WO2003068869A2 - Enductions pour materiaux supports destinees a bloquer le passage de l'oxygene - Google Patents

Enductions pour materiaux supports destinees a bloquer le passage de l'oxygene Download PDF

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Publication number
WO2003068869A2
WO2003068869A2 PCT/EP2003/001065 EP0301065W WO03068869A2 WO 2003068869 A2 WO2003068869 A2 WO 2003068869A2 EP 0301065 W EP0301065 W EP 0301065W WO 03068869 A2 WO03068869 A2 WO 03068869A2
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Prior art keywords
weight
optionally
chr
copolymerizable
ethylenically unsaturated
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PCT/EP2003/001065
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German (de)
English (en)
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WO2003068869A3 (fr
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Hermann Seyffer
Erich Beck
Markus Schmid
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Basf Aktiengesellschaft
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Priority to AU2003210206A priority Critical patent/AU2003210206A1/en
Publication of WO2003068869A2 publication Critical patent/WO2003068869A2/fr
Publication of WO2003068869A3 publication Critical patent/WO2003068869A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/142—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic

Definitions

  • the present invention relates to flat coatings of films, papers, cardboards or cartons for the production of barrier coatings.
  • packaging materials based on foils, paper, cardboard or cardboard are often equipped with a coating to increase the oxygen, fat and aroma density of the packaging material. Equipping the packaging material in this way is also referred to as a barrier coating.
  • Packaging materials that are equipped with a barrier coating are used in a variety of ways, for example for packaging foods such as ready meals, dairy products, nuts, vegetables or fruit.
  • the aroma density (aroma barrier) of the packaging material is also an important quality criterion for the packaging of food and flavored consumer goods, such as washing powder.
  • PVDC polyvinylidene chloride
  • copolymers of vinylidene dichloride have been used to produce such barrier coatings.
  • Such materials are, however, in view of their environmental compatibility, especially in their disposal, e.g. through combustion, problematic. There has been no shortage of attempts. To replace polyvinylidene chloride and its copolymers with chlorine-free polymers.
  • barrier coatings For example, polyvinyl acetate, polyethylene-polyvinyl alcohol copolymers and comparable substances for the production of barrier coatings have been described.
  • the barrier coatings obtainable in this case have only inadequate application properties.
  • these products show a high solubility in water. The aforementioned products are therefore not acceptable for use in packaging food.
  • EP-A 700 731 describes a process for the production of packaging materials with oxygen barriers, in which a packaging substrate is coated with a dispersion comprising a copolymer of ethylenically unsaturated carboxylic acids, dicarboxylic acids, their half-esters or anhydrides and optionally other monomers and polyester.
  • a disadvantage of these systems is that they are relatively sensitive to moisture.
  • the object of the present invention was to develop coated carrier materials which are moisture-stable and have low oxygen permeability.
  • the object was achieved by a process for the production of packaging materials with oxygen barrier properties, in which a carrier material containing a coating agent (I)
  • (AI) at least one polymerizable compound having one or more copolymerizable, ethylenically unsaturated groups
  • (A2) optionally at least one further polymerizable compound having one or more copolymerizable, ethylenically unsaturated groups,
  • the carrier materials obtainable in this way generally have an oxygen permeability of not more than 100 cm 3 / (m 2 xdx bar), based on a layer thickness of 100 ⁇ m. Below this value, this document speaks of an oxygen barrier property.
  • Suitable substrates for packaging such as e.g. Films, for example made of metal or plastic, which can also be foamed, paper, cardboard or cardboard are used.
  • Suitable films can, for example, consist of or contain polyolefins, for example (co) polymers of ethylene, propylene, 1-butene, 2-butene, isobutene or styrene, or of polyalkylene terephthalates, for example made of polyethylene terephthalate, polypropylene terephthalate or polybutylene terephthalate.
  • polyolefins for example (co) polymers of ethylene, propylene, 1-butene, 2-butene, isobutene or styrene
  • polyalkylene terephthalates for example made of polyethylene terephthalate, polypropylene terephthalate or polybutylene terephthalate.
  • polyethylenes are those which are produced by the high-pressure or low-pressure process (high-pressure or low-pressure polyethylene).
  • LDPE low density polyethylene
  • HMW-LDPE high density polyethylene
  • Polyethylenes from the low pressure process are largely linear and unbranched (HDPE), have degrees of crystallinity of 60-80% and a density of approx. 0.94-0.965 g / cm 3 and molar masses of approx. 20 200000-5000000 g / mol resp . 3000000-6000000 g / mol (HD-HMW-PE or UHMW-HD-PE).
  • HDPE linear and unbranched
  • MDPE Medium density products made from blends of low and high density polyethylenes are also commercially available.
  • VLD-PE Linear polyethylenes with densities ⁇ 0.918 g / cm 3
  • polypropylenes are those with an average relative molar mass of approx. 150000-600000 g / mol or also copolymers of propylene with ethylene (EPM, EPDM).
  • the spatial orientation of the chains in polypropylene films can be achieved by uni- or bisaxial stretching (OPP films). Stretched polypropylene films are preferred.
  • polybutenes are those with molar masses of 700000-3000000 g / mol, especially those with melting points of 40 125-130 ° C and a density of 0.91-0.92 g / cm 3 .
