EP2570196B1 - Utilisation de complexes de polyélectrolytes pour la fabrication de films polymères ayant des propriétés de barrière à l'oxygène - Google Patents

Utilisation de complexes de polyélectrolytes pour la fabrication de films polymères ayant des propriétés de barrière à l'oxygène Download PDF

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EP2570196B1
EP2570196B1 EP12195417.6A EP12195417A EP2570196B1 EP 2570196 B1 EP2570196 B1 EP 2570196B1 EP 12195417 A EP12195417 A EP 12195417A EP 2570196 B1 EP2570196 B1 EP 2570196B1
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cationic
polymers
polymer
polyelectrolyte
coating
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EP2570196A3 (fr
EP2570196A2 (fr
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Carmen-Elena Cimpeanu
Thomas Breiner
Dieter Urban
Karl-Heinz Schumacher
Volker Schädler
Heiko Diehl
Hermann Seyffer
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BASF SE
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to the use of polyelectrolyte complexes to give packaging materials made of polymer films an oxygen barrier.
  • Polymer construction components of the polyelectrolyte complex are applied to the polymer film in polymerized form.
  • the polymer film is coated with a composition comprising a polyelectrolyte complex made from anionic polymer and cationic surfactant, or the polymer film is coated with at least three alternating layers, one of two adjacent layers each containing an anionic polyelectrolyte building component and the other of two neighboring layers containing a cationic polyelectrolyte building component and polyelectrolyte complexes form at the mutual, adjacent interfaces of the alternating layers.
  • the packaging materials used have oxygen barrier properties, i.e. that they have the lowest possible transmission or the lowest possible permeability for oxygen. Since polymer films used as packaging materials, for example made from polyolefins such as polyethylene or oriented polypropylene or from polyesters such as e.g. from polyethylene terephthalate, as a rule, in pure, uncoated form, show a relatively high permeability to oxygen, various measures have been proposed to increase the oxygen barrier properties of the packaging materials.
  • the WO 03/068869 describes a method for producing packaging materials with oxygen barrier properties, wherein a carrier material is coated with a polymerizable compound and the compound is then polymerized on the carrier material.
  • the EP 2 014 730 describes a coating composition for forming a gas barrier film based on a polycarboxylic acid polymer which is crosslinked by means of a zinc compound.
  • the WO 07/002322 describes coated polymer films with oxygen barrier properties.
  • the coating composition is a solution of a maleic acid / acrylic acid copolymer and a vinyl alcohol / vinylamine copolymer. After coating, the two copolymers of the coating composition crosslink on the polymer film.
  • the WO 98/31719 describes coating compositions for barrier coatings.
  • the compositions contain an ethylenically unsaturated acid monomer and a polyamine which contains a built-in crosslinker. After coating, crosslinking takes place by triggering a free-radically induced polymerization.
  • the document US 6 060 410 A. describes a method for coating a substrate with a polyelectrolyte complex previously prepared from anionic polymer and cationic surfactant.
  • the document CN 1 857 918 A. describes multilayer barrier films with cationic and anionic polyelectrolytes. Chitosan is used as the cationic polyelectrolyte.
  • the document US 6,524,569 B1 describes the generation of a gel by forming a polyionic complex by reacting a soluble anionic polymer with a soluble cationic polymer.
  • the object of the present invention was to provide a further composition and method which enables the production of packaging with good oxygen barrier properties, in particular also in the area of folds, creases and corners.
  • the packaging should be as temperature-resistant as possible, flexible and non-blocking and as little as possible harmful substances such as Contain metals.
  • the invention relates to the use of at least one polyelectrolyte complex to give packaging materials made of polymer films an oxygen barrier, polymeric structural components of the polyelectrolyte complex being applied to the polymer film in polymerized form and at least one polymer film on at least one side with a previously made of anionic polymer and cationic Coated composition containing surfactant-coated polyelectrolyte complex is coated; or wherein a polymer film is coated on at least one side with at least three alternating layers, one of two adjacent layers each containing at least one anionic polyelectrolyte building component and the other of two adjacent layers containing at least one cationic polyelectrolyte building component and located at the mutual, adjacent interfaces of the at least one form three alternating layers of polyelectrolyte complexes, characterized in that a cationic polymer is used as the cationic polyelectrolyte constituent component, which is selected from the group consisting of polymers containing vinylimidazolium units
  • the invention also relates to a coated polymer film, wherein at least one side of the polymer film is coated with at least three alternating layers, one of two adjacent layers each containing at least one anionic polyelectrolyte construction component and the other of two adjacent layers containing at least one cationic polyelectrolyte construction component mentioned above and polyelectrolyte complexes form at the mutual, adjacent interfaces of the at least three alternating layers.
  • the coating produced according to the invention with the polyelectrolyte complex has oxygen barrier properties.
  • the barrier properties can be measured using the permeability test described in the examples.
  • oxygen barrier property means a reduced transmission or permeability to oxygen compared to an uncoated substrate.
