EP0960159A1 - Appret pour films plastiques - Google Patents

Appret pour films plastiques

Info

Publication number
EP0960159A1
EP0960159A1 EP98906258A EP98906258A EP0960159A1 EP 0960159 A1 EP0960159 A1 EP 0960159A1 EP 98906258 A EP98906258 A EP 98906258A EP 98906258 A EP98906258 A EP 98906258A EP 0960159 A1 EP0960159 A1 EP 0960159A1
Authority
EP
European Patent Office
Prior art keywords
primer
poly
vinyl alcohol
layer
films
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Withdrawn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
EP98906258A
Other languages
German (de)
English (en)
Other versions
EP0960159A4 (fr
Inventor
Dennis Emmett Mcgee
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.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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 Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0960159A1 publication Critical patent/EP0960159A1/fr
Publication of EP0960159A4 publication Critical patent/EP0960159A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the invention relates to a primer for plastic films which comprises a blend of poly(vinyl alcohol) and an adhesion promoter, specifically poly(ethylene imine) and/or a hardened epoxy resin.
  • the invention provides plastic films with excellent oxygen- barrier properties.
  • poly(vinyl alcohol) is a water-soluble synthetic polymer made by alcoholysis of polyvinyl acetate. Among other things, it is known for utility as a laminating adhesive. When used in packaging films, poly(vinyl alcohol) has been described as providing a film which is impervious to oils, fats and waxes and to be an excellent oxygen barrier. For this reason, poly(vinyl alcohol) is often used as barrier coatings on thermoplastic films. No single unmodified polymeric film, however, has the gas and moisture barrier characteristics and adhesion property needed for packaging.
  • the multilayer film of Knoerzer et al. includes a polymeric substrate having a primer coating on at least one surface of the substrate, a layer of cross-linked poly(vinyl alcohol) on the coating, and a layer of a blend of a poly(vinyl alcohol) homopolymer or copolymer and an ethylene acrylic acid copolymer on the cross-linked layer.
  • This reference also discloses that an optional metal layer can be deposited on the blend layer.
  • U.S. Patent No. 4,214,039 to Steiner et al. is directed to thermoplastic films which include a film substrate having a primer coating layer applied to it, and a vinylidene chloride polymer as a top coat applied on the primer coating layer.
  • These films require two separate layers of primer and polymer in order to obtain both chemical barrier and adhesion properties.
  • Many coaters only have two stations for applying coating to one side of a film at a time.
  • the present invention relates to a primer for plastic films and the use of the primer in packaging materials.
  • the primer includes a blend of poly( vinyl alcohol) and an adhesion promoter, specifically poly(ethylene imine) and/or a hardened epoxy resin.
  • the invention is useful to improve the oxygen-barrier properties of a plastic film.
  • the hardened epoxy resin is in an amount of about 15 to about 35 parts per hundred poly(vinyl alcohol).
  • the primer can further include an glyoxal in an amount of about 10 to about 20 parts per hundred poly(vinyl alcohol).
  • the primer can further include choline chloride.
  • the adhesion promoter is preferably polyethyleneimine.
  • the packaging material of the present invention includes (a) a packaging substrate that has a first surface layer and a second surface layer; (b) a precoating layer having a primer coated on at least one surface layer of the substrate, wherein the primer is a blend of poly( vinyl alcohol), an adhesion promoter and/or an epoxy resin; and (c) optionally a top coat layer and/or a metallic layer deposited thereon the precoating layer.
  • packaging films having a unique primer layer are produced.
  • the unique blend of the primer layer of the present invention provides excellent oxygen barrier properties.
  • the primer layers of the present invention can have a coating layer and/or a metallic layer deposited thereon, and thus offer greater barrier properties and sealant strength. For example, an unexpected synergy between the primer and top coats provides additional barrier enhancement.
  • Figure 1 is a plot showing the concentration of primer ingredients vs. oxygen barrier properties of the uncoated film
  • Figure 2 is a plot showing the concentration of primer ingredients vs. oxygen barrier properties for the coated films
  • Figure 3 is a plot showing the concentration of primer ingredients vs. oxygen barrier properties for the metallized film.
  • Figure 4 is a plot showing the concentration of primer ingredients vs. crimp-seal strength for coated films for seals formed at 127° C; and Figure 5 is another plot showing the concentration of primer ingredients vs. crimp-seal strength for coated films for seals formed at about 104°C.
