WO2003093004A1 - Film thermoplastique a base de polypropylene - Google Patents

Film thermoplastique a base de polypropylene Download PDF

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Publication number
WO2003093004A1
WO2003093004A1 PCT/US2003/010152 US0310152W WO03093004A1 WO 2003093004 A1 WO2003093004 A1 WO 2003093004A1 US 0310152 W US0310152 W US 0310152W WO 03093004 A1 WO03093004 A1 WO 03093004A1
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WO
WIPO (PCT)
Prior art keywords
polypropylene
thermoplastic film
layer
skin layer
isotactic
Prior art date
Application number
PCT/US2003/010152
Other languages
English (en)
Inventor
Dan-Cheng Kong
Michael D. Cleckner
Original Assignee
Exxonmobil Corporation
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
Priority claimed from US10/135,321 external-priority patent/US7195818B2/en
Application filed by Exxonmobil Corporation filed Critical Exxonmobil Corporation
Priority to CA002480774A priority Critical patent/CA2480774A1/fr
Priority to EP03728329A priority patent/EP1499495A1/fr
Priority to AU2003233478A priority patent/AU2003233478B8/en
Publication of WO2003093004A1 publication Critical patent/WO2003093004A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a thermoplastic film containing a core layer and an enhanced printing skin layer.
  • the core layer comprises an orientation-enhancing polymer, a polypropylene homopolymer, a beta-crystal nucleators of polypropylene, and optionally a water absorption additive.
  • the thermoplastic film is an oriented film and may be opaque.
  • Water based ink printing on standard thermoplastic polypropylene film requires a long time to dry. This is a particular problem when standard thermoplastic polypropylene films are used with ink-jet printing. Additionally, for good adhesion when using films with water-based pressure sensitive adhesives or with cold glues, good drying and adhesion properties are desired. Further, breathable films with good water vapor transmission are desired for bags, absorbent articles and garments.
  • Park et al, U.S. Patent 4,632,869 discloses an opaque, biaxially oriented film structure having a polymer matrix with strata of cavitated voids, in which the voids contain spherical void-initiating particles of polybutylene terephthalate (PBT).
  • the structure may also include thermoplastic skin layers, and the film can also include pigments such as TiO or colored oxides.
  • Park et al, U.S. Patent 4,758,462 discloses an opaque, biaxially oriented film with a cavitated core layer and transparent skin layers. Colored light absorbing pigments such as carbon black or iron oxide are added to the core and/or the skins to decrease light transmission through the film.
  • Patent 6,194,060 discloses an opaque, oriented polymeric film structure, suitable for food packaging, comprising: (a) a core layer containing a thermoplastic polymeric matrix material which has a first surface and a second surface, the core layer having a plurality of voids, substantially all or all of the voids being free from a void-initiating particle and at least some of the voids being interconnected with an adjacent void in the polymeric matrix material, the number of voids not containing a void-initiating particle being sufficient to impart a significant degree of opacity to the film structure; and (b) at least one outer or skin layer containing a thermoplastic polymeric material and an effective amount of a nucleating agent to suppress cavitation in said at least one outer or skin layer.
  • the film structure is stated to have a smooth surface and to be tailorable to provide a controlled permeability.
  • Amon et al U. S. Patent 6,303,233, discloses a uniaxially heat- shrinkable, biaxially oriented, multilayer film having a polypropylene-containing core layer containing at least 70 wt. % of the multilayer film and at least one polyolefin-containing skin layer adjacent the core layer, which is prepared by biaxially orienting a coextrudate and thereafter orienting the coextrudate by stretching 10 to 40% in the machine direction.
  • the core layer contains isotactic polypropylene, a modifier which reduces the crystallinity of the polypropylene- containing core layer and a nucleating agent.
  • the modifiers include atactic polypropylene, syndiotactic polypropylene, ethylene-propylene copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 terpolymer, and linear low density polyethylene.
  • the nucleating agent is said to improve long term dimensional stability.
  • the skin layer can be high density polyethylene on both sides or high density polyethylene on one side and isotactic polypropylene on the other side.
  • U. S. Patent 6,183,856 discloses a process for forming film structures which have a plurality of voids, at least some of the voids not containing a void-initiating particle and at least some of the voids being interconnected with an adjacent void in the polymeric matrix material, with the number of voids being sufficient to impart a significant degree of opacity in the film structure.
