CA2125883C - Low oxygen transmissive film - Google Patents

Low oxygen transmissive film Download PDF

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Publication number
CA2125883C
CA2125883C CA 2125883 CA2125883A CA2125883C CA 2125883 C CA2125883 C CA 2125883C CA 2125883 CA2125883 CA 2125883 CA 2125883 A CA2125883 A CA 2125883A CA 2125883 C CA2125883 C CA 2125883C
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Prior art keywords
cross
film according
linking agent
polyvinyl alcohol
formaldehyde
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Expired - Fee Related
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CA 2125883
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French (fr)
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CA2125883A1 (en
Inventor
Anthony Robert Knoerzer
Robert Edward Touhsaent
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ExxonMobil Oil Corp
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ExxonMobil Oil Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/042Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/048Forming gas barrier coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/052Forming heat-sealable coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00Characterised by the use 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised 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
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2813Heat or solvent activated or sealable
    • Y10T428/2817Heat sealable
    • Y10T428/2826Synthetic resin or polymer
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2843Web or sheet containing structurally defined element or component and having an adhesive outermost layer including a primer layer
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31909Next to second addition polymer from unsaturated monomers
    • Y10T428/31913Monoolefin polymer
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31909Next to second addition polymer from unsaturated monomers
    • Y10T428/31913Monoolefin polymer
    • Y10T428/3192Next to vinyl or vinylidene chloride polymer

Abstract

A low oxygen transmissive film combination having a substrate with a surface having a surface free energy of at least about 35 dynes/cm, a primer coating on one or both sides and an oxygen transmissive inhibiting layer of a polyvinyl alcohol) and a cross-linking agent with a proportion of catalytically active sulfuric acid.

Description

LOW OXYGEN TRANSMISSIVE FILM
This invention relates to a flexible, multilayer film having low o:~ygen transmissive characteristics.
Certain polymeric films employed for the packaging ~of foods inherent:Ly permit the transmission of oxygen from the outside of the film to the inside of a package made up of t:he film. Oxygen permits rapid deterioration of ;=oods packaged in such a container, therefore, its exclusion or control is desired.
In accordance with the present invention, a film combination compr_~ses a polymeric substrate susceptible of transmitting oxygen, at least one side thereof having been treated to a surface-free energy of at least 35 dynes/cm,; at least one treated side having a primer coating thereon; and on the primer coating, an oxygen tran~;mission inhibiting layer of polyvinyl alcohol) containing a cross-linking agent catalyzed with sulfuric acid.
The substrates contemplated herein include any polymeric film substrate oriented or unoriented which inherently permit: the transmission of oxygen and wherein the utility of such film would call for a minimizatior_ of tree transmission of oxygen. In most cases, the ~~ource of the oxygen referred to herein is atmospheric oxygen. While nylon, polyethylene terephthalate and polycarbonate films are contemplated herein, a pa.rticu7_arly preferred class of films are the polyolefins. Within the polyolefin class, homopolymers and copolymers of propylene are preferred.
Particularly preferred are isotactic polypropylenes containing at least 80% by weight of isotactic polypropylene. The preferred base substrate layer can be homopolypropylene having a melting point range from 321° to 336°F. A commercially available material of this description is ARCO W472*. The preferred su.bstrat:e can also be coextruded with a thin * Trade-mark WU 93112931 ~ ~ ~ ~ ~ ~ ~ PCT/US92/111'':"'~~, _2-skin layer, in an amount from 2 to 12% of the total thickness, of a copolymer of propylene and another olefin, e.g., ethylene and/or butene-1. The other olefin can be present in the copolymer in an amount from 1 to 7 wt$.

In order to inhibit effectively the amount of oxygen transmitted through the base layer, the base layer must be 1) treated to a surface free energy of at least 35 dynes/cm, 2) have a primer coating applied thereto, and 3) have a coating on the primer of an oxygen transmission inhibiting layer of polyvinyl alcohol) containing a cross-linking agent catalyzed with sulfuric acid.