  • PVC films are also conceivable, the polyvinyl chloride generally having a molar mass of 30,000 to 130,000 g / mol.
  • Soft PVC is preferred, which has a content of 45 plasticizers of generally more than 12% by weight.
  • Polystyrene can be used with a molecular weight of 170,000 to 1000000 g / mol and a density of approx. 1.05 g / cm 3 .
  • paper is understood to be a flat material consisting essentially of fibers of predominantly vegetable origin, which is formed by dewatering a fibrous substance suspension on a sieve, producing a fiber felt which is then compressed and dried.
  • Paper with a basis weight of up to 225 g / m 2 can be used, with a basis weight of more than 225 g / m 2 one speaks of cardboard.
  • Cardboard generally has a basis weight of 150-600 g / m 2 and is usually stiffer than paper of the same basis weight.
  • the coated film system ie carrier material and coating
  • the coated film system generally also has a low water vapor permeability in addition to the low oxygen permeability desired according to the invention, generally below 25 g / ( m 2 X d), based on 100 ⁇ m layer thickness, at 39 ° C. and 90% relative humidity, preferably below 20, particularly preferably below 15, very particularly preferably below 10 and in particular below 5 g / (m 2 X d).
  • the film system has, in addition to the low oxygen permeability, a relatively high water vapor permeability of generally more than 100 g / (m 2 xd), based on 100 m layer thickness, at 39 ° C. and 90% relative humidity, preferably more than 250 and particularly preferably more than 500 g / (m 2 xd).
  • the carrier material or film system can also be provided with a so-called XSB coating.
  • These can be, for example, styrene and butadiene and, if appropriate, further monomers in copolymerized form and, if appropriate, coatings containing other constituents, such as, for example, those as claimed in DE-Al 27 41 824 or those as described in EP-AI 393 451, there in particular from column 2, line 16 to column 8, line 53.
  • Preferred coatings are those which contain hydrogenated styrene-butadiene copolymers, as described in DE-Al 101 03 065.
  • the carrier material is coated with a coating composition (I) described below in a manner known per se.
  • One subject of this application is the use of radiation-curable coating compositions as an oxygen barrier.
  • the coating compositions (I) which can be used according to the invention to achieve an oxygen barrier generally have an increased hydrophilicity.
  • the individual components are known per se. They usually contain at least one radical polymerizable group.
  • Preferred coating compositions (I) are those in which (AI) and (A2) and (B) are capable of dissolving at least 2% by weight of distilled water homogeneously together at 25 ° C., particularly preferably at least 5% by weight, very particularly preferably at least 10, in particular at least 15% by weight and exceptionally preferably at least 20% by weight.
  • Polymerizable groups can be those which have unsaturated bonds, preferably carbon-carbon double bonds.
  • Radically polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinylaromatic groups, vinyl and vinylidene chloride groups, N-vinylamides, vinylpyrrolidones, vinyl lactams, vinyl esters, (meth) acrylic esters or acrylonitriles.
  • Acrylic and methacrylic groups are preferred, particularly preferably acrylic groups.
  • the coating compositions which can be used according to the invention are preferably radiation-curable.
  • a radiation-curable coating composition (I) which can be used according to the invention contains
  • (A2) optionally at least one further polymerizable compound having one or more copolymerizable, ethylenically unsaturated groups, (B) optionally monofunctional reactive diluent,
  • Compounds (AI) which are free-radically polymerizable are compounds having one or more, i.e. at least two, copolymerizable, ethylenically unsaturated groups.
  • Examples of a compound (AI) with a copolymerizable, ethylenically unsaturated group are acrylic acid, methacrylic acid, (meth) acrylonitrile, (meth) acrylamide, maleic acid, fumaric acid, 3-acryloylpropionic acid, hydroxyethyl (meth) acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, Oligoethylene glycol monoacrylate, ethylene glycol monomethyl ether acrylate, diethylene glycol monomethyl ether acrylate, dimethylaminoethyl (meth) acrylate, phenol glycidyl ether acrylate, acrylates of glycidyl ethers of monoalcohols, such as, for example Methanol, ethanol, n-propanol, iso-propanol, n-butanol or 1-hexanol, N-vinyl pyrrolidone and N-vinyl caprolactam.
  • Compounds (AI) are preferably (meth) acrylate compounds, particularly preferred are the acrylate compounds, i.e. the derivatives of acrylic acid.
  • Preferred (meth) acrylate compounds (AI) contain, for example, at least 2, preferably 2 to 10 and particularly preferably
  • the number-average molecular weight M n of the compounds (AI) is preferably less than 10,000, particularly preferably less than 5000, very particularly preferably less than 3000 g / mol and more than 180 g / mol (determined by gel chromatography with polystyrene as Standard and tetrahydrofuran as eluent).
  • Preferred (meth) acrylate compounds (AI) may be mentioned (Meth) acrylic acid esters and in particular acrylic acid esters of highly functional alcohols, in particular those which, besides the hydroxyl groups, contain no further functional groups or at most ether groups.
