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WO1997035910A1 - Formulations polyamides pour stratifies gaufres - Google Patents

Formulations polyamides pour stratifies gaufres Download PDF

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Publication number
WO1997035910A1
WO1997035910A1 PCT/CA1997/000200 CA9700200W WO9735910A1 WO 1997035910 A1 WO1997035910 A1 WO 1997035910A1 CA 9700200 W CA9700200 W CA 9700200W WO 9735910 A1 WO9735910 A1 WO 9735910A1
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WIPO (PCT)
Prior art keywords
weight
component
acid
alkyl
percent
Prior art date
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PCT/CA1997/000200
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English (en)
Inventor
Nicholas Farkas
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Dupont Canada Inc.
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Application filed by Dupont Canada Inc. filed Critical Dupont Canada Inc.
Priority to AU20202/97A priority Critical patent/AU2020297A/en
Publication of WO1997035910A1 publication Critical patent/WO1997035910A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/28—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer comprising a deformed thin sheet, i.e. the layer having its entire thickness deformed out of the plane, e.g. corrugated, crumpled
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2377/00—Polyamides
    • 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 and formable polyamide films with high temperature thermal stability. These properties permit the films to be used in monolayer structures, such as embossed laminates for high temperature insulating or cushioning applications.
  • a number of film formulations are described, and some of these are novel resin formulations.
  • BACKGROUND OF THE INVENTION Industry is always seeking new packaging and insulating materials that are cheaper and lighter and offer unique properties.
  • a particular concern is the need for insulating materials that may be used in high temperature applications such as in heat shielding vehicle interiors when accidents or engine failures produce unsafe high temperature conditions which may be harmful to vehicle occupants at worst, or at best damaging to the interiors of such vehicles.
  • 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
  • polymer backbone Specifically, they are referred to as low temperature Nylons (LTN).
  • Typical polyamides such as Nylon 6 and Nylon 66, do not possess an adequate combination of thermal stability, formability and heat-sealabitity for commercially making embossed laminated structures This is especially true when these polymers are first made into film, and then fed to an embossing and laminating process SUMMARY OF THE INVENTION
  • the basic formulation covered by the Saltman patent possesses the right combination of high temperature thermal stability, formability and heat stability to permit the manufacture of resins and films for use in the heat shielding applications described previously
  • the addition of LTN significantly improves heat sealabi ty and formability of the formulation
  • Other embodiments of the formulation include elimination of the polymeric grafting agent, the addition of other tougheners, and increased levels of the conventional polyamides as claimed in the Saltman patent
  • the invention provides a variety of formulations, based on the basic Saltman formulation which exhibit properties which make the resultant resins and films useful in the types of applications envisaged earlier. Uses of the present formulations may extend to packaging and cushioning applications where high temperature properties are desirable, for example in stoves, furnaces, aircraft and so forth.
  • 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.
  • One important such application is in bubble pack structures for heat-shielding applications in automobiles, as noted.
  • the film for such use would pass an oven test at 200°C for one hour.
