WO2020163079A1 - Films et enveloppes de couche pour articles d'hygiène - Google Patents

Films et enveloppes de couche pour articles d'hygiène Download PDF

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Publication number
WO2020163079A1
WO2020163079A1 PCT/US2020/014505 US2020014505W WO2020163079A1 WO 2020163079 A1 WO2020163079 A1 WO 2020163079A1 US 2020014505 W US2020014505 W US 2020014505W WO 2020163079 A1 WO2020163079 A1 WO 2020163079A1
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WIPO (PCT)
Prior art keywords
film
ethylene
backsheet
mol
films
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PCT/US2020/014505
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English (en)
Inventor
Haiyin Hua
Xiao-chuan WANG
Zhen-yu ZHU
Arash SARHANGI FARD
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Exxonmobil Chemical Patents Inc.
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Publication of WO2020163079A1 publication Critical patent/WO2020163079A1/fr

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Classifications

    • 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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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

  • the invention relates to hygiene articles, such as diapers and sanitary napkins, with improved backsheets.
  • the backsheets comprise polyethylene compositions in combination with a masterbatch to prove improved performance.
  • Hygiene products such as disposable diapers for infants and adults, incontinent pads, sanitary napkins, and pantiliners constitute maj or industries and serve important functions for different demographics of the population.
  • such hygiene products are made from a skin-facing layer or an inner topsheet (also called a cover or front sheet) which is liquid- permeable to facilitate entry of the fluid exudate from the wearer into the hygiene product, a core of highly absorbent material for absorbing liquid received through the topsheet, and an outer backsheet formed of a liquid impermeable plastic to eliminate leakage of fluid from the hygiene product.
  • the backsheet may be vapor impermeable or vapor permeable. If vapor permeable, the product is said to be“breathable”.
  • films useful as backsheets comprising a polyethylene composition in an amount from about 25 wt% to about 45 wt% and a masterbatch in an amount from about 55 wt% to about 75 wt%.
  • the films have a water vapor transmission rate of less than or equal to about 550 g/m 2 per day in accordance with test method ASTM E96.
  • the films are highly filled and comprise CaCCh in an amount greater than or equal to 45 wt%.
  • the films have an MD trouser tear of from about 155 cN to about 160 cN as measured by ASTM 1938.
  • the films have a dart impact from about 5.0 g/pm to about 15.0 g/pm.
  • masterbatch comprises from about 65 wt% to about 70 wt% CaCCb.
  • the polyethylene composition has a melt index (MI) of about 0.5 g/10 min and a density of 0.918 g/cm 3 .
  • the film has an MD 1% secant modulus of from about 270.00 mN to about 330.00 mN.
  • the film has a TD 1% secant modulus from about 50 mN to about 60 mN.
  • the film has an MD 10% offset from about 10 mN to about 20 mN.
  • the film has an MD 5% force from about 3.0 N to about 4.0 N.
  • the film has an MD tensile at break of about 20.0 mN to 24.0 mN. In an aspect, the film has an MD elongation at break of from about 66% to about 70%. In an aspect, the film has a TD 10% offset from about 1.40 mN to 1.50 mN. In an aspect, the film has a TD 5% force from about 1.35 N to about 1.45 N. In an aspect, the film has a TD tensile at break from about 1.80 mN to 1.90 mN. In an aspect, the film has a TD elongation at break of at least 500%. In an aspect, the film is a blown film. In an aspect, the film is a cast film. In an aspect, the film has a layer distribution of 1/3/1.
  • hygiene articles comprising a breathable backsheet of any one of the present films described herein.
  • the hygiene article can further comprise at least one top sheet and at least one absorbent core.
  • the hygiene article can be a diaper, a sanitary napkin, an adult incontinence pad and a pantiliner.
  • R 1 is hydrogen
  • R 2 is an alkyl group.
  • a “linear alpha-olefin” is an alpha-olefin as defined in this paragraph wherein R 1 is hydrogen, and R 2 is hydrogen or a linear alkyl group.
  • A“catalyst system” as used herein may include one or more polymerization catalysts, activators, supports/carriers, or any combination thereof.
  • CDBI composition distribution breadth index
  • copolymer refers to polymers having more than one type of monomer, including interpolymers, terpolymers, or higher order polymers.
  • C n group or“C n compound” refers to a group or a compound with total number carbon atoms“n.”
  • a C m -C n group or compound refers to a group or a compound having total number of carbon atoms in a range from m to n.
  • a C1-C50 alkyl group refers to an alkyl compound having 1 to 50 carbon atoms.
  • cyclopentadiene and “cyclopentadienyl” are abbreviated as“Cp.”
  • the term“masterbatch” is a solid or liquid additive used to impart certain properties to polyethylene compositions and alleviate issues with insufficient dispersion.
  • concentration of the additive (such as CaCCL) in the masterbatch is typically much higher than in the end-use polymer.
  • metallocene catalyst refers to a catalyst having at least one transition metal compound containing one or more substituted or unsubstituted Cp moiety (typically two Cp moieties) in combination with a Group 4, 5, or 6 transition metal.
  • a metallocene catalyst is considered a single site catalyst.
  • Metallocene catalysts generally require activation with a suitable co-catalyst, or activator, in order to yield an "active metallocene catalyst", i.e., an organometallic complex with a vacant coordination site that can coordinate, insert, and polymerize olefins.