  • multifunctional alcohols are, for example, bifunctional alcohols, such as ethylene glycol, propylene glycol and their more highly condensed homologs, for example such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol etc., 1,2-, 1,3- or 1,4-butanediol, 1 , 5-pentanediol, 1, 6-hexanediol, 3-methyl-l, 5-pentanediol, neopentyl glycol, alkoxylated phenolic compounds such as ethoxylated or propoxylated bisphenols, 1,2-, 1,3- or 1,4-cyclohexanedi- methanol, trifunctional and higher functional alcohols
  • alkoxylation products are preferred in a known manner by reacting the above alcohols with alkylene oxides
  • Ethylene and / or propylene oxide particularly preferably ethylene oxide.
  • the degree of alkoxylation per hydroxyl group is 0 to 20, preferably 0 to 10 and preferably 0 to 5, i.e. 1 mol of hydroxyl groups can be alkoxylated with up to 20 mol of alkylene oxides.
  • (meth) acrylate compounds (AI) are those compounds which can be obtained by reacting (meth) acrylic acid with the glycidyl ethers of the above-mentioned polyfunctional alcohols.
  • epoxy (meth) acrylates can be obtained by reacting epoxides with (meth) acrylic acid.
  • suitable epoxides are epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.
  • Epoxidized olefins can be, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, preference is given to ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide, propylene oxide or epichlorohydrin and very particularly preferably ethylene oxide and epichlorohydrin.
  • Aromatic glycidyl ethers are e.g. B. Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphe nol-S-diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, for example 2, 5-bis [(2, 3-epoxypropoxy) phenyl] octahydro-4, 7-methano-5H-indene) (CAS no ,
  • Aliphatic glycidyl ethers are, for example, ° 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1, 1, 2, 2-tetrahedron [4- (2,3-epoxypropoxy) phenyl] CAS No. [27043-37-4]), diglycidyl ether of polypropylene glycol ( ⁇ , ⁇ -bis (2, 3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and of hydrogenated bisphenol A (2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, (CAS No. [13410-58-7]).
  • the epoxy (meth) acrylates preferably have a number average molecular weight M n of 340 to 20,000, particularly preferably from 340 to 10,000 g / mol and very particularly preferably from 480 to 3000 g / mol; the content of (meth) acrylic groups is preferably 1 to 5, particularly preferably 2 to 4 per 1000 g of epoxy (meth) acrylate (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).
  • R 1 is an n-times substituted, aliphatic, cycloaliphatic or aromatic organic group with 2 to 20 carbon atoms,
  • R 2 and R 3 independently of one another are hydrogen or methyl
  • Y is a spacer group having 1 to 20 carbon atoms
  • n is an integer between 2 and 10, preferably between 2 and 5, particularly preferably between 2 and 4 and in particular between 2 and 3, and
  • n is an integer between 0 and 100, preferably 0 and 50, particularly preferably between 1 and 30 and in particular between 2 and 20
  • n-valent alcohols which form the basis for the n-times substituted organic group
  • Ethylene glycol, propylene glycol and their more highly condensed homologs e.g. Diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol etc., 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl- l, 5-pentanediol, alkoxylated phenolic compounds, such as ethoxylated or propoxylated bisphenols, trimethylolpropane, trimethylolethane, neopentylglycol, pentaerythritol, 2-methyl-l, 3-propanediol, glycerol, ditrimethylolpropane, dipentaerythritol, bisphenol A, bisphenol A, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane,
  • Y stands for example for a group of the formula
  • R 5 and R 7 independently of one another denote a single bond or an alkylene or arylene radical having 1 to 18, preferably 2 to 10, particularly preferably 2 to 7 carbon atoms, for example cis-1, 2-ethenylene, .trans-1, 2 -Ethenylene, 1,2-ethylene, 1, 3-propylene, 1,4-butylene, 1,6-hexylene, 1, 10-decylene, 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene , 4-carboxy-l, 3-phenylene, 2-carboxy-l, 4-phenylene, 4-carboxy-l, 2-phenylene, 1,2-, 1,3- or 1,4-cyclohexylene or 1,2 -Cyclohexenyls.
  • the proportion of propoxylated groups, ie R 2 or R 3 is methyl, is less than 50 mol%, preferably less than 20 mol%, based on the total number of ethylene oxide and propylene oxide groups, particularly preferably less than 10 mol% and very particularly preferably 0 mol%.
  • hydrophilic according to the invention which are capable of homogeneously dissolving at least 2% by weight of distilled water at 25 ° C., particularly preferably at least 5% by weight, very particularly preferably at least 10% by weight, in particular at least 15% by weight and exceptionally preferred at least 20% by weight.
  • Bisphenol A diglycidyl ether diacrylate is equally preferred.
  • Compounds (AI) are often used in a mixture with other polymerizable compounds having a plurality of copolymerizable, ethylenically unsaturated groups (A2) and / or with compounds (B) which serve as reactive diluents.
  • the further polymerizable compounds which can be used as (A2) and have one or more copolymerizable, ethylenically unsaturated groups are known per se, other than (meth) acrylate compounds as described in (A1).
  • These are preferably those which are able to dissolve less than 5% by weight of distilled water homogeneously at 25 ° C., particularly preferably less than 2% by weight.
  • Compounds (A2) with one or more copolymerizable, ethylenically unsaturated groups are, for example, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, norbornyl acrylate, stearyl acrylate, phenoxyethyl acrylate and the acrylate of trimethylolpropane formal.