  • the present invention provides a heat formable laminating film made from a multi-phase thermoplastic resin composition
  • a multi-phase thermoplastic resin composition comprising the following main 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 graft 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 polyamide resin comprising 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, the melting point of the polyamide being less than 200°C, having graft sites and also forming the , wherein the semi-crystalline polyamide
  • component i from about 29 to about 54% by weight of component i), from about 8 to about 70% by weight of component iii), and from about 0.8 to about 45% by weight of component iv);
  • component B from about 17 to about 54% by weight of component i), from about 1 to about 40% by weight of component ii), from about 5 to about 69% by weight of component iii), and from about 0.5 to about 45% by weight of component iv); such that the sum of components i) and ii) equals from about 29 to about 72% by weight;
  • component i from about 55 to about 90% by weight of component i), from about 10 to about 45% by weight of components iii) or v) or mixtures thereof;
  • component i from about 15 to about 89% by weight of component i), from about 1 to about 40% by weight of component ii), from about 10 to about 45% by weight of component iii) or v) or mixtures thereof; and such that the sum of components i) and ii) equals from about 55 to about 90% by weight;
  • component i E. from about 30 to about 91 % by weight of component i), from about 1.5 to about 70% by weight of component iii), and from about 0 15 to about 45% by weight of component
  • a novel multi-phase resin composition comprising as the mam components from about 17 to about 54% by weight of (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 graft sites and forming the continuous phase of the composition, wherein the semi-crystalline polyamides have a melting point greater than 200°C, from about 1 to about 40 % by weight of (n) at least one polyamide resin comprising 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, the melting point of the polyamide being less than 200°C, having graft sites and also forming the continuous phase of the composition, and with the
  • Yet another embodiment is directed to a novel multi-phase resin composition
  • a novel multi-phase resin composition comprising as the main components: from about 15 to about 89% by weight of (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 graft sites and forming the continuous phase of the composition, wherein the semi-crystalline polyamides have a melting point greater than 200°C; from about 1 to about 40 % by weight of (ii) at least one polyamide resin comprising 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, the melting point of the polyamide being less than 200°C, having graft sites and also forming the
  • the ends balance of the low temperature nylon has been found to affect the processing and properties of the final film product.
  • low temperature nylon, specifically D12, with balanced or carboxyl rich ends in the formulation reduces filter pressure drops and melt viscosities during film production, and improves film dimensional stability during heating - compared to the incorporation of D12 having amine-rich ends.
  • a most preferred form of the present formulation comprises from about 17 to about 54% by weight, more preferably, from about 18 to about 47% by weight, and most preferably, from about 19 to about 40% by weight of Nylon 6 (component i); from about 1 to about 40% by weight, more preferably about 10 to about 40% by weight; most preferably from about 20 to about 40% by weight of Nylon D12 (low temperature nylon), (component ii); from about 5 to about 69%, more preferably from about 1 1 to about 58% by weight, and most preferably from about 15 to about 48% by weight of ethylene E/X/Y (component iii); from about 0.5 to about 45% by weight, more preferably from about 2 to about 28%, most preferably from about 3 to about 16% by weight of EBAGMA (component iv); with the total amount of nylon ranging preferably from about 29 to about 72% by weight, more preferably from about 38 to about 71 % by weight, and most preferably from about 45 to about 70% by weight.
  • component i
  • the formulation B comprises from about 55 to about 80% by weight of components (i) and (ii), with the nylon component always in the majority (the SURLYN ® and EBAGMA components are in the minority), but component (i) may range from about 20 to about 60% by weight, and component (ii) may range from about 10 to about 35% by weight.
  • the formulations disclosed herein may include antioxidants, heat stabilizers or mixtures thereof. Typically these comprise from about 0.05 to about 5.0% by weight, preferably from about 0.05 to about 2.0% by weight.
  • Organic heat stabilizers have been found to be better than the metal halide heat stabilizers, such as Cul/KI, in terms of retention of film physical properties after oven aging for one hour at 200°C.
  • Irganox ® 1010/1098 is a preferred example of such a material. This substance also reduces filter pluggage and reduces pressure during the production of the film.
  • Other optional ingredients may be selected from flame retardants, anti-blocking agents, slip additives, pigments or dyes, processing aids, plasticizers and ultra-violet blocking agents. These may be used in suitable quantities as are well known to those skilled in the art.
  • the invention also provides an embossed laminate formed from the above multi-phase composition. It comprises an embossed layer of the composition heat sealed to an unembossed layer of the same or similar composition.
  • the invention provides a high temperature heat shield assembly comprising at least one layer of embossed laminate as described above, having adhered thereto at least one layer of a reflective material.
  • the assembly may comprise a plurality of layers arranged in suitable sequence to produce a heat shield effect, with at least one reflective layer as an exterior layer and at least one embossed laminate layer as an interior layer.
  • the layers of such an assembly are usually adhered by means of suitable high temperature adhesives, well known to those skilled in the art.
  • cushioning and protective assemblies may be constructed in a similar fashion to the heat shielding assemblies described above.
