WO1996016877A1 - Stratifies pourvus de revetements - Google Patents

Stratifies pourvus de revetements Download PDF

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Publication number
WO1996016877A1
WO1996016877A1 PCT/GB1995/002760 GB9502760W WO9616877A1 WO 1996016877 A1 WO1996016877 A1 WO 1996016877A1 GB 9502760 W GB9502760 W GB 9502760W WO 9616877 A1 WO9616877 A1 WO 9616877A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
substrate
container
stiffening
pvoh
Prior art date
Application number
PCT/GB1995/002760
Other languages
English (en)
Inventor
Jan Eggestad
Mohan Lal Sankuja
Paul Thottathil
Original Assignee
Elopak Systems Ag
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 Elopak Systems Ag filed Critical Elopak Systems Ag
Priority to AU39322/95A priority Critical patent/AU3932295A/en
Priority to EP95937118A priority patent/EP0793605A1/fr
Priority to JP8517156A priority patent/JPH10509123A/ja
Publication of WO1996016877A1 publication Critical patent/WO1996016877A1/fr
Priority to MXPA/A/1997/003842A priority patent/MXPA97003842A/xx

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides
    • 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
    • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
    • B32B2329/04—Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2377/00—Polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • This invention relates to laminates with coatings, and concerns in particular the provision of coatings, especially barrier coatings, of packaging board to provide laminate that is subsequently going to be converted into containers for foodstuffs, detergent chemicals and the like.
  • Conventional laminates used in packaging are basically a layer of paperboard, giving stiffness and the necessary support to the container, coated with low density polyethylene (LDPE) on both sides to protect the paperboard against moisture penetration from either the contents or the surroundings, and to give sealability.
  • LDPE low density polyethylene
  • barrier layer typically a layer of aluminium foil, to give additional protection to the contents against the penetration thereinto of oxygen and other, possibly harmful, substances from the environment.
  • the barrier requirements vary in dependence upon the intended contents of the container.
  • a gable-top carton is a versatile container, suitable for many different products.
  • Typical products that can be packed in such cartons are foodstuffs (such as milk and orange juice) and detergents and fabric softeners; such products need to be protected against leakages and against weight loss through moisture transmission.
  • many of these products - especially detergents and the like - also normally contain perfume, and in order to protect the environment from the smell (which could unpleasantly contaminate other products in the immediate neighbourhood) a barrier against gas permeation is needed. It is therefore commonly known that these products need a laminate with a barrier layer - a barrier laminate - and that the barrier should be of a kind appropriate to the task it is to perform.
  • the conventional laminate incorporating aluminium foil as its barrier layer is suitable for packaging many of these products, but the environmental impact of the aluminium foil
  • a packaging carton should consist of a laminate comprising inner and outer layers which serve to stiffen the laminate, and an intermediate layer by way of which the inner and outer layers are tied together.
  • the inner layer and the intermediate layer both serve as relatively good barriers to O 2 migration, the intermediate layer being EVOH or PA extruded or co-extruded onto the inner layer, which comprises M-PET (metallized polyethylene terephthalate), G-PET
  • M-OPP metalized, oriented polypropylene
  • G-OPP glass-coated, OPP
  • greaseproof paper the coated surface of the M-PET, G-PET, M-OPP, or
  • an aluminium-metallized EVOH film constitutes the inner stiffening layer and has been extrusion-laminated by an intermediate LDPE layer to the outer stiffening layer.
  • the aforementioned laminates have the disadvantages that they require costly equipment for their manufacturing, even though the polymer they use does make an efficient and satisfactory barrier layer.
  • US-A-4206249 teaches a process for producing a paper container having high impermeability to liquid comprising spray coating (by means of hot-melt airless spraying) a polymerizable solution containing at least a prepolymer and a photo-sensitizer and, if necessary, a reactive diluent onto a wall surface of a previously fabricated paper container, and causing the prepolymer (and reactive diluent) to polymerize by ultraviolet irradiation to thereby form a liquid impermeable coating on the wall surface of the container.
  • Spraying and then UV irradiation of containers is a disadvantageous way of producing a barrier coating, being inefficient in time required and unreliable in consistency of coating thickness and curing, especially for the interiors of containers of a high height/width ratio.
  • the invention tackles the problems of the prior art by suggesting that a layer of some suitable material typically polyvinyl alcohol (known either as PVA or PVOH) or PA - could be formed on the basic paperboard (with or without the usual LDPE coatings thereon) in a quite different way, and specifically by a chemical grafting [graft polymerisation] process.
  • PVA polyvinyl alcohol
  • PA PA
