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WO2000022031A1 - Film de nylon facilement thermoscellable - Google Patents

Film de nylon facilement thermoscellable Download PDF

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Publication number
WO2000022031A1
WO2000022031A1 PCT/CA1999/000738 CA9900738W WO0022031A1 WO 2000022031 A1 WO2000022031 A1 WO 2000022031A1 CA 9900738 W CA9900738 W CA 9900738W WO 0022031 A1 WO0022031 A1 WO 0022031A1
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WO
WIPO (PCT)
Prior art keywords
weight
film
acid
ethylene
alkyl
Prior art date
Application number
PCT/CA1999/000738
Other languages
English (en)
Inventor
Oliver Harold Vogt
Mario Lutterotti
Natasha Noronha
Original Assignee
Dupont Canada, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dupont Canada, Inc. filed Critical Dupont Canada, Inc.
Priority to CA002346755A priority Critical patent/CA2346755A1/fr
Priority to EP99938086A priority patent/EP1123343A1/fr
Priority to AU52733/99A priority patent/AU5273399A/en
Publication of WO2000022031A1 publication Critical patent/WO2000022031A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to heat sealable polyamide film for single or multiple use packaging in high temperature environment applications.
  • the film may be used in multilayer film structures as the sealant film or as a monolayer film structure. It is particularly useful in circumstances where barrier properties, chemical resistance and heat tolerance are required.
  • the polyamide layer or film provides a relatively inert film that may be used to package a variety of substances.
  • the prior art has proposed the use of nylon in or as the resin of choice for producing film for packaging for use in high temperature environments, in particular bags.
  • nylon has not been found to be suitable for producing heat sealable film on a production scale.
  • the film has not been capable of providing a tough durable seal when sealed to itself, and adhesives and/or solvents have been required to seal it, either by application to the seal interface areas or by the use of an adhesive or tie layer in the film structure.
  • the sealing window has also been quite narrow which meant production was difficult.
  • nylon films can be heat sealed but the heat seal temperature range (seal temperature to burn through temperature) is small. Furthermore, the resultant seal tends to be brittle because the material is heated to its melting point and then cools slowly, resulting in a severe increase in the crystallinity of the base material. For all practical purposes, nylon has not been regarded as being capable of providing a tough durable seal.
  • Dry cleaning methods involve the use of non-aqueous based solvents which remove oily stains and soiling, but are less effective for removing protein based stains and particulates such as clay soils.
  • non-aqueous based solvents usually hydrocarbons may be combined with other substances in order to effect total cleaning of a garment.
  • garments or clothing that are dry cleaned are comprised of wool, silk or blends of such fabrics, or delicate fabrics, or garments of complex or delicate construction that are not easily subjected to aqueous cleaning methods.
  • a typical home dry cleaning system can comprise a substrate or carrier sheet, which contains various cleaning agents contained within a plastic bag.
  • the garments to be cleaned are placed in the plastic bag, together with the substrate or sheet containing the solvents and the like, with the bag being sealed and then placed in a clothes dryer for tumbling at a temperature which will allow the cleaning solvents to penetrate the garments for removal of soiling and staining from, and for refreshment of the garments.
  • the plastic bag or package that is used for this dry cleaning operation must therefore be heat resistant, have barrier properties, be chemically resistant, be tough and durable enough to withstand multiple use applications, and not stick to the dryer surfaces or to itself, and remain integral in use.
  • the patent details the types of cleaning agents used, the substrates that may be employed to contain the cleaning agents, the type of fabric that may be subjected to the dry cleaning process, and the actual method of dry cleaning employing the bag.
  • U.S. Patent No. 5,547,476 issued August 20, 1996 to Siklosi et al the disclosures of which are incorporated herein by reference, there is described a home dry cleaning process.
  • the containment bag is referred to as a flexible bag.
  • the flexible container at col. 6, line 59 to col. 7, line 14 is described.
  • the container should be large enough to contain the fabrics to be cleaned.
  • the container may be manufactured from any economical material such as polyester, polypropylene, and the like, with the proviso that it must not melt if used in contact with a hot air dryer.
