EP0379487A1 - Materiau multicouche thermostable et etanche aux gaz et procede de production dudit materiau - Google Patents

Materiau multicouche thermostable et etanche aux gaz et procede de production dudit materiau

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Publication number
EP0379487A1
EP0379487A1 EP88906838A EP88906838A EP0379487A1 EP 0379487 A1 EP0379487 A1 EP 0379487A1 EP 88906838 A EP88906838 A EP 88906838A EP 88906838 A EP88906838 A EP 88906838A EP 0379487 A1 EP0379487 A1 EP 0379487A1
Authority
EP
European Patent Office
Prior art keywords
polymer
layer
layers
gastight
stable
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Withdrawn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
EP88906838A
Other languages
German (de)
English (en)
Inventor
Christer BERGSTRÖM
Peter Nikko
Hans Martensson
Maria Stjernberg
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.)
Neste Oyj
Original Assignee
Neste Oyj
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 SE8702914A external-priority patent/SE457960B/sv
Priority claimed from FI875772A external-priority patent/FI875772A/fi
Application filed by Neste Oyj filed Critical Neste Oyj
Publication of EP0379487A1 publication Critical patent/EP0379487A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B32B27/06—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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • 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
    • 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
    • B32B2383/00—Polysiloxanes

Definitions

  • the present invention relates to a gastight, heat- stable, multilayered material and to a method for pro ⁇ duction thereof.
  • Impermeable polymers containing vinyl alcohol are previously known and are in principle of two kinds: olefin/vinyl alcohol copolymers with random distribu ⁇ tion of the mer units, and olefin/vinyl alcohol block copolymers.
  • the former are usually ethylene/vinyl alcohol copolymers, but propylene/vinyl alcohol copo- lymers have also been developed.
  • ethylene/vinyl alcohol copolymers are produced by hydrolysis of ethylene/vinyl acetate copolymers.
  • the hydrolysis takes place with the aid of alcohol, and the mixture may be either acid or basic.
  • the hydrolysis may be carried out in the solid state, the molten state, or in solution.
  • the brands containing 20-30 mole% vinyl alcohol are used in the first place for injection mould ⁇ ing and for the powder coating of steel tubing, and are made from ethylene/vinyl acetate copolymer produced by high-pressure technique. Brands containing 60-80 mole% vinyl alcohol are also available on the market and are used mainly for gastight layers in multilayered products. They are produced by adding ethylene to the polyvinyl acetate process and hydrolysing the product in a manner similar to the production of polyvinyl alcohol (PVA) from polyvinyl acetate. If there is less than 60 mole% vinyl alcohol , the gas-tightness of the product goes down steeply.
  • PVA polyvinyl alcohol
  • the ethylene/vinyl alcohol copolymer contains more than 60 mole% vinyl alcohol, it forms o- noclinic crystals (the same as PVA), and when it contains less than 20 mole% vinyl alcohol, it forms rhombic crys- tals (the same as polyethylene). In the range between these limit values, a mixed crystal structure is formed. Only the monoclinic crystal structure is sufficiently impermeable for barrier applications.
  • a PVA chain is chemically bonded to a polyolefin chain, for example by means of a hydrolysable silane.
  • the hydrolysable silane is first bonded to the polyolefin chain by copolymerising or grafting the unsaturated silane, or by bonding to the polyolefin chain another functional hydrolysable silane, such as a ino silane.
  • the polyolefin modified with hydrolysable silane is then mixed in the molten state with PVA, whereby the silane undergoes hydrolysis and reacts chemically with PVA, and an olefin/vinyl alcohol block copolymer is formed.
  • Polyvinyl alcohol (PVA) is mainly used as a dls- persing agent in suspension polymerisations of PVC, and it is possible, by controlling the molecular weight of PVA and its degree of hydrolysation, to control the properties of the PVC.
  • PVA has a sufficiently high degree of hydrolysation, it is water-soluble.
  • the water-solubility and difficulties encountered in process ⁇ ing restrict the use of PVA in the plastics industry.
  • Dry PVA is interesting in itself because it has excellent barrier properties (gas-tightness). To avoid these shortcomings, the above-mentioned ethylene/vinyl al ⁇ cohol coplymer (EVOH) was developed.
  • EVOH gas-tightness
  • air humidity for example by applying a polyethylene film on both sides.
  • EVOH does not adhere to polyethylene, and an adhesion plastic (for example Admer) must also be used between these components.
  • Admer an adhesion plastic
  • a coextruded five-layer construction like this is highly exacting and expensive.
  • EVOH and adhesion plastics are very expensive.
  • EVOH may also be mixed with plastic and is then less susceptible to moisture.
  • EVOH is mixed with, for example, polyethylene terephthalate (PET), whereby bottles of higher gas-tightness are obtained than by coextrusion.
