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Publication numberUS20010038897 A1
Publication typeApplication
Application numberUS 09/901,427
Publication dateNov 8, 2001
Filing dateJul 9, 2001
Priority dateApr 17, 1998
Also published asUS6677013
Publication number09901427, 901427, US 2001/0038897 A1, US 2001/038897 A1, US 20010038897 A1, US 20010038897A1, US 2001038897 A1, US 2001038897A1, US-A1-20010038897, US-A1-2001038897, US2001/0038897A1, US2001/038897A1, US20010038897 A1, US20010038897A1, US2001038897 A1, US2001038897A1
InventorsKevin Curie, Randolph Davidson, Sahin Emre
Original AssigneeCurie Kevin James, Davidson Randolph Lee, Sahin Emre
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Transparent multilayer polypropylene container with barrier protection
US 20010038897 A1
Abstract
A multilayer plastic container comprises a layer of a polypropylene and a layer of EVOH directly adjacent the layer of polypropylene wherein at least one of the polypropylene and EVOH layers comprises an adhesive such as maleic anhydride concentrate mixed therein to adhere the layer of polypropylene to the layer of EVOH.
Images(1)
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Claims(9)
We claim:
1. A multilayer injection molded container comprising:
a first layer comprising polypropylene; and
a second layer comprising a material selected from the group consisting of EVOH and nylon, directly adjacent to said first layer;
wherein at least one of said first and second layer further comprises an adhesive mixed therein.
2. The container of
claim 1
wherein said first layer contains approximately 0.01% to 0.20% maleic anhydride.
3. The container of
claim 1
wherein said first layer contains approximately 0.015% maleic anhydride.
4. The container of
claim 1
wherein said container has a haze value of less than approximately 29% measured through a section of the bottle having a total thickness of greater than approximately 15 mils.
5. The container of
claim 1
wherein said container has a haze value of approximately 10%-12% measured through a section of the bottle having a total thickness of greater than approximately 15 mils.
6. The container of
claim 1
wherein said second layer comprises EVOH.
7. The container of
claim 1
wherein said second layer comprises MXD6 nylon.
8. The container of
claim 1
wherein said second layer comprises nylon 6.
9. The container of
claim 1
wherein said second layer comprises nylon 6/66.
Description
  • [0001]
    This application claims the priority of U.S. provisional patent application Ser. No. 60/082,118 filed on Apr. 17, 1998, the entirety of which is incorporated herein by reference.
  • BACKGROUND OF THE INVENTION
  • [0002]
    1. Field of the Invention
  • [0003]
    This invention relates generally to transparent multilayer containers; specifically, to transparent multilayer containers having a layer of polypropylene and a layer of a barrier material which provides oxygen, carbon dioxide and moisture protection.
  • [0004]
    2. Background Art
  • [0005]
    Many products that can be filled and stored in plastic containers require carbon dioxide, oxygen and moisture barrier protection to keep the products fresh for extended periods of time. Such products include, by way of example only, certain carbonated beverages, fruit juices, beer, sauces, ketchup, jams, jellies and dry foods such as instant coffee and spices. Most commercially acceptable transparent multilayer containers that provide carbon dioxide and oxygen barrier protection are made of at least one layer comprising a polyester such as polyethylene terephthalate (“PET”) and a layer comprising ethylene vinyl alcohol copolymer (“EVOH”). The layer of EVOH in such containers provides excellent carbon dioxide and oxygen barrier protection. EVOH can also act as a chemical or fragrance barrier to keep flavors fresh for various products such as orange juice.
  • [0006]
    PET has limited moisture barrier protection compared with polypropylene. As a result, liquid products stored in PET containers experience moisture loss resulting in product weight loss and dry products stored in PET containers absorb more moisture than products stored in polypropylene containers. In addition, PET bottles have limited hot fill capabilities due to a low glass transition temperature of PET. Additionally, the injection molding process temperatures of PET and EVOH are significantly different thus creating difficulties in molding these two materials together in, for instance, multi-layer injection molding systems.
  • [0007]
    It is known to use polypropylene, instead of PET, for an inner and outer layer of multilayer containers in extrusion blow molding applications. One advantage of polypropylene over PET is that polypropylene provides containers with better hot fill properties. Furthermore, polypropylene and EVOH have relatively similar melting temperatures, which makes it easier to maintain proper injection molding or extrusion molding systems.
  • [0008]
    Unfortunately, however, polypropylene does not bond to EVOH without the assistance of an additional agent. As a result, known containers made with polypropylene and EVOH require a layer of an adhesive between each layer of polypropylene and the layer of EVOH. Accordingly, multilayer polypropylene containers with carbon dioxide and oxygen barrier protection have typically had at least five layers of material: a first layer of polypropylene, a first layer of adhesive, a layer of EVOH, a second layer of adhesive and a second layer of polypropylene.