  • the walls of the container should be substantially impermeable to water vapour and solvent vapour under the intended use conditions and the package may be sealed by means such as strings or wires or various snap closures.
  • ZIPLOC ® closures and NELCRO ® type closures are proposed, although contact adhesives, adhesive tape, zipper type closures and the like are also proposed.
  • the container can be of any convenient size but should not be so large as to interfere with the operation of the dryer. In particular, it should not be so large as to block any air vents.
  • line 29 further discussion of the bag is found.
  • a nylon film is proposed as the material.
  • the proposal is for using nylon only bags, or core extruded nylon and/or polyester or nylon and/or polyester outer and/or inner layers surrounding a less thermally suitable inner core such as polypropylene. It is also proposed that the bag be constructed using a non-woven outer shell comprising a heat resistant material such as nylon or polyethylene terepthalate and an inner sheet of a polymer which provides a vapour barrier. It is proposed that whatever the bag structure, it must be capable of retaining its integrity under conditions of thermal stress at temperatures up to at least about 204 °C to 260 °C.
  • a heat-sealable polyamide film which may be used in multilayered structures for use in packaging.
  • these polyamides comprise at least one pendant alkyl branch having 1 to 3 carbon atoms within at least two amide linkages along the polymer backbone and at least one sequence of at least seven consecutive carbon atoms, excluding carbon atoms in pendant alkyl branches, if any, within at least two amide linkages along the polymer backbone.
  • LTN low temperature Nylons
  • thermoplastic material having available graft sites, said thermoplastic material being at least one continuous phase of the composition, an ethylene copolymer containing an unsaturated mono-carboxylic acid, and a polymeric grafting agent having reactive groups capable of reacting with the mono-carboxylic acid in the ethylene copolymer and with the available graft sites in the thermoplastic material.
  • thermoplastic material having available graft sites, said thermoplastic material being at least one continuous phase of the composition
  • an ethylene copolymer containing an unsaturated mono-carboxylic acid and a polymeric grafting agent having reactive groups capable of reacting with the mono-carboxylic acid in the ethylene copolymer and with the available graft sites in the thermoplastic material.
  • polymeric grafting agent having reactive groups capable of reacting with the mono-carboxylic acid in the ethylene copolymer and with the available graft sites in the thermoplastic material.
  • toughened multiphase thermoplastic compositions consisting of essentially one phase containing 60 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to 40 percent by weight of at least one other phase containing particles of at least one polymer having a particle size in the range of 0.01 to 3.0 microns and being adhered to the polyamide, the at least one polymer having a tensile modulus in the range of 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix to tensile modulus of said at least one polymer being greater than 10 to 1.
  • the polymer is either branched or straight chain, but the nylon is conventional nylon.
  • the toughened polymer is useful for making molded and extruded parts.
  • PCT Patent Application No. CA97/00200 filed March 24, 1997 in the name of Farkas, the disclosure of which is incorporated herein by reference there is described a heat formable laminating film which is used to produce embossed laminates.
  • the film is formed from a multiphase thermoplastic resin composition which may include low temperature nylon, the presence of which significantly improves heat sealability and formability of the resin formulation. It has now been found that some of the above disclosed formulations have particular utility in producing film for packages that are for use in high temperature environments. However, the films must be produced by modifying the typical production methods in order to control the crystallinity of the film so that it possesses the heat sealability.
  • a film for manufacturing heat sealable packages for use in a high temperature environment wherein the sealant layer or film comprises the following components: i) at least one polyamide resin selected from aliphatic and semi-aromatic polyamides that can be either semi-crystalline or amorphous in structure having a number average molecular weight of at least about 5000, having reactive sites and forming the continuous phase of the composition, wherein the semi- crystalline polyamides have a melting point greater than 200°C; ii) at least one ethylene copolymer, E/X/Y, where E is ethylene and is at least 50 % by weight of E/X/Y, X is from 1-35 % by weight of an acid containing unsaturated mono-carboxylic acid, and Y is 0-49 % by weight of a moiety derived from at least one alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof where the alkyl acrylate, alkyl me
  • A from about 29 to about 54% by weight of component i), from about 8 to about 70% by weight of component ii), and from about 0.8 to about 45% by weight of component iii); B. from about 55 to about 90% by weight of component i), from about 10 to about 45% by weight of components ii) or iv) or mixtures thereof; and C. from about 30 to about 91 % by weight of component i), from about 1.5 to about 70% by weight of component ii), and from about 0.15 to about 45 % by weight of component iii).