  • the invention comprises a primer for plastic film and the use of the primer in packaging materials.
  • the primer is a blend of poly (vinyl alcohol) and an adhesion promoter and/or a hardened epoxy resin.
  • the primer of the invention can be used as a primer layer for coatings and/or metallization of a substrate such as oriented polypropylene or other plastic film.
  • the primed and coated or primed and metallized film has enhanced oxygen barrier properties. Synergistic oxygen barrier properties have been found in that the barrier properties are better than expected based on the oxygen barrier contribution of the individual layers.
  • the poly(vinyl alcohol) in the blend of the present invention refers to any commercially available poly(vinyl alcohol), e.g., ENANOL 71-30, an E.I. DuPont product.
  • adhesion promoter examples include, but are not limited to,hardened epoxy as described by U.S. Patent No. 4,214,039 to Steiner which is incorporated herein by refernce and polyethyleneimine, in which polyethyleneimine is preferred.
  • the amount of the epoxy resin can range from between about 15 and about 35 parts per hundred parts poly( vinyl alcohol). Higher epoxy levels are found to degrade barrier properties, 25 parts per hundred parts poly(vinyl alcohol) result in good oxygen barrier properties.
  • the primer coating can further contain a cross-linking agent in an amount ranging from about 10 and 20 parts per hundred parts poly(vinyl alcohol). A higher level is useful to promote cross-linking of the PNOH primer.
  • Suitable examples of the cross-linking agent in the present invention include, but are not limited to, glyoxal, melamine formaldehyde, glutaraldehyde, with glyoxal being preferred. It is contemplated that sealable coatings such as acrylic coatings and low temperature sealable coatings will adhere well to the primer of this invention.
  • the coating weight of the primer of this invention is most easily controlled by the solids level. It is preferred to apply the primer at about 6% solids, which with our application method provides a primer coat weight of about 0.4 g/1000 square inches
  • the coating weights of coatings applied to the primer of this invention are typical to those used in the film coating industry. Examples in this disclosure range between about 0.6% to about 1.3% solids which provides about 0.6 to about 1.3 g/msi, coating weight, depending upon the coating applied. However, this range should not be construe as limiting.
  • Choline chloride can also be added to the primer formulation in amounts of about 0.25 parts per hundred poly(vinyl alcohol).
  • the packaging material of the present invention includes (a) a packaging substrate that has a first surface layer and a second surface layer; (b) a precoating layer having a primer coated on at least one surface layers of the substrate, wherein the primer is a blend of poly (vinyl alcohol), an adhesion promoter and/or an epoxy resin; and (c) optionally a top coat layer and/or a metallic layer deposited thereon the precoating layer.
  • the blend in the primer can further include a cross-linking agent and/or choline chloride.
  • the packaging substrate of the present invention includes any polymeric film substrate which inherently permits the transmission of oxygen and water vapor, and wherein the utility of such film for packaging purposes would call for a minimization of such transmission.
  • the polymeric materials include, but are not limited to, nylon, polyethylene teraphthaplate, polycarbonate, and polyolefins.
  • the substrate is a polyolefin including, but not limited to polyethylene, polypropylene, polybutylene, terpolymers, copolymers, and blends thereof. More preferably, the substrate is an oriented polypropylene.
  • Examples of the packaging substrate of the present invention can also include paperboards and fiberboard. Suitable examples of the paperboards and fiberboards can include, but are not limited to, glassine papers and clay coated papers.
  • the packaging substrate of the present invention can be of any desired thickness. Generally, to ensure good machinability on high speed packaging equipment, the thickness of the substrate is from about 10 to about 50 microns, preferably, from about 10 to about 35 microns, and more preferably from about 12 to about 25 microns. At least one surface of the packaging substrate of the present invention is coated with a precoating layer by any coating method known in the art, e.g., gravure coating.
  • the polymeric substrate can be pretreated to enhance the adhesion of the precoating layer to the polymeric substrate by any pretreatment known in the art.
  • Pretreatments well known in the art include, but are not limited to, flame treatment, plasma treatment, chemical treatment and corona discharge treatment that are well known in the art.
  • Flame treatment and corona discharge treatment are preferred with corona discharge treatment being particularly more preferred.
