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WO2002061013A1 - Composition adaptee a la fabrication de joints et joints fabriques a partir de cette composition - Google Patents

Composition adaptee a la fabrication de joints et joints fabriques a partir de cette composition Download PDF

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Publication number
WO2002061013A1
WO2002061013A1 PCT/US2002/003928 US0203928W WO02061013A1 WO 2002061013 A1 WO2002061013 A1 WO 2002061013A1 US 0203928 W US0203928 W US 0203928W WO 02061013 A1 WO02061013 A1 WO 02061013A1
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WO
WIPO (PCT)
Prior art keywords
seal
closure
polypropylene
cap
pet
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2002/003928
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English (en)
Inventor
David Mark Gale
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of WO2002061013A1 publication Critical patent/WO2002061013A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0655—Polyesters

Definitions

  • the present invention provides for polymeric compositions which are highly suitable for use in closures for containers when a combination of low permeability, melt processibility, and conformability is required.
  • BACKGROUND OF THE INVENTION For decades if not for centuries there has been a need for providing seals of one sort or another to prevent the exchange of chemicals between some enclosed volume and the surrounding medium. Seals range from gaskets disposed between two lengths of pipe in an oil pipeline to the wax employed in home canning using mason jars. In the overwhelming preponderance of situations, a seal will perform its function satisfactorily if it prevents bulk mass transfer.
  • a leading method is to employ multilayer sheeting structures as cap liners, wherein one or more of the layers comprises a low permeability material.
  • Another approach is to mix a chemical scavenger, such as an oxygen scavenger, into the formulation of the cap liner, to deter diffusion of the critical species.
  • Blends comprising highly crystalline polyesters, incompatible polyolefins, and olefin ionomers are known.
  • Patents 5747127 and 5843545 disclose blends of polyester, polyolefin, and olefin ionomer useful for thermoformed, non- oriented thin-walled articles such as dual-ovenable trays. Improved low temperature impact strength is cited.
  • Compositions disclosed have a minimum of 86% by weight. The preferred composition has 90-94% polyethylene terephthalate (PET), 1-3% ionomer, and 5-7% polyolefin.
  • the present invention provides for a seal comprising 80-100% by weight of a composition consisting essentially of 20-80% by weight of one or more polyesters, 5-25% by weight of one or more olefin ionomers, and 5-75% of one or more polyolefins, said seal further comprising up to 20% of one or more adjuvants such as are commonly employed in the art to enhance processibility or product performance.
  • the present invention provides for a composition comprising 65-75% by weight of one or more polyesters, 12-18 % of one or more polyolefins, and 12-18% of one or more of olefin ionomers, the composition being characterized by an oxygen permeability value of less than 30 cc-mil/100 in 2 /day/bar at 30°C.
  • a preferred composition is further characterized by a flexural modulus of 200-250 Kpsi.
  • the composition has an improved oxygen barrier.
  • the present invention further provides for a shaped article comprising the seal of the invention.
  • Figure 1 shows one embodiment of the seal of the invention consisting of a flat disk provided with a circumferential edge bead well- designed for use as a seal for beer bottle.
  • Figure 2 shows a second embodiment of the seal of the invention.
  • the seal possesses sufficiently high modulus to be self supporting in the form of a concave disk, the design particularly well suited for carbonated beverages.
  • Figure 3 shows one embodiment of the shaped article of the invention in the form of a recloseable bottle cap wherein the seal of the invention is the shaped article.
  • the bottle cap is provided with a circular ridge provided for engaging the inside surface of a bottle so that the mouth of the bottle is disposed in the circular groove on the inside of the bottle cap.
  • the bottle cap is provided with internal threads for engaging the externally threaded neck of a bottle, and with a tamper- indicating ring.
  • Figure 4 depicts another embodiment of the shaped article of the invention in the form of a recloseable bottle cap wherein the seal of Figure 1 is disposed within the cap, the cap being made of a composition not of the invention.