  • Active catalyst systems generally include not only the metallocene complex, but also an activator, such as an alumoxane or a derivative thereof (preferably methyl alumoxane), an ionizing activator, a Lewis acid, or a combination thereof.
  • an activator such as an alumoxane or a derivative thereof (preferably methyl alumoxane), an ionizing activator, a Lewis acid, or a combination thereof.
  • Alkylalumoxanes typically methyl alumoxane and modified methylalumoxanes
  • the catalyst system can be supported on a carrier, typically an inorganic oxide or chloride or a resinous material such as, for example, polyethylene or silica.
  • the term“substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group.
  • methylcyclopentadiene is a Cp group substituted with a methyl group.
  • MI melt index
  • polymers are shear thinning, which means that their resistance to flow decreases as the shear rate increases. This is due to molecular alignments in the direction of flow and disentanglements.
  • MI is determined according to ASTM D-1238-E (190°C/2.16 kg), also sometimes referred to as h or I2 . 16.
  • MIR Melt index ratio
  • melt strength is a measure of the extensional viscosity and is representative of the maximum tension that can be applied to the melt without breaking.
  • Extensional viscosity is the polyethylene composition’s ability to resist thinning at high draw rates and high draw ratios.
  • melt processing of polyolefins the melt strength is defined by two key characteristics that can be quantified in process-related terms and in rheological terms.
  • extrusion blow molding and melt phase thermoforming a branched polyolefin of the appropriate molecular weight can support the weight of the fully melted sheet or extruded portion prior to the forming stage. This behavior is sometimes referred to as sag resistance.
  • “M n ” is number average molecular weight
  • “M w ” is weight average molecular weight
  • “M z ” is z-average molecular weight.
  • all molecular weight units e.g., M w , M n , M z ) including molecular weight data are in the unit of g-moT 1 .
  • MWD molecular weight distribution
  • PDI polydispersity index
  • olefin refers to a linear, branched, or cyclic compound comprising carbon and hydrogen and having a hydrocarbon chain containing at least one carbon-to-carbon double bond in the structure thereof, where the carbon-to-carbon double bond does not constitute a part of an aromatic ring.
  • the term olefin includes all structural isomeric forms of olefins, unless it is specified to mean a single isomer or the context clearly indicates otherwise.
  • the term“polymer” refers to a compound having two or more of the same or different“mer” units.
  • A“homopolymer” is a polymer having mer units that are the same.
  • A“copolymer” is a polymer having two or more mer units that are different from each other.
  • A“terpolymer” is a polymer having three mer units that are different from each other. “Different” in reference to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer is said to have a“propylene” content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from propylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a copolymer can be terpolymers and the like.
  • the term“shear thinning ratio” refers to the complex viscosity at 190°C at 0.01 rad/s over the complex viscosity at 190°C at 100 rad/s (or the nearest measured point).
  • substantially uniform comonomer distribution is used herein to mean that comonomer content of the polymer fractions across the molecular weight range of the ethylene-based polymer vary by ⁇ 10.0 wt%.
  • a substantially uniform comonomer distribution refers to ⁇ 8.0 wt%, ⁇ 5.0 wt%, or ⁇ 2.0 wt%.
  • the term“supported” refers to one or more compounds that are deposited on, contacted with, vaporized with, bonded to, incorporated within, adsorbed or absorbed in, or on, a support or carrier.
  • the terms“support” and“carrier” can be used interchangeably and include any support material including, but not limited to, a porous support material or inorganic or organic support materials.
  • Non-limiting examples of inorganic support materials include inorganic oxides and inorganic chlorides.
  • Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene, divinyl benzene, polyolefins, or polymeric compounds, zeolites, talc, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene, divinyl benzene, polyolefins, or polymeric compounds, zeolites, talc, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • viscosity is a measure of resistance to shearing flow. Shearing is the motion of a fluid, layer-by-layer, like a deck of cards. When polymers flow through straight tubes or channels, the polymers are sheared and resistance is expressed in terms of viscosity.
  • Extensional or“elongational viscosity” is the resistance to stretching.
  • the elongational viscosity plays a role.
  • the resistance to stretching can be three times larger than in shearing.
  • the elongational viscosity can increase (tension stiffening) with the rate, although the shear viscosity decreased.
  • the“bending stiffness” is a measure of the resistance of film deformation when bent, and can be calculated the by following equation:
  • S b is the bending stiffness, measured in mN*mm
  • M is the moment width
  • b is the width
  • R is the radius of the curvature.
  • Bending stiffness can be measured by applying opposing forces at various points on a beam and measuring the resulting curvature of the beam. For example, in the 3 -point method, force is applied in one direction on the ends and in the opposite direction in the center, and the resulting radius of the curvature is measured.
  • Various measurements described herein are based on certain test standards. For example, measurements of tensile strength in the machine direction (MD) and transverse direction (TD) are based on ASTM D882. Measurements of MD Trouser Tear and TD Trouser Tear are based on by ASTM 1938. Measurements for 1% Secant Modulus are based on ASTM D 790A. Methods of tensile tests are set out in ASTM D-882-02 and ASTM D- 6693. Methods for testing Elmendorf tear strength are set out in ASTM D-l 922-09. Methods for testing hot tack and heat seal mode are set out in ASTM F-1921.