  • [0009]
    Additionally, known polypropylene containers with barrier protection have haze values of approximately 29%-35% or greater. While it is known to injection stretch blow mold containers with a single layer of clarified polypropylene to make a transparent bottle having lower haze values, such containers do not have many commercial purposes for food applications because they do not provide significant carbon dioxide or oxygen barrier protection.
  • SUMMARY OF THE INVENTION
  • [0010]
    The transparent containers of the present invention have a layer comprising polypropylene and a layer comprising a barrier material such as ethylene vinyl alcohol copolymer, nylon or a blend of ethylene vinyl alcohol copolymer and nylon, adjacent to the polypropylene layer wherein at least one of the polypropylene layer and the barrier layer comprises an adhesive mixed therein.
  • [0011]
    It is one of the principal objectives of the present invention to provide multilayer plastic containers that also provide oxygen, carbon dioxide and moisture barrier protection having a haze value of less than 25%.
  • [0012]
    It is another object of the present invention to provide containers having a layer of a polypropylene/adhesive mixture and a layer of barrier material directly adjacent the layer of polypropylene/adhesive mixture.
  • [0013]
    It is another object of the present invention to provide containers having a layer of a polypropylene and a layer of barrier material/adhesive mixture directly adjacent the layer of polypropylene.
  • [0014]
    It is another object of the present invention to provide commercially acceptable, cost effective containers having a layer comprising polypropylene and a layer comprising a barrier material adjacent to the polypropylene layer, wherein the containers may be used for carbonated beverages, fruit juices, sauces and beer.
  • [0015]
    It is still another object of the present invention to provide a polypropylene bottle having at least two layers and having a haze value of less than 25%.
  • [0016]
    It is further an object of the present invention to use two different materials with similar melting temperature to provide more compatible injection molding systems.
  • BRIEF DESCRIPTION OF DRAWINGS
  • [0017]
    [0017]FIG. 1 is a perspective view of a multilayer container according to the present invention.
  • [0018]
    [0018]FIG. 2 is a sectional view of a wall of the container shown in FIG. 1.
  • [0019]
    [0019]FIG. 3 is a perspective view of a preform according to the present invention that is used to make a multilayer container.
  • DETAILED DESCRIPTION OF THE DRAWINGS
  • [0020]
    Referring now to FIG. 1, there is shown a transparent, multilayer plastic container, specifically a bottle 10, according to the teaching of the present invention. The bottle 10 has a top end 12 and a bottom end 14. A body portion 20 extends between the top end 12 and the bottom end 14 and forms a cylindrical wall 22. Although the container illustrated is a bottle, it is noted that various other containers can be made according to the present invention as well.
  • [0021]
    As best illustrated in the cross-sectional view of the cylindrical wall 22 shown in FIG. 2, the bottle 10 is preferably constructed of three layers, namely an inner layer 24, a middle layer 26 and an outer layer 28. Both the inner layer 24 and the outer layer 28, which are structural layers, are made of a material comprising at least polypropylene. The polypropylene can be a homopolymer or a copolymer. The comonomer can be selected from the group consisting of ethylene, butylene, or other alpha-olefins from C5-C8. A preferred comonomer is ethylene wherein the ethylene is up to 3.0 weight % of the polypropylene copolymer. The polypropylene may also contain additives such as clarifying agents. Clarifying agents are exemplified by: Milliken Chemical, Division of Milliken & Co.'s Millad 3988 clarifying agent or Mitsui Toatsu Chemicals, Inc.'s NC4 clarifying agent. Other clarifiers such as sorbitol and benzoates can also be used. Such clarifying agents typically comprises 0.1-0.3% by weight of the polypropylene. The middle layer 26 is preferably made of a material comprising at least an ethylene vinyl alcohol copolymer (EVOH). The middle layer 26 of EVOH provides carbon dioxide and oxygen barrier resistance that allows a product to be stored within the bottle 10 for an extended period of time without spoiling. Note that while the middle layer 26 is preferably made of a material comprising EVOH, the middle layer can comprise any appropriate barrier material, such as nylon or a blend of ethylene vinyl alcohol copolymer and nylon as well without departing from the present invention. An appropriate nylon is exemplified by MXD6, nylon 6 and nylon 6/66. An appropriate adhesive (discussed in detail below) is chosen dependant upon the material of the middle layer 26 to bond the inner and outer layers 24, 28 thereto.