  • Figure 5 depicts another embodiment of the shaped article of the invention in the form of a recloseable bottle cap wherein the seal of Figure 2 is disposed within the cap, the cap being made of a composition not of the invention.
  • the present invention is a polymeric seal and a composition therefor, the seal suitable for use between two surfaces which are attached together or, in the alternative, for use in providing closure to an enclosed volume.
  • the polymeric seal is a gasket between two lengths of pipe carrying a fluid in order to prevent leakage of the fluid into the external environment, and/or leakage of the external environment into the fluid.
  • the polymeric seal is a cap liner in a carbonated beverage (such as beer or soda) bottle which prevents leakage of the beverage out of the bottle, provides a barrier to diffusive as well as bulk mass transport of CO out of the bottle, and a barrier to diffusive as well as bulk mass transport of atmospheric O 2 into the bottle.
  • the cap or cap liner is suitable for various foods (e.g. salad dressing), cosmetics and/or other household products (e.g. cleaning chemicals).
  • Such caps or closures can be polypropylene (PP), polyethylene (PE) or metal lined with a cap liner.
  • the composition is in the form of a continuous tube disposed to convey fluids, particularly body fluids, susceptible to diffusive contamination from the external environment such as from water, oxygen, of carbon dioxide, among others.
  • compositions suitable for use in the seal of the invention provide a desirable balance of the resilience, conformability, and processibility of the polyolefins and polyolefin copolymers currently in widespread commercial use as seals and the permeability of polyesters, specifically polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the seal suitable for the present invention must readily conform to the small surface irregularities common to the mouths of mass-produced bottles and other containers; insufficient conformability leads to leakage. In the case of recloseable containers, the seal must also exhibit high recovery from deformation because upon resealing, the seating of the seal on the bottle mouth may not be exactly the same as the previous time.
  • compositions suitable for the seal of the present invention exhibit a tensile modulus of 160-280 Kpsi, preferably 200-250 Kpsi, coupled with an ultimate elongation of 5-200%, preferably 25-100%.
  • tensile properties are determined according to ASTM D638. Values of the ultimate elongation in excess of ca. 200% are ⁇ uggestive of a material which will be excessively susceptible to permanent deformation under pressure causing material creep and the formation of a leak.
  • composition suitable for the present invention must meet the further requirement of an oxygen permeability (OPV), determined according to ASTM D3985-95, of less than about
  • the seal according to the present invention comprises 80-100% by weight of a composition consisting essentially of 20-80% by weight of one or more polyesters, 5-25% by weight of one or more olefin ionomers, 5-75% of one or more polyolefins, said seal further comprising up to 20%, preferably up to 10%, most preferably up to 5% of one or more adjuvants such as are commonly employed in the art to enhance processibility or product performance.
  • the greater the concentration of polyester the greater the barrier to oxygen or carbon dioxide permeation with concomitant increase in modulus and decrease in processibility. Polyesters are well known in the art, as describer in Plastics
  • polyesters suitable for the practice of the present invention are characterized by a Goodyear intrinsic viscosity of 0.4-1.2 dl/g with 0.6-0.85 dl/g preferred. Goodyear intrinsic viscosity is determined by dissolving the polymer in a 50/50 weight % mixture of trifluoroacetic acid and dichloromethane at 19°C and the intrinsic viscosity is measured using a Viscotek Foreign fluoViscometer Model Y900.
  • the viscosity data which is reported represents correlated intrinsic viscosity values in 60/40 wt% phenol/1, 1,2,2-tetrachloroethane following ASTM D 4603-96.
  • the solution is diluted to measure viscosity at several lower concentrations.
  • the intrinsic viscosity is the limit of the fraction (In V)/C as C approaches zero, where C is the concentration of the polymer solution, and In V is the natural log of the viscosity. Values are reported in dl/g.
  • polyesters comprising an aromatic ring (aromatic polyesters) such as polyalkylene terephthalate polymers.
