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Patent US4716061 - Polypropylene/polyester nonoriented heat sealable moisture barrier film and bag - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA nonoriented, heat sealable, coextruded, moisture barrier film is disclosed. This film has a base layer ("A") of polypropylene homopolymer, polypropylene copolymer or combinations thereof, a heat sealant layer ("C") of polyester/copolyester or blends thereof and a tie layer ("B") of modified polyethylene...http://www.google.com/patents/US4716061?utm_source=gb-gplus-sharePatent US4716061 - Polypropylene/polyester nonoriented heat sealable moisture barrier film and bagAdvanced Patent SearchPublication numberUS4716061 APublication typeGrantApplication numberUS 06/810,110Publication dateDec 29, 1987Filing dateDec 17, 1985Priority dateDec 17, 1985Fee statusLapsedPublication number06810110, 810110, US 4716061 A, US 4716061A, US-A-4716061, US4716061 A, US4716061AInventorsJohn P. WinterOriginal AssigneePresto Products, IncorporatedExport CitationBiBTeX, EndNote, RefManPatent Citations (48), Non-Patent Citations (12), Referenced by (60), Classifications (18), Legal Events (9) External Links: USPTO, USPTO Assignment, EspacenetPolypropylene/polyester nonoriented heat sealable moisture barrier film and bagUS 4716061 AAbstract A nonoriented, heat sealable, coextruded, moisture barrier film is disclosed. This film has a base layer ("A") of polypropylene homopolymer, polypropylene copolymer or combinations thereof, a heat sealant layer ("C") of polyester/copolyester or blends thereof and a tie layer ("B") of modified polyethylene homopolymer, modified polyethylene copolymer, modified polypropylene homopolymer, modified polypropylene copolymer, an unmodified polyethylene copolymer or combinations thereof between the base layer ("A") and the heat sealant layer ("C"). This film has three layers ("ABC") or five layers ("CBABC"). This film exhibits a very broad heat seal range and has a moisture vapor transmission rate of from about 0.20 to about 1.0 g/100in.sup.2 /24 hr. This film has a wide variety of applications as a packaging film including such demanding uses as the inside of a microwave popcorn bag. This film significantly improves the shelf life of microwave popcorn compared to conventional films used for this product. This film also exhibits excellent heat seal properties to itself as well as a wide variety of diverse substrates.
I claim: 1. A nonoriented, heat sealable, coextruded, moisture barrier film comprising:a base layer selected from the group consisting of a polypropylene homopolymer, a polypropylene copolymer and combinations thereof; a heat sealant layer selected from the group consisting of a polyester, a copolyester and combinations thereof; and a tie layer between the base layer and the heat sealant layer selected from the group consisting of a modified polyolefin blend, an unmodified polyethylene copolymer and combinations thereof. 2. The nonoriented, heat sealable, coextruded moisture barrier film of claim 1 wherein the peel strength provided by the tie layer exceeds 600 g/in.
3. The nonoriented, heat sealable, coextruded, moisture barrier film of claim 1 wherein the nonoriented, heat sealable, coextruded moisture barrier film has a moisture vapor transmission rate of from about 0.20 to about 1.0 g/100 in.sup.2 /24 hr.
4. The nonoriented, heat sealable, coextruded, moisture barrier film of claim 3, wherein the nonoriented, heat sealable, coextruded, moisture barrier film has a moisture vapor transmission rate of from about 0.20 to 0.50 g/100 in.sup.2 /24 hr.
18. The nonoriented, heat sealable, coextruded, moisture barrier film of claim 16 wherein the nonoriented, heat sealable, coextruded moisture barrier film has a moisture vapor transmission rate of from about 0.20 to about 1.0 g/100 in.sup.2 /24 hr.
19. The nonoriented, heat sealable, coextruded, moisture barrier film of claim 18, wherein the nonoriented, heat sealable, coextruded, moisture barrier film has a moisture vapor transmission rate of from about 0.20 to 0.50 g/100.sup.2 /24 hr.
BACKGROUND AND SUMMARY OF THE INVENTION The present invention relates to packaging film. Specifically, the present invention relates to multiple layer heat sealable nonoriented packaging films exhibiting excellent moisture barrier properties.
The film of the present invention is unique in that the polyester/copolyester layer is utilized as the heat sealant layer. Typically, laminations and coextrusions of this type utilize polyethylene homopolymers or copolymers as the heat sealant layer. The present invention discloses surprising results when using polyester/copolyester as the heat sealant. In particular, it has been found that the film of the present invention can be utilized in extremely high temperature demanding applications and in providing differential seal properties. Furthermore, the preferred embodiment discloses a specific copolyester which provides heat seal properties heretofor unobtainable with polyethylenes or other polyesters/copolyesters. Specifically, these properties include a broad heat seal range to a wide variety of substrates and the ability to withstand extremely high temperatures up to 500 fact that the film of the present invention may contain up to 90% w/w of olefins (base layer and tie layer), which melt at 250 suprisingly such film can be used in high temperature applications such as microwave popcorn bags where temperatures can exceed 500
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates a multilayer film of the present invention with a heat sealant layer on one side, ("ABC") film.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the invention is exemplified in FIG. 1 in which a three layer ("ABC") film is generally designated 10. Layer 11 of film 10 is a base layer ("A") selected from the group consisting of a polypropylene homopolymer, a polypropylene copolymer and combinations thereof. Layer 12 is a tie layer ("B") selected from the group consisting of a modified polyethylene homopolymer, a modified polyethylene copolymer, a modified polypropylene homopolymer, a modified polypropylene copolymer, an unmodified polyethylene copolymer and combinations thereof. Layer 13 is a heat sealant layer ("C") comprising a polyester or copolyester resin or blend thereof.