  • the oxygen permeability for polymer films coated according to the invention is preferably less than 30%, in particular less than 20% or less than 10%, e.g. between 1% and 3% of the value of the uncoated polymer film (measured at 23 ° C and 0% relative humidity).
  • the oxygen barrier layer containing the polyelectrolyte complex is provided with moisture protection in order to prevent or at least greatly reduce an impairment of the barrier effect by high atmospheric humidity.
  • Moisture protection can be provided by an additional coating with a material that has a barrier effect against water vapor or air humidity. Alternatively or cumulatively, coextrusion with such a material can also be carried out.
  • Polyolefins, in particular polyethylene, are suitable, for example.
  • the moisture protection is preferably formed by coating with a polyolefin or by coextrusion of a polyolefin with at least one substance selected from polyelectrolyte complexes, anionic polyelectrolyte construction components and anionic polyelectrolyte construction components.
  • Polyelectrolytes are ionic polymers.
  • polyelectrolyte complexes are the reaction products of oppositely charged ionic polyelectrolyte assembly components, at least one of the assembly components being a cationic or an anionic polymer.
  • Polyelectrolyte complexes which can be used according to the invention are formed, for example, from an anionic polymer and from a cationic polymer or from an anionic polymer and from a non-polymeric, cationic surfactant, or from cationic polymer and from a non-polymeric, anionic surfactant.
  • Polyelectrolyte complexes of cationic polymer and anionic polymer or of an anionic polymer and non-polymeric are preferred.
  • cationic surfactant As a rule, the polyelectrolyte complexes have a defined stoichiometric composition, ie the equivalent ratio of anionic and cationic groups in these complexes is at or close to 1. However, the polyelectrolyte complexes can also be predominantly anionically or predominantly cationically charged. According to the invention, in addition to such polyelectrolyte complexes, a cationic or an anionic polymer can also be present in excess, ie in free, non-complexed form.
  • Anionic polymers are polymers with anionic groups, especially organic polymers with carboxylate, phosphate or sulfate groups.
  • the corresponding acids can also be used, provided that they are either neutralized by bases contained in the reaction medium or are converted into anionic groups by basic groups of the cationic polymer.
  • Suitable anionic polymers are e.g. those formed by free-radical polymerization of ethylenically unsaturated, free-radically polymerizable anionic polymers. This also includes copolymers of at least one anionic monomer and one or more different nonionic copolymerizable monomers.
  • ethylenically unsaturated anionic monomers are monoethylenically unsaturated C 3 to C 10 or C 3 to C 5 carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, itaconic acid and the alkali metal acid -, alkaline earth metal or ammonium salts of these acids.
  • the preferred anionic monomers include acrylic acid, methacrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid.
  • Aqueous dispersions of polymers based on acrylic acid are particularly preferred.
  • the anionic monomers can be polymerized either alone to give homopolymers or as a mixture with one another to give copolymers. Examples of this are the homopolymers of acrylic acid, homopolymers of methacrylic acid or copolymers of acrylic acid and maleic acid, copolymers of acrylic acid and methacrylic acid and copolymers of methacrylic acid and maleic acid.
  • the polymerization of the anionic monomers can also be carried out in the presence of at least one other ethylenically unsaturated monomer.
  • These monomers can be non-ionic or can carry a cationic charge.
  • nonionic comonomers are acrylamide, methacrylamide, NC 1 - to C 3 -alkyl acrylamides, N-vinylformamide, acrylic acid esters of monohydric alcohols with 1 to 20 C atoms such as especially methyl acrylate, ethyl acrylate, isobutyl acrylate and n-butyl acrylate, methacrylic acid esters of monohydric alcohols with 1 to 20 carbon atoms, for example methyl methacrylate and ethyl methacrylate, as well as vinyl acetate and vinyl propionate.
  • Suitable cationic monomers which can be copolymerized with the anionic monomers are dialkylaminoethyl acrylates, dialkylaminoethyl methacrylates, dialkylaminoethyl acrylates, dialkylaminoethyl methacrylamides, dialkylaminopropylacrylamide and dialkylimidylamides, dialkylammonylamides, dialkylammonylamides, dialkylammonylamides, dialkylammonylamides, dialkylammonylamides, dialkylamidylamides, dialkylamidylamides, dialkylamidylamides, dialkylamidylamides, dialkylamidylamides, dialkylamidylamides, and dialkylamidylamides, Individual examples of cationic monomers are dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl
  • the basic monomers can be completely or only partially neutralized or quaternized, e.g. 1 to 99% each.
  • the preferred quaternizing agent for the basic monomers is dimethyl sulfate.
  • the quaternization of the monomers can also be carried out using diethyl sulfate or using alkyl halides such as methyl chloride, ethyl chloride or benzyl chloride.
  • the cationic monomers are used at most in an amount such that the resulting polyelectrolyte complexes carry an anionic charge overall at pH ⁇ 6.0 and a temperature of 20 ° C.
  • the excess anionic charge in the resulting amphoteric polymers is e.g. at least 5 mol%, preferably at least 10 mol%.