  • the compounds (A2) can be, for example, uretha (meth) acrylates.
  • Urethane (meth) acrylates are e.g. obtainable by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or (meth) acrylic acid and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.
  • the polyurethanes which can be used according to the invention as (A2) essentially contain as structural components: a) at least one organic aliphatic, aromatic or cycloaliphatic di-or polyisocyanate, b) at least one compound with at least one isocyanate-reactive group and at least one radically polymerizable unsaturated group and c) optionally at least one compound with at least two isocyanate-reactive groups ,
  • Component a) includes, for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates with an NCO
  • the diisocyanates are preferably isocyanates having 4 to 20 carbon atoms.
  • Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradeca ethylene diisocyanate, tetra diisocyanate, tetramethyl diisocyanate, tetramethyl diisocyanate , 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) ethane, l-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane ( Isophorone diisocyanate), 1,
  • Mixtures of the diisocyanates mentioned can also be present.
  • Hexa ethylene diisocyanate, 1,3-bis (isocyanato-methyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane are preferred.
  • Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates of linear or branched ten C 4 -C 2 n-alkylene diisocyanates, cycloaliphatic diisocyanates with a total of 6 to 20 C atoms or aromatic diisocyanates with a total of 8 to 20 C atoms or mixtures thereof.
  • Aliphatic or cycloaliphatic di- and polyisocyanates e.g. the aliphatic or cycloaliphatic diisocyanates mentioned above, or mixtures thereof.
  • Isocyanurate group-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates are particularly preferred.
  • the isocyanurates present here are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues which have more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 3 to 4.5.
  • Uretdione diisocyanates with aromatically, aliphatically and / or cycloaliphatically bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bound and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the uretdione diisocyanates can be used in the preparations according to the invention as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • This biuret polyisocyanates containing groups generally have an NCO content of 18 to 22% by weight and an average NCO functionality of 3 to 4.5.
  • These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.
  • Polyisocyanates containing oxadiazinetrione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.
  • the polyisocyanates 1) to 6) can be used in a mixture, if appropriate also in a mixture with diisocyanates.
  • Compounds b) which have at least one group which is reactive toward isocyanate and at least one radical-polymerizable group are suitable as component b).
  • Groups reactive towards isocyanate can be, for example, -OH, -SH, -NH and -NHR 6 , where R 6 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n -Butyl, isobutyl, SeJc-butyl or tert-butyl means.
  • Components b) can e.g. Monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid,
  • esters or amides of (meth) acrylic acid with amino alcohols for. B. 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-l-propanol, l-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes such as ethylenediamine or diethylenetriamine , or vinyl acetic acid can be used.
  • Unsaturated polyether or polyesterols or polyacrylate polyols with an average OH functionality of 2 to 10 are also suitable.
  • amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N Hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide or N-hydroxyalkylmaleinimides such as N-hydroxyethylmaleinimide.
  • hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide
  • N Hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide
  • N-hydroxyalkylmaleinimides such
  • 2-Hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate are preferably used, 1, 6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol ono-, di- and tri (meth) acrylate as well as 4-hydroxybutyl vinyl ether, 2 -Aminoethyl (meth) acrylate, 2-amino-propyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-amino-butyl (meth) acrylate, 6-aminohe
  • Component c) is a compound which has at least two groups which are reactive toward isocyanate, for example -OH, -SH, -NH or -NHR 4 , in which R 4 is, independently of one another, hydrogen, methyl, ethyl, isopropyl, n-propyl , n-butyl, iso-Bu- can mean tyl, sefc-butyl or tert-butyl.
  • diols or polyols such as hydrocarbon diols having 2 to 20 carbon atoms, e.g. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 1,6-hexanediol, 1,10-decanediol, bis- (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol , 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalinediol, etc., their esters with short-chain dicarboxylic acids, such as adipic acid, cyclohexanedicarboxylic acid, their carbonates, prepared by reaction of Diols with phosgen
  • Diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, pentaerythritol, 1,2- and 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1 are also conceivable.
  • Unsaturated polyether or polyesterols or polyacrylate polyols with an average OH functionality of 2 to 10 are also suitable, as are polyamines, e.g. Polymers containing polyethyleneimine or free amine groups, e.g. Poly-N-vinylformamide.
  • cycloaliphatic diols such as e.g. Bis- (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1-cyclohexanediol, cyclooctanediol or norbornanediol.
  • the polyurethanes which can be used according to the invention as (A2) are obtained by reacting components a), b) and c) with one another.
  • the molar composition a): b): c) per 3 mol reactive isocyanate groups in a) is usually as follows: b) 1.5-3.0, preferably 2.0-2.9, particularly preferably 2.0-2.5 and in particular 2.0-2.3 mol of isocyanate-reactive groups and
  • the urethane (meth) acrylates can still contain free isocyanate groups, but more than 70% of the isocyanate groups present in a) before the reaction are preferably completely reacted, particularly preferably more than 80%, entirely particularly preferably more than 90% and in particular more than 95%.
  • the urethane (meth) acrylates preferably have a number average molecular weight M n of 500 to 20,000, in particular from 750 to 10,000, particularly preferably 750 to 3000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4, moles of (meth) acrylic groups per 1000 g urethane (meth) acrylate.