The tie layer ("B") comprises polyolefin or preferably a modified polyolefin blend selected from the group consisting of a polyethylene homopolymer, a polyethylene copolymer, a polypropylene homopolymer, a polypropylene copolymer and combinations thereof preferably modified to promote adhesion between the base layer ("A") and heat sealant layer ("C"). The use of tie layers is well known in coextrusion to bond or "tie" together layers of different polymers which otherwise would not adhere. Preferably, a compound having a functional group is utilized to modify the polyethylene homopolymer, polyethylene copolymer, polypropylene homopolymer, polypropylene copolymer or combinations thereof to promote adhesion between the base layer ("A") and the heat sealant layer ("C"). Such compounds are usually polar compounds. Preferred polar compounds include carboxylic acids and carboxylic acid anhydrides. The tie layer comprises from about 5% to about 33% mil/mil of the total film thickness, preferably from about 8% to about 20% mil/mil. If more than one tie layer ("B") is utilized, for example, in a five layer ("C'B'AB"C"") film, the first tie later ("B'") is a first modified polyolefin blend, a first modified polyethylene copolymer or combinations thereof, and the second tie layer, ("B"") is a second modified polyolefin blend, a second unmodified polyethylene copolymer or combinations thereof. The first tie layer may be the same as or of a different specific composition than the second tie layer provided that both are polyolefinic blends as described herein. The same applies if more than two tie layers ("B") are utilized in a multilayer film. Examples of commercial tie layers include the Plexar series from Norchem, Inc., CXA series from E. I. DuPont de Nemours and Company and the UF series from Mitsui. One type of tie layer is described in U.S. Pat. No. 4,477,532 assigned to Chemplex Company. This tie layer which is discussed in detail below is described as a modified polyolefin blend consisting essentially of about 0.1-40 parts by weight in said blend of a non-elastomeric graft copolymer of about 70-99.999 wt. % of a non-polar ethylene homopolymer or copolymer backbone having a density of at least 0.915 grafted with about 30-0.001 wt. % of at least one grafting monomer comprising at least one polymerizable ethylenically unsaturated carboxylic acid or carboxylic acid anhydride for a total of 100% and about 99.9-60 parts by weight of a substantially elastomer free blending resin mixture of about 25-75 wt. % of a linear low density polyethylene of a density of about 0.915 to less than 0.94, having a substantial absence of long-chain branching and a high degree of short-chain branching and about 75-25 wt. % of a non-elastomeric polypropylene for a total of 100%. The unsaturated carboxylic acids or acid anhydrides used as the grafting monomers include compounds such as acrylic acid, methacrylic acid, maleic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid anhydride bicyclo (2,2,2)oct-5-ene-2,3-dicarboxylic acid anhydride, 2-cyclopentenyl acetic acid and abietic acid. 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro(4,4)- non-7-ene, bicyclo(2,2,1)hept-5 -ene-2,3-dicarboxylic acid anhydride, x-methylbicyclo(2,2,1) hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthalic anhydride, x-methylnorborn-5-ene-2,3-dicarboxylic acid anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, Nadic anhydride, methyl Nadic anhydride, Himic anhydride, methyl Himic anhydride and other fused ring monomers such as described in U.S. Pat. Nos. 3,873,643 and 3,882,194, both assigned to Chemplex Company. Cografting monomers such as described in U.S. Pat. No. 3,882,194 are also useful for preparing the graft copolymers. Included among the conjugated unsaturated esters suitable for cografting are dialkyl maleates, dialkyl fumarates, dialkyl itaconates, dialkyl mesaconates, dialkyl citraconates, alkylacrylates, alkyl crotonates, alkyl tiglates and alkyl methacrylates where alkyl represents aliphatic, aryl-aliphatic and cycloaliphatic groups containing 1-12 carbon atoms. Esters particularly useful in the cografted copolymers of this invention are dibutyl maleate, diethyl fumarate and dimethyl itaconate. Among the acids and acid anhydrides particularly useful in the cografted copolymers of this invention are maleic anhydride, tetrahydrophthalic anhydride, x-methylbicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid anhydride and bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid anhydride. It is often desirable to use more than one monomer in either or both classes of monomers in order to control the physical properties of the final products. The method in general consists of heating a mixture of the polymer or polymers and the monomer or monomers with or without a solvent. The mixture can be heated to above the melting point of the polyolefin with or without a catalyst. Thus, the grafting occurs in the presence of air, hydroperoxides, other free radical catalysts or in the essential absence of those materials where the mixture is maintained at elevated temperatures and (if no solvent is used) preferably under high shear. The graft and cograft copolymers of Chemplex Company are recovered by any method or system which separates or utilizes the graft copolymer that is produced. Thus, the term includes recovery of the copolymer in the form of precipitated fluff, pellets, powders and the like, as well as further chemically reacted or blended pellets, powders and the like or in the form of shaped articles formed directly from the resulting copolymer. Any of the commonly known hydroperoxides which have a half life of at least 1 minute at 145 layer. Such hydroperoxides have the general formula R-0-OH, wherein R is an organic radical. Among the suitable hydroperoxides are t-butyl hydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide, and cumene hydroperoxide, as well as others known in the art. The elevated temperature causes rapid decomposition of the hydroperoxide which catalyzes the reaction between the pololefin and monomer to form the graft copolymer. Obviously, the more homogeneous the mixture prior to heating, the less mixing will be required of the solution or molten composition. Generally, in order to obtain a desirable conversion, it has been found that some form of mixing is highly desirable in the absence of a solvent even when a uniform mixture of all of the components of the composition is formed prior to heating. In general, when a solvent is not used, the composition should be heated to a temperature above about 130 and it is preferred to use the temperatures ranging from about 200 -360 generally to be avoided in order to avoid substantial decomposition of the polymeric ingredients. However, if the decomposition products are not undesirable in the product, as in the production of high melt index waxes, higher temperatures may be employed. The reaction time required is quite short, being of the magnitude of from a few seconds to about twenty minutes, although extended heating times do not substantially affect the product and may be employed when desired for any reason. A convenient method of accomplishing the reaction is to premix the ingredients and then extrude the composiion through a heated extruder. Other mixing means, such as a Brabender mixer, a Banbury mixer, roll mills and the like may also be employed for the process. In order to prevent undue increase in molecular weight with a possiblity of some crosslinking at elevated temperatures, it is desirable to carry out the reaction in a closed vessel. A conventional single or multiple screw extruder accomplishes this result without the use of auxiliary equipment and for this reason is a particulary desirable reaction vessel.