The preferred substrate must be properly prepared ..

to receive the primer layer followed by the cross-linked polyvinyl aleohol). This proper treatment involves treating the surface to a surface tension level of at Least 35 and preferably from 38 to 45 dynes/cm in accordance with ASTM Standard D2578-84.

The treatment can be flame treatment, plasma treatment, chemical treatment or corona discharge treatment.

Flame treatment and corona discharge treatment are preferred with corona discharge treatment being particularly preferred.

Commercially available corona discharge treatment equipment can be obtained from Solo Systems, Inc., Garland, Texas: Corotec Corporation, Collinsville, Connecticut: 8oftal Electronics, Hamburg, W. Germany:

and others. Using, for example, Softal Electronics equipment, a treater can have an air gap of about 0.050 in. when treating polypropylene film of about 0.9 mils.

The film can be treated to a surface free energy from 42 to 44 dynes/cm.

After this treatmer_t, a suitable primer material is coated onto the treated surface.

Preferred primer materials are those disclosed in U.S. Patent No. 4,564,559. These include a primer produced by condensing a monoaldehyde with an interpolymer of acrylamide or methacrylamide and at least one ot=her unsaturated monomer. Further included is a material resulting from condensing aminoaldehyde with acrylamide o=r methacrylamide and subsequently interpolymerizing the condensation product with at least one other unsaturated monomer in the presence of a Cl-Cf alkanol. A preferred primer coating resin of this type comprisE=_s a copolymer containing up to 90o by weight of st:yrene,, up to 80% by weight of an alkyl acrylate, up to 15% by weight of methacrylic acid and 5% to 25% by weight of acrylamide which has been condensed with a ;solution of formaldehyde in n-butanol containing from 0..2 to 3 equivalents of formaldehyde for each amide group in the copolymer. Another primer resin of this type is a 50o solid solution of a copolymer resin containing 38.5 parts of styrene, 44 parts of ethyl acrylate, 2.5 parts of methacrylic acid and 15 part; of ac:rylamide which has been condensed with 5.2 parts of formaldehyde in n-butanol.
A parti.cular7_y preferred primer material for the structure contemplated herein has been found to be poly(ethyler..eimine). The imine primer provides an overall adhe:sively active surface for thorough and secure bonding wit-h the subsequently applied cross linked polyvinyl alcohol). It has been found that an effective coating solution concentration of the poly(ethylen.eimine) applied from either aqueous or organic solvent media, such as ethanol, is a solution comprising from 0.1 to 0.6% by weight of the poly(ethylen.eimine). A commercially available material of this type is known as "Polymin P"*, a product of BASF-Wyandotte Corporation.
* Trade-mark W0 93/1293a ' , PCT/US92/11116 y -4_ Another particularly preferred primer material is the reaction product of an epoxy resin with an acidified aminoethylated vinyl polymer. The .
contemplated epoxy resins are glycidyl ethers of polyhydroxy compounds. Typical polyhydroxy compounds which may be used include bisphenol A, ring-substituted bisphenol A, resorcinol, hydroquinone, phenol-formaldehyde, Novolac resins, aliphatic diols, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexane-diol, glycerol, lower alkyl hydantoins and mixtures thereof. The preferred epoxy resins of the present invention are those made by the glycidation reaction between epichlorohydrin and bisphenol A.
Epoxy resins of this type are commonly classified by their epoxy equivalent weight (EEW) which is defined by the weight of resin in grams which contains one gram equivalent of epoxy groups. Resins with an EEW from 170 to 280 may be used in the present invention, but the preferred range is 180 to 210.