  • PET polyethylene terephthalate
  • EVOH may also be mixed with polyolefins, whereby sufficient gas-tightness and adhesion to polyo ⁇ lefins are simultaneously obtained. In the present invention, an easier way of utilis ⁇ ing the good barrier properties of polyvinyl alcohol has now been found.
  • the product comprises, in addition to a layer based on the above- mentioned mixture of polyvinyl alcohol and polyolefin, at least one layer of a polymer derived from an olefin copolymer containing hydrolysable silane groups.
  • the gastight heat-stable, multilayered material according to the invention is thus characterised in that it consists of a layer of a first polymer which consists of a mixture of 99-1% by weight polyolefin and 1-99% by weight polyvinyl alcohol and, optionally, a plasticiser containing alcohol groups, there being provided on at least one side of this layer a layer of a second polymer derived from an olefin copolymer containing hydrolysable silane groups.
  • the method for production of a gastight heat-stable, multilayered material according to the invention is characterised in that there is provided, on at least one side of a layer of a first polymer consisting of a mixture of 99-1% by weight polyolefin and 1-99% by weight polyvinyl alcohol and, optionally, a plasticiser contain ⁇ ing alcohol groups, a layer of a second polymer derived from an olefin copolymer containing hydrolysable silane groups, and that there is provided, before said first and second polymer layers are brought together, a sila- nol condensation catalyst in a layer separate from said second polymer.
  • the layer based on a mixture of polyolefin and polyvinyl alcohol is characterised in that it includes, in mixture, 99-1% by weight poly ⁇ olefin and 1-99% by weight polyvinyl alcohol and, op- tionally, a plasticiser containing alcohol groups.
  • the material preferably contains at most 10% by weight plasticiser.
  • Polyolefin/PVA mixtures are not novel in themselves, but they have not been used in the form of tight multi- layered products in the manner taught by the present invention.
  • polyolefin/PVA mixtures are known in the art, use being made of the hydrophilic properties.
  • U.S. Patent 4,529,539 such mixtures have been impregnated with electrolyte, and elecrrical- ly conductive plastic products have been obtained in this manner.
  • Japanese Patent 60147473 discloses electrically conductive plastic products consisting of polyolefin/PVA/carbon black mixtures
  • U.S. Patent 3,984,358 discloses ion exchangers consisting of poly ⁇ olefin/PVA mixtures.
  • Japanese Patent 77024976 discloses batteries in which there is provided, between the anode and the cathode, a polyolefin/PVA mixture serving as a drying agent, and Japanese Patent 54020057 has developed PVA mixtures that can be successfully dispersed in water.
  • Japanese Patent 70001747 the stainability of polyolefin fibres has been improved by admixture of PVA.
  • the hygroscopic properties of polyolefin/PVA mixtures have also be utilised for coating cement and strengthening cement with polyolefin/PVA fibres (JP 5922328 and JP 79036095). PVA also improves the adhesion to cement.
  • PVA can be mixed with polyolefins in the molten state in any proportions whatsoever, whereby a mixture is obtained which consists of two phases, a continuous phase and a dispersed phase. When the diameter of the dispersed phase is sufficiently small, a trans ⁇ parent film is obtained. Such a good dispersion is obtained only if the mixture is efficient enough. Normal extruders are not good enough in this respect, and compounding is required before the final product is extruded.
  • the polyvinyl alcohol may be of the grade commonly used in suspension poly ⁇ merisation of PVC, and may be completely or partly hydrolysed (with vinyl acetate as comonomer) , or any other polymer containing 0.5-100% by weight vinyl alcohol .
  • plasticisers are usually alcohol compounds which enter the PVA crystals and reduce the degree of crystallinity of the polyvinyl alcohol and the rigidity and brittleness of PVA and of polyolefin/PVA mixtures.
  • Suitable plasticisers are, for example, glycerol, trimethylol propane and tri- ethylene glycol.
  • the plasticisers may be added by impregnating at elevated temperature either the poly ⁇ vinyl alcohol before compounding or the polyvinyl/PVA mixture after compounding, or they may be added in connection with the compounding, either before melting the polymer components or after melting, or in some other way, depending on the type of plasticiser.
  • polyolefin/PVA mixtures may be produced by using as polyolefin high-pressure poly- ethylene (LDPE), low-pressure polyethylene (HDPE, LMDPE, LLDPE, VLDPE, ULDPE), polypropylene (PP) , poly-1-butene (PB), poly-4-methyl-l-pentene (TPX) or other polyolefin- based plastics, rubbers or additives.
  • LDPE polyolefin high-pressure poly- ethylene
  • HDPE low-pressure polyethylene
  • LMDPE low-pressure polyethylene
  • LLDPE low-pressure polyethylene
  • PP polypropylene
  • PB poly-1-butene
  • TPX poly-4-methyl-l-pentene
  • copolymers of the above-mentioned polymers such as ethylene-methylacrylate (EMA), ethylene-ethylacrylate (EEA), ethylene-butylacrylate (EBA) and ethylene-vinyl- acetate (EVA), and propylene-ethylene copolymers or block copolymers.