  • Suitable reactive diluents are free-radically polymerizable compounds, preferably radiation-curable compounds, having an ethylenically unsaturated, copolymerizable group, or mixtures thereof.
  • Examples include ⁇ , ß-unsaturated carboxylic acids, C 1 -C 20 alkyl (meth) acrylates, vinyl atenas with up to 20 C atoms, vinyl esters of carboxylic acids containing up to 20 C atoms, ethylenically unsaturated nitriles, vinyl ethers from 1 to Alcohols containing 10 carbon atoms and aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds.
  • (meth) acrylic acid is used in the context of this document for acrylic acid and methacrylic acid.
  • ⁇ , ⁇ -unsaturated carboxylic acids which can be used are acrylic acid, methacrylic acid, maleic acid or its half-ester, 3-acrylic oxypropionic acid, maleic anhydride, fumaric acid or its half-ester or crotonic acid.
  • Preferred (meth) acrylic acid alkyl esters are those having a C 1 -C 8 -alkyl radical, such as methyl methacrylate, methyl acrylate and ethyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
  • vinyl aromatic compounds e.g. Vinyl toluene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene are considered.
  • nitriles are acrylonitrile and methacrylonitrile.
  • Suitable vinyl ethers are e.g. Vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
  • butadiene, isoprene, as well as ethylene, propylene and isobutylene may be mentioned as non-aromatic hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds.
  • N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam can also be used.
  • Preferred compounds (B) are acrylic acid esters and ⁇ , ⁇ -unsaturated carboxylic acids.
  • Photoinitiators known to those skilled in the art can be used as photoinitiators (C), e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietiker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London.
  • mono- or bisacylphosphine oxides such as are described in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2.4 , 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO), ethyl 2, 4, 6-trimethylbenzoylphenylphosphinate, Irgacure® 819 from Ciba Specialty Chemicals (bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide), benzophenone, hydroxyacetophenone, hydroxyacetophenone xylic acid and its derivatives or mixtures of these photoinitiators.
  • 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO)
  • ethyl 2, 4, 6-trimethylbenzoylphenylphosphinate ethyl 2, 4, 6-trimethylbenzoylphenylpho
  • Examples include benzophenone, acetophenone, acetone naphthoquinone, methylethyl ketone, valerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberon, 4-morpholinobenzophenone, 4-morpholinodeoxybenzyl, pinophenonylbenzyl, p '-Methoxyacetophenone, ß-methylanthraquinone, tert-butylanthraquinone, anthraquinonecarboxylic acid ester, benzaldehyde, tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluoro-non, 1 , 3, 4-triacetylbenzene, thioxanthene-9
  • Benzil ketals such as benzil dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-l-one, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Chloroanthraquinone, 2-amylanthraquinone and 2, 3-butanedione.
  • Non-yellowing or little yellowing photoinitiators of the phenylglyoxalic acid ester type are also suitable, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • acylphosphine oxides examples include the listed acylphosphine oxides, benzophenones, hydroxyacetophenones and phenylglyoxylic acids.
  • mixtures of different photoinitiators can also be used.
  • Installable photoinitiators can also be used. Installable photoinitiators have polymerizable groups bonded to the basic photoinitiator structure via spacer groups. Such built-in photoinitiators are described, for example, in DE-A 195 24 812, EP-A 281 941, WO 00/24527.
  • Preferred among these are 4-acryloxy-2'-chlorobenzophenone, 4-acryloxy-3'-chlorobenzophenone, 4-acryloxy-4'-chlorobenzophenone, 4- (6'-acrylic-oxy-2 '-oxa-1' -oxo-hexyloxy) benzophenone or 1, l-dimethyl-l-hydroxy- '- (2' '-acryloxyethoxy) -acetophenone.
  • the photoinitiators can be used alone or in combination with a photopolymerization promoter, e.g. of the benzoic acid, amine or similar type can be used.
  • Additives (D) include, for example, antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, brighteners, antistatic agents, flame retardants, thickeners, thixotropic agents, flow control agents, binders, antifoams, fragrances, surface-active agents , Viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers.
  • antioxidants for example, antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, brighteners, antistatic agents, flame retardants, thickeners, thixotropic agents, flow control agents, binders, antifoams, fragrances, surface-active agents , Viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers.
  • one or more initiators which can be activated photochemically and / or thermally can be added, for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert.-butyl peroxide, azobis-isobutyronitrile, cyclohexylsulfonylacetyl peroxide, di-isopropyl percarbonate, f -Butyl peroctoate or benzopinacol, as well as, for example, those thermally activatable initiators which have a half-life at 80 ° C.
  • di-t-butyl peroxide cumene hydroperoxide
  • dicumyl per- oxide t-butyl perbenzoate
  • silylated pinacoles e.g. B.
  • ADDID 600 from Wacker or amine N-oxides containing hydroxyl groups, such as 2, 2, 6, 6-tetra-methylpiperidine-N-oxyl, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl etc.
  • chelating agents e.g. Ethylenediamine acetic acid and its salts and ⁇ -diketones are used.