  • the primer coating of the present invention is a blend of poly(vinyl alcohol), an adhesion promoter and/or an epoxy resin.
  • the blend in the primer coating can further include a cross-linking agent and/or choline chloride.
  • the thickness of the precoating layer is from about 0.5 to about 2.0 microns, preferably, from about 0.7 to about 1.5 microns, and more preferably from about 1.0 to about 1.5 microns.
  • the weight ratio of the adhesion promoter and/or epoxy resin and polyvinyl alcohol is from about 0.15 to about 0.35, preferably from about 0.20 to about 0.30, and more preferably from about 0.22 to about 0.28.
  • the weight ratio of the cross-linking agent and polyvinyl alcohol is from about 0.05 to about 0.4, preferably from about 0.10 to about 0.30, and more preferably from about 0.11 to about 0.12.
  • the precoating layer of the present invention can optionally have a top coat layer and/or a metallic layer deposited thereon.
  • the top coat layer can be applied on top of the precoating layer by any manner known in the art, e.g., gravure coating.
  • the function of the top coat layer is to provide additional barriers and/or sealability and/or machinability and/or printability. Examples of coating materials to be used as a top coat layer are described in
  • the coating materials include, but are not limited to, emulsions or solutions comprising poly(vinylidene) chloride, poly(vinyl chloride), poly(vinyl alcohol), ethylene acrylic acid copolymer, and acrylic.
  • the thickness of the coating layer is up to 5.0 microns.
  • the metal layer is deposited on the top layer by a manner known in the art, e.g., vacuum metallization or plasma deposition.
  • the metal layer provides the packaging material with extra barrier and sealant properties.
  • metals for the metal layer can include, but are not limited to, aluminum and aluminum oxide.
  • EXAMPLE 1 PACKAGING FILMS OF THE PRESENT INVENTION This example illustrates the chemical barrier and adhesion properties of the packaging films of the present invention. Chemical barrier and adhesion tests were performed on eight film substrates having various coating compounds.
  • Each of the eight film substrates was coated with eight different precoating layers of primer blends.
  • the primer blends were applied utilizing a reverse direct gravure coating.
  • the coated films were passed through a dry-air oven at about 125 ft/min. and at a temperature of 200 °F.
  • the primer blends include PNOH, epoxy primer, and glyoxal.
  • the primer blends are illustrated in Table 1.
  • Each of the eight precoating layer was then coated with a top coating layer of an EAA formulation.
  • the EAA formulation was applied utilizing a reverse direct gravure coater. The coated films were passed through a dry air oven at a temperature of 200 °F.
  • the EAA formulation included lOOphr M4983 (Michernprime manufactured by Michelman), 1.5phr NaOH; 4phr carnaube wax emulsion (obtained from Michelman), 0.3phr silloid and 0.4phr talc.
  • the resulting films were tested for oxygen transmission.
  • the dried films were then tested in an oxygen-permeability device in which a stream of dry oxygen was passed through an aqueous salt solution-permeated pad to control the gas moisture content and then through the films, disposed at right angles to the stream with the top coating layer upstream.
  • the oxygen transmitted was determined and the amount of oxygen passed per unit area of film per time period was calculated.
  • the results of oxygen barrier tests are shown in Table 2.
  • the packaging films of the present invention have low gas transmission and excellent adhesion property.
  • the unique blend of the precoating layer of the present invention provides both chemical barrier and adhesion properties offer by the conventional packaging films.
  • the blend of the precoating layer of the packaging films of the present invention eliminates the required primer layers of the conventional films.
  • EXAMPLE 3 METALLIZED PACKAGING FILMS This example illustrates the chemical barrier and adhesion properties of conventional metallized packaging films and metallized packaging films of the present invention. Chemical barrier and adhesion tests were performed on nine MC550 film substrates (made by Mobil) having various coating compounds.
  • the primer blends include PNOH, EAA, epoxy primer, and glyoxal.
  • the primer blends are illustrated in Table 3.
  • Each of the precoating layers was then metallized with a metal.
  • the resulting films were tested for water vapor transmission, oxygen transmission, and adhesion properties. The results of the tests are illustrated in Table 4.
  • Oriented polypropylene film samples (Samples 1-21) were primed with primer formulations described in the following table.
  • M4983 is Michemprime manufactured by Michelman.
  • M215 is a carnaube wax emulsion obtained from Michelman.
  • SR344 is Tospearl 145 obtained by Toshiba Silicone Co.