  • EMA ethylene-methylacrylate
  • EEA ethylene-ethylacrylate
  • EBA ethylene-butylacrylate
  • EVA ethylene-vinyl- acetate
  • propylene-ethylene copolymers or block copolymers such as ethylene-methylacrylate (EMA), ethylene-ethylacrylate (EEA), ethylene-butylacrylate (EBA) and ethylene-vinyl- acetate (EVA)
  • the gastight polyolefin/PVA mixture according to the invention for improving the barrier characteristics may be produced by mixing 1-99% by weight polyolefin, 99-1% by weight polyvinyl alcohol and, optionally, a plasticiser containing alcohol groups. All requisite components may be added to a melt mixer simultaneuously in the form of a dry mix, premixed in the solid or molten state, or the different components may be added sepa- rately. Plasticising may also be carried out after com ⁇ pounding, and it is also possible to proceed such that the plasticiser is admixed to the PVA component, where ⁇ by one gains the advantage that the entire mixture need not be plasticised.
  • a first polymer consisting of the above-mentioned polyolefin/polyvinyl alcohol mixture is provided, on one or both sides, with a layer of a second polymer derived from a silane group-contain- ing olefin copolymer.
  • the multilayered product may be produced by coextrusion, (co)extrusion coating, (co)ex ⁇ trusion lamination, glue lamination, or some other tech ⁇ nique, and these production methods may also be com ⁇ bined. Coextrusion is preferred at present.
  • adhesion-improving sub- stance which is selected among substances catalytical- ly promoting a condensation of silanol with hydroxyl groups (for example the substances mentioned in the Dow Corning paper Silicones in Protective Coatings, p. 548, in the Treatise on Coatings, Vol. 1. part 3, * Marcel Dekker, 1972).
  • adhesion improving substances that can be incorporated in the first and/or the second po ⁇ lymer, mention may be made of benzoic acid and tetra- isopropyl titanate.
  • Suitable products incorporating the gastight ma ⁇ terial according to the invention include films, blow- moulded bottles and containers, sheets, tubing, injec ⁇ tion moulded vessels, deep-drawn films and sheets, li- quid packaging cartons, etc.
  • films blow- moulded bottles and containers, sheets, tubing, injec ⁇ tion moulded vessels, deep-drawn films and sheets, li- quid packaging cartons, etc.
  • such tight and multilayered products are used in packaging food ⁇ stuffs when oxygen impermeability is desired, but impermeability to carbon dioxide or some other gas may also be desirable.
  • tightness against fats, chemicals and odour is required of foodstuff, packages as well as technical products.
  • the specific combination of materials in the mul ⁇ tilayered material according to the invention gives improved barrier properties, such as low permeability to oxygen and other gases and, furthermore, high heat stability.
  • the combination of layers of cross ⁇ linked silane group-containing olefin copolymer makes it possible to achieve a heat stability to temperatures of up to about 170°C.
  • the multilayered ma ⁇ terial is useful for different types of packages, for example of the type Bag-in-Box, for e.g. foodstuffs, and other products that are to be heat-treated, for example autoclaved.
  • the second polymer layer of the multilayered mate ⁇ rial which polymer is derived from a crosslinkable olefin copolymer incorporating hydrolysable silane groups, will now be described in detail.
  • the layer or layers of the silane group-contain- ing olefin copolymer are crosslinked after production of the multilayered material by so-called moisture hardening during which the silane groups are hydro- lysed under the action of water and split off alco ⁇ hol to form silanol groups.
  • the silanol groups are then crosslinked under the action of a so-called sila ⁇ nol condensation catalyst by a condensation reaction during which water is split off.
  • thin layer is here meant a thickness corresponding to film and sheet, i.e. up to about 2 mm, preferably about 1 mm at most, and more pre- ferred about 0.6 mm at most.
  • a further disadvantage is that any gel lumps nor clogging the equipment will be discharged and show up in the product as disfiguring undesired lumps which, if they occur in thin layers, such as films and sheets, are unacceptable and usually make the product useless.
  • precuring retarders Undesired precuring may be prevented by incorporat ⁇ ing in the polymer composition substances counteracting precuring, so-called precuring retarders.
  • precuring retarders may be in the form of drying agents.
  • the use of precuring retarders implies that there is intro- pokerd into the polymer composition a further component, which makes the composition more expensive and, besides, may be undesirable, for example in packages in contact with food products. It therefore is an advantage if the addition of such further components as precuring re- tarders can be avoided.
  • the present invention obviates the above-mentioned disadvantages by providing the silanol condensation catalyst in a layer separate from the second polymer, i.e. either in the layer consisting of a mixture of polyolefin and polyvinayl alcohol or in another separate layer, such as a layer provided between the first and the second polymer and containing the silanol condensation catalyst.