  • [0022]
    The inner and outer layers 24, 28 are the structural layers of the bottle and provide additional moisture barrier protection for the product to be contained in the bottle 10. The thickness of the inner and outer layers 24, 28 and the thickness of the middle layer 26 are determined by factors such as the type of product to be filled in the container, the desired shelf life of the product, etc. Typically the thickness of the layers are in the range of between approximately 5 mils to 10 mils for each of the inner and outer layers 24, 28 and between approximately 0.1 mils to 2.0 mils for the middle layer 26.
  • [0023]
    The bottle 10 can be stretch blow molded from a preform 30 (FIG. 3), by using conventional stretch blow molding techniques. In one embodiment, the preform 30 is made by an injection molding process such as the injection molding processes described in U.S. Pat. Nos. 4,511,528 and 4,712,990, which are hereby incorporated by reference. Alternatively, the bottle may be made by extrusion blow molding techniques such as the process described in U.S. Pat. No. 5,156,857, which is hereby incorporated by reference.
  • [0024]
    With regard to injection molding applications, the process temperatures of polypropylene and EVOH are approximately the same. Therefore, the process temperatures of the materials to comprise the inner and outer layers 24, 28 and the materials to comprise the middle layer 26 are also approximately the same despite the addition of an adhesive (discussed in detail below) to at least one of the inner and outer layers 24, 28 and the middle layer 26. Accordingly, it is easier to maintain proper flow temperatures for the material forming each layer 24, 26, 28 and, therefore, control the flows of these layers having only two different materials as opposed to controlling five layers of three distinct materials (i.e., polypropylene, adhesive and EVOH) which may have different process temperatures. The process temperature of the polypropylene and EVOH is approximately between 180-235 C. (with or without the adhesive discussed in detail below). It is specifically contemplated, however, that the present invention may be accomplished with material other than the preferred polypropylene and EVOH.
  • [0025]
    In order to bond each of the inner and outer layers 24, 28 to the middle layer 26, the material of at least one of the inner and outer layers 24, 28 and the middle layer 26 comprises an adhesive mixed therein. Thus, in a first embodiment of the present invention, the inner and outer layers 24, 28 may comprise a mixture of polypropylene and an adhesive (“polypropylene/adhesive mixture”) while the middle layer 26 is comprised of EVOH without an added adhesive. Examples of this first embodiment are provided below.
  • [0026]
    In a second embodiment, the middle layer 26 may be made of a material comprised of EVOH and an adhesive (“EVOH/adhesive mixture”) while the inner and outer layers 24, 28 are comprised of a polypropylene without an added adhesive. Examples of this second embodiment are provided below.
  • [0027]
    In a third embodiment, the inner and outer layers 24, 28 are made of the polypropylene/adhesive mixture and the middle layer is made of the EVOH/adhesive mixture.
  • [0028]
    Sufficient adhesion for purposes of this invention means achieving a bond between the middle layer 26 and each of the inner and outer layers 24, 28 to prevent delamination during forming of the bottle 10 or other container and withstanding normal package handling and distribution. For some applications, sufficient adhesion would also mean a sufficient bond between the layers to withstand hot filling of the container at temperatures of 190-210 F. The amount of adhesive used must also provide sufficient adhesion for purposes of injection molding the preform and stretch blow molding the container from the preform. Importantly, using the lowest possible percentage of adhesive is desirable because the adhesive is relatively expensive compared to polypropylene and EVOH.
  • [0029]
    It has been found that the greater the percentage of adhesive evenly distributed within any layer of the bottle 10 (referred to herein as a “mixed-adhesive layer”), the better that layer will adhere to an adjacent layer. This correlation is due to two facts. First, the adhesive force that a mixed-adhesive layer may exert on an adjacent layer of a container depends, at least in part, upon the amount of adhesive available at the outer surface of that mixed-adhesive layer. Second, as the percentage of adhesive agent evenly mixed and distributed throughout any composite material used to construct a mixed-adhesive layer is increased, the amount of adhesive agent which will be exposed at an outer surface of that mixed-adhesive layer (and thereby made available for adhesion to an adjacent layer) will also necessarily increase. Additionally, the percentage of the adhesive agent in the mixed-adhesive layer, which is exposed at the outer surface of that mixed-adhesive layer, is inversely proportional to the thickness of that mixed-adhesive layer. That is, a thinner mixed-adhesive layer will produce greater adhesive potential from a given quantity of adhesive agent, than will a relatively thicker mixed-adhesive layer comprised of the same given quantity of adhesive agent.
