13 2015-11-19 Clopay Plastic Products Company, Inc. Film thermoplastique mince, microporeux et perméable à l'air
EP4177054A1 (fr) 2014-05-13 2023-05-10 Berry Film Products Company, Inc. Film thermoplastique mince, microporeux et perméable à l'air
EP3142858B1 (fr) 2014-05-13 2024-07-03 Berry Film Products Company, Inc. Film thermoplastique mince, microporeux et perméable à l'air
US20170232652A1 (en) * 2016-02-17 2017-08-17 Berry Plastics Corporation Gas-permeable barrier film and method of making the gas-permeable barrier film
US11472085B2 (en) * 2016-02-17 2022-10-18 Berry Plastics Corporation Gas-permeable barrier film and method of making the gas-permeable barrier film

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ATE226887T1 (de) 2002-11-15
EP0921943B1 (fr) 2002-10-30
CA2261610A1 (fr) 1998-02-12
EP0921943A1 (fr) 1999-06-16
DE69716744D1 (de) 2002-12-05
AU3824797A (en) 1998-02-25
WO1998005502A1 (fr) 1998-02-12
AU740098B2 (en) 2001-11-01

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