  • Davidson et al, EP0865909 discloses biaxially oriented heat shrinkable polyolefin films for use as labels, having a layer of a polypropylene- based resin with microvoids therein. The microvoids having been formed by stretching a web containing the beta form of polypropylene.
  • Davidson et al, EP0865910, and Davidson et al, EP0865912 disclose biaxially oriented polyolefin opaque films having a thickness of not more than 50 ⁇ m having a layer of a polypropylene-based resin with microvoids therein. The microvoids having been formed by stretching a web containing the beta form of polypropylene at an area stretch ration of at least 15:1.
  • Davidson et al, EP0865913 discloses biaxially oriented heat shrinkable polyolefin films having a layer of a polypropylene-based resin with microvoids therein. The microvoids having been formed by stretching a web containing the beta form of polypropylene, the film having a shrinkage after 10 minutes at 130 °C of at least 10% in at least one direction.
  • Davidson et al, EP0865914 discloses biaxially oriented high gloss polyolefin films having a layer of a polypropylene-based resin with microvoids therein and at least one olefin copolymer outer layer thereon. The microvoids having been formed by stretching a web containing the beta form of polypropylene.
  • Jacoby et al, U.S. Patent 5,594,070 discloses oriented microporous films prepared from polyolefin resin compositions comprising an ethylene- propylene block copolymer having an ethylene content of about 10 to about 50 wt.%, a propylene homopolymer or random propylene copolymer having up to about 10 wt. % of a comonomer of ethylene or an ⁇ -olefin of 4 to 8 carbon atoms, and components selected from a low molecular weight polypropylene, a beta- spherulite nucleating agent and an inorganic filler.
  • the microporous films are said to have improved breathability, strength, toughness and break elongation.
  • Jacoby et al U. S. Patent 5,310,584, discloses a thermoformable sheet comprising a resinous polymer of propylene and an effective amount of a beta-spherulite nucleating agent, a process for making the sheet and articles thermoformed from the sheet.
  • Xu et al U. S. Patent 5,134,174, discloses polypropylene microporous films having a porosity of 30-35%o, an average pore size of 200-800 A, a permeation coefficient for nitrogen of 1-5 x 10 " ml/cm sec atm and a tensile strength of greater than 60 MPA in all directions within the film plane.
  • the films are prepared by the consecutive steps of biaxial stretching a non-porous starting film of high beta-crystal content and heat setting the stretched film.
  • Patent 6,072,005 discloses a breathable film, having certain physical and barrier properties, made from a stretched impact modified polyolefin matrix and a particulate filler.
  • the impact modified polyolefin matrix includes at least one impact polypropylene copolymer, alone or in combination with other polymers.
  • the film, and laminates including the film are stated to provide moisture breathability and barrier to penetration by liquids.
  • Disclosed uses for laminates including the film include diaper outercovers and other applications requiring breathability and resistance to penetration by liquids.
  • thermoplastic polypropylene film requires a long time to dry. This is a particular problem when standard thermoplastic polypropylene film are used with ink-jet printing.
  • the film of the present invention provides for superior water absorption and is particularly effective for water-based printing. Further, the film of the present invention shows good drying due to good water vapor permeability when it is used with a water-based pressure sensitive adhesive or with a cold glue as a label. Another advantage is when the film of the present invention is used as a label with a pressure sensitive adhesive, due to the paper tear property, the film of the present invention may be used as evidence of tampering.
  • the film of the present invention may be used as a tamper evident label, for water-based ink printing applications, for ink-jet printing and as a synthetic paper.
  • the film of the present invention may also be used as a printable surface for solvent based inks and UV-curable inks.
  • the film may also be used in applications where breathable films are employed and good water vapor transmission are desired.
  • a backsheet component in a personal care absorbent article such as a diapers, training pants, incontinence garments, feminine hygiene products and the like.
  • the relative humidity and temperature within the diaper or other product can be reduced by using breathable films and laminates.
  • the film may be used as a cover or bag for produce.