  • the last-mentioned layer may consist of, for example, a so-called master batch layer of the silanol condensation catalyst.
  • the catalyst may be included in an optional adhesion layer of adhesion plastic (for coextrusion) or adhesive (for lamination).
  • Crosslinking of the second polymer i.e. the silane group-containing olefin copolymer, is carried out by subjecting the second polymer to the action of water and causing the silanol condensation catalyst to diffuse into the layer or layers of the second po- 1ymer.
  • the layer or layers of the second polymer are re ⁇ stricted to polymers derived from silane group-contain- ing olefin copolymers.
  • the reason for this is that it was found, when the invention was in progress, that the aim of the invention cannot be achieved with all silane- containing olefin polymers.
  • the desired result is not obtained with silane-containing graft polymers, even if the silanol condensation catalyst according to the invention is incorporated in another layer free from crosslinkable silane.
  • the silanol condensation catalyst is originally provided in another layer, and undesired precuring thus should be precluded, such pre- curing still occurs and imparts to the film a grainy, unacceptable appearance.
  • silane-containing graft polymers also leads to free monomer residues in the final product, resulting in an obnoxious smell, and may constitute a health hazard, for example in food packagings. In addi ⁇ tion, free monomer may cause discoloration (yellowing) of the product. It was therefore found necessary, in the context of this invention, to utilise for the crosslink- able polymer a silane group-containing olefin copolymer and to provide the silanol condensation catalyst in layer separate from the polymer, i.e. either in the layer of the first polymer or in another separate layer between the layers of the first and the second polymer. The com ⁇ bination of these two requirements thus is important to the invention.
  • the crosslinkable polymer ma ⁇ terial according to the invention is a silane-containing copolymer by which is meant an olefin polymer, preferably an ethylene polymer containing crosslinkable silane groups provided in the polymer by copolymerisation.
  • the manner in which the crosslinkable silane groups are attached to the polymer chain thus is critical; according to the invention, for example unsaturated silane compounds can be copolymerised with olefins, or a ino silane compounds can react with acrylate esters, whereas the invention does not include graft polymers in which peroxides are decomposed and the silane compound is grafted on the finished polymer by radical reaction.
  • the silane-containing polymer has preferably been obtained by copolymerisation of an olefin, preferably ethylene, and an unsaturated silane compound which is represented by the formula
  • R is an ethylenically unsaturated hydrocarbyl group
  • R" is a hydrocarbyl group
  • Y is a hydrolysable group
  • n is 0, 1 or 2. If there is more than one Y-group, these need not be identical.
  • unsaturated silane com- pound examples are those in which R is vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, or gamma-(meth)acryloxy alkyl, Y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy or an alkyl or arylamino group, and R 1 is a methyl, ethyl, propyl, decyl or phenyl group.
  • vinyl trimethoxy silane vinyl trismethoxyethoxy silane
  • vinyl triethoxy silane gamma-(meth)acryloxy- propyl trimethoxy silane
  • gamma-(meth)acryloxy propyl triethoxy silane vinyl triacetoxy silane.
  • An unsaturated silane compound especially preferred at present is represented by the formula
  • each A which is the same or different is a hydrocarbyl group having 1-8 carbon atoms, preferably 1-4 carbon atoms.
  • the copolymerisation of the olefin (ethylene) and the unsaturated silane compound may be carried out under any suitable conditions causing copolymerisation of the two monomers.
  • polymerisation may be carried out in the presence of one or more further comonomers copoly- merisable with the two monomers.
  • como ⁇ nomers are: (a) vinyl carboxylate esters, such as vinyl acetate and vinyl pivalate; (b) (meth)acrylates, such as methyl Cmeth)aerylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (c) olefinically unsaturated car- boxylic acids, such as (meth)acrylic acid, aleic acid and fumaric acid; (d) (meth)acrylic acid derivatives, such as (meth)acrylonitrile and (meth)acrylamide; and (e) vinyl ethers, such as vinyl methyl ether and vinyl phenyl ether.
  • vinyl esters of monocarboxylic acids having 1-4 carbon atoms are pre ⁇ ferred, such as vinyl acetate, and (meth)acrylates of alcohols having 1-4 carbon atoms, such as methyl (meth)- acrylate.
  • An especially preferred comonomer is butyl- acrylate. Two or more such olefinically unsaturated compounds may be used in combination.
  • the expression " (meth)acrylic acid” is here intended to comprise both acrylic acid and methacrylic acid.