  • [0030]
    From the foregoing it will be understood that because the middle layer 26 of the present invention is thinner (preferably between 0.1 and 2.0 mils) than each of the outer layers 24, 28 (preferably between 5 mils and 10 mils), mixing an adhesive into the middle layer 26, as in the second preferred embodiment of the present invention, will necessarily decrease the amount of adhesive necessary to bond the inner and outer layers 24, 28 to the middle layer 26 relative to the first embodiment of the present invention in which the adhesive is dispersed within the inner and outer layers 24, 28. Moreover, because the second embodiment of the present invention only requires adhesive to be mixed into a single layer rather than into two layers (as required by the first embodiment of the present invention described above), the total quantity of adhesive required for the second embodiment is further reduced relative to the quantity of adhesive required for the first embodiment. Regardless of which embodiment of the present invention is employed, however, the amount of adhesive required to acquire the requisite bonding of the middle layer 26 to both the inner and outer layers 24, 28 is reduced relative to prior methods of bonding polypropylene to EVOH which place an entire layer of adhesive between each of the inner and outer layers 24, 28 and the middle layer 26. Moreover, as discussed above, the complexity of molding preforms to achieve such bonding is likewise reduced by elimination of the adhesive layers.
  • [0031]
    In one embodiment of the present invention, bottles are made having a haze value of less than approximately 29%. In another embodiment, the bottles have a haze value of 10-12%. A haze value is defined as the percent of total light which, in passing through the specimen, deviates through forward scatter by more than 0.044 rad (2.5) on the average. The preferred test to obtain the haze value of the bottle is ASTM Method D-1003 as defined in the 1995 Annual Book of ASTM Standards, Volume 8.01.
  • First Embodiment
  • [0032]
    The adhesive used to make the polypropylene/adhesive mixture for the first embodiment of the present invention is a maleic anhydride modified polypropylene. The amount of adhesive that must be blended into the polypropylene depends on the maleic anhydride concentration of the adhesive. Enough adhesive must be added such that the resulting polypropylene/adhesive mixture has a maleic anhydride content of approximately 0.01%-0.20% by weight of the total mixture. (For example: 10% of adhesive containing 0.15% maleic anhydride.) The polypropylene/adhesive mixture can contain between 0-98% by weight polypropylene and between 2-100% by weight adhesive. It has been found that the greater the percentage of adhesive used, the better the layer of EVOH will adhere to the structural layer. However, it has been found that sufficient adhesion between the layers is achieved using polypropylene/adhesive mixtures containing as low as approximately 0.01%-0.015% maleic anhydride. The middle layer 26, as provided by the prescripts of first embodiment, is comprised of EVOH without the presence of an adhesive therein.
  • [0033]
    The following are examples of the first embodiment of the present invention:
  • EXAMPLE 1
  • [0034]
    A three-layer coinjection molded preform was made having inner and outer structural layers 24 and 28 which are made from a polypropylene/adhesive mixture containing about 85% polypropylene and 15% adhesive and a middle layer 26 of EVOH. The polypropylene was Solvay 4285. The adhesive was Morton EFM-2E02. The EVOH selected for the middle layer 26 was Evalca LCE-105A (having a 44% ethylene content). The preform was then stretch blow molded to form a transparent container having a haze value of approximately 10-12% measured through a section of the bottle having a thickness of approximately 15-20 mils.
  • EXAMPLE 2
  • [0035]
    A multilayer coinjection molded preform was made as in Example 1 except that the percentages of polypropylene and adhesive in the inner and outer layers 24 and 28 were 90% polypropylene and 10% adhesive. The preform was stretch blow molded to form a transparent container having a haze value of approximately between 10-12% measured through a section of the container having a thickness of approximately 15-20 mils.
  • EXAMPLE 3
  • [0036]
    A three-layer container was made by a coextrusion blow molding process. The layers were extruded together to form a tube. The tube was blow molded in a mold to form the container. The layers 24 and 28 were made from a polypropylene/adhesive mixture containing about 90% polypropylene and 10% adhesive. The polypropylene was Montell SR256M. The adhesive is Morton EFM-2E02. The EVOH selected for the middle layer 26 was Evalca LCE105A.
  • EXAMPLE 4
  • [0037]
    A multilayer coinjection molded preform was made as in Example 1 except that the EVOH used was Evalca LCF-104AW (having a 32% ethylene content). The preform was then stretch blow molded to form a transparent container.
  • EXAMPLE 5
  • [0038]
    A multilayer coinjection molded preform was made as in Example 1 except that the EVOH used was Evalca LCL 101A (having a 27% ethylene content). The preform was then stretch blow molded to form a transparent container.
  • EXAMPLE 6
  • [0039]
    A multilayer coinjection molded preform was made as in Example 1 except that the EVOH used was Nippon Gohsei Soamol DC3203. The preform was then stretch blow molded to form a transparent container.