  • the invention provides a method for producing a heat formed, flexible, thermoplastic, embossed laminate, wherein a resin is formed by blending the components of one of the formulations described above, and the resin is extruded, passed through a die and immediately into an embossing and laminating process.
  • the invention provides a method for producing a heat formed, flexible, thermoplastic, embossed laminate, wherein a resin is formed by blending the components of one of the formulations described above, and the resin is extruded and passed though a die to form a film or sheet or layer which is subsequently subjected to an embossing and laminating process.
  • the embossed laminate is manufactured in accordance with known methods and equipment for manufacturing such materials.
  • An example of both a suitable method and apparatus is described in Fielding U.S. Patent No. 3,586,565 issued June 22, 1971 , the disclosure of which is hereby incorporated by reference.
  • the bosses or cells are generally closed to provide insulating value and may be of any suitable shape, with bubbles, diamonds, squares and the like being examples of typical shapes.
  • a typical insulating structure for use in a heat shield application, such as in motor vehicles comprises at least one layer of the present embossed laminate adhered to at least one layer of a reflective layer.
  • the reflective layer may be selected from any number of materials suitable for this purpose. Examples include metal foil and sheet metal. Alternatively, thin metal layers may be applied to the film surface by standard metallization techniques such as vacuum deposition.
  • the structure may comprise at least one embossed laminate film layer as described above and at least one layer selected from wood, paper, and synthetic plastics.
  • the film used to make the laminate of this invention is typically from about 1 to about 4 mils thick.
  • the reflective layer is typically about 3 mils.
  • the films, sheets, layers of the formulations of this invention may range in thickness from about 1 to about 20 mils, preferably from about 0.5 to about 10 mils, and most preferably about 1 to about 4 mils thick (the last as stated above). It is also possible to replace one of the outer metal layers with a non-reflective layer, such as paper, wood, synthetic plastics material or any other suitable material.
  • Component Broadest Formulation Preferred Formulation Most Preferred Ranges % By Weight Ranges % By weight Formulation Ranges Based on Total of Main Based on Total of Main % By Weight Based on Components Components Total of Main About prefaces each About prefaces each Components Number Number About prefaces each Number
  • Component 1-40 a 5-35 b 10-30 c
  • Component v (a grafted polyolefin), or mixtures thereof
  • Component Broadest Formulation Preferred Formulation Most Preferred Ranges % By Weight Ranges % By weight Formulation Ranges Based on Total of Main Based on Total of Main % By Weight Based Components Components on Total of Main About prefaces each About prefaces each Components Number Number About prefaces each Number
  • 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 Examples of polyamides include polyhexamethylene adipamide (Nylon 66), polyhexamethylene azelaamide (Nylon 69), polyhexamethylene sebacamide (N
  • Nylon 1 1 Nylon 12
  • Nylon 1212 amorphous nylons
  • Most preferred polyamides include Nylon 66, Nylon 612 and
  • Nylon 6 Nylon 6 It is to be understood that this component may comprise blends of two or more nylons COMPONENT ii)
  • the polyamides used in component ii) are best described as low temperature polyamides. Typically, they are prepared from
  • At least one alpha, omega aminocarboxylic acid having the formula of H 2 N-R(1 )-COOH, in which R(1 ) is an aliphatic moiety having at least six methylene groups and at least one pendant alkyl branch having 1 to 3 carbon atoms, or
  • diamines examples include 1 ,6 hexamethylene diamine; 1 ,8 octamethylene diamine; 1 ,10 decamethylene diamine and 1 ,12- dodecamethylene diamine.
  • examples of a branched diamine include 2-methyl-pentamethylene diamine, but other branched diamines having C1-C3 alkyl branches may be used.
  • dicarboxylic acids examples include 1 ,6-hexanedioic acid (adipic acid); 1 ,7-heptanedioic acid (pimelic acid); 1 ,8-octanedioic acid (suberic acid); 1 ,9-nonanedioic acid (azelaic acid); 1 ,10-decanedioic acid (sebacic acid) and 1 ,12-dodecanedioic acid.