Moisture barrier of films is commonly referred to as the Moisture Vapor Transmission Rate or MVTR. The MVTR is a laboratory measurement of the amount of moisture vapor which passes through a known area of film over a specified period of time. An example of the units of measurement is "grams per 100 square inches per 24 hours" (g/100 in.sup.2 /24 hrs.). Lower MVTR values correspond to better barrier films.
TABLE 1______________________________________1.0 mil pp/film         0.3 gm/100 in.sup.2 /24 hrs______________________________________
The acceptable MVTR range is from about 0.20 to about 1.0 g/100 in.sup.2 /24 hr. for the base layer ("A") and the preferred MVTR range of same is from about 0.20 to about 0.50 g/100 in.sup.2 /24 hr.
EXAMPLE 1 A base layer 11 ("A") consisting of a PP homopolymer with a density of 0.900 and melt flow index of 5 was coextruded with a heat sealant layer 13 ("C") consisting of a copolyester and a tie layer 12 ("B") consisting of a modified EVA, producing an "ABC" three layer film. One commercial PP polymer with these physical properties and used in this example is CD 4062 manufactured by Exxon Chemical Company. The copolyester used was made by reacting two glycols, ethylene glycol and diethylene glycol with terephthalic acid. This copolyester can be chemically defined as poly (ethylene-co-diethylene terephthalate) hereinafter referred to as diethylene glycol copolyester. One commercial copolyester of this formulation and used in this example is KODABOND 5116 manufactured by Eastman Chemical Products Inc. KODABOND is a registered trademark of Eastman Chemical Products, Inc. To reduce the coefficient of friction (COF) of the heat sealant layer when converted to film, a slip and antiblock master batch was added to the copolyester resin. The master batch comprised of 83 parts diethylene glycol copolyester, 7 parts silica and 10 parts silicone. This master batch was added to the copolyester to a final concentration of 8% w/w. The tie layer ("B") was a 18% EVA (polyethylene copolymer) chemically modified to promote adhesion to polyesters. This modification involved attaching functional groups onto the polyethylene backbone. One commercial tie layer having the ability for adhering polyester/copolyester resins to polypropylenes and utilized in this example is PLEXAR 326 manufactured by Norchem, Inc. PLEXAR is a registered trademark of Norchem, Inc. Norchem, Inc. is the successor corporation of Chemplex Company and PLEXAR is generally described in U.S. Pat. Nos. 4,477,532, 3,882,194 and 3,873,643. The base layer 11 ("A") resin was placed into a first extruder, the tie layer 12 ("B") resin was placed into a second extruder and the heat sealant layer 13 ("C") resin was placed into a third extruder. The resins were coextruded through an ("ABC") cast coextrusion feedblock and cast film die and then quenched on a chilled roll. The resultant film had a total thickness of 1.5 mil (0.0015 inches) of which 1.1 mil was the base layer 11 and the tie and heat sealant layers were each 0.2 mil thick.
EXAMPLE 2 The film of example 1 except the resultant film had a total thickness of 1.1 mil (0.0011 inches) of which 0.7 mil was base layer and the tie and heat sealant layers were each 0.2 mil thick.
EXAMPLE 3 The film of example 1 except that a polyester was used as the heat sealant layer 13 ("C").
EXAMPLE 4 The film of example 2 except that EMA was used as the tie layer 12 ("B").
EXAMPLE 5 To produce a moisture barrier heat sealable film commonly known to the art, an ("AB") two layer cast coextruded film was produced using the PP of example 1 as the base layer and ethylene vinyl acetate EVA (polyethylene copolymer) with 5% vinyl acetate (VA) content as the heat sealant layer. A tie layer was not required as PP and EVA will bond without a tie layer. This type of EVA is widely used as the heat sealant on many common packaging films.
TABLE 3______________________________________Moisture Vapor Barrier Transmission Rategm/100 in.sup.2 /24 hrs.______________________________________  Example 1          0.30  Example 2          0.44______________________________________
TABLE 4______________________________________           Seal Peel StrengthSeal Temperature           (gram/inch)(______________________________________200             200         0225             500         0250             600       1350300             675       1500350             750       1500______________________________________
Table 6 contains data on the heat sealing properties of the films of examples 1 and 5. This data illustrates the superior sealing properties of the copolyester heat sealant used in example 1 compared to that of the EVA heat sealant used in example 5. In particular, the copolyester sealant of example 1 provides a gradual increase in seal strength with temperature providing peelable seals (peelable defined as less than 800 grams/in) while the EVA sealant of Example 5 provided a peelable seal at only one temperature, 225 the pulling force. This narrow seal range exhibited by the example 5 film is a disadvantage in packaging machinery operation.