  • EXAMPLE 7
  • [0040]
    A multilayer coinjection molded preform was made as in Example 1 except that the barrier was nylon, specifically Mitsubishi's MXD6-6121 nylon. The preform was then stretch blow molded to form a transparent container.
  • EXAMPLE 8
  • [0041]
    A multilayer coinjection molded preform was made as in Example 1 except that the polypropylene was Fina 7426MZ. The preform was then stretch blow molded to form a transparent container.
  • EXAMPLE 9
  • [0042]
    A multilayer coinjection molded preform was made as in Example 1 except that the polypropylene was Montell SR256M. The preform was then stretch blow molded to form a transparent container.
  • EXAMPLE 10
  • [0043]
    A multilayer coinjection molded preform was made as in Example 1 except that the polypropylene/adhesive mixture layer was 100% Mitsui Admer QB510A. The preform was then stretch blow molded to form a transparent container.
  • [0044]
    The bottles made in Examples 1-10 of the first embodiment above are transparent, exhibit good strength and provide excellent carbon dioxide, oxygen and moisture barrier protection. The bottles can also withstand being hot filled.
  • Second Embodiment
  • [0045]
    The EVOH/adhesive mixture used for the middle layer 26 of the second embodiment was comprised of Evalca XEP403 resin. The inner and outer layers 24, 28 are comprised of polypropylene without the presence of a maleic anhydride therein.
  • [0046]
    The following are examples of the second embodiment of the present invention:
  • EXAMPLE 1
  • [0047]
    A three-layer coinjection molded preform was made having inner and outer structural layers 24 and 28 made from 100% polypropylene. The polypropylene was Solvay 4285. The middle layer 26 was made from 100% Evalca XEP403 resin. The preform was then stretch blow molded to form a transparent container.
  • EXAMPLE 2
  • [0048]
    A multilayer coinjection molded preform was made as in Example 1 of the second embodiment except that the polypropylene used for the inner and outer structural layers 24 and 28 was Fina 7426MZ and the middle layer 26 was comprised of Evalca XEP403 having 100 ppm of Cobalt. The preform was then stretch blow molded to form a transparent container.
  • [0049]
    The bottles made in Examples 1 and 2 of the second embodiment are transparent, exhibit good strength and provide carbon dioxide, oxygen and moisture barrier protection.
  • [0050]
    From the foregoing description, it will be apparent that the transparent multilayer polypropylene containers having a barrier layer of the present invention have a number of advantages, some of which have been described above and others of which are inherent in the transparent multilayer polypropylene containers of the present invention. Also, it will be understood that modifications can be made to the transparent multilayer polypropylene containers having a barrier layer of the present invention without departing from the teachings of the invention. Accordingly the scope of the invention is only to be limited as necessitated by the accompanying claims.
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2927106 *Feb 25, 1957Mar 1, 1960Phillips Petroleum CoProduction of solid polymer
US2928756 *Mar 19, 1956Mar 15, 1960Phillips Petroleum CoProcess for coating polyethylene with a higher melting polyolefinic composition and article therefrom
US2929807 *May 13, 1957Mar 22, 1960Phillips Petroleum CoPolymerization process for producing copolymers of ethylene and higher 1-olefins
US2930726 *Jul 9, 1956Mar 29, 1960Phillips Petroleum CoComposition comprising pitch and chlorinated polyolefin, article prepared therefrom, and method of making
US2930788 *Jan 22, 1957Mar 29, 1960Phillips Petroleum CoProduction of solid polymer
US2936303 *Apr 25, 1958May 10, 1960Phillips Petroleum CoOlefin polymerization
US2969348 *Aug 20, 1956Jan 24, 1961Phillips Petroleum CoEthylene polymerization catalyst and process