  • the present invention provides a packaging container comprising a plurality of layers of differing substances at least one of which is a suitable stiffening layer and at least another of which is a suitable layer which is bonded directly or indirectly onto the stiffening layer by chemical grafting.
  • the invention provides a packaging material in the form of a laminate comprising a plurality of layers of differing substances at least one of which is a suitable substrate and at least another of which is a suitable layer which has been formed in situ directly or indirectly on the substrate by chemical grafting.
  • the laminate may take the form of film or board.
  • the invention provides a method for making a packaging material or a packaging container of the invention - that is, in the form of or made from a laminate comprising a plurality of layers of differing substances at least one of which is a suitable substrate or stiffening layer and at least another of which is a layer suitable for some other purpose - in which method the said other layer is bonded directly or indirectly onto the substrate or stiffening layer by chemical grafting.
  • the invention provides a packaging material and a packaging container - that is, it provides a material and a container each of which is intended for use in the packaging of products such as foodstuffs, e.g. milk, yoghurt and fruit juices, and such as basic household chemicals, e.g. washing powders, liquid detergents, and fabric softeners.
  • the packages will normally be in the form of gable-top or flat-top cartons.
  • the packaging material/container is in the form of, or made from, a laminate comprising a plurality of layers of differing substances at least one of which is a stiffening material and suitable substrate.
  • Typical such substrates are of fibrous and/or plastics substances, for example polymers and fibrous cellulose-based materials such as paperboard (of an appropriate weight), which may already have a coating thereon of a waxy substance such as LDPE, and fabrics woven out of fibrous synthetic polymers such as polyethylene (PE) itself.
  • At least another of the layers making up the laminate packaging material of the invention is a chemically-grafted layer. Because this layer is bonded on by chemical grafting - that is, it is chemically attached (by strong covalent bonds) to the molecules making up the underlying layer - the layers themselves may be more firmly interconnected, and thus less likely to delaminate, than if they relied upon mere physical bonding (as is the case with common extrusion and gluing). Moreover, the conventional use of tie layers can be avoided.
  • the chemically-grafted layer may have one or more of a number of functions. Thus, it may serve as a barrier to oxygen or water vapour, for instance - and/or it may act as an oxygen scavenger and/or it may have some microbiological function.
  • a material that will effect some biological control on the contents of any container made from the laminate For example, there might be included a substance having a high affinity either for biological cells or for some growth factor for the cells, or there might be incorporated a material having either some direct inhibiting effect on cell growth or an indirect effect (as by removing necessary oxygen).
  • the packaging material is a board to be formed into cartons
  • the grafted layer may be bonded either directly to a stiffening layer/substrate, such as paperboard, or indirectly thereto, such as via an intermediate layer of
  • the grafted layer may be either a surface layer of the board or it may itself be covered by a further layer, for example an LDPE one.
  • Typical barrier layers are much the same as those polymeric materials already used in the Art to provide good oxygen/moisture barriers save that they are grafted (and perhaps polymerised) into place rather than being merely physically affixed to the substrate.
  • Such materials are various PAs and PVOH [although PVOH tends to be water soluble, and so, if it is likely to be exposed to water, may need a protective surface coating, typically of an acrylic polymer such as NEOCRYL A10512, from ICI].
  • PVDC Poly-vinylidene chloride
  • PVDC also makes excellent barrier layers, although its use is restricted in view of possible toxic side effects of the initial raw materials.
  • the present invention provides a packaging container comprising a plurality of layers of differing substances at least one of which is a suitable stiffening layer and at least another of which is a layer comprised of PVOH which is bonded directly or indirectly onto the stiffening layer by chemical grafting.
  • a packaging container comprising a plurality of layers of differing substances at least one of which is a suitable stiffening layer and at least another of which is a layer comprised of PVOH which is bonded directly or indirectly onto the stiffening layer by chemical grafting.
  • a laminate comprising a plurality of layers of differing substances at least one of which is a suitable substrate and at least another of which is a layer comprised of PVOH which has been formed in situ directly or indirectly on the substrate by chemical grafting.
  • the invention provides a method for making a material or a packaging container of the invention - that is, in the form of or made from a laminate comprising a plurality of layers of differing substances at least one of which is a suitable substrate or stiffening layer and at least another of which is a PVOH layer - in which method the PVOH layer is bonded directly or indirectly onto the substrate or stiffening layer by chemical grafting.