  • the present films approach polyethylene films with respect to heat sealability, but their thermal stability is higher than polyolefin films.
  • the heat sealing temperature window and forming window are sufficiently broad to permit their use in many commercial applications.
  • the film for such uses would pass an oven test at 200°C for one hour.
  • the film formulation may include additional optional ingredients selected from flame retardants, heat stabilizers, antioxidants, anti-blocking agents, slip additives, pigments or dyes, processing aids, plasticizers and ultra-violet blocking agents. Of these optional ingredients, most desired are heat stabilizers, antioxidants and flame retardants.
  • the amount of antioxidants, heat stabilizers and mixtures thereof that may be included in the film formulation may range from 0.05 to 5.0% by weight, more preferably, the range is from 0.05 to 2.0% by weight.
  • the flame retardant may comprise from about 1% to about 40% by weight of the total resin composition and is selected preferably from organic halogen based retardants, metal hydroxides, melamine chemistry based retardants, and red phosphorus can also be used in combination with a synergist to enhance flame retardancy.
  • Synergists include antimony trioxide, zinc, borate, zinc stannate and powdered silicone are also preferably present. The selection of the synergist is based on the intended application.
  • the amount of synergist may be about 10%, e.g. 2 parts flame retardant to 1 part synergist. More preferably, the flame retardant comprises from about 5% to about 30% by weight of the total resin composition.
  • an improved method for producing a film wherein the formulation for the resin is as set out above and the resin is extruded and passed through a die to form a film or film layer and the film is optionally subjected to a print treatment, the improvement comprising a) intimately mixing the components of the resin formulation for the film to ensure thorough mixing and uniformity of melt blend; b) subjecting the film as it exits the die to quenching at a temperature as low as 20 °C to solidify the formulation to as low a crystallinity as possible; and c) reheating the solidified film to a temperature of from just above the quench temperature up to about 90 °C to increase its crystal structure in a controlled way in order to stabilize the film.
  • the invention provides a package that may be used in a high temperature environment and is manufactured from a film having the formulation as set out above.
  • the bag is heat sealed to itself along at least one of its sides and has an opening through which product to be packaged may be placed.
  • the film could be produced as a flat web and then formed into a tube by using a lap seal. In this way only the bottom of the bag would be permanently sealed with the top or free end having a resealable closure, if desired, applied thereto.
  • the bag could be made from a flat web that is folded in half on itself, with the side and one end being permanently sealed.
  • the opening of the bag may be sealed in any conventionally known manner. Thus it may be permanently sealed so that the bag requires destruction of the seal to open, or it may be provided with a closure that permits it to be opened and closed any number of times, thus allowing the package to be reused.
  • the package may be sealed by means such as strings or wires or various snap closures. ZIPLOC ® closures and VELCRO ® type closures may be proposed, although contact adhesives, adhesive tape, zipper type closures and the like may also be employed.
  • a single or multiple use heat resistant dry cleaning bag for use in a domestic clothes dryer for a dry cleaning operation, the bag being heat sealed to itself along at least one of its outer edges, and having a reclosable opening for placing items to be dry cleaned in the bag, the bag being formed from a film having a formulation as set forth above, and having barrier properties so as to permit dry cleaning substances to be placed therein and the bag may be tumbled in a domestic dryer for dry cleaning the items.
  • the bag can be of any convenient size but should not be so large as to interfere with the operation of the dryer. In particular, it should not be so large as to block any air vents.
  • the film may be selected from films of suitable thickness such as, for example, 1 to 3 mils thick.
  • suitable thickness such as, for example, 1 to 3 mils thick.