  • Measurements for puncture resistance are based on ASTM D 5748, which is designed to provide load versus deformation response under biaxial deformation conditions at a constant relatively low test speed (change from 250 mm/min to 5 mm/min after reach pre-load (0.1 N)).
  • Measurements of dart-drop are made in accordance with ASTM D1709 and/or ISO 7765-1, method "A”. Density is determined using test methods set out in ASTM D-4703 and ASTM D-1505/ISO 1183.
  • Light transmission percent (or haze) measurements are based on ASTM D1003 using a haze meter Haze-Guard Plus AT-4725 from BYK Gardner and defined as the percentage of transmitted light passing through the bulk of the film sample that is deflected by more than 2.
  • the present hygiene articles generally comprise a) at least one top sheet; b) at least one absorbent core; and c) at least one backsheet.
  • the backsheet generally has a body-facing side oriented towards the body of the wearer of the article and a garment-facing side oriented towards the undergarment of the wearer of the article.
  • the at least one backsheet can comprise a film.
  • the subject films comprise a polyethylene composition in an amount from about 25 wt% to about 45 wt% and a masterbatch in an amount from about 55 wt% to about 75 wt%.
  • the films can be blown or cast films and are highly filled, comprising CaCCb in an amount greater than or equal to 45 wt%.
  • the present films have an MD trouser tear of from about 155 cN to about 160 cN as measured by ASTM 1938.
  • the film has a water vapor transmission rate of less than or equal to about 550 g/m 2 per day in accordance with test method ASTM E96.
  • the film has a dart impact from about 5.0 g/ pm to about 15.0 g/ pm.
  • the masterbatch comprises from about 65 wt% to about 70 wt% CaCCh.
  • the polyethylene composition has a melt index (MI) of about 0.5 g/10 min and a density of 0.918 g/cm 3 .
  • the hygiene articles are useful items and may be diapers (e.g., infants and adults), sanitary pads, sanitary napkins, and pantiliners.
  • An exemplary multi-layered hygiene article is provided below, having seven total layers. The number of layers is not critical and may vary from several layers, for example, three or more, to many more layers, for example, five or more, ten or more, fifteen or more, and twenty or more layers.
  • the topsheet is typically the layer of the hygiene article which is oriented towards and contacts the body of the wearer, and is therefore the first layer to receive the bodily discharges.
  • the topsheet is normally made of a single layer, but may also comprise more than one layer (e.g., a central topsheet layer and two overlapping lateral stripes).
  • a single non-woven material may be used but the topsheet may be composed of several layers and treated to become hydrophilic so the liquid can pass through.
  • the topsheet is normally permeable to liquids, i.e., allow liquids to pass through the topsheet without significantly retarding or obstructing the transmission of such liquids therethrough.
  • topsheets may be made, for example, from nonwoven materials or perforated polyolefmic films.
  • An exemplary topsheet is a relatively hydrophobic 20 gsm spunbonded nonwoven web comprising bicomponent fibers of the sheath/core type (e.g., polypropylene/polyethylene polymers).
  • the topsheet may be treated with a surfactant to enhance liquid penetration to the core.
  • the surfactant may be non-ionic and should be nonirritating to the skin.
  • the topsheet may have a plurality of apertures to permit liquids deposited thereon to pass through to the core more quickly.
  • the hygiene articles further comprise an absorbent core disposed between the topsheet and the backsheet.
  • absorbent core refers to a material or combination of materials suitable for absorbing, trapping, distributing, and/or storing fluids, for example, urine, blood, menses, and/or other exudates. It may optionally be separately wrapped.
  • the size and shape of the absorbent core may be such that the surface of the core in the horizontal plane is substantially smaller than the surface of the topsheet.
  • substantially smaller it is meant that the surface of the absorbent core is at least about 10% smaller than the surface of the topsheet or at least about 25% smaller than the surface of the topsheet.
  • the absorbent core may be generally centered in the middle of the article.
  • the absorbent core may be disposed away from the periphery of the article to provide improved flexibility along the edges of the article.
  • an absorbent core having a substantially smaller surface than the topsheet By providing an absorbent core having a substantially smaller surface than the topsheet, several benefits may be achieved.
  • the amount of core material used is reduced, lowering the overall costs of manufacturing the article.
  • a core having a smaller surface also increases the overall flexibility of the article because the regions of the article not provided with a core are generally less rigid than the region where the core is situated.
  • the absorbent core may be fashioned into many shapes, for example, rounded, oval, rectangular, and square. For example, it is typical for absorbent cores to be rectangular for ease of manufacturing. However, flexibility and compatibility with various styles of undergarments may be better with cores having a curved shape (such as an oval shape) without comprising right angles. [0052]
  • the absorbent core may be made of any suitable materials.
  • suitable liquid-absorbent materials include comminuted wood pulp which is generally referred to as airfelt; creped cellulose wadding; absorbent gelling materials including superabsorbent polymers such as hydrogel-forming polymeric gelling agents; chemically stiffened, modified, or cross-linked cellulose fibers; meltblown polymers including co- form; synthetic fibers including crimped polyester fibers; tissue including tissue wraps and tissue laminates; capillary channel fibers; absorbent foams; absorbent sponges; synthetic staple fibers; peat moss; foamed polyethylene or polypropylene compositions; nonwoven polyethylene or polypropylene materials; or any equivalent material; or combinations thereof.