  • PVOH is bonded to cellulose, for example paperboard, or to PE.
  • the grafted layer is bonded either directly or indirectly to the substrate.
  • the layer formed thereon by chemical grafting may either be formed directly thereon, so that it is bonded directly to the underlying paperboard material, or, as is generally preferred, the paperboard substrate may have an intermediate coating (of LDPE, say) so that the layer is formed on the intermediate coating and thus indirectly on the paperboard.
  • the grafted layer is most conveniently formed in situ by graft polymerisation - that is to say, the substrate is exposed to monomer- or prepolymer-type chemicals which react not only with each other, to form the layer, but also with the substrate, so "grafting" themselves, and the layer, chemically to the substrate (as already noted, with the chemicals usually employed, the graft is by way of covalent bonds, and so a properly-formed grafted layer should adhere strongly to the substrate).
  • Graft polymerisation is in general a fairly standard technique.
  • the surface on which the graft polymer is to be formed is, if necessary, first treated with an initiator (to provide active sites at which grafting can take place), and then it is treated with the "monomer" to be grafted (this "monomer” can with advantage be a low molecular weight prepolymer), possibly in the presence of one or more co-monomer and/or cross-linking agents (to assist in the creating of a tight film).
  • a typical initiator is silver perchlorate (which can be regenerated in situ using hydrogen peroxide), which is a free-radical generator, and provides a multiplicity of free bonds/radicals on the substrate surface to which the polymer-forming monomer can then attach itself.
  • the monomer (or prepolymer) will naturally be one appropriate to the layer required.
  • a typical PVOH starting material is that polyvinyl alcohol prepolymer sold by Air Products under the name AIRVAL 523, while a typical prepolymer of PVDC is that available from Dow Chemicals under the name SARAN FC310.
  • a possible acrylic/PVDC prepolymer is Prepolymer 76 Res M3 153, from Unical Chemicals.
  • the monomer may be used with a co-polymer or cross-linker.
  • a co-polymer or cross-linker examples include the silane monomer Silane A1100, available from Union Carbide, sodium vinyl sulphonate, available from Air Products, the acrylic Prepolymer 76 Res 5517, from Unical Chemicals, and hydroxy ethyl acrylate, available from Dow Chemicals.
  • Another cross-linker is the polyaziridine CX-100, from ICI.
  • the grafted layer is normally placed on the inside surface zone of the laminate that defines, say, the carton blank to be produced, although it need not cover the whole of that surface zone. However, if it does extend over those inside surface portions which are to be heat- and pressure-sealed in forming the carton then the grafted layer should be, or include, a substance which enables this sealing.
  • Multilayer packaging laminates made with grafted layers can be relatively inexpensive, and have been shown to have good oxygen- and moisture-barrier characteristics, and are thus suitable for use with cartons and containers for all sorts of materials, including many foodstuffs and household chemicals.
  • Formulations identified in the Table below (in each case except Formulation No: 24 the initiator used was silver perchlorate, as 0.1 parts by weight of a 0.1% solution: in No: 24 it was 0.1 pbw of 0.1% silver nitrate solution) were prepared as described hereinafter and then used to form barrier coating layers on LDPE substrates.
  • the substrates were provided by conventional milk-packaging laminate consisting of paperboard extrusion-coated on both faces with LDPE. Where the formed barrier coating layers were water soluble (shown by the asterisk in the Table) they were given a water-resistant topcoat as described hereinafter.
  • the resultant coated laminate substrate was then tested for oxygen and moisture permeability by the Tests described below: the Results of these Tests are also shown in the Table.
  • A1100 silane monomer added with stirring. The other ingredients were then added with continuous stirring cross-linker followed by co-monomer, then the regenerator and lastly the initiator.
  • prime coat was a water soluble polymerised vinyl alcohol it was given a protective top coat, as follows:-
  • NEOCRYL A612 50pbw NEOCRYL A612 were mixed into a container of 16pbw de-ionised water. Separately, 1pbw of crosslinker polyaziridine CX-100 were mixed with 0.1pbw of 0.1% urea peroxide solution. The two were then stirred into a mixture of 11pbw de-ionised water and 6.5pbw butyl cellosolve. The thus-prepared Formulation was used to provide the required top coat.
  • samples of each Formulation were applied to the substrates using a conventional Meyer rod applicator.
  • the layer was then cured in an oven at 100°C for 2-5 minutes (in an air-circulating oven this curing time can be reduced to merely seconds).
  • prime coat needed a top coat
  • the latter was applied to the cured prime coat in exactly the same way that the prime coat had been applied to the substrate with a Meyer rod applicator, followed by curing at 100°C for 2-5 minutes.
  • each such board included a paperboard stiffening layer of a 300g/m 2 weight carrying (both inside and outside) an LDPE layer
  • the coating was found to be between 0.1 and 0.2 mil (2.5 and 5 microns) thick.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