  • the presence of the nylon in the film ensures that the bag has the required vapour and moisture barrier properties and is also chemically resistant to the cleaning substances that may be selected for incorporation into the bag. It is important that the closure have the same properties as the film used in the bag and this must be considered when selecting the type of closure for the bag.
  • the bags can be manufactured using conventional bag manufacturing equipment or such equipment suitably modified.
  • the broadest range encompasses blends of conventional nylon and Zytel ® FN with from 1 to 80% weight conventional nylon.
  • the preferred range encompasses from 10 to 70 % weight of conventional nylon.
  • the most preferred range encompasses from 30 to 60% weight of conventional nylon in the blend.
  • the combination of the three components i) and ii) and iii) is such that the polyamide must be the continuous phase in the formulation. If the polyolefm phase is the continuous phase, then the film will have a low melting point.
  • Figures 1 to 3 illustrate DSC (Differential Scanning Calorimetry) curves for film used to make packages in accordance with the present invention.
  • Figure 4 is a schematic representation of a cast film production line that may be used to manufacture the film of the present invention.
  • the polyamide of component i) embraces those semi-crystalline and amorphous resins having a number average molecular weight of at least 5000 and commonly referred to as nylons.
  • Suitable polyamides include those described in U.S. Patents Nos. 2,071,250; 2,071,251; 2,130,523; 2,130,948; 2,241,322; 2,312,966; 2,512,606; and 3,393,210.
  • the polyamide resin can be produced by condensation of equimolar amounts of an aliphatic or aromatic dicarboxylic acid containing from 4 to 12 carbon atoms with a diamine, in which the diamine contains from 4 to 14 carbon atoms.
  • Excess diamine can be employed to provide an excess of amine end groups over carboxyl end groups in the polyamide.
  • polyamides include poly hexamethylene adipamide (Nylon 66), polyhexamethylene azelaamide (Nylon 69), polyhexamethylene sebacamide (Nylon 610), and polyhexamethylene dodecanoamide (612 Nylon), the polyamide produced by ring opening of lactams, i.e., polycaprolactam, polylauric lactam, poly-11-aminoundecanoic acid, bis ⁇ araaminocyclohexyl) methane dodecanoamide.
  • polyamides prepared by the copolymerization of two of the above polymers or terpolymerization of the above polymers or their components, e.g., 6T/DT, a copolymer of terephthalic acid (T) and 2-methylpentamethylenediamine (D) and hexamethylenediamine (6).
  • the polyamides are semi-crystalline and aliphatic or semi-aromatic with a melting point in excess of 200?C, or they are amorphous.
  • Preferred polyamides include Nylon 6,6, Nylon 6, Nylon 612, Nylon 11, Nylon 12, Nylon 1212, amorphous nylons, Nylon 6/6,6 copolymers.
  • Suitable ethylene copolymers include ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methyaorylic acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylaic acid/n- butyl methacrylate, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/ethyl vinyl ether, ethylene/methacrylic acid/butyl vinyl ether ethylene/acrylic acid/-methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate, ethylene/acrylic acid/n
  • Preferred ethylene copolymers that contain a monocarboxylic acid moiety for use in the compositions of the present invention include ethylene/methacrylic acid, ethylene/acrylic acid, ethylene/methacrylic acid/n-butyl acrylate, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methylacrylate and ethylene/acrylic acid/methylacrylate copolymers.
  • the most preferred ethylene copolymers for use in the compositions of the present invention are ethylene/methacrylic acid, ethylene/acrylic acid copolymers, ethylene/methacrylic acid/n-butyl acrylate and ethylene/methacrylic acid/methylacrylate terpolymers.
