EP2970613A1 - Films contenant des minéraux - Google Patents

Films contenant des minéraux

Info

Publication number
EP2970613A1
EP2970613A1 EP14722042.0A EP14722042A EP2970613A1 EP 2970613 A1 EP2970613 A1 EP 2970613A1 EP 14722042 A EP14722042 A EP 14722042A EP 2970613 A1 EP2970613 A1 EP 2970613A1
Authority
EP
European Patent Office
Prior art keywords
film
density polyethylene
film layer
high density
calcium carbonate
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP14722042.0A
Other languages
German (de)
English (en)
Inventor
Jr. Harry B. Wilfong
Patrick J. HOVER
Danny G. HILLARD
Todd Shaw
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hilex Poly Co LLC
Original Assignee
Hilex Poly Co LLC
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 Hilex Poly Co LLC filed Critical Hilex Poly Co LLC
Priority claimed from PCT/US2014/029387 external-priority patent/WO2014144816A1/fr
Publication of EP2970613A1 publication Critical patent/EP2970613A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Definitions

  • the present invention is for film products as more fully set forth herein.
  • a film is set forth that has at least one film layer that comprises by weight at least about 40% inorganic filler material and at least about 10% high density polyethylene, including any high density polyethylene carrier in the inorganic filler material.
  • the film layer comprises, by weight, at least about 40% calcium carbonate and at least about 10%> high density polyethylene, including any high density polyethylene carrier in the calcium carbonate and wherein the film has been stretched in the machine direction.
  • Fig. 1 depicts an exemplary embodiment of a multilayer film of the present invention.
  • a film of the present invention may include at least one film layer having an inorganic filler material.
  • inorganic filler material and mineral are used interchangeably.
  • inorganic filler materials in films of the present invention may include calcium carbonate, talc, zinc oxide, titanium oxide, clay, diatomaceous earth, and combinations thereof.
  • the inorganic filler material may include calcium carbonate.
  • such inorganic filler materials may cause cavitation or microvoids in the film. Without intending to be bound by theory, it is believed that such cavitation or microvoids may result from air entrapped within a film surrounding the inorganic filler material. As a result, some embodiments of such films may have a lower density and increased yield as compared with similar polyolefm films that lack inorganic filler materials.
  • At least one film layer may be composed of at least about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or 75% inorganic filler material, including each intermittent value in the foregoing range.
  • a film may be composed of at least 50% inorganic filler material.
  • Other components of such a film layer may include any suitable polyolefm, including, without limitation, high density polyethylene, high molecular weight high density polyethylene (HMW-HDPE), low density polyethylene, linear low density polyethylene, polypropylene, metalized biaxially-oriented polypropylene.
  • a mineral-containing layer may include high density polyethylene, either alone or in combination with other polyolefms.
  • the high density polyethylene may be high molecular weight high density polyethylene.
  • reference film composition percentages reference to a film indicates a film layer, recognizing that optional additional layers present in a final multilayer film product are not accounted for in such values.
  • the present invention includes a film having by weight about (or alternatively at least about) 40 to 65% calcium carbonate, about (or alternatively at least about) 20 to 40% high density polyethylene, and optionally about (or alternatively at least about) 5 to 15% of either low density polyethylene or any additional polyethylene having a melt index of about 1.8 to 3.0 g/10 mins.
  • the film may have a calcium content of about 56% by weight, whereas in other embodiments the film may have a calcium carbonate content of about 40, 45, 50, 55, 60, or 65%>.
  • the present invention includes a film having a calcium carbonate content of at least 40%.
  • the present invention includes a film having a calcium carbonate content of at least 50%.
  • the film may have a high density polyethylene content by weight of about 20, 25, 30, 35, 40, 45, or 50%>, and some embodiments of the film may include by weight 5, 10, or 15% low density polyethylene or another polyethylene having a melt index of about 1.8 to 3.0 g/10 mins. Any combination of the materials in the foregoing ranges is encompassed within the scope of the present invention, and in some embodiments no other components are present in the film except for high density polyethylene, low density polyethylene, and calcium carbonate.
  • a calcium masterbatch may be used in forming a film or film layer, wherein a calcium masterbatch may include both calcium carbonate and a suitable carrier, such as high density polyethylene.
  • a calcium masterbatch having 70% calcium carbonate and 30% high density polyethylene such as a calcium carbonate in pellet form (having 70% calcium powder and 30% high density carrier resin by weight) available as T986B1 from Heritage Plastics in Picayune, MS, may be employed for some embodiments of the present invention.
  • about 50% to about 80% calcium masterbatch may be used in forming a film or film layer.