  • the absorbent core can comprise superabsorbent polymers (SAP), normally distributed within a matrix of cellulosic fibers, for example, in order to reduce the thickness of the absorbent core.
  • SAP superabsorbent polymers
  • the absorbent core can be a monolayer or can be a laminate of two or more layers.
  • the core may comprise a fluid impermeable barrier layer on its backsheet-facing side to prevent fluids retained by the absorbent core from striking through the hygiene article.
  • General information regarding absorbent cores may be found in, for example, WO 2002/007662 and WO 1991/019471.
  • the general function of the backsheet is to prevent discharges absorbed by the core from escaping the hygiene article.
  • the backsheet may include any suitable material. Typically, these materials are generally flexible, liquid resistant, and impermeable to liquids.
  • the backsheet generally comprises at least a film that may be monolayer or two or more layers.
  • the films may be cast or blown films, optionally, embossed and/or oriented or stretched, in either direction: Machine Direction (MD) or Transverse Direction (TD), either on-line or off line.
  • MD Machine Direction
  • TD Transverse Direction
  • This backsheet may also contain fillers, pigment, various additives, and any combination thereof.
  • the backsheet may also be a laminate with non-woven fabric.
  • the backsheet film may have an average backsheet thickness of 24 pm or less, alternatively, 20 pm or less, 15 pm or less, alternatively, 14 pm or less, 12 pm or less, 11 pm or less, and alternatively, 10 pm or less.
  • average backsheet thickness refers to the thickness of a film, typically, expressed in microns of the film, prior to any additional conversion or treatments such as embossing. As thickness measurements on embossed films are difficult to obtain, the gauge of the film is may be expressed in gram per square meter or gsm, equal to the weight of one square meter of film. Typically, 10 pieces of 10 square centimeters each are cut out of the film and the weight is multiplied by 10 to obtain gsm.
  • the backsheet film may have an average backsheet thickness of 35 grams per square meter (gsm) or less, alternatively, 30 gsm or less, 25 gsm or less, 20 gsm or less, 15 gsm or less, 12 gsm or less, or 10 gsm or less.
  • gsm grams per square meter
  • breathable backsheets which are permeable to vapor are known as breathable backsheets and are used in breathable hygiene articles. These breathable backsheets provide a cooler garment and permit some drying of the article while being worn. In general, these breathable backsheets are intended to allow the passage of vapor, typically expressed as Water Vapor Transmission Rate (“WVTR”) through them while retarding the passage of liquid.
  • WVTR Water Vapor Transmission Rate
  • Breathable backsheets may be obtained by creating microvoids in one or more layers of the backsheet.
  • Microcavities may be created by the incorporation of fillers, such as calcium carbonate (CaCCb) or other suitable materials, into one or more layers of the backsheet followed by an orientation or stretching process.
  • suitable materials include organic fillers such as polystyrene in polyethylene or water-swellable fillers such as silica or hydrogel.
  • the backsheet has a garment-facing side and an opposite body-facing side.
  • the garment-facing side of the backsheet can comprise a non-adhesive area and an adhesive area.
  • the adhesive area may be provided by any conventional means. Pressure sensitive adhesives have been commonly found to work well for this purpose.
  • the polyethylene compositions useful in the subject films can comprise from about 50.0 mol% to about 100.0 mol% of units derived from ethylene.
  • the lower limit on the range of ethylene content can be from 50.0 mol%, 75.0 mol%, 80.0 mol%, 85.0 mol%, 90.0 mol%, 92.0 mol%, 94.0 mol%, 95.0 mol%, 96.0 mol%, 97.0 mol%, 98.0 mol%, or 99.0 mol% based on the mol% of polymer units derived from ethylene.
  • the polyethylene composition can have an upper limit on the range of ethylene content of 80.0 mol%, 85.0 mol%, 90.0 mol%, 92.0 mol%, 94.0 mol%, 95.0 mol%, 96.0 mol%, 97.0 mol%, 98.0 mol%, 99.0 mol%, 99.5 mol%, or 100.0 mol%, based on polymer units derived from ethylene.
  • the polyethylene compositions can be produced by polymerization of ethylene and, optionally, an alpha-olefin comonomer having from 3 to 10 carbon atoms.
  • Alpha-olefin comonomers are selected from monomers having 3 to 10 carbon atoms, such as C 3 -C 10 alpha-olefins or C 4 -C 8 alpha-olefins.
  • Alpha-olefin comonomers can be linear or branched or may include two unsaturated carbon-carbon bonds, i.e., dienes.
  • Suitable comonomers include linear C 3 -C 10 alpha-olefins and alpha-olefins having one or more C 1 -C 3 alkyl branches or an aryl group.