TABLE 6______________________________________Heat Sealing   Heat Seal StrengthTemperature    (g/in)(______________________________________200            200         0225            500        400250            600       1,600*300            675       1,600*350            750       1,600*______________________________________ *Seal stretched and did not peal.
TABLE 7______________________________________Heat Seal Strength to Various Substrates(Sealed at 40 p.s.i. 0.5 sec. dwell, 350Substrate      Example 1 Example 5______________________________________Paper          300 g     100 g/inOriented PET   500 g     0 g/inPVC            1000 g    0 g/in______________________________________
Another advantage of the copolyester heat sealant film of example 1 is its ability to contain hot materials, such as microwave popcorn during cooking, without melting. EVA heat sealants, as used in example 5 soften and melt above 200 under heat, yielding a high temperature surface stable above 500 F.
EXAMPLE 6 For producing a five layer ("CBABC") film, the three resins of example 1 are coextruded through a five layer ("CBABC") cast coextrusion feedblock. The film's total thickness is 1.9 mil comprising a core base layer ("A") of 1.1 mil and pairs of tie and heat sealant layers ("B") and ("C") with each layer being 0.2 mil. The resultant film is heat sealable on both sides having the ability to form both lap and fin seals.
EXAMPLE 7 Using a three layer spiral coextrusion blown film die, the film of example 1 is produced. The base layer polymer is placed into a first extruder, the tie layer into a second and the heat sealant into a third extruder. The polymers are coextruded through a three layer ("ABC") spiral blown film coextrusion die. The base layer ("A") polymer is extruded into the outermost spiral channel, the tie layer ("B") polymer is extruded into the center (middle) channel and the heat sealant layer ("C") polymer is extruded into the innermost channel. The three layers are combined just prior to the final land of the die and then cooled by conventional blown film techniques.
EXAMPLE 8 Film of examples 1 and 2, OL MYLAR (a commercial OPET containing a heat seal coating) and PVDC coated OL MYLAR were separately used as the inside liner of a laminate bag.
TABLE 8______________________________________Moisture Vapor Transmission Rates of Laminates(g/100 in.sup.2 /24 hrs.)Film                MVTR______________________________________OL MYLAR            2.4PVDC coated OL MYLAR               0.25Example 1           0.30Example 2           0.44______________________________________
TABLE 9______________________________________Heat Seal Peel Strengths(grams/inch)      Heat Seal TemperatureFilm         250                   300                             350______________________________________OL MYLAR     420    g/in    700  g/in 910   g/inPVDC coated OL        420            700       910MYLARExample 1    400            700       900Example 2    400            700       900______________________________________
EXAMPLE 9 Bags 19 of FIG. 3A, described in example 8, were filled with 74 grams of popping corn and 24 grams of shortening, 25. The tops of the bags were then heat sealed. The resultant package is a complete microwave popcorn product well known to the art. These bags, made with the 3 different films, were used for several aging studies. These studies measure the loss of pop volume due to a reduction of corn moisture content upon aging.
Two types of aging studies were performed: ambient conditions (75 F., 40% humidity) for 6 months and accelerated conditions (90 35% humidity) for 3-4 weeks.
EXAMPLE 10 The comparative prior art film of example 5 was used to make laminate bags as described in example 8 and compared to bags made with a film of this invention (example 1 film). When used for microwave popcorn bags, the bags made with the film of example 5 showed excessive leakage (cooking oil) and did not have a peelable seal at the bag top making it difficult to open the bag and remove the cooked product (popcorn). The leakage with the bags made with example 5 film is a result of the EVA heat sealant and HDPE base layer melting. The film of example 1 did not melt as the copolyester sealant crystallized providing a high temperature barrier to melting.
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2004Apr 13, 2010Playtex Products, Inc.Waste disposal device including a geared rotating cartridgeUS7707808Feb 16, 2007May 4, 2010Playtex Products, Inc.Cassette for an automated waste disposal deviceUS7708188Sep 2, 2004May 4, 2010Playtex Products, Inc.Waste disposal device including a hamper accessible through a movable doorUS7712285Sep 2, 2004May 11, 2010Playtex Products, Inc.Waste disposal device including a sensing mechanism for delaying the rotation of a cartridgeUS7757467Apr 17, 2003Jul 20, 2010Playtex Products, Inc.Disposable cassette for incremental withdrawal of tubular plastic with malodor-counteractant capacityUS7794849Apr 16, 2009Sep 14, 2010Exxonmobil Oil CorporationThermoplastic film structures with a low melting point outer layerUS7958704Sep 2, 2004Jun 14, 2011Playtex Products, Inc.Waste disposal device including a mechanism for scoring a flexible tubing dispensed from a cartridgeUS8091325Sep 28, 2005Jan 10, 2012Playtex Products, Inc.Waste disposal device including a diaphragm for twisting a flexible tubing dispensed from a cartridgeUS8282539Dec 22, 2008Oct 9, 2012Exopack, LlcMulti-layered bags and methods