1. Field of the Invention
The present invention relates to package systems that include a peelable seal, and in particular, the present invention relates to compositions and methods for forming such peelable seals.
2. Background Art
Packaging is an important feature in selling and marketing most products. Food products, in particular, have rather stringent packaging requirements in order to preserve freshness and enhance shelf life. Certain medical devices also present strict packaging requirements in order to preserve sterility of such devices. In such applications, the package is typically vacuum-packed or gas-flushed and subsequently hermetically sealed. Although efficient packaging of products is mandatory, various aesthetic properties of a product package are also important. For example, the appearance of a product is important in appealing to consumers. Moreover, in many applications and, in particular, for food products reusability and ease of opening of a package are also important considerations. In many applications, the ability to easily open a package will depend on the mechanical properties of the seal.
One particularly important packaging structure utilizes a peelable seal. In at least one prior art packaging system, a peelable seal is formed by coating a heat sealable polymeric material onto a metal foil. Since packaging incorporating such seals are often impervious to air and contaminants, peelable seals must also be impervious to these materials. When a package having a peelable seal is opened, a sealing layer may be peeled away from a substrate. It is desirable for such peeling to be achievable with a low and relatively constant peel force. The elastic properties of the peelable seal are such that failure of the seal does not occur from flexing and normal handling of the package. In some prior art packaging, peelable seals are constructed from multi-layered sheets. Examples of packaging systems having such seals include tray-type food packages, bottles or blister packages, and the like. Although some of the prior art peelable sealing packages work reasonably well, it has been difficult to construct packaging systems that consistently form hermetic seals that resist leaking while being easily opened by an end user. Moreover, such prior art peelable packaging systems tend to operate over relatively narrow ranges, and in particular narrow temperature ranges. Narrow sealing temperature ranges tend to result in packaging defects. For example, on the low end of the usable temperature range leaking seals may be formed (not hermetically sealed). On the high end of the usable temperature range, non-peelable seal are formed which tear when opened.
Accordingly, there exists a need for improved peelable packaging systems that resist leaking, provide a hermetic seal, and open easily.
The present invention solves one or more problems of the prior art by providing in at least one embodiment a peelable sealing structure. The peelable sealing structure of this embodiment advantageously includes a sealing surface that is formable into a peelable seal upon contact with a sealing substrate at all temperatures in a peelable seal temperature range. Moreover, the peelable sealing structure of this embodiment comprises a thermoplastic polymer, and an additive dispersed within at least a portion of the thermoplastic polymer.
In another embodiment of the present invention, a peelable sealing structure is useful for forming a peelable seal at the opening of a container. The peelable sealing structure of this embodiment comprises a sealing layer and one or more optional additional layers. Advantageously, the sealing layer includes a functionalized organoclay dispersed with a thermoplastic polymer. The incorporation of functionalized organoclay particles within commonly used heat sealable thermoplastic polymers is found to provide a consistent peel strength over a broad range of heat sealing conditions. Moreover, the blend of commercially available organoclay polymer concentrates with a wide range of polyolefin sealant resins advantageously exhibits a peel strength inversely proportional to the percent load of organoclay. Although sealed interfaces utilizing the sealing layer peels in a consistent pattern, the hermetic integrity of the seal is not compromised even when the seal specimens include wrinkles, pleats and gusset configurations in various bag/pouch package styles.
In another embodiment of the present invention, a packaging system incorporating the peelable sealing structures of the invention is provided. The packaging system of the invention includes a container section and a peelable sealing section attached to the container section. The sealing section includes the sealing layer of the invention set forth above.
Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventors. The Figures are not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the invention and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.
Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary, percent, “parts of,” and ratio values are by weight; the term “polymer” includes “oligomer,” “copolymer,” “terpolymer,” and the like; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
It is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
It must also be noted that, as used in the specification and the appended claims, the singular form “a”, “an”, and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
Throughout this application, where publications are referenced, the disclosures of these publications in their entireties are hereby incorporated by reference into this application in their entirety to more fully describe the state of the art to which this invention pertains.
The term “organoclay” as used herein means organically modified clay. Typically, such modification renders a clay more compatible and therefore mixable with polymers.