  • branched dicarboxylic acids examples include 2-methyl glutaric acid, but other branched dicarboxylic acids having C1-C 3 alkyl branches may be used.
  • D12 is a homopolymer of 2-methylpentamethylene diamine and dodecanedioic acid.
  • the copolymer of D12/612 is a copolymer of 2- methylpentamethylene diamine, hexamethylene diamine and dodecanedioic acid. These represent preferred nylon choices.
  • alpha, omega amino carboxylic acids are aminocaproic acid, amino octanoic acid, amino decanoic acid, amino undecanoic acid and aminododecanoic acid. It should be noted that the aminocarboxylic acid may be in the form of a lactam, especially when the aliphatic moiety has six methylene groups.
  • Examples of branched alpha, omega amino carboxylic acids are 2-methyl-amino dodecanoic acid and 2-methyl-amino decanoic acid although others may be used.
  • nitriles examples include 1 ,5 aminocapronitrile, adiponitrile, 1 ,11 -amino undecanonitrile, 1 ,10-am ⁇ no decanodinitriie and 2-methyl- 1 ,11 -amino undecanonitrile although others may be used.
  • monomers (a)-(c) listed herein may be used to prepare the polyamides of the present invention.
  • these other monomers include, but are not limited to, aromatic dicarboxylic acids, aromatic diamines, alicyclic dicarboxylic acids, and alicyclic diamines.
  • aromatic dicarboxylic acids include terephthalic and isophthalic acids.
  • An example of an alicyclic dicarboxylic acid is 1 ,4-bismethylene cyclohexyl dicarboxylic acid.
  • An example of an alicyclic diamine is 1 ,4-bismethylene diamino cyclohexane.
  • the polyamides of the present invention can be semi-crystalline or amorphous.
  • the polyamide is semi-crystalline, it is desirable that such polyamide exhibit a melting point less than 200°C and a broad melting profile, which is herein defined as the range of temperature from the onset of the melting curve in a differential scanning calorimetry (DSC) test to the maximum melting peak that is measured, of greater than about 45°C.
  • the polyamides may be manufactured using processes well known in the art.
  • the polyamides may be polymerized from salts of the diamine and dicarboxylic acid.
  • the polyamides may be polymerized using the corresponding nitriles, as discussed above.
  • the polyamide may be in the form of a homopolymer polymerized from one diamine and one dicarboxylic acid, an aminocarboxylic acid, an amino alkyl nitrile, or one diamine and a dinitrile.
  • the polyamide may be a copolymer polymerized from at least one diamine with more than one dicarboxylic acid or at least one dicarboxylic acid with more than one diamine or a combination of at least one diamine, at least one dicarboxylic acid and at least one aminocarboxylic acid, optionally containing nitriles.
  • the copolymer preferably contains at least about 20 mole percent of branched moieties, more preferably at least about 30 mole percent and most preferably at least about 50 mole percent of branched moieties, based on the total amount of the aliphatic moieties in the polyamide.
  • the polyamide when semi-crystalline, has a melting point of less than 200°C, more preferably between about 120°C to about 180°C, and most preferably between about 140°C to about 180°C. It is also preferred that the polyamide has a broad melting profile of greater than about 45°C, preferably greater than about 50°C, and most preferably greater than about 55°C.
  • 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- butyl methacrylate, ethylene/methacrylic acid/ethyl vinyl ether and ethylene/acrylic acid/butyl
  • 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®.
  • These 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
  • 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.
  • the 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.
  • COMPONENT V 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.
  • 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 polyolefin 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 iii) in Formulations C and D as noted before in this disclosure.
  • 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 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.
  • polyamide films will depend on several factors including, but not limited to, extruder hold-up time and screw design, melt processing temperature, quenching rate and degree of quenching, film thickness, the amount of and type of additional components, as well as the amount of and type of the particular polyamide as described herein.
  • the polyamide resins described herein may also be coextruded or laminated with polyolefins or grafted polyolefin, particularly polyethylene, grafted polyethylene or grafted polypropylene, especially using tie or adhesive layers between the polyamide and polyolefin.