US2969408 *Dec 30, 1955Jan 24, 1961Phillips Petroleum CoProcess and catalyst for polymerization of olefins
US2970991 *Oct 11, 1956Feb 7, 1961 cines
US2972604 *Sep 10, 1956Feb 21, 1961Phillips Petroleum CoChlorosulfonation of ethylene polymers
US2973241 *Oct 26, 1956Feb 28, 1961Phillips Petroleum CoMethod for producing high crystalline 1-olefin polymers of decreased flammability by treatment with nitric acid and resulting products
US3023180 *Aug 17, 1959Feb 27, 1962Phillips Petroleum CoVulcanizable halogenated polyethylene compositions containing phosphorus
US3023198 *Jun 3, 1957Feb 27, 1962Phillips Petroleum CoPolymerization of vinyl ethers
US3024227 *Dec 30, 1955Mar 6, 1962Phillips Petroleum CoLow pressure process for production of olefin polymers with a peroxide containing catalyst
US3035953 *Mar 24, 1958May 22, 1962Phillips Petroleum CoLaminates of aluminum and solid polymers of 1-olefins
US3074616 *Jul 13, 1959Jan 22, 1963Phillips Petroleum CoArticle of blend of a copolymer of ethylene and 1-butene and polyisobutylene
US3075026 *May 13, 1958Jan 22, 1963Phillips Petroleum CoPolymerization of propylene or butenes with vci4 catalyst to form liquid polymers
US3076776 *Oct 30, 1958Feb 5, 1963Phillips Petroleum CoMethod for improving the extrudability of crystalline polyolefins with aliphatic alcohols
US3084149 *Oct 22, 1956Apr 2, 1963 Polymerization of
US3086957 *Jan 30, 1958Apr 23, 1963Phillips Petroleum CoHalogenated ethylene polymer compositions and method for preparing same
US3086958 *Nov 17, 1958Apr 23, 1963Phillips Petroleum CoBlends of high pressure type polyethylene with cracked highly crystalline 1-olefin polymers
US3118857 *Mar 9, 1961Jan 21, 1964Phillips Petroleum CoSolid polyolefin containing an aryl substituted polyolefin and having improved clarity
US3119798 *Jan 27, 1960Jan 28, 1964Phillips Petroleum CoProduction of solid olefin polymers
US3119801 *Aug 1, 1957Jan 28, 1964 Recovery of olefin polymers fkom
US3120506 *Sep 7, 1960Feb 4, 1964Phillips Petroleum CoProduction of olefin polymers
US3123583 *Jul 2, 1956Mar 3, 1964 Procedure for compositions of
US3124622 *May 22, 1961Mar 10, 1964 Production of olefins from aldehydes
US3127370 *May 28, 1958Mar 31, 1964 Method of making fiber-grade polyethylene
US3130188 *Oct 7, 1960Apr 21, 1964Phillips Petroleum CoCatalyst and process for producing olefin polymers
US3165504 *Feb 27, 1961Jan 12, 1965Phillips Petroleum CoCatalyst and process for producing olefin polymers
US3172872 *Sep 19, 1960Mar 9, 1965 Diolefin rubbers stabilized with mercaptans and quinones
US3174957 *Mar 25, 1959Mar 23, 1965Phillips Petroleum CoCopolymerization of ethylene with higher olefins
US3176347 *Nov 30, 1962Apr 6, 1965Phillips Petroleum CoApparatus for producing thermoplastic tubing
US3177188 *Jun 27, 1960Apr 6, 1965Phillips Petroleum CoOlefin polymerization process utilizing a free metal as the catalyst
US3177193 *Jul 15, 1960Apr 6, 1965Phillips Petroleum CoProcess of improving the moldability and extrudability of solid olefin polymers
US3182049 *Apr 15, 1963May 4, 1965Phillips Petroleum CoProduction of solid olefin polymers
US3183221 *Dec 30, 1960May 11, 1965Phillips Petroleum CoRubbery polymer of a heavy petroleum hydrocarbon, process of making same, and blendsthereof with a rubbery diene polymer
US3188258 *Dec 30, 1957Jun 8, 1965Phillips Petroleum CoBonding of olefin polymers
US3228896 *May 16, 1961Jan 11, 1966Phillips Petroleum CoMethod of making microporous polyolefin articles and product therefrom
US3231650 *Mar 11, 1960Jan 25, 1966Phillips Petroleum CoNon-woven polyolefin fabrics and method of preparing same
US3232920 *Mar 9, 1961Feb 1, 1966Phillips Petroleum CoPreparation of rubbery polymers of butadiene
US3245975 *Oct 6, 1959Apr 12, 1966Phillips Petroleum CoProcess for production of rubbery polymers
US3258456 *Jan 14, 1963Jun 28, 1966Phillips Petroleum CoProduction of polyolefin films
US3299016 *Sep 3, 1963Jan 17, 1967Phillips Petroleum CoPolymers of 1-monoolefins and an alkenyl acetylene and process for preparing same