The term “roughness average” (“Ra”) as used herein means the mean height of a surface as calculated over the entire measured length or area in accordance with ANSI B46.1. It is usually provided in micrometers or micro-inches.
The term “peelable seal” as used herein means a seal that has a peel force of between 0.5 lbs per one inch of sample width and a force that tears the seal. Typically, the upper limit is less than or equal to 5 lbs per inch of sample width. In other variation, the upper limit is less than or equal to 4 lbs per inch of sample width or less than the tear strength on the film substrate.
The term “peel force” as used herein means force to separate two layers as defined in ASTM F-88 which is incorporated by references. For example, this is the force necessary to separate two layers of one inch width by pulling.
The term “seal initiation temperature” as used herein refers to the lowest temperature at which a seal is formed with a peel force of 0.5 lbs. per inch. Specifically, the seal initiation temperature is the temperature of a surface (typically metal) contacting a layer or layers that are to be sealed thereby promoting such sealing. In some variations, the surface contacts the layer(s) with a dwell time from about 0.5 to 1 seconds with a pressure from 5 psi to 1200 psi.
The term “peelable seal temperature range” means the range of temperatures at which a seal between two materials is formed such that the peel force is between 0.5 lbs per one inch of sample width and a force that tears the seal as set forth above.
With reference to
In an embodiment of the present invention, a peelable sealing structure is provided. The peelable sealing structure of this embodiment comprises a thermoplastic polymer and an additive dispersed within at least a portion of the thermoplastic polymer. The peelable sealing structure defines a sealing surface that is formable into a peelable seal at all temperatures within a peelable seal temperature range. In a variation of this embodiment, the peelable seal temperature range is from a seal initiation temperature to a temperature that is that is at least 50° F. degrees above the seal initiation temperature. In another embodiment of the present invention, the peelable seal temperature range is from a seal initiation temperature to a temperature that is that is at least 75° F. degrees above the seal initiation temperature. In still another embodiment of the present invention, the peelable seal temperature range is from a seal initiation temperature to a temperature that is at least 100 F degrees above the seal initiation temperature. Typically, for packaging applications the seal initiation temperature ranges from about 170° F. to about 350° F. In another variation, for packaging applications the seal initiation temperature ranges from about 170° F. to about 250° F.
With reference to
It should be appreciated that in each of the variations of
It has surprisingly been discovered that sealing layers formed from this composition have improved and uniform peel performance as described more completely below. Sealed interfaces utilizing peelable sealing structure 150 peel in a consistent pattern, the hermetic integrity of the seal is not compromised even when the film specimens include wrinkles, pleats and gusset configurations in various bag/pouch package styles. Peelable sealing structure 150 exhibits a consistent peelable behavior in the following combinations: 1) sealing layer 152 contacting another sealing layer of analogous or the same composition; 2) sealing layer 152 contacting a structure formed from neat sealant (e.g. organoclay/polyethylene layer against a neat polypropylene layer, organoclay/polyethylene layer against neat polyester layer, organoclay/polyethylene layer against a neat polyethylene layer). Processing aids such as antiblocking agents, antioxidants, slip additives, and the like are optionally included into the sealing layers and do not affect the peel pattern of sealing structure 150.
Additional layers 154, 156 are used to provide a number of useful features to the present embodiment. For example, additional layers 154, 156 may provide structural support, heat resistance, barrier properties, and improved appearance to packaging systems that incorporate peelable sealing sections. It should also be appreciated that the present embodiment encompasses, in addition to single layer peelable sealing structures, multilayer structures having any number of additional layers. In each variation of the present embodiment, the multilayer sealing structures include peelable sealing having the compositions described herein.
Sealing layer 152 is further characterized by various physical and structure variations and refinements which depend to some extent on the specific packaging desired. In one variation of the present embodiment, sealing layer 152 has a thickness from about 6 microns to about 120 microns. In another variation of the present embodiment, sealing layer 152 has a thickness from about 6 microns to about 30 microns. In still another variation of the present embodiment, sealing layer 152 has a thickness from about 40 microns to about 120 microns. Sealing layer 152 is further distinguished from analogous layers formed without or with insufficient amounts of organoclay in having a higher degree of surface roughness. In one refinement, sealing layer 152 has a surface roughness characterized by a roughness average from about 1500 to about 5000 angstroms. In another refinement, sealing layer 152 has a surface roughness characterized by a roughness average from about 2000 to about 4000 angstroms. It should be readily appreciated that in variations of the present invention, the degree and the quality of the surface roughness depends both on the methods and process parameters used to form sealing layer 152. The sealing layers of various embodiments also exhibit somewhat higher tensile moduli than analogous layers without organoclay. In one refinement, the sealing layer 152 has a tensile modulus from about 500 to about 2000 MPa.
