WO2008137285A1 - Batch inclusion packages - Google Patents

Batch inclusion packages Download PDF

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Publication number
WO2008137285A1
WO2008137285A1 PCT/US2008/060769 US2008060769W WO2008137285A1 WO 2008137285 A1 WO2008137285 A1 WO 2008137285A1 US 2008060769 W US2008060769 W US 2008060769W WO 2008137285 A1 WO2008137285 A1 WO 2008137285A1
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WO
WIPO (PCT)
Prior art keywords
package
ingredient
elastomer
film
layer
Prior art date
Application number
PCT/US2008/060769
Other languages
French (fr)
Inventor
Ravi Rao
Prashant Mogre
Original Assignee
Dow Global Technologies Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Publication of WO2008137285A1 publication Critical patent/WO2008137285A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates

Definitions

  • This invention relates to batch inclusion packages made from compositions comprising polyolefin plastomers together with an inorganic, filler particularly calcium carbonate.
  • the packages are made from films and are used to contain and protect powders, pellets and flowable materials, wherein the entire package (that is, film and contents) can be added to a mixture during production of a product, for example, placing the package into the extruder/ mixer simultaneously with the contained product.
  • Batch inclusion packages are widely used to contain materials such as carbon black, titanium dioxide powder, elastomers (rubbers), polystyrene pellets and other chemicals.
  • the batch inclusion packages minimize dust health hazards and possible fire hazards, as well as waste, since the entire package and its contents are processed during use of the contents. It is desired to also be able to package bitumen or asphalt in a batch inclusion bag.
  • the batch inclusion package has numerous requirements when used in such a manner. These include compatibility with the material to be contained, low melting temperature, a narrow softening range, and extrudability. In the case of packaging bitumen the bags must be able to withstand the higher temperatures of these materials, typically around 165°C.
  • USP 4,248,348 (Butler et al.) discloses a package comprising an article (such as an unvulcanized rubber) packaged in a film.
  • the film is made from an ethylene /vinyl acetate copolymer containing an antiblock agent.
  • USP '348 teaches that polyethylene film is not suitable for overwrapping bales of rubber, because when the bale (including the film wrapper) is charged into a suitable mixer, the polyethylene film is not sufficiently dispersed and causes defects in the end product.
  • USP 5,120,787 discloses a method of compounding a rubber by using a bag or liner made from an ethylene /vinyl acetate copolymer.
  • USP 4,394,473 discloses packages comprising an article (for example, unvulcanized or vulcanized rubber) packaged in a bag made from syndiotactic 1,2-polybutadiene containing an antiblock additive. USP '473 also teaches that the use of polyethylene bags results in incompatibility problems.
  • EPA 0 270 902 discloses the use of bags made from copolymers of at least one olefin monomer (for example, ethylene) and acrylic or methacrylic acid, or ionomers thereof, used to package particulate elastomer materials.
  • olefin monomer for example, ethylene
  • acrylic or methacrylic acid or ionomers thereof
  • LDPE high pressure low density polyethylene
  • LLDPE linear low density polyethylene
  • Branched, high pressure low density polyethylene (LDPE) and blends of LDPE with small amounts of traditional (that is, Ziegler polymerized) linear low density polyethylene (LLDPE), typically less than 10 percent LLDPE, are sometimes used to make batch inclusion bags which are used to contain carbon black. The carbon black is then used to make tires.
  • LLDPE linear low density polyethylene
  • filler preferably inorganic filler and most preferably calcium carbonate
  • the inorganic is added in an amount of from 15 to 60 percent by weight of the film layer.
  • Calcium carbonate is the preferred filler.
  • the resulting compounded resin can be made into blown films which can be used as preformed bags or tube stock to be converted into bags via a form-fill-seal process at the producer. Bags made from such resin are particularly suited for packaging bitumen or similar materials as they can be hot filled, have adequate hot tack strength and are particularly miscible with molten bitumen.
  • the present invention relates to a package which comprises:
  • the protective film for use in the present invention comprises at least one polyolefin plastomer or elastomer.
  • Elastomers are known in the art and mean a material which at room temperature can be stretched under low stress to at least twice its original length and upon immediate release of the stress, will return with force to its approximate original length. Plastomers are also generally known in the art. For poly ethylenes, plastomers will generally contain 20 percent or less of the comonomer (preferably 1-octene) and will have a density of 0.90 g/cm 3 or more, and for elastomers the level of comonomer content is generally over 20 percent and the density is less than 0.90 g/cm 3 .
  • the preferred polyolefin based plastomers and /or elastomers include polyethylene plastomers and elastomers, polypropylene plastomers and elastomers, and segmented ethylene-alpha-olefin block copolymers.
  • Polyethylene based elastomers and plastomers include homogeneously branched linear ethylene polymers such as those in U.S. Patent No. 3,645,992 and substantially linear ethylene polymers such as those described in U.S. Patent 5,272,236, U.S. Patent 5,278,272, U.S. Patent 5,582,923 and US Patent 5,733,155 and/or blends thereof (such as those disclosed in US
  • Polyethylene based polymers also include high pressure copolymers of ethylene such as ethylene vinyl acetate interpolymer, ethylene acrylic acid interpolymer, ethylene ethyl acetate interpolymer, ethylene methacrylic acid interpolymer, ethylene methacrylic acid ionomer, and the like.
  • the substantially linear ethylene polymers are preferred.
  • Substantially linear ethylene polymers are commercially available from The Dow Chemical Company under the trade name AFFINITYTM.
  • Propylene based elastomers and plastomers include the propylene based plastomers and elastomers described in WO03/040442, and US application 60/709688 filed August 19, 2005 (each of which is hereby incorporated by reference in its entirety - some of these materials are commercially available from The Dow Chemical Company under the trade name VERSIFYTM), and the propylene based plastomers and elastomers sold by ExxonMobil Chemical company under the trade name of VISTAMAXXTM.
  • the propylene based elastomers and plastomers are most preferred.