  • Suitable preferred polyesters include but are not limited to polyethylene terephthlate (PET), polypropylene terephthlate, polybutylene terephthalate, random and block copolymers comprising monomer units derived from both terephthalic and isophthalic acids and their respective condensation products with ethylene glycol, and copolymers comprising monomer units derived from both terephthalic acid and naphthalene-2,6-dicarboxylic acids and their respective condensation products with ethylene glycol PET/PEN copolymers (formed from terephthalic and naphthalene-2,6-dicarboxylic acids). Most preferred is PET.
  • PET polyethylene terephthlate
  • PET polypropylene terephthlate
  • polybutylene terephthalate random and block copolymers comprising monomer units derived from both terephthalic and isophthalic acids and their respective condensation products with ethylene glycol
  • copolymers comprising monomer units
  • the compositions comprising ca. 20% PET are the most highly processible with the best sealing properties but exhibit OPV of ca. 200 cc-mil/ 100 cm 2 /day/bar which is acceptable for the practice of the present invention but not preferred. It is further found in the practice of the present invention that increasing the concentration of PET to ca. 65% results in an OPV of ca. 60 cc-mil/ 100cm 2 /day/bar. That is to say, a ca. 3-fold increase in the PET concentration results in a reduction in OPV by ca. 67%. It is therefore a very surprising result in the practice of the invention that a further increase of PET concentration to ca. 70% results in a further reduction in OPV of 50% to ca. 30 cc-mil/ 100 cm 2 /day/bar.
  • the ionomer in the composition of the invention is a copolymer of ethylene, 4-25 weight-% of an unsaturated carboxylic acid represented by the formula
  • R1 CH CR 2 COOH
  • R 1 and R 2 are independently H, methyl, ethyl, or propyl, and wherein 1 to 90% of the acid groups are neutralized to Na, Mg, Li or Zn salts; and 0 to 25% of an alkyl methacrylate represented by the formula
  • R 3 is hydrogen or methyl and where R 4 is alkyl having 1 to 8 carbons.
  • the ionomer is a copolymer of ethylene and ca. 10-20% by weight of methacrylic acid ca. 50-70% neutralized with Na + or Zn +2 .
  • Suitable ionomers are available commercially under the trade name
  • ASTM D12378 of the ionomer suitable for the practice of the invention ranges from 0.1 - 20 g/10 min, with 0.5 - 2.0 preferred, and
  • the polyolefin resin component of the composition of the invention is a C1-C6 alpha polyolefin homo- or copolymer characterized by a melt index of 0.5-120 g/10 min (2160 gram weight at 230°C according to
  • Polypropylene homopolymer characterized by a melt index of 5 to 20 g/10 min. is preferred.
  • the polyolefin resin is present in the composition of the invention at a concentration of 5- 75% by weight.
  • Seals suitable for the practice of the present invention may include, but are not limited to, up to 20% by weight, preferably up to 10% by weight, most preferably up to 5% by weight, of one or more adjuvants such as are commonly employed in the art to enhance processibility or product performance. As a general rule, these adjuvants will be combined with the composition of the invention during melt processing. Such adjuvants are well known to one of skill in the art. They include, but are not limited to, plasticizers, pigments, mineral fillers, oxygen scavengers, release agents, stabilizers, compatiblizers, and polymeric materials.
  • Pigments include titanium dioxide or carbon black; fillers include clays, diatomaceous earth, mineral fillers, cotton linters, hollow glass balls (microspheres), wood flour, or the like; polymeric materials include terpolymers of ethylene, n-butyl acrylate and glycidyl methacrylate, a maleic acid modified ethylene- propylene-diene rubbers. Rubber toughening, such as by the addition of maleic acid modified ethylene-propylene-diene rubbers may result in a reduction in the barrier offered by the composition.
  • the resins of this invention may also be fiber reinforced, for example with glass fibers.