  • Surlyn® is an example of a suitable commercially available product. Zinc- neutralized Surlyn® is preferred for nylon over sodium-neutralized Surlyn®. COMPONENT iii)
  • polymeric grafting agents include ethylene copolymers copolymerized with monomers containing one or more reactive moieties said monomers selected from unsaturated epoxides of 4-11 carbon atoms, such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, and glycidyl itaconate, unsaturated isocyanates of 2-11 carbon atoms, such as vinyl isocyanate and isocyanato-ethyl methylacrylate, aziridine and monomers containing, silanes such as alkoxy or alkyl silanes, alkylating agents such as alkyl halides, or alpha-halo ketones or aldehydes or oxazoline, and the polymeric grafting agent may additionally contain an alkyl acrylate, alkyl methacrylate, carbon monoxide, sulfur dioxide and/or alkyl vinyl ether, where the al
  • Preferred polymeric grafting agents for use in the compositions of the present invention include ethylene/glycidyl acrylate, ethylene/n-butyl acrylate/glycidyl acrylate, ethylene/methylacrylate/glycidyl acrylate, ethylene/glycidyl methacrylate, ethylene/n-butyl acrylate/glycidyl methacrylate and ethylene/methylacrylate/glycidyl methacrylate copolymers.
  • the most preferred grafting agents for use in the compositions of the present invention are copolymers derived from ethylene/n-butyl acrylate/glycidyl methacrylate and ethylene/glycidyl methacrylate.
  • level of reactive component e.g. glycidyl methacrylate will affect the degree of crosslinking with the nylon, and may be adjusted appropriately to the desired level as known by those skilled in the art.
  • the graft monomers, and mixtures thereof, used to prepare the graft polymers can be selected from the group consisting of ethylenically unsaturated acidic monomers or their derivatives including acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 5-norbornene-2,3- dicarboxylic acid, maleic anhydride, monosodium maleate, disodium maleate, itaconic anhydride, citraconic anhydride, monomethyl fumarate and monomethyl maleate.
  • ethylenically unsaturated acidic monomers or their derivatives including acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 5-norbornene-2,3- dicarboxylic acid, maleic anhydride, monosodium maleate, disodium maleate, itaconic anhydride, citraconic anhydride, monomethyl fumarate and monomethyl maleate.
  • the graft monomers can be selected from ethylenically unsaturated monomers containing amino or hydroxy functional groups including vinyl pyridines, vinyl silanes, 4- vinyl pyridine, vinyltriethoxysilane and allyl alcohol.
  • the grafting monomers, and mixtures thereof, can be present in the graft polymer in an amount of from 0.05 to 5% wt. and would be grafted onto a C 2 -C 20 polyolefm including polyethylene, polypropylene, ethylene propylene diene terpolymer, as well as copolymers of ethylene with, but not limited to, vinyl acetate, carbon monoxide, or ethylenically unsaturated carboxylic acids or esters thereof.
  • This component acts as an alternative toughener in the formulation.
  • Grafted polyethylene, grafted polypropylene, and grafted rubber may be used as noted earlier, and these may be used in combination with non-grafted polyethylenes, polypropylenes and rubbers.
  • This component may be used interchangeably with component ii) in Formulation B.
  • the heat-sealable polyamide film may be formed by a cast film process or by a blown film process. Both types of film processes are known in the art of manufacture of polyamide films.
  • the film may be a monolayer film or a multilayer film, the film being for example an extrusion coated, a coextruded film or a laminate. Either the monolayer film or the coextruded film may be in an unoriented condition, in the form of monoaxially oriented film or in the form of biaxially oriented film.
  • the polyamide resins described herein may also be coextruded or laminated with polyolefins or grafted polyolefm, particularly polyethylene, grafted polyethylene or grafted polypropylene, especially using tie or adhesive layers between the polyamide and polyolefm.
  • the heat-sealable polyamide films may be laminated to polyolefins or other barrier polymers using conventional processes.
  • the heat-sealable polyamides may be coated with poly vinylene dichloride (PVDC), EVOH, PVOH or other suitable barrier coatings and then laminated to itself to form a higher barrier heat-sealable structure.
  • compositions of the present invention may be treated with a corona discharge (ED) in order to improve the properties of the resins with respect to bonding of coatings, inks, adhesives or the like.
  • ED corona discharge
  • the additives such as, but not limited to, moisturizing agents, heat stabilizers, flame retardants, fillers, anti-blocking agents, slip additives, pigments or dyes, processing aids, anti-oxidants, plasticizers or ultra violet blocking agents may be melt blended with each other under high shear.