  • Segmented ethylene-alpha-olefin block copolymers include those discussed for example in WO 2005/090427, WO 2005/090425 and WO 2005/090426, each of which are hereby incorporated by reference in their entirety.
  • the polyolefin plastomer or elastomer for use in a batch inclusion package application is generally selected based on the processability of the polymer into batch inclusion packaging material and through manufacturing process in which the batch inclusion package is used. For example, a polymer having a density low enough to ensure adequate melting during use is required, but not too low so that the resultant film has too much stretch during the hot fill process or subsequent palletization and transportation of the filled bags. The film also must have enough strength and must not soften too much prior to or during the manufacturing process.
  • a polyolefin plastomer or elastomer polymer can have a higher Il ⁇ /l2 value, which can provide a more stable bubble during blown film production of batch inclusion film.
  • the melt index of the polymer also must be selected based on the bubble stability and/or film strength. Selection of a polymer for use in a particular batch inclusion package is thus based on a variety of factors and the foregoing parameters are intended to be illustrative and not limiting.
  • the melting range of the polyolefin plastomer or elastomer is preferably relatively narrow, so that the polymer melts quickly when it reaches the appropriate temperature.
  • the narrow melting range of the polymer is indicated by the difference between the melting point and the softening point.
  • the melting point is relatively close to the Vicat Softening point (typically within 9-25°C) of the polymer, such that the bag does not soften too much during transport and to prevent "strings" of poorly blended/unmelted polymer from forming during use of the bag in the end-user's manufacturing process.
  • Vicat Softening point is measured herein in accordance with ASTM D 1525-87 using 0.125 inch (thick) plaques having a diameter of 1 inch prepared according to ASTM D-1928-90-C. Heating rate B of the ASTM test is used (120 ⁇ 12 °C/hour).
  • the films of the present invention preferably have a Vicat Softening point in the range of from 60 0 C to 103 0 C
  • Preferred polyethylene based resins are will have a melt index ("MI” or "I 2 ”) between 0.3 and5 g/10min (190 0 C, 2.16kg).
  • Preferred polypropylene based resins will have a melt flow rate (MFR) between 1 and 10 g/10min (230 0 C, 2.16kg).
  • the polyolefin plastomer or elastomer is a substantially linear polyethylene.
  • the preferred density for substantially linear ethylene /alpha-olef in polymers (as measured in accordance with ASTM D-792) for use in the present invention is generally less than about 0.94 g/cm ⁇ , preferably from 0.87 g/cm ⁇ to 0.92 g/cm ⁇ .
  • the density of the preferred substantially linear ethylene /alpha-olef in polymers used in the present invention is generally dependent upon the processability of the substantially linear ethylene /alpha-olef in polymer into batch inclusion packaging materials and packages, the strength required of the batch inclusion packaging material, and the manufacturing process in which the batch inclusion package is used.
  • the density of the substantially linear ethylene /alpha-olef in polymer used to make the batch inclusion package is from 0.87 g/cm3 to 0.917 g/cm3.
  • the molecular weight of the preferred substantially linear ethylene /alpha-olef in polymers for use in the present invention is conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formerly known as "Condition (E)" and also known as I2). Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear.
  • the melt index for the preferred substantially linear ethylene /alpha-olef in polymers useful herein is generally that useful in forming film in conventional film forming manufacturing operations, such as cast film, blown film and extrusion coating techniques. The melt index will generally be from 0.1 grams/ 10 minutes (g/10 min) to 20 g/10 min, preferably from 0.3 g/10 min to 5 g/10 min.
  • the melt index measurement is conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190 0 C /10 kg (formerly known as "Condition (N)" and also known as Il ⁇ )-
  • the ratio of these two melt index terms is the melt flow ratio and is designated as Il ⁇ /l2-
  • the I10/I2 ratio for the linear is at least about 5.63, preferably at least about 7, especially at least about 8 or above.
  • the I10/I2 ratio indicates the degree of long chain branching, that is, the higher the Il ⁇ /l2 ratio, the more long chain branching in the polymer.
  • the Il ⁇ /l2 ratio of the preferred substantially linear ethylene /alpha-olef in polymers is at least about 5.63, preferably at least about 7, especially at least about 8.
  • the upper limit of Il ⁇ /l2 ratio for the preferred homogeneously branched substantially linear ethylene /alpha-olef in polymers is about 50 or less, preferably about 30 or less, and especially about 20 or less.
  • the polyolefin plastomer or elastomer is a propylene based plastomer or elastomer or "PBPE".
  • PBPE propylene based plastomer or elastomer
  • PBPE propylene based elastomers and /or plastomers
  • the preferred density for PBPE is generally less than about 0.888 g/cm3, preferably from 0.867 g/cm3 to 0.888 g/cm3.
  • the density of the preferred PBPE used in the present invention is generally dependent upon the processability of the PBPE into batch inclusion packaging materials and packages, the strength required of the batch inclusion packaging material, and the manufacturing process in which the batch inclusion package is used. Generally for elastomers, the density of the
  • PBPE used to make the batch inclusion package is from 0.867 g/cm ⁇ to 0.888 g/cm 3 .
  • the molecular weight of the preferred PBPE polymers for use in the present invention is conveniently indicated using a melt flow rate measurement according to ASTM D-1238, Condition 230°C/2.16 kg and also known as I2). Melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear.
  • the melt flow rate for the preferred substantially PBPE polymers useful herein is generally that useful in forming film in conventional film forming manufacturing operations, such as cast film, blown film and extrusion coating techniques.
  • the melt flow rate will generally be from 1 grams/ 10 minutes (g/10 min) to 10 g/10 min, preferably from 2 g/10 min to 5 g/10 min.
  • the polyolefin plastomers or elastomers used in the film of the batch inclusion packages are preferably used as the only polymer components.
  • other polymers including two or more different polyolefin plastomers or elastomers can be blended and/or multilayered extruded and /or multilayered laminated to modify the film processing, film stiffness, film barrier properties, film strength, film melting characteristics, or other desirable film characteristics.