  • 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 polyvinylene dichloride (PVDC), EVOH, PVOH or other suitable barrier coatings and then laminated to itself to form a higher barrier heat-sealable structure.
  • PVDC polyvinylene dichloride
  • 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 resins may contain 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.
  • 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.
  • the components described above are 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 i.e., component i)., optionally also ii).
  • thermoplastic, component i., optionally ii). is at least one of the continuous phases in all of the compositions of the present invention even though the thermoplastic, component i)., optionally ii)., comprises less, and in fact, in many cases substantially less than 50 volume %.
  • polyamides (a) and (b) forms one phase, so the combined polyamide phase should be preferred as the continuous phase.
  • a metal perforated plate was installed on the surface of the skin- packaging base, allowing the vacuum holes to pull heated film into these perforations.
  • the perforated metal sheet is 45.7 cm (18 inches) by 30.5 cm (12 inches) by 0.48 cm (3/16 inches) deep.
  • the holes are 0.95 cm (3/8 inches) in diameter, and are staggered at 60 degree angles.
  • the holes are spaced 1.43 cm (9/16 inch) apart, center to center.
  • the three variable cycle settings on the Packsafe machine are the "preheat”, "heat-hold” and “vacuum” cycles
  • the film is placed in a moveable frame and raised to about 6 35 cm (2 5 inches) away from a series of overhead IR heaters During the period known as the s "preheat” , the film is heated by IR wires for a given period of time Then the cage is lowered onto the perforated plate as vacuum is being drawn through the holes in the perforated plate This period is known as the "heat-hold” Finally, the heated film is pulled into the holes in the perforated plate by the applied vacuum for a given period of time (IR heaters now turned off) called the "vacuum cycle"
  • the amount of vacuum drawn through the holes in the perforated plate can also be altered, going from about 20 mm Hg up to 140 mm Hg
  • the ability of the film to form bubbles is rated on a scale of 0 to 4.
  • the heat seals were obtained using a Se ⁇ tinal Model 12 ASL/1 heat sealer, using the following conditions
  • thermocouple embedded in the upper jaw The temperature during heat-sealing was measured by the thermocouple embedded in the upper jaw, and thus is referred to as
  • Thermal stability is measured by placing the film under test in a hot-air oven, and heating the film for one hour at 200 deg C. A visual and manual inspection of the film was done after the oven heating to see if the film had melting or become embrittled.
  • EXAMPLE 1 Pellets of Zytel FN® 726 were melt extruded in a 2.54 cm Killion single screw extruder, having an L/D of 24: 1 , at a melt processing temperature of 233 to 239 deg C using a 120/60/80 mesh filter pack.
  • the extrudate was extruded through a 5 cm diameter spiral blown film die having a die gap of 0.076 cm (30 mils). Bubble formability, heat-sealability and thermal stability tests were conducted on these films. In addition, a commercially available
  • Salt and Pepper blends (a dry pellet mixture) of various compositions were melt extruded in a 2.0 cm Welding Engineers twin- screw extruder, with non-intermeshing, counter-rotating screws, having an IJD of about 60.
  • the melt was processed at either 240 deg C, 260 C or 280 deg C using a 125 micron filter screen. A vacuum was applied to the vent port.
  • the melt was extruded through a 15 cm flat film die having a die gap of 0.064 cm (25 mils).
  • the extrudate was quenched on a chill roll set at a temperature of 30 deg C to form a film having a thickness of about 51 microns.
  • Bubble formability, heat- sealability and thermal stability tests were conducted on these films, in addition, comparison films made from Nylon 6 (BASF BS700A Nylon 6, with 50 RV) and Nylon 66 (50 RV in formic acid) were made.