  • Plasticizers such as polyethylene glycol, dioctyl phthlate or dioctyl adipate, and / or anti-plasticizers (0.1 to 5%), such as methyl 4-hydroxy-benzoate, dimethyl terephthlate, or others known in the art may be added to variously improve moldability, control crystallinity and/or improve barrier. Small amounts (say 0.001 - 3%) of known nucleating agents, such as sodium acetate, may also be added to control crystallinity and increase set-up rate in the mold.
  • nucleating agents such as sodium acetate
  • additives may modify the properties of the composition with which it is combined.
  • some additives are well known to improve barrier (e.g., anti-plasticizers, certain clays, mica etc.), whereas some additives tend to reduce barrier (e.g., rubber particles used as tougheners); likewise, some additives increase modulus, e.g. glass fiber, or decrease modulus, e.g., plasticizers.
  • barrier e.g., anti-plasticizers, certain clays, mica etc.
  • some additives tend to reduce barrier (e.g., rubber particles used as tougheners); likewise, some additives increase modulus, e.g. glass fiber, or decrease modulus, e.g., plasticizers.
  • the skilled individual when using additives, will therefore adjust the overall composition of the seal of the invention to maintain the desired property balance.
  • Slip and antiblock additives may be used. These additives are useful in controlling removal torque of the liner/closure.
  • the most preferred composition of the invention comprises 65-75% PET, 12-18% polypropylene, and 12-18% of an ethylene copolymer containing 12-18% methacrylic acid, the acid being 55-60% converted to the sodium or zinc salt.
  • the component polymers are in the preferred compositional and melt index range hereinabove indicated.
  • the most preferred composition of the invention exhibits a very surprising combination of high processibility, excellent sealing performance, and unexpectedly low OPV of less than 30 cc-mil/100 cm 2 /day/bar.
  • the preferred composition of the invention may contain up to 5% of the adjuvants hereinabove described, particularly of a pigment and an internal release agent. More preferably, the preferred composition will contain up to 2% of said adjuvants.
  • OPV OPV below about 30 cc-mil/100 sq. in. /day/bar which is characteristic of the most preferred embodiment of the composition of the invention, effectively guarantees that the contents of the tightly sealed bottle will not be exposed to oxidation as a result of permeation through the seal for a period of several months.
  • flexural modulus of the highly preferred composition of the invention is in the range of 200 to 250 Kpsi, and tensile strain at break is 25% - 100%.
  • the composition of this invention may be prepared in a variety of mixing processes known in the art, and, in general, a wide process latitude is exhibited.
  • Melt blending which is preferred, may be effected in any suitable mixing device such as a twin-screw extruder, a single screw extruder (optionally equipped with a static mixer assembly), a rubber mill, a Banbury mixer or the like.
  • the melt temperature must be kept below 300°C with the range of 260-295 usually employed to get a good balance of high flow and productivity with low decomposition.
  • the preblending step can be skipped and the various ingredients can be blended in situ in the injection molding or film extruder. In situ blending is in general cheaper, so when it is practical and efficacious to do, it is preferred.
  • compositions suitable for the practice of the invention will offer equivalent properties or processibility. While the compositions suitable for the practice of the present invention are melt processible, some combinations result in more uniform extrudates and molded articles than others, as indicated by the error bars shown in Table 8 hereinbelow. For example, while some combinations of ingredients can readily be processed into film without a preliminary melt blending step, others cannot. In particular, it has been found in the practice of the invention that some compositions did not form uniform extrudates, though such compositions represent only a small fraction of the total number encompassed in the present invention.
  • the present invention provides for a closure for a container having a sealable opening, said closure comprising a seal and a means for reversibly sealingly contacting said seal to said sealable opening.
  • the seal of the invention is employed in a bottle cap, most particularly a cap to a beer bottle.
  • the seal may be a component, known in the art as a "cap liner," contained within a larger cap made from a different material, or it may be an integral structural component of a cap which is fabricated from the seal composition.