  • the various ingredients may first be combined with one another in what is commonly referred to as a "salt and pepper" blend, i.e., a pellet blend, of each of the ingredients, or they may be combined with one another via simultaneous or separate metering of the various components, or they may be divided and blended in one or more passes into one or more sections of mixing equipment such as an extruder, Banbury, Buess Kneader, Ferrell continuous mixer, or other mixing equipment.
  • mixing equipment such as an extruder, Banbury, Buess Kneader, Ferrell continuous mixer, or other mixing equipment.
  • the thermoplastic and polymeric grafting component be combined first, then the acid-containing copolymer be added downstream.
  • thermoplastic, component i) is at least one of the continuous phases in all of the compositions of the present invention even though the thermoplastic, component i) comprises less, and in fact, in some cases substantially less than 50 volume %.
  • the films were made from a ZytelTM FN727 resin and a Nylon 6 resin mixture in the following combinations:
  • Film #1 60% / 40% ZytelTM FN727 resin / Nylon 6 resin mixture
  • Film #2 70% / 30% ZytelTM FN727 resin / Nylon 6 resin mixture
  • Film #3 50% / 50% ZytelTM FN727 resin / Nylon 6 resin mixture
  • Film #4 40% / 60% ZytelTM FN727 resin / Nylon 6 resin mixture
  • Film #5 50% / 50% with 9% by weight flame retardant mix (6% BPS and 3 % antimony trioxide)
  • Film #6 50% / 50% with 18% flame retardant mix 12% by weight BPS* and 6% by weight Antimony Trioxide (flame retardant mix)
  • BPS is brominated polystyrene flame retardant.
  • a commercial example is FERRO PYROCHEKTM 68PB.
  • the antimony trioxide is AMPSEC.
  • ZytelTM FN727 is a DuPont toughened heat stabilized Nylon 6 based resin.
  • the DSC results shown in the accompanying Figures 1 to 3 are for the film of Sample Film #4.
  • a cast filmline shown generally at 1 that represents the preferred method for producing the film la of the invention.
  • the cast film line comprises a twin screw compounding extruder 12 which achieves an intimate mixture of recipe components delivered to the extruder 12 from hopper 10 and feeder 11. This intimate mixing can be achieved in other ways usually involving separate steps, which can be more costly and time corisuming.
  • a melt pump 12a Next is a melt pump 12a, a filter 13, a die 14, an ultra low temperature quench roll 15 which helps to achieve the desired amorphous structure.
  • the annealing roll 16 follows, to heat treat the film la to control the level of crystallinity.
  • the final quench roll 17 reduces the film temperature to room temperature for final windup on winder 33.
  • Slit device 20 allows the film to be edge trimmed to a suitable width or slit as required.
  • Pull roll 31 maintains tension, through the line prior to final windup, after which the cross web Beta Gauging System 18 provides the data for cross web die profile correction.
  • the steam cabinet 19 provides an optional process to stabilize moisture content in the film.
  • the high energy corona print treatment 29 makes the film more receptive to printing inks and laminating adhesives.
  • the resin recipe of the present invention inhibits crystal growth and in combination with the film process forms a film with a low initial crystallinity.
  • the resulting film heat seals easily and makes a tough, strong and durable heat seal that allows production of a bag for use in high temperature environments.
  • Tables IV and N are included to provide some comparison between the properties of the films of the present invention and standard polyamide films such as Nylon 6 and Nylon 6,6.
  • DSC method is not an ASTM method. Heat sample from room temperature to 290 °C isothermally for 5 minutes. Cool down sample to room temperature at a ramp rate of 10°C/minute. Then hold the sample at room temperature for 5 minutes. Then increase temperamre again up to 290 °C at same ramp rate. This provides data for DSC.
  • Table VI sets out the data that is plotted in Figures 1 to 3. Each sample has 3 data curves
  • the very first thing to notice about the data is that the melting energy per unit weight for pure nylon 6 and pure nylon 6,6 is very much larger than for the Film Samples (#1 through #7) of the present invention.