  • Nylon 6 BASF BS700A Nylon 6, with 50 RV
  • Nylon 66 50 RV in formic acid
  • the following blends as set out in Table VIII were made into film:
  • Blend D Nylon 6//g-PE//Surlyn* 9320 (60/ 5//35 ratio)
  • Blend E Nylon 6//g-PE//Surlyn'* 9520 (60//5/ 35 ratio)
  • Blend F Nylon 6//Surlyn'" 9520 (60//40 blend ratio)
  • the Zytel FN ® 727 and Blend D contain anti-oxidants and are heat-stabilized. However, none of the other components have been heat-stabilized, so the thermal stability tests are only useful for indicating whether the film would melt or not when placed in the oven for one hour at 200°C.
  • the results of bubble formability are given in Table X, while those of heat-sealability and oven heat-resistance are given in Table XI.
  • the minimum acceptable bubble rating is assumed to be 3. Using this criteria, the claimed blends all pass the forming criteria, as does the LLDPE film, while both the comparative Nylon 6 film and the commercially available Nylon 6 film do not pass this criteria. TABLE XI
  • Blend F 250 270 2600 Did not melt
  • a “salt and pepper”, or dry blend, of the following composition was prepared.
  • Surlyn® 30.0 % EBAGMA (Elvalloy®): 10.0 %
  • Anti-oxidant Cul/KI/Aium. Distearate 7:1 :0.5): 0.48 %
  • Zytel FN ® 727 was also used, which is a partially grafted, multi-phase flexible thermoplastic composition.
  • the above two formulations were each separately melt extruded in a 53 mm W&P twin screw extruder at a melt processing temperature of 245°C and using a 125 micron filter. The melt was extruded through a 122 cm flat film die. The extrudate was quenched on a chill roll set at a temperature of 31 °C to form a film having a thickness of 53 microns.
  • the Nylon 6 component has a relative viscosity (in formic acid) of 50, while the D12 polymer has a relative viscosity (in formic acid) of 50.
  • a control for bubble formability and heat stability was also tested, which is a commercially available polyethylene/Nylon6/polyethylene coextrusion, this structure being 51 microns thick with the Nylon core layer being 5 microns thick.
  • both the "salt and pepper” blend (dry pellet blend) and the Zytel FN ® formulation have good heat-sealability, formability and oven stability.
  • the dry blend, containing the D12 polyamide, has a lower heat-seal initiation temperature and a higher maximum bond strength than the Zytel FN ® formulation Both retain their film physical properties to a much greater extent than the poly/Nylon/poly coextrusion.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

Pellicules pour stratification en polyamide thermoscellables et thermoformables présentant une stabilité thermique à des températures élevées. Ces propriétés permettent d'utiliser lesdites pellicules dans des structures monocouche, telles que les stratifiés gaufrés destinés à des applications d'isolation ou de calage à des températures élevées. L'invention concerne également une composition de résine thermoplastique pluriphasée pouvant être utilisée dans la fabrication de stratifiés gaufrés thermoformables, et comprenant au moins une résine polyamide dont le point de fusion est supérieur à 200 °C, au moins une résine polyamide dont le point de fusion est inférieur à 200 °C, le reste étant composé essentiellement de polymères éthylène.