  • the film may also be used in surgical gowns, protective workwear, wound dressings and bandages, where an objective is to provide good water vapor transmission and make the item more comfortable to the wearer.
  • the opaque film of the present invention is different from the conventional opaque polypropylene films. Conventional opaque polypropylene films are cavitated by organic polymers or inorganic fillers.
  • beta-crystal growth during polypropylene film casting is controlled, followed by orientation, to create the high permeability opaque film.
  • the core layer comprises an orientation-enhancing polymer, a polypropylene homopolymer, a beta crystal nucleator of polypropylene, and optionally a water absorption additive.
  • the orientation-enhancing polymer comprises an
  • the orientation-enhancing polymer assists in making the biaxial tenter frame orientation for the film of this invention. Without the orientation- enhancing polymer, it is difficult to make a reliable biaxial oriented film with only polypropylene loaded with beta-crystal nucleator, due to film split and high mechanical stress in the TD orientation.
  • the addition of orientation-enhancing polymer in the core layer improves the tenter frame orientation stability especially above 4 times orientation in the transverse direction without film split. Further, the opacity of the film may be maintained.
  • the core layer preferably comprises 1 to 99 wt.% polypropylene and
  • the core layer comprises 10 to 90 wt.% polypropylene homopolymer and 90 to 10 wt.% orientation-enhancing polymer (based on total polymers) and the beta crystal nucleator for polypropylene.
  • the core layer comprises 30 to 70 wt.% polypropylene homopolymer and 70 to 30 wt.% orientation-enhancing polymer (based on total polymers) and the beta crystal nucleator for polypropylene.
  • the core layer is made from an impact polypropylene masterbatch with a beta crystal nucleator of polypropylene and a water absorption additive, or the core layer is made from an impact polypropylene masterbatch with a beta crystal nucleator of polypropylene, an isotactic polypropylene, and a water absorption additive.
  • the core layer may also be made from: An (isotactic propylene)-ethylene heterophasic copolymer masterbatch with a beta crystal nucleator of polypropylene and an isotactic polypropylene; An impact polypropylene masterbatch with a beta crystal nucleator of polypropylene and a metallocene isotactic polypropylene; An (isotactic propylene)-ethylene heterophasic copolymer, ethylene-propylene-ethylidene norbornene elastomer, isotactic polypropylene masterbatch with a beta crystal nucleator of polypropylene and an isotactic polypropylene that has a different m-pentad than the isotactic polypropylene in the isotactic polypropylene masterbatch; or An (isotactic propylene)-ethylene heterophasic copolymer, ethylene-propylene rubber, polyethylene, isotact
  • the orientation-enhancing polymer may be a blend comprising alpha-olefm-propylene elastomer and (isotactic propylene)-ethylene heterophasic copolymer.
  • the (isotactic propylene)-ethylene heterophasic copolymer is generally produced by two reactors.
  • the isotactic propylene homopolymer matrix is made with 60 to 95% by weight based on the weight of the whole final polymer in the first reactor, and then transferred to the second reactor where ethylene and propylene are polymerized to create ethylene-propylene elastomer about 5 to 40% by weight based on the weight of the whole final polymer, dispersed in the homopolymer phase.
  • the alpha-olefm-propylene elastomer comprises ethylene- propylene elastomer, butylene-propylene elastomer, pentene-propylene elastomer, hexene-propylene elastomer, octene-propylene elastomer, ethylene-propylene- ethylidene norbornene elastomer and ethylene-propylene-vinyl norbornene elastomer.
  • the polypropylene homopolymer is an isotactic polypropylene.
  • the isotactic polypropylene preferably has an m-pentad greater than 85%o by NMR spectroscopy measurement.
  • a mixture of isotactic polypropylenes may be used, preferably, the mixture comprises at least two polypropylene polymers having different m-pentads by NMR spectroscopy measurement.
  • the difference between m-pentads is at least 1%.
  • Polypropylene is capable of crystallizing in several crystal forms.
  • the alpha or monoclinic form of polypropylene is the most stable and prevalent form. Without control, the beta or hexagonal form may be found in commercially available polypropylene, but usually at low levels.
  • the beta form of polypropylene may be produced more effectively by using a beta nucleating agent.
  • beta crystal nucleators of polypropylene any know types of beta nucleators may be used.
  • Jacoby U.S. Patent 4,386,129, and Jacoby, U.S. Patent 4,975,469, disclose a process of forming a film containing nucleating agents to produce beta- form spherulites and then selectively extracting the beta-spherulites.