US3299186 *Mar 29, 1965Jan 17, 1967Phillips Petroleum CoMelt blending of polyolefins
US3303239 *Dec 23, 1963Feb 7, 1967Phillips Petroleum CoOlefin polymerization
US3304281 *Dec 31, 1962Feb 14, 1967Phillips Petroleum CoBlends of rubbery polymers
US3308073 *Apr 9, 1962Mar 7, 1967Phillips Petroleum CoPorous polyolefin objects
US3310505 *Mar 11, 1963Mar 21, 1967Phillips Petroleum CoProduction of thermoplastic materials
US3313786 *Mar 12, 1964Apr 11, 1967Phillips Petroleum CoPolymers of 1-monoolefins and fulvenes
US3313794 *Oct 18, 1963Apr 11, 1967Phillips Petroleum CoProcess for production of polyethylene
US3317502 *Oct 21, 1963May 2, 1967Phillips Petroleum CoPolymerization of olefins in the presence of a coordination catalyst and carbonyl sulfide
US3318721 *Jan 17, 1964May 9, 1967Phillips Petroleum CoCoated polyolefin structure, composition and method for making the same
US3372140 *Sep 13, 1965Mar 5, 1968Phillips Petroleum CoStabilized olefin polymers
US3429862 *Mar 7, 1966Feb 25, 1969Phillips Petroleum CoProcess and catalysts for production of olefin polymers
US3436380 *Nov 12, 1964Apr 1, 1969Phillips Petroleum CoPolymerization and recovery of olefin polymers
US3444153 *Aug 16, 1965May 13, 1969Phillips Petroleum CoPolymerization process and catalyst for olefins
US3445367 *Nov 22, 1965May 20, 1969Phillips Petroleum CoCatalyst and process for making olefin polymers of narrow molecular weight distribution
US3445543 *Dec 13, 1965May 20, 1969Phillips Petroleum CoCured blend of diene block copolymer,olefin rubber and polystyrene
US3452120 *May 21, 1964Jun 24, 1969Phillips Petroleum CoBlending solid olefin polymers with rubber
US3489729 *Sep 8, 1964Jan 13, 1970Phillips Petroleum CoPolymerization process for making vulcanizable rubbery polymer
US3513152 *Apr 29, 1966May 19, 1970Phillips Petroleum CoThermally stable olefin polymer
US3554961 *Oct 7, 1968Jan 12, 1971Phillips Petroleum CoIodine,chlorine or bromine stabilized olefin polymers
US3565853 *Oct 21, 1968Feb 23, 1971Phillips Petroleum CoOrganic nitrite stabilized olefin polymers
US3579478 *Jan 6, 1969May 18, 1971Phillips Petroleum CoPolyolefin stabilization
US3579602 *Apr 3, 1967May 18, 1971Phillips Petroleum CoOlefin conversion process and catalysts therefor
US3586731 *Apr 3, 1967Jun 22, 1971Phillips Petroleum CoOlefin conversion and catalysts therefor
US3590095 *Apr 18, 1968Jun 29, 1971Phillips Petroleum CoConversion of ethylene-propylene feed to isoamylenes and linear olefins
US3878033 *Mar 10, 1971Apr 15, 1975Phillips Petroleum CoForming parisons with nucleated inner layer
US3882259 *Mar 30, 1973May 6, 1975Toyo Seikan Kaisha LtdLaminate of ethylene/vinyl alcohol copolymer, ethylene/vinyl acetate copolymer and polyolefins
US3932692 *Aug 20, 1973Jan 13, 1976Toyo Seikan Kaisha LimitedResinious laminates having improved gas permeation and delamination resistance
US3950459 *Feb 11, 1975Apr 13, 1976Phillips Petroleum CompanyContinuous process for producing, reheating, and blow molding parisons
US4182457 *Aug 3, 1977Jan 8, 1980Toyo Seikan Kaisha LimitedMultilayer container
US4198327 *Dec 22, 1976Apr 15, 1980Mitsui Petrochemical Industries Ltd.Grafted polyolefin composition having improved adhesiveness
US4451512 *Jun 24, 1983May 29, 1984Toyo Seikan Kaisha, Ltd.Multi-layer plastic vessel
US4501779 *Oct 5, 1981Feb 26, 1985American Can CompanyHeat resistant heat shrinkable film
US4501797 *Dec 1, 1982Feb 26, 1985American Can CompanyUnbalanced oriented multiple layer film
US4511610 *Sep 29, 1983Apr 16, 1985Toyo Seikan Kaisha Ltd.Multi-layer drawn plastic vessel
US4741936 *Dec 2, 1986May 3, 1988Toyo Seikan Kaisha, Ltd.Laminate preform for a multi-layer polyester bottle
US4803102 *Oct 27, 1987Feb 7, 1989American National Can CompanyMultiple layer packaging films and packages formed therefrom
US4894267 *Sep 28, 1987Jan 16, 1990Bettle Iii GriscomBlow-molded plastic bottle with barrier structure for food packages
US4923395 *Nov 16, 1988May 8, 1990Husky Injection Molding Systems Ltd.Oven for blow molding machine