  • a cap liner contained within a larger cap made from a different material
  • FIG. 1 One embodiment of the seal of the invention is shown schematically in Figure 1 wherein the seal of the invention consists of a flat disk, 11 , provided with a circumferential edge bead, 12, designed to provide structural integrity when pressed between the mouth of a bottle and the bottle cap, and a thinner, continuous central portion, 13, designed to cover the mouth of the bottle.
  • the seal of the invention will vary in thickness and design depending upon the particular requirements of a specific application. In many applications, a thickness of 125 micrometers will be satisfactory, with the edge bead, if one is included, being ca. 25% thicker.
  • Figure 2 shows a second embodiment of the seal of the invention.
  • This embodiment is very similar to that in Figure 1.
  • the seal 15 possesses sufficiently high modulus to be self supporting in the form of a concave disk 14.
  • the seals in Figures 1 and 2 are embodiments designed for incorporation into a separate cap or closure generally made from a different material - that is, the seals in Figures 1 and 2 are highly suitable for use as cap liners. This is further illustrated in Figures 4 and 5 respectively.
  • Figure 4 depicts a recloseable bottle cap, 41 , wherein the seal of Figure 1 , 42, is disposed within the cap as shown.
  • FIG. 5 depicts a recloseable bottle cap, 51 , close in design to that of Figure 4 but differing in that the seal of Figure 2, 52, is disposed therewithin.
  • Figure 3 shows an embodiment of the invention in the form of a recloseable bottle cap, 31 , made from a composition of the invention so that the seal is an integral part of the bottle cap - in a sense, the bottle cap is the seal.
  • the cap is provided with a circular ridge, 32, thereby forming a circular groove, 33, between the ridge and the internal wall of the cap so that when the cap is engaged with the container (not shown) the mouth of the container will be sealingly disposed in the circular groove.
  • a tamper- indicating ring, 34 of a type which is widely employed in the art.
  • a further embodiment of the invention is the non-resealable closure in the form of the familiar metal bottle cap having incorporated there within a seal of the invention.
  • the cap is removed by use of the well-known bottle opener, or by a manually exerted twist.
  • the cap still possesses the inherent property of reversibly sealingly engaging the mouth of the bottle since the cap is sealed in place, and then removed.
  • Caps with separate cap liners, caps having integral sealing structures, and other sealing closures are in widespread commercial use in a myriad of designs, well-known to one of skill in the art, and to the general public. No particular design is better than any other for the practice of the present invention, and the practitioner hereof may choose the design best suited for the intended application.
  • the particular composition and design of the seal of the invention is chosen according to the tradeoffs among sealing requirements, stiffness to prevent bowing under pressure, permeation, and cost.
  • the closure is a cap formed from a polyolefin, most preferably from polypropylene, and the seal of the invention is incorporated therein as a cap liner.
  • a cap is formed comprising polypropylene with a seal disposed therewithin in the form of a cap liner, the seal comprises 65-75% PET, 12-18% polypropylene, and 12-18% of an ethylene copolymer containing 12-18% methacrylic acid, the acid being 55-60% converted to the sodium salt.
  • the component polymers are in the preferred compositional and melt index range hereinabove indicated.
  • the seal exhibits a very surprising combination of high processibility, excellent sealing performance, and unexpectedly low OPV of less than 30 cc-mil/100 cm 2 /day/bar.
  • the preferred plastic cap or closure preferably a polyolefin cap, more preferably a polypropylene cap, may be formed by injection molding, compression molding, thermoforming, extrusion/stamping or any related processes at melt temperatures below about 300°C, usually 260-295°C.
  • Commercial scale injection molding usually employs a multi-cavity machine. These methods are well known in the art. In general, special equipment or procedures are not required.