  • the comonomers are used in the preparation of the anionic polyelectrolyte complexes, for example, in amounts such that the resulting polymer dispersions are water-soluble when diluted with water and at pH values above 7.0 and a temperature of 20 ° C. and have an anionic charge.
  • the amount of nonionic and / or cationic comonomers is e.g. 0 to 99, preferably 5 to 75% by weight and usually in the range of 5 to 25% by weight.
  • copolymers examples are copolymers of 25 to 90% by weight of acrylic acid and 75 to 10% by weight of acrylamide.
  • Homopolymers of acrylic acid which are obtainable by radical polymerization of acrylic acid in the absence of other monomers are particularly preferred.
  • the anionic polymer contains 2-acrylamido-2-methyl-propanesulfonic acid (AMPS).
  • AMPS 2-acrylamido-2-methyl-propanesulfonic acid
  • the amount of AMPS can be, for example, from 0.1 to 15 mol% or from 0.5 to 10 mol%, based on the amount of all monomers.
  • the polymerization can additionally be carried out in the presence of at least one crosslinking agent. Copolymers with a higher molar mass are then obtained than when the anionic monomers are polymerized in the absence of a crosslinking agent.
  • the incorporation of a crosslinker into the polymers also leads to a reduced solubility of the polymers in water. Depending on the amount of crosslinking agent polymerized in, the polymers become water-insoluble, but are swellable in water. All compounds which have at least two ethylenically unsaturated double bonds in the molecule can be used as crosslinkers.
  • crosslinkers are triallylamine, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, methylene bisacrylamide, N, N'-divinylethylene urea, allyl ethers containing at least two allyl groups or vinyl ethers containing at least two vinyl groups of polyhydric alcohols, such as e.g.
  • crosslinking agents are used in the preparation of the dispersions according to the invention, the amounts of crosslinking agent used in each case are, for example, 0.0005 to 5.0, preferably 0.001 to 1.0,% by weight, based on the total monomers used in the polymerization.
  • Preferred crosslinkers are pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, N, N'-divinylethylene urea, at least two allyl groups containing allyl ethers of sugars such as sucrose, glucose or mannose and triallylamine and mixtures of these compounds.
  • crosslinked copolymers of acrylic acid and / or methacrylic acid are preferably prepared by at least acrylic acid and / or methacrylic acid in the presence of pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, N, N'-divinylethylene urea two allyl groups containing allyl ethers of sugars such as sucrose, glucose or mannose or triallylamine and mixtures of these compounds are polymerized.
  • the resulting polyelectrolyte complexes are soluble or swellable in dilute aqueous solution at pH values> 7.0.
  • the cationic polymers used to form the polyelectrolyte complexes are preferably water-soluble, ie they have a solubility in water of at least 1 g / l at 20 ° C.
  • Cationic polymers are polymers with cationic groups, especially organic polymers with quaternary ammonium groups. Polymers with primary, secondary or tertiary amine groups can also be used, provided that they are protonated either by acids contained in the reaction medium or by acid groups of the anionic polymer and thus converted into cationic groups.
  • the amine or ammonium groups of the cationic polymer can be present as substituents or as part of the polymer chain. They can also be part of an aromatic or non-aromatic ring system.
  • the basic monomers can also be in the form of the salts with mineral acids or in quaternized form.
  • the average molecular weights M w of the cationic polymers are at least 500. They are, for example, in the range from 500 to 1 million, preferably from 1,000 to 500,000 or 2,000 to 100,000.
  • the copolymers of vinylimidazolium methosulfate and N-vinylpyrrolidone listed under (a) contain, for example, 10 to 90% by weight of N-vinylpyrrolidone in copolymerized form.
  • N-vinylpyrrolidone instead of N-vinylpyrrolidone, at least one compound from the group of ethylenically unsaturated C 3 - to C 5 -carboxylic acids such as in particular acrylic acid or methacrylic acid or the esters of these carboxylic acids with monohydric alcohols containing 1 to 18 C atoms such as methyl acrylate, ethyl acrylate can be used as comonomer , Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate or n-butyl methacrylate.
  • Polydiallyldimethylammonium chloride is preferably used as the group (b) polymer. Also suitable are copolymers of diallyldimethylammonium chloride and dimethylaminoethyl acrylate, copolymers of diallyldimethylammonium chloride and dimethylaminoethyl methacrylate, copolymers of diallyldimethylammonium chloride and diethylaminoethylacrylate, copolymers of diallyldimethylammonyldimide and copolymer of dimethylamino propyl amidylamethylimidylamethylimidylammonyldiamidylamethylidylamethylidylamethylidylammonyldimethylamidylamethylidylamethylidylammonyldimethylamidylamethylidylamethylidylamylidylamethylidylamylidylamethylidylamethylidylamethylidy
  • Polymers (c) containing vinylamine units can be obtained by polymerizing N-vinylformamide, if appropriate in the presence of comonomers, and hydrolysing the vinylformamide polymers with elimination of formyl groups to form amino groups.