  • one embodiment of the present invention includes a film may comprise about 56% calcium carbonate, about 34% high density polyethylene, and about 10% low density polyethylene or another polyethylene having a melt index of about 1.8 to 3.0 g/10 mins.
  • a film of the present invention may contain by weight 50.4% calcium and 49.6% high density polyethylene.
  • a film of the present invention may contain calcium carbonate and high density polyethylene, wherein calcium carbonate accounts for at least about 40% of the film by weight.
  • a film of the present invention may contain calcium carbonate and high density polyethylene, wherein calcium carbonate accounts for at least about 50% of the film by weight.
  • a film or film layer of the present invention may consist essentially of inorganic filler materials, such as calcium carbonate, and high density polyethylene. Any of the foregoing references to high density polyethylene may alternative include high molecular weight high density polyethylene.
  • Films of the current invention can have varying thicknesses or gauges.
  • a film of the present invention may be 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, or 2.5 mils.
  • films of the present invention may have a thickness of at least 0.75 mil.
  • Some embodiments of the present invention include films having a thickness that is generally consistent.
  • the gauge variation of some films of the present invention may be less than 20%. In other embodiments, the gauge variation may be less than 10%. In still other embodiments, the gauge variation may be less than 5%. In yet other embodiments, the gauge variation may be less than 2%.
  • films of the present invention may be oriented, or stretched, in the machine direction only ("MDO"), such as after an extrusion process.
  • MDO draw-stretch ratio for a film may vary depending upon the components of the film and the properties desired. In some embodiments, the draw-stretch ratio may be in the range of about 1 : 1 up to about 8: 1, including each intermittent value therebetween. In other embodiments, an MDO draw-stretch ratio of about 1.1 : 1 to about 3:1 may be utilized, including each intermittent value therebetween. In still other embodiments, an MDO draw- stretch ratio of about 2: 1 to about 2.5: 1 may be used, including each intermittent value therebetween.
  • Such films having been stretched in the machine-direction only after an extrusion processes may provide comparatively advantageous properties, such as yield, tensile strength, and flatness, that are similar to biaxially- oriented polypropylene films.
  • some embodiments of such films may provide decreased gauge variation within the film.
  • a film may include additional film layers.
  • films of the present invention may include a layer comprising high molecular weight high density polyethylene (HMW-HDPE), low density polyethylene, linear low density polyethylene, polypropylene, metalized biaxially-oriented polypropylene, any other polyolefms, other mineral-containing layers, combinations of any of the foregoing, and/or other film layers.
  • HMW-HDPE high molecular weight high density polyethylene
  • low density polyethylene low density polyethylene
  • linear low density polyethylene linear low density polyethylene
  • polypropylene polypropylene
  • metalized biaxially-oriented polypropylene any other polyolefms
  • other mineral-containing layers combinations of any of the foregoing, and/or other film layers.
  • some embodiments of the present invention include films having at least a first film layer containing inorganic filler material and at least a second film layer have either no inorganic filler material or less inorganic filler material as compared with the first film layer.
  • Multilayer films of the present invention may be prepared using coextrusion blown-film processes, extrusion lamination processes, or adhesive lamination processes, all of which are readily known within the art.
  • a high stalk extrusion process may be employed, as is common in the art with high molecular weight, high density polyethylene.
  • a food packaging film product may be prepared as an adhesive lamination and include the following layers: (A) layer of metalized biaxially-oriented polypropylene, (B) optional layer of virgin low density polyethylene or linear low density polyethylene, (C) mineral-containing layer having calcium carbonate and high density polyethylene, and (C) optional printing layer as described below.
  • the present invention includes a film or film layer prepared by coextruding an inorganic filler material and high density polyethylene.
  • a film of the present invention may include a polypropylene layer if temperature resistance and/or tear resistance are desired.
  • some film products may include multiple mineral-containing film layers, such as two, three, four, or more such mineral- containing layers as disclosed herein.
  • the present invention further includes films having a single layer and films having multiple layers.
  • the preparation of multi-layer films using multiple extruders is well known to a person having ordinary skill in the art.
  • a coextrusion process may be used to prepare a film having a mineral-containing layer and a high density polyethylene skin layer.
  • one or more layer of a film product may have the same composition.
  • one or more or all layers of a multilayer film product may have a different composition.