  • Both Jacoby patents disclose quinacridone compounds, bisodium salts of o-phthalic acids, aluminum salts of 6-quinizarin sulfonic acid and isophthalic and terephthalic acids as beta nucleating agents.
  • Wolfschwenger et al U.S. Patent 5,681,922, discloses the use of dicarboxylic acid salts of metals of the second main group of the Periodic Table as beta nucleating agents.
  • a two component beta nucleators may be used.
  • Shi et al U.S. Patent 5,231,126, discloses the use of a mixture of a dibasic organic acid and an oxide, hydroxide or salt of a metal of group II A of the Periodic Table.
  • Ikeda et al U.S. Patent 5,491,188, Ikeda et al, U.S. Patent 6,235,823, and Ikeda et al, EP 0632095, discloses the use of certain types of amide compounds as beta nucleators.
  • Hayashida et al U.S. Patent 6,005,034, discloses various types of beta nucleators.
  • the beta-nucleating agent is preferably a two component beta nucleator formed by the mixing of Components A and B.
  • Component A is an organic dibasic acid, such as pimelic acid, azelaic acid, o-phthalic acid, terephthalic and isophthalic acid and the like.
  • Component B is an oxide, hydroxide or an acid salt of a Group II metal e.g. magnesium, calcium, strontium and barium.
  • the acid salt of Component B may come from inorganic or organic acid such as carbonate, stearate etc.
  • Component B may also be one of the additives of polypropylene, that already is present in the polypropylene material.
  • the proportion of component A is in the range of 0.0001 -5% by weight, most preferably 0.01-1 wt %, the proportion of component B is 0.0001-
  • the beta crystal nucleator of polypropylene is not a red dye.
  • the beta nucleators are incorporated into the resinous polymer before the film is formed. More preferably, the beta nucleators are combined with the impact polypropylene polymer or the polypropylene homopolymer in the form of a master batch before the sheet is formed. [0042]
  • the amount of beta nucleators used should be enough to obtain the desired degree of void formation upon stretching.
  • the amount of beta nucleators may also be used to control the degree of opacity.
  • Preferred amounts of beta nucleators are from 0.0002 to 8 wt.%> based on the weight of polypropylene, more preferably 0.005 to 2 wt.%, and 0.01 to 2 wt.%.
  • the printable skin layer of the present invention can be in direct contact with the core layer or may be on at least one intermediate layer.
  • the printable skin layer may be of any thickness.
  • the printable skin layer has thickness of 1.25 ⁇ m or greater, more preferably, a thickness of 2.5 ⁇ m or greater, most preferably, a thickness of 3.75 ⁇ m or greater.
  • the printable skin layer comprises an impact polypropylene copolymer and a beta crystal nucleator of polypropylene.
  • water absorption additives may be included in the printable skin layer.
  • the printable skin layer comprises a polypropylene homopolymer, an orientation-enhancing polymer, a beta crystal nucleator of polypropylene, and a water absorption additive, and the printable skin layer is surface treated by any known method, such as corona flame or plasma.
  • the intermediate layer when present, may be made of any type of compatible material and have any thickness. Separate from the intermediate layer between the core layer and the printable skin layer, the film may also contain one or more other intermediate layers. For example, the film may contain an intermediate layer between the core layer and an outer layer.
  • the intermediate layer comprises a polypropylene homopolymer, an orientation- enhancing polymer, a beta crystal nucleator of polypropylene, a water absorption additive, and inorganic particles.
  • the composition of the intermediate layer is the same as that of the core layer.
  • the intermediate layer may be of any thickness.
  • the intermediate layer has a thickness greater than 2.5 ⁇ m. More preferably, the intermediate layer has thickness greater than the thickness of the printable skin layer.
  • the total weight percentage of the water absorption additive of the intermediate layer is greater than the total weight percentage of the water absorption additive of the printable skin layer.
  • Any water absorption additive may be used as the water absorption additive.
  • the water absorption additive is at least one selected from the group consisting of an inorganic additive, for example, CaCO 3 , BaCO 3 , clay, talc, and silica, and a hygroscopic polymer.
  • the percentage of inorganic additive can be from 5 wt% to 30 wt%, preferably from 10 wt% to 20 wt%>, more preferably 12 wt% to 18 wt%.
  • the percentage of organic hygroscopic polymer can be from 1 wt%> to 10 wt%, preferably from 1 wt% to 6 wt%>, more preferably 2 wt%> to 4 wt%.