  • the degree of hydrolysis of the polymers can be, for example, 1 to 100% and is usually in the range from 60 to 100%.
  • the average molecular weights M w are up to 1 million.
  • Polymers containing vinylamine units are sold, for example, as Catiofast® brands by BASF SE.
  • Polymers of group (d) containing ethyleneimine units are also commercial products. They are sold, for example, under the name Polymin® by BASF SE, for example Polymin® SK. These cationic polymers are polymers of ethyleneimine which are prepared by polymerizing ethyleneimine in an aqueous medium in the presence of small amounts of acids or acid-forming compounds such as halogenated hydrocarbons, for example chloroform, carbon tetrachloride, tetrachloroethane or ethyl chloride, or are condensation products made from compounds containing epichlorohydrin and amino groups such as mono- and polyamines, for example dimethylamine, diethylamine, ethylenediamine, diethylenetriamine and Triethylene tetramine or ammonia. For example, they have molecular weights M w of 500 to 1 million, preferably 1000 to 500,000.
  • This group of cationic polymers also includes graft polymers of ethyleneimine onto compounds which have a primary or secondary amino group, e.g. Polyamidoamines from dicarboxylic acids and polyamines.
  • the polyamidoamines grafted with ethyleneimine can optionally also be reacted with bifunctional crosslinking agents, for example with epichlorohydrin or bis-chlorohydrin ethers of polyalkylene glycols.
  • Polymers containing dialkylaminoalkyl acrylate and / or dialkylaminoalkyl methacrylate units are suitable as cationic polymers of group (e). These monomers can be used in the form of the free bases, but preferably in the form of the salts with mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid and in quaternized form in the polymerization. Examples of suitable quaternizing agents are dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride, cetyl chloride or benzyl chloride. Both homopolymers and copolymers can be prepared from these monomers.
  • Suitable comonomers are acrylamide, methacrylamide, N-vinylformamide, N-vinylpyrrolidone, methyl acrylate, ethyl acrylate, methyl methacrylate and mixtures of the monomers mentioned.
  • Cationic polymers of group (f) are polymers containing dimethylaminoethyl acrylamide or dimethylaminoethyl methacrylamide units, which preferably contain the basic monomers in the form of the salts with mineral acids or in quaternized form. These can be homopolymers and copolymers.
  • Examples are homopolymers of dimethylaminoethyl acrylamide which is completely quaternized with dimethyl sulfate or with benzyl chloride, homopolymers of dimethylaminoethyl methacrylamide which is completely quaternized with dimethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride, and copolymers of acrylamide and dimethylaminoethyl acrylate quaternized with dimethyl sulfate.
  • Aqueous dispersions of polyelectrolyte complexes can be prepared by radically polymerizing the anionic monomers under consideration, optionally in the presence of other monomers, in an aqueous medium in the presence of cationic polymers.
  • the amount of basic or cationic monomers can be chosen so that the resulting polymer complexes always carry an excess of anionic charge, determined at pH 7 and 20 ° C.
  • the charge density of the polyelectrolytes or polyelectrolyte complexes can be determined using D. Horn, Progr. Colloid & Polymer Sci., Vol. 65, 251-264 (1978 ) respectively.
  • Basic polymers are preferably used in the form of the salts with mineral acids or organic acids such as formic acid or acetic acid in the polymerization. These salts are otherwise formed during the polymerization anyway, because the polymerization is carried out at a pH ⁇ 6.0.
  • the polymerization can optionally also be carried out in the presence of at least one chain transfer agent.
  • Chain transfer agents are organic compounds which contain sulfur in bound form, such as dodecyl mercaptan, thiodiglycol, ethylthioethanol, di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane 1,2-diol, 1,4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, Mercaptosuccinic acid, thioacetic acid and thiourea, aldehydes, organic acids such as formic acid, sodium formate or ammonium formate, alcohols such as in particular isopropano
  • One or more chain transfer agents can be used in the polymerization. If they are used in the polymerization, they are used, for example, in an amount of 0.01 to 5.0, preferably 0.2 to 1% by weight, based on the total monomers.
  • the chain transfer agents are preferably used together with at least one crosslinker in the polymerization. By varying the amount and the ratio of chain transfer agent and crosslinking agent, it is possible to control the rheology of the resulting polymers.
  • Chain transfer agents and / or crosslinkers can be introduced during the polymerization, for example in the aqueous polymerization medium, or metered together or separately from the monomers, depending on the progress of the polymerization, into the polymerization batch.
  • initiators are usually used which form free radicals under the reaction conditions.
  • Suitable polymerization initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, sodium or potassium persulfate, redox catalysts and azo compounds such as 2,2-azobis (N, N-dimethyleneisobutyramidine) dihydrochloride, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile) and 2,2-azobis (2-amidinopropane) dihydrochloride.
  • the initiators are used in the amounts customary for the polymerization.
  • Azo starters are preferably used as polymerization initiators.
  • the polymerization can also be initiated with the help of high-energy rays such as electron beams or by irradiation with UV light.