of manufacturing the sameUS8356578Sep 23, 2011Jan 22, 2013Jenkins Dennis BWaste encapsulating animal litterUS8357414 *Aug 25, 2010Jan 22, 2013Cryovac, Inc.Package with on-demand product elevationUS8440316Jun 19, 2006May 14, 2013Playtex Products, Inc.Odor transmission-resistant polymeric filmUS8604399Oct 19, 2009Dec 10, 2013Exopack, LlcMicrowavable bags for use with liquid oil and related methodsUS20120052165 *Aug 25, 2010Mar 1, 2012Cryovac, Inc.Package With On-Demand Product ElevationUS20120196102 *Jan 31, 2011Aug 2, 2012Fina Technology, Inc.Coextruded Cast Film StructuresUS20120201936 *Feb 9, 2011Aug 9, 2012Elizabeth WinogradMicrowave Popcorn Packaging with a Clear Bag and an Interior Anti-Scorch SurfaceCN1073131C *Aug 14, 1996Oct 17, 2001三井化学株式会社Adhesive polypropyelen resin composite and multiple-layer laminated body using said resin compositeEP0418836A2 *Sep 18, 1990Mar 27, 1991Hercules IncorporatedMultilayer oriented film containing polypropylene and co-polyesterEP0746468A1 *Dec 21, 1995Dec 11, 1996Courtaulds Films (Holdings) LimitedPolymeric filmsWO1994013475A1 *Dec 9, 1992Jun 23, 1994Cynthia BennettBiaxially oriented copolyester/polyolefin bi- or trilayer film and method for making the sameWO1994013478A1 *Dec 9, 1992Jun 23, 1994Cynthia BennettBiaxially oriented penbb film for glazing, optical and weatherable applicationsWO2010117835A1Mar 31, 2010Oct 14, 2010Cryovac, Inc.Packaging with on-demand oxygen generationWO2011044027A1Oct 4, 2010Apr 14, 2011Cryovac, Inc.Suspension packaging with on-demand oxygen generationWO2011163165A1Jun 21, 2011Dec 29, 2011Cryovac, Inc.Package comprising on-demand collapsible support member* Cited by examinerClassifications U.S. Classification428/34.3, 426/127, 428/41.3, 428/218, 264/176.1, 428/35.4, 428/447, 428/483, 426/110, 428/516, 426/107, 428/347, 426/234, 428/330, 428/520International ClassificationB32B27/08Cooperative ClassificationB32B27/08European ClassificationB32B27/08Legal EventsDateCodeEventDescriptionMar 7, 2000FPExpired due to failure to pay maintenance feeEffective date: 19991229Dec 26, 1999LAPSLapse for failure to pay maintenance feesJul 20, 1999REMIMaintenance fee reminder mailedMay 30, 1995FPAYFee paymentYear of fee payment: 8May 31, 1991FPAYFee paymentYear of fee payment: 4Feb 21, 1989ASAssignmentOwner name: REYNOLDS CONSUMER PRODUCTS, INC.,Free format text: MERGER;ASSIGNORS:PRESTO PRODUCTS, INC., A CORP. OF WI (MERGED INTO);PRESTO INDUSTRIES INC., A CORP.OF DE (CHANGED TO);REYNOLDS CONSUMER PRODUCTS, INC., A DE CORP.;REEL/FRAME:005026/0381;SIGNING DATES FROMFeb 7, 1989CCCertificate of correctionApr 7, 1986ASAssignmentOwner name: PRESTO PRODUCTS, INCORPORATED, 670 NORTH PERKINS SFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:COCA-COLA COMPANY, THE;REEL/FRAME:004530/0096Effective date: 19860401Dec 19, 1985ASAssignmentOwner name: COCA-COLA COMPANY THE, 310 NORTH AVENUE, ATLANTA,Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:WINTER, JOHN P.;REEL/FRAME:004533/0366Effective date: 19851218RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google

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national geographic | eBay
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58,214 results for national geographic
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Cheap Flights to Barro, Llanes $181.00 in 2017 | Expedia
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GOSSIP OF THE CYCLERS; Dissatisfaction with a Section of the Rules of the Road May Lead to Its Amendment. THE COLOR LINE IN RACING Becker's Assault on Major Taylor Revives the Question -- History of the Twenty-four-Hour Record Now Held by Cordang -- Cycle Tubing of Bamboo Fibre and Paper. - The New York Times
Archives|GOSSIP OF THE CYCLERS; Dissatisfaction with a Section of the Rules of the Road May Lead to Its Amendment. THE COLOR LINE IN RACING Becker's Assault on Major Taylor Revives the Question -- History of the Twenty-four-Hour Record Now Held by Cordang -- Cycle Tubing of Bamboo Fibre and Paper.
https://nyti.ms/1H94s2R
GOSSIP OF THE CYCLERS; Dissatisfaction with a Section of the Rules of the Road May Lead to Its Amendment. THE COLOR LINE IN RACING Becker's Assault on Major Taylor Revives the Question -- History of the Twenty-four-Hour Record Now Held by Cordang -- Cycle Tubing of Bamboo Fibre and Paper.
ProvisionsView Full Article in Timesmachine »
A version of this archives appears in print on October 3, 1897, on Page 17 of the New York edition with the headline: GOSSIP OF THE CYCLERS; Dissatisfaction with a Section of the Rules of the Road May Lead to Its Amendment. THE COLOR LINE IN RACING Becker's Assault on Major Taylor Revives the Question -- History of the Twenty-four-Hour Record Now Held by Cordang -- Cycle Tubing of Bamboo Fibre and Paper. Order Reprints| Today's Paper|Subscribe

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minniev • Senior Member • Posts: 2,679
In reply to LouHolland • Jul 24, 2014
Thanks Lou for the comments and the work which does gather in some more detail and makes more out of that little light on the larger raft. Here is what I'm not sure about: the distortion you see in the histogram might have been caused by me. The fog was even thicker and the scene more invisible than in my first post. To get some detail, I tinkered with the histogram itself, lopping off pieces on both ends to redistribute values. I love shooting in fog, but it can be challenging to render both what you saw and what you didn't see but wish you had.