  • a closure system may be child- resistant (a typical mechanism requires the closure to be squeezed and/or pushed down while turning); dispensing (allows for optionally opening to dispense a portion of the contents, sometimes a measured portion, without completely removing the closure; non-refillable (for example, contains a non-removable mechanism such as a glass marble between valves to prevent refill); tamper-indicating, or the like.
  • EXAMPLES As indicated in Table 1 , there were prepared various compositions of PET polyester or a copolymer thereof with PEI, 0.9 melt index Surlyn® 8920 ionomer resin available from the DuPont Company, Wilmington DE, and 11 melt index Aristech D115 polypropylene available from Aristech Chemical Corp, Pittsburgh, PA. Pellets of the respective ingredients were tumble blended at the desired composition and then fed to a 28 mm twin screw extruder manufactured by Werner and Pfleiderer, Paramus NJ wherein they were melt blended and formed into blend pellets. The extruder was equipped with medium shear general purpose screws.
  • Tensile and flex bars were fabricated from the pellets so produced by injection molding into a warm mold in a model 200-TP-6.5/6.5, 200 ton, 6 ounce injection molding machine manufactured by HPM Corp. Hartford, CT. A general-purpose polyethylene screw was employed. Maximum stress, ultimate elongation and tensile modulus were determined according to ASTM D638 2-stage, and flexural modulus was determined according to ASTM D790. Films having a thickness of 10 mils were melt cast in the same twin screw extruder described above fitted with a 10" coat-hanger style film die, and the oxygen permeability thereof were determined according to ASTM D3985-95 using a MOCON "OXTRAN" model 1000 manufacture by Modern Controls, Inc Minneapolis, MN. Water permeability measurements were made using a MOCON "PERMATRAN” model W600.
  • Example 5 and Comparative Example B The methods, equipment and materials of Examples 1-4 were employed except that Crystar 3934 PET, available from DuPont, with an IN. of 0.67, was employed in place of the Laser-plus PET in the previous examples. Fabrication conditions are shown in Table 3, and test results are shown in Table 4. Oxygen permeability was not determined.
  • Example 6 and Comparative Example C The methods, equipment and materials of Examples 1-4 were employed except that Crystar 3991 , an 80/20 PET/PEI copolymer, available from DuPont, with an IN. of 0.67, was employed in place of the Laser-plus PET in the previous examples. Fabrication conditions are shown in Table 5, and test results are shown in Table 6. Oxygen permeability was not determined.
  • pellets of each of the ingredients were dry- mixed and dried prior to feeding directly to the 28 mm Werner and Pfleiderer twin screw extruder which was fitted with a 10" coat-hanger style film die. There was no preliminary melt blending step. Ingredients were Laser-plus PET, Surlyn® 8920 and Aristech D-115A PP. Ten-mil films that were melt cast were tested for oxygen permeability. Compositions and results are shown in Table 7. Film density measured by the well-known gradient tube method (CCI /heptane) at 23°C.
  • Rucoflex® S-101 is manufactured by the Ruco Company, Hicksvclude, NY and Columbus GA. ** Leaked on testing
  • Ebagma is a terpolymer of ethylene, n-butyl acrylate and glycidyl methacrylate available under the name Elvaloy® PT or PTW from the DuPont Company, Wilmington, DE
  • Table 9 shows additional examples of compositions made using techniques described elsewhere herein. These blends were made from PET, polypropylene and ionomer (columns B and C); using PET, polypropylene, ionomer and an aliphatic polyester [namely Rucoflex(R) S- 101 , polyethylene adipate; columns F, G and H]; a composition using PET, polypropylene, polyethylene adipate and an adjunct polymer made from ethylene, n-butyl acrylate and glycidyl methacrylate (available from the DuPont company, Wilmington, DE under the trade name Elvaloy® PT or PTW; column J); as well as comparison examples in columns A, D, E and I.
  • Table 10 provides data to show an advantage in barrier of using a mixture of PET and polyethylene adipate as polyester portion of the terblends of this invention vs. using just PET.