  • the polymerization of the anionic monomers is carried out batchwise, for example, by introducing the monomers and at least one cationic compound into a polymerization zone and metering the polymerization initiator in portions or continuously.
  • a semi-continuous procedure is preferred, in which water and polymerization initiator are initially charged and at least one anionic monomer and at least one cationic polymer are metered in continuously under polymerization conditions.
  • the initiator can also be introduced into the polymerization zone continuously or in portions, but separately from the monomer feed and the metering of cationic polymer.
  • the polymerization is usually carried out in all cases with the exclusion of oxygen under an inert gas atmosphere, for example under nitrogen or helium.
  • the polymerization temperatures are, for example, in the range from 5 to 100 ° C., preferably 15 to 90 ° C. and most of the time at 20 to 70 ° C. The polymerization temperature depends very much on the particular initiator that is used.
  • the concentration of the polyelectrolyte complexes in the solutions or aqueous dispersions used for coating is preferably at least 1% by weight, in particular at least 5% by weight and up to 50 or up to 60% by weight.
  • the content of polyelectrolyte complexes in the aqueous dispersion is usually 1 to 40% by weight or 5 to 35% by weight, in particular 15 to 30% by weight.
  • Preferred aqueous dispersions of the polyelectrolyte complexes have a viscosity of 100 to 150,000 mPas, or 200 to 5,000 mPas (measured with a Brookfield viscometer at 20 ° C., 20 at pH values below 6.0 and a temperature of 20 ° C. Rpm, spindle 4).
  • the polyelectrolyte complexes have different molecular weights.
  • the average molecular weight M w of the polyelectrolyte complexes is, for example, 1,000 to 10 million, preferably 5,000 to 5 million, and is usually in the range from 10,000 to 3 million. Molecular weight is determined using light scattering.
  • the average particle size of the dispersed polyelectrolyte complexes is, for example, 0.1 to 200 ⁇ m, preferably 0.5 to 70 ⁇ m. You can e.g. B. with the help of optical microscopy, light scattering or freeze fracture electron microscopy.
  • the polymer films are coated with a composition comprising a polyelectrolyte complex previously prepared from anionic polymer and cationic surfactant.
  • Suitable anionic polymers are those mentioned above.
  • preferred anionic polymers are built up from Acrylic acid or methacrylic acid as the only monomers or as monomers in addition to nonionic comonomers, for example polyacrylates, composed of acrylic acid or methacrylic acid and acrylic acid or methacrylic acid esters of monohydric alcohols having 1 to 20, preferably 1 to 12, carbon atoms.
  • Suitable cationic surfactants are non-polymeric substances which have both a cationic or cationizable group, in particular a protonated amine group or preferably a quaternary ammonium group, and also a hydrophobic group, for example an alkyl or aryl group with at least 6 C atoms.
  • Preferred cationic surfactants are surfactants which contain a quaternary ammonium group, for example those of the general formula N (+) R 1 R 2 R 3 R 4 X (-) where R1 to R4 independently of one another are aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups each having 1 to 22 carbon atoms, where in each case at least one of the radicals R1 to R4 has at least 8 carbon atoms and where X - represents an anion, for example a halogen, acetate, phosphate, nitrate or alkyl sulfate, preferably a chloride.
  • R1 to R4 independently of one another are aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups each having 1 to 22 carbon atoms, where in each
  • the aliphatic groups can also contain cross-links or other groups such as, for example, further amino groups.
  • suitable cationic surfactants are the chlorides or bromides of alkyldimethylbenzylammonium salts, alkyltrimethylammonium salts, for example cetyltrimethylammonium chloride or bromide, tetradecyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, dialkyldimethylammonium chlorides or bromides, alkylpyridinium salts, for example lauryl- or cetylpyridinium chloride, alkylamidoethyltrimethylammonium ether sulfates as well as compounds with cationic Character such as amine oxides, for example alkylmethylamine oxides or alkylaminoethyldimethylamine oxides. Cetyltrimethylammonium salts, alkyltrimethylammonium salts
  • a polymer film is coated on at least one side with at least three alternating layers, one of two adjacent layers each containing at least one anionic polyelectrolyte construction component and the other of two adjacent layers containing at least one cationic polyelectrolyte construction component and adhering to the mutual, adjacent ones Interfaces of the at least three alternating layers can form polyelectrolyte complexes.
  • the combination of the first to third coating of the polymer film gives oxygen barrier properties.
  • polyelectrolyte components can be used as anionic polymers, cationic polymers and cationic surfactants.
  • a sandwich structure of three layers is preferred, the outer layers each containing at least one identical or different anionic polymer and the middle layer containing at least one cationic polymer.
  • Anionic polymers are in particular olefin / (meth) acrylic acid copolymers.
  • Cationic polymers are in particular polyvinylamines or fully or partially hydrolyzed polyvinylformamides.
  • Anionic polyelectrolyte constituent components which are suitable for all embodiments are, in particular, anionic polymers which can be prepared from monomers selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -carboxylic acids, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid and salts of these acids.