  • Suitable fillers include silicates, e.g. B. by hydrolysis of silicon tetrachloride available silicates such as Aerosil from Degussa, silica, talc, clay, mica, aluminum silicates, magnesium silicates, calcium carbonates, calcium and barium sulfates, aluminum hydroxides and oxides etc. or organic fillers such as e.g. Polyacrylic acids, for example with a molecular weight between 2000 and 300000, or cellulose.
  • silicates e.g. B. by hydrolysis of silicon tetrachloride available silicates such as Aerosil from Degussa, silica, talc, clay, mica, aluminum silicates, magnesium silicates, calcium carbonates, calcium and barium sulfates, aluminum hydroxides and oxides etc.
  • organic fillers such as e.g. Polyacrylic acids, for example with a molecular weight between 2000 and 300000, or cellulose.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, T ⁇ azme and Benzot ⁇ azol (the latter available as Tmuvm brands from Ciba specialty chemistry) and Benzophenone. These may be used alone or together with suitable free-radical scavengers, examples being sterically hindered amines such as 2, 2, 6, 6-tetra- 'methylpiperidine, 2, 6-di-tert. -butylpiperidine or its derivatives, e.g. B. bis- (2, 2, 6, 6-tetra-methyl-4-piperidyl) sebacinate can be used.
  • Stabilizers are usually used in amounts of 0.1 to 5.0% by weight, based on the solid components contained in the preparation.
  • suitable stabilizers are, for example, N-oxyls, such as 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl, 4-oxo-2, 2,6, 6-tetramethyl-piperidine-N-oxyl , 4-acetoxy-2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 2,2,6, 6-tetramethyl-piperidine-N-oxyl, 4, 4 ', 4''tris ( 2,2,6, 6-tetramethyl-piperidine-N-oxyl) phosphite or 3-oxo-2, 2.5, 5-tetramethyl-pyrrolidine-N-oxyl, phenols and naphthols, such as p-aminophenol , p-nitrosophenol, 2-tert.
  • N-oxyls such as 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl, 4-oxo-2, 2,6, 6-tetramethyl-piperidine-N-oxyl , 4-acetoxy-2
  • quinones such as hydroquinone or hydroquinone monomethyl ether
  • aromatic amines such as N, N-diphenylamine, N-nitrosodipheny- lamin
  • phenylenediamines such as N, N'-dialkyl-para-phenylenediamine
  • alkyl radicals can be the same or different and each independently consist of 1 to 4 carbon atoms and can be straight-chain or branched
  • hydroxylamines such as N, N-diethylhydroxylamine
  • urea derivatives such as urea or thiourea
  • phosphorus-containing compounds such as triphenylphosphine, triphenylphosphite or triethylphosphite or sulfur-containing compounds such as diphenyl sulfide or phenothiazine.
  • compositions for coating compositions (I) are, for example
  • (A2) 0-80% by weight, preferably 0-60, particularly preferably 0-50 and in particular 0- " 40% by weight, (B) 0-70% by weight, preferably 5-50, particularly preferably 6-40 and in particular 10 - 30% by weight, (C) 0 - 20% by weight, preferably 0.5 - 15, particularly preferably 1 - 10 and in particular 2 - 5% by weight and (D) 0 - 50% by weight, preferably 2 - 40, particularly preferably 3 - 30 and in particular 5 - 20% by weight,
  • coating compositions (I) in which (Al) and (A2) and (B) together can dissolve at least 2% by weight of distilled water homogeneously, particularly preferably at least 5% by weight, very particularly preferably at least 10, in particular at least 15 wt%, and exceptionally preferably at least 20 "wt%.
  • Dispersion is used in this document as a generic term according to Rö pp Chemie Lexikon - CD Version 1.0, Stuttgart / New York: Georg Thieme Verlag, 1995, and includes emulsions, suspensions and solutions.
  • Suitable solvents (III) are, for example, water, methanol, ethanol, isopropanol, n-propanol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, acetone, isobutyl methyl ketone, diethyl ketone,.
  • Methyl propionate, ethyl propionate, butyl propionate, ethylene carbonate, 1, 2-propylene carbonate or 1, 3-propylene carbonate, water is preferred.
  • (I) and optionally components (AI), (A2), (B), (C) and / or (D) can be dispersed in the solvent (III).
  • the proportion of (III) in the respective solution is determined by its solution properties. It can be between 10 and 99% by weight, preferably between 20 and 98% by weight and particularly preferably between 30 and 95% by weight.
  • the mixtures according to the invention are prepared by intimately mixing components (I), or their individual components (A) to (D), and, if appropriate, the solvent (III) in any order. If necessary, this can be done under protective gas.
  • the temperature during production is not restricted and is generally limited by the freezing or glass transition temperature and by the boiling point or the curing temperature of the respective components or mixtures.
  • the temperature is from 0 ° C to 80 ° C, preferably from 10 ° C to 70 ° C and particularly preferably from 20 ° C to 60 ° C.
  • the coating materials (I) are coated with the coating materials by customary methods known to the person skilled in the art, at least one mixture according to the invention, for example in the form of a dispersion or without solvent (III), onto the substrate to be coated in the desired
  • Starch is applied and the volatile constituents of the dispersion are removed, if appropriate with heating. If desired, this process can be repeated one or more times.