With reference to
Still referring to
With reference to
With reference to
As set forth above, the peelable sealing structures of the various embodiments of the invention include an additive such as organoclays. Examples of useful organoclays include, but are not limited to, kaolinite, montmorillonite-smectite clays, bentonite clays, illite clays, and combinations thereof. U.S. Pat. Nos. 5,780,376, 5,739,087, 6,034,163, and 5,747,560 provide specific examples of nanoclays that are useful in practicing the present invention. The entire disclosure of each of these patents is hereby incorporated by reference. In one refinement of the present invention, the organoclay is present in an amount from 1 wt % to 20 wt % of the combined weight of the thermoplastic polymer and the organoclay. In another refinement of the present embodiment, the organoclay is present in an amount from 2 wt % to 10 wt % of the combined weight of the thermoplastic polymer and the organoclay.
The organoclay used in peelable sealing layer 152 typically comprises a plurality of particles. In one variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 200 nm. In another variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 100 nm. In another variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 50 nm. In still another variation, the organoclay comprises a plurality of particles having spatial dimensions greater than or equal to 1 nm. In still another variation, the organoclay comprises a plurality of particles having spatial dimensions greater than or equal to 5 nm. In another variation, the organoclay comprises platelets having an average separation of at least 20 angstroms. In yet another variation, the organoclay comprises platelets having an average separation of at least 30 angstroms. In still another variation, the organoclay comprises platelets having an average separation of at least 40 angstroms. Typically, before combining with the thermoplastic polymer, the organoclay comprises platelets having an average separation between from 20 to 45 angstroms. Advantageously, upon combining with the thermoplastic, the organoclay remains in this exfoliated state such that the average separation is maintained or increased.
As set forth above, peelable sealing layer 152 also includes a thermoplastic polymer. Suitable thermoplastic polymers include, but are not limited to, nylons, polyolefins, polystyrenes, polyesters, polycarbonates, and mixtures thereof. In a variation, the thermoplastic polymer comprises a component selected from the group consisting of ethylene acrylic acid, ethylene ethyl acrylate, ethylene ionomers (e.g., the Surlyn® line of resins available from E.I. du Pont de Nemours and Company), and combinations thereof. Polyolefins are particularly useful thermoplastic polymers in the practice of the invention. In one variation, the polyolefin is selected from the group consisting of homopolymers and copolymers of ethylene, propylene, vinyl acetate, and combinations thereof. A blend of polyolefins with ethylene vinyl acetate (“EVA”) is found to be particularly useful in forming peelable seals especially when the additive is an organoclay.
The container sections of the various embodiments of the invention are formed from virtually any material used for packaging. Such materials include, but are not limited to, paper, metal foil, polymeric sheets, metalized polymeric sheets, and combinations thereof. More specific examples include, oriented or non-oriented polyester, oriented or non-oriented polypropylene, oriented or non-oriented nylon, and combinations thereof. Each of these materials may be coated or uncoated. Examples of useful coatings include, but are not limited to, varnishes, lacquers, adhesives, inks, and barrier materials (i.e., PVDC). Useful materials for packaging medical devices include high density polyolefins. Tyvek® (a synthetic material made of high-density polyethylene fibers) commercially available from Dupont, Inc. is an example of a such a material used for packaging medical devices.
In yet another embodiment of the present invention, a method of forming the packaging systems set forth above is provided. With reference to
In a variation of the present embodiment, a thermoplastic polymer is combined with an organoclay by mixing a master batch with a neat polymer. In this variation, the master batch comprising the organoclay and at least a portion of the thermoplastic polymer. In this refinement, the master batch typically includes from 10 to 80 wt % organoclay.
The step of forming sealing layer 152 is accomplished by any method capable of producing layers or films from thermoplastic compositions. Examples of such methods include, but are not limited to, extrusion, co-extrusion, blow molding, casting, extrusion blow molding, and film blowing.