  • ML71513 is a synthetic wax obtained from Michelman.
  • D8500 is Daran 8500 obtained from Hampshire Chemical.
  • Each of the samples were tested for oxygen barrier properties and for sealability and the results of the testing are reported in Table 5 and Figures 1 to 5.
  • ACNB 5ELVANOL 90/50 80 124 B 000 125 37 00 25 665 20 200 7 100 0 25 15 0 025 1403
  • ACN8 6ELVANOL 90/50 80 B05 000 113 32 00 16 1034 20 200 5 loo 0 35 20 0 025 1553
  • Figure 1 is a plot showing the concentration of primer ingredients vs. oxygen barrier properties of the uncoated film.
  • Figures 1 shows that high concentrations of poly(vinyl alcohol), which correspond to lower concentrations of epoxy, provide better oxygen barrier properties as does an increased coating weight.
  • Figure 2 is a plot showing the concentration of primer ingredients vs. oxygen barrier properties for the coated film.
  • Figure 2 shows that, after top coating, all samples demonstrated better oxygen barrier properties than could be expected on the basis of the barrier contribution of the individual components.
  • the low temperature sealable coating gave an oxygen barrier of 117 cm 3 / 100 rVday, which is approximately the barrier given by this gauge of polypropylene coated with polyethylene imine (129 cm 3 / 100 in 2 /day).
  • the mean barrier for the samples that were coated with the low temperature sealable coating was about 3.7 cmVlOO in 2 /day.
  • the barrier contribution of the low temperature sealable coating layer is about 1300 cmVlOO in 2 /day. Therefore, the expected oxygen transmission of the primed and coated film combination is expected to be no better than 3.69 cm 3 /100 in 2 /day.
  • the expected value was calculated from the approximate barriers of the component layers:
  • the value (1/3.7) includes the barrier of the oriented polypropylene and the primer.
  • the value (1/300) was arrived at by subtracting the reciprocal of the barrier for polyethylene imine primed oriented polypropylene (1/117) from the reciprocal of the observed barrier of low temperature sealable coated polyethylene imine on the same gauge of oriented polypropylene (1/129).
  • the actual mean value for the six samples was about 2.1 cm 3 / 100 in 2 /day . This value is lower than the mean value for any group of samples that only had the primer. It is about two-times as good as expected.
  • the polyvinylidene chloride coated When a polyvinylidene chloride coated was applied to the primed film, at a relatively low coating weight the polyvinylidene chloride provided an oxygen barrier of about 0.85 cm 3 / 100 in 2 /day on epoxy-primed film which without the coating provided an oxygen barrier of 124 cm 3 / 100 in 2 /day. Therefore, the polyvinylidene chloride layer contributed 0.86 cm 3 / 100 in 2 /day to the barrier. If this coating is applied to a base sheet with a barrier of 2.6 cmVlOO in 2 /day, then the expected oxygen barrier should be about 0.81 cmVlOO in 2 /day. For the six polyvinylidene chloride coated samples, the mean value was 0.05 cmVlOO in 2 /day. This is sixteen times better than expected.
  • Figure 3 is a plot showing the concentration of primer ingredients vs. oxygen barrier properties for the metallized film. Unlike the coated film samples, the metallized films show better barrier properties at low poly(vinyl alcohol) coating weights. When polyethylene imine or epoxy primed film was metallized the oxygen barrier values ranged from 1.5 to cm 3 / 100 in 2 /day. Switching to the poly(vinyl alcohol) primer, the mean oxygen transmission value was about 0.13 cmVlOO in 2 /day.
  • FIG. 4 is a plot showing the concentration of primer ingredients vs. crimp- seal strength for coated films for seals formed at 127° C. the best results were achieved with a low temperature sealable coating but good effects were achieved with polyvinylidene chloride (Daran 8500) which performed better than acrylic. The improvement appears to relate to adhesion to primer. Higher epoxy levels in the primer improved the adhesion to the coatings.
  • Figure 5 is another plot showing the concentration of primer ingredients vs. crimp-seal strength for coated films for seals formed at about 104°C. Similar results are achieved at lower temperatures. Surprisingly the low temperature sealable coating achieved improved seals at lower temperatures. At 82 °C the low temperature sealable coating still had seals of )400 g/in.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne un apprêt pour films plastiques qui comprend un mélange de poly(alcool de vinyle) et un promoteur d'adhésion, plus particulièrement poly(éthylène imine) et/ou une résine époxy durcie. L'invention peut servir à améliorer l'imperméabilité à l'oxygène d'un film plastique.
EP98906258A 1997-02-10 1998-02-06 Appret pour films plastiques Withdrawn EP0960159A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US3758597P 1997-02-10 1997-02-10
US37585P 1997-02-10
PCT/US1998/002498 WO1998034982A1 (fr) 1997-02-10 1998-02-06 Appret pour films plastiques