Un contenant de conditionnement ou une feuille d'emballage comprend un stratifié composé de couches de différentes substances dont l'une est une couche ou substrat de rigidification et une autre, au moins, est une couche liée directement ou indirectement à la couche ou substrat de rigidification au moyen d'un greffage chimique.
PCT/GB1995/002760 1994-11-26 1995-11-27 Stratifies pourvus de revetements WO1996016877A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU39322/95A AU3932295A (en) 1994-11-26 1995-11-27 Laminates with coatings
EP95937118A EP0793605A1 (fr) 1994-11-26 1995-11-27 Stratifies pourvus de revetements
JP8517156A JPH10509123A (ja) 1994-11-26 1995-11-27 コーティングを有するラミネート
MXPA/A/1997/003842A MXPA97003842A (en) 1994-11-26 1997-05-23 Laminated materials with coating

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9423906.8 1994-11-26
GB9423906A GB9423906D0 (en) 1994-11-26 1994-11-26 Laminates with coatings

Publications (1)

Publication Number Publication Date
WO1996016877A1 true WO1996016877A1 (fr) 1996-06-06

Family

ID=10765027

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1995/002760 WO1996016877A1 (fr) 1994-11-26 1995-11-27 Stratifies pourvus de revetements

Country Status (5)

Country Link
EP (1) EP0793605A1 (fr)
JP (1) JPH10509123A (fr)
AU (1) AU3932295A (fr)
GB (1) GB9423906D0 (fr)
WO (1) WO1996016877A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2394815A1 (fr) 2010-06-08 2011-12-14 Farbotex S.p.A. Récipient en carton pour emballer des liquides et son procédé de fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206249A (en) * 1977-09-06 1980-06-03 Nihon Dixie Company Limited Process for producing a paper container having high impermeability to liquid
WO1992001558A1 (fr) * 1990-07-26 1992-02-06 Elopak Systems Ag Stratifies et materiaux de conditionnement ameliores
JPH06327045A (ja) * 1993-05-17 1994-11-25 Nec Corp セクター拡散ページング方式

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206249A (en) * 1977-09-06 1980-06-03 Nihon Dixie Company Limited Process for producing a paper container having high impermeability to liquid
WO1992001558A1 (fr) * 1990-07-26 1992-02-06 Elopak Systems Ag Stratifies et materiaux de conditionnement ameliores
JPH06327045A (ja) * 1993-05-17 1994-11-25 Nec Corp セクター拡散ページング方式

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 80, no. 10, 11 March 1974, Columbus, Ohio, US; abstract no. 48876u, HIRANO ET AL.: "Polyvinyl alcohol film having excellent moisture proof property an barrier property for gas" page 35; column 1; *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2394815A1 (fr) 2010-06-08 2011-12-14 Farbotex S.p.A. Récipient en carton pour emballer des liquides et son procédé de fabrication

Also Published As

Publication number Publication date
MX9703842A (es) 1997-09-30
JPH10509123A (ja) 1998-09-08
GB9423906D0 (en) 1995-01-11
AU3932295A (en) 1996-06-19
EP0793605A1 (fr) 1997-09-10

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