  • the comonomer content in the copolymer may amount to about 40% by weight, preferably about 0.5-35% by weight, and most preferred about 1-25% by weight of the copolymer.
  • the silane-containing polymer of the present invention contains the silane compound in a content of 0.001-15% by weight, preferably 0.01-5% by weight, and most preferred 0.1-4% by weight.
  • silanol condensation catalysts may be used for the present invention. More particu ⁇ larly, they are selected among carboxylates of metals, such as tin, zinc, iron, lead and cobalt, organic bases, inorganic acids and organic acids.
  • silanol condensation catalysts are dibutyl tin dilaurate, dibutyl tin diacetate, dioctyl tin dilaurate, stannoacetate, stannocaprylate, lead naph ⁇ thenate, zinc caprylate, colbalt naphthenate, ethyl amines, dibutyl amine, hexyl amines, pyridine, inorganic acids, such as sulphuric acid and hydrochloric acid, and orga ⁇ nic acids, such as toluene sulphonic acid, acetic acid, stearic acid, and maleic acid.
  • Especially preferred catalyst compounds are the tin carboxylates.
  • the amount of silanol condensation catalyst employed usually is of the order 0.001-10% by weight, preferably 0.01-5% by weight, especially 0.03-3% by weight, relative to the amount of silane-containing polymer in the com ⁇ position.
  • the crosslinkable polymer may contain different addi ⁇ tives, as is usually the case in polymer compositions. Examples of such additives are miscible thermoplastics, stabilisers, lubricants, fillers, colourants and foaming agents.
  • miscible polyolefins such as polyethylene of low density, medium density and high density, polypropylene, chlorinated polyethy ⁇ lene, and various copolymers including ethylene and one or more other monomers (such as vinyl acetate, methyl acrylate, propylene, butene, hexene and the like).
  • the above-mentioned polyolefin may be used alone or in mixture with several polyolefins.
  • the polyolefin content of the composition may amount to 70% by weight, based upon the sum of the amounts of this polyolefin and the silane-containing polymer.
  • inorganic fillers such as silicates, for example . kaolin, talc, montmorillonite, zeolite, mica, silica, calcium silicate, asbestos, glass powder, glass fiber, calcium carbonate, gypsum, magnesium carbonate, magne ⁇ sium hydroxide, carbon black, titanium oxide and the like.
  • the amount of this inorganic filler may be up to 60% by weight, based upon the sum of the weights of the filler and the silane-containing polymer.
  • the oxygen permeability of the films was determined by means of an OX-TRAN 1000 apparatus (ASTM D 3985).
  • the brands of polyolefin, polyvinyl alcohol and silanol condensation catalyst used in the tests of the Examples are stated in the Table below.
  • a barrier compound was produced by mixing polyvinyl alcohol (PVA) and polyolefin (PO) in the molten state with the aid of Berstorff mixer, applying the following temperature profile (°C): 190-210-220-230-230-160-200- 200-200-200; the yield of the mixer was 80 kg/h.
  • PVA polyvinyl alcohol
  • PO polyolefin
  • Test 2 the compound mix was impregnated with 0.6% by weight of glycerol/water mixture (85:15) before the film was run.
  • the oxygen permeability can be controlled by controlling the amount of PVA.
  • Example 2 First polymer (polyolefin/polyvinyl alcohol mixture) As in Example 2, compound mixes were prepared in a Buss Kokneader. From the compound mixes, films with a thickness of 100 ⁇ m were made by pressing. The compo ⁇ sition of the films obtained, the production conditions and the oxygen permeability characteristics are given in Table 3.
  • Test 13 the compound mix was, prior to film pressing, impregnated with 5% by weight of glycerol/ water mixture (85:15).
  • First polymer polyolefin/polyvinyl alcohol mixture
  • second polymer olefin copolymer with hydrolysable silane groups
  • a barrier of plastic based on a mixture of PVA and polyolefin can be coextruded with a polyolefin modified with hydrolysable silane, such as ethylene-vinyl trimethoxy silane copolymer, and that an improved adhesion between the layers is obtained under certain conditions.
  • hydrolysable silane such as ethylene-vinyl trimethoxy silane copolymer
  • chemical substances exist (benzoic acid, tetraisopropyl titanate etc. ) which accelerate the condensation reaction between silanol (in e.g. Visico) and hydroxy groups (in e.g. PVA), and in this manner the adhesion between barrier plastic, such as EVOH or PVA/polyolefin mixture, and Visico is increased.
  • the adhesion is improved no matter to which layer the adhesion-improving substance is added. It can also be seen that adding a silanol condensation catalyst (such as DOTDL or DBTDL) to any one of the layers causes crosslinking of the layers modified with hydrolysable silane, ' whereby heat stability is obtained. However, adding the silanol condensation catalyst to a layer modified with hydrolysable silane will cause gel formation upon extrusion. Regardless of whether there is adhesion or no adhesion between the layers, or whether the layers modified with hydrolysable silane are crosslinked or not, a satisfactory oxygen barrier is obtained, and this barrier is mainly dependent on the composition of the barrier layer.
  • a silanol condensation catalyst such as DOTDL or DBTDL