  • the pure nylon films do not heat seal well because of their inherent crystallinity and brittleness.
  • the two parameters that can be controlled on this tester are the “Dwell Time” (i.e. the amount of time the electric impulse is applied to the material) and the amount of “Heat” (electric impulse) applied.
  • the Vertrod Sealer both parameters are controlled by way of calibrated knobs and in our test the knobs were set at predetermined values and each sample sealed at those conditions.
  • the essence of the method of the present invention resides in the following steps of the method:
  • the 3 roll process with the annealing roll is unique in the cast film industry.
  • the annealing temperature is used in combination with the cast temperature to achieve the unique physical properties of the film of the invention.
  • the formulation for the film comprises a total polyamide component of Nylon 6 that may range from about 70 to about 95 % by weight, more preferably 80 to 90% by weight.
  • the ethylene copolymer may comprise from about 7.5% to about 20% by weight, more preferably about 3.75% to about 15% by weight.
  • the polymeric grafting component may comprise from about 1.25% to about 10% by weight, more preferably about 2.5% to about 5.0% by weight.

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Abstract

L'invention concerne un film destiné à la fabrication d'emballages thermoscellables à applications uni ou pluriservice dans un environnement haute température. La couche ou le film de scellement comprend les composants ci-après : i) au moins une résine polyamide choisie parmi des polyamides aliphatiques et semi-aromatiques, ayant une structure semi-cristalline ou amorphe, un poids moléculaire moyen d'au moins 5000 environ, et des sites de greffage, et formant la phase continue de la composition, lesdits polyamides semi-cristallins ayant un point de fusion supérieur à 200 °C; ii) au moins un copolymère d'éthylène, E/X/Y, où E représente éthylène et au moins 50 % en poids de E/X/Y, X représente de 1 à 35 % en poids d'un acide renfermant un acide mono-carboxylique insaturé, et Y représente de 0 à 49 % en poids d'une fraction provenant d'au moins un alkyl-acrylate, un alkyl-méthacrylate, un alkyl-vinyl-éther, un monoxyde de carbone, du dioxyde de soufre, ou de mélanges de ces produits, le groupe alkyle contenant de 1 à 12 atomes de carbone, et les groupes acides de la fraction contenant l'acide étant neutralisés par 0-100 % en poids d'un ion métal; iii) au moins un agent polymère de greffage renfermant des groupes réactifs choisis parmi l'un au moins des groupes ci-après, à savoir epoxides, isocyanates, aziridines, silanes, halogénures d'alkyle, alpha-halo cétones et aldéhydes, ou oxazoline, lequel réagit avec les fractions contenant l'acide du composant ii) et réagit, en outre, avec les sites de greffage du composant i), et iv) au moins une polyoléfine en C2-C20 sélectionnée dans le groupe constitué de polyéthylène, de polypropylène, d'un terpolymère diénique d'éthylène propylène, des copolymères d'éthylène à acétate de vinyle, de monoxyde de carbone, ou d'acides ou d'esters carboxyliques éthyléniquement insaturés de ces composés, sur lesquels sont greffés de 0,05 à 5 % en poids environ de monomères ou de mélanges de monomères sélectionnés dans le groupe constitué de monomères acides éthyléniquement insaturés ou leurs dérivés, à condition qu'un retardateur de flamme soit toujours présent.