  • Comonomer examples include propylene, 1-butene, 3- methyl-1 -butene, 3, 3-dimethyl-l -butene, 1-pentene, 1-pentene with one or more methyl, ethyl, or propyl substituents, 1 -hexene, 1 -hexene with one or more methyl, ethyl, or propyl substituents, 1-heptene, 1-heptene with one or more methyl, ethyl, or propyl substituents, 1- octene, 1-octene with one or more methyl, ethyl, or propyl substituents, 1-nonene, 1-nonene with one or more methyl, ethyl, or propyl substituent
  • Exemplary combinations of ethylene and comonomers include: ethylene 1 -butene, ethylene 1-pentene, ethylene 4-methyl- 1-pentene, ethylene 1 -hexene, ethylene 1-octene, ethylene decene, ethylene dodecene, ethylene 1 -butene 1 -hexene, ethylene 1 -butene 1-pentene, ethylene 1 -butene 4-methyl- 1-pentene, ethylene 1 -butene 1-octene, ethylene 1 -hexene 1- pentene, ethylene 1 -hexene 4-methyl- 1-pentene, ethylene 1 -hexene 1-octene, ethylene 1- hexene decene, ethylene 1 -hexene dodecene, ethylene propylene 1-octene, ethylene 1-octene 1-butene, ethylene 1-octene 1-pentene, ethylene 1-octene 4-methyl-
  • the foregoing list of comonomers and comonomer combinations are merely exemplary and are not intended to be limiting.
  • the comonomer is 1 -butene, 1 -hexene, or 1-octene
  • monomer feeds are regulated to provide a ratio of ethylene to comonomer, e.g., alpha-olefin, so as to yield a polyethylene having a comonomer content, as a bulk measurement, of from about 0.1 mol% to about 20 mol% comonomer.
  • the comonomer content is from about 0.1 mol% to about 4.0 mol%, or from about 0.1 mol% to about 3.0 mol%, or from about 0.1 mol% to about 2.0 mol%, or from about 0.5 mol% to about 5.0 mol%, or from about 1.0 mol% to about 5.0 mol%.
  • reaction temperature may be regulated so as to provide desired LLDPE compositions.
  • molecular weight control agent such as Eh
  • the amount of comonomers, comonomer distribution along the polymer backbone, and comonomer branch length will generally delineate the density range.
  • Comonomer content is based on the total content of all monomers in the polymer.
  • the polyethylene copolymer has minimal long chain branching (i.e., less than 1.0 long-chain branch/1000 carbon atoms, preferably particularly 0.05 to 0.50 long-chain branch/1000 carbon atoms). Such values are characteristic of a linear structure that is consistent with a branching index (as defined below) of g' vis > 0.980, 0.985, > 0.99, > 0.995, or 1.0.
  • long chain branches can be present (i.e., less than 1.0 long-chain branch/1000 carbon atoms, preferably less than 0.5 long-chain branch/1000 carbon atoms, particularly 0.05 to 0.50 long-chain branch/1000 carbon atoms).
  • the polyethylene compositions can have a density greater than or equal to (“>”) about 0.930 g/cm 3 , > about 0.935 g/cm 3 , > about 0.940 g/cm 3 , > about 0.945 g/cm 3 , > about 0.950 g/cm 3 , > about 0.955 g/cm 3 , and > about 0.960 g/cm 3 .
  • polyethylene compositions can have a density less than or equal to (“ ⁇ ”) about 0.960 g/cm 3 about 0.945 g/cm 3 , e.g., ⁇ about 0.940 g/cm 3 , ⁇ about 0.937 g/cm 3 , ⁇ about 0.935 g/cm 3 , and ⁇ about 0.930 g/cm 3 .
  • ranges include, but are not limited to, ranges formed by combinations any of the above-enumerated values, e.g., from about 0.930 to about 0.945 g/cm 3 , about 0.930 to about 0.935 g/cm 3 , about 0.9350 about to 0.940 g/cm 3 , about 0.935 to about 0.950 g/cm 3 , etc.
  • Density is determined using chips cut from plaques compression molded in accordance with ASTM D- 1928-C, aged in accordance with ASTM D-618 Procedure A, and measured as specified by ASTM D-1505.
  • the polyethylene compositions have an MI according to ASTM D-1238-E (190°C/2.16 kg) reported in grams per 10 minutes (g/10 min), of > about 0.10 g/10 min, e.g.,
  • the polyethylene compositions can have an MI (I2 . 16) ⁇ about 3.0 g/10 min, ⁇ about 2.0 g/10 min, ⁇ about 1.5 g/10 min, ⁇ about 1.0 g/10 min, ⁇ about 0.75 g/10 min, ⁇ about 0.50 g/10 min, ⁇ about 0.40 g/10 min, ⁇ about 0.30 g/10 min, ⁇ about 0.25 g/10 min, ⁇ about 0.22 g/10 min, ⁇ about 0.20 g/10 min, ⁇ about 0.18 g/10 min, or ⁇ about 0.15 g/10 min.
  • the ranges include, but are not limited to, ranges formed by combinations any of the above-enumerated values, for example: from about 0.1 to about 5.0; about 0.2 to about 2.0; and about 0.2 to about 0.5 g/10 min.
  • the polyethylene compositions can have a melt index ratio (“MIR”) that is a dimensionless number and is the ratio of the high load MI to the MI, or I21 . 6/I2 . 16, as measured in accordance with ASTM D-1238.
  • MIR melt index ratio
  • the MIR of the polyethylene compositions described herein is from about 25 to about 80, alternatively, from about 25 to about 70, alternatively, from about 30 to about 55, and alternatively, from about 35 to about 50.
  • the polyethylene compositions can have High Load Melt Index (“HLMI”) also referred to herein as or hi as measured in accordance with ASTM D-1238, condition F (190°C/21.6 kg). Any given polymer composition has an MI and an MIR. As such, the HLMI is fixed and can be calculated if the MI and MIR are known.