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un matériau multicouche thermostable et étanche aux gaz et à un procédé pour sa production. Le matériau multicouche se compose d'une couche d'un premier polymère qui contient un mélange de 99 à 1% en poids de polyoléfine et de 1 à 99% en poids d'alcool polyvinylique et, éventuellement, un agent plastifiant contenant des groupes d'alcool. Ledit matériau comporte en outre sur au moins un côté de ladite couche une couche d'un second polymère obtenue à partir d'un copolymère d'oléfine contenant des groupes silane hydrolysables. Le premier polymère se compose par exemple d'un mélange de polyéthylène et d'alcool polyvinylique alors que le second polymère se compose d'un copolymère réticulé d'éthylène et de silane alkoxy vinylique, tel que du silane triméthoxy vinylique réticulé par hydrolyse et par condensation des groupes silane sous l'action d'une quantité d'eau et d'un catalyseur. Lors de la production du matériau multicouche, le catalyseur est contenu dans une couche séparée de la couche ou des couches de copolymère contenant les groupes silane réticulables, par exemple dans la couche constituée par le mélange de polyoléfine/alcool polyvinylique, le catalyseur effectuant ensuite une migration dans la couche ou les couches de copolymères contenant les groupes silane et réticulant ces couches. Le matériau multicouche est de préférence produit par co-extrusion. On peut améliorer l'adhésion entre les couches en plaçant des couches d'adhésion entre lesdites couches ou en incorporant un agent améliorant l'adhésion, tel que de l'acide benzoïque ou du titanate de tétraisopropyle, dans n'immporte laquelle desdites couches.
EP88906838A 1987-07-20 1988-07-15 Materiau multicouche thermostable et etanche aux gaz et procede de production dudit materiau Withdrawn EP0379487A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SE8702914 1987-07-20
SE8702914A SE457960B (sv) 1987-07-20 1987-07-20 Saett vid framstaellning av ett flerskiktat polymermaterial av silan innehaallande olefinsampolymer
FI875772 1987-12-30
FI875772A FI875772A (fi) 1987-12-30 1987-12-30 Gastaett material.