  • Cationic polyelectrolyte constituent components suitable for all embodiments are in particular cationic polymers selected from the group consisting of polymers containing vinylimidazolium units, polymers containing polydiallyldimethylammonium halides, polymers containing vinylamine units, polymers containing dialkylaminoalkyl acrylamide units, polymer dialkylaminoalkylamido amyl units, polymer containing dialkylaminoalkylamino amyl acrylates from the group consisting of compounds of the general formula N (+) R 1 R 2 R 3 R 4 X (-) where R1 to R4 independently of one another denote alkyl groups each having 1 to 22 carbon atoms, with at least one of the radicals R1 to R4 each having at least 8 carbon atoms and wherein X - represents an anion, for example a halogen, acetate, phosphate, nitrate or alkyl sulfate, preferably a chloride.
  • a preferred combination in particular for embodiments with alternating layers, is the combination of one or more wholly or partially hydrolyzed polyvinylformamides with one or more homopolymers or copolymers of acrylic acid or methacrylic acid.
  • film substrates suitable for packaging are coated with an aqueous solution or dispersion of at least one polyelectrolyte complex or at least one structural component of a polyelectrolyte complex.
  • Suitable substrates are in particular polymer films.
  • the solutions or dispersions used for coating may contain further additives or auxiliary substances, e.g. Thickener for adjusting the rheology, wetting aids or binders.
  • Polymer foils preferred as carrier material are foils made of oriented polypropylene or polyethylene, where the polyethylene can have been produced both by the high pressure and by the low pressure polymerization process of ethylene.
  • Other suitable carrier films are, for example, films made of polyester, such as polyethylene terephthalate, films made of polyamide, polystyrene and polyvinyl chloride.
  • the carrier material is biodegradable films, e.g. made of biodegradable aliphatic-aromatic copolyesters and / or polylactic acid, for example Ecoflex® or Ecovio® films. Suitable copolyesters are e.g.
  • alkane diols especially C2 to C8 alkane diols such as e.g. 1,4-butanediol, from aliphatic dicarboxylic acids, in particular C2 to C8 dicarboxylic acids such as e.g. Adipic acid and from aromatic dicarboxylic acids such as e.g. Terephthalic acid.
  • the thickness of the carrier films is generally in the range from 10 to 200 ⁇ m, for films made of polyamide 30 to 50 ⁇ m, for films made of polyethylene terephthalate 10 to 40 ⁇ m, for films made of polyvinyl chloride about 100 ⁇ m and for films made of polystyrene at around 30-75 ⁇ m.
  • the application can be carried out, for example, on coating machines in such a way that the coating composition is applied to a carrier film made of a plastic. If web-shaped materials are used, the polymer dispersion is usually applied from a tub via an application roller and leveled using an air brush. Other ways of applying the coating are achieved, for example, with the aid of the reverse gravure process, with a spray process or with a roller doctor or with other coating processes known to the person skilled in the art.
  • the low and high pressure processes known from printing technology are also suitable for producing a barrier coating using a polyelectrolyte complex.
  • the different polymers are applied alternately per print job.
  • the flexographic printing processes known to the person skilled in the art as high-pressure processes the engraving process as an example of gravure printing and offset printing as an example of planographic printing are to be mentioned. Modern digital printing, inkjet printing, electrophotography or direct imaging can also be used.
  • the polyelectrolyte complex is first formed in situ on the packaging material by using two, three or more coating compositions simultaneously or in one working step, e.g. by a cascade coating, one of the coating compositions containing at least one anionic polymer and the other coating composition containing at least one cationic polymer. It is preferred that at least one first coating composition is applied, which contains at least one cationic polymer with primary, secondary or tertiary amine groups and then at least one second coating composition is applied, which contains at least one anionic polymer with acid groups.
  • the cationic polymers with amino groups are e.g.
  • the anionic polymers with acid groups are e.g.
  • the carrier film can be subjected to a corona treatment beforehand.
  • the amounts applied to the flat materials are, for example, preferably 1 to 10 g (polymer, solid) per m 2 , preferably 2 to 7 g / m 2 for films, or preferably 10 to 30 g / m 2 for paper or cardboard.
  • the solvent is evaporated.
  • the material can be guided through a dryer channel, which can be equipped with an infrared radiation device. Then the coated and dried material passed over a cooling roller and finally wound up.
  • the thickness of the dried coating is preferably 0.5 to 50 ⁇ m, particularly preferably 2 to 20 ⁇ m.
  • the substrates coated with the polyelectrolyte complex show an excellent barrier effect against oxygen, especially in the case of kinks, folds and corners.
  • the coated substrates can be used as such as packaging, preferably for food.
  • the coatings have very good mechanical properties and show e.g. good blocking behavior and essentially show no cracks.
  • the packaging means In order to obtain special surface or coating properties of the packaging means, for example good printability, even better sealing and blocking behavior, good water resistance, it can be advantageous to overcoat the coated substrates with top layers which additionally impart these desired properties.