value: This website is a website about digital cameras and digital photography, established in November 1998. The website provides comprehensive reviews of digital cameras, lenses and accessories, buying guides, user reviews, and forums for individual cameras, as well as general photography forums.


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Hotel bedroom in the valley, Moena, Italy - Booking.com
bedroom in the valley (Homestay), Moena (Italy) Deals
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Life_Of_High comments on GAME THREAD: Orlando Magic (17-40) @ Toronto Raptors (30-25) - (Feb. 23, 2014)jump to contentmy subredditsannouncementsArtAskRedditaskscienceawwblogbookscreepydataisbeautifulDIYDocumentariesEarthPornexplainlikeimfiveFitnessfoodfunnyFuturologygadgetsgamingGetMotivatedgifshistoryIAmAInternetIsBeautifulJokesLifeProTipslistentothismildlyinterestingmoviesMusicnewsnosleepnottheonionOldSchoolCoolpersonalfinancephilosophyphotoshopbattlespicsscienceShowerthoughtsspacesportstelevisiontifutodayilearnedTwoXChromosomesUpliftingNewsvideosworldnewsWritingPromptsedit subscriptionsfront-all-random | gadgets-sports-gaming-pics-worldnews-videos-AskReddit-aww-Music-funny-news-movies-books-history-food-philosophy-television-Jokes-Art-DIY-space-Documentaries-Fitness-askscience-nottheonion-todayilearned-personalfinance-gifs-listentothis-IAmA-TwoXChromosomes-creepy-nosleep-GetMotivated-WritingPrompts-LifeProTips-EarthPorn-explainlikeimfive-Showerthoughts-Futurology-photoshopbattles-mildlyinteresting-dataisbeautiful-tifu-OldSchoolCool-UpliftingNews-InternetIsBeautiful-sciencemore » nbacommentsrelatedWant to join? Log in or sign up in seconds.|Englishlimit my search to /r/nbause the following search parameters to narrow your results:subreddit:subredditfind submissions in "subreddit"author:usernamefind submissions by "username"site:example.comfind submissions from "example.com"url:textsearch for "text" in urlselftext:textsearch for "text" in self post contentsself:yes (or self:no)include (or exclude) self postsnsfw:yes (or nsfw:no)include (or exclude) results marked as NSFWe.g. subreddit:aww site:imgur.com dogsee the search faq for details.advanced search: by author, subreddit...this post was submitted on 23 Feb 201467 points (92% upvoted)shortlink: remember mereset passwordloginLinkTextnbasubscribeunsubscribe310,676 readers2,357 users here nowSubmit
a community for 6 yearsmessage the moderatorsMODERATORSMavericksheroinhero[MIA] Alonzo MourningcatmoonBullspiglet24BullsWiggles420[GSW] Stephen Curryswollencornholio[NOP] Anthony DavisLieutenantKumar[MIL] Andrew Bogutiamtheraptor[POR] Damian LillardDrTom[CHA] Gerald Wallacehercules-rockefeller[HOU] Tracy McGradyDisgruntled_Fridge...and 8 more »discussions in /r/nba<>X333 points · 255 comments Kobe's shooting numbers based on sweatbands/sleeves [OC]22 points · 19 comments Bucks discuss setting $15-an-hour 'wage floor,' hiring from minority neighborhoods, and allowing workers to unionize33 points · 48 comments NBA trivia: Shaquille O'neal got swept 6 times in his career. From 1994-1999, Shaq got swept 5 times!27 points · 42 comments I've never seen anything like this before -Kobe assists Hill off Serge Ibaka's backside· 13 comments BIG 14/15 REGULAR SEASON SUMMARY IN NUMBERS !104 points · 335 comments Markieff Morris states his future won't be in PHX.· 7 comments Report: Nikola Pekovic will be the new president of Partizan Belgrade17 points · 28 comments Random Fact: Landry Fields made $11,904.76 per minute played with the Raptors.20 points · 9 comments Kevin McHale with 56 points, 16 rebounds (10 offensive), 4 assists, 3 blocks for Celtics vs. Pistons51 points · 268 comments Marc Gasol has shot 39.9% over the last 2 years in the playoffs. Wouldn't any other elite player be crucified for that?666768GAME THREAD: Orlando Magic (17-40) @ Toronto Raptors (30-25) - (Feb. 23, 2014) (self.nba)submitted 1 year ago by Raptorsswagmaster_ak47207 commentssharesorry, this has been archived and can no longer be voted onloading...sorted by: besttopnewhotcontroversialoldrandomq&ayou are viewing a single comment's thread.view the rest of the comments →[–][TOR] José CalderónABondaxFan 0 points1 point2 points 1 year ago (1 child)sorry, this has been archived and can no longer be voted onWe need to think of some good nicknames for Nando guys.
permalinkembedsavegive gold[–]RaptorsLife_Of_High 0 points1 point2 points 1 year ago (0 children)sorry, this has been archived and can no longer be voted onRambo De Colo
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Cd Jazz Odessey Oscar Peterson | eBay Please enable JavaScript Our new search experience requires JavaScript to be enabled. Please enable JavaScript on your browser, then try again.