Publications (2)

Publication Number Publication Date
EP0960159A1 true EP0960159A1 (fr) 1999-12-01
EP0960159A4 EP0960159A4 (fr) 2001-04-04

Family

ID=21895138

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98906258A Withdrawn EP0960159A4 (fr) 1997-02-10 1998-02-06 Appret pour films plastiques

Country Status (10)

Country Link
EP (1) EP0960159A4 (fr)
JP (1) JP2001511211A (fr)
KR (1) KR20000070911A (fr)
CN (1) CN1246879A (fr)
AR (1) AR011658A1 (fr)
AU (1) AU735361B2 (fr)
BR (1) BR9807569A (fr)
CA (1) CA2280050A1 (fr)
ID (1) ID23409A (fr)
WO (1) WO1998034982A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024200607A1 (fr) 2023-03-28 2024-10-03 Innovia Films Limited Film barrière

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0200957D0 (en) 2002-01-17 2002-03-06 Secr Defence Novel polymer and uses thereof
GB0421706D0 (en) * 2004-09-30 2004-11-03 Univ Belfast "Polymer Material"
EP2592114B1 (fr) * 2010-07-09 2018-11-07 The Nippon Synthetic Chemical Industry Co., Ltd. Composition de copolymère d'éthylène/ester vinylique saponifié et structure à couches multiples utilisant la composition
US9303179B2 (en) 2012-11-02 2016-04-05 Michelman, Inc. Primer coating for metallized gas barrier films
CN104962146A (zh) * 2015-07-03 2015-10-07 海南必凯水性涂料有限公司 一种高阻氧自粘性聚乙烯醇涂料及其制备方法
CN104961903A (zh) * 2015-07-03 2015-10-07 海南赛诺实业有限公司 一种高阻氧无底胶聚乙烯醇涂布薄膜及其制造方法
BR112019004799A2 (pt) * 2016-09-14 2019-06-04 Basf Se método de formar uma película polimérica revestida com óxido de metal ou metalizada, película de polímero, embalagem, e, uso de uma solução aquosa.
CN109747971A (zh) * 2017-11-08 2019-05-14 林紫绮 阳离子水性溶液制造防止墨料污染包装材料的方法
JP7567790B2 (ja) * 2019-07-10 2024-10-16 Ａｇｃ株式会社 ガラス基体およびその製造方法
EP4200132A1 (fr) * 2020-12-11 2023-06-28 Sonoco Development, Inc. Contenants à barrière durable et procédés
US11884466B2 (en) 2020-12-11 2024-01-30 Sonoco Development, Inc. Sustainable barrer containers and methods
DE102021114174A1 (de) * 2021-06-01 2022-12-01 Mondi Ag Folienverbund, Folienverpackung sowie Verfahren zur Herstellung eines Folienverbundes
CN114854155B (zh) * 2022-04-06 2023-08-22 杭州师范大学 一种高强度、抗冻和透明的导电pva/季铵盐弹性体

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US4214039A (en) * 1979-04-23 1980-07-22 Mobil Oil Corporation Polypropylene film with primer of a water dispersed epoxy resin coating
US5192620A (en) * 1991-11-08 1993-03-09 Mobil Oil Corporation Metallized composite film structure and method
WO1996016799A1 (fr) * 1994-12-02 1996-06-06 Mobil Oil Corporation Film multicouche thermosoudable comprenant une couche d'alcool polyvinylique

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US5552212A (en) * 1990-12-13 1996-09-03 Mobil Oil Corporation High barrier film combination
US5487940A (en) * 1991-12-23 1996-01-30 Mobil Oil Corp. Oxygen and moisture barrier metallized film structure
JPH06228347A (ja) * 1993-01-29 1994-08-16 Teijin Ltd 制電易接着性ポリエステルフイルム
US5496649A (en) * 1994-07-21 1996-03-05 Mobil Oil Corp. Cross-linked PVOH coatings having enhanced barrier characteristics
US5547764A (en) * 1994-12-22 1996-08-20 Mobil Oil Corporation Method of producing PVOH coatings with enhanced properties

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Publication number Priority date Publication date Assignee Title
US4214039A (en) * 1979-04-23 1980-07-22 Mobil Oil Corporation Polypropylene film with primer of a water dispersed epoxy resin coating
US5192620A (en) * 1991-11-08 1993-03-09 Mobil Oil Corporation Metallized composite film structure and method
WO1996016799A1 (fr) * 1994-12-02 1996-06-06 Mobil Oil Corporation Film multicouche thermosoudable comprenant une couche d'alcool polyvinylique

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Title
See also references of WO9834982A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024200607A1 (fr) 2023-03-28 2024-10-03 Innovia Films Limited Film barrière

Also Published As

Publication number Publication date
BR9807569A (pt) 2000-02-01
EP0960159A4 (fr) 2001-04-04
WO1998034982A1 (fr) 1998-08-13
ID23409A (id) 2000-04-20
KR20000070911A (ko) 2000-11-25
CA2280050A1 (fr) 1998-08-13
JP2001511211A (ja) 2001-08-07
AU6152898A (en) 1998-08-26
CN1246879A (zh) 2000-03-08
AR011658A1 (es) 2000-08-30
AU735361B2 (en) 2001-07-05

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