Still referring to
The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and scope of the claims.
Nanoblend™ MB 2001 or Nanoblend™ MB 2101 (“master batches”) is mixed with a commercial polyethylene (“PE”) blend pouch sealant in a single-screw extruder with the sealant layer of the invention formed in a second film blowing operation. The tensile properties of the resulting films are evaluated in accordance to ASTM D638 (Table 1) with a test speed of 50 mm/min. Prior to testing, all samples are annealed for 21 days at 30° C. Films that include an organoclay are found to have a higher modulus than films without organoclay without sacrificing strength or max. elongation. The increase in modulus being 75% for 3 wt % organoclay, 150% for 6 wt % organoclay, and 240% for 9 wt % organoclay.
Table 2 summarizes the results of VICAT Heat Deflection Testing. The Vicat Softening Temperature is observed to increase with increasing organoclay content with a sample having 9 wt % nanoclay exhibiting a 23° C. increase in softening temperature. The data of Table 2 implies that crystallinity is substantially uneffected by the addition of organoclay to the polyethylene sealant composition.
Crystallization temperature and melting temperature are also evaluated. These measurements are performed by measuring the enthalpies of fusion and crystallization in accordance with ASTM D 3417.
Tables 3 and 4 provide surface roughness measurements for sealing layers formed by the present invention. In these examples, a coextruded bi-layer is formed. The smoother side is from an HDPE layer not having organoclay. The rougher side is a LLDPE/EVA layer having organoclay. The organoclay-containing layers of the present invention are found to have a higher degree of roughness than analogous samples not having organoclay. Moreover, the sample having 6 wt % organoclay has a greater amount of surface roughness than the sample having 5 wt % organoclay thereby showing that the amount of surface roughness tends to increase in the range of about 10% or less.
A series of 25.4 mm seals are made at a pressure of about 1000 psi with a sealing time of about 8 seconds. In these experiments a hydraulic press is used. Although these conditions are harsher than the conditions used in typical commercial sealing operations, the formations of peelable seals at these conditions further illustrates the ability of the formulations of the present invention to form peelable seal.
In still another embodiment of the present invention, a peelable seal adapted to provide a leak-proof seal having one or more wrinkles incorporated therein is provided. With reference to
The details of the composition of sealing layers 252 and 254 are the same as those set forth above. In particular, at least one of the first sealing layer 252 and second sealing layer 254 include a thermoplastic polymer and an additive dispersed within the thermoplastic polymer. In a variation, the additive is present in a sufficient amount to form peelable seal 280 between the first sealing layer 252 and second sealing layer 254 at all temperatures within a peelable seal temperature range. As set forth above, in a refinement, the peelable seal temperature range is from a seal initiation temperature to a temperature that is at least 100 F degrees above the seal initiation temperature. In a particularly useful variation, the additive is an organoclay dispersed within at least a portion of the thermoplastic polymer. In such a variation, one or both of first sealing layer 252 and second sealing layer 254 have a seal initiation temperature from about 170° F. to about 350° F. Additional details for the additive, the organoclay and the thermoplastic polymer are set forth above.
With reference to
While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.
This application is a division of U.S. application Ser. No. 13/357,994 filed Jan. 25, 2012, which is a continuation of U.S. Ser. No. 12/980,312 filed Dec. 28, 2010, now U.S. Pat. No. 8,110,286 issued Feb. 7, 2012, which is a continuation of U.S. application Ser. No. 12/031,450 filed Feb. 14, 2008, now U.S. Pat. No. 7,871,697 issued Jan. 18, 2011, which is a continuation-in-part of U.S. application Ser. No. 11/602,650 filed Nov. 21, 2006, now U.S. Pat. No. 7,871,696 issued Jan. 18, 2011, the disclosures of which are hereby incorporated in their entirety by reference herein.