  • the substrates precoated with polyelectrolyte complexes show good overcoatability. It can be overcoated again using the above-mentioned process, or it can be coated several times in a continuous process without winding and unwinding the film in the meantime.
  • the oxygen barrier layer is thus inside the system, the surface properties are then determined by the top layer.
  • the top layer adheres well to the fat barrier layer. It is particularly preferred to apply a moisture protection coating which ensures the effectiveness of the oxygen barrier layer even at higher atmospheric humidities.
  • the oxygen transmission or the oxygen permeability was determined on coatings on polymer films at the relative humidity specified in each case.
  • the oxygen permeability (transmission) is measured, which is then converted to a layer thickness of 1 ⁇ m and given as oxygen permeability with the unit cm 3 (1 ⁇ m) / (m 2 xdx bar), where d is the time in days.
  • the determination is based on ASTM-D 3985.
  • a polymer film made of polyethylene terephthalate with a thickness of 25 ⁇ m was coated with a layer of 10 parts by weight of ethylene / methacrylic acid copolymer and 90 parts by weight of poly (ethyl acrylate) with a thickness of 13 ⁇ m.
  • Foil C (according to the invention):
  • a polymer film made of polyethylene terephthalate with a thickness of 25 ⁇ m was coated with a first layer of 10 parts by weight of ethylene / methacrylic acid copolymer and 90 parts by weight of poly (ethyl acrylate) with a thickness of 8 ⁇ m.
  • a second layer of polyvinylamine (more than 95% hydrolyzed poly (N-vinylformamide) with a thickness of 4 ⁇ m was coated.
  • another layer with 10 parts by weight of ethylene / methacrylic acid copolymer and 90 parts by weight of poly (ethyl acrylate) with a thickness of 8 ⁇ m third layer.
  • Oxygen transmission slide A 70 cm 3 / (m 2 xd)
  • Oxygen transmission slide B 90 cm 3 / (m 2 xd)
  • Oxygen transmission foil C 3 cm 3 / (m 2 xd)
  • Oxygen permeability film C 60 cm 3 (1 ⁇ m) / (m 2 xdx bar)
  • a polymer film made of oPP (oriented polypropylene) with a thickness of 30 ⁇ m was coated with a w / w dispersion of a polyelectrolyte complex composed of cetyltrimethylammonium chloride (CTAC) and a copolymer of 80 parts by weight of acrylic acid, 10 parts by weight of hydroxyethyl acrylate and 10 Parts by weight of methyl acrylate, neutralized with NaOH.
  • CTAC cetyltrimethylammonium chloride
  • the w / w dispersion of the polyelectrolyte complex was prepared by mixing the copolymer with the cationic surfactant in water.
  • CTAC is added as a complexing agent. The mixture is stirred until a homogeneous emulsion is formed.
  • the layer thickness of the layer of the polyelectrolyte complex on the oPP film was 3 ⁇ m.
  • the oxygen barrier effect was measured at 50% relative humidity. Oxygen permeability: 62 cm 3 (1 ⁇ m) / (m 2 xdx bar)
  • Example 3 IR measurements to detect the formation of polyelectrolyte complexes in a first experiment, polyacrylic acid (35% in water) and polyvinylamine (6.1% in water) were mixed in a mass ratio of 1: 1.7 and stirred. An IR spectrum was recorded from the solid reaction product formed. In the IR spectrum are the absorptions of the NH vibrations (3300 cm -1 ) of the polyvinylamine disappeared and new absorptions of the carboxylation at 1530 cm -1 and 1390 cm -1 have arisen. This indicates the formation of a polyelectrolyte complex.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paper (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Utilisation d'au moins un complexe de polyélectrolyte pour conférer à des matériaux d'emballage en films polymères une barrière à l'oxygène, des composants constitutifs polymères du complexe de polyélectrolyte étant appliqués sous forme polymérisée sur le film polymère, et
    au moins un film polymère étant revêtu sur au moins un côté avec une composition contenant un complexe de polyélectrolyte fabriqué auparavant à partir d'un polymère anionique et d'un tensioactif cationique,
    ou un film polymère étant revêtu sur au moins un côté avec au moins trois couches alternées, respectivement une couche parmi deux couches voisines contenant au moins un composant constitutif de polyélectrolyte anionique et l'autre couche parmi deux couches voisines contenant au moins un composant constitutif de polyélectrolyte cationique, et des complexes de polyélectrolyte pouvant se former sur les interfaces voisines opposées desdites au moins trois couches alternées,
    caractérisée en ce qu'en tant que composant constitutif de polyélectrolyte cationique, un polymère cationique est utilisé, qui est choisi dans le groupe constitué par les polymères contenant des unités vinylimidazolium, les polyhalogénures de diallyldiméthylammonium, les polymères contenant des unités vinylamine, les polymères contenant des unités éthylène-imine, les polymères contenant des unités acrylate de dialkylaminoalkyle, les polymères contenant des unités méthacrylate de dialkylaminoalkyle, les polymères contenant des unités dialkylaminoalkylacrylamide et les polymères contenant des unités dialkylaminoalkylméthacrylamide ; ou en ce qu'en tant que composant constitutif de polyélectrolyte cationique, un tensioactif cationique est utilisé.