  • the side of the core layer opposite to the printable skin layer may contain an outer skin layer.
  • the outer skin layer preferably comprises at least one polymer selected from the group consisting of an impact polypropylene polymer, a polypropylene homopolymer, a polypropylene copolymer, such as propylene- ethylene copolymer, a metallocene polypropylene, a syndiotactic polypropylene, blend of an isotactic polypropylene and a syndiotactic polypropylene, blend of an isotactic polypropylene and an atactic propylene, a metallocene isotactic propylene copolymer and an (isotactic propylene)-ethylene heterophasic copolymer.
  • the outer skin layer may optionally contain a beta crystal nucleator of polypropylene.
  • the outer skin layer may be the same blend as the core layer or may comprise a different blend of components.
  • the outer skin layer comprises an (isotactic propylene)-ethylene heterophasic copolymer and a beta crystal nucleator of polypropylene or the outer skin layer is made from an impact polypropylene masterbatch with a beta crystal nucleator of polypropylene.
  • the outer skin layer may also be surface treated by any known method, such as by corona, flame or plasma, to be a printable layer.
  • the outer skin layer may also be used as the coating adhesive, or other surface coating.
  • the film of the present invention may be a two layer film [a core layer (B) and a printable skin layer (C)] ("B/C") or a three layer film [a core layer (B), a printable skin layer (C) and an outer skin layer (A)] ("A/B/C").
  • the film of the present invention may also contain one or more intermediate layers (I).
  • the film of the present invention may comprise four layers, five layers or more.
  • the film of the present invention may include multiple core layers, multiple printable skin layers and multiple outer skin layers and other types of layers. Such as A/B/B/C, A/I/B/I/C and A/B/I/C layer arrangements.
  • One preferable embodiment is a five-layer arrangement containing an intermediate layer between the core layer and the printable skin layer and an intermediate layer between the core layer and the outer layer.
  • the film may be uniaxially oriented at from 3 to 10 times of orientation ratio.
  • the film may be biaxially oriented from 3 to 6 times of orientation ratio in the machine direction (MD) and 4 to 10 times of orientation ratio in the transverse direction (TD).
  • MD and TD orientations may be performed sequentially or simultaneously by the tenter frame orientation method.
  • the film may be made by any known method, preferably by coextrusion of the layers.
  • the film layers in accordance with the present invention can include one or more additives used in the film art.
  • additives used in the film art.
  • fillers organic or inorganic
  • pigments organic or inorganic
  • stabilizers UV absorbers
  • slip agents antistatic agents, antiblock agents, and etc.
  • the inorganic fillers may be located in the core layer or in the intermediate layers when present, such as in a five layer film.
  • the inorganic fillers preferably are at least one of CaCO 3 , BaCO 3 , clay, talc, silica, mica and TiO 2 .
  • the organic fillers may be preferably located in the core layer.
  • the organic fillers preferably are at least one of a polybutylene terephthalate, a polyamide, a polyethylene terephthalate, a cyclic olefin copolymer, a polystyrene, and a syndiotactic polystyrene.
  • WVTR water vapor transmission rate
  • the film is greater than 4.0 g/m 2 /day. More preferably, the
  • WVTR is at least 15 g/m 2 /day.
  • the light transmission of the film as measured by ASTM
  • D1003 is less than 35%. More preferably, the light transmission is less than 30%.
  • Total film thickness of the enhanced printing film is from 20 ⁇ m to
  • the film thickness is greater than 30 ⁇ m.
  • a three-layer oriented opaque film, A/B/C is made via tenter-frame sequential orientation at 4 times in MD orientation and 8 times in TD orientation.
  • the A-layer about 2.5 ⁇ m poly-gauge thickness comprises polypropylene impact copolymer and beta-nucleators of polypropylene.
  • the B-layer about 30 ⁇ m poly- gauge thickness comprises 60wt% of polypropylene, FINA3371 from Fina Oil Company, 40wt% of impact polypropylene copolymer with beta crystal nucleator of polypropylene, ARISTECH BI4020TSP from Sunoco Chemicals.
  • the C-layer is the same as A-layer.
  • the film has light transmission about 10.6% and WVTR about 127g/m 2 /day.
  • the A-layer surface is treated with corona.
  • An ink-jet printing with Canon S600 printer was applied on the A-layer surface. Good ink drying was observed for red, blue, yellow, and green colors.
  • the C-layer was coated with cold glue adhesive.
  • the label was applied on the bottle. A paper tear was observed when the label was removed from the bottle. [0066] The ink drying test was conducted by, thirty minutes after printing, covering the printed surface with a plain paper. Good ink drying occurred when there was no ink transferred to the plain paper.