Number | Name | Date | Kind |
---|---|---|---|
3616898 | Massie | Nov 1971 | A |
3879492 | Bontinick | Apr 1975 | A |
3885977 | Lachman et al. | May 1975 | A |
4058645 | Steiner | Nov 1977 | A |
4361237 | Heiremans et al. | Nov 1982 | A |
4367312 | Bontinck et al. | Jan 1983 | A |
4488647 | Davis | Dec 1984 | A |
4512479 | Hain et al. | Apr 1985 | A |
4533509 | Gust et al. | Aug 1985 | A |
4623398 | Goodman et al. | Nov 1986 | A |
4752342 | Tatum et al. | Jun 1988 | A |
4771935 | Hekal | Sep 1988 | A |
4810541 | Newman et al. | Mar 1989 | A |
4970113 | Yamada | Nov 1990 | A |
5145737 | Boiron et al. | Sep 1992 | A |
5334643 | Gage | Aug 1994 | A |
5392986 | Beer et al. | Feb 1995 | A |
5437911 | Rohrka et al. | Aug 1995 | A |
5449552 | Bochow et al. | Sep 1995 | A |
5527576 | Maul et al. | Jun 1996 | A |
5626929 | Stevenson | May 1997 | A |
5634969 | Cody et al. | Jun 1997 | A |
5716698 | Schreck et al. | Feb 1998 | A |
5739087 | Dennis | Apr 1998 | A |
5747560 | Christiani et al. | May 1998 | A |
5773136 | Alder et al. | Jun 1998 | A |
5780376 | Gonzales et al. | Jul 1998 | A |
5830547 | MacKenzie et al. | Nov 1998 | A |
5912084 | Hausmann et al. | Jun 1999 | A |
5958531 | Stevenson | Sep 1999 | A |
5997968 | Dries et al. | Dec 1999 | A |
6006913 | Ludemann et al. | Dec 1999 | A |
6034163 | Barbee et al. | Mar 2000 | A |
6036765 | Farrow et al. | Mar 2000 | A |
6355732 | Beer | Mar 2002 | B1 |
6358622 | Shida et al. | Mar 2002 | B1 |
6359052 | Trexler et al. | Mar 2002 | B1 |
6384121 | Barbee et al. | May 2002 | B1 |
6417262 | Turner et al. | Jul 2002 | B1 |
6423768 | Khouri | Jul 2002 | B1 |
6444742 | Rong et al. | Sep 2002 | B1 |
6451426 | Kong et al. | Sep 2002 | B2 |
6465543 | Alexandre et al. | Oct 2002 | B1 |
6521678 | Chaiko | Feb 2003 | B1 |
6521690 | Ross et al. | Feb 2003 | B1 |
6548587 | Bagrodia et al. | Apr 2003 | B1 |
6552114 | Turner et al. | Apr 2003 | B2 |
6599622 | Chu et al. | Jul 2003 | B1 |
6642296 | Fisher | Nov 2003 | B2 |
6709759 | Mueller et al. | Mar 2004 | B2 |
6713152 | Chen et al. | Mar 2004 | B2 |
6723403 | Ishii et al. | Apr 2004 | B2 |
6767951 | Nair et al. | Jul 2004 | B2 |
6770697 | Drewniak et al. | Aug 2004 | B2 |
6815025 | Kawamura et al. | Nov 2004 | B2 |
6838508 | Hsiao et al. | Jan 2005 | B2 |
6849313 | Mechelaere et al. | Feb 2005 | B2 |
6896956 | Kong | May 2005 | B2 |
6913809 | Wolak | Jul 2005 | B2 |
7135508 | Chaiko et al. | Nov 2006 | B2 |
7141293 | Peiffer et al. | Nov 2006 | B2 |
7157516 | Chaiko | Jan 2007 | B2 |
7166656 | Majumdar et al. | Jan 2007 | B2 |
7186452 | Peiffer et al. | Mar 2007 | B2 |
7205040 | Peiffer et al. | Apr 2007 | B2 |
7211306 | Peiffer et al. | May 2007 | B2 |
7267858 | Ono et al. | Sep 2007 | B2 |
7329453 | Peiffer et al. | Feb 2008 | B2 |
7354635 | Malfait et al. | Apr 2008 | B2 |
7368165 | Sankey et al. | May 2008 | B2 |
7368496 | Kim et al. | May 2008 | B2 |
7371793 | Gong et al. | May 2008 | B2 |
7393581 | Kim et al. | Jul 2008 | B2 |
7396578 | Peiffer et al. | Jul 2008 | B2 |