  • the application to the carrier material can in a known manner, for. B. by spraying, spraying, dipping, filling, knife coating, air blade, brushing, rolling, rolling or pouring, or using the so-called reverse gravure process.
  • the carrier film can be subjected to a corona treatment beforehand.
  • the coating thickness is generally in a range from about 2 to 500 g / m 2 and preferably 2 to 100 g / m 2 .
  • Films are coated in particular with quantities of up to 50, preferably 1-20 and particularly preferably between 1 and 10 g / m 2 , papers, cardboards and cartons with quantities between 2 and 30, preferably 10 to 20 g / m 2 (calculated in each case without Solvent (III)).
  • the solvent (III) evaporates.
  • the carrier film can be passed through a dryer channel, for example, in the case of continuous work, which can be equipped with an infrared radiation device.
  • the coated and dried film is then passed over a cooling roll and finally wound up.
  • the thickness of the dried coating is preferably up to 50 ⁇ m, particularly preferably 1 to 20 and very particularly preferably 1-10 ⁇ m.
  • the preferred viscosity of the coating compositions (I) is not limited per se, but is determined by the chosen method of application at the respective application temperature. For example, when applied over rollers, it should generally not be more than 500 mPas. When applying using a doctor blade, 1000 mPas should not be exceeded. In the case of rolling, rolling or casting, the viscosity is preferably set so that a continuous, continuous film is obtained on the support.
  • a method for coating carrier materials in which a coating composition (I), onto which carrier material is applied, optionally dried, thermally treated at the curing temperature indicated above and then, if appropriate at temperatures up to the curing temperature, with electron beams or UV Exposure cures under an oxygen-containing atmosphere or preferably under an inert gas.
  • a coating composition (I) onto which carrier material is applied, optionally dried, thermally treated at the curing temperature indicated above and then, if appropriate at temperatures up to the curing temperature, with electron beams or UV Exposure cures under an oxygen-containing atmosphere or preferably under an inert gas.
  • the method of coating of substrates may also be carried out so that cured after application of the coating composition initially with electron beams' or UV exposure under oxygen or, preferably, under inert gas and subsequently at the curing temperature is thermally treated.
  • the films formed on the carrier material can only be cured thermally.
  • the coatings are cured both by irradiation treatment with high-energy radiation as well as thermally, or only by radiation.
  • thermal and / or radiation curing can take place after each coating process.
  • the finished coating has a glass transition temperature above the usage temperature, usually above room temperature.
  • coating of carrier materials can also be carried out as follows, where:
  • step iii) optionally irradiating the film formed in step ii) with high-energy radiation, the film being prehardened, and then, if appropriate, mechanically processing the object coated with the prehardened film or bringing the surface of the precured film into contact with another substrate,
  • Steps iv) and iii) can also be carried out in the reverse order.
  • H. the film can first be cured thermally and then with high-energy radiation.
  • Typical curing temperatures for oriented polypropylene are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
  • the temperature should not exceed 80 ° C., preferably 60 ° C.
  • the temperature can also be up to 150 ° C., preferably up to 140 ° C., particularly preferably from up to 120 and very particularly preferably be raised up to 100 ° C.
  • the temperature can remain the same or be raised during the course of the hardening process.
  • the curing time is usually between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • active energy rays are ultraviolet, X-ray and electron beams; ultraviolet and electron beams are preferred.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps and high-pressure lamps as well as fluorescent tubes, pulsed lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, electron flash devices, which enables radiation curing without a photoinitiator, or radiation.
  • High-pressure mercury vapor lamps, lasers, pulsed lamps (flashing light), halogen lamps or excimer lamps are used as radiation sources, for example.
  • the radiation dose usually sufficient for crosslinking in UV curing is in the range from 80 to 3000 mJ / cm 2 .
  • radiation sources can also be used for curing, e.g. two to four.
  • the irradiation can optionally also be carried out with the exclusion of oxygen, e.g. B. are carried out under an inert gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Irradiation can also be carried out by covering the coating material with transparent media. Transparent media are e.g. B. plastic films, glass or liquids, eg. B. water. Irradiation in the manner as described in DE-A 199 57 900 is particularly preferred.
  • Another preferred form of coating and curing is the application of the coating materials between two carrier materials, at least one of which is transparent to the radiation used for radiation curing.
  • the loading Layering compound also act as a lamination adhesive.
  • the substrates coated with the coating composition show an excellent barrier effect against oxygen, even when exposed to moisture.
  • the coated substrates can be used as such as packaging.
  • the coatings have very good mechanical properties and show e.g. Gloss, transparency and good blocking behavior and show essentially no cracking.
  • the packaging means for example, good printability, even better sealing and blocking behavior, good water resistance
  • the substrate pre-coated with the oxygen barrier shows good top coatability. It can be overcoated again using a method mentioned above, or it can be coated several times in a continuous process without intermediate winding and unwinding, for example the film.
  • 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 oxygen barrier layer.
  • oxygen-impermeable coatings can be easily applied to the carrier materials mentioned at the beginning, e.g. on films made of oriented polypropylene or polyethylene, the polyethylene having been produced both by the high pressure and by the low pressure polymerization processes of ethylene.