  2. Utilisation selon la revendication précédente, caractérisée en ce que la couche contenant le complexe de polyélectrolyte est munie d'une protection contre l'humidité.
  3. Utilisation selon la revendication précédente, caractérisée en ce que la protection contre l'humidité est formée par revêtement avec une polyoléfine ou par coextrusion d'une polyoléfine avec au moins une matière choisie parmi les complexes de polyélectrolyte, les composants constitutifs de polyélectrolyte anioniques et les composants constitutifs de polyélectrolyte cationiques.
  4. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le revêtement avec le complexe de polyélectrolyte a lieu de telle sorte que
    (a1) le film polymère est muni sur au moins un côté avec un premier revêtement, qui contient au moins un polymère anionique,
    (b1) le premier revêtement est muni d'un deuxième revêtement, qui contient au moins une matière cationique, choisie parmi les tensioactifs cationiques et les polymères cationiques, et
    (c1) le deuxième revêtement est muni d'un troisième revêtement, qui contient au moins un polymère anionique ; ou de telle sorte que
    (a2) le film polymère est muni sur au moins un côté d'un premier revêtement, qui contient au moins une matière cationique, choisie parmi les tensioactifs cationiques et les polymères cationiques,
    (b2) le premier revêtement est muni d'un deuxième revêtement, qui contient au moins un polymère anionique, et
    (c2) le deuxième revêtement est muni d'un troisième revêtement, qui contient au moins une matière cationique, choisie parmi les tensioactifs cationiques et les polymères cationiques.
  5. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce qu'en tant que composant constitutif de polyélectrolyte anionique, un polymère anionique est utilisé, qui est choisi parmi les polymères qui peuvent être fabriqués à partir de monomères choisis dans le groupe constitué par les acides carboxyliques en C3 à C10 monoéthyléniquement insaturés, l'acide vinylsulfonique, l'acide styrène-sulfonique, l'acide acrylamidométhylpropane-sulfonique, l'acide vinylphosphonique et les sels de ces acides.
  6. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce qu'en tant que composant constitutif de polyélectrolyte cationique, un tensioactif cationique est utilisé, qui est choisi dans le groupe constitué par les composés de la formule générale :

            N(+)R1R2R3R4 X(-)

    dans laquelle R1 à R4 signifient indépendamment les uns des autres des groupes alkyle contenant chacun 1 à 22 atomes C, au moins un des radicaux R1 à R4 comprenant au moins 8 atomes C, et X- représente un anion.
  7. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère cationique est un polyvinylformamide entièrement ou partiellement hydrolysé et le polymère anionique est un homopolymère ou un copolymère d'acide acrylique ou d'acide méthacrylique.
  8. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que deux compositions de revêtement sont appliquées simultanément ou immédiatement l'une après l'autre en une étape de travail, une des compositions de revêtement contenant un polymère anionique et l'autre composition de revêtement contenant un polymère cationique.
  9. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le matériau du film polymère est choisi parmi le polyéthylène téréphtalate, le polypropylène orienté, le polyéthylène et les copolyesters aliphatiques-aromatiques biodégradables.
  10. Film polymère revêtu, au moins un côté du film polymère étant revêtu avec au moins trois couches alternées, respectivement une couche parmi deux couches voisines contenant au moins un composant constitutif de polyélectrolyte anionique et l'autre couche parmi deux couches voisines contenant au moins un composant constitutif de polyélectrolyte cationique, et des complexes de polyélectrolyte pouvant se former sur les interfaces voisines opposées desdites au moins trois couches alternées, caractérisé en ce qu'en tant que composant constitutif de polyélectrolyte cationique, un polymère cationique est utilisé, qui est choisi dans le groupe constitué par les polymères contenant des unités vinylimidazolium, les polyhalogénures de diallyldiméthylammonium, les polymères contenant des unités vinylamine, les polymères contenant des unités éthylène-imine, les polymères contenant des unités acrylate de dialkylaminoalkyle, les polymères contenant des unités méthacrylate de dialkylaminoalkyle, les polymères contenant des unités dialkylaminoalkylacrylamide et les polymères contenant des unités dialkylaminoalkylméthacrylamide ; ou en ce qu'en tant que composant constitutif de polyélectrolyte cationique, un tensioactif cationique est utilisé.
EP12195417.6A 2009-08-24 2010-08-17 Utilisation de complexes de polyélectrolytes pour la fabrication de films polymères ayant des propriétés de barrière à l'oxygène Active EP2570196B1 (fr)

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PCT/EP2010/061925 WO2011023587A2 (fr) 2009-08-24 2010-08-17 Utilisation de complexes de polyélectrolytes pour produire des feuilles polymères à propriétés de barrière à oxygène

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