Publications (1)

Publication Number Publication Date
EP0379487A1 true EP0379487A1 (fr) 1990-08-01

Family

ID=26158278

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88906838A Withdrawn EP0379487A1 (fr) 1987-07-20 1988-07-15 Materiau multicouche thermostable et etanche aux gaz et procede de production dudit materiau

Country Status (4)

Country Link
EP (1) EP0379487A1 (fr)
JP (1) JPH03500747A (fr)
DK (1) DK16190A (fr)
WO (1) WO1989000501A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389695A1 (fr) * 1989-03-28 1990-10-03 Neste Oy Matériau étanche aux gaz
CA2051797A1 (fr) * 1990-09-24 1992-03-25 Sally A. Kline Composites thermoplastiques a barriere de pontage
NO941448D0 (no) * 1993-05-14 1994-04-21 Dow Corning Barrierefilm for emballasje og framgangsmåte for framstilling av samme
ES2381217T3 (es) * 2008-07-15 2012-05-24 Dow Global Technologies Inc. Método para hacer una estructura laminada de vidrio/película de poliolefina
US20140202533A1 (en) * 2010-12-21 2014-07-24 Dow Global Technologies Llc Thermoplastic polyolefin copolymer lamination film, laminated structures and processes for their preparation
CN115216244B (zh) * 2022-07-19 2023-06-06 佛山(华南)新材料研究院 一种复合热熔胶膜及其制备方法与应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069368A (en) * 1976-10-01 1978-01-17 Minnesota Mining And Manufacturing Company Workable and curable epoxy-terminated silane films
JPS5693542A (en) * 1979-12-27 1981-07-29 Mitsubishi Petrochemical Co Bridged polyethylene resin laminated film or sheet
CA1233739A (fr) * 1982-12-28 1988-03-08 Mobil Oil Corporation Films isolants
US4464438A (en) * 1983-05-02 1984-08-07 Mobil Oil Corporation Blends of polyvinyl alcohol and ethylene-vinyl alcohol copolymer as grease resistant melt extrudable films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8900501A1 *

Also Published As

Publication number Publication date
DK16190D0 (da) 1990-01-19
WO1989000501A1 (fr) 1989-01-26
JPH03500747A (ja) 1991-02-21
DK16190A (da) 1990-01-19

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