  • suitable carrier films are, for example, films made of polyester, such as polyethylene terephthalate, films made of polyamide, polystyrene and polyvinyl chloride. Papers and metal foils such as aluminum foil are also suitable as carrier foils.
  • 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 200 ⁇ m and for films made of polystyrene at around 20 ⁇ m.
  • the coated carrier material system according to the invention generally has an oxygen permeability below 100 cm 3 / (m 2 xdx bar) based on 100 ⁇ m, particularly preferably below 50 and very particularly preferably below 20 and in particular below 10. Furthermore, the coated film systems according to the invention act as fat barriers against migration of fats, oils and waxes through the coated film system, and as aroma barriers against the migration of aroma substances, especially terpenes and terpenoid flavors and aroma substances.
  • the coating can equally improve water resistance, gloss, non-blocking, sliding behavior, hardness and bondability.
  • additives (D) known per se to the person skilled in the art can optionally be added to the coating composition (I).
  • the coatings of the invention are water resistant, i.e. they show on contact with moisture, e.g. in the Cobb test (DIN 53132), no detachment or stickiness.
  • coated carrier materials according to the invention are particularly suitable as packaging systems, particularly preferably in the food sector.
  • the coating is preferably on the side facing outwards, i.e. on the side facing away from the food.
  • the carrier material can be coated in another way before or after the coating, e.g. be printed. If desired, after coating with the coating composition (I) e.g. there is a gloss coating.
  • the coating compositions used in the examples and comparative examples were solvent-free, i.e. used as 100% systems. 4% by weight of Irgacure® 184 from Ciba Specialty Chemicals were used as photoinitiators.
  • the UV radiation was carried out using a system from the IST company using a medium-pressure mercury lamp with an output of 120 W / cm and a distance of 15 cm from the substrate at a belt feed of 5 m / min.
  • the oxygen permeability was determined on coatings on a oriented polypropylene film determined at 0% relative humidity. First, the oxygen permeability is measured, which is then converted to a layer thickness of 100 ⁇ m and specified as oxygen permeability with the unit cm 3 / (m 2 xdx bar), where d is the time in days. The determination is based on ASTM-D 3985-81.
  • the aliphatic urethane acrylate from Comparative Example 1 was mixed 1: 1 (w / w) with acrylic acid.

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Abstract

L'invention concerne un procédé pour réaliser des moyens d'emballage bloquant le passage de l'oxygène. Selon ce procédé un matériau support est recouvert d'un agent d'enduction (I) avant d'être durci, lequel agent d'enduction comprend (A1) au moins un composé polymérisable contenant un ou plusieurs groupes copolymérisables et éthyléniquement insaturés, (A2) éventuellement au moins un autre composé polymérisable contenant un ou plusieurs groupes copolymérisables et éthyléniquement insaturés, (B) éventuellement un groupe copolymérisable et éthyléniquement insaturé contenant des diluants réactifs, (C) éventuellement un photoinitiateur et (D) éventuellement d'autres additifs.
PCT/EP2003/001065 2002-02-18 2003-02-04 Enductions pour materiaux supports destinees a bloquer le passage de l'oxygene WO2003068869A2 (fr)

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DE2002106831 DE10206831A1 (de) 2002-02-18 2002-02-18 Beschichtungen für Trägermaterialien zur Erreichung einer Sauerstoffbarriere

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WO2011023587A2 (fr) 2009-08-24 2011-03-03 Basf Se Utilisation de complexes de polyélectrolytes pour produire des feuilles polymères à propriétés de barrière à oxygène
WO2012175433A1 (fr) 2011-06-22 2012-12-27 Basf Se Films polymères revêtus à propriétés de barrière contre l'oxygène
US9574100B2 (en) 2011-06-22 2017-02-21 Basf Se Coated polymer foils with oxygen barrier properties

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Publication number Priority date Publication date Assignee Title
WO2011023587A2 (fr) 2009-08-24 2011-03-03 Basf Se Utilisation de complexes de polyélectrolytes pour produire des feuilles polymères à propriétés de barrière à oxygène
WO2011023587A3 (fr) * 2009-08-24 2011-11-24 Basf Se Utilisation de complexes de polyélectrolytes pour produire des feuilles polymères à propriétés de barrière à oxygène
EP2570196A2 (fr) 2009-08-24 2013-03-20 Basf Se Utilisation de complexes de polyélectrolytes pour la fabrication de films polymères ayant des propriétés de barrière à l'oxygène
US8980437B2 (en) 2009-08-24 2015-03-17 Basf Se Use of polyelectrolyte complexes for producing polymer foils with oxygen-barrier properties
EP2570196A3 (fr) * 2009-08-24 2017-07-19 Basf Se Utilisation de complexes de polyélectrolytes pour la fabrication de films polymères ayant des propriétés de barrière à l'oxygène
WO2012175433A1 (fr) 2011-06-22 2012-12-27 Basf Se Films polymères revêtus à propriétés de barrière contre l'oxygène
US9574100B2 (en) 2011-06-22 2017-02-21 Basf Se Coated polymer foils with oxygen barrier properties

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AU2003210206A1 (en) 2003-09-04
AU2003210206A8 (en) 2003-09-04
WO2003068869A3 (fr) 2003-12-24

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