7413800 | Wood, Jr. et al. | Aug 2008 | B2 |
7638573 | Wang et al. | Dec 2009 | B2 |
7645829 | Tse et al. | Jan 2010 | B2 |
7695809 | Maksymkiw et al. | Apr 2010 | B1 |
7871696 | Kinigakis et al. | Jan 2011 | B2 |
7871697 | Kinigakis et al. | Jan 2011 | B2 |
8110286 | Kinigakis et al. | Feb 2012 | B2 |
8470397 | Kinigakis et al. | Jun 2013 | B2 |
20010012557 | Willham et al. | Aug 2001 | A1 |
20010035593 | Peiffer et al. | Nov 2001 | A1 |
20020009563 | Kawamura et al. | Jan 2002 | A1 |
20020122977 | Fujimatsu et al. | Sep 2002 | A1 |
20020137834 | Barbee et al. | Sep 2002 | A1 |
20020165306 | Gilmer et al. | Nov 2002 | A1 |
20030100656 | Majumdar et al. | May 2003 | A1 |
20030129331 | Chen et al. | Jul 2003 | A1 |
20030144398 | Cody et al. | Jul 2003 | A1 |
20030144938 | Lahre et al. | Jul 2003 | A1 |
20030152735 | Koike | Aug 2003 | A1 |
20030219585 | Yamanaka et al. | Nov 2003 | A1 |
20040024102 | Hayes et al. | Feb 2004 | A1 |
20040067284 | Sankey et al. | Apr 2004 | A1 |
20050037191 | Ikenoya | Feb 2005 | A1 |
20050042468 | Peiffer et al. | Feb 2005 | A1 |
20050074619 | Peiffer et al. | Apr 2005 | A1 |
20050121822 | Peiffer et al. | Jun 2005 | A1 |
20050208282 | Wood et al. | Sep 2005 | A1 |
20050249903 | Kendig et al. | Nov 2005 | A1 |
20050249906 | Sankey et al. | Nov 2005 | A1 |
20050266257 | Lee et al. | Dec 2005 | A1 |
20050276940 | Stevenson | Dec 2005 | A1 |
20050282948 | Li et al. | Dec 2005 | A1 |
20060046595 | Imaizumi et al. | Mar 2006 | A1 |
20060094810 | Kim et al. | May 2006 | A1 |
20060094811 | Kim et al. | May 2006 | A1 |
20060111499 | Kim et al. | May 2006 | A1 |
20060121224 | Kim et al. | Jun 2006 | A1 |
20060122311 | Kim et al. | Jun 2006 | A1 |
20060122312 | Kim et al. | Jun 2006 | A1 |
20060128867 | Marx et al. | Jun 2006 | A1 |
20060141183 | Williamson et al. | Jun 2006 | A1 |
20060141241 | Carespodi et al. | Jun 2006 | A1 |
20060172098 | Stevenson | Aug 2006 | A1 |
20060199890 | Fasulo et al. | Sep 2006 | A1 |
20060211804 | Kim et al. | Sep 2006 | A1 |
20060222797 | Bekele | Oct 2006 | A1 |
20060240204 | Ling et al. | Oct 2006 | A1 |
20060269707 | Berbert | Nov 2006 | A1 |
20070078212 | Kim et al. | Apr 2007 | A1 |
20070104395 | Kinigakis et al. | May 2007 | A1 |
20070199481 | Roelofs | Aug 2007 | A1 |
20070267737 | Chen et al. | Nov 2007 | A1 |
20080009579 | Gong et al. | Jan 2008 | A1 |
20080118688 | Kinigakis et al. | May 2008 | A1 |
20080131636 | Kinigakis et al. | Jun 2008 | A1 |
20080152850 | Paterson | Jun 2008 | A1 |
20080176980 | Torkelson et al. | Jul 2008 | A1 |
20080255296 | Gibbons et al. | Oct 2008 | A1 |
20080299317 | Hable | Dec 2008 | A1 |
20090036580 | Qian et al. | Feb 2009 | A1 |
20090279813 | Pokusa et al. | Nov 2009 | A1 |
20090292055 | Jarus et al. | Nov 2009 | A1 |
20100092793 | Aithani et al. | Apr 2010 | A1 |
Number | Date | Country |
---|---|---|
4410235 | Sep 1995 | DE |
0684970 | Aug 1998 | EP |
1080881 | Mar 2001 | EP |
0772553 | Apr 2001 | EP |
1344642 | Sep 2003 | EP |
1356925 | Oct 2003 | EP |