  • a three-layer oriented opaque film, A/B/C is made via tenter-frame sequential orientation at 4 times in MD orientation and 8 times in TD orientation.
  • the A-layer about 3.75 ⁇ m comprises 70wt% of impact polypropylene copolymer with beta-nucleators of polypropylene, Aristech BI4020TSP and 30wt%> of HDPE with CaCO 3 masterbatch T4228 from A. Schulman (50% CaCO 3 and 50 % HDPE).
  • the B-layer about 30 ⁇ m comprises 60wt% polypropylene with beta- nucleators and 40wt% (isotactic propylene)-ethylene heterophasic copolymer, Basell 8523 from Basell.
  • the C-layer about 2.5 ⁇ m comprises impact polypropylene copolymer with beta-nucleators, Aristech BI4020TSP.
  • the film has light transmission about 10.7%.
  • the A-layer is treated with corona. An ink- jet printing was applied on the A-layer surface. Good ink drying was observed for red, blue, yellow, green and black colors
  • a five-layer oriented opaque film, P/Q/R/S/T is made by tenter- frame sequential orientation at 4 times in MD orientation and 8 times in TD orientation.
  • the P-layer about 1.25 ⁇ m comprises 70wt% of impact polypropylene copolymer masterbatch with beta-crystal nucleator of polypropylene, BI4020SP from Sunoco Chemicals, and 30wt% of HDPE masterbatch with CaCO 3 , T4228 from A. Schulman (50% CaCO 3 and 50 % HDPE).
  • the Q-layer about 5 ⁇ m comprises 65 wt% of impact polypropylene copolymer masterbatch with beta-crystal nucleator of polypropylene, BI4020SP from Sunoco Chemicals, and 35wt% of HDPE masterbatch with CaCO 3 , T4228 from A. Schulman (50% CaCO 3 and 50 % HDPE).
  • the core layer, R-layer, about 25 ⁇ m comprises 60wt%> of isotactic polypropylene masterbatch with beta-crystal nucleator of polypropylene, BEPOL 022SP from Sunoco Chemicals, and 40wt% of (isotactic propylene)-ethylene heterophasic copolymer, BASELL 8523 from Basell Company.
  • the S-layer about 2.5 ⁇ m has the same composition as the core layer.
  • the T-layer about 2.5 ⁇ m comprises impact polypropylene copolymer with beta crystal nucleator of polypropylene, BI4020SP from Sunoco Chemicals.
  • the film has light transmission about 10.2%.
  • the P-layer is treated with corona. Inkjet printing is applied on the P-layer surface. Good ink drying is observed for red, blue, yellow, green, and black colors.
  • a five-layer oriented opaque film, P/Q/R/S/T is made by tenter- frame sequential orientation at 4 times in MD orientation and 8 times in TD orientation.
  • the P-layer about 1.25 ⁇ m comprises 70wt%> of impact polypropylene copolymer masterbatch with beta-crystal nucleator of polypropylene, BI4020SP from Sunoco Chemicals, and 30 wt% of polypropylene masterbatch with CaCO 3 , T39600 from A. Schulman (50% CaCO 3 and 50 % polypropylene).
  • the Q-layer about 5 ⁇ m comprises 68.6 wt%> of impact polypropylene copolymer masterbatch with beta-crystal nucleator of polypropylene, BI4020SP from Sunoco Chemicals, 30wt% of polypropylene masterbatch with CaCO 3 , T39600 from A. Schulman (50% CaCO 3 and 50 % polypropylene), and 1.4wt% of hygroscopic polymer, POLYOX WSRN-80 from Union Carbide.
  • the core layer, R-layer, about 25 ⁇ m comprises 60wt% of polypropylene masterbatch with beta-crystal nucleator of polypropylene, and 40 wt% of (isotactic propylene)-ethylene heterophasic copolymer, BASELL 8523 from Basell Company.
  • the S-layer about 2.5 ⁇ m has the same structure as the core layer.
  • the T-layer about 2.5 ⁇ m has impact polypropylene copolymer masterbatch with beta-crystal nucleator of polypropylene, BI4020SP from Sunoco Chemicals.
  • the film has light transmission about 8.4%>.
  • the P-layer is treated with corona. An ink-jet printing is applied on the P-layer surface. Good ink drying is observed for red, blue, yellow, green, and black colors.
  • a three-layer oriented opaque film, A/B/C is made by tenter-frame sequential orientation at 4 times in MD orientation and 8 times in TD orientation.
  • the A-layer about 3.75 ⁇ m comprises 58.5wt% of isotactic polypropylene, PP4612 from ExxonMobil Chemicals, 300 ppm of beta-crystal nucleator of polypropylene, NJ STAR NU- 100 from New Japan Chemicals, 27wt% of polypropylene masterbatch with CaCO 3 , T39600 from A.
  • the B-layer about 32.5 ⁇ m comprises 60 wt%> of polypropylene, PP4612 from ExxonMobil Chemicals, and 40 wt%> of impact polypropylene copolymer with beta crystal nucleator for polypropylene, BI4020SP from Sunoco Chemicals.
  • the C-layer about 1.25 ⁇ m is propylene-ethylene-butene- 1 terpolymer, Chisso7510 from Chisso Chemicals, Japan.
  • the film has light transmission about 7.9%).
  • the A-layer is treated with corona.
  • An ink-jet printing is applied on the A- layer surface. Good ink drying is observed for red, blue, yellow, green and black colors.