  • polyethylene compositions can have minimal long chain branching (i.e., less than 1.0 long-chain branch/1000 carbon atoms, particularly 0.05 to 0.50 long-chain branch/1000 carbon atoms).
  • minimal long chain branching i.e., less than 1.0 long-chain branch/1000 carbon atoms, particularly 0.05 to 0.50 long-chain branch/1000 carbon atoms.
  • Such values are characteristic of a linear structure that is consistent with a branching index of g' v is 3 0.980, 0.985, > 0.99, > 0.995, or 1.0. While such values are indicative of little to no long chain branching, some long chain branches may be present (i.e., less than 1.0 long-chain branch/1000 carbon atoms, or less than 0.5 long-chain branch/1000 carbon atoms, particularly 0.05 to 0.50 long-chain branch/1000 carbon atoms).
  • the polyethylene compositions can have an orthogonal comonomer distribution.
  • orthogonal comonomer distribution is used herein to mean across the molecular weight range of the ethylene polymer, comonomer contents for the various polymer fractions are not substantially uniform and a higher molecular weight fraction thereof generally has a higher comonomer content than that of a lower molecular weight fraction.
  • Both a substantially uniform and an orthogonal comonomer distribution may be determined using fractionation techniques such as gel permeation chromatography-differential viscometry (“GPC-DV”), temperature rising elution fraction-differential viscometry (“TREF-DV”) or cross-fractionation techniques.
  • the present polyethylene compositions typically have a broad composition distribution as measured by Composition Distribution Breadth Index (“CDBI”) or solubility distribution breadth index (“SDBI”).
  • CDBI Composition Distribution Breadth Index
  • SDBI solubility distribution breadth index
  • Polymers produced using a catalyst system described herein have a CDBI less than 50%, or less than 40%, or less than 30%.
  • the polymers have a CDBI of from 20% to less than 50%.
  • the polymers have a CDBI of from 20% to 35%.
  • the polymers have a CDBI of from 25% to 28%.
  • Exceed XPTM metallocene polyethylene are commercially available from ExxonMobil Chemical Company, Houston, TX.
  • Exceed XPTM mPE can provide step-out performance with respect to, for example, dart drop impact strength, flex-crack resistance, and machine direction (“MD”) tear, as well as maintaining stiffness at lower densities.
  • Exceed XPTM mPE can provide optimized solutions for a good balance of melt strength, toughness, stiffness, and sealing capabilities which makes this family of polymers well-suited for blown film/sheet solutions.
  • Exceed XPTM 8358 polyethylene compositions comprise ethylene 1 -hexene copolymer. This polyethylene composition offers step-out toughness, high flex-crack resistance and increased output with excellent bubble stability for a range of film applications.
  • ExceedTM XP 8358ML has a density of .918 g/cm 3 and a melt index of 0.5 g/10 min.
  • Exceed XPTM 1018 polyethylene compositions may comprise ethylene 1 -hexene copolymers. This polyethylene composition offers step-out toughness, high flex-crack resistance and increased output with excellent bubble stability for a range of film applications.
  • ExceedTM XP 8358ML may have a density of .918 g/cm 3 and a melt index of 1.0 g/10 min
  • ENABLE® mPE metallocene polyethylene compositions
  • ENABLE® mPE metallocene polyethylene compositions
  • ASTM® mPE metallocene polyethylene compositions
  • Applications for ENABLE products include food packaging, form fill and seal packaging, heavy duty bags, lamination film, stand up pouches, multilayer packaging film, and shrink film.
  • an ENABLETM 20-05 polyethylene compositions are ethylene 1- hexene copolymers designed for blown film, formulated and non-formulated.
  • ENABLE 20- 05TM polymer has a density of 0.920 g/cm 3 and a melt index of 0.5 g/10 min.
  • Conventional catalysts refer to Ziegler Natta catalysts or Phillips-type chromium catalysts. Examples of conventional-type transition metal catalysts are discussed in U.S. Patent Nos. 4,115,639, 4,077,904 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741.
  • the conventional catalyst compounds that may be used in the processes disclosed herein include transition metal compounds from Groups 3 to 10, preferably 4 to 6 of the Periodic Table of Elements.
  • M is a metal from Groups 3 to 10, or Group 4, or titanium; R is a halogen or a hydrocarbyloxy group; and x is the valence of the metal M, preferably x is 1, 2, 3 or 4, or x is 4.
  • R include alkoxy, phenoxy, bromide, chloride and fluoride.
  • Non limiting examples of conventional-type transition metal catalysts where M is titanium include TiC13, TiC14, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)C13, Ti(OC4H9)3Cl, Ti(OC3H7)2C12, Ti(OC2H5)2Br2, TiC13.1/3AlC13 and Ti(OC12H25)C13.
  • Conventional chrome catalysts may include Cr03, chromocene, silyl chromate, chromyl chloride (Cr02C12), chromium-2-ethyl- hexanoate, chromium acetylacetonate (Cr(AcAc)3).
  • Cr02C12 chromium-2-ethyl- hexanoate
  • Cr(AcAc)3 chromium acetylacetonate
  • Non-limiting examples are disclosed in U.S. Patent Nos. 2,285,721, 3,242,099 and 3,231,550.
  • many conventional- type catalysts require at least one cocatalyst. A detailed discussion of cocatalysts may be found in U.S. Patent No. 7,858,719, Col. 6, line 46, to Col. 7, line 45.