1144494 | Jul 2004 | EP |
1475229 | Nov 2004 | EP |
1496085 | Jan 2005 | EP |
1529799 | May 2005 | EP |
1591236 | Nov 2005 | EP |
1785447 | May 2007 | EP |
2769867 | Apr 1999 | FR |
10146931 | Jun 1998 | JP |
10-259017 | Sep 1998 | JP |
11035907 | Feb 1999 | JP |
11035907 | Feb 1999 | JP |
2000-169634 | Jun 2000 | JP |
2000198170 | Jul 2000 | JP |
2003-285873 | Jul 2003 | JP |
2004-331188 | Nov 2004 | JP |
9742258 | Nov 1997 | WO |
9748554 | Dec 1997 | WO |
9952972 | Oct 1999 | WO |
0039200 | Jul 2000 | WO |
03011961 | Feb 2003 | WO |
03035391 | May 2003 | WO |
03040199 | May 2003 | WO |
03091020 | Nov 2003 | WO |
2004080808 | Sep 2004 | WO |
2005040268 | May 2005 | WO |
2005056644 | Jun 2005 | WO |
2005116132 | Dec 2005 | WO |
2006045896 | May 2006 | WO |
2006058952 | Jun 2006 | WO |
2006071833 | Jul 2006 | WO |
2007012805 | Feb 2007 | WO |
2007019142 | Feb 2007 | WO |
2007090265 | Aug 2007 | WO |
2007093798 | Aug 2007 | WO |
2007106671 | Sep 2007 | WO |
2007115310 | Oct 2007 | WO |
2007121048 | Oct 2007 | WO |
2007121049 | Oct 2007 | WO |
2007123582 | Nov 2007 | WO |
2007130755 | Nov 2007 | WO |
2007146390 | Dec 2007 | WO |
2008043750 | Apr 2008 | WO |
2008053205 | May 2008 | WO |
2008127485 | Oct 2008 | WO |
Entry |
---|
International Search Report for PCT/US09/33677, Completed by the USPTO on Mar. 13, 2009, 3 Pages. |
Extended European Search Report for EP 07115566.7, Completed by the European Patent Office on Jan. 14, 2008, 9 Pages. |
Roussel et al. TAPPI 2005, 12 Pages, “The Use of Calcium Carbonate in Polyolefins Offers Significant Improvement in Productivity.” |
Hwo., Journal of Plastic Film and Sheeting Oct. 1987, vol. 3, p. 245-260, “Polybutylene Blends as Easy Open Seal Coats for Flexible Packaging and Lidding.” |
Xin Dai, Qingkun Shang, Qiong Jia, Shichun Li, Yanhua Xiu, Preparation and Properties of HDPE/CACO/OMMT, Ternary Nanocomposite, published online in Wiley InterScience (www.interscience.wiley.com), 2009 Society of Plastics Engineers, 6 pages. |
Michael Tolinski, Trends in Polyolefin and Additive Use, Copyright 2009, Michael Tolinski, Published by Elsevier, Inc., 11 pages. |
International Search Report dated Mar. 15, 2012, from related International PCT/US2009033677, 6 pages. |
PolyOne, Nanoblend (TM), Concentrates MB2001 Polyethylene, www.PolyOne.com, 2003, 1 page. |
PolyOne, Nanoblend (TM), Concentrates MB2101 Polyethylene, www.PolyOne.com, 2003, 1 page. |
Nanocor, Nanocomposites Using Special Purpose Nanomer, (Oct. 2004), 2 pages. |
Nanocor, General information about Nanomer-Nanoclay, (Dec. 2004), 1 page. |
Number | Date | Country | |
---|---|---|---|
20130272631 A1 | Oct 2013 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13357994 | Jan 2012 | US |
Child | 13912887 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 12980312 | Dec 2010 | US |
Child | 13357994 | US | |
Parent | 12031450 | Feb 2008 | US |
Child | 12980312 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 11602650 | Nov 2006 | US |
Child | 12031450 | US |