Although the specific structure of the epoxy resin is not critical to the primer employed in the present invention, important considerations in the selection of the epoxy resin revolve around its physical state. For example, it must be liquid and capable of being readily dispersed or dissolved with the second component or curing agent as described hereinbelow. If the epoxy resin is of low viscosity, it may be stirred directly into the second component, i.e., curing agent, however, it is preferred to employ the epoxy resin in an aqueous emulsion.
The second component in the epoxy primer composition of the present invention is an amino modified acrylic polymer which is water soluble. This polymer is a curing agent for the epoxy compound. The preferred material is described in U.S. Patent No.
... ,.n... .,. ~ . r l .." ~ .v~,. . , .., , , , ... . ,. ~' . . ~ . .. .. . ' .. ..,.
. ., d<... !,': ~ v' i i 3,719,629. This material may be generically described as an acidified aminoethylated interpolymer having pendent aminoalkylate groups. This material is produced by polymerizing acrylate, methacrylate, styrene or other suitable monomers with sufficient methacrylic or acrylic acids to give a -COOH content of 7.5 to 12.5%. Solvent polymerization techniques are preferred. The polymer is then reacted with ethyleneimine monomer and acidified with hydrochloric acid to render the polymer water-soluble.
In one embodiment of the present invention, a liquid epoxy resin is emulsified in a solution of the curing agent by rapid stirring, the resultant dispersion is diluted with water to the desired concentration for coating, usually from 2 to 20~
solids. When mixing the epoxy resin with the curing agent, it is generally preferred to use a stoichiometric equivalent balance of epoxy and amine groups.
However, it has been found that the stoichiometric ratio may be varied over a wide range, from 1 epoxy to 3 amine groups through 3 epoxy groups to 1 amine group.
Any of the above described primers can be employed in an amount .from 0.001 to 3.5 g/m'.
The polyvinyl alcohol) employed herein can be any commercially available material. For example, ELVANOL*
71-30, an E. I. duPont product. The polyvinyl alcohol) coating solution is prepared by dissolving the polymer in hot water, cooling and mixing both with a suitable cross-linking agent and sulfuric acid as the catalyst. The cross-linking agent can be a melamine or urea-formaldehyde resin. Commercially available cross-linkers also would include PAREZ*613, a methylated melamine formaldehyde; CYMEL*373, a methylated melamine formaldehyde; CYMEL*401, a trimethylol melamine urea formaldehyde; glyoxal or borax, * Trade-mark (each instance) etc. Sulfuric acid as the cross-linker catalyst has been discovered to be far superior to nitric acid, ammonium chloride and ammonium nitrate.
Cross-.Linking is carried out to make the polyvinyl alcohol) less moisture sensitive but it is essential that this does not occur before the coating weight is applied and evenly distributed. This is effected by making up the aqueous solution so that the initial concentration is too low for this to occur but, as drying oc curs, the concentration increases and the rate of cro:~s-linking is heightened.
Suitable concentrations have been found to be from 1 to 35, preferably from 4 to 8 wt% of the solution, being polymer plus cross-linking agent plus sulfuric acid in a catalytically active amount. If the solids content is higher, the solution becomes too viscous; if lower, good water resistance is not obtained. From 5%
to 30o, typ:~_cally 15% cross-linking agent is used with from O.lo to 7.5%, typically 20 of the sulfuric acid catalyst. A preferred formulation comprises the following solids ~~ontent: 85.5 wto polyvinyl alcohol); 12.8 wt'a methylated melamine formaldehyde;
and 1.7 wto sulfuric acid. The sulfuric acid employed can have a :~treng~~h from 0.1 to 1.0, molarity. A
catalytical=_y active amount can be from 0.1 to 20 wt. °
o.
The aqueous polyvinyl alcohol) solutions were prepared by disso:Lving sufficient ELVANOL* 71-30 in hot water to form 8 wto solutions which were then cooled.