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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)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention porte sur un film thermoplastique renfermant une couche centrale et une couche superficielle d'impression améliorée. La couche centrale comprend un polymère améliorant l'orientation, un homopolymère de polypropylène et un nucléateur bêta-cristal de polypropylène. Le film thermoplastique peut être utilisé pour améliorer l'impression au cours de laquelle on préfère utiliser des films respirants ayant une bonne transmission de la vapeur d'eau.
PCT/US2003/010152 2002-05-01 2003-04-01 Film thermoplastique a base de polypropylene WO2003093004A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002480774A CA2480774A1 (fr) 2002-05-01 2003-04-01 Film thermoplastique a base de polypropylene
EP03728329A EP1499495A1 (fr) 2002-05-01 2003-04-01 Film thermoplastique a base de polypropylene
AU2003233478A AU2003233478B8 (en) 2002-05-01 2003-04-01 Thermoplastic film based on polypropylene

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/135,321 US7195818B2 (en) 2002-05-01 2002-05-01 Sealable multi-layer opaque film
US10/135,321 2002-05-01
US10/278,241 2002-10-23
US10/278,241 US6828019B2 (en) 2002-05-01 2002-10-23 Thermoplastic film

Publications (1)

Publication Number Publication Date
WO2003093004A1 true WO2003093004A1 (fr) 2003-11-13

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PCT/US2003/010152 WO2003093004A1 (fr) 2002-05-01 2003-04-01 Film thermoplastique a base de polypropylene

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EP (1) EP1499495A1 (fr)
AU (1) AU2003233478B8 (fr)
CA (1) CA2480774A1 (fr)
WO (1) WO2003093004A1 (fr)

Cited By (12)

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WO2005040270A1 (fr) * 2003-10-16 2005-05-06 Treofan Germany Gmbh & Co. Kg Pellicule moulee transparente ou coloree utilisee dans la fabrication d'etiquettes par moulage
WO2007132826A1 (fr) 2006-05-16 2007-11-22 Toray Industries, Inc. Film de polypropylÈne blanc À orientation biaxiale, plaque rÉflÉchissante, et feuille de rÉception pour enregistrement par transfert thermique
DE102006034252A1 (de) * 2006-07-21 2008-01-24 Tesa Ag Monoaxial verstreckte Polypropylenfolie mit hohem Weiterreißwiderstand in Querrichtung
WO2013116434A3 (fr) * 2012-01-31 2013-12-05 Avery Dennison Corporation Film en copolymère de polypropylène résistant aux chocs orienté
WO2014091309A2 (fr) * 2012-10-24 2014-06-19 Braskem S.A. Composition polymère présentant des propriétés de barrière améliorées
US9636895B2 (en) 2006-06-20 2017-05-02 Avery Dennison Corporation Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof
US9662867B2 (en) 2006-06-14 2017-05-30 Avery Dennison Corporation Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US9676532B2 (en) 2012-08-15 2017-06-13 Avery Dennison Corporation Packaging reclosure label for high alcohol content products
EP3007665A4 (fr) * 2013-06-13 2017-06-21 3M Innovative Properties Company Article d'hygiène personnelle et récipient pour ce dernier
USRE46911E1 (en) 2002-06-26 2018-06-26 Avery Dennison Corporation Machine direction oriented polymeric films and methods of making the same
WO2020131709A3 (fr) * 2018-12-17 2020-10-08 Taghleef Industries, Inc. Film imprimable
US11459488B2 (en) 2014-06-02 2022-10-04 Avery Dennison Corporation Films with enhanced scuff resistance, clarity, and conformability

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EP0632095A2 (fr) * 1993-05-20 1995-01-04 New Japan Chemical Co.,Ltd. Article étirable poreux de résine à base de polypropylène et procédé pour sa préparation
US5594070A (en) * 1990-12-21 1997-01-14 Amoco Corporation Oriented polymeric microporous films
EP0865909A1 (fr) * 1997-03-18 1998-09-23 Hoechst Trespaphan GmbH Etiquettes

Patent Citations (3)