Skip to main contenteBayShop by categoryEnter your search keywordAll CategoriesAntiquesArtBabyBooksBusiness & IndustrialCameras & PhotoCell Phones & AccessoriesClothing, Shoes & AccessoriesCoins & Paper MoneyCollectiblesComputers/Tablets & NetworkingConsumer ElectronicsCraftsDolls & BearsDVDs & MovieseBay MotorsEntertainment MemorabiliaGift Cards & CouponsHealth & BeautyHome & GardenJewelry & WatchesMusicMusical Instruments & GearPet SuppliesPottery & GlassReal EstateSpecialty ServicesSporting GoodsSports Mem, Cards & Fan ShopStampsTickets & ExperiencesToys & HobbiesTravelVideo Games & ConsolesEverything ElseAdvanced or register':' style="margin-right:3px">Hi -User-!'.replace(/-User-/,escape(a)))+"")}catch(b){document.write("")}})();Hi (Sign in to bid or buy)Daily DealsGift CardsSellHelp & ContactMy eBayExpand My eBaySummaryBids/OffersWatch listWish listAll listsPurchase historySellingMy CollectionsFollowed searchesMessagesNotification Refine your search for Cd Jazz Odessey Oscar Peterson
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835 East North Street,
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Melamine Foam: Cleaning Products & Supplies | eBay
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Browse RelatedBrowse RelatedMr Clean Magic EraserMagic SpongeMelamine BoardJML Magic EraserMelamine TablewareHigh Density FoamPin BoardReclaimed TimberAlso shop inAlso shop inHome, Furniture & DIYHousehold & Laundry SuppliesCleaning Products & Supplies
Buy it nowFree P&P255 watching | 2924 sold	View detailsNo need for chemicals, use with water for cleaning use dry for dusting. 100 x 60 x 20mm. we will do all we can to chase any of this up. It's all about the quality and density of these sponges. 40,dudl...Condition:NewTime left:9d 5h 23m
User ID fab1direct (Feedback score 10658)
£1.95Buy it nowor Best OfferFree P&P160 watching | 2035 soldThe most popular sought after magic sponge! These sponges contain Melamine meaning no cleaning agents are needed, just add water and clean your dirty surfaces. The magic sponge can remove the most stu...5-10 Magic Cleaning Foam Sponge Eraser Stain Remover Melamine Pad Multi Purpose
£2.97Buy it nowFree P&P19+ watching | 200+ soldAre you Looking for High Quality Magic Cleaning Foam Sponge Eraser Stain Remover?. Look no Further! Rinse the dirty sponge with cold water after use and let it dry. Made of eco materials, clean most o...Magic Sponge Sponges 10 Pack Cleaning Melamine Foam Eraser Stain Dirt Remover✔Amazing Quality✔10 Pcs/Set✔Fast & Free Post✔UK Stock✔
£1.69Buy it nowFree P&PMade of eco materials, clean most of dust, stain without detergent. No need for chemicals, use with water for cleaning use dry for dusting. Can be cut into any sizes for a suitable shape.Magic Sponge cleaning Melamine Foam Eraser Stain Dirt Remover UK 10 pack
£1.89Buy it nowor Best OfferFree P&PHot 10 X Multi-functional Cleaning Magic Sponge Eraser Melamine Cleaner Pad Foam. Material: Melamine foam Sponge. This magic sponge removes stain or dirt with water. This sponge can be cut into any si...Melamine Magic Sponge Sponges Foam Dirt Stain Cleaner Remover Reusable UK STOCK
£2.98Buy it nowFree P&P6+ watching | 15+ soldMelamine Magic Cleaning Sponge. No Need For Chemicals - Just Use Warm Water. Multi Use Cleaning Sponge.100 Melamine Foam Eraser Multi-functional Home Cleaning Cleaner Pad Magic Sponge
£9.29Buy it nowFree P&P6 watching | 14 soldThis Magic High Oil-absorption Nano Sponge is the perfect solution. 99.9 percent naturally antibacterial, do not contain chemical cleaning ingredients, non-toxic and do not harm the skin. 100pcs x Cle...10 Pack Magic Cleaning Sponge Melamine Foam Eraser Stain Dirt Remover Pad UKUK SELLER - 1000's SOLD ONLINE - QUICK DESPATCH
£2.19Buy it nowFree P&P16 watching | 165 soldAdd a drop of water and effectively remove stains that other normal sponges struggle with. Can be used in a variety of ways depending on your need. Daily use for cleansing.5x Magic Cleaning Foam Sponge Eraser Stain Remover Melamine Pad Multi Purpose UKUK SELLER HIGH QUALITY FAST DISPATCH 1000's Sold
£1.80(£0.36 / Unit)Buy it nowFree P&P7 watching | 155 soldThe most popular sought after magic sponge! These sponges contain Melamine meaning no cleaning agents are needed, just add water and clean your dirty surfaces. The magic sponge can remove the most stu...100 Pack Magic Cleaning Sponge Melamine Foam Eraser Stain Dirt Remover Pad UK
£19.99Buy it nowFree P&PWe will do all we can to chase any of this up. 100 x 60 x 20 mm. great for car's original colour leather. time to do this.it can save so much hassle and money.3 x Magic Cleaning Sponge Foam Eraser Stain Remover Melamine Pad Multi Purpose
£1.99Buy it nowFree P&P13 watching | 125 soldMagic Sponge that effortlessly removes stubborn scuffs and blemishes. Erase A Stain. Will removes scuffs from interior door panels, kick plates, luggage compartment, boot, estate car load area, seat b...60/80/100PCS Magic Sponge Eraser Cleaning Melamine Multi-functional Foam Cleaner
£4.69Buy it nowFree P&P13+ watching | 38+ soldMade of eco materials, clean most of dust, stain without detergent. Do not sterilize sponge in hot water or detergent. Name: Nano cleaning sponge. Soak sponge in the water, squeeze out water slightly;...10 Magic Scouring Sponge Pack Cleaning Melamine Foam Eraser Stain Dirt Remove UK
£2.98(£0.30 / 100g)Buy it nowFree P&PMagic Sponge Eraser melamine cleaner,multi-functional Cleaning 100x60x20mm. Cut off the power if used on electric appliances. This sponge removes stain/dirt with water. 100% new.10 X Pack Magic Sponges Cleaning Melamine Foam Eraser Stain Dirt Remover Tool✔High Quality✔10 Pcs/Set✔Fast & Free Post✔UK Seller✔
£2.95Buy it nowFree P&PNo need for chemicals, use with water for cleaning use dry for dusting. Made of eco materials, clean most of dust, stain without detergent. Can be cut into any sizes for a suitable shape. Recommend to...Magic Cleaning Sponges - Melamine Foam Eraser Stain Dirt Remover Pad Block Eco
£1.89(£0.19 / Unit)Buy it nowFree P&PMelamine Sponges. APPROX Size is 9cm x 5cm. Magic Sponge Souring Pad Dish Cleaning Melamine Foam Eraser Stain Dirt Remover.