  • the table compares the oxygen barrier of films containing PET compared to PET plus polyethylene adipate, with the ratio of the barrier of PET divided by the barrier of PET plus polyethylene adipate shown as a factor representing the improvement.
  • This advantage carried over to the terblends of this invention compare, for example, columns F and B in Table 9.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des compositions polymériques spécialement adaptées à une utilisation dans des fermetures de récipients lorsqu'une combinaison entre faible perméabilité, aptitude au traitement par fusion et conformabilité est requise.
PCT/US2002/003928 2001-02-01 2002-01-30 Composition adaptee a la fabrication de joints et joints fabriques a partir de cette composition Ceased WO2002061013A1 (fr)

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US26556301P 2001-02-01 2001-02-01
US60/265,563 2001-02-01

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9248943B2 (en) 2012-02-18 2016-02-02 Anheuser-Busch, Llc Container closure
WO2022029260A1 (fr) * 2020-08-07 2022-02-10 Basf Se Mélanges thermoplastiques
WO2023088806A1 (fr) * 2021-11-22 2023-05-25 Basf Se Mélanges thermoplastiques

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303573A (en) * 1981-01-07 1981-12-01 E. I. Du Pont De Nemours And Company Molding blends comprising polyester, ionomer resin and grafted EPDM
EP0211649A2 (fr) * 1985-08-06 1987-02-25 E.I. Du Pont De Nemours And Company Procédé pour la production d'articles rigides en polytéréphtalate d'éthylène ayant une faible perméabilité aux gaz et aux liquides organiques
US4771108A (en) * 1985-05-20 1988-09-13 Imperial Chemical Industries Plc Polymeric film
EP0517171A2 (fr) * 1991-06-04 1992-12-09 Du Pont-Mitsui Polychemicals Co., Ltd. Matériau d'emballage de polyester
DE4119218A1 (de) * 1991-06-11 1992-12-17 Du Pont Int Polyester-dichtungsschichten bei mehrschichten-verpackungen
WO1993000403A1 (fr) * 1991-06-25 1993-01-07 E.I. Du Pont De Nemours And Company Compositions d'etancheite pouvant etre aisement detachees
US5747127A (en) * 1994-12-06 1998-05-05 Shell Oil Company Polyester composition for use in thermoforming dual-ovenable trays

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US4303573A (en) * 1981-01-07 1981-12-01 E. I. Du Pont De Nemours And Company Molding blends comprising polyester, ionomer resin and grafted EPDM
US4771108A (en) * 1985-05-20 1988-09-13 Imperial Chemical Industries Plc Polymeric film
EP0211649A2 (fr) * 1985-08-06 1987-02-25 E.I. Du Pont De Nemours And Company Procédé pour la production d'articles rigides en polytéréphtalate d'éthylène ayant une faible perméabilité aux gaz et aux liquides organiques
EP0517171A2 (fr) * 1991-06-04 1992-12-09 Du Pont-Mitsui Polychemicals Co., Ltd. Matériau d'emballage de polyester
DE4119218A1 (de) * 1991-06-11 1992-12-17 Du Pont Int Polyester-dichtungsschichten bei mehrschichten-verpackungen
WO1993000403A1 (fr) * 1991-06-25 1993-01-07 E.I. Du Pont De Nemours And Company Compositions d'etancheite pouvant etre aisement detachees
US5747127A (en) * 1994-12-06 1998-05-05 Shell Oil Company Polyester composition for use in thermoforming dual-ovenable trays

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9248943B2 (en) 2012-02-18 2016-02-02 Anheuser-Busch, Llc Container closure
US10112750B2 (en) 2012-02-18 2018-10-30 Anheuser-Busch, Llc Beverage container sealing system
WO2022029260A1 (fr) * 2020-08-07 2022-02-10 Basf Se Mélanges thermoplastiques
WO2023088806A1 (fr) * 2021-11-22 2023-05-25 Basf Se Mélanges thermoplastiques

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