  • Metallocene catalysts are generally described as containing one or more ligand(s) and one or more leaving group(s) bonded to at least one metal atom, optionally with at least one bridging group.
  • the ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof. These ligand(s) and the ring(s) or ring system(s) can comprise one or more atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements.
  • the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof.
  • the ring(s) or ring system(s) comprise carbon atoms including, but not limited to, Cp ligands or Cp-type ligand structures or other similarly functioning ligand structures such as pentadiene, cyclooctatetraendiyl, or imide ligands.
  • the metal atom is selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements. In an aspect, the metal is a transition metal from Groups 4 through 12.
  • the metal is a transition metal from Groups 4, 5 or 6. In an aspect, the metal is a transition metal from Group 4.
  • Exemplary metallocene catalysts and catalyst systems are described in, for example, U.S. Patent Nos. 4,530,914, 4,871,705, 4,937,299, 5,017,714, 5,055,438, 5,096,867, 5,120,867,
  • the catalysts described above are suitable for use in any olefin pre-polymerization or polymerization process or both.
  • Suitable polymerization processes include solution, gas phase, slurry phase, and a high-pressure process, or any combination thereof.
  • a desirable process is a gas phase polymerization of one or more olefin monomers having from 2 to 30 carbon atoms, from 2 to 12 carbon atoms in an aspect, and from 2 to 8 carbon atoms in an aspect.
  • Other monomers useful in the process include ethylenically unsaturated monomers, diolefms having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
  • Non-limiting monomers may also include norbomene, norbomadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbomene, dicyclopentadiene and cyclopentene.
  • Hydrogen gas is often used in olefin polymerization to control the final properties of the polyolefin. See, Polypropylene Handbook 76-78 (Hanser Publishers, 1996). Increasing concentrations (partial pressures) of hydrogen increase the melt flow rate (“MFR”) and/or MI of the polyolefin generated. The MFR or MI can thus be influenced by the hydrogen concentration.
  • the amount of hydrogen in the polymerization can be expressed as a mole ratio relative to the total polymerizable monomer (ethylene, for example) or to the blend of ethylene and hexane or propene.
  • the amount of hydrogen used in the polymerization process is an amount necessary to achieve the desired MFR or MI of the final polyolefin resin.
  • the mole ratio of hydrogen to total monomer (3 ⁇ 4: monomer) is in a range of from greater than 0.0001 in an aspect, from greater than 0.0005 in an aspect, from greater than 0.001 in an aspect, less than 10 in an aspect, less than 5 in an aspect, less than 3 in an aspect, and less than 0.10 in an aspect, wherein a desirable range may comprise any combination of any upper mole ratio limit with any lower mole ratio limit described herein.
  • the amount of hydrogen in the reactor at any time may range to up to 5000 ppm, up to 4000 ppm in an aspect, up to 3000 ppm in an aspect, from 50 ppm and 5000 ppm in an aspect, and from 100 ppm and 2000 ppm in an aspect.
  • a continuous cycle is often employed where one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
  • a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • Blown film extrusion involves the process of extruding the polyethylene composition (also referred to sometimes as a resin) through a die (not shown) followed by a bubble-like expansion.
  • Advantages of manufacturing film in this manner include: (1) a single operation to produce tubing; (2) regulation of film width and thickness by control of the volume of air in the bubble; (3) high extruder output and haul-off speed; (4) elimination of end effects such as edge bead trim and nonuniform temperature that can result from flat die film extrusion; and (5) capability of biaxial orientation (allowing uniformity of mechanical properties).
  • a melt comprising the polyethylene composition with or without a blend partner is extruded through an annular slit die (not shown) to form a thin walled tube.
  • Air is introduced via a hole in the center of the die to blow up the tube like a balloon.
  • a high-speed air ring (not shown) blows onto the hot film to cool it.
  • the foam film is drawn in an upward direction, continually cooling, until it passes through nip rolls (not shown) where the tube is flattened to create what is known as a 'lay -flat' tube of film.
  • This lay-flat or collapsed tube is then taken back down the extrusion tower (not shown) via more rollers.
  • air inside the bubble may also be exchanged.
  • the lay-flat film is either wound or the edges of the film are slit off to produce two flat film sheets and wound up onto reels to produce a tube of film
  • each layer may comprise a“neat” polymer with optional processing aids and/or additives or may comprise a blend of polymers with optional processing aids and/or additives.
  • an additive may be present up to 1.0, or 2.0, or 3.0 wt% by weight of the polymer composition described herein.
  • An additive may be added before, during, or after the formation of the polyethylene composition and/or resulting article/extrudate
  • ethylene-based polymers of certain embodiments may be characterized as having long-chain branches.
  • Long- chain branches can represent the branches formed by reincorporation of vinyl-terminated macromers.
  • the number of carbon atoms on the long-chain branches ranges from a chain length of at least one carbon more than two carbons less than the total number of carbons in the comonomer to several thousands.
  • a long-chain branch of an ethylene/hexene ethylene-based polymer is at least five (5) carbons in length (i.e., 6 carbons less 2 equals 4 carbons plus one equals a minimum branch length of five carbons for long-chain branches).
  • Particular ethylene-based polymers can have a 0.05 to 1.0, particularly 0.05 to 0.5, 0.1 to 0.4, or 0.2 to 0.3, long-chain branches per 1000 carbon atoms.
  • Ethylene-based polymers having levels of long-chain branching greater than 1.0 long-chain branch per 1000 carbon atoms may have some beneficial properties, e.g., improved processability, shear thinning, and/or delayed melt fracture, and/or improved melt strength.
  • long-chain branching can be determined using 13 C nuclear magnetic resonance (NMR) spectroscopy and to a limited extent; e.g., for ethylene homopolymers and for certain copolymers, and it can be quantified using the method of Randall Journal ofMacromolecular Science, Rev. Macromol. Chem. Phys., C29 (2&3), p. 285-297).
  • NMR nuclear magnetic resonance
  • the branching index, g' is inversely proportional to the amount of branching. Thus, lower values for g' indicate relatively higher amounts of branching.
  • the branching index due to long-chain branching may be calculated from the experimentally determined value for g' as described by Scholte, et al, in J. App. Polymer ScL, 29, pp. 3763-3782 (1984).
  • the degree of long-chain branching in ethylene-based polymers may be quantified by determination of the branching index.
  • the branching index g' is defined by the following equation:
  • IV BI is the intrinsic viscosity of the branched ethylene-based polymer
  • IVun is the intrinsic viscosity of the corresponding linear ethylene-based polymer having the same weight average molecular weight and molecular weight distribution as the branched ethylene-based polymer, and in the case of copolymers and terpolymers, substantially the same relative molecular proportion or proportions of monomer units.
  • a method for determining intrinsic viscosity of polyethylene is described in Macromolecules, 2000, 33, 7489-7499.
  • Intrinsic viscosity may be determined by dissolving the linear and branched polymers in an appropriate solvent, e.g., trichlorobenzene, typically measured at 135°C. Another method for measuring the intrinsic viscosity of a polymer is ASTM D-5225-98 - Standard Test Method for Measuring Solution Viscosity of Polymers with a Differential Viscometer, which is incorporated by reference herein in its entirety.
  • the average intrinsic viscosity, of a sample can be calculated by:
  • the hygiene articles of the present invention may be produced by any conventional means.
  • the different layers may thus be assembled using standard means such as embossing (e.g. thermal bonding), ultrasonic bonding, gluing/using adhesives or any combination of the aforementioned.
  • the converting line may comprise a printing step wherein the ink is applied to the backsheet of the article.
  • the backsheet may also comprise dyes or colorants.
  • the at least one backsheet comprises film comprising a polyethylene composition in an amount from about 25 wt% to about 45 wt% and a masterbatch in an amount from about 55 wt% to about 75 wt%, wherein the film is highly filled and comprises CaCCb in an amount greater than or equal to 45 wt% and the film has an MD trouser tear of from about 155 cN to about 160 cN as measured by ASTM 1938.
  • the masterbatch comprises from about 65 wt% to about 70 wt% CaCCb.
  • the film comprises the polyethylene composition having a melt index of about 0.5 g/10 min and a density of 0.918 g/cm 3 . The film has a dart impact from about 5.0 g/pm to about 15.0 g/pm.
  • the at least one backsheet may further be oriented, optionally, in the machine direction (MD) and/or transverse direction (TD). This may be done in-line with the film production or off-line on a stand-alone unit.
  • MD machine direction
  • TD transverse direction
  • the at least one backsheet is cast film, optionally, a monolayer cast film or multilayer cast film.
  • the at least one backsheet is blown film, optionally, a coextruded blown film.
  • the blown film may be a monolayer blown film or a multilayer blown film.
  • the at least one backsheet may be embossed, either in-line with film production or off line in a stand-alone embossing unit.
  • the embossing may be done with heated rollers or at ambient temperature.
  • the backsheet is an important functional layer in diaper, feminine care and adult incontinence products, and provides barrier to bio-fluids while providing breathability at the same time.
  • the films described herein can be produced from cast film or blown film processing followed by machine direction orientation (“MDO”). During stretching at machine direction, microcavities are formed around Calcium Carbonate particles in the film leading to breathability. While the MDO process improves film stiffness, it can result in detrimental tear properties. Tear is a key property in this application as it provides mechanical strength during assembly.
  • EXCEEDTM is the trademark for a family of polyethylene compositions where we have demonstrated its superior tear performance in films. As shown in Tables 1A and IB below, we tested EXCEEDTM polyethylene compositions in highly filled films. Blown breathable film was produced with a die diameter of 180 mm and die gap of 1.5 mm having an output of 130 kg/hr. Film samples were run at 50 grams per square meter (gsm) with layer distribution at 1/3/1. The film was then stretched approximately 2.7 times with offline MDO to 20 gsm. The films were then test for various mechanical properties, liquid barrier and breathability.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

Abstract

L'invention concerne des articles d'hygiène comprenant au moins une enveloppe de couche. Les enveloppes de couche peuvent comprendre des films constitués d'une composition de polyéthylène en une quantité d'environ 25% à environ 45% en poids et un mélange maître en une quantité d'environ 55% à environ 75% en poids, le film étant rempli et comprenant du CaC03 en une quantité supérieure ou égale à 45% en poids.
PCT/US2020/014505 2019-02-06 2020-01-22 Films et enveloppes de couche pour articles d'hygiène WO2020163079A1 (fr)

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