To these solutions were added a 20 wt% aqueous melamine formaldehyde solution and the appropriate amount of aqueous ammonium ~~hloride solutions and sulfuric acid solutions to provide the formulations shown in the Table below.. The cross-linked polyvinyl alcohol) can be present ..n an amount of from 0.2 to 3 g/m2.
* Trade-mark -Examples Samples as :shown :in the following Table were prepared as follows: A homopolymer polypropylene core is coextruded with skin layers of an ethylene-propylene random copo7_ymer. The random copolymer contains approximate7_y 3-5'-o by weight of ethylene. The extruded film is bia~:ially oriented to 4-5 times machine direction and 7-1c) times transverse direction to yield a film having a thickness of approximately 1 milt The thickness of: the :skin layers is approximately 120 of the film and the skin layers are approximately of equal thickness.
This film combinat=ion is corona discharge treated in accordance with commonly employed prior art techniques to produce a surface with a wetting tension of about 42 dynes/cm. The treated film is precoated on both sides with 0.1 wta poly(ethyleneimine), i.e., the above-identified BASF-Wyandotte Corporation "Polymin P"*
product. The film is air-dried at 100°C. This coating weight is too low to be measured, but is calculated to be in the r~.nge o1. 0.002 grams per m'. This primer coated treated substrate is then coated on one side with an acrylate coating to a coating weight of about 1.0 g/m-'. If PVOH is applied first, the barrier is improved. Tr.is is due to the additional heat that is used to dry the acrylic. This acrylate coating is an aqueous ammoniaca7_ solution of terpolymer latex resulting from the polymerization of about 56o by weight of methyl methacrylate, about 40% by weight of methyl acrylate, and about 4o by weight of methacrylic acid. The opposite surface of this film structure was coated with the appropriate solution of polyvinyl alcohol), cross-linking agent and catalyst. The solutions were applied utilizing a reverse direct gravure coater and the coated film is passed through a * Trade-mark _ g _ dry-air oven at from 100-125°C. This produces a coating weight of 0.5 g/m2.
The dried fi:Lms are then tested in an oxygen-permeability device in which a stream of dry oxygen is passed through an aqueous salt solution-permeated pad to control t:he gas moisture content and then through the films, c~isposE~d at right angles to the stream, with the cross-linked polyvinyl alcohol) coating upstream.
The oxygen transmitted was determined and the amount of oxygen passed per unit area of film per time period is calculated. The sulfuric acid catalyzed systems are superior to any ot=her catalyzed system for inhibiting the transmi~~sion of oxygen through a packaging type film. The rubbing resistance of the sulfuric acid catalyzed s~.~stems are also outstanding as shown by the data of the Table..
TOZ AND RUBBING RESISTANCE OF PVOH COATING
(H~S04 vs NH4C1) P 613* Rubbing TOZ(cc/lOOinz ) 2 0 Sample Catalyst Xlink Resistance at 75o RH App. 50o RH
Code (phr) (phr) OWK 1WK 3WK 1WK 3WK
C2388L NH4C1: 2.0 15 100 70 50 7.07 C2389L NH4C1: 2.0 15 100 70 50 9.94 ~~Virton P"*~~NH4C1: 2.5 20 70 70 70 8.63 8.5 -50.0 180-OlP HZS04: 2.0 15 50 30 0 4.19 3.53 220-O1P HZSO4: 2.0 25 50 50 0 4.69 3.86 L9-05P HzS04: 2.0 20 50 30 0 3.14 3.24 L9-lOP Nil Pli1 100 100 100 4.64 7.03 L9-11P HzS04: 3.0 20 10 0 0 1.69 2.78 *"Parez 613"**, a methylated melamine formaldehyde The cross--linked polyvinyl alcohol) coated films described above ax,e intended to be adhesively laminated to either oriented or unoriented commercially available ** Trade-rr.ark thermoplastic films such as homopolymer polypropylene film, polypropylene with coated layers, polypropylene with slip ac~ditive~s, polypropylene with coextruded layers, opac;ue polypropylene, polyethylene, nylon, polyethylene terephthalate, polycarbonate, polystyrene, etc. A parti_cular_Ly preferred class of films are the polyolefins.