  • at least one layer may contain an inorganic filler material, such as calcium carbonate in amount such as of at least about 50%.
  • a layer may contain at least about 10% to about 70% inorganic filler material, including in embodiments prepared using a three-layer coextrusion die.
  • a skin layer of a film may contain from about 10% to about 30% inorganic filler material and a center (or core) layer may contain from about 40% to about 80% inorganic filler material.
  • the gauge of each layer of a resultant film may be adjusted such that the percentage of each layer to the total resulting film product may be varied.
  • multiple identical film layers may be fused together to form a thicker single film or film layer, particularly, but not exclusively, to form a mineral-containing film layer having a desired thickness of about 1.5 mils or greater.
  • a desired film layer having a thickness of 2.0 mils and comprised of a blend of calcium carbonate and high density polyethylene may be prepared by fusing, with heat, two film layers of 1.0 mil thickness each with the same calcium carbonate and high density polyethylene blend.
  • such fused film layers may have a density of about 0.72 g/cc.
  • additional layers may also be added to such fused mineral-containing layers to form multilayer films.
  • Some embodiments of the present invention may include a film containing a mineral, such as calcium carbonate, having a rough or matted surface, which may result in a less desirable printing surface. Without intending to be bound by theory, such a rough or matted surface may result from voids in the film caused by the calcium carbonate particles.
  • a skin layer may be provided that may serve as a printing layer, wherein such skin layer has a decreased amount of mineral material or no mineral material.
  • Such a printing layer may include any suitable polymer or polymer blend, including, without limitation, any of the compositions provided above for an additional layer and combinations thereof. Due to the absence or decreased amount of mineral material, such skin layer may provide improved printing in some embodiments.
  • one or more film layers may include a color component.
  • a printing skin layer may contain titanium oxide (Ti0 2 ), which may provide a white color to the film.
  • Ti0 2 may be included within any film layer during the extrusion process.
  • such coloring component may be provided at about 2% of the weight of the extrusion materials for that film layer.
  • Ti0 2 may be provided in the range from about 2% to about 10% in any given layer, such as to provide a desired color and/or to provide a desired opacity of the film.
  • the coloring component may be present at up to about 2% of the weight of the extrusion materials for that film layer.
  • films and film layers of the present invention may be prepared using any suitable process.
  • films are prepared using blown film extrusion processes.
  • coextrusion processes may be used to prepare some multilayer film products of the present invention.
  • multilayer films of the present invention may be prepared using extrusion lamination or adhesive lamination processes. Such processes are readily known within the art.
  • films of the present invention are suitable for numerous uses.
  • film products of the present invention may be used with food products (such as butcher paper), freezer paper, packaging materials, bags, and other products.
  • food products such as butcher paper
  • freezer paper such as butcher paper
  • packaging materials such as butcher paper
  • bags such as bags
  • other products such as butcher paper
  • the foregoing description of illustrative embodiments of the invention has been presented only for the purpose of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Numerous modifications, substitutions, alterations, and adaptations thereof will be apparent to those of ordinary skill in the art without departing in any way from the scope of the present invention. It will be further understood that each of the embodiments described above and the components thereof may also find utility in additional combinations or in isolation. As such, further modifications and equivalents of the invention herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the invention as described herein.

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

Abstract

La présente invention concerne des films contenant un ou plusieurs matériaux de charge inorganique. De tels films peuvent posséder une couche simple et peuvent être multicouche, et une ou plusieurs couches de tels films multicouche peuvent contenir un ou plusieurs matériaux de charge inorganique. Dans certains modes de réalisation, le matériau de charge inorganique peut comprendre du carbonate de calcium.
EP14722042.0A 2013-03-15 2014-03-14 Films contenant des minéraux Withdrawn EP2970613A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361800916P 2013-03-15 2013-03-15
PCT/US2014/029387 WO2014144816A1 (fr) 2013-03-15 2014-03-14 Films contenant des minéraux

Publications (1)

Publication Number Publication Date
EP2970613A1 true EP2970613A1 (fr) 2016-01-20

Family

ID=54842931

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14722042.0A Withdrawn EP2970613A1 (fr) 2013-03-15 2014-03-14 Films contenant des minéraux

Country Status (1)

Country Link
EP (1) EP2970613A1 (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014144816A1 *

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