PCT/CA1999/000738 1998-10-09 1999-08-10 Film de nylon facilement thermoscellable WO2000022031A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002346755A CA2346755A1 (fr) 1998-10-09 1999-08-10 Film de nylon facilement thermoscellable
EP99938086A EP1123343A1 (fr) 1998-10-09 1999-08-10 Film de nylon facilement thermoscellable
AU52733/99A AU5273399A (en) 1998-10-09 1999-08-10 Easily heat sealable nylon film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10383598P 1998-10-09 1998-10-09
US60/103,835 1998-10-09

Publications (1)

Publication Number Publication Date
WO2000022031A1 true WO2000022031A1 (fr) 2000-04-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1999/000738 WO2000022031A1 (fr) 1998-10-09 1999-08-10 Film de nylon facilement thermoscellable

Country Status (4)

Country Link
EP (1) EP1123343A1 (fr)
AU (1) AU5273399A (fr)
CA (1) CA2346755A1 (fr)
WO (1) WO2000022031A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1170334A2 (fr) * 2000-06-23 2002-01-09 Degussa AG Composition à base de polyamide résistante aux chocs à basse température
SG103879A1 (en) * 1998-02-04 2004-05-26 Solvay Advanced Polymers Llc Flame retardant anti-drip polyamide compositions
WO2012082290A1 (fr) * 2010-12-13 2012-06-21 3M Innovative Properties Company Mélanges de copolymère greffé et de polyamide
US8476360B2 (en) 2002-08-12 2013-07-02 Exxonmobil Chemical Patents Inc. Calendered films of plasticized blends of plastomer and impact copolymer
US20190241335A1 (en) * 2018-02-05 2019-08-08 Flexopack S.A. Ovenable thermoforming film
US20220259431A1 (en) * 2019-08-28 2022-08-18 Toyobo Co., Ltd. Gas-barrier polyamide film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778990B (zh) * 2021-02-05 2022-06-03 西南石油大学 一种用于油田注水井的污水混配暂堵剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299744A (en) * 1980-06-06 1981-11-10 American Hoechst Corporation High impact polyamides
WO1988003543A1 (fr) * 1986-11-14 1988-05-19 E.I. Du Pont De Nemours And Company Compositions thermoplastiques partiellement greffees
US5175210A (en) * 1991-06-14 1992-12-29 Shell Oil Company Polymer blends
WO1997035910A1 (fr) * 1996-03-25 1997-10-02 Dupont Canada Inc. Formulations polyamides pour stratifies gaufres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299744A (en) * 1980-06-06 1981-11-10 American Hoechst Corporation High impact polyamides
WO1988003543A1 (fr) * 1986-11-14 1988-05-19 E.I. Du Pont De Nemours And Company Compositions thermoplastiques partiellement greffees
US5175210A (en) * 1991-06-14 1992-12-29 Shell Oil Company Polymer blends
WO1997035910A1 (fr) * 1996-03-25 1997-10-02 Dupont Canada Inc. Formulations polyamides pour stratifies gaufres

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG103879A1 (en) * 1998-02-04 2004-05-26 Solvay Advanced Polymers Llc Flame retardant anti-drip polyamide compositions
EP1170334A2 (fr) * 2000-06-23 2002-01-09 Degussa AG Composition à base de polyamide résistante aux chocs à basse température
EP1170334A3 (fr) * 2000-06-23 2003-01-29 Degussa AG Composition à base de polyamide résistante aux chocs à basse température
US6579581B2 (en) 2000-06-23 2003-06-17 Degussa Ag Polymer blend having good low-temperature impact strength
KR100843503B1 (ko) * 2000-06-23 2008-07-04 데구사 게엠베하 저온 충격 강도가 우수한 성형 조성물
US8476360B2 (en) 2002-08-12 2013-07-02 Exxonmobil Chemical Patents Inc. Calendered films of plasticized blends of plastomer and impact copolymer
WO2012082290A1 (fr) * 2010-12-13 2012-06-21 3M Innovative Properties Company Mélanges de copolymère greffé et de polyamide
US8975342B2 (en) 2010-12-13 2015-03-10 3M Innovative Properties Company Blends of grafted copolymer and polyamide
KR101772730B1 (ko) 2010-12-13 2017-08-29 쓰리엠 이노베이티브 프로퍼티즈 컴파니 그래프팅된 공중합체와 폴리아미드의 블렌드
US20190241335A1 (en) * 2018-02-05 2019-08-08 Flexopack S.A. Ovenable thermoforming film
US20220259431A1 (en) * 2019-08-28 2022-08-18 Toyobo Co., Ltd. Gas-barrier polyamide film

Also Published As

Publication number Publication date
EP1123343A1 (fr) 2001-08-16
CA2346755A1 (fr) 2000-04-20
AU5273399A (en) 2000-05-01

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