PCT/CA1997/000200 1996-03-25 1997-03-24 Formulations polyamides pour stratifies gaufres WO1997035910A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20202/97A AU2020297A (en) 1996-03-25 1997-03-24 Polyamide formulations for embossed laminates

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US1415096P 1996-03-25 1996-03-25
US60/014,150 1996-03-25

Related Child Applications (2)

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US09155146 A-371-Of-International 2000-02-03
US10/208,271 Division US20030100685A1 (en) 1996-03-25 2002-07-29 Polyamide formulations for embossed laminates

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998055815A1 (fr) * 1997-06-06 1998-12-10 Shailesh Doshi Procede de formage sans solvant pour panneaux d'echangeur thermique
WO2000022031A1 (fr) * 1998-10-09 2000-04-20 Dupont Canada, Inc. Film de nylon facilement thermoscellable
WO2000063286A1 (fr) * 1999-04-15 2000-10-26 E.I. Du Pont De Nemours And Company Composition thermoplastique moulable par embouage
EP1170334A2 (fr) * 2000-06-23 2002-01-09 Degussa AG Composition à base de polyamide résistante aux chocs à basse température
US6797222B2 (en) 1999-04-15 2004-09-28 E. I. Du Pont De Nemours And Company Slush molding process
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
WO2009105205A1 (fr) * 2008-02-20 2009-08-27 Sealed Air Corporation (Us) Film d'emballage
US20120024348A1 (en) * 2010-07-30 2012-02-02 E.I. Du Pont De Nemours And Company Cross-linkable ionomeric encapsulants for photovoltaic cells
US12226967B2 (en) 2020-06-18 2025-02-18 Saint-Gobain Performance Plastics Corporation Multifunctional film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109749080B (zh) 2018-12-26 2020-06-09 浙江新和成特种材料有限公司 半芳香族聚酰胺树脂及其制备方法

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US4174358A (en) * 1975-05-23 1979-11-13 E. I. Du Pont De Nemours And Company Tough thermoplastic nylon compositions
US4299744A (en) * 1980-06-06 1981-11-10 American Hoechst Corporation High impact polyamides
EP0356978A2 (fr) * 1988-08-29 1990-03-07 E.I. Du Pont De Nemours And Company Nylons renforcés caractérisés par une faible déposition de moulage
US5091478A (en) * 1986-11-14 1992-02-25 E. I. Du Pont De Nemours And Company Partially grafted thermoplastic compositions
WO1995015992A1 (fr) * 1993-12-07 1995-06-15 Dupont Canada Inc. Polyamides et pellicules thermo-soudables de polyamides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174358A (en) * 1975-05-23 1979-11-13 E. I. Du Pont De Nemours And Company Tough thermoplastic nylon compositions
US4174358B1 (fr) * 1975-05-23 1992-08-04 Du Pont
US4299744A (en) * 1980-06-06 1981-11-10 American Hoechst Corporation High impact polyamides
US5091478A (en) * 1986-11-14 1992-02-25 E. I. Du Pont De Nemours And Company Partially grafted thermoplastic compositions
EP0356978A2 (fr) * 1988-08-29 1990-03-07 E.I. Du Pont De Nemours And Company Nylons renforcés caractérisés par une faible déposition de moulage
WO1995015992A1 (fr) * 1993-12-07 1995-06-15 Dupont Canada Inc. Polyamides et pellicules thermo-soudables de polyamides

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998055815A1 (fr) * 1997-06-06 1998-12-10 Shailesh Doshi Procede de formage sans solvant pour panneaux d'echangeur thermique
WO2000022031A1 (fr) * 1998-10-09 2000-04-20 Dupont Canada, Inc. Film de nylon facilement thermoscellable
US6797222B2 (en) 1999-04-15 2004-09-28 E. I. Du Pont De Nemours And Company Slush molding process
WO2000063286A1 (fr) * 1999-04-15 2000-10-26 E.I. Du Pont De Nemours And Company Composition thermoplastique moulable par embouage
EP1170334A2 (fr) * 2000-06-23 2002-01-09 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
EP1170334A3 (fr) * 2000-06-23 2003-01-29 Degussa AG Composition à base de polyamide résistante aux chocs à basse température
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
WO2009105205A1 (fr) * 2008-02-20 2009-08-27 Sealed Air Corporation (Us) Film d'emballage
US20120024348A1 (en) * 2010-07-30 2012-02-02 E.I. Du Pont De Nemours And Company Cross-linkable ionomeric encapsulants for photovoltaic cells
WO2012016053A1 (fr) * 2010-07-30 2012-02-02 E. I. Du Pont De Nemours And Company Agents d'encapsulation ionomères réticulables pour des cellules photovoltaïques
US8609980B2 (en) 2010-07-30 2013-12-17 E I Du Pont De Nemours And Company Cross-linkable ionomeric encapsulants for photovoltaic cells
US12226967B2 (en) 2020-06-18 2025-02-18 Saint-Gobain Performance Plastics Corporation Multifunctional film

Also Published As

Publication number Publication date
CA2248123A1 (fr) 1997-10-02
AU2020297A (en) 1997-10-17

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