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US5594070A (en) * 1990-12-21 1997-01-14 Amoco Corporation Oriented polymeric microporous films
EP0632095A2 (fr) * 1993-05-20 1995-01-04 New Japan Chemical Co.,Ltd. Article étirable poreux de résine à base de polypropylène et procédé pour sa préparation
EP0865909A1 (fr) * 1997-03-18 1998-09-23 Hoechst Trespaphan GmbH Etiquettes

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE46911E1 (en) 2002-06-26 2018-06-26 Avery Dennison Corporation Machine direction oriented polymeric films and methods of making the same
WO2005040270A1 (fr) * 2003-10-16 2005-05-06 Treofan Germany Gmbh & Co. Kg Pellicule moulee transparente ou coloree utilisee dans la fabrication d'etiquettes par moulage
CN100540597C (zh) * 2003-10-16 2009-09-16 特里奥凡德国有限公司及两合公司 用于模内标记场合的透明和着色铸塑膜
WO2007132826A1 (fr) 2006-05-16 2007-11-22 Toray Industries, Inc. Film de polypropylÈne blanc À orientation biaxiale, plaque rÉflÉchissante, et feuille de rÉception pour enregistrement par transfert thermique
US8512828B2 (en) 2006-05-16 2013-08-20 Toray Industries, Inc. Biaxially oriented white polypropylene film, reflection plate and receiving sheet for thermal transfer recording
TWI421166B (zh) * 2006-05-16 2014-01-01 Toray Industries 雙軸配向白色聚丙烯膜、反射板及感熱轉印記錄用收受片
US9662867B2 (en) 2006-06-14 2017-05-30 Avery Dennison Corporation Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US9636895B2 (en) 2006-06-20 2017-05-02 Avery Dennison Corporation Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof
DE102006034252A1 (de) * 2006-07-21 2008-01-24 Tesa Ag Monoaxial verstreckte Polypropylenfolie mit hohem Weiterreißwiderstand in Querrichtung
CN109355023B (zh) * 2012-01-31 2021-09-21 艾利丹尼森公司 取向的抗冲共聚物聚丙烯膜
CN109355023A (zh) * 2012-01-31 2019-02-19 艾利丹尼森公司 取向的抗冲共聚物聚丙烯膜
AU2013215135B2 (en) * 2012-01-31 2016-09-15 Avery Dennison Corporation Oriented impact copolymer polypropylene film
CN104080874A (zh) * 2012-01-31 2014-10-01 艾利丹尼森公司 取向的抗冲共聚物聚丙烯膜
WO2013116434A3 (fr) * 2012-01-31 2013-12-05 Avery Dennison Corporation Film en copolymère de polypropylène résistant aux chocs orienté
JP2015513564A (ja) * 2012-01-31 2015-05-14 エーブリー デニソン コーポレイションＡｖｅｒｙ Ｄｅｎｎｉｓｏｎ Ｃｏｒｐｏｒａｔｉｏｎ インパクトコポリマーポリプロピレン延伸フィルム
US9676532B2 (en) 2012-08-15 2017-06-13 Avery Dennison Corporation Packaging reclosure label for high alcohol content products
WO2014091309A3 (fr) * 2012-10-24 2014-11-27 Braskem S.A. Composition polymère présentant des propriétés de barrière améliorées
WO2014091309A2 (fr) * 2012-10-24 2014-06-19 Braskem S.A. Composition polymère présentant des propriétés de barrière améliorées
EP3007665A4 (fr) * 2013-06-13 2017-06-21 3M Innovative Properties Company Article d'hygiène personnelle et récipient pour ce dernier
US10376420B2 (en) 2013-06-13 2019-08-13 3M Innovative Properties Company Personal hygiene article and container for the same
US11459488B2 (en) 2014-06-02 2022-10-04 Avery Dennison Corporation Films with enhanced scuff resistance, clarity, and conformability
WO2020131709A3 (fr) * 2018-12-17 2020-10-08 Taghleef Industries, Inc. Film imprimable
US11752739B2 (en) 2018-12-17 2023-09-12 Taghleef Industries Inc. Printable film
AU2019405454B2 (en) * 2018-12-17 2023-12-14 Taghleef Industries, Inc. Printable film

Also Published As

Publication number Publication date
CA2480774A1 (fr) 2003-11-13
AU2003233478B8 (en) 2008-07-03
AU2003233478B2 (en) 2008-06-12
EP1499495A1 (fr) 2005-01-26
AU2003233478A1 (en) 2003-11-17

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