US4981906 *May 27, 1988Jan 1, 1991Monsanto Kasei CompanyHeat and impact resistant thermoplastic resin composition
US4990382 *Sep 11, 1987Feb 5, 1991Continental Plastic Containers, Inc.Plastic container with glass-like appearance, parison for and method of making same
US5011720 *Jul 10, 1989Apr 30, 1991Owens-Illinois Plastic Products Inc.Multilayer containers and method of making same
US5085822 *Aug 27, 1990Feb 4, 1992Nissei Asb Machine Co., Ltd.Method for stretch blow molding and uniformly cooling a hollow heat-resistant
US5183706 *Aug 3, 1990Feb 2, 1993W. R. Grace & Co.-Conn.Forming web for lining a rigid container
US5281360 *Jan 31, 1990Jan 25, 1994American National Can CompanyBarrier composition and articles made therefrom
US5487940 *Aug 31, 1994Jan 30, 1996Mobil Oil Corp.Oxygen and moisture barrier metallized film structure
US5512338 *Jul 21, 1994Apr 30, 1996Mobil Oil Corp.Oxygen, flavor/odor, grease/oil and moisture barrier film structures
US5616353 *Jan 24, 1994Apr 1, 1997Champion International CorporationMethod for extending shelf life of citrus juice
US5631030 *May 5, 1995May 20, 1997Electra Form, Inc.Cooled injection core for an integrated injection blow mold machine
US5730919 *Nov 13, 1995Mar 24, 1998Minnesota Mining And Manufacturing CompanyMethod of forming multilayered barrier structures
US5874115 *Jan 23, 1996Feb 23, 1999Systec Engineering Knauer Gmbh & Co. KgInjection blow molding machine
US6037022 *Sep 16, 1997Mar 14, 2000International Paper CompanyOxygen-scavenging filled polymer blend for food packaging applications
US6037063 *Sep 7, 1993Mar 14, 2000E. I. Du Pont De Nemours And CompanyHigh barrier, coextruded compositions useful in the manufacture of clear, heat-stable articles and methods relating thereto
US6042906 *Aug 12, 1997Mar 28, 2000Toyo Seikan Kaisha, Ltd.Flavor-retaining plastic multi-layer container
US6239210 *Dec 3, 1999May 29, 2001Pechiney Emballage Flexible EuropeBarrier compositions and articles made therefrom
US6677013 *Apr 16, 1999Jan 13, 2004Pechiney Emballage Flexible EuropeTransparent multilayer polypropylene container with barrier protection
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7857515Jun 15, 2007Dec 28, 2010S.C. Johnson Home Storage, Inc.Airtight closure mechanism for a reclosable pouch
US7874731Jun 15, 2007Jan 25, 2011S.C. Johnson Home Storage, Inc.Valve for a recloseable container
US7887238Jun 15, 2007Feb 15, 2011S.C. Johnson Home Storage, Inc.Flow channels for a pouch
US7946766Jun 15, 2007May 24, 2011S.C. Johnson & Son, Inc.Offset closure mechanism for a reclosable pouch
US7967509Jun 15, 2007Jun 28, 2011S.C. Johnson & Son, Inc.Pouch with a valve
US8231273Dec 17, 2010Jul 31, 2012S.C. Johnson & Son, Inc.Flow channel profile and a complementary groove for a pouch
US20030124229 *Feb 22, 2001Jul 3, 2003Kenichi HamaPlastic container for dry solid food
US20060029822 *Aug 2, 2005Feb 9, 2006Brown Michael JContainers incorporating polyester-containing multilayer structures
US20070166490 *Jan 13, 2006Jul 19, 2007Sonoco Development, Inc.Transparent and colored container
WO2016210067A1 *Jun 23, 2016Dec 29, 2016Nypro Inc.Food product container and composition for same
Classifications
U.S. Classification428/36.6
International ClassificationB32B27/32, B65D1/02, B32B27/08
Cooperative ClassificationY10T428/31746, Y10T428/31757, Y10T428/1383, Y10T428/1379, Y10T428/1352, B32B27/08, B32B27/32, B65D1/0215
European ClassificationB65D1/02B1, B32B27/32, B32B27/08
Legal Events
DateCodeEventDescription
Mar 30, 2007ASAssignment
Owner name: BALL CORPORATION, COLORADO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PECHINEY PLASTIC PACKAGING, INC.;PECHINEY PLASTIC PACKAGING (CANADA) INC.;ALCAN PACKAGING FLEXIBLE FRANCE;REEL/FRAME:019084/0590;SIGNING DATES FROM 20060323 TO 20060328
May 21, 2008ASAssignment
Owner name: ALCAN PACKAGING FLEXIBLE FRANCE, FRANCE
Free format text: CHANGE OF NAME;ASSIGNOR:PECHINEY EMBALLAGE FLEXIBLE EUROPE;REEL/FRAME:020976/0272
Effective date: 20051105