Claims (12)

What is claimed is:
1. A polymeric film having reduced oxygen transmissive characteristics produced by the process comprising:
coating at least one side of a polymeric substrate adapted for receipt of an oxygen barrier with a solution of poly (vinyl alcohol), a cross-linking agent selected from the group consisting of urea formaldehyde, melamine formaldehyde, methylated melamine formaldehyde and trimethylol melamine urea formaldehyde, and an acid catalyst; and cross-linking said poly (vinyl alcohol) to provide said oxygen barrier, said acid catalyst being sulfuric acid.
2. The film according to claim 1, wherein said formaldehyde-containing cross-linking agent is methylated melamine formaldehyde.
3. The film according to claim 1, wherein said oxygen barrier includes from about 5%
to about 30% by weight of said cross-linking agent.
4. The film according to claim 1, wherein said solution is aqueous.
5. The film according to claim 4, wherein said aqueous solution is prepared by the steps of:

a) adding said polyvinyl alcohol) to water of sufficient temperature to dissolve said polyvinyl alcohol);

b) cooling said water and dissolved polyvinyl alcohol); and c) adding an effective amount of said cross-linking agent and said acid catalyst to said cooled water to provide said aqueous solution.
6. The film according to claim 5, further comprising the step of drying said aqueous solution to remove water therefrom and facilitate cross-linking of said polyvinyl alcohol).
7. The film according to claim 5, wherein said aqueous solution includes a solid content comprising from about 5% to about 30% by weight of said cross-linking agent and from 0.1 % to about 7.5% by weight of said acid catalyst.
8. A polymeric film having reduced oxygen transmissive characteristics produced by the process comprising:

providing a polymeric substrate having at least one side which has been treated to a surface tension level of at least about 35 dynes/cm;
applying a primer coating to said at least one side; and coating said at least one side with an aqueous solution of polyvinyl alcohol), cross-linking agent and acid catalyst and thereafter allowing said polyvinyl alcohol) to cross-link to provide an effective oxygen barrier, said acid catalyst being sulfuric acid and said cross-linking agent being selected from the group consisting of urea formaldehyde, melamine formaldehyde, methylated melamine formaldehyde and trimethylol melamine urea formaldehyde.
9. The film according to claim 8, wherein said oxygen barrier includes from about 5%
to about 30% by weight of said cross-linking agent.
10. The film according to claim 8, wherein said primer comprises poly(ethyleneimine).
11. The film according to claim 8, wherein said substrate comprises a polyolefin.
12. The film according to claim 8, further comprising an acrylic heat seal layer adhered to one side of said polymeric substrate.
CA 2125883 1991-12-23 1992-12-18 Low oxygen transmissive film Expired - Fee Related CA2125883C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US81249391A 1991-12-23 1991-12-23
US07/812,493 1991-12-23
PCT/US1992/011116 WO1993012931A1 (en) 1991-12-23 1992-12-18 Low oxygen transmissive film

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Publication Number Publication Date
CA2125883A1 CA2125883A1 (en) 1993-07-08
CA2125883C true CA2125883C (en) 2003-10-21

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US (1) US5380586A (en)
EP (1) EP0618864A1 (en)
JP (1) JP3050916B2 (en)
AU (1) AU677171B2 (en)
CA (1) CA2125883C (en)
SG (1) SG77106A1 (en)
TW (1) TW216436B (en)
WO (1) WO1993012931A1 (en)

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EP0618864A4 (en) 1994-07-22
TW216436B (en) 1993-11-21
EP0618864A1 (en) 1994-10-12
JP3050916B2 (en) 2000-06-12
WO1993012931A1 (en) 1993-07-08
JPH07506304A (en) 1995-07-13
CA2125883A1 (en) 1993-07-08
AU3332993A (en) 1993-07-28
SG77106A1 (en) 2000-12-19
US5380586A (en) 1995-01-10
AU677171B2 (en) 1997-04-17

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