£1.39Buy it nowFree P&P15 watching | 3 soldFunny Dish sponge 3D fruit strong Clean cloth cotton washing dishes scouring pad household Kitchen Tool Cleaning Supplies. Color/ Pattern: Strawberry,Cantaloupe, Mango, Sweet Orange (as you choose).10 Pack Magic Cleaning Sponge Melamine Foam Eraser Stain Dirt Remover Nano UKUK'S CHEAPEST SELLER HIGH QUALITY FAST DISPATCH
£2.49Buy it nowFree P&PThe most popular sought after magic sponge! These sponges contain Melamine meaning no cleaning agents are needed, just add water and clean your dirty surfaces. The magic sponge can remove the most stu...5-10 Magic Cleaning Foam Sponge Eraser Stain Remover Melamine Pad Multi Purpose
£2.97Buy it nowFree P&P10+ watching | 38+ soldAre you Looking for High Quality Magic Cleaning Foam Sponge Eraser Stain Remover?. Look no Further! Rinse the dirty sponge with cold water after use and let it dry. Made of eco materials, clean most o...60/80/100PCS Magic Sponge Eraser Cleaning Melamine Multi-functional Foam Cleaner
£4.39Buy it nowFree P&P13+ watching | 38+ soldMade of eco materials, clean most of dust, stain without detergent. Do not sterilize sponge in hot water or detergent. Name: Nano cleaning sponge. Soak sponge in the water, squeeze out water slightly;...10 Pack Magic Cleaning Sponge Melamine Foam Eraser Stain Dirt Remover Pad UK
£2.89Buy it nowFree P&P100 Pack Magic Cleaning Sponge Melamine Foam Eraser Stain Dirt Remover Pad UK
£18.09Buy it nowFree P&PMade of eco materials, clean most of dust, stain without detergent. Can be cut into any sizes for a suitable shape. Rinse the dirty sponge with cold water after use and let it dry. Scrub on stain area...10 Pack Magic Cleaning Sponge Melamine Foam Eraser Stain Dirt Remover Pad UK
£5.98Buy it nowFree P&P15 watching | 140 soldCan be cut into any form for a suitable shape. Removes dirt, stain with water no need for chemicals. Sponge Size: 10 x 6 x 2cm.Magic Melamine Sponge- Foam Eraser Dirt Remover Cleaner Kitchen
£1.24Buy it nowFree P&PMagic Melamine Sponges. Get amazing value with our high quality magic melamine sponges. Ideal for all your cleaning needs, with no need for added chemicals, just water. Use dry for dust.20 Magic Cleaning Foam Sponge Eraser Stain Remover Melamine Pad Multi Purpose UKUK SELLER HIGH QUALITY FAST DISPATCH 1000's Sold
£4.39Buy it nowFree P&P3 watching | 52 soldThe most popular sought after magic sponge! These sponges contain Melamine meaning no cleaning agents are needed, just add water and clean your dirty surfaces. The magic sponge can remove the most stu...100PCS Magic Sponge Eraser Cleaning Melamine Multi-functional Foam Cleaner JE
£3.45Buy it nowFree P&P19+ watching | 68+ sold
Description:.100PCS Magic Sponge Eraser Cleaning Melamine Multi-functional Foam Cleaner Grey#
£3.14Buy it nowFree P&P33 watching | 186 soldCan withstand high temperature of 280 degrees, the material is sponge, you can use the cleaning agent. Made of eco materials, clean most of dust, stain without detergent. Color: Grey. Soak sponge in t...20/50/100x Melamine Foam Magic Sponge Eraser Multi-functional Home Cleaning Pads
£3.78Buy it nowFree P&P17+ watching | 68+ sold20/50/100 X Cleaning Magic Sponge Eraser. Material: Melamine foam Sponge. This magic sponge removes stain or dirt with water. This sponge can be cut into any size for a suitable shape. removes stains ...50PCS BIG MAGIC SPONGE ERASER CLEANING MELAMINE FOAM CLEANER 110X 70 X 30MM £4.68Buy it nowor Best OfferFree P&P56 watching | 400 soldCleaning Magic Sponge Eraser Melamine Cleaner Multi-functional Foam White. 50x Cleaning Magic Sponge Eraser Melamine Cleaner. This magic sponge removes stain or dirt with water.It is a strong multi-fu...100PCS Magic Sponge Eraser Cleaning Melamine Multi-functional Foam Cleaner BMP
£3.55Buy it nowFree P&PFeatures:
Good for clean sink, bathroom, refrig...5 Pack Magic Cleaning Sponge Melamine Foam Eraser Stain Dirt Remover Pad UK
£5.98Buy it nowFree P&P15 watching | 201 soldCan be cut into any form for a suitable shape. Removes dirt, stain with water no need for chemicals. Sponge Size: 10 x 6 x 2cm.See all results
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