  • Batch inclusion films made with appropriate blends of the polyolefin plastomer or elastomer and other polymer components would still maintain enhanced performance.
  • Some useful polymer blend components include, for example, high pressure low density polyethylene (LDPE), ethylene /vinyl acetate copolymer (EVA), polybutylene (PB), linear high density polyethylene (HDPE) having a density from 0.941 to 0.965 g/crn ⁇ and heterogeneously branched linear low density polyethylene (LLDPE) having a density from 0.87 to 0.94 g/cm ⁇ .
  • LDPE high pressure low density polyethylene
  • EVA ethylene /vinyl acetate copolymer
  • PB polybutylene
  • HDPE linear high density polyethylene
  • LLDPE heterogeneously branched linear low density polyethylene
  • the polyolefin plastomers or elastomers comprise at least about 50 percent of the polymer blend composition, more preferably at least about 80 percent of the polyolefin plastomer or elastomer blend composition.
  • LDPE, and PP based bitumen bags are known, but have very poor miscibility in the heated bitumen. Nevertheless, small amounts of these materials may be blended with the plastomers /elastomers, but at levels greater than about 20 percent these materials may have a deleterious effect on the solubility of the bags.
  • the polyolefin plastomer or elastomer will comprise from 20 to 80 percent by weight of the film, more preferably from 20 to 65 percent, and even more preferably from 35 to 50 percent.
  • the second component in the at least one film layer used in the packages of the present invention is an inorganic filler.
  • the inorganic filler is added in an amount of from 15 to 60 percent by weight of the layer, preferably, 20 to 55 percent by weight of the layer, or 30 to 55 percent by weight, and more preferably from 40 to 50 percent by weight of the layer.
  • any inorganic filler can be used, including materials such as titanium dioxide, talc, silica, barium sulfate, diatomaceous earth, aluminosilicates, carbon black, and calcium carbonate, with calcium carbonate generally being most preferred.
  • calcium carbonate is used, it has an average particle size of less than 3 microns with a top cut of 11 microns.
  • the second component can be added via any means known in the art. Preferred methods include adding as a masterbatch in a dryblending operation. Alternative methods include compounding (via single screw or twin screw extruder) the inorganic filler into the second component (resin) to form a compound.
  • the films used in the present invention may also contain other additives such as plasticizers, antioxidants (for example, hindered phenolics
  • cling additives for example, polyisobutylene (PIB)
  • heat stabilizers for example, pigments, light stabilizers (for example, CyasorbTM UV 531 benzophenone made by Cyanamid and TinuvinTM 622 hindered amine light stabilizer made by Ciba Geigy Corp.), processing aids (for example, polyethylene glycols, fluoropolymers, fluoroelastomers, waxes), flame retardants (for example, AmgardTM CPC 102 phosphorous based flame retardants made by Albright and Wilson Americas), lubricants (for example, waxes, stearates, mineral oils), slip agents (for example, erucamide, oleamide), antiblock additives (for example, silicon dioxide), cross-linking agents (for example, peroxides, (for example, Booster
  • Films and film structures having the novel properties described herein can be made using conventional hot blown film or cast film fabrication techniques.
  • Conventional hot blown film processes are described, for example, in The Encyclopedia of Chemical Technology, Kirk- Othmer, Third Edition, John Wiley & Sons, New York, 1981, Vol. 16, pp. 416-417 and Vol. 18, pp. 191-192, the disclosures of which are incorporated herein by reference.
  • the films may be monolayer or multilayer films, but at least one layer of the film structure comprises the modified polyolefin elastomer or plastomer previously described.
  • the inner layer will comprise the modified polyolefin plastomer or elastomer.
  • the inner layer is the layer adjacent to the material contained in the package.
  • the inner layer can be coextruded with the other layer(s) or the inner layer can be laminated onto another layer(s) in a secondary operation, such as that described in "Coextrusion For Barrier Packaging" by WJ. Schrenk and CR. Finch, Society of Plasties Engineers RETEC Proceedings, June 15-17 (1981), pp. 211-229, the disclosure of which is incorporated herein by reference.
  • a monolayer film can also be produced via tubular film (that is, blown film techniques) or flat die (that is, cast film) as described by K.R. Osborn and W.A. Jenkins in "Plastic Films, Technology and Packaging Applications” (Technomic Publishing Co., Inc. (1992)), the disclosure of which is incorporated herein by reference, and. optionally, the film can go through an additional post-extrusion step of adhesive or extrusion lamination to other packaging material layers to form a multilayer structure. If the film is a coextrusion of two or more layers (also described by Osborn and Jenkins), the film may still be laminated to additional layers of packaging materials, depending on the other physical requirements of the final packaging film. "Laminations Vs. Coextrusion" by D.
  • Extrusion coating is yet another technique for producing multilayer packaging materials. Similarly to cast film, extrusion coating is a flat die technique. A film layer can be extrusion coated onto a substrate either in the form of a monolayer or a coextruded extrudate.
  • the modified polyolefin plastomer or elastomer described herein comprises at least one layer of the total multilayer film structure, preferably the inner layer.
  • Other layers of the multilayer structure include but are not limited to barrier layers, and/or tie layers, and/or structural layers. Various materials can be used for these layers, with some of them being used as more than one layer in the same film structure.
  • HDPE high density polyethylene
  • EAA ethylene /acrylic acid
  • EAA ethylene /methacry lie acid
  • ionomers LLDPE, HDPE, LDPE, polypropylene (including homopolymer, random co polymers and impact copolymers) and graft adhesive polymers (for example, maleic anhydride grafted polyethylene).
  • the multilayer film structures comprise from 2 to 7 layers.
  • the thickness of the film comprising the modified polyolefin plastomer or elastomer is typically from 60 micrometers to 250 micrometers, preferably from 100 micrometers to 225 micrometers, with 150 to 200 micrometers being most preferred.
  • the films of the present invention can also be characterized in terms of their physical properties.
  • the preferred films of the present invention will have a Peak Load of at least 30 N as measured by ASTM 5747-95 (modified by using a probe diameter of 0.50mm instead of 0.75 mm as specified in the ASTM method), more preferably a Peak Load greater than 45N.
  • the elongation at Peak Load for the preferred films will be greater than 30mm, more preferably greater than 35mm
  • Puncture resistance for the films can be determined using ASTM D 5748-95 modified by using a probe diameter of 0.50mm instead of 0.75 mm as specified in the ASTM method.
  • the puncture resistance for the preferred films will be greater than 30mm more preferably greater than 35mm.
  • the total energy for the preferred films will be greater than 1.0J more preferably greater than 1.5J, as determined by ASTM 5748-95.
  • the Dart impact for the films can be determined according to ASTM D 1709-01, method B.
  • the Dart impact for the preferred films will be greater than 90Og, more preferably greater than 120Og.
  • the films and film structures made from the modified polyolefin plastomer or elastomer are preferably made into bags either in- line via the form-fill-seal process or off line in the form of preformed bags (also known as valve bags).
  • the bags of the present invention can be hot filled with the desired product (for example bitumen) above the melting point of the bag, using cooling means such as by suspending the bags in a water bath or through the use of sprayed water. Alternatively chilled air or other gas could be used to keep the bags from prematurely melting during hot-filling. After filling, the bags are sealed, thereby reducing noxious vapors from the solidifying bitumen.
  • modified polyolefin plastomers and elastomers in batch inclusion bags and films affords numerous advantages.
  • the modified polymers have excellent processability in making blown film and also have low melting points and softening ranges, relative to other materials.
  • the modified plastomers and elastomers are also highly miscible with bitumen allowing them to become fully integrated with the bitumen when used, for example, in asphalt applications. It should be noted that the filler used in the bag will often also be a desirable additive in the bitumen, thereby offering additional advantages.
  • Table 1 summarizes the modified polymers used to make films for use in these Examples.
  • the filler was added via a masterbatch comprising 60 percent by weight CaCO 3 in a polymer carrier resin such as LDPE resin.
  • Blown film is made from the materials described in Table 1.
  • the films are made as monolayer blown films (A/ A/ A) on a three layer (A/B/C) coextrusion blown film line (Reifenhauser), with a layer ratio of 1:2:1.
  • the blown film line details are as follows: Die Diameter-250mm; Die Gap-2.3mm; Screw Diameter- A - 60 mm, B -70mm, and C - 60 mm.
  • Resins are dry blended with masterbatches via the gravimetric blending stations on the extruders. Processing parameters for various resins and their combination are given below.
  • the films produced have a thickness of 165 microns.
  • 250 ml of bitumen is added to a beaker and heated using a mantle heater having temperature controller to reach the desired temperatures (150 0 C, 200 0 C or 250 0 C).
  • a sample of each film having the dimensions of 25mm x 25mm is obtained and introduced to the molten bitumen. Temperature is monitored with a mercury thermometer to ensure there was no fluctuation before sample was introduced.
  • the film samples are introduced with tweezers slowly into the molten bitumen and a stopwatch is used to monitor the changes over time. At 15 minutes intervals, sample is picked up using tweezers for visual inspection and a qualitative record of the amount of material remaining is made.

Abstract

Batch inclusion packages made from films and film structures are disclosed. The films and film structures have at least one layer comprising a polyolefin plastomer or elastomer together with relatively high levels of inorganic filler. The batch inclusion packages are useful in wrapping or containing various materials, such as asphalt or bitumen, as the packages are very miscible in such materials.

Description

BATCH INCLUSION PACKAGES
Cross-Reference to Related Applications
This application is a non-provisional application claiming priority from the U.S. Provisional Patent Application No. 60/915,507, filed on May 2, 2007, entitled "BATCH INCLUSION PACKAGES," the teachings of which are incorporated by reference herein, as if reproduced in full hereinbelow.
Field of the Invention
This invention relates to batch inclusion packages made from compositions comprising polyolefin plastomers together with an inorganic, filler particularly calcium carbonate. The packages are made from films and are used to contain and protect powders, pellets and flowable materials, wherein the entire package (that is, film and contents) can be added to a mixture during production of a product, for example, placing the package into the extruder/ mixer simultaneously with the contained product. Background and Summary of the Invention
Batch inclusion packages are widely used to contain materials such as carbon black, titanium dioxide powder, elastomers (rubbers), polystyrene pellets and other chemicals. The batch inclusion packages minimize dust health hazards and possible fire hazards, as well as waste, since the entire package and its contents are processed during use of the contents. It is desired to also be able to package bitumen or asphalt in a batch inclusion bag. The batch inclusion package has numerous requirements when used in such a manner. These include compatibility with the material to be contained, low melting temperature, a narrow softening range, and extrudability. In the case of packaging bitumen the bags must be able to withstand the higher temperatures of these materials, typically around 165°C.
USP 4,248,348 (Butler et al.) discloses a package comprising an article (such as an unvulcanized rubber) packaged in a film. The film is made from an ethylene /vinyl acetate copolymer containing an antiblock agent. USP '348 teaches that polyethylene film is not suitable for overwrapping bales of rubber, because when the bale (including the film wrapper) is charged into a suitable mixer, the polyethylene film is not sufficiently dispersed and causes defects in the end product. Similarly, USP 5,120,787 (Drasner) discloses a method of compounding a rubber by using a bag or liner made from an ethylene /vinyl acetate copolymer. The bag or liner is directly compounded into the mixer and becomes part of the rubber compound. USP 4,394,473 (Winter et al.) discloses packages comprising an article (for example, unvulcanized or vulcanized rubber) packaged in a bag made from syndiotactic 1,2-polybutadiene containing an antiblock additive. USP '473 also teaches that the use of polyethylene bags results in incompatibility problems.
EPA 0 270 902 discloses the use of bags made from copolymers of at least one olefin monomer (for example, ethylene) and acrylic or methacrylic acid, or ionomers thereof, used to package particulate elastomer materials.
Branched, high pressure low density polyethylene (LDPE) and blends of LDPE with small amounts of traditional (that is, Ziegler polymerized) linear low density polyethylene (LLDPE), typically less than 10 percent LLDPE, are sometimes used to make batch inclusion bags which are used to contain carbon black. The carbon black is then used to make tires. However, the melting and softening characteristics of LDPE limits its use as a batch inclusion packaging material.
Use of traditional LLDPE in batch inclusion is limited because of its relatively high melting point and broad softening range. US 5,525,659 discloses batch inclusion bags made from a particular class of LLDPE, namely substantially linear ethylene polymers.
It would be desirable to have batch inclusion bags which maintain their durability during hot filling and yet are even more miscible with the contents when used.
It has been discovered that the addition of relatively high amounts of filler, preferably inorganic filler and most preferably calcium carbonate, leads to improved miscibility of polyolefin based plastomers and /or elastomers with bitumen, asphalt or similar materials. The inorganic is added in an amount of from 15 to 60 percent by weight of the film layer. Calcium carbonate is the preferred filler. The resulting compounded resin can be made into blown films which can be used as preformed bags or tube stock to be converted into bags via a form-fill-seal process at the producer. Bags made from such resin are particularly suited for packaging bitumen or similar materials as they can be hot filled, have adequate hot tack strength and are particularly miscible with molten bitumen.
Detailed Description of the Invention In a first aspect, the present invention relates to a package which comprises:
(A) an ingredient; (B) a protective film comprising at least one layer comprising i) at least one polyolefin plastomer or elastomer or segmented ethylene-alpha-olefin block copolymer, and ii) an inorganic filler in an amount of from 15 to 60 percent by weight of the layer, wherein the protective film (B) is miscible with the ingredient under conditions in which the ingredient is used.
The protective film for use in the present invention comprises at least one polyolefin plastomer or elastomer. Elastomers are known in the art and mean a material which at room temperature can be stretched under low stress to at least twice its original length and upon immediate release of the stress, will return with force to its approximate original length. Plastomers are also generally known in the art. For poly ethylenes, plastomers will generally contain 20 percent or less of the comonomer (preferably 1-octene) and will have a density of 0.90 g/cm3or more, and for elastomers the level of comonomer content is generally over 20 percent and the density is less than 0.90 g/cm3.
The preferred polyolefin based plastomers and /or elastomers include polyethylene plastomers and elastomers, polypropylene plastomers and elastomers, and segmented ethylene-alpha-olefin block copolymers. Polyethylene based elastomers and plastomers include homogeneously branched linear ethylene polymers such as those in U.S. Patent No. 3,645,992 and substantially linear ethylene polymers such as those described in U.S. Patent 5,272,236, U.S. Patent 5,278,272, U.S. Patent 5,582,923 and US Patent 5,733,155 and/or blends thereof (such as those disclosed in US
3,914,342 or US 5,854,045). Each of these references is hereby incorporated by reference in their entirety. Polyethylene based polymers also include high pressure copolymers of ethylene such as ethylene vinyl acetate interpolymer, ethylene acrylic acid interpolymer, ethylene ethyl acetate interpolymer, ethylene methacrylic acid interpolymer, ethylene methacrylic acid ionomer, and the like. The substantially linear ethylene polymers are preferred. Substantially linear ethylene polymers are commercially available from The Dow Chemical Company under the trade name AFFINITY™. Propylene based elastomers and plastomers include the propylene based plastomers and elastomers described in WO03/040442, and US application 60/709688 filed August 19, 2005 (each of which is hereby incorporated by reference in its entirety - some of these materials are commercially available from The Dow Chemical Company under the trade name VERSIFY™), and the propylene based plastomers and elastomers sold by ExxonMobil Chemical company under the trade name of VISTAMAXX™. The propylene based elastomers and plastomers are most preferred. Segmented ethylene-alpha-olefin block copolymers include those discussed for example in WO 2005/090427, WO 2005/090425 and WO 2005/090426, each of which are hereby incorporated by reference in their entirety.
The polyolefin plastomer or elastomer for use in a batch inclusion package application is generally selected based on the processability of the polymer into batch inclusion packaging material and through manufacturing process in which the batch inclusion package is used. For example, a polymer having a density low enough to ensure adequate melting during use is required, but not too low so that the resultant film has too much stretch during the hot fill process or subsequent palletization and transportation of the filled bags. The film also must have enough strength and must not soften too much prior to or during the manufacturing process. In addition, a polyolefin plastomer or elastomer polymer can have a higher Ilθ/l2 value, which can provide a more stable bubble during blown film production of batch inclusion film. The melt index of the polymer also must be selected based on the bubble stability and/or film strength. Selection of a polymer for use in a particular batch inclusion package is thus based on a variety of factors and the foregoing parameters are intended to be illustrative and not limiting.
In some embodiments the melting range of the polyolefin plastomer or elastomer is preferably relatively narrow, so that the polymer melts quickly when it reaches the appropriate temperature. Generally, the narrow melting range of the polymer is indicated by the difference between the melting point and the softening point. For the preferred polyolefin plastomers or elastomers used in the present invention, the melting point is relatively close to the Vicat Softening point (typically within 9-25°C) of the polymer, such that the bag does not soften too much during transport and to prevent "strings" of poorly blended/unmelted polymer from forming during use of the bag in the end-user's manufacturing process.
Vicat Softening point is measured herein in accordance with ASTM D 1525-87 using 0.125 inch (thick) plaques having a diameter of 1 inch prepared according to ASTM D-1928-90-C. Heating rate B of the ASTM test is used (120 ± 12 °C/hour). The films of the present invention preferably have a Vicat Softening point in the range of from 600C to 1030C
Preferred polyethylene based resins are will have a melt index ("MI" or "I2") between 0.3 and5 g/10min (1900C, 2.16kg). Preferred polypropylene based resins will have a melt flow rate (MFR) between 1 and 10 g/10min (2300C, 2.16kg).
In one preferred embodiment, the polyolefin plastomer or elastomer is a substantially linear polyethylene. The preferred density for substantially linear ethylene /alpha-olef in polymers (as measured in accordance with ASTM D-792) for use in the present invention is generally less than about 0.94 g/cm^, preferably from 0.87 g/cm^ to 0.92 g/cm^. The density of the preferred substantially linear ethylene /alpha-olef in polymers used in the present invention is generally dependent upon the processability of the substantially linear ethylene /alpha-olef in polymer into batch inclusion packaging materials and packages, the strength required of the batch inclusion packaging material, and the manufacturing process in which the batch inclusion package is used. Generally for elastomers, the density of the substantially linear ethylene /alpha-olef in polymer used to make the batch inclusion package is from 0.87 g/cm3 to 0.917 g/cm3.
The molecular weight of the preferred substantially linear ethylene /alpha-olef in polymers for use in the present invention is conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formerly known as "Condition (E)" and also known as I2). Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear. The melt index for the preferred substantially linear ethylene /alpha-olef in polymers useful herein is generally that useful in forming film in conventional film forming manufacturing operations, such as cast film, blown film and extrusion coating techniques. The melt index will generally be from 0.1 grams/ 10 minutes (g/10 min) to 20 g/10 min, preferably from 0.3 g/10 min to 5 g/10 min.
Another measurement useful in characterizing the molecular weight of the preferred substantially linear olefin polymers is conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 1900C /10 kg (formerly known as "Condition (N)" and also known as Ilθ)- The ratio of these two melt index terms is the melt flow ratio and is designated as Ilθ/l2- Generally, the I10/I2 ratio for the linear is at least about 5.63, preferably at least about 7, especially at least about 8 or above. For the substantially linear ethylene /alpha-olef in polymers used in the batch inclusion packages of the invention, the I10/I2 ratio indicates the degree of long chain branching, that is, the higher the Ilθ/l2 ratio, the more long chain branching in the polymer. Generally, the Ilθ/l2 ratio of the preferred substantially linear ethylene /alpha-olef in polymers is at least about 5.63, preferably at least about 7, especially at least about 8. Generally, the upper limit of Ilθ/l2 ratio for the preferred homogeneously branched substantially linear ethylene /alpha-olef in polymers is about 50 or less, preferably about 30 or less, and especially about 20 or less.
In another preferred embodiment, the polyolefin plastomer or elastomer is a propylene based plastomer or elastomer or "PBPE". These materials comprise at least one copolymer with at least about 50 weight percent of units derived from propylene and at least about 5 weight percent of units derived from a comonomer other than propylene. Suitable propylene based elastomers and /or plastomers are taught in WO03/ 040442, and US application 60/709688 (filed August 19, 2005), each of which is hereby incorporated by reference in its entirety The preferred density for PBPE (as measured in accordance with ASTM D-792) for use in the present invention is generally less than about 0.888 g/cm3, preferably from 0.867 g/cm3 to 0.888 g/cm3. The density of the preferred PBPE used in the present invention is generally dependent upon the processability of the PBPE into batch inclusion packaging materials and packages, the strength required of the batch inclusion packaging material, and the manufacturing process in which the batch inclusion package is used. Generally for elastomers, the density of the
PBPE used to make the batch inclusion package is from 0.867 g/cm^ to 0.888 g/cm3. The molecular weight of the preferred PBPE polymers for use in the present invention is conveniently indicated using a melt flow rate measurement according to ASTM D-1238, Condition 230°C/2.16 kg and also known as I2). Melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear. The melt flow rate for the preferred substantially PBPE polymers useful herein is generally that useful in forming film in conventional film forming manufacturing operations, such as cast film, blown film and extrusion coating techniques. The melt flow rate will generally be from 1 grams/ 10 minutes (g/10 min) to 10 g/10 min, preferably from 2 g/10 min to 5 g/10 min.
The polyolefin plastomers or elastomers used in the film of the batch inclusion packages are preferably used as the only polymer components. However, other polymers, including two or more different polyolefin plastomers or elastomers can be blended and/or multilayered extruded and /or multilayered laminated to modify the film processing, film stiffness, film barrier properties, film strength, film melting characteristics, or other desirable film characteristics. Batch inclusion films made with appropriate blends of the polyolefin plastomer or elastomer and other polymer components would still maintain enhanced performance. Some useful polymer blend components include, for example, high pressure low density polyethylene (LDPE), ethylene /vinyl acetate copolymer (EVA), polybutylene (PB), linear high density polyethylene (HDPE) having a density from 0.941 to 0.965 g/crn^ and heterogeneously branched linear low density polyethylene (LLDPE) having a density from 0.87 to 0.94 g/cm^. Preferably the polyolefin plastomers or elastomers comprise at least about 50 percent of the polymer blend composition, more preferably at least about 80 percent of the polyolefin plastomer or elastomer blend composition. LDPE, and PP based bitumen bags are known, but have very poor miscibility in the heated bitumen. Nevertheless, small amounts of these materials may be blended with the plastomers /elastomers, but at levels greater than about 20 percent these materials may have a deleterious effect on the solubility of the bags.
Preferably the polyolefin plastomer or elastomer will comprise from 20 to 80 percent by weight of the film, more preferably from 20 to 65 percent, and even more preferably from 35 to 50 percent. The second component in the at least one film layer used in the packages of the present invention is an inorganic filler. The inorganic filler is added in an amount of from 15 to 60 percent by weight of the layer, preferably, 20 to 55 percent by weight of the layer, or 30 to 55 percent by weight, and more preferably from 40 to 50 percent by weight of the layer. It is believed that any inorganic filler can be used, including materials such as titanium dioxide, talc, silica, barium sulfate, diatomaceous earth, aluminosilicates, carbon black, and calcium carbonate, with calcium carbonate generally being most preferred. Preferably when calcium carbonate is used, it has an average particle size of less than 3 microns with a top cut of 11 microns.
The second component can be added via any means known in the art. Preferred methods include adding as a masterbatch in a dryblending operation. Alternative methods include compounding (via single screw or twin screw extruder) the inorganic filler into the second component (resin) to form a compound.
The films used in the present invention may also contain other additives such as plasticizers, antioxidants (for example, hindered phenolics
(for example, Irganox® 1010 made by Ciba Geigy Corp.), phosphites (for example, Irgafos® 168)), cling additives (for example, polyisobutylene (PIB)), heat stabilizers, pigments, light stabilizers (for example, Cyasorb™ UV 531 benzophenone made by Cyanamid and Tinuvin™ 622 hindered amine light stabilizer made by Ciba Geigy Corp.), processing aids (for example, polyethylene glycols, fluoropolymers, fluoroelastomers, waxes), flame retardants (for example, Amgard™ CPC 102 phosphorous based flame retardants made by Albright and Wilson Americas), lubricants (for example, waxes, stearates, mineral oils), slip agents (for example, erucamide, oleamide), antiblock additives (for example, silicon dioxide), cross-linking agents (for example, peroxides, (for example, Booster™ made by DuPont)), antifogging agents (for example, Atmer™ 100 sorbitan ester made by ICI), impact modifiers (for example, Paxon™ Pax Plus rubber modified film resin made by Allied Corp.), antistatic agents (for example, Armostat 410 ethoxylated tertiary amine made by Akzo Chemicals, Inc.), and the like, to the extent that they do not interfere with the function of the batch inclusion package. The list of additives is merely illustrative and is not all inclusive or limiting. Suitable Films and Film Structures
Films and film structures having the novel properties described herein can be made using conventional hot blown film or cast film fabrication techniques. Conventional hot blown film processes are described, for example, in The Encyclopedia of Chemical Technology, Kirk- Othmer, Third Edition, John Wiley & Sons, New York, 1981, Vol. 16, pp. 416-417 and Vol. 18, pp. 191-192, the disclosures of which are incorporated herein by reference.
The films may be monolayer or multilayer films, but at least one layer of the film structure comprises the modified polyolefin elastomer or plastomer previously described. Preferably the inner layer will comprise the modified polyolefin plastomer or elastomer. The inner layer is the layer adjacent to the material contained in the package. The inner layer can be coextruded with the other layer(s) or the inner layer can be laminated onto another layer(s) in a secondary operation, such as that described in "Coextrusion For Barrier Packaging" by WJ. Schrenk and CR. Finch, Society of Plasties Engineers RETEC Proceedings, June 15-17 (1981), pp. 211-229, the disclosure of which is incorporated herein by reference. A monolayer film can also be produced via tubular film (that is, blown film techniques) or flat die (that is, cast film) as described by K.R. Osborn and W.A. Jenkins in "Plastic Films, Technology and Packaging Applications" (Technomic Publishing Co., Inc. (1992)), the disclosure of which is incorporated herein by reference, and. optionally, the film can go through an additional post-extrusion step of adhesive or extrusion lamination to other packaging material layers to form a multilayer structure. If the film is a coextrusion of two or more layers (also described by Osborn and Jenkins), the film may still be laminated to additional layers of packaging materials, depending on the other physical requirements of the final packaging film. "Laminations Vs. Coextrusion" by D. Dumbleton (Converting Magazine (September 1992), the disclosure of which is incorporated herein by reference, also discusses lamination versus coextrusion. Monolayer and coextruded films can also go through other post extrusion techniques, such as a biaxial orientation process.
Extrusion coating is yet another technique for producing multilayer packaging materials. Similarly to cast film, extrusion coating is a flat die technique. A film layer can be extrusion coated onto a substrate either in the form of a monolayer or a coextruded extrudate.
Generally for a polymer blend and /or a multilayer film structure, the modified polyolefin plastomer or elastomer described herein comprises at least one layer of the total multilayer film structure, preferably the inner layer. Other layers of the multilayer structure include but are not limited to barrier layers, and/or tie layers, and/or structural layers. Various materials can be used for these layers, with some of them being used as more than one layer in the same film structure. Some of these materials include: high density polyethylene (HDPE), , ethylene /vinyl acetate (EVA) copolymers, ethylene /acrylic acid (EAA) copolymers, ethylene /methacry lie acid (EMAA) copolymers, ionomers, LLDPE, HDPE, LDPE, polypropylene (including homopolymer, random co polymers and impact copolymers) and graft adhesive polymers (for example, maleic anhydride grafted polyethylene). Generally, the multilayer film structures comprise from 2 to 7 layers.
The thickness of the film comprising the modified polyolefin plastomer or elastomer (whether as a monolayer film or layer in a multilayer film structure) is typically from 60 micrometers to 250 micrometers, preferably from 100 micrometers to 225 micrometers, with 150 to 200 micrometers being most preferred.
The films of the present invention can also be characterized in terms of their physical properties. In general the preferred films of the present invention will have a Peak Load of at least 30 N as measured by ASTM 5747-95 (modified by using a probe diameter of 0.50mm instead of 0.75 mm as specified in the ASTM method), more preferably a Peak Load greater than 45N. The elongation at Peak Load for the preferred films will be greater than 30mm, more preferably greater than 35mm Puncture resistance for the films can be determined using ASTM D 5748-95 modified by using a probe diameter of 0.50mm instead of 0.75 mm as specified in the ASTM method. The puncture resistance for the preferred films will be greater than 30mm more preferably greater than 35mm. The total energy for the preferred films will be greater than 1.0J more preferably greater than 1.5J, as determined by ASTM 5748-95. The Dart impact for the films can be determined according to ASTM D 1709-01, method B. The Dart impact for the preferred films will be greater than 90Og, more preferably greater than 120Og. Suitable Batch Inclusion Structures
The films and film structures made from the modified polyolefin plastomer or elastomer are preferably made into bags either in- line via the form-fill-seal process or off line in the form of preformed bags (also known as valve bags). The bags of the present invention can be hot filled with the desired product (for example bitumen) above the melting point of the bag, using cooling means such as by suspending the bags in a water bath or through the use of sprayed water. Alternatively chilled air or other gas could be used to keep the bags from prematurely melting during hot-filling. After filling, the bags are sealed, thereby reducing noxious vapors from the solidifying bitumen.
Use of the modified polyolefin plastomers and elastomers in batch inclusion bags and films affords numerous advantages. The modified polymers have excellent processability in making blown film and also have low melting points and softening ranges, relative to other materials. The modified plastomers and elastomers are also highly miscible with bitumen allowing them to become fully integrated with the bitumen when used, for example, in asphalt applications. It should be noted that the filler used in the bag will often also be a desirable additive in the bitumen, thereby offering additional advantages.
Experimental: Blown Film Examples
In order to demonstrate the beneficial nature of the present invention a series of films were made and their miscibility with bitumen evaluated.
Table 1 summarizes the modified polymers used to make films for use in these Examples. When present, the filler was added via a masterbatch comprising 60 percent by weight CaCO3 in a polymer carrier resin such as LDPE resin.
Table 1
Figure imgf000017_0001
Blown film is made from the materials described in Table 1.
The films are made as monolayer blown films (A/ A/ A) on a three layer (A/B/C) coextrusion blown film line (Reifenhauser), with a layer ratio of 1:2:1. The blown film line details are as follows: Die Diameter-250mm; Die Gap-2.3mm; Screw Diameter- A - 60 mm, B -70mm, and C - 60 mm. Resins are dry blended with masterbatches via the gravimetric blending stations on the extruders. Processing parameters for various resins and their combination are given below. The films produced have a thickness of 165 microns.
Table 2
Figure imgf000019_0001
In order to evaluate the miscibility of these films in bitumen,
250 ml of bitumen is added to a beaker and heated using a mantle heater having temperature controller to reach the desired temperatures (1500C, 2000C or 2500C). A sample of each film having the dimensions of 25mm x 25mm is obtained and introduced to the molten bitumen. Temperature is monitored with a mercury thermometer to ensure there was no fluctuation before sample was introduced. The film samples are introduced with tweezers slowly into the molten bitumen and a stopwatch is used to monitor the changes over time. At 15 minutes intervals, sample is picked up using tweezers for visual inspection and a qualitative record of the amount of material remaining is made. Each time before sample is picked up, the bitumen is gently stirred using a glass rod to ensure a uniform temperature of the molten bitumen. At the end of 1 hour, the testing is stopped and the molten bitumen is sieved to inspect the sample. The quantity of film remaining in the bitumen is not able to be quantified due to the contamination with bitumen; therefore this test relied on qualitative visual observation. The result is recorded as 'Miscible' or 'Immiscible'. "Immiscible" means there was visible film remaining on the sieve surface, whereas "miscible" means that there was no visible trace of the film. The resulting observations are presented in Table 3
Table 3
Figure imgf000021_0001
The results show that the poly olefin elastomers and plastomers with the inorganic filler (Examples 1, 2, and 4) are more miscible in the bitumen.

Claims

We Claim:
1. A package which comprises: (A) an ingredient; (B) a protective film comprising at least one layer comprising i) at least one polyolefin plastomer or elastomer or segmented ethylene-alpha-olefin block copolymer, and ii) an inorganic filler in an amount of from 15 to 60 percent by weight of the layer, wherein the protective film (B) is miscible with the ingredient under conditions in which the ingredient is used.
2. The package of claim 1 wherein the package has been hot filled at a temperature above approximately 100°C. 3. The package of claim 1 wherein the package has been hot filled at a temperature above approximately 100°C and promptly cooled using a fluid cooling medium.
3. The package of claim 1 wherein the polyolefin plastomer or elastomer is selected from the group consisting of polyethylene plastomers and elastomers and polypropylene plastomers and elastomers.
4. The package of Claim 4 wherein the polyolefin plastomer or elastomer is selected from the group consisting of substantially linear polyethylene, metallocene linear polyethylenes (mLLDPE) and PBPEs.
5. The package of Claim 1 wherein the inorganic filler is calcium carbonate.
6. The package of Claim 6 wherein the calcium carbonate is present in an amount of from 20 to 55 percent by weight of the layer.
7. The package of Claim 7 wherein the calcium carbonate is present in an amount of from 40 to 50 percent by weight of the layer.
8. The package of Claim 1 wherein the ingredient is bitumen, asphalt or modified bitumen or asphalt.
9. A method of incorporating an ingredient into a finished article comprising
(A) filling a package with the ingredient
(B) sealing the package
(C) heating the package to a temperature which exceeds the melting temperature of the package
(D) mixing the melted package with the ingredient wherein the package comprises i) a polyolefin plastomer or elastomer and ii) an inorganic filler, and wherein the package is fully miscible with the ingredient.
10. The method of Claim 10 wherein step A occurs while cooling the package.
11. The method of Claim 11 wherein the package is cooled by immersing the package in a cooling medium.
12. The method of Claim 12 wherein the cooling medium is water.
13. The method of Claim 11 wherein the package is cooled by blowing air or other inert gas.
14. The method of Claim 10 wherein the polyolefin plastomer or elastomer is selected from the group consisting of polyethylene plastomers and elastomers and polypropylene plastomers and elastomers.
15. The method of Claim 15 wherein the polyolefin plastomer or elastomer is selected from the group consisting of substantially linear polyethylene, metallocene catalyzed polyethylenes and PBPEs.
16. The method of Claim 10 wherein the inorganic filler is calcium carbonate.
17. The method of Claim 17 wherein the calcium carbonate is present in an amount of from 20 to 55 percent by weight of the layer.
18. The method of Claim 18 wherein the calcium carbonate is present in an amount of from 40 to 50 percent by weight of the layer.
19. The method of Claim 10 wherein the ingredient is bitumen, asphalt or modified bitumen or asphalt.
20. The method of Claim 10 wherein step (A) occurs at a temperature greater than or equal to 1000C.
PCT/US2008/060769 2007-05-02 2008-04-18 Batch inclusion